1
XPS study and electronic structure of non-doped and Cr+ ion implanted CuO thin films
Ungeheuer, K; Bocirnea, AE; Marszalek, KW; Tokarz, W; Pikulski, DA; Kakol, Z; Galca, AC
JUL 12 2025, SCIENTIFIC REPORTS, 15, 25255
DOI: 10.1038/s41598-025-08421-4
Show abstract
CuO is a p-type semiconductor that can be found useful in various applications, sensing, photocatalysis or photovoltaics. Better material performance can be achieved by doping. In our study the doping was done using Cr ions and implantation method. Thin film samples were characterised with X-ray photoelectron spectroscopy (XPS) technique to study chemical properties of the films' surface and to determine the in-depth compositional profile of the films before and after annealing of an implanted sample. Spectroscopic ellipsometry was used to extract the dielectric function of CuO thin films. Depolarization measurements are shown as a useful method to quickly study differences between similar samples. XPS measurements proved that before annealing there is a peak of Cr concentration in depth of the sample, which is no longer present after annealing. Measurement of film resistance as function of temperature in range of 150-300 degrees C resulted with 0.82 eV bandgap. Electronic structure obtained with density functional theory calculations (DFT) showed that with Cr doping the energy band gap narrows and the material should become metallic.
2
Influence of Proton Irradiation on Thin Films of AZO and ITO Transparent Conductive Oxides-Simulation of Space Environment
Ungeheuer, K; Rybak, J; Bocirnea, AE; Pikulski, DA; Galca, AC; Marszalek, KW
JAN 2025, APPLIED SCIENCES-BASEL, 15, 754
DOI: 10.3390/app15020754
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Featured Application Optoelectronic devices in space missions.Abstract Transparent conductive oxides are essential materials for many optoelectronic applications. For new devices for aerospace and space applications, it is crucial to know how they respond to the space environment. The most important issue in commonly used low-Earth orbits is proton radiation. This study examines the effects of high-energy proton irradiation (226.5 MeV) on thin films of aluminium-doped zinc oxide (AZO) and indium tin oxide (ITO). We use X-ray diffraction and electron microscopy observations to see the changes in the structure and microstructure of the films. The optical properties and homogeneity of the materials are determined by spectrophotometry and spectroscopic ellipsometry (SE). Analysis of the chemical states of the elements with X-ray photoelectron spectroscopy (XPS) gives insight into what proton irradiation changes at the surface of the oxides. All measurements show that ITO is less influenced than AZO. The proton energy and fluence used in this study simulate about a hundred years in low Earth orbit. This research demonstrates that both transparent conductive oxide thin films can function under simulated space conditions, with ITO showing superior resilience. The ITO film was more homogenous in terms of the total thickness measured with SE, had fewer defects and adsorbates present on the surface, as XPS analysis proved, and did not show a difference after irradiation regarding its optical properties, transmission, refractive index, or extinction coefficient.
3 Open Access
α-MoO3 Micro- and Nanoparticles as Catalysts for Biofuel Production
de Medeiros, SASL; de Oliveira, ALM; Duarte, TM; Kennedy, BJ; Rostas, AM; Negrila, CC; Galca, AC; Maia, AD; Sambrano, JR; Dantas, MC; Farias, AF; dos Santos, IMG
MAR 7 2025, ACS APPLIED NANO MATERIALS, 8
DOI: 10.1021/acsanm.4c01239
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Herein, alpha-MoO3 micro- and nanoparticles were synthesized by a modified Pechini method, and the impact of the crystal structure and crystal growth orientation on the formation of ionic defects and, consequently, on the catalytic performance of the materials in the ethylic transesterification reaction for biodiesel production was investigated. Structural refinements from X-ray diffraction data and Raman spectra revealed the formation of alpha-MoO3 in a Pbnm orthorhombic phase, with nanoplate-like morphology at 500 degrees C (thickness between 100 and 260 nm) or ribbon-like morphology at 700 degrees C (thickness between 400 and 900 nm). An anisotropic crystal orientation along the [010] direction was observed with an increase of the calcination temperature. We emphasize the dependence of the orientation change with the elimination of ionic-type defects (oxygen vacancies and reduced Mo5+ centers) by the temperature using complementary techniques such as X-ray photoelectron and electron paramagnetic resonance spectroscopies. The catalytic activity of the samples depends on the orientation process and the presence of defects that act as acid-active sites on the catalyst surface and therefore play an important role in biodiesel production. This effect was confirmed by surface stability and reactivity simulated by density functional theory calculations, suggesting that the Mo and O surface terminals greatly impacted the interface catalytic reaction. The highest catalytic performance toward the biodiesel conversion (89% of conversion at 150 degrees C for 2 h) was achieved for the polycrystalline catalyst calcined at 500 degrees C, which was correlated with random crystal orientation and the presence of reduced Mo5+ and oxygen vacancy centers on the different facets exposed on the surface. The biodiesel production was confirmed by H-1 and C-13 NMR spectroscopy and gas chromatography analysis.
4
Effects of cationic substitution on the properties of Sb1-xBixSeI (x=0-1) compounds
Sadurni, MD; Timmo, K; Mikli, V; Krustok, J; Danilson, M; Suchodolskis, A; Radu, C; Bocirnea, AE; Galca, AC; Grossberg-Kuusk, M; Kauk-Kuusik, M
AUG 10 2025, JOURNAL OF ALLOYS AND COMPOUNDS, 1037, 182292
DOI: 10.1016/j.jallcom.2025.182292
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Pnictogen chalcohalide semiconductors are emerging materials with broad potential in energy-related applications, including solar cells, photocatalysis, photodetectors, batteries, supercapacitors, thermoelectric and piezoelectric generators. Their compositional flexibility allows fine tuning of structural and optoelectronic properties. In this study, microcrystalline powders of Sb1-xBixSeI (x = 0-1) were synthesized from binary precursors by a solid-state method in evacuated quartz ampoules. Energy dispersive spectroscopy confirmed the successful substitution of Sb with Bi in Sb1-xBixSeI. The formation of solid solutions was also supported by Raman spectroscopy and X-ray diffraction (XRD). All materials exhibited needle-shaped crystal morphologies and orthorhombic crystal structure (Pnma), regardless of the Bi/Sb ratio. XRD patterns shifted toward smaller angles with increasing Bi content, indicating lattice expansion. Calculated lattice parameters (b and c) increased linearly with Bi incorporation, while the lattice parameter (a) remained constant. Raman spectra exhibited characteristic peaks at 182 cm- 1 for Bi-Se vibration and 209 cm- 1 for Sb-Se vibration, with intensity ratios reflecting Bi content. UV-Vis-NIR diffuse reflectance spectroscopy revealed a direct band gap that decreased from 1.7 eV (SbSeI) to 1.29 eV (BiSeI). Room-temperature photoluminescence measurements exhibited a single emission band, shifting from 1.75 eV to 1.41 eV with increasing Bi content. Ultraviolet photoelectron spectroscopy indicated a shift in the valence band maximum from 0.44 eV (SbSeI) to 1.1 eV (BiSeI). These findings highlight the tunability of Sb1-xBixSeI compounds, offering pathways for optimizing their properties for specific optoelectronic applications.
5
Superstrate structured Sb2S3 thin-film solar cells by magnetron sputtering of Sb and post-sulfurization
Gilshtein, E; Gupta, HM; Enevoldsen, AMP; Besleaga, C; Galca, AC; Canulescu, S
OCT 2025, MATERIALS & DESIGN, 258, 114621
DOI: 10.1016/j.matdes.2025.114621
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This study explores the fabrication and optimization of superstrate-structured antimony sulfide (Sb2S3) thin-film solar cells using RF magnetron sputtering of antimony (Sb) followed by sulfurization. The study systematically investigates the effects of varying absorber and buffer layer thicknesses on the photovoltaic performance of FTO/ CdS/Sb2S3/Spiro-OMeTAD/Au solar cell devices. Analytical techniques confirmed the structural and chemical properties of the Sb2S3 films obtained after Sb post-sulfurization, demonstrating improved crystallinity and a composition consistent with a primarily Sb2S3 phase. Optimizing the Sb2S3 absorber thickness to 100 nm resulted in a maximum power conversion efficiency of the champion device of 2.76%, with enhanced short-circuit current density (J(sc)) up to 14 mA/cm(2) and open-circuit voltage (V-oc) of up to 650 mV. The device exhibited semi-transparency up to 20% in the wavelength range of 380-740 nm, making it suitable for indoor and building-integrated photovoltaic applications. The results underscore the potential of magnetron-sputtered Sb2S3 for emerging transparent thin-film photovoltaics while highlighting the importance of thickness control and interface engineering for efficiency improvements.
6
Bioengineered Y2O3 nanorods and their potential blue-emitting phosphors
Diallo, A; Ndiaye, S; Tite, T; Yahsi, U; Diculescu, VC; Seck, A; Dioum, A; Ngom, BD; Ahmad, I; Galca, AC; Azizi, S
MAR 22 2025, BULLETIN OF MATERIALS SCIENCE, 48, 50
DOI: 10.1007/s12034-025-03406-5
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This article describes a new synthesis of nanoscaled Y2O3 that is bioinspired. It has been confirmed that Callistemon viminalis flower extract works well as a chelator when used to bioengineer high-shape anisotropy nanorods of single-phase Y2O3 . X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, fourier transform infrared spectroscopy and photoluminescence spectroscopy were used to analyse the structural, morphological, surface and optical features. The photoluminescent spectra of the bio-engineered nanorods show blue emissions. As the annealing temperature was increased from 300 to 500 degrees C, the blue colour purity values of the synthesized Y2O3 nanorods were 58.1, 80.7 and 77.0% at 300, 400 and 500 degrees C respectively. The chromaticity coordinates (0.2020, 0.1931), (0.1660, 0.1082) and (0.1714, 0.1226) from the photoluminescence spectra of the biosynthesized Y2O3 nanorods were used to determine these values. The CIE y-component coordinate values of the bioengineered blue-emitting nanophosphors suggest their potential for applications in display technology and white light-emitting diodes.
7
Experimental and theoretical perspective on band gap modulation in Sr modified BaTiO3 capacitors 2+
Zidi, Y; Khaldi, O; Patru, RE; Leonat, LN; Enculescu, M; Toma, V; Stepanova, A; Ben Younes, R; Galca, AC
MAY 2025, CERAMICS INTERNATIONAL, 51
DOI: 10.1016/j.ceramint.2025.01.591
Show abstract
The present study investigates the influence of strontium (Sr) content on the intrinsic properties of barium strontium titanate (Ba1-xSrxTiO3, BST) which was successfully prepared by the conventional solid-state reaction with different concentrations of strontium (x = 0, 0.3, 0.5, 0.6, 0.7, 1). The resulting samples were characterized by X-ray diffraction, scanning electron microscopy, Raman spectroscopy and diffuse reflectance spectroscopy, the dielectric properties being also investigated. Structural and vibrational analyses reveal a structural phase transition from tetragonal to cubic at x = 0.4, with a linear decline of the tetragonality ratio as well as a shrinkage in the unit cell volume that occur with increasing Sr content. The morphological study shows that the grain size decreases as the Sr content increases in the tetragonal phase. Yet, upon the phase transition from tetragonal to cubic, the grain size initially increases, followed by a subsequent decrease with further Sr addition. It has been found that the band gap shows a decrease as Sr content increases. The temperature dependence of the dielectric parameters reveals that the Curie temperature as well as the dielectric constant and the loss tangent are strongly affected by the addition of Sr. The activation energy derived from the dielectric response, was found to be in the range 0.685-1.065eV, suggesting the dominance of doubly ionized oxygen vacancy for conduction and relaxation mechanism. Ab initio calculations were done employing the Linear Combination of Atomic Orbitals (LCAO) method. The bandgap energy (Eg) and the structural parameters were calculated using various types of exchange-correlation functionals (PWGGA, PBE, B3LYP and PBE0). A good agreement with the experimental results is achieved using the PBE0 functional. This study contributes to a better understanding of the structure-property relationship in BaSrTiO3 and provides valuable insights for optimizing its performance in various technological applications.
8
Exploring the Synthesis of Cu2(Zn,Cd)SnS4 at High Temperatures as a Route for High-Efficiency Solar Cells
El Khouja, O; Gong, YC; Jimenez-Arguijo, A; Guerra, MJ; Medaille, AG; Scaffidi, R; Basak, A; Radu, C; Flandre, D; Vermang, B; Giraldo, S; Placidi, M; Li-Kao, ZJ; Galca, AC; Saucedo, E
MAY 2025, PROGRESS IN PHOTOVOLTAICS, 33
DOI: 10.1002/pip.3899
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The present research explores for the first time the intricate relationship between sulfurization temperature at unusual high temperatures (up to 700 degrees C) and the structural/optoelectronic properties of Cu-2(Zn,Cd)SnS4 (CZCTS) thin films, synthesized via a two-step sequential process involving the precursor film deposition using aprotic molecular ink followed by thermal treatment in sulfur atmosphere. X-ray diffraction patterns confirms the tetragonal structure. Scanning Electron Micrographs revealed significant grain growth, with grain sizes increasing from similar to 0.3 mu m at 620 degrees C to similar to 1.5 mu m at 680 degrees C, effectively reducing grain boundary recombination. Energy dispersive X-ray spectroscopy demonstrated a Cu-poor and Zn-rich composition, with a consistent Cd incorporation of similar to 3.7 at%. Raman spectroscopy showcases the homogeneity and purity of the CZCTS crystalline structure. Precise control of the sulfurization temperature plays a crucial role in determining the photovoltaic characteristics of CZCTS-based solar cells. By increasing the grain size and preventing the thermal decomposition of the CZTS phase, the photovoltaic performance peaked at a sulfurization temperature of 680 degrees C, achieving a power conversion efficiency (PCE) of 10.4%, with an open-circuit voltage of 0.701 V, a short-circuit current density of 24.3 mA/cm(2) and a fill factor of 60.8%. External quantum efficiency reached a maximum of 83.3% at 580 nm. The bandgap of the CZCTS absorber was determined to be 1.48 eV, optimal for photovoltaic applications. However, further increasing the sulfurization temperature to 700 degrees C resulted in a lower PCE of 8.5%, attributed to interface degradation and secondary phase formation. Temperature-dependent current-voltage measurements revealed a reduction in recombination losses, with an activation energy of 1.24 eV at the CZCTS/CdS interface, indicating effective defect passivation by Cd incorporation. The optimized films, sulfurized at 680 degrees C, displayed an absorber thickness of similar to 1.2 mu m after sulfurization, providing efficient light absorption and charge transport. The findings not only emphasize the critical role of sulfurization temperature in engineering CZCTS film and subsequently their functionality but also provide valuable insights for fine tuning their performance in the field of photovoltaic applications.
9
High-Performance and Ultrafast Symmetric Supercapacitors Based on Cu(II)-Doped SrSnO3 Perovskites
Silva, A; Aleinawi, MH; Erdem, E; Kennedy, BJ; Galca, AC; dos Santos, IMG; Rostas, AM; de Oliveira, ALM
AUG 28 2025, JOURNAL OF PHYSICAL CHEMISTRY C, 129
DOI: 10.1021/acs.jpcc.5c03126
Show abstract
Herein, Cu(II)-doped SrSnO3 perovskites (SrSn1-x Cu x O3, namely SSO:Cux) were prepared by a modified Pechini method and applied as supercapacitors (SCs) for the first time. The effect of dopant concentration (x = 1, 2.5, and 5 mol %) was investigated to fine-tune the structural and electronic properties to design potential candidates as SCs. The SSO:Cux samples were characterized by conventional XRD and synchrotron XRD (S-XRD) combined with Rietveld refinements and spectroscopic analyses, such as Raman, FTIR, UV-vis, EPR, and XANES/NEXAFS. The electrochemical performance of the SSO:Cux samples was investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic cycling with potential limitation (GCPL). It was evidenced that incorporating 2.5 mol % Cu(II) into the SrSnO3 perovskite lattice (SrSn0.975Cu0.025O3, SSO:Cu2.5) led to a significant change in structural disorder and electronic properties, which play an essential role in creating a mixture of point defects such as reduced Sn3+ and Cu+ cations, and oxygen vacancies (VO). The SC device constructed with the SSO:Cu2.5 material showed a specific capacitance of 613 F g-1 at a scan rate of 1 mV s-1, with a remarkable specific energy density and specific energy power of 25.42 W h kg-1 and 32678.57 W kg-1, respectively, which are higher than those observed for any other available perovskite-based SCs. This performance was primarily attributed to the formation of mixed Sn4+/Sn3+ and Cu2+/Cu+ cations, which alter the structural and electronic properties of SrSnO3. Our findings indicate that an improved capability to store high energy and power may be achieved by fine-tuning the Cu(II) dopant concentration in the lattice and controlling the formation of undesired phases. This offers experimental guidance to design other Cu-doped perovskites as alternative materials for energy storage applications.
10 Open Access
Experimental and theoretical perspective on band gap modulation in Sr modified BaTiO3 capacitors <SUP>2+</SUP>
Zidi, Y; Khaldi, O; Patru, RE; Leonat, LN; Enculescu, M; Toma, V; Stepanova, A; Ben Younes, R; Galca, AC
MAY 2025, CERAMICS INTERNATIONAL, 51
DOI: 10.1016/j.ceramint.2025.01.591
Show abstract
The present study investigates the influence of strontium (Sr) content on the intrinsic properties of barium strontium titanate (Ba1-xSrxTiO3, BST) which was successfully prepared by the conventional solid-state reaction with different concentrations of strontium (x = 0, 0.3, 0.5, 0.6, 0.7, 1). The resulting samples were characterized by X-ray diffraction, scanning electron microscopy, Raman spectroscopy and diffuse reflectance spectroscopy, the dielectric properties being also investigated. Structural and vibrational analyses reveal a structural phase transition from tetragonal to cubic at x = 0.4, with a linear decline of the tetragonality ratio as well as a shrinkage in the unit cell volume that occur with increasing Sr content. The morphological study shows that the grain size decreases as the Sr content increases in the tetragonal phase. Yet, upon the phase transition from tetragonal to cubic, the grain size initially increases, followed by a subsequent decrease with further Sr addition. It has been found that the band gap shows a decrease as Sr content increases. The temperature dependence of the dielectric parameters reveals that the Curie temperature as well as the dielectric constant and the loss tangent are strongly affected by the addition of Sr. The activation energy derived from the dielectric response, was found to be in the range 0.685-1.065eV, suggesting the dominance of doubly ionized oxygen vacancy for conduction and relaxation mechanism. Ab initio calculations were done employing the Linear Combination of Atomic Orbitals (LCAO) method. The bandgap energy (Eg) and the structural parameters were calculated using various types of exchange-correlation functionals (PWGGA, PBE, B3LYP and PBE0). A good agreement with the experimental results is achieved using the PBE0 functional. This study contributes to a better understanding of the structure-property relationship in BaSrTiO3 and provides valuable insights for optimizing its performance in various technological applications.
11
Gas-Assisted Spray Fabrication of Reticulated TiO2 Scaffolds for Perovskite Solar Applications
Handor, S; Tomulescu, AG; Stancu, V; Razouk, A; Galca, AC; Leonat, LN
JUN 5 2025, MICROMACHINES, 16, 685
DOI: 10.3390/mi16060685
Show abstract
This study presents a systematic approach to engineering the electron transport layer (ETL) in perovskite solar cells using a spray deposition technique to fabricate sequentially compact and mesoporous titanium dioxide (c-TiO2, m-TiO2) films. The spray coating method leads to the development of a distinct reticulated morphology characterized by well-defined wavy-like surface features and significantly increased roughness-at least twice that of spin-coated mesoporous films. The increased interfacial area between the mesoporous TiO2 and the perovskite layer facilitates more efficient charge transfer, contributing to higher device performance. By optimizing the deposition parameters, particularly the number of spray cycles for the m-TiO2 layer, we achieve a significant enhancement in device performance, with improvements in power conversion efficiency (PCE), reduced series resistance, and minimized hysteresis. Our results demonstrate that an optimal film thickness promotes better perovskite anchoring, while excessive deposition impedes light transmission and increases sheet resistance. These findings advance the practical fabrication of high-performance perovskite solar cells using simple solution-processing techniques and highlights the potential of scalable spray deposition methods for industrial-scale fabrication.
12
Improved sulfurization process for enhancing the microstructure and transport properties of spray pyrolysis-deposited Cu2ZnSnS4 films
El Khouja, O; Popescu, B; Assahsahi, I; Negrila, CC; Leonat, LN; Nouneh, K; Touhami, ME; Galatanu, A; Galca, AC
NOV 2025, CERAMICS INTERNATIONAL, 51
DOI: 10.1016/j.ceramint.2025.08.041
Show abstract
Cu2ZnSnS4 (CZTS) is an emerging material with significant potential as an absorber layer for solar cells. Precise control over the film preparation process is crucial for attaining optimal transport, electrical, and optical properties. This study investigates the effect of sulfurization duration on the properties of CZTS films deposited onto soda lime glass substrates via spray pyrolysis, followed by annealing at 550 degrees C in a sulfur-rich environment under argon flow. X-ray diffraction and Raman spectroscopy confirmed the formation of monophasic CZTS, with the highest phase purity observed for films sulfurized for 5 min. Scanning electron microscopy demonstrated notable morphological and microstructural enhancements due to the sulfurization process, while energydispersive spectroscopy confirmed near-ideal stoichiometric composition (Cu:Zn:Sn:S approximate to 2:1:1:4). Optical spectroscopy determined the band gap of the films to be between 1.40 and 1.50 eV. The electrical transport properties were investigated up to 130 degrees C, revealing p-type conductivity, with Seebeck coefficients ranging from 30 to 70 mu V K-2 and low electrical resistivity, displaying semiconductor-like behavior. The maximum power factor achieved was 0.36 mu W mK-2 at 130 degrees C for the sample sulfurized for 5 min. These findings suggest that a 5-min sulfurization time is optimal for producing single-phase CZTS films characterized by uniform morphology, accurate stoichiometric composition, and an ideal direct band gap. Given its favorable thermoelectric properties, CZTS shows significant promise as a material for thermoelectric applications, particularly in waste heat recovery systems. The results indicate that CZTS films could be further optimized for use in thermoelectric devices, and future studies could focus on enhancing their thermoelectric performance by adjusting sulfurization conditions and exploring material modifications.
13
Optical characterization of Sm3+doped phosphate glasses for potential orange laser applications
Bayoudhi, D; Bouzidi, C; Matei, E; Secu, M; Galca, AC
JAN 2024, JOURNAL OF LUMINESCENCE, 265, 120204
DOI: 10.1016/j.jlumin.2023.120204
Show abstract
Undoped and Sm3+doped 45P2O5-45Na2O-2Al2O3-8BaO glasses were synthesized by the melt-quenching technique. The glass structure and luminescence properties were investigated by using Raman spectroscopy, scanning electron microscopy (SEM), spectroscopic ellipsometry, Judd-Ofelt theory and photoluminescence. Electron microscopy showed the homogeneity of samples. Raman spectroscopy revealed that the overall struc-ture of the glass was unaffected by the doping of Sm3+ and ellipsometry was used to measure the optical constants. Judd-Ofelt (JO) analysis was performed on the absorption bands of Sm3+ (4f5) and the three phenomenological parameters (omega 2, omega 4, and omega 6) were computed and then used to determine radiative properties such as the radiative transition probability (Ar), the fluorescent branching ratio (beta r), the stimulated emission cross-section (sigma e) and the radiative lifetime (tau rad). Photoluminescence (PL) spectrum showed the typical four transitions of Sm3+ at wavelengths of 564, 600, 645 and 703 nm corresponding to 4G5/2 -> 6H5/2, 6H7/2, 6H9/2 and 6H11/2, respectively. The spectroscopic quality factors omega 4/omega 6, the predicted lifetime (tau rad) calculated using the JO method and the experimentally lifetime (tau exp) for the 4G5/2level were calculated and discussed. The glass color purity is as high as 98%, which makes it a potential candidate for laser emission.
14
Magnetocaloric properties of La0.9K0.1MnO3 and La0.8K0.1Pb0.1MnO3 bulk perovskite manganites
Bouzid, SA; Elhamouchi, N; Sajieddine, M; Aitmellal, O; Kuncser, V; Galca, AC; Iacob, N; Enculescu, M; Essoumhi, A
NOV 2024, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 35, 2138
DOI: 10.1007/s10854-024-13873-x
Show abstract
In the present work, we report the synthesis and investigations of La0.9K0.1MnO3 and La0.8K0.1Pb0.1MnO3 bulk samples which could be potential magnetocaloric materials for magnetic refrigeration close to room temperature. A flash combustion reaction and sintering at 1200 degrees C for 10 h are used to prepare the bulk materials. Both compounds crystallized into a rhombohedral structure with R3\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\overline{3 }$$\end{document}c space group confirmed by X-ray powder diffraction results. Scanning electron microscopy analysis, combined with XRD peak profiles is performed to estimate the particle/crystallite size of the samples. Moreover, the Curie temperature, TC, is found to be higher in lead-rich sample due to the enhancement of the grain size and the Mn3+-O-Mn4+ double exchange (DE) interaction. Therefore, the bulk sample La0.8K0.1Pb0.1MnO3 shows a room temperature phase transition of 289 K as well as a higher saturation magnetization. The La0.8K0.1Pb0.1MnO3 bulk compound exhibits a high and sharp peak in magnetic entropy change up to 5.5 Jkg-1 K-1 under 5 T at the magnetic transition temperature TC. To compare the magnetocaloric performances of the studied compounds, relative cooling power (RCP) was employed. The obtained experimental results revealed that the increase in particle size influences severely the magnetocaloric properties.
15 Open Access
Reticulated mesoporous TiO2 scaffold for self-cleaning surfaces
Besleaga, C; Tomulescu, AG; Zgura, I; Stepanova, A; Galca, AC; Laafar, S; Zorila, FL; Alexandru, M; Pintilie, I; Iliescu, M
NOV 1 2024, CERAMICS INTERNATIONAL, 50
DOI: 10.1016/j.ceramint.2024.08.072
Show abstract
Interest in self-cleaning coatings is rising due to their potential to enhance comfort and quality of life in polluted urban environments, driving the search for materials with optimal physical properties. Convergent with this goal, this study investigates the wetting properties and photo-catalytic efficiency of reticulated TiO2 layers. It shows that these properties are significantly influenced by the topographical characteristics of the TiO2 surface, which can be precisely controlled through variations in pulverization pressure and low-temperature post-annealing treatments. Post-deposition annealing of the TiO2 layers achieves 100 % self-cleaning efficiency for both thick and thin films, with optical transmission ranging from approximately 60 %-80 % in the visible spectrum. Additionally, the TiO2 layers exhibited promising capabilities for eliminating pathogenic microorganisms and disinfecting surfaces. The underlying causal factors of these remarkable and technologically promising surface features are explored and discussed.
16 Open Access
Investigation of kesterite to stannite phase transition and band gap engineering in Cu2Zn1-xCoxSnS4 thin films prepared by sol-gel spin coating
El Mahboub, E; El Khouja, O; Bocirnea, AE; Zakaria, S; Galca, AC; Mansori, M; El Hichou, A
NOV 1 2024, APPLIED SURFACE SCIENCE, 672, 160848
DOI: 10.1016/j.apsusc.2024.160848
Show abstract
In this study, the Cu2Zn1-xCoxSnS4 (CZn1-xCoxTS) films with partial cation substitution of cobalt are synthetized by sol gel spin coating, followed by sulfurization treatment. The incorporation of cobalt cation in the CZTS crystalline lattice as well as the phase transition from kesterite to stannite were confirmed by the X-ray diffraction (XRD) and Raman spectroscopy data. The XRD pattern shows peak-shifting toward higher 2 theta by increasing the Co concentration, indicating a decrease in lattice parameters. The red shift of Raman peaks by increasing x from 0 to 0.6, confirms the phase transition. The CZn1-xCoxTS morphology was observed by scanning electron microscopy, showing large grain size as x increases and a good distribution of elements for all films. Xray photoelectron spectroscopy was employed to study the valence of cations/anions and to probe the chemical bonds. The optical band gap showed a parabolic behavior versus the molar ratio Co/(Co + Zn), this deviation from Vegard's law being induced by the difference in electronegativity between cobalt and zinc. The pure CZTS has a band gap of 1.47 eV, while for CZn0.6Co0.4TS the gap is 1.17 eV, which indicates that the incorporation of cobalt cation produces a red-shift of the band to band transition energy.
17 Open Access
Two-step process for the fabrication of direct FLG\MoS2 heterostructures
Buruiana, AT; Bocirnea, AE; Sava, F; Matei, E; Tite, T; Mariana, A; Simandan, ID; Galca, AC; Velea, A
AUG 1 2024, MATERIALS CHEMISTRY AND PHYSICS, 322, 129530
DOI: 10.1016/j.matchemphys.2024.129530
Show abstract
MoS2 has proven its efficacy in flexible electronics, transistor devices, and various biological and chemical applications. However, it is still challenging to achieve large-area MoS2 monolayers with desired material quality and electrical properties to fulfill the requirement for practical applications. Moreover, the main strategy for the preparation of a 2D heterostructure it is based on the sequential stacking of the layered materials using wet or dry transfer methods which introduces many defects. This paper presents an economically viable and straightforward two-step methodology to obtain MoS2 thin films, encompassing magnetron sputtering deposition of Mo and subsequent annealing in a sulfur-rich environment. This approach successfully yielded MoS2 thin films on Si\SiO2 substrates. Additionally, heterostructures consisting of few layer graphene (FLG) and MoS2 were directly obtained using the same method. The utilization of grazing incidence X-ray diffraction verified the formation of the hexagonal MoS2 phase, a finding further confirmed by Raman spectroscopy. X-ray photoelectron spectroscopy (XPS) investigations revealed the successful sulfurization process, with surface-bound oxides forming only subsequent to air exposure. Comprehensive assessment involving X-ray reflectivity, atomic force microscopy and XPS collectively inferred the fabrication of thin films comprised of a small number of MoS2 layers covering the entire substrate. Electrical assessments exhibited an electrical hysteresis, demonstrating its potential for memristor applications. Overall, this study outlines a cost-effective fabrication method for producing nanoscale MoS2 thin films with excellent properties, avoiding the use of toxic gases such as H2S. These findings contribute to the potential development of cutting-edge applications.
18 Open Access
The Influence of SnO2 and Noble Metals on the Properties of TiO2 for Environmental Sustainability
Goncearenco, E; Morjan, IP; Fleaca, C; Dutu, E; Criveanu, A; Viespe, C; Galca, AC; Maraloiu, AV; Stan, MS; Fort, CI; Scarisoreanu, M
APR 2024, SUSTAINABILITY, 16, 2904
DOI: 10.3390/su16072904
Show abstract
In order to find solutions to current worldwide environmental problems, it is crucial to develop sustainable nanomaterials, ideally with multifunctional properties. Considering this, novel TiO2-SnO2@NMs (noble metals: Au and Ag) composites, for use as sustainable nanomaterials, were successfully prepared via a two-step synthesis process consisting of laser pyrolysis followed by the chemical impregnation of the collected materials with noble metals. The addition of SnO2 favors the transformation of TiO2 from a mixture with a majority Anatase phase to one with a Rutile phase majority. With consideration for their level of environmental toxicity, the features of the synthesized nanomaterials were structurally, morphologically, and optically described and assessed for environmental protection applications as gas sensors and photocatalysts. In the case of the Surface Acoustic Wave sensor, based on a pure TiO2 nanopowder, a notable difference in the frequency shift was detected in comparison to the other examined sensors. All sensors responded to the CH4 concentrations tested (0.02-0.1%). On the other hand, when methyl orange was photodegraded under visible light, the results obtained using NMs for decoration revealed that the photocatalytic activity of TiO2-SnO2@NMs was significantly improved compared to the TiO2-SnO2 binary composite, which already has an enhanced photocatalytic activity, compared to pure TiO2. Overall, this work produces nanoparticles that exhibit better sensory and photocatalytic features, as well as higher levels of biocompatibility with skin cells, for use as eco-friendly nanomaterials for a sustainable future.
19 Open Access
Effect of transition metal ions on the dielectric properties of chromium potassium phosphates
Mighri, Z; Patru, RE; Leonat, LN; El Khouja, O; Nasri, H; Rostas, AM; Galca, AC
DEC 25 2024, JOURNAL OF ALLOYS AND COMPOUNDS, 1009, 176870
DOI: 10.1016/j.jallcom.2024.176870
Show abstract
Potassium ions are important for developing electrode materials because they have similar properties to lithium and sodium ions. Mixed chromium phosphates (KMIICr(PO4)2) II Cr (PO 4 ) 2 ) with substituted M II sites using divalent elements (M = Ni, Co, Cu) were synthesized using a solid-state reaction method. The samples were analyzed using various techniques such as powder X-ray diffraction, Fourier transform infrared, Raman, and electron paramagnetic resonance spectroscopy. The proposed phosphates had a monoclinic phase structure with a P21/n 1 /n space group, and they contained large tunnels occupied by K+ + cations. The dielectric properties showed that the Ni-based phosphates had slower dielectric relaxation, while the Co and Cu-based phosphates had quicker polarization and depolarization processes. Additionally, the resistance of the grains decreased from Ni to Co to Cu-based phosphates, indicating easier charge movement in each material, consistent with the increase in conductive losses and a.c. conductivity when changing the M II ions.
20 Open Access
Hybrid supercapacitors based on X-site Ba(II) ions substituted by Sr(II) in Langbeinite-type phosphates
Mighri, Z; Yildirim, ID; Leonat, LN; El Khouja, O; Erdem, E; Nasri, H; Galca, AC; Rostas, AM
AUG 2024, MATERIALIA, 36, 102147
DOI: 10.1016/j.mtla.2024.102147
Show abstract
The compounds KBa 1-x Sr x Cr 2 (PO 4 ) 3 (with x = 0.00; 0.25; 0.50; 0.75; 1.00) were synthesized by a solid-state reaction, and they were thoroughly characterized by different spectroscopic and microscopic techniques. Their structures were indexed in a cubic system with a P2 1 3 space group forming a 3D framework built on CrO 6 octahedra and PO 4 tetrahedra sharing vertices leading to identical Cr 2 P 3 O 18 (U) units. The interconnection between the tetrahedral and octahedral groups leads to the formation of two large closed cavities (K, M II )(1) and (K, M II )(2), statistically occupied by K + and M 2+ (M = Ba, Sr) atoms. Electron paramagnetic resonance spectroscopy confirmed the presence of paramagnetic Cr 3+ ions, showing the effects of substituting the Ba 2+ ions with smaller Sr 2+ ions on the dipolar coupling between the Cr 3+ centers. The obtained materials and active carbon were used as electrode materials in hybrid SC devices. At the same time, their electrochemical properties were assessed by potentiostatic electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge measurements, showing promising results with a maximal specific capacitance (3.86 F/g), energy density (343 mWh/kg), and power density (30.9 kW/kg) in the case of KBa 0.5 Sr 0.5 Cr 2 (PO 4 ) 3 , proving them as good candidates for positive and/or negative electrode materials for energy storage applications.
21
Growth and optimization of spray coated Cu 2 BaSnS 4 thin films for solar photovoltaic application
Kadari, AS; Ech-Chergui, AN; Ghediya, PR; Guendouz, A; Guezzoul, M; El Khouja, O; Bocirnea, AE; Driss-Khodja, K; Amrani, B; Galca, AC
AUG 2024, MATERIALIA, 36, 102178
DOI: 10.1016/j.mtla.2024.102178
Show abstract
Quaternary multicomponent Cu2BaSnS4 (CBTS) has emerged as a potential absorber material due to its abundant and nontoxic constituents, high absorption coefficient (10-4 cm-1) and suitable bandgap (1.5-2.0 eV) for the solar photovoltaic application. In this study, polycrystalline CBTS thin layers have been deposited by a typical spray pyrolysis technique on glass substrates using different substrate temperatures (Ts = 200, 250, 300 and 350 degrees C) followed by annealing in a sulfur-rich atmosphere at 550 degrees C under an argon flow. The (micro-)structural, compositional, and optical properties of both types of films have been studied. Analysis of x-ray diffractogram (XRD) patterns for all acquired films showed the presence of polycrystalline CBTS alongside various secondary phases, including Cu2SnS3 being predominant. Nonetheless, the XRD of the films deposited at 250 degrees C and annealed at 550 degrees C showed only the CBTS phase. Raman spectroscopy confirm the formation of the trigonal phase of CBTS. The presence of Cu, Ba, Sn and S in CBTS thin films was confirmed by X-ray photoelectron spectroscopy and Energy-dispersive X-ray spectroscopy. Scanning electron micrographs show a smooth and dense structure with enhanced crystallinity and improved uniformity. Overall, the physical properties of CBTS thin films were found to be spray deposition temperature dependent. An appropriate optical band gap of 1.6 to 1.8 eV and a compact structure indicate their prospective for solar cell applications.
22 Open Access
DC current-voltage and impedance spectroscopy characterization of nCdS/pZnTe HJ (vol 14, 12955, 2024)
Lungu, I; Patru, RE; Galca, AC; Pintilie, L; Potlog, T
JUL 12 2024, SCIENTIFIC REPORTS, 14, 16115
DOI: 10.1038/s41598-024-66982-2
23 Open Access
DC current-voltage and impedance spectroscopy characterization of nCdS/pZnTe HJ
Lungu, I; Patru, RE; Galca, AC; Pintilie, L; Potlog, T
JUN 5 2024, SCIENTIFIC REPORTS, 14, 12955
DOI: 10.1038/s41598-024-63615-6
Show abstract
This paper describes the electrical and dielectric behavior of the nCdS/pZnTe HJ by current-voltage, capacitance-voltage characteristics, and impedance spectroscopy in a temperature interval 220-350 K. A microcrystalline p-ZnTe layer and n-CdS were grown on glass/ZnO substrate by closed space sublimation method. As frontal contact to CdS, the transparent ZnO and as a back contact to ZnTe, silver conductive paste (Ag) treated at 50 degrees C in vacuum were used. The current-voltage results of nCdS/pZnTe HJ show a rectifying behavior. The junction ideality factor, barrier height, and series resistance values were extracted from the rectifying curves at different temperatures. The built-in voltage, carrier concentration and depletion width were obtained from the capacitance-voltage measurements. Analysis of the J-V-T and C-V-T characteristics shows that the thermionic emission and recombination current flow mechanisms dominate in the nCdS/pZnTe HJ. The dielectric study reveals that the experimental values of the AC conductivity, dielectric constant, dielectric loss, the imaginary part of the electric modulus are found to be very sensitive to frequency and temperature. The dielectric constant and dielectric loss are observed to be high at the low frequency region. The increase in the values of electric modulus with the frequency implies an increase in the interfacial polarization at the interface of nCdS/pZnTe HJ. Jonscher's universal power law shows that with increasing frequency, AC conductivity increased. The results conductivity show that the ionic conductivity and interfacial polarization are the main parameters affecting the dielectric properties of the device when the temperature changes.
24
A-site K-doped lanthanum manganite nanocrystalline La0.67Ba0.33MnO3 for room-temperature micro-scale magnetic cooling
Oumezzine, M; Rostas, AM; Bocirnea, AE; Hlil, E; Galca, AC
MAR 5 2024, JOURNAL OF ALLOYS AND COMPOUNDS, 976, 173257
DOI: 10.1016/j.jallcom.2023.173257
Show abstract
Bulk nanocrystalline La0.67Ba0.33_xKxMnO3 (with x = 0, 0.05, 0.1, and 0.2) manganites have been prepared by the modified sol-gel method (Pechini). The single-phase rhombohedral crystal structure with the R-3c (no. 167) space group was verified by X-ray diffraction (XRD) and sustained by Rietveld refinement. As follows from the results of XRD structural analyses, the increase in K-doping triggers an increase in the distortion of the MnO6 octahedra, which eventually causes the narrowing of the eg bandwidth. Mn is in a mixed valence state of Mn4+/ Mn3+ as inferred by X-ray photoelectron spectroscopy. Magnetic measurements confirm that the Curie tem-perature decreases from 348 K for La0.67Ba0.33MnO3 to 316 K for La0.67Ba0.13K0.20MnO3. The increasing of the Mn4+ ion concentration at the B-site sublattice and A-site ionic disorder (sigma 2) breaks up the double exchange interaction between the Mn3+ and Mn4+ ions. The ferromagnetic to paramagnetic second-order magnetic phase transition at TC is also confirmed by electron paramagnetic resonance. According to magnetic field-dependent magnetization isotherms at different temperatures, La0.67Ba0.13K0.20MnO3 shows a relatively large magneto -caloric effect (1400 mJ cm_ 3 K_ 1 at 316 K under 5 T applied magnetic field), which raises the possibility of using this material for room-temperature micro-scale magnetic cooling.
25
Electrodeposition mechanism of Cu 2 CoSnS 4 thin films onto FTO-coated glass: Effect of some additives
Layachi, OA; Moujib, A; El Khouja, O; Galca, AC; Boudouma, A; Azmi, S; Nini, M; Nohair, M; Khoumri, E
APR 15 2024, JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 959, 118177
DOI: 10.1016/j.jelechem.2024.118177
Show abstract
In this study, we synthesized thin films of semiconductor Cu 2 CoSnS 4 (CCTS). We investigated the mechanism of CCTS electrodeposition precursor onto fluorine -doped tin oxide (FTO) surface. This investigation utilized various mixed additives (Trisodium citrate, Glycine, and Boric acid) through voltammetric and chronoamperometric techniques. The polarization cathodic indicated that the additives narrowing the potential range for electrodeposition of the four elements. The reduction of S 2 O 3 2- was mainly induced by the effect of metal ions. The current transient was analyzed using the Astley and Scharifker-Hills models. Trisodium citrate electrolyte showed an instantaneous model followed by 3D diffusion -limited growth. Both trisodium citrate mixed with glycine and trisodium citrate mixed with boric acid shifted towards the progressive nucleation model. Trisodium citrate with tartaric acid showed a strong agreement with progressive nucleation. In -situ electrochemical impedance spectroscopy (EIS) evaluated a low charge transfer resistance for CCTS precursor electrodeposition in trisodium citrate electrolyte. The X-ray diffraction and Raman analysis study revealed the stannite structure of the obtained Cu 2 CoSnS 4 thin film. The morphological properties and thickness of the films were investigated using a scanning electron microscope (SEM). The compositions were determined using energy dispersive spectroscopy which indicated different atomic ratios of Cu-Co-Sn-S. The maximum absorption was observed within the 1.5 eV range for the film deposited in the Trisodium citrate bath, as determined by spectroscopic ellipsometry.
26
First Sharp Diffraction Peak features of the intermediate phase glasses and amorphous thin films in the non-stoichiometric (GeS4)x(AsS3)1-x system
Ciobanu, M; Galca, AC; Sava, F; Zaki, MY; Velea, A; Tsiulyanu, D
MAY 31 2023, THIN SOLID FILMS, 773, 139828
DOI: 10.1016/j.tsf.2023.139828
Show abstract
Grazing incidence X-ray scattering (GIXRS) patterns of thin solid films based on non-stoichiometric chalcogenide glasses (ChG) from the pseudo - binary system (GeS4)x(AsS3)1-x were studied with a focus on the First Sharp Diffraction Peak (FSDP), assigned to the middle range order (MRO) of the glassy material. The films were grown using explosive thermal evaporation in vacuum (10-4 Pa) of pulverized ChG, prepared from previously synthesized bulk glasses, onto mono-crystalline silicon substrates. Scanning Electron Microscopy (SEM) and EnergyDispersive X-ray (EDX) spectroscopy were used to examine the morphology and elemental composition of the films, which were found to have similar composition to the bulk glasses. However, it was revealed that the molecular structure of the grown amorphous films differs from that of the initial ChG bulk material, as indicated by changes in the composition-dependent position and width of the FSDP. Additionally, the intensities of the FSDP in the films were higher compared to those of the bulk samples, suggesting that the molecular-like structure of ChGs is more pronounced in the form of thin films grown from the vapor phase.
27 Open Access
Partial replacement of Pb<SUP>2+</SUP> in MAPbI2.6Cl0.4 perovskite films and their photovoltaic performance
Derbali, S; Nouneh, K; Leonat, LN; Stancu, V; Tomulescu, AG; Galca, AC; Touhami, ME; Pintilie, I; Florea, M
APR 2023, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 34, 903
DOI: 10.1007/s10854-023-10318-9
Show abstract
Replacing lead atoms in halide perovskite materials is of significant importance for the development of environmentally friendly perovskite solar cells. In this paper, we investigated the effect of doping the MAPbI(2.6)Cl(0.4) hybrid perovskite (MA-methyl ammonium) with non-toxic elements, such as alkaline earth metal ions (Mg2+) and transition metal ions (Zn2+). The structural, morphological, and optical properties of the prepared samples were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV-Vis. spectroscopy. Finally, the doped films were used as photoactive layers in solar devices in order to evaluate their photovoltaic performance. Zn proved to be more appropriate to replace partially Pb and films with higher quality were obtained. As a result, the MAPb1(-x)Zn(x)I(2.6)Cl(0.4) based solar cells have demonstrated a slight improvement of the photovoltaic performances, resulting in a uniform and narrower PCEs (power conversion efficiency) range, compared to pristine MAPbI(2.6)Cl(0.4) based devices.
28
Cu2SnSe3 phase formation from different metallic and binary chalcogenides stacks using magnetron sputtering
Zaki, MY; Sava, F; Simandan, ID; Buruiana, AT; Mihai, C; Velea, A; Galca, AC
JAN 2023, MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING, 153, 107195
DOI: 10.1016/j.mssp.2022.107195
Show abstract
Cu2SnSe3 (CTSe) is a polyvalent material that can be used as an absorber layer for thin film solar cells or as a starting layer for the synthesis of CZTSe or CZTSSe compounds. Obtaining CTSe single phase films with opti-mized properties for thin film solar cells is a difficult task. A systematic study using both metallic and binary chalcogenides precursors for the formation of the CTSe phase was not performed. The films consisting of four different stacks (Sn\Cu, SnSe2\Cu, Sn\Cu2Se, and SnSe2\Cu2Se) were prepared by magnetron sputtering on soda lime glass (SLG) and molybdenum (Mo) coated SLG substrates, followed by annealing at 550 degrees C under Sn + Se atmosphere. X-ray diffraction and Raman spectroscopy results indicated the formation of a single CTSe phase in most of the stacks deposited on both substrates. Scanning electron microscopy images showed compact surfaces with large grains in the films deposited on Mo substrate, while the films on SLG have more voids on their sur-faces. The elemental analysis measured by energy dispersive spectroscopy revealed stoichiometric films on Mo, and copper and tin rich compositions on SLG substrates. The band gap values inferred by conventional spec-troscopy are between 0.81 and 1.95 eV. It was found that the SnSe2\Cu and Sn\Cu2Se stacks are preferred for the formation of a single CTSe phase, with dense surface morphology, a stoichiometric composition, and an optimal absorber layer band gap. This study opens the way to comprehend the formation reactions during the seleni-zation of metallic and binary chalcogenides precursors towards the optimization of kesterite absorber for photovoltaic device fabrication.
29
Structural, Frequency and Temperature Dependent Dielectric Properties of Zn<SUP>2+</SUP> Substituted Ni-Co Based Spinel Ferrite (ZnxNi0.8-xCo0.2Fe2O4)
Oumezzine, M; Iuga, A; Enculescu, M; Galca, AC
MAY 1 2023, ECS JOURNAL OF SOLID STATE SCIENCE AND TECHNOLOGY, 12, 053008
DOI: 10.1149/2162-8777/acd6bb
Show abstract
Zinc substituted nickel-cobalt ferrites, i.e., ZnxNi0.8-xCo0.2Fe2O4 (x = 0.0, 0.05, 0.10 and 0.20) with average crystallite size 100 nm were synthesized by citrate-gel auto-combustion method to investigate effects of Zn2+ substitution on the structural and dielectric properties. Both X-ray diffraction (XRD) and IR spectroscopy studies confirms the formation of pure cubic spinel structure. Variation of lattice parameter infers Vegard's law linear dependence with the addition of Zn2+ concentration. The temperature-dependent behavior of dielectric and modulus spectra has been studied within the frequency range 100 Hz-100 kHz for different temperatures between 100 K and 400 K. It was concluded that the dielectric responses of ZnxNi0.8-xCo0.2Fe2O4 are found to be frequency dependent and thermally activated. Also, In the Zn doped ferrites variations of dielectric loss (tan d) and the imaginary part of electric modulus (M") show the presence of the non-Debye type of dielectric relaxation. Rise in Zinc concentration leads to a decrease in dielectric constant (e (r)) due to the declining of Fe3+-O-M2+ conducting network (M is Co or Ni). Here, we report a low loss tangent factor of the order of 8x10-3 0.6Zn(0.2)Co(0.2)Fe(2)O(4) make this composition suitable for high frequency-applications at room temperature. The activation energy is calculated from electric modulus formalism and DC electrical conductivity and found to increase with further substitution of Zn2+ concentration.
30 Open Access
Pulsed laser deposited V2O3 thin-films on graphene/aluminum foil for micro-battery applications
Tite, T; Ungureanu, C; Buga, M; Stavarache, I; Matei, E; Negrila, CC; Trupina, L; Spinu-Zaulet, A; Galca, AC
MAR 15 2023, JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 933, 117290
DOI: 10.1016/j.jelechem.2023.117290
Show abstract
The development of new thin-film cathodes triggered a recent research interest in energy storage applications. Over the past years, vanadium oxides have been extensively explored as promising electrodes for batteries owing to their rich valence states and remarkable electrochemical properties. Herein, we report on the synthe-sis of undoped and Sn doped V2O3 thin-films on graphene (G)/Al foil by pulsed laser deposition followed by rapid thermal annealing in N2 at low temperature (similar to 430 degrees C). The obtaining V2O3 phase on graphene/Al foil (G/Al) has been confirmed by X-ray diffraction and Raman and X-ray photoelectron spectroscopy analyses. The synthesized vanadium oxide films were tested as cathodes in coin cells. The electrochemical properties have been systematically investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge discharge (GCD) measurements. A superior electrochemical performance was observed for the V2O3 on G/Al structures, with an initial capacity of around 300 mAh g-1, with respect to the bare G/Al electrode. The use of the Sn-doped (5 mol%) V2O3 thin-films improved slightly the initial capac-ity up to a value of ca. 311 mAh g-1. Both V2O3/G/Al and Sn-doped V2O3/G/Al exhibited excellent cycling performances after 40 cycles with a capacity maintenance at a C-rate C/20 of 317 mAh g-1. Long-term cycling test (up to 200 cycles) showed that the Sn doping could be an excellent strategy to improve the stability of the electrodes, which yielded a capacity loss of only 0.128% per cycle. Possible mechanisms are presented and dis-cussed. This work could serve as point of reference for future developments in the field of batteries employing vanadium oxide-based thin-films deposited by physical vapor deposition techniques.
31 Open Access
TiO2 Phase Ratio's Contribution to the Photocatalytic Activity
Stepanova, A; Tite, T; Ivanenko, I; Enculescu, M; Radu, C; Culita, DC; Rostas, AM; Galca, AC
OCT 25 2023, ACS OMEGA, 8
DOI: 10.1021/acsomega.3c05890
Show abstract
Photocatalysis is one of the approaches for solving environmental issues derived from extremely harmful pollution caused by industrial dyes, medicine, and heavy metals. Titanium dioxide is among the most promising photocatalytic semiconductors; thus, in this work, TiO2 powders were prepared by a hydrothermal synthesis using titanium tetrachloride TiCl4 as a Ti source. The effect of the hydrochloric acid (HCl) concentration on TiO2 formation was analyzed, in which a thorough morpho-structural analysis was performed employing different analysis methods like XRD, Raman spectroscopy, SEM/TEM, and N-2 physisorption. EPR spectroscopy was employed to characterize the paramagnetic defect centers and the photogeneration of reactive oxygen species. Photocatalytic properties were tested by photocatalytic degradation of the rhodamine B (RhB) dye under UV light irradiation and using a solar simulator. The pH value directly influenced the formation of the TiO2 phases; for less acidic conditions, the anatase phase of TiO2 crystallized, with a crystallite size of approximate to 9 nm. Promising results were observed for TiO2, which contained 76% rutile, showing a 96% degradation of RhB under the solar simulator and 91% under UV light after 90 min irradiation, and the best result showed that the sample with 67% of the anatase phase after 60 min irradiation under the solar simulator had a 99% degradation efficiency.
32 Open Access
Partial Replacement of Dimethylformamide with Less Toxic Solvents in the Fabrication Process of Mixed-Halide Perovskite Films
Stancu, V; Tomulescu, AG; Leonat, LN; Balescu, LM; Galca, AC; Toma, V; Besleaga, C; Derbali, S; Pintilie, I
FEB 2023, COATINGS, 13, 378
DOI: 10.3390/coatings13020378
Show abstract
The technology of perovskite solar cells (PSC) is getting close to breaching the consumer market. Yet, one of the current challenges is to reduce the toxicity during their fabrication by reducing the use of the toxic solvents involved in the perovskite fabrication process. A good solubilization of lead halides used in hybrid perovskite preparation is required, and it is only possible with polar solvents. A mixture of dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is the most popular solvent combination for a perovskite precursor solution. DMF is necessary to ensure a good dissolution of lead iodide, but it is also the most toxic solvent. In this paper, we study the replacement of the dimethylformamide with presumably less toxic alternatives, such as N-methyl-2-Pyrrolidone (NMP) and ethyl acetate (EA), for the preparation of the K(0.1)FA(0.7)MA(0.2)PbI(2.8)Cl(0.2) (KFAMA) hybrid perovskite. The perovskite thin films were investigated by various characterization techniques: X-ray diffraction, atomic force microscopy, scanning electron microscopy, and UV-vis spectroscopy, while the photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. The present study shows that by keeping the same deposition parameters as when only DMF solvent is used, the partial solvent substitution with NMP and EA gives promising results for reducing the toxicity of the fabrication process of KFAMA-based PSCs. Thus, with no specific optimization of the deposition process, and for the maximum possible partial substitution of DMF with NMP and EA solvents, the loss in the power conversion efficiency (PCE) value is only 35% and 18%, respectively, associated with the more structural defects promoted by NMP and EA.
33
From non-stoichiometric CTSe to single phase and stoichiometric CZTSe films by annealing under Sn plus Se atmosphere
Zaki, MY; Sava, F; Simandan, ID; Buruiana, AT; Bocirnea, AE; Stavarache, I; Velea, A; Galca, AC; Pintilie, L
NOV 1 2023, CERAMICS INTERNATIONAL, 49
DOI: 10.1016/j.ceramint.2023.08.056
Show abstract
One of the new materials for next-generation thin film solar cells is Cu2ZnSnSe4 (CZTSe). However, achieving a single-phase CZTSe compound remains a challenge. This study describes the development of Cu2ZnSnSe4 thin films through the sequential deposition of stacked films of non-stoichiometric Cu2SnSe3 (CTSe) and ZnSe by magnetron sputtering. The structural, morphological, and electrical properties as well as the surface chemistry of the films were investigated and compared depending on the growth sequence of the thin films. By using Raman spectroscopy and grazing incidence X-ray diffraction, the tetragonal CZTSe structure was confirmed. Scanning electron microscopy and energy-dispersive spectroscopy measurements of the morphological and compositional properties indicated large grains and dense surfaces with an elemental composition close to the desired stoichiometry in SLG\SnSe2\Cu\ZnSe and SLG\SnSe2\Cu2Se\ZnSe stacks. To ascertain the surface chemistry and unique characteristics of the produced films, additional X-ray photoemission spectroscopy experiments were carried out. The optimal band gap values for the absorber layers were found using conventional spectroscopy, and they ranged from 0.88 to 1.47 eV. According to the electrical measurements, all the films were p-type and have high carrier concentrations between 1016 and 1020 cm-3. Our findings demonstrate that employing a sequential deposition approach and annealing in different atmospheres can yield CZTSe absorber layers with desirable properties, overcoming the challenge of non-stoichiometric CTSe precursors.
34
Efficient NLO Materials Based on Poly(ortho-anisidine) and Polyaniline: A Quantum Chemical Study
Kenane, A; Hadji, D; Argoub, K; Yahiaoui, A; Hachemaoui, A; Toubal, K; Benkouider, AM; Rasoga, O; Stanculescu, A; Galca, AC
JAN 2023, JOURNAL OF ELECTRONIC MATERIALS, 52
DOI: 10.1007/s11664-022-10022-0
Show abstract
In this paper, we theoretically investigate the linear and nonlinear optical activity of polymers based on poly(ortho-anisidine) and polyaniline using density functional theory. The PBE0 exchange correlation functional is used to predict their dipole moment, mean polarizability, polarizability anisotropy, and the static first hyperpolarizability. The polymers show high hyper-Rayleigh scattering first hyperpolarizability, which make them suitable for nonlinear optical devices. The relationship between the first hyperpolarizability and the energy gap is also taken into account. [GRAPHICS] .
35
Structural and Electrical Properties of Novel Cr/Fe Mixed Transition-Metal Phosphates
Mighri, Z; Souiwa, K; Rostas, AM; Patru, RE; Bocirnea, AE; Iacob, N; Kuncser, V; El Khouja, O; Leonat, LN; Hidouri, M; Nasri, H; Galca, AC
MAY 24 2023, INORGANIC CHEMISTRY, 62
DOI: 10.1021/acs.inorgchem.2c04389
Show abstract
The phosphate KCoCr-(PO4)(2) and iron-substitutedvariants KCoCr1-x Fe x (PO4)(2) (x =0.25, 0.5, and 0.75) were synthesized by a solid-state reaction route,while a high substitution level of Fe was achieved. Their structureswere refined using powder X-ray diffraction and indexed in a monoclinicsystem with a P2(1)/n spacegroup. A 3D framework with six-sided tunnels parallel to the [101]direction was formed in which the K atoms are located. Mo''ssbauerspectroscopy confirms the exclusive presence of octahedral paramagneticFe(3+) ions, with isomer shifts increasing slightly with x substitution. Electron paramagnetic resonance spectroscopyconfirmed the presence of paramagnetic Cr3+ ions. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present higher ionic activity. Relative to the electrochemicalactivity of K, these materials could be good candidates for positiveand/or negative electrode materials for energy storage applications. The synthesized phosphate KCoCr-(PO4)(2) and Fe-substituted variants KCoCr1-x Fe x (PO4)(2) (x = 0.25, 0.5, and 0.75) present a 3D frameworkwith six-sided tunnels in which the K atoms are located. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present improved ionic activity, making these materials goodcandidates for positive and/or negative electrode materials for energystorage applications.
36
Understanding the Photocatalytic Activity of Sodium Hexatitanate Nanoparticles for Pollutants Degradation: A Spectroscopic Insight
Teixeira, ARFA; de Oliveira, ALM; Neatu, F; Kuncser, AC; Galca, AC; Rostas, AM; dos Santos, IMG
MAR 24 2023, ACS APPLIED NANO MATERIALS, 6
DOI: 10.1021/acsanm.2c05577
Show abstract
Sodium hexatitanate (Na2Ti6O13) nanoparticles have been synthesized by the hydrothermal method with microwave and conven-tional heating, after which their photocatalytic properties toward an azo dye pollutant degradation have been investigated. Insights into the dynamics and reactivity of the species involved in the photocatalytic mechanism of the (Na2Ti6O13) samples were precisely investigated, for the first time, by X-band electron paramagnetic resonance (EPR) spectroscopy under different experimental conditions. X-ray diffraction structural analysis revealed that all samples crystallized in a monoclinic C2/m structure, with different short-range structural order according to the employed heating, as indicated by Raman. Field-emission scanning electron microscopy and transmission electron microscopy results revealed the formation of rod-and fiber-like nanoparticles with different diameters and lengths. EPR measurements indicated the presence of different Ti3+ point defects and F centers in the samples. X-ray photoelectron spectroscopy analysis proved the presence of oxygen-related defects, but no Ti3+ was detected on the surface. Spin trapping experiments monitored the generation of hydroxyl (OH center dot) radicals over UV-irradiation time. Various parameters contribute to the photocatalytic activity of the samples; however, the type of defect and particle morphology appeared as key factors for enhanced efficiency. Our study provides significant information about paramagnetic defects in Na2Ti6O13 materials and their role in photocatalysis to design other Ti-based photocatalysts.
37
Growth and characterization of Cu-Ni-Sn-S films electrodeposited at different applied potentials
El Khouja, O; Nouneh, K; Touhami, ME; Matei, E; Stancu, V; Enculescu, M; Galca, AC
MAR 2023, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 34, 760
DOI: 10.1007/s10854-023-10173-8
Show abstract
Cu2NiSnS4 (CNTS) absorber layers are elaborated by electrodeposition at various applied potentials followed by sulfurization treatment at 450 degrees C under sulfur atmosphere. The microstructural investigations revealed the presence of Cu4SnS4 secondary phases which can be reduced using an applied potential of -1.15 V vs. Ag/AgCl. Using the corresponding cathodic potential for Ni2+, the competing detrimental hydrogen evolution regresses the morphology and composition. The film with the highest Ni concentration has a band gap of 1.44 eV as inferred from diffuse reflectance data. The Randles cell model is probed by electrochemical impedance spectroscopy.
38
TiO2/ZIF-67 nanocomposites synthesized by the microwave-assisted solvothermal method: a correlation between the synthesis conditions and antimicrobial properties
Campos, RD; de Oliveira, ALM; Rostas, AM; Kuncser, AC; Negrila, CC; Galca, AC; Félix, C; Castellano, L; da Silva, FF; dos Santos, IMG
JAN 30 2023, NEW JOURNAL OF CHEMISTRY, 47
DOI: 10.1039/d2nj04415c
Show abstract
Zeolitic imidazole frameworks (ZIFs) and TiO2 based composites have recently attracted interest to control pathogenic microorganism growth. In this context, two novel TiO2/ZIF-67 nanocomposites were synthesized by the microwave-assisted solvothermal method using two different routes: one pot composite (OPC) and two step composite (TSC) syntheses. X-ray powder diffraction and vibrational spectroscopy data revealed the formation of crystalline ZIF-67 and disordered TiO2 in the OPC composite, while both phases were crystalline in the TSC sample. Sphere-like morphologies were obtained for both materials, as indicated by SEM and TEM images. XPS measurements showed mixed-valence Ti (Ti3+/Ti4+) and Co (Co2+/Co3+) on the surface of both materials, while EPR analysis confirmed the presence of Co2+ ions and oxygen-related defects. The results showed that TiO2 has no antimicrobial activity against Staphylococcus aureus, while the TSC has higher and the OPC has lower activity than pure ZIF-67. Highly efficient biocidal activity at a concentration of 2.5 mg mL(-1) was observed for the TSC. The difference in the antimicrobial performance of the nanocomposites can be correlated with the balance between structural order/disorder, which depends on the synthesis route used, and the material solubility. The results also indicate the release of Co ions and the ligand as a possible mechanism together with redox reactions to inactivate bacteria. Thus, this work provides simple and promising synthesis routes to obtain TiO2/ZIF-67 nanocomposites for potential use as new antimicrobial agents.
39 Open Access
Tuning the infrared resonance of thermal emission from metasurfaces working in near-infrared
Rasoga, O; Dragoman, D; Dinescu, A; Dirdal, CA; Zgura, I; Nastase, F; Baracu, AM; Iftimie, S; Galca, AC
MAY 9 2023, SCIENTIFIC REPORTS, 13, 7499
DOI: 10.1038/s41598-023-34741-4
Show abstract
We simulated numerically and demonstrated experimentally that the thermal emittance of a metasurface consisting of an array of rectangular metallic meta-atoms patterned on a layered periodic dielectric structure grown on top of a metallic layer can be tuned by changing several parameters. The resonance frequency, designed to be in the near-infrared spectral region, can be tuned by modifying the number of dielectric periods, and the polarization and incidence angle of the incoming radiation. In addition, the absorbance/emittance value at the resonant wavelength can be tuned by modifying the orientation of meta-atoms with respect to the illumination direction.
40
ZnS stacking order influence on the formation of Zn-poor and Zn-rich Cu2ZnSnS4 phase
Zaki, MY; El Khouja, O; Nouneh, K; Touhami, ME; Matei, E; Azmi, S; Rusu, MI; Grigorescu, CEA; Briche, S; Boutamart, M; Badica, P; Burdusel, M; Secu, M; Pintilie, L; Galca, AC
MAY 2022, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 33
DOI: 10.1007/s10854-022-08160-6
Show abstract
This paper reports the synthesis and characterization of Cu2ZnSnS4 (CZTS) absorber films, prepared by a two-step electrodeposition of a ZnS (zinc sulfide) binary and a CZT (copper, zinc and tin) ternary precursors on Mo/Ti/Si substrates. The as-electrodeposited ZnS/CZT and CZT/ZnS stacks were thermally treated in a tubular furnace in sulfur environment at 550 degrees C. The role of the ZnS buffer layer is to provide a zinc and sulfur reservoir, needed to complete the formation of kesterite phase. X-ray diffraction and Raman analyses revealed the formation of the CZTS phase. The surface morphology and chemical composition of the films were studied using a scanning electron microscope. The bandgap values inferred from diffuse reflectance data, are discussed with respect to the stoichiometry which is considerably affected by the order of the stacks. Room-temperature photoluminescence of the CZT/ZnS sample showed a board PL band of 1.51 eV. It was found that the film with a ZnS layer on top is preferred for the formation of a Zn-rich single CZTS phase.
41
Effect of chlorine and bromine on the perovskite crystal growth in mesoscopic heterojunction photovoltaic device
Mehdi, H; Leonat, LN; Stancu, V; Saidi, H; Enculescu, M; Tomulescu, AG; Toma, V; Pintilie, I; Bouazizi, A; Galca, AC
JUN 1 2022, MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING, 143, 106558
DOI: 10.1016/j.mssp.2022.106558
Show abstract
Organic-inorganic hybrid perovskite solar cells are within the emerging photovoltaic technologies. The combination of different halogen ions, in certain fill fractions, is one of the methods to improve the perovskite film properties. Herein, fabrication and characterization of perovskite cells in standard mesoscopic architecture using one-step deposition method has been done. The role of the halogen ions (Chlorine or Bromine) on crystal structure growth and photoelectric performance has been investigated. X-ray diffraction, scanning electron microscopy, atomic force microscopy and optical microscopy analysis were performed. The microstructure, composition and morphology of CH3NH3PbI1.8Br1.2 and CH3NH3PbI1.8Cl1.2 films are dissimilar, although identical fabrication method was used. Same holds for optical properties, band gap energies of 1.84 eV and 1.63 eV, respectively, being obtained. Integrated in solar cells, the maximum power conversion efficiency of the Br based devices is beyond 10%, while for those based on Cl, the efficiency drops around 5%.
42
Enhanced magnetocaloric properties of La0.8K0.2-xPbxMnO3 nanoparticles by optimizing Pb doping concentrations
Bouzid, SA; Essoumhi, A; Rostas, AM; Kuncser, AC; Negrila, CC; Iacob, N; Galatanu, A; Popescu, B; Sajieddine, M; Galca, AC; Kuncser, V
JUN 15 2022, CERAMICS INTERNATIONAL, 48
DOI: 10.1016/j.ceramint.2022.02.239
Show abstract
Polycrystalline La(0.8)K(0.2-x)Pb(x)MnO3 (x = 0.05, 0.10, 0.15, 0.20) ceramics were successfully prepared by flash combustion route and their structural, morphological, magnetic and magnetocaloric properties were investi-gated. Structural analyses using X-ray diffraction reveal that all samples are crystallized in the rhombohedral structure and belong to R c space group. The increase of Pb doping does not modify the crystalline structure but changes the grain size and lattice parameters. X-ray photoelectron spectroscopy (XPS) fitting results of Mn 2p peaks confirmed the coexistence of Mn3+ and Mn4+ ions which contribute to the double exchange interactions improving the ferromagnetic order in the samples. The magnetization's temperature and magnetic field de-pendences indicate a second-order ferromagnetic-paramagnetic transition of the ceramics. A significant mag-netic entropy change near room temperature was observed for La0.8K0.1Pb0.1MnO3, showing considerable magnetocaloric properties. Furthermore, electron paramagnetic resonance spectroscopy (EPR) was also used to examine the ferromagnetic-paramagnetic transition.
43
Temperature-induced phase transition and tunable luminescence properties of Ce<SUP>3+</SUP>-Mn<SUP>2+</SUP>-Zr<SUP>4+</SUP> tri-doped LaPO4 phosphor
AitMellal, O; Oufni, L; Messous, MY; Matei, E; Rostas, AM; Galca, AC; Secu, M
JUL 2022, OPTICAL MATERIALS, 129, 112567
DOI: 10.1016/j.optmat.2022.112567
Show abstract
Tunable blue-white-orange emitting LaPO4:Ce3+/Mn2+/Zr4+(LPCMZ) phosphors have been synthesized by co precipitation followed by calcination. The X-ray diffraction (XRD) shows the phase transition from hexagonal to monoclinic between 600 and 700 ?C, accompanied by the increase of average nanocrystallites size from 8 to 64 nm. The Raman measurements revealed the vibrational modes associated with the LPCMZ crystalline phases, where the band positions and the full width at half maximum values depend on the structural parameters and nanocrystals size. For low-temperature calcination of 500 ?C, scanning electron microscopy (SEM) revealed nanoclusters composed of thinner nanoneedles, which developed into a rod-like self-assembly shape for higher calcination temperatures at around 900 ?C. Electron paramagnetic resonance (EPR) spectroscopy reveals a broad isotropic EPR signal, assigned to agglomerated/clustered Mn2+ ions, which are dispersed only at high temperatures above 900 ?C. The photoluminescence spectra recorded under UV-excitation of Ce3+ ions showed the Mn2+ green/red (546, 630 nm) emissions due to an energy transfer (ET) between Ce3+ and Mn2+. Depending on the calcination temperature, the Mn2+ emission color can be finely adjusted from blue to white and orange.
44 Open Access
A Two-Step Magnetron Sputtering Approach for the Synthesis of Cu2ZnSnS4 Films from Cu2SnS3\ZnS Stacks
Zaki, MY; Sava, F; Simandan, ID; Buruiana, AT; Stavarache, I; Bocirnea, AE; Mihai, C; Velea, A; Galca, AC
2022 JUN 27 2022, ACS OMEGA
DOI: 10.1021/acsomega.2c02475
Show abstract
Cu2ZnSnS4 (CZTS) is regarded as one of the emerging materials for next-generation thin film solar cells. However, its synthesis is complex, and obtaining a single-phase CZTS thin film is difficult. This work reports the elaboration of Cu2ZnSnS4 thin films by a sequential magnetron sputtering deposition of Cu2SnS3 (CTS) and ZnS as stacked films. Initially, the CTS films were prepared on a soda lime glass substrate by annealing Cu and SnS2 stacked layers. Second, ZnS was deposited by magnetron sputtering on the CTS films. The CTS\ZnS stacks were then annealed in Sn + S or S atmospheres. The tetragonal CZTS structure was obtained and confirmed by grazing incidence X-ray diffraction and Raman spectroscopy. The morphological and compositional characteristics, measured by scanning electron microscopy and energy-dispersive spectroscopy, revealed large grains and dense surfaces with the elemental composition close to the intended stoichiometry. Additional X-ray photoemission spectroscopy measurements were performed to determine the surface chemistry and particularities of the obtained films. The optical properties, determined using conventional spectroscopy, showed optimal absorber layer band gap values ranging between 1.38 and 1.50 eV. The electrical measurements showed that all the films are p-type with high carrier concentrations in the range of 10(15) to 10(20) cm(-3). This new synthesis route for CZTS opens the way to obtain high-quality films by an industry-compatible method.
45 Open Access
Effect of the stacking order, annealing temperature and atmosphere on crystal phase and optical properties of Cu2SnS3
Zaki, MY; Sava, F; Simandan, ID; Buruiana, AT; Mihai, C; Velea, A; Galca, AC
MAY 13 2022, SCIENTIFIC REPORTS, 12, 7958
DOI: 10.1038/s41598-022-12045-3
Show abstract
Cu2SnS3 (CTS) is emerging as a promising absorber for the next generation thin film solar cells (TFSC) due to its excellent optical and electronic properties, earth-abundance and eco-friendly elemental composition. In addition, CTS can be used as precursor films for the Cu2ZnSnS4 (CZTS) synthesis. The optical properties of CTS are influenced by stoichiometry, crystalline structure, secondary phases and crystallite size. Routes for obtaining CTS films with optimized properties for TFSC are still being sought. Here, the CTS thin films synthesized by magnetron sputtering on soda lime glass (SLG) using Cu and SnS2 targets in two different stacks, were studied. The SLG\Cu\SnS2 and SLG\SnS2\Cu stacks were annealed in S and Sn + S atmospheres, at various temperatures. Both stacks show a polymorphic structure, and higher annealing temperatures favor the monoclinic CTS phase formation. Morphology is influenced by the stacking order since a SnS2 top layer generates several voids on the surface due to the evaporation of SnS, while a Cu top layer provides uniform and void-free surfaces. The films in the copper-capped stack annealed under Sn + S atmosphere have the best structural, morphological, compositional and optical properties, with tunable band gaps between 1.18 and 1.37 eV. Remarkably, secondary phases are present only in a very low percent (< 3.5%) in samples annealed at higher temperatures. This new synthesis strategy opens the way for obtaining CTS thin films for solar cell applications, that can be used also as intermediary stage for CZTS synthesis.
46
The influence of Zr<SUP>4+</SUP> doping on the structural and photoluminescence properties of LaPO4:Ce<SUP>3+</SUP>/Mn<SUP>2+</SUP> phosphors
AitMellal, O; Oufni, L; Messous, MY; Rostas, AM; Galca, AC; Toma, ; Matei, E; Secu, M
NOV 2022, JOURNAL OF LUMINESCENCE, 251, 119226
DOI: 10.1016/j.jlumin.2022.119226
Show abstract
A series of LaPO4:Ce3+/Mn2+/xZr(4+) (LPOCM:xZr(4+)) (0% <= x Mn2+) being discussed in detail. Under UV-excitation of Ce3+, typical green-red PL emission is observed for the LPOCM:xZr(4+) phosphors, which is attributed to the T-4(1)(G) -> (6)A(1)(S) transition of the Mn2+ ion. The charge compensation strategy achieved the Mn2+ PL-enhancement and color-tuning effect in LPOCM:xZr(4+) phosphors. A strong blue emission with color purity of up to 97% is observed in the Ce3+ singly-doped sample. Cold white light emission can be obtained by doping 5% Zr4+ in LPOCM phosphor under UV irradiation. The corresponding CIE 1931 coordinates were inferred to be (0.309, 0.329), close to the standard white emission (0.330, 0.330). The color was tuned towards whitish-orange/red emissions for higher Zr4+ concentrations (15% and 30%). These findings indicate that the charge compensation approach can greatly improve the PL and color-tunable properties of LPOCM:xZr(4+) phosphors.
47 Open Access
New Chalcogenide Glass-Ceramics Based on Ge-Zn-Se for IR Applications
Velea, A; Sava, F; Badica, P; Burdusel, M; Mihai, C; Galca, AC; Matei, E; Buruiana, AT; El Khouja, O; Calvez, L
JUL 2022, MATERIALS, 15, 5002
DOI: 10.3390/ma15145002
Show abstract
The consumer market requests infrared (IR) optical components, made of relatively abundant and environmentally friendly materials, to be integrated or attached to smartphones. For this purpose, three new chalcogenides samples, namely Ge23.3Zn30.0Se46.7 (d_GZSe-1), Ge26.7Zn20.0Se53.3 (d_GZSe-2) and Ba4.0Ge12.0Zn17.0Se59.0I8.0 (d_GZSe-3) were obtained by mechanical alloying and processed by spark plasma sintering into dense bulk disks. Obtaining a completely amorphous and homogeneous material proved to be difficult. d_GZSe-2 and d_GZSe-3 are glass-ceramics with the amount of the amorphous phase being 19.7 and 51.4 wt. %, while d_GZSe-1 is fully polycrystalline. Doping with barium and iodine preserves the amorphous phase formed by milling and lowers the sintering temperature from 350 degrees C to 200 degrees C. The main crystalline phase in all of the prepared samples is cubic ZnSe or cubic Zn0.5Ge0.25Se, while in d_GZSe-3 the amorphous phase contains GeSe4 clusters. The color of the first two sintered samples is black (the band gap values are 0.42 and 0.79 eV), while d_GZSe-3 is red (E-g is 1.37 eV) and is transparent in IR domain. These results are promising for future research in IR materials and thin films.
48
Layered SnSe nanoflakes with anharmonic phonon properties and memristive characteristics
Buruiana, AT; Bocirnea, AE; Kuncser, AC; Tite, T; Matei, E; Mihai, C; Zawadzka, N; Olkowska-Pucko, K; Kipczak, L; Babinski, A; Molas, MR; Velea, A; Galca, AC
OCT 15 2022, APPLIED SURFACE SCIENCE, 599, 153983
DOI: 10.1016/j.apsusc.2022.153983
Show abstract
Understanding the phonon anharmonicity and temperature-dependent behavior of phonons that affect the thermal transport properties in 2D materials is crucial for developing efficient thermoelectric and memristor devices. SnSe has attracted significant interest because of its potential applications for developing such novel devices. Here, orthorhombic SnSe nanoflakes with a thickness of less than 100 nm and oriented along the [100] crystal axis were obtained using physical vapor transport at atmospheric pressure. Polarization-resolved Raman spectroscopy of SnSe nanoflakes was performed at a temperature of 5 K. Temperature-dependent frequencies and linewidths of Raman modes in tin selenide were fitted according to the anharmonic phonon coupling theory. The results indicate that both two and three order processes are responsible for the phonon decay in tin selenide. The memristive property was confirmed by electrical measurements of SnSe devices. SnSe memristors have an operating current of 10-4 A, similar to other transition-metal dichalcogenide memristors, but are more energy efficient than memristors based on defect migration, with a threshold voltage of 3 V.
49
Structural and transport properties of Cu2CoSnS4 films prepared by spray pyrolysis
El Khouja, O; Assahsahi, I; Nouneh, K; Touhami, ME; Secu, M; Talbi, A; Khaaissa, Y; Matei, E; Stancu, V; Galatanu, A; Galca, AC
NOV 1 2022, CERAMICS INTERNATIONAL, 48
DOI: 10.1016/j.ceramint.2022.07.185
Show abstract
In the present work, stannite Cu2CoSnS4 (CCTS) films were elaborated using spray pyrolysis method on soda-lime glass, at different deposition temperatures (T-d = 250, 300, and 350 degrees C), followed by different chosen sulfurization temperatures (T-s = 450, 500, and 550 degrees C). X-ray diffraction (XRD) revealed the nearly single-phase formation of CCTS films at 300 degrees C deposition temperature. After sulfurization in argon flow, the XRD lines become narrower, the average crystallite size expanding above 70 nm. The Raman spectroscopy analysis confirmed the stannite structure formation, as well as the presence CoS2 secondary phases, which reduces at higher sulfurization temperature (550 degrees C). The energy dispersive spectroscopy results indicated atomic ratios of Cu/Co/Sn/S close to the ideal stoichiometric ratio 2:1:1:4. The room temperature photoluminescence emission is recorded with maximum in the 1.35-1.40 eV range. Thermoelectric properties are measured up to 130 degrees C, the films show poor power factor as a result of small positive Seebeck coefficients 10-45 Of K -1 and low electrical conductivity despite of having relatively high carrier concentration (similar to 10(20) cm(-3)).
50
Bulk and surface characteristics of co-electrodeposited Cu2FeSnS4 thin films sulfurized at different annealing temperatures
El Khouja, O; Negrila, CC; Nouneh, K; Secu, M; Touhami, ME; Matei, E; Stancu, V; Enculescu, M; Kuncser, V; Galca, AC
JUN 15 2022, JOURNAL OF ALLOYS AND COMPOUNDS, 906, 164379
DOI: 10.1016/j.jallcom.2022.164379
Show abstract
In this study, stannite, Cu2FeSnS4 (CFTS), absorber films were obtained by electrodeposition on Molybdenum-coated soda-lime substrates, followed by sulfurization treatment at certain temperatures in the 400-550 degrees C range. The purposes of this work were to control the manufacturing of CFTS films with good stoichiometry, high crystallinity and to study the annealing temperature impact on CFTS films properties. The X-ray diffraction and the Raman spectroscopy measurement distinguished the CFTS phase formation, with a presence of SnS2 secondary phase. The energy dispersive spectroscopy results reveal compositional differences between samples as well as the in-depth gradients. The photoluminescence emission band around 1.35-1.40 eV is slightly below the direct bandgap inferred from the conventional spectroscopy (diffuse reflectance). X-ray photoelectron spectroscopy results indicate clearly a high amount of Sn on the surface. The Conversion Electron Mossbauer unveiled the presence of Fe in the chalcogenide unit cell. The electrochemical characteristics of the synthesized films are also given. (c) 2022 Elsevier B.V. All rights reserved.
51
Influence of the synthesis parameters on the transport properties of Mg2Si0.4Sn0.6 solid solutions produced by melting and spark plasma sintering
Assahsahi, I; Popescu, B; Enculescu, M; Galatanu, M; Galca, AC; El Bouayadi, R; Zejli, D; Galatanu, A
APR 2022, JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS, 163, 110561
DOI: 10.1016/j.jpcs.2021.110561
Show abstract
In this work, the influence of the preparation route on the structural, morphological, and thermoelectric properties of the Mg2Si0.4Sn0.6 solid solutions is investigated. The synthesis based on melting the constituent elements in a closed graphite crucible followed by spark plasma sintering allows mixing elements with a large difference of their melting temperatures and a good control of sample stoichiometry. The optimized synthesis route is validated by the doped V and Sb samples, which yield good thermoelectric performance. The n-type doping leads to two orders of magnitude increase of the carrier concentration, and thus a subsequent increase of the electrical conductivity, which, in turn, augments greatly the power factor of the Mg1.98V0.02Si0.385Sn0.6Sb0.015 to 42.61 x10(-4) Wm(-1)K 2 at 650K. Although doping slightly enlarges the thermal conductivity, a peak value of the figure of merit ZT similar to 1.15 is obtained at 723K, which is 20 times higher than the ZT of un-doped material.
52 Open Access
Magnetocaloric and Giant Magnetoresistance Effects in La-Ba-Mn-Ti-O Epitaxial Thin Films: Influence of Phase Transition and Magnetic Anisotropy
Oumezzine, M; Chirila, CF; Pasuk, I; Galca, AC; Leca, A; Borca, B; Kuncser, V
NOV 2022, MATERIALS, 15, 8003
DOI: 10.3390/ma15228003
Show abstract
Magnetic perovskite films have promising properties for use in energy-efficient spintronic devices and magnetic refrigeration. Here, an epitaxial ferromagnetic La0.67Ba0.33Mn0.95Ti0.05O3 (LBMTO-5) thin film was grown on SrTiO3(001) single crystal substrate by pulsed laser deposition. High-resolution X-ray diffraction proved the high crystallinity of the film with tetragonal symmetry. The magnetic, magnetocaloric and magnetoresistance properties at different directions of the applied magnetic field with respect to the ab plane of the film were investigated. An in-plane uni-axial magnetic anisotropy was evidenced. The LBMTO-5 epilayer exhibits a second-order ferromagnetic-paramagnetic phase transition around 234 K together with a metal-semiconductor transition close to this Curie temperature (T-C). The magnetic entropy variation under 5 T induction of a magnetic field applied parallel to the film surface reaches a maximum of 17.27 mJ/cm(3) K. The relative cooling power is 1400 mJ/cm(3) K (53% of the reference value reported for bulk Gd) for the same applied magnetic field. Giant magnetoresistance of about 82% under 5 T is obtained at a temperature close to T-C. Defined as the difference between specific resistivity obtained under 5 T with the current flowing along the magnetic easy axis and the magnetic field oriented transversally to the current, parallel and perpendicular to the sample plane, respectively, the in-plane magneto-resistance anisotropy in 5 T is about 9% near the T-C.
53
Potassium-containing triple-cation mixed-halide perovskite materials: Toward efficient and stable solar cells
Derbali, S; Nouneh, K; Florea, M; Leonat, LN; Stancu, V; Tomulescu, AG; Galca, AC; Secu, M; Pintilie, L; Touhami, ME
MAR 25 2021, JOURNAL OF ALLOYS AND COMPOUNDS, 858, 158335
DOI: 10.1016/j.jallcom.2020.158335
Show abstract
In this paper, potassium based triple cation mixed-halide perovskite films were explored in order to enhance the stability and photovoltaic performance of perovskite based solar cells. It was found that adding potassium (K+) to a double cation mixed halide perovskite (FA(0.80)MA(0.20)PbI(2.8)Cl(0.2)), structural, morphological and optoelectronic properties of perovskites are improved. The perovskite films were prepared by one-step spin coating method with and without K+ and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The results indicate that potassium incorporation reduces significantly the yellow non-perovskite delta-phase formation and improves the perovskite film quality, thus contributing to the reduction of hysteresis, improves the stability and increases the PCE up to 12.51%. Furthermore, the doped devices exhibit reduced hysteresis and provide remarkable shelf stability by retaining more than 70% of the initial efficiency with low humidity over 850 h. (C) 2020 Elsevier B.V. All rights reserved.
54
Alternative lignopolymer-based composites useful as enhanced functionalized support for enzymes immobilization
Lite, C; Ion, S; Tudorache, M; Zgura, I; Galca, AC; Enache, M; Maria, GM; Parvulescu, VI
NOV 1 2021, CATALYSIS TODAY, 379
DOI: 10.1016/j.cattod.2020.05.060
Show abstract
Amino-derivatized lignocomposite (ADL-composite) has been designed as an artificial lignin polymer (P1) of monolignol (coniferyl alcohol, CA) enhanced by aniline insertion (P2). The derivatized lignopolymeric (P2) layer covered the surface of a methacrylate particles (SC2/SC6) functionalized previously with amino phenolic crosslinker (p-phenylenediamine (p-Ph-2-NH2) or p-amino-2-hydroxybenzoic acid (p-NH2-SalA)). One-pot biocatalytic approach allowed to combine the preparation of the polymeric materials and also its attachment on the particles surface. Thus, the monolignol (CA) will be oxi-copolymerized together with aniline on the amino prefunctionalized support surface. The oxidation process was performed using H2O2 reagent and catalyzed by peroxidase enzyme (horseradish peroxidase, HRP). The biocatalytic process was evaluated in term of aromatic monomers (CA and aniline) conversion. The chemical structure and properties of the resulted ADL-composites were investigated using specific techniques (e.g. FTIR, TPD, TGA, static contact angle, elemental analysis, and gel permeation chromatography). Attachment of P1/P2 polymer on the particles improved the hydrophobicity and also the basicity of the composite surface. Lipase enzyme was immobilized on the ADL-composites for testing the applicability of ADL-composites for biocatalyst preparation. SEM analysis allowed to notice the modification of ADL-composites surface after enzyme immobilization. Immobilized lipase exhibited better activity compared with free lipase demonstrating the efficiency of ADL-composite as support for enzyme immobilization.
55
Electro-active properties of nanostructured films of cytosine and guanine nucleobases
Socol, M; Trupina, L; Galca, AC; Chirila, C; Stan, GE; Vlaicu, AM; Stanciu, AE; Boni, AG; Botea, M; Stanculescu, A; Pintilie, L; Borca, B
OCT 8 2021, NANOTECHNOLOGY, 32, 415702
DOI: 10.1088/1361-6528/ac10e4
Show abstract
The discovery of multifunctional properties related to electro-activity of organic systems of biomolecules is important for a variety of applications, especially for devices in the realm of biocompatible sensors and/or bioactuators. A further step towards such applications is to prepare thin films with the required properties. Here, the investigation is focused on the characterization of films of guanine and cytosine nucleobases, prepared by thermal evaporation-an industrial accessible deposition technique. The cytosine films have an orthorhombic non-centrosymmetric structure and grow in two interconnected nanostructured fractal patterns, of nearly equal proportion. Piezoresponse force microscopy images acquired at room temperature on the cytosine films display large zones with antiparallel alignment of the vertical components of the polarization vector. Guanine films have a dense nano-grained morphology. Our studies reveal electrical polarization switching effects which can be related to ferroelectricity in the films of guanine molecules. Characteristic ferroelectric polarization-electric-field hysteresis loops showing large electrical polarization are observed at low temperatures up to 200 K. Above this temperature, the guanine films have a preponderant paraelectric phase containing residual or locally induced nano-scopic ferroelectric domains, as observed by piezoresponse force microscopy at room temperature.
56 Open Access
Micrometer Sized Hexagonal Chromium Selenide Flakes for Cryogenic Temperature Sensors
Buruiana, AT; Sava, F; Iacob, N; Matei, E; Bocirnea, AE; Onea, M; Galca, AC; Mihai, C; Velea, A; Kuncser, V
DEC 2021, SENSORS, 21, 8084
DOI: 10.3390/s21238084
Show abstract
Nanoscale thermometers with high sensitivity are needed in domains which study quantum and classical effects at cryogenic temperatures. Here, we present a micrometer sized and nanometer thick chromium selenide cryogenic temperature sensor capable of measuring a large domain of cryogenic temperatures down to tenths of K. Hexagonal Cr-Se flakes were obtained by a simple physical vapor transport method and investigated using scanning electron microscopy, energy dispersive X-ray spectrometry and X-ray photoelectron spectroscopy measurements. The flakes were transferred onto Au contacts using a dry transfer method and resistivity measurements were performed in a temperature range from 7 K to 300 K. The collected data have been fitted by exponential functions. The excellent fit quality allowed for the further extrapolation of resistivity values down to tenths of K. It has been shown that the logarithmic sensitivity of the sensor computed over a large domain of cryogenic temperature is higher than the sensitivity of thermometers commonly used in industry and research. This study opens the way to produce Cr-Se sensors for classical and quantum cryogenic measurements.
57 Open Access
Influence of Deposition Method on the Structural and Optical Properties of Ge2Sb2Te5
Simandan, ID; Sava, F; Buruiana, AT; Galca, AC; Becherescu, N; Burducea, I; Mihai, C; Velea, A
JUL 2021, MATERIALS, 14, 3663
DOI: 10.3390/ma14133663
Show abstract
Ge2Sb2Te5 (GST-225) is a chalcogenide material with applications in nonvolatile memories. However, chalcogenide material properties are dependent on the deposition technique. GST-225 thin films were prepared using three deposition methods: magnetron sputtering (MS), pulsed laser deposition (PLD) and a deposition technique that combines MS and PLD, namely MSPLD. In the MSPLD technique, the same bulk target is used for sputtering but also for PLD at the same time. The structural and optical properties of the as-deposited and annealed thin films were characterized by Rutherford backscattering spectrometry, X-ray reflectometry, X-ray diffraction, Raman spectroscopy and spectroscopic ellipsometry. MS has the advantage of easily leading to fully amorphous films and to a single crystalline phase after annealing. MS also produces the highest optical contrast between the as-deposited and annealed films. PLD leads to the best stoichiometric transfer, whereas the annealed MSPLD films have the highest mass density. All the as-deposited films obtained with the three methods have a similar optical bandgap of approximately 0.7 eV, which decreases after annealing, mostly in the case of the MS sample. This study reveals that the properties of GST-225 are significantly influenced by the deposition technique, and the proper method should be selected when targeting a specific application. In particular, for electrical and optical phase change memories, MS is the best suited deposition method.
58 Open Access
The Effect of the Deposition Method on the Structural and Optical Properties of ZnS Thin Films
Simandan, ID; Sava, F; Buruiana, AT; Burducea, I; Becherescu, N; Mihai, C; Velea, A; Galca, AC
SEP 2021, COATINGS, 11, 1064
DOI: 10.3390/coatings11091064
Show abstract
ZnS is a wide band gap material which was proposed as a possible candidate to replace CdS as a buffer layer in solar cells. However, the structural and optical properties are influenced by the deposition method. ZnS thin films were prepared using magnetron sputtering (MS), pulsed laser deposition (PLD), and a combined deposition technique that uses the same bulk target for sputtering and PLD at the same time, named MSPLD. The compositional, structural, and optical properties of the as-deposited and annealed films were inferred from Rutherford backscattering spectrometry, X-ray diffraction, X-ray reflectometry, Raman spectroscopy, and spectroscopic ellipsometry. PLD leads to the best stoichiometric transfer from target to substrate, MS makes fully amorphous films, whereas MSPLD facilitates obtaining the densest films. The study reveals that the band gap is only slightly influenced by the deposition method, or by annealing, which is encouraging for photovoltaic applications. However, sulphur vacancies contribute to lowering the bandgap and therefore should be controlled. Moreover, the results add valuable information towards the understanding of ZnS polymorphism. The combined MSPLD method offers several advantages such as an increased deposition rate and the possibility to tune the optical properties of the obtained thin films.
59
Phosphate bioglass thin-films: Cross-area uniformity, structure and biological performance tailored by the simple modification of magnetron sputtering gas pressure
Tite, T; Popa, AC; Chirica, IM; Stuart, BW; Galca, AC; Balescu, LM; Popescu-Pelin, G; Grant, DM; Ferreira, JMF; Stan, GE
MAR 1 2021, APPLIED SURFACE SCIENCE, 541, 148640
DOI: 10.1016/j.apsusc.2020.148640
Show abstract
Currently, there is a considerable time-lag in the industrialisation of innovative technological solutions for the functionalization of osseous implants, with ever-demanding healthcare requirements (e.g., controlled release of therapeutic ions, match of biomaterial degradation - bone growth rates, antimicrobial efficiency). As third-generation biomaterials, phosphate bio-glasses (PBGs) have demonstrated an ability to stimulate specific biological responses from tissue to molecular level, by successfully coupling bioactive and resorbable material properties. Here, radio-frequency magnetron sputtered (RF-MS) PBGs were explored as sacrificial resorbable layers for prospective biomedical implant designs. A PBG powder with a 50-P2O5, 35-CaO, 10-Na2O and 5-Fe2O3 composition (mol%) was used as source (target) material. The influence of the argon working pressure (0.2-1 Pa) - one of the most prominent RF-MS variables - on the morphology, structure, uniformity, composition, degradation rate and cytocompatibility of PBG films was investigated. The engineered modification of physical-chemical and biological features of the PBG sputtered films was multi-parametrically surveyed by AFM, EDXS, spectroscopic ellipsometry, GIXRD, FTIR spectroscopy measurements and in vitro assays. Results suggested that the film thickness, composition, density and structure were preserved over a uniformity region having a diameter of similar to 30 mm, irrespective of sputtering pressure. The network connectivity and the surface porosity of the films were found to have antagonistic roles with respect to the in vitro degradation performance. The possibility of fine tuning the composition, structure and thereby biological interaction of the PBG films by conveniently modifying the sputtering pressure was shown (i.e., permitting their complete controlled degradation, without cytotoxic effects). This work is the first to show in vitro cytocompatibility outcomes of sputtered PBG films and their cross-area uniformity, and thus, it could prove to be an important technological step in their future biomedical application and suggest implications for future industrial scale-up.
60 Open Access
Structural and optical properties of amorphous Si-Ge-Te thin films prepared by combinatorial sputtering
Mihai, C; Sava, F; Simandan, ID; Galca, AC; Burducea, I; Becherescu, N; Velea, A
JUN 3 2021, SCIENTIFIC REPORTS, 11, 11755
DOI: 10.1038/s41598-021-91138-x
Show abstract
The lack of order in amorphous chalcogenides offers them novel properties but also adds increased challenges in the discovery and design of advanced functional materials. The amorphous compositions in the Si-Ge-Te system are of interest for many applications such as optical data storage, optical sensors and Ovonic threshold switches. But an extended exploration of this system is still missing. In this study, magnetron co-sputtering is used for the combinatorial synthesis of thin film libraries, outside the glass formation domain. Compositional, structural and optical properties are investigated and discussed in the framework of topological constraint theory. The materials in the library are classified as stressed-rigid amorphous networks. The bandgap is heavily influenced by the Te content while the near-IR refractive index dependence on Ge concentration shows a minimum, which could be exploited in applications. A transition from a disordered to a more ordered amorphous network at 60 at% Te, is observed. The thermal stability study shows that the formed crystalline phases are dictated by the concentration of Ge and Te. New amorphous compositions in the Si-Ge-Te system were found and their properties explored, thus enabling an informed and rapid material selection and design for applications.
61
Activation ability of Gd dopant in the ZnSe single crystals
Goncearenco, EP; Rostas, AM; Galca, AC; Colibaba, G; Nedeoglo, DD
OCT 2021, JOURNAL OF LUMINESCENCE, 238, 118314
DOI: 10.1016/j.jlumin.2021.118314
Show abstract
Rare-earth elements are widely used as doping materials as they considerably change the semiconductor optical, electrical, magnetic and radiative properties. This work explores the influence of Gadolinium (Gd) as a dopant on the radiative, optical and magnetic properties of the Zinc Selenide (ZnSe). ZnSe single crystals were grown by the physical transport method and doped during the growth process using a GdSe source. A wide range of characterization equipment was employed to analyze the obtained ZnSe:Gd single crystals. Intracenter radiative transition of the Gd has not been detected. Gd ions activate the background impurities, causing radiative transitions from the conduction band to the Cu2+ level and intracenter transitions within V3+, V2+ and Cr2+ ions. At the same time, the edge band intensity is dependent on the dopant concentration. Optical transmittance decreases, but the position of the fundamental absorption band is unchanged. Single crystals have a zinc blende crystal structure, and Gd ions do not form complexes with native defects or background impurities.
62
Experimental and numerical simulation of deposition time effect on ZnS thin films for CZTS-based solar cells
Khaaissa, Y; Talbi, A; Nouneh, K; El Khouja, O; Ahmoum, H; Galca, AC; Belahmar, A; Li, GJ; Wang, Q
SEP 2021, OPTICAL AND QUANTUM ELECTRONICS, 53, 487
DOI: 10.1007/s11082-021-03143-z
Show abstract
High-quality ZnS thin films as buffer layer have been successfully synthesized and simulated using the low-cost Mist CVD technique and the SCAPS-1D software for different deposition times (30, 40, 50, and 60 min). The structural, morphological, and optical properties of the prepared ZnS films have been investigated using X-ray diffraction (XRD), scanning electronic microscopy (SEM), atomic force microscopy (AFM), and UV-Vis spectrophotometer. The time deposition effect on ZnS films' efficiency as a buffer layer has been evaluated. XRD pattern confirms the hexagonal/cubic structure of the prepared samples, with (111) as preferred orientation. Raman spectra confirm XRD findings by the two peaks located at 348 cm(-1) and 697 cm(-1) which correspond to ZnS samples' cubic and hexagonal structures. Scanning electronic microscopy (SEM) and atomic force microscopy (AFM) images show densely uniform grains with precise shapes and boundaries covering the entire sample's surface with a relative roughness for all deposition times. The optical transmittance shows an average of 78% in the visual field of light with an optical band gap varying between 3.69 and 3.80 eV. Numerical simulation of ZnO:Al/ZnS/CZTS/Mo cell using SCAPS-1D software shows that the sample deposited for 30 min presents the best performance with an efficiency of up to 8.9%.
63
Secondary phases and their influence on optical and electrical properties of electrodeposited Cu2FeSnS4 films
El Khouja, O; Galca, AC; Zaki, MY; Talbi, A; Ahmoum, H; Nouneh, K; Touhami, ME; Taibi, M; Matei, E; Enculescu, M; Pintilie, L
NOV 2021, APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING, 127, 887
DOI: 10.1007/s00339-021-05038-y
Show abstract
Cu-Fe-Sn-S have been electrodeposited on indium tin oxide coated glass (ITO/glass) substrates, varying only the deposition time, followed by sulfurization in argon atmosphere at a temperature of 500 degrees C. X-ray diffraction patterns confirmed the formation of polycrystalline CFTS and other secondary phases. The Raman spectroscopy results confirm the formation of stannite phase, by the existence of the most intense peak at 330 cm(-1) corresponding to A-symmetry vibrational mode, while the SnS2 surface phase reduces upon increasing deposition time. The inferred bandgaps by specular transmission are in 1.4-1.7 eV range, influenced by the detected orthorhombic Cu4SnS4 and rhodostannite secondary phases. The electrical measurements confirm the p-type nature of the films, while density of free carriers is relatively high (similar to 10(19) cm(-3)), leading to extremely low resistivity in the Omega cm range.
64
Magneto-optical properties of borophosphate glasses co-doped with Tb<SUP>3+</SUP> and Dy<SUP>3+</SUP>ions
Dinca, MC; Sava, BA; Galca, AC; Kuncser, V; Iacob, N; Stan, GE; Boroica, L; Filip, AV; Elisa, M
SEP 15 2021, JOURNAL OF NON-CRYSTALLINE SOLIDS, 568, 120967
DOI: 10.1016/j.jnoncrysol.2021.120967
Show abstract
Glasses from lithium-aluminum-zinc-boron-phosphorous oxide system co-doped with terbium (Tb3+) and dysprosium (Dy3+) oxides were studied for magneto-optical applications in lasers. The Fourier Transform Infrared and Raman Spectroscopy complementary analysis suggested the depolymerization of the borophosphate glass network by adding and increasing the rare-earth (RE) oxide content. Main UV-vis absorption maxima of Tb and Dy ions were identified at 348 and 1266 nm. Spectroscopic ellipsometry indicated a maximum refractive index of 1.56, at 400 nm, for the highest RE content. The Verdet constant amplified by increasing the RE content, reaching for the 9 mol% RE co-doped sample a value of -0.075 min/Oe/cm at 630 nm. The Faraday rotation angle was additionally confirmed by using a Faraday Cell Device, being also related to the specific paramagnetic behavior evidenced by Superconducting Quantum Interference Device magnetometry. The magneto-optical properties recommend such vitreous co-doped materials for magneto-optical devices.
65
Multilevel Memristive GeTe Devices
Velea, A; Dumitru, V; Sava, F; Galca, AC; Mihai, C
MAR 2021, PHYSICA STATUS SOLIDI-RAPID RESEARCH LETTERS, 15, 2000475
DOI: 10.1002/pssr.202000475
Show abstract
Phase-change memories have reached an advanced degree of maturity, although, to be able to meet the increasing storage demand, multilevel capability is needed. A GeTe memristor is obtained in an amorphous state and it is subjected to a specific thermal treatment which initiates the transition toward the crystalline state. It is found that this crystalline state initialization process is highly beneficial for subsequently obtaining a large number of intermediate resistive states between the high and low resistive states. Multiple resistance levels are achieved by operating the devices in both DC sweeps and rectangular pulse modes in the low-voltage subthreshold regime. The conduction is modeled using a space charge limited conduction model, showing three distinct conduction regions in the high resistive state which merge toward a single conduction region as the low resistive state is approached. The obtained memristors can be used as multilevel nonvolatile memories or as synapses in neuromorphic computing.
66
Argon pressure dependent optoelectronic characteristics of amorphous tin oxide thin films obtained by non-reactive RF sputtering process
Ziani, N; Galca, AC; Belkaid, MS; Stavarache, I
MAY 2021, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 32
DOI: 10.1007/s10854-021-05861-2
Show abstract
In this work, amorphous tin oxide thin films were deposited by non-reactive radio frequency magnetron sputtering. A ceramic SnO2 target was used, while different working pressures were employed. The target to substrate distance was fixed to 17 cm, and the substrate was not intentionally heated. The properties of SnO2 (thickness, refractive index dispersion, optical band gap, resistivity, free carriers concentration, carriers mobility, carriers majority type and their scattering time) have been inferred from spectroscopic ellipsometry, conventional UV-Vis spectroscopy and specific Hall electrical measurements. Thickness and refractive index are slightly dependent on the deposition conditions, while the optical band gap, free carriers concentration and their mobilities are changing from sample to sample. The evolution of the optical band gap and carriers concentration is correlated to the active defects concentration. Amorphous SnO2 films grown at 0.4 Pa have the lowest resistivity of 0.86 Omega cm, a carrier concentration of 1.05x10(18)cm(-3) Vs. The average optical transmittance in visible spectrum is 76%.
67 Open Access
Synthesis and Characterization of Cu2ZnSnS4 Thin Films Obtained by Combined Magnetron Sputtering and Pulsed Laser Deposition
Zaki, MY; Sava, F; Buruiana, AT; Simandan, ID; Becherescu, N; Galca, AC; Mihai, C; Velea, A
SEP 2021, NANOMATERIALS, 11, 2403
DOI: 10.3390/nano11092403
Show abstract
Cu2ZnSnS4 (CZTS) is a complex quaternary material, and obtaining a single-phase CZTS with no secondary phases is known to be challenging and dependent on the production technique. This work involves the synthesis and characterization of CZTS absorber layers for solar cells. Thin films were deposited on Si and glass substrates by a combined magnetron sputtering (MS) and pulsed laser deposition (PLD) hybrid system, followed by annealing without and with sulfur powder at 500 degrees C under argon (Ar) flow. Three different Cu2S, SnS2, and ZnS targets were used each time, employing a different target for PLD and the two others for MS. The effect of the different target arrangements and the role of annealing and/or sulfurization treatment were investigated. The characterization of the absorber films was performed by grazing incidence X-ray diffraction (GIXRD), X-ray reflectometry (XRR), Raman spectroscopy, scanning electron microscopy, and regular transmission spectroscopy. The film with ZnS deposited by PLD and SnS2 and Cu2S by MS was found to be the best for obtaining a single CZTS phase, with uniform surface morphology, a nearly stoichiometric composition, and an optimal band gap of 1.40 eV. These results show that a new method that combines the advantages of both MS and PLD techniques was successfully used to obtain single-phase Cu2ZnSnS4 films for solar cell applications.
68
Structural, morphological and optical properties of Cu-Fe-Sn-S thin films prepared by electrodeposition at fixed applied potential
El Khouja, O; Galca, AC; Nouneh, K; Zaki, MY; Touhami, ME; Taibi, M; Matei, E; Negrila, CC; Enculescu, M; Pintilie, L
MAR 1 2021, THIN SOLID FILMS, 721, 138547
DOI: 10.1016/j.tsf.2021.138547
Show abstract
Cu-Fe-Sn-S films were obtained on indium tin oxide / glass substrates by a low-cost electrodeposition using an aqueous solution of CuSO4, FeSO4, SnSO4, and Na2S2O3 at room temperature followed by high-temperature sulfurization (500 degrees C) in argon flow. A range of cathodic potentials have been used for electrodeposition, those being chosen after a preliminary cyclic voltammetry study. The coatings were characterized using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, X-ray Photoelectron Spectroscopy and conventional spectroscopy (diffuse reflectance and specular transmission). The results are discussed with respect to the used applied potential.
69
Investigation of Ba0.6Sr0.4TiO3 thick films by means of a novel THz-TDS approach
Nedelcu, L; Annino, G; Chirila, C; Trupina, L; Galca, AC; Banciu, MG
MAR 15 2020, APPLIED SURFACE SCIENCE, 506, 144807
DOI: 10.1016/j.apsusc.2019.144807
Show abstract
Ba0.6Sr0.4TiO3 (BST) ferroelectric thick films were grown on MgO(001) and Al2O3 (0 0 0 1) single-crystal substrates by using a pulsed laser deposition method. Structural, morphological, optical, and terahertz characterization of the BST films were performed by X-ray Diffraction, Atomic Force Microscopy, Spectroscopic Ellipsometry (SE), and Terahertz Time-Domain Spectroscopy (THz-TDS). Single-phase samples with strong preferred (1 1 1) orientation and surface roughness lower than 1.5% of their thicknesses have been obtained for both types of substrates. SE was employed to extract the thickness and optical properties by using a 3-layer optical model (substrate/thin film/roughness). The inferred refractive index @630 nm is around 2.05, while the optical interference is visible until 3.3 eV. The THz-TDS measurements in transmission set-up were carried out one after the other on substrates before and after the BST film deposition. The standard THz-TDS analysis of double-layer samples proved difficult to complete in the cases in which a thin or thick film is deposited on a much thicker substrate of known dielectric properties. However, we have been able to extract the complex dielectric permittivity in the THz domain for BST samples with thicknesses of few microns, by developing a specific procedure of data analysis.
70 Open Access
Graphene Oxide Concentration Effect on the Optoelectronic Properties of ZnO/GO Nanocomposites
Boukhoubza, I; Khenfouch, M; Achehboune, M; Leontie, L; Galca, AC; Enculescu, M; Carlescu, A; Guerboub, M; Mothudi, BM; Jorio, A; Zorkani, I
AUG 2020, NANOMATERIALS, 10, 1532
DOI: 10.3390/nano10081532
Show abstract
In this work, the effects of graphene oxide (GO) concentrations (1.5 wt.%, 2.5 wt.%, and 5 wt.%) on the structural, morphological, optical, and luminescence properties of zinc oxide nanorods (ZnO NRs)/GO nanocomposites, synthesized by a facile hydrothermal process, were investigated. X-ray diffraction (XRD) patterns of NRs revealed the hexagonal wurtzite structure for all composites with an average coherence length of about 40-60 nm. A scanning electron microscopy (SEM) study confirmed the presence of transparent and wrinkled, dense GO nanosheets among flower-like ZnO nanorods, depending on the GO amounts used in preparation. Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) absorption spectroscopy, and photoluminescence (PL) measurements revealed the impact of GO concentration on the optical and luminescence properties of ZnO NRs/GO nanocomposites. The energy band gap of the ZnO nanorods was independent of GO concentration. Photoluminescence spectra of nanocomposites showed a significant decrease in the intensities in the visible light range and red shifted suggesting a charge transfer process. The nanocomposites' chromaticity coordinates for CIE 1931 color space were estimated to be (0.33, 0.34), close to pure white ones. The obtained results highlight the possibility of using these nanocomposites to achieve good performance and suitability for optoelectronic applications.
71
Synthesis and characterization of a titanium phosphate-tellurite glass for Faraday rotators
Elisa, M; Boroica, L; Sava, BA; Iordache, SM; Iordache, AM; Vasiliu, IC; Stefan, RC; Galca, AC; Kuncser, V; Eftimie, M
JUL 2020, JOURNAL OF THE AMERICAN CERAMIC SOCIETY, 103
DOI: 10.1111/jace.17071
Show abstract
This work is focused on investigation of thermal, structural, optical, magnetic, and magneto-optical properties of novel titanium phosphate-tellurite glass applied as Faraday rotators. The glass belonging to the system 35Li(2)O-10Al(2)O(3)-5TiO(2)-45P(2)O(5)-5TeO(2) was prepared by a nonconventional wet route of raw materials processing, followed by melting-quenching-annealing steps. Some important physical properties of the investigated glass have been measured and calculated, providing knowledge related to glass compactness, electronic structure, glass forming capability, etc. XRD analysis evidenced an amorphous network structure of the investigated glass. The optical absorption in the Vis domain is mainly due to Ti3+ ions and Te-2 clusters formed during the glass melting process. A relatively low optical absorption is noticed over 600 nm that activates a significant Faraday magneto-optical effect. Photoluminescence bands in the blue, red, and infrared domains are observed, caused by Te-2 clusters formed during the glass melting process. The magnetization in dependency on applied magnetic field reveals a complex behavior of the glass, depending on temperature. Thus, it is found a ferromagnetic behavior up to 2000 Oe, a paramagnetic component up to 40 000 Oe, followed by a diamagnetic one over 40 000 Oe. Faraday rotation angle and Verdet constant values in the visible domain are correlated with the reduced TeO2 content of the glass.
72
Third-order optical nonlinearity properties of CdCl2-modifed Ge-Sb-S chalcogenide glasses
Lu, XS; Li, JH; Yang, L; Zhang, RN; Zhang, YD; Ren, J; Galca, AC; Secu, M; Farrell, G; Wang, PF
JAN 15 2020, JOURNAL OF NON-CRYSTALLINE SOLIDS, 528, 119757
DOI: 10.1016/j.jnonerysol.2019.119757
Show abstract
We developed a new type of chalcohalide glasses with physicochemical and nonlinear optical properties that are tunable by composition. It is found that more than 60 mol.% CdCl2 heavy metal halide can be dissolved into the ternary Ge Sb S system and forming stable glasses. The visible-light transparency range is extended to shorter wavelengths with the addition of CdCl2, which is beneficial for the optical quality control and infra-red (IR) system alignment. The third-order optical nonlinearity (TONL) is studied using the femtosecond Z-scan method. The results show that both the nonlinear refractive index and two photon absorption co-efficient decrease with CdCl2. Benefiting from the favorable property-tailoring effects of CdCl2, the TONL figure of merit (FOM) can be improved to meet the requirement (FOM < 1) for all-optical switching and IR photonic applications.
73
Magneto-functionalities of La 1-x A x MnO 3 (A = K; Ba) synthesized by flash combustion method
Bouzid, SA; Galca, AC; Sajieddine, M; Kuncser, V; Rostas, AM; Iacob, N; Enculescu, M; Amarande, L; Pasuk, I; Essoumhi, A
OCT 25 2020, JOURNAL OF ALLOYS AND COMPOUNDS, 839, 155546
DOI: 10.1016/j.jallcom.2020.155546
74 Open Access
A New Zinc Phosphate-Tellurite Glass for Magneto-Optical Applications
Elisa, M; Stefan, RC; Vasiliu, IC; Iordache, SM; Iordache, AM; Sava, BA; Boroica, L; Dinca, MC; Filip, AV; Galca, AC; Bartha, C; Iacob, N; Rusu, MI; Eftimie, M; Kuncser, V
SEP 2020, NANOMATERIALS, 10, 1875
DOI: 10.3390/nano10091875
Show abstract
This work investigates the structural, magnetic and magneto-optical properties of a new zinc phosphate-tellurite glass belonging to the 45ZnO-10Al(2)O(3)-40P(2)O(5)-5TeO(2)system. The glass was prepared by a wet method of processing the starting reagents followed by suitable melting-stirring-quenching-annealing steps. Specific parameters such as density, average molecular mass, molar volume, oxygen packaging density, refractive index, molar refractivity, electronic polarizability, reflection loss, optical transmission, band gap and optical basicity have been reported together with thermal, magnetic and magneto-optical characteristics. Absorption bands appear in the blue and red visible region, while over 600 nm the glass becomes more transparent. FTIR and Raman spectra evidenced phosphate-tellurite vibration modes proving the P(2)O(5)and TeO(2)network forming role. Magnetic measurements reveal the diamagnetic character of the Te-doped glass with an additional weak ferromagnetic signal, specific to diluted ferromagnetic oxides. Positive Faraday rotation angle with monotonous decreasing value at increasing wavelength was evidenced from magneto-optical measurements. The final product is a composite material comprising of a non-crystalline vitreous phase and Te-based nanoclusters accompanied by oxygen vacancies. The metallic-like Te colloids are responsible for the dark reddish color of the glass whereas the accompanying oxygen vacancies might be responsible for the weak ferromagnetic signal persisting up to room temperature.
75 Open Access
Secondary Crystalline Phases Influence on Optical Properties in Off-Stoichiometric Cu2S-ZnS-SnS2 Thin Films
Sava, F; Diagne, O; Galca, AC; Simandan, ID; Matei, E; Burdusel, M; Becherescu, N; Becherescu, V; Mihai, C; Velea, A
OCT 2020, MATERIALS, 13, 4624
DOI: 10.3390/ma13204624
Show abstract
Cu2ZnSnS4 (CZTS) is an economically and environmentally friendly alternative to other toxic and expensive materials used for photovoltaics, however, the variation in the composition during synthesis is often followed by the occurrence of the secondary binary and ternary crystalline phases. These phases produce changes in the optical absorption edge important in cell efficiency. We explore here the secondary phases that emerge in a combinatorial Cu2S-ZnS-SnS2 thin films library. Thin films with a composition gradient were prepared by simultaneous magnetron sputtering from three binary chalcogenide targets (Cu2S, SnS2 and ZnS). Then, the samples were crystallized by sulfurization annealing at 450 degrees C under argon flow. Their composition was measured by energy dispersive X-ray spectroscopy (EDX), whereas the structural and optical properties were investigated by grazing incidence X-ray diffraction (GIXRD), Raman spectroscopy and optical transmission measurements. As already known, we found that annealing in a sulfur environment is beneficial, increasing the crystallinity of the samples. Raman spectroscopy revealed the presence of CZTS in all the samples from the library. Secondary crystalline phases such as SnS2, ZnS and Cu-S are also formed in the samples depending on their proximity to the binary chalcogenide targets. The formation of ZnS or Cu-S strongly correlates with the Zn/Sn and Cu/Zn ratio of the total sample composition. The presence of these phases produces a variation in the bandgap between 1.41 eV and 1.68 eV. This study reveals that as we go further away from CZTS in the composition space, in the quasi-ternary Cu2S-ZnS-SnS2 diagram, secondary crystalline phases arise and increase in number, whereas the bandgap takes values outside the optimum range for photovoltaic applications.
76
Towards phase pure kesterite Cu2ZnSnS4 absorber layers growth via single step free sulfurization electrodeposition under a fix applied potential on Mo substrate
Azmi, S; Moujib, A; Layachi, OA; Matei, E; Galca, AC; Zaki, MY; Secu, M; Rusu, MI; Grigorescu, CEA; Khoumri, EM
NOV 25 2020, JOURNAL OF ALLOYS AND COMPOUNDS, 842, 155821
DOI: 10.1016/j.jallcom.2020.155821
Show abstract
This work presents a new synthesis and characterization of Kesterite Cu2ZnSnS4 films by one step electrodeposition with free sulfurization annealing treatment at different applied potentials. This study highlights the effect of applied potential and annealing treatment on the properties of CZTS deposited films. X-ray Diffraction and Raman spectroscopy were employed to assess the structure and composition of the films elaborated at -1V, -1.1V, and -1.2V vs Saturated Calomel Electrode (SCE). The morphological and optical properties were studied using Scanning Electron microscopy and photoluminescence spectroscopy (PL), respectively. The structural properties are improved by annealing treatment, while -1.1V vs SCE was found to be the optimum applied potential to prepare the Kesterite CZTS thin film with a bandgap around 1.5 eV. (C) 2020 Elsevier B.V. All rights reserved.
77 Open Access
Low power non-volatile memory switching in monolayer-rich 2D WS2 and MoS2 devices
Mihai, C; Sava, F; Galca, AC; Velea, A
FEB 1 2020, AIP ADVANCES, 10, 025102
DOI: 10.1063/1.5140717
Show abstract
Memristors characterized by non-volatile memory resistance switching are promising candidates for building brain inspired computing architectures. However, existing memristive devices are still far from the energy efficiency of petaflops per joule exhibited by biological neural networks. Therefore, to achieve the goal of ultra-low power operation, it is necessary to develop new materials for the active layer in memristors. Here, we show highly energy efficient memristive devices built from liquid-exfoliated 2D WS2 and MoS2 nanosheets, enriched in monolayers using a cascade centrifugation method. Lateral devices with electrochemically inert electrodes were built using the drop casting method. The devices show non-volatile resistive switching with a remarkable low energy consumption. This work contributes to the realization of energy efficient and high performance neuromorphic computing applications. (c) 2020 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
78
Influence of doping the inorganic cation with Eu or Sb on the properties of perovskite films
Stancu, V; Leonat, LN; Tomulescu, AG; Derbali, S; Pintilie, L; Besleaga, C; Galca, AC; Neatu, F; Neatu, T; Florea, M; Pintilie, I
JUL 2020, PHYSICA SCRIPTA, 95, 075707
DOI: 10.1088/1402-4896/ab90be
Show abstract
This study reports on the results obtained after doping the [CH3NH3](0.94)[C3N2H5](0.06)PbI2.6Cl0.4 mixt halide perovskite with europium or antimony (Eu3+/Sb3+) at the 'B site'. This way two new complex compounds were obtained, [CH3NH3](0.94)[C3N2H5](0.06)Pb1-yByI2.6Cl0.4 (B = Eu or Sb and y = 0-0.05) as perovskite precursor solutions and deposited as thin films. The properties of the perovskite films were investigated by various characterization techniques: x-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), UV-vis spectroscopy while the photovoltaic parameters were determined by measuring the IV curves of the corresponding solar cells. We find that doping the mixt halide perovskite with very small quantities of Sb improves the quality of the perovskite films and further improves the stability of perovskite solar cells.
79
Exploring the effect of aliovalent substitution of Pb<SUP>2+</SUP> by Eu<SUP>3+</SUP> on structural, morphological and optical properties of CH3NH3PbI3 perovskite films
Derbali, S; Nouneh, K; Florea, M; Neatu, F; Neatu, S; Leonat, LN; Secu, M; Tomulescu, AG; Stancu, V; Pintilie, L; Touhami, ME; Galca, AC
APR 2020, PHYSICA SCRIPTA, 95, 044003
DOI: 10.1088/1402-4896/ab5baa
Show abstract
In this work, the effect of aliovalent substitution of Pb2+ by Eu3+ on structural, morphological and optical properties of CH3NH3PbI3 (MAPbI(3)) was studied, aiming to improve the properties of perovskite films used in solar cells application. The surface morphology, the microstructure and the optical properties of the obtained films containing different Europium (Eu) concentrations were characterized by atomic force microscopy, x-ray photoelectron spectroscopy, x-ray diffraction, UV-vis spectroscopy and photoluminescence spectroscopy.
80
Influence of boric acid concentration on the properties of electrodeposited CZTS absorber layers
Zaki, MY; Nouneh, K; Touhami, ME; Matei, E; Badica, P; Burdusel, M; Negrila, CC; Baibarac, M; Pintilie, L; Galca, AC
MAY 2020, PHYSICA SCRIPTA, 95, 054001
DOI: 10.1088/1402-4896/ab6afd
Show abstract
This work involves the synthesis and characterization of Cu2ZnSnS4 (CZTS) layers. The films were prepared on Mo/glass substrates by single-step electrodeposition method followed by sulfurization at 500 degrees C under argon flow. The effect of boric acid concentration on the crystallographic structure, compositional and morphological properties of CZTS films was investigated, with the objective to understand the growth behavior and to enhance the film properties. Cyclic Voltammetry was used in order to estimate the adequate deposition potential for the CZT alloy. The x-ray diffraction analysis showed the formation of the kesterite phase in all the samples. The Raman and x-ray photoelectron spectroscopy studies confirmed the existence of the CZTS phase. The scanning electron microscopy was employed to inspect the films structure. The results indicated that increasing the concentration of boric acid affects the physico-chemical properties of the films.
81
Synthesis and characterization of conducting aniline and o-anisidine nanocomposites based on montmorillonite modified clay
Kenane, A; Galca, AC; Matei, E; Yahiaoui, A; Hachemaoui, A; Benkouider, AM; Bartha, C; Istrate, MC; Galatanu, M; Rasoga, O; Stanculescu, A
JAN 2020, APPLIED CLAY SCIENCE, 184, 105395
DOI: 10.1016/j.clay.2019.105395
Show abstract
A study on clay mineral polymer nanocomposites (CPN), namely polyaniline/montmorillonite-cetyltrimethylammonium bromide (PANI/Mt-CTAB), poly o-anisidine/montmorillonite-cetyltrimethylammonium bromide (poly(o-ANIS)/Mt-CTAB) and poly o-anisidine-co-aniline/montmorillonite-cetyltrimethylammonium bromide (poly(o-ANIS-co-ANI)/Mt-CTAB), synthesized by oxidative chemical polymerization method is presented. The nanocomposites have been characterized by Fourier transform infrared spectroscopy, UV-vis spectroscopy, and cyclic voltammetry, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, cyclic voltammetry and thermogravimetry and differential scanning calorimetry analysis. By UV-vis measurements different electronic transitions for the CPNs were pointed out. The voltammograms indicate that the synthetized materials are electroactive. The FTIR analysis reveals the characteristic bands of the polymers and of the Mt-CTAB. The shift of the bands to higher/lower wavenumbers demonstrate the interaction between the pristine polymers macromolecular chains and the montmorillonite (Mt). The intercalation of the polymers inside the mineral clay was confirmed by the increased interlayer distance connected with the position of the 011 diffraction plane of the Mt., and the intercalation and exfoliation states were highlighted in the scanning and transmission electron microscopy images. The obtained results are encouraging in respect with the purpose to use them in the field of photovoltaic applications.
82
Animal Origin Bioactive Hydroxyapatite Thin Films Synthesized by RF-Magnetron Sputtering on 3D Printed Cranial Implants
Chioibasu, D; Duta, L; Popescu-Pelin, G; Popa, N; Milodin, N; Iosub, S; Balescu, LM; Galca, AC; Popa, AC; Oktar, FN; Stan, GE; Popescu, AC
DEC 2019, METALS, 9
DOI: 10.3390/met9121332
Show abstract
Ti6Al4V cranial prostheses in the form of patterned meshes were 3D printed by selective laser melting in an argon environment; using a CO2 laser source and micron-sized Ti6Al4V powder as the starting material. The size and shape of prostheses were chosen based on actual computer tomography images of patient skull fractures supplied in the framework of a collaboration with a neurosurgery clinic. After optimizations of scanning speed and laser parameters, the printed material was defect-free (as shown by metallographic analyses) and chemically homogeneous, without elemental segregation or depletion. The prostheses were coated by radio-frequency magnetron sputtering (RF-MS) with a bioactive thin layer of hydroxyapatite using a bioceramic powder derived from biogenic resources (Bio-HA). Initially amorphous, the films were converted to fully-crystalline form by applying a post-deposition thermal-treatment at 500 degrees C/1 h in air. The X-ray diffraction structural investigations indicated the phase purity of the deposited films composed solely of a hexagonal hydroxyapatite-like compound. On the other hand, the Fourier transform infrared spectroscopic investigations revealed that the biological carbonatation of the bone mineral phase was well-replicated in the case of crystallized Bio-HA RF-MS implant coatings. The in vitro acellular assays, performed in both the fully inorganic Kokubo's simulated body fluid and the biomimetic organic-inorganic McCoy's 5A cell culture medium up to 21 days, emphasized both the good resistance to degradation and the biomineralization capacity of the films. Further in vitro tests conducted in SaOs-2 osteoblast-like cells showed a positive proliferation rate on the Bio-HA RF-MS coating along with a good adhesion developed on the biomaterial surface by elongated membrane protrusions.
83
Structural characterisation and thermal stability of SnSe\GaSb stacked films
Sava, F; Borca, CN; Galca, AC; Socol, G; Grolimund, D; Mihai, C; Velea, A
JAN 2 2019, PHILOSOPHICAL MAGAZINE, 99, 72
DOI: 10.1080/14786435.2018.1529442
Show abstract
We have investigated the effect of thermal annealing on the structure of single and stacked phase change memory films based on SnSe and GaSb. Samples were prepared by pulsed laser deposition and investigated by X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) methods. Electrical resistance versus temperature investigations showed crystallisation temperatures of 292 degrees C and 198 degrees C for SnSe and GaSb single films, respectively. Above the transition temperature, GaSb crystallises into a face-centered cubic structure, whereas SnSe has an orthorhombic arrangement. Annealing at three temperatures (160 degrees C, 250 degrees C and 350 degrees C) of the SnSe\GaSb stacked films promotes bond breaking, atom diffusion between the two layers and formation of new phases. At 160 degrees C, GaSb films crystallise partially and no effect is observed on the crystallinity of SnSe films. After 250 degrees C, rhombohedral SnSb emerges in addition to GaSb complete crystallisation. A major, completely new, body-centered orthorhombic unindexed quaternary Ga-Sn-Sb-Se phase formation was observed in the samples annealed at 350 degrees C. The GaSb crystallites are fully dissolved and we have observed the formation of a minor hexagonal SnSe2 phase. The analysis of EXAFS data, measured at Se and Ga K-edges, revealed changes in the local atomic environment as a function of the annealing temperature. A tetrahedral configuration is obtained for the Ga atoms in both as-deposited and annealed samples, whereas Se is mostly bivalent in the amorphous samples and has an octahedral arrangement in crystalline SnSe. Our results show that inter-layer diffusion should always be considered and evaluated when designing memory cells composed of stacked phase change chalcogenide films.
84
Carbon-based sprayed electrodes for pyroelectric applications
Chirila, C; Botea, M; Iuga, A; Tomulescu, AG; Balescu, L; Galca, AC; Boni, AG; Leonat, L; Pintilie, I; Pintilie, L
AUG 15 2019, PLOS ONE, 14
DOI: 10.1371/journal.pone.0221108
Show abstract
A carbon-based layer was deposited by spraying on top of a ferroelectric layer grown by sol-gel on Si (001) substrate and its properties as electrode and absorber for pyroelectric detection were tested. It was found that the electric properties of the ferroelectric capacitor with top carbon-based sprayed electrode (CBSE) are comparable with those of the capacitors with standard top SrRuO3 (SRO)/Au electrode. Pyroelectric measurements show that the pyroelectric signal recorded on ferroelectric capacitors with top CBSE electrode is 2.5 times greater than for top SRO/Au electrode for low frequency range. The value of the pyroelectric coefficient was estimated to 9.73.10(-4) C/m(2)K for CBSE electrodes and 3.36.10(-4) C/m(2)K for SRO/Au respectively. The fabrication process of CBSE is of low cost, easy to implement and with high throughput making it attractive for manufacturing various devices like pyroelectric detector, thermal imaging, solar cells, etc.
85
Structural and optical properties of ZnO thin films grown by rapid atmospheric mist chemical vapor technique
Derbali, S; Nouneh, K; Galca, AC; Touhami, ME; Secu, M; Matei, E; Leonat, LN; Pintilie, L; El Harfaoui, N; Fahoume, M
JUL 2019, OPTICAL AND QUANTUM ELECTRONICS, 51
DOI: 10.1007/s11082-019-1937-2
Show abstract
In this work, the effect of deposition time on the structural and optical properties of ZnO films deposited by Ultrasonic Spray Mist-CVD was studied aiming the application in perovskite solar cells, as holes blocking layer. Crystallinity, surface morphology and optical properties of the ZnO films were investigated by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), conventional and Photoluminescence (PL) spectroscopies, respectively. The XRD measurement proves the existence of the hexagonal wurtzite phase and a high degree of crystallinity with [001] preferential orientation. The SEM study shows that the films possess a compact structure. Smooth and homogenous surface was confirmed also by AFM. The obtained results indicate that ZnO films deposited by a simple, safe and cost-effective method present a great potential for application in perovskite solar cells.
86
Thermal, structural, magnetic and magneto-optical properties of dysprosium-doped phosphate glass
Elisa, M; Stefan, R; Vasiliu, IC; Rusu, MI; Sava, BA; Boroica, L; Sofronie, M; Kuncser, V; Galca, AC; Beldiceanu, A; Volceanov, A; Eftimie, M
OCT 1 2019, JOURNAL OF NON-CRYSTALLINE SOLIDS, 521
DOI: 10.1016/j.jnoncrysol.2019.119545
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The work is dedicated to the investigation of optical, structural, magnetic and magneto-optical properties of an aluminophosphate glass doped with Dy3+ ions, for specific applications as Faraday rotators in the visible spectral domain. The vitreous material belongs to the 16Li(2)O-8Al(2)O(3)-6BaO center dot 60P(2)O(5)-10Dy(2)O(3) system. Optical homogeneity measured by a polariscopic method, as well as by polarimetry and interferometry revealed an optical quality glass. Time dependent electrical conductance measurements have shown a high chemical strength of the glass. Optical absorption of the doped glass in the visible domain evidenced the specific absorption lines of dysprosium ions, whereas structural investigations made by FTIR and Raman spectroscopy put in evidence the vitreous network forming role of phosphorous pentoxide. Magnetic and magneto-optical measurements demonstrated paramagnetic features of the doped glass, as well as a Verdet constant of about -0.05 min/Oe/cm at 600 nm wavelength.
87
One-Pot Enzymatic Production of Lignin-Composites
Ion, S; Opris, C; Cojocaru, B; Tudorache, M; Zgura, I; Galca, AC; Bodescu, AM; Enache, M; Maria, GM; Parvulescu, VI
APR 20 2018, FRONTIERS IN CHEMISTRY, 6
DOI: 10.3389/fchem.2018.00124
Show abstract
A novel and efficient one-pot system for green production of artificial lignin bio-composites has been developed. Monolignols such as sinapyl (SA) and coniferyl (CA) alcohols were linked together with caffeic acid (CafAc) affording a polymeric network similar with natural lignin. The interaction of the dissolved SA/CA with CafAc already bound on a solid support (S-C2/S-C6 CafAc) allowed the attachment of the polymeric product direct on the support surface (S-C2/S-C6-CafAc-L-1 and S-C2/S-C6-CafAc-L-2, from CA and SA, respectively). Accordingly, this procedure offers the advantage of a simultaneous polymer production and deposition. Chemically, oxi-copolymerization of phenolic derivatives (SA/CA and CAfAc) was performed with H2O2 as oxidation reagent using peroxidase enzyme (2-1B mutant of versatile peroxidase from Pleurotus eryngii) as catalyst. The system performance reached a maximum of conversion for SA and CA of 71.1 and 49.8%, respectively. The conversion is affected by the system polarity as resulted from the addition of a co-solvent (e.g., MeOH, EtOH, or THF). The chemical structure, morphology, and properties of the bio-composites surface were investigated using different techniques, e.g., FTIR, TPD-NH3, TGA, contact angle, and SEM. Thus, it was demonstrated that the SA monolignol favored bio-composites with a dense polymeric surface, high acidity, and low hydrophobicity, while CA allowed the production of thinner polymeric layers with high hydrophobicity.
88
Structural and optical properties of optimized amorphous GeTe films for memory applications
Galca, AC; Sava, F; Simandan, ID; Bucur, C; Dumitru, V; Porosnicu, C; Mihai, C; Velea, A
NOV 1 2018, JOURNAL OF NON-CRYSTALLINE SOLIDS, 499, 7
DOI: 10.1016/j.jnoncrysol.2018.07.007
Show abstract
Chalcogenide amorphous materials, such as GeTe, are known to exhibit deposition dependent optical and structural properties. The formation of a single and homogeneous amorphous GeTe (a-GeTe) phase is questionable since the deposited films can be mixtures of monoelemental nanoclusters. In this work, we employed two deposition techniques, pulsed laser deposition from a polycrystalline GeTe target and co-sputtering from two distinct Ge and Te targets, respectively, to obtain a-GeTe films. To improve the homogeneity of the amorphous phase obtained by magnetron sputtering, the substrate temperature was varied from room temperature up to 180 degrees C. The samples were investigated by X-ray diffraction, X-ray reflectometry, X-ray photoelectron spectroscopy and spectroscopic ellipsometry. It was found that the film mass density, optical bandgap, refractive index and absolute reflectivity become progressively larger with increasing substrate temperature, due to the minimization of voids fraction and the number of dangling bonds in the amorphous structure. Moreover, X-ray photoelectron spectroscopy results prove the formation of Ge-Te bonds and therefore of the GeTe alloy at the optimal substrate temperature of 180 degrees C. This study reveals the importance of optimizing the deposition conditions for obtaining a specific amorphous phase, which enables the atomic rearrangements responsible for fast phase-change needed in memory applications.
89
Effect of Li doping on the electric and pyroelectric properties of ZnO thin films
Trinca, LM; Galca, AC; Boni, AG; Botea, M; Pintilie, L
JAN 1 2018, APPLIED SURFACE SCIENCE, 427, 37
DOI: 10.1016/j.apsusc.2017.08.009
Show abstract
Un-doped ZnO (UDZO) and Li-doped ZnO (LZO) polycrystalline thin films were grown on platinized silicon by pulsed laser deposition (PLD). The electrical properties were investigated on as-grown and annealed UDZO and LZO films with capacitor configuration, using top and bottom platinum electrodes. In the case of the as-grown films it was found that the introduction of Li increases the resistivity of ZnO and induces butterfly shape in the C-V characteristic, suggesting ferroelectric-like behavior in LZO films. The properties of LZO samples does not significantly changes after thermal annealing while the properties of UDZO samples show significant changes upon annealing, manifested in a butterfly shape of the C-V characteristic and resistive-like switching. However, the butterfly shape disappears if long delay time is used in the C-V measurement, the characteristic remaining non-linear. Pyroelectric signal could be measured only on annealed films. Comparing the UDZO results with those obtained in the case of Li: ZnO, it was found that the pyroelectric properties are considerably enhanced by Li doping, leading to pyroelectric signal with about one order of magnitude larger at low modulation frequencies than for un-doped samples. Although the results of this study hint towards a ferroelectric-like behavior of Li doped ZnO, the presence of real ferroelectricity in this material remains controversial. (C) 2017 Elsevier B.V. All rights reserved.
90
Thermal Stress Effect on the Structure and Properties of Single and Double Stacked Films of GeTe and SnSe
Sava, F; Borca, CN; Galca, AC; Socol, G; Grolimund, D; Mihai, C; Velea, A
JUN 2018, PHYSICA STATUS SOLIDI B-BASIC SOLID STATE PHYSICS, 255
DOI: 10.1002/pssb.201700552
Show abstract
The thermal stress effect on the structure of phase change memory materials, namely single films and double stacked films of GeTe and SnSe, is evaluated. The crystallization temperatures of GeTe and SnSe single films are 138 degrees C and 292 degrees C, respectively. The films are amorphous before annealing and crystallize in rhombohedral and orthorhombic structures afterwards. Ge is tetrahedrally bonded and Se is bivalent after deposition. Both Ge and Se have an octahedral configuration after annealing. The double stacked structure is studied in the as-deposited state and after annealing at temperatures of 100, 210, and 350 degrees C. Pulsed laser deposition produces the crystallization of both as-deposited layers when stacked, mostly of SnSe, but also some crystalline GeTe is present. GeTe fully crystallizes after annealing at 210 degrees C, in the face-centred cubic structure. Annealing at 350 degrees C leads to the evaporation of a significant quantity of Se and to the formation of a cubic Ge0.75Sn0.25Te solid solution. Ge has an octahedral coordination, while Se is tetrahedrally bonded as a result of a combination of bivalent amorphous Se and octahedral Se from crystalline SnSe. The study shows that diffusion between layers at high annealing temperatures might suppress the memory property and determines the formation of irreversible solid solutions.
91
Bismuth and lead oxides codoped boron phosphate glasses for Faraday rotators
Sava, BA; Boroica, L; Elisa, M; Shikimaka, O; Grabco, D; Popa, M; Barbos, Z; Iordanescu, R; Niculescu, AM; Kuncser, V; Galca, AC; Eftimie, M; Monteiro, RCC
APR 15 2018, CERAMICS INTERNATIONAL, 44, 6025
DOI: 10.1016/j.ceramint.2017.12.205
Show abstract
New magneto-optical vitreous materials were obtained by melting-quenching technique comprising wet route raw materials preparation. The glass has the following composition in oxide mol. % 10 Li2O, 9 Al2O3, 5 ZnO, (35; 20; 50) B2O3,,(35; 50; 20) P2O5, 3 Bi2O3, 3 PbO, phosphorus and boron oxide being the vitreous network formers. It was also prepared a similar reference glass composition but without Bi2O3 and PbO. Optical and structural characterization by ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FTIR) and Raman Spectroscopy of the bulk glasses showed a transmission over 90%, metaphosphate structure of glass together with Q(2) boron oxide units and P-O-B bonds. The mechanical parameters, hardness (H), Youngs modulus (E) and fracture toughness (KO of boron phosphate glasses, evaluated by micro- and nanoindentation techniques, demonstrated mostly higher values in comparison with those for alumino-phosphate glasses due to mixed borophosphate network. Thermal behavior was investigated by Differential Scanning Calorimetry (DSC) putting in evidence the vitreous transition temperature which decreases with about 45 degrees C when Bi and Pb oxides were added and two crystallization effects. The diamagnetic character of a highly transparent Bi and Pb oxide co doped boron phosphate glass was confirmed by ellipsometry, and the glass presented high magneto-optical properties at the top of the commercial bulk products.
92
Effect of mixing complexing agents on the properties of electrodeposited CZTS thin films
Zaki, MY; Nouneh, K; Touhami, ME; Belakhmima, RA; Galca, AC; Pintilie, L; Enculescu, M; Baibarac, M; Taibi, M
SEP 2018, OPTICAL MATERIALS, 83, 256
DOI: 10.1016/j.optmat.2018.06.030
Show abstract
This work involves the synthesis and characterization of Cu2ZnSnS4 (CZTS) layers. The films were prepared on ITO/glass substrate by ecofriendly and simple single-step electrodeposition method followed by sulfurization and annealing at 500 degrees C under Argon flow. By using two different complexing agents, the electrodeposition process can give better results. Therefore, the effect of combining the trisodium citrate - TC to multiple cornplexing agents (cetyl trimethyl ammonium bromide - CTAB, ethylene diamine tetra acetic acid - EDTA, Boric Acid - BA, Glutamic Acid - GA and Tartaric Acid - TA) is investigated. The characterization of the absorber films was done by X-ray diffraction (XRD) analysis, Raman spectroscopy, Scanning Electron Microscopy and Diffuse Reflectivity. The combination of TC and CTAB is suggested to be the best pair of complexing agents within the combinations used in this work.
93
Magnetic and magneto-optical properties of Bi and Pb-containing aluminophosphate glass
Elisa, M; Iordanescu, R; Vasiliu, C; Sava, BA; Boroica, L; Valeanu, M; Kuncser, V; Galca, AC; Volceanov, A; Eftimie, M; Melinescu, A; Beldiceanu, A
JUN 1 2017, JOURNAL OF NON-CRYSTALLINE SOLIDS, 465, 58
DOI: 10.1016/j.jnoncrysol.2016.11.010
Show abstract
Bi3+, Pb2+ and Bi3+-Pb2+-containing aluminophosphate glasses were obtained by unconventional wet method, the molar formula of the glasses being: i) 58LiPO(3), 29Al(PO3)(3), 10Ba(PO3)(2), 3Bi(2)O(3); ii) 58LiPO(3), 29Al(PO3)(3), 10Ba(PO3)(2), 3PbO and iii) 6LiPO(3), 3Al(PO3)(3), 1Ba(PO3)(2), 10Bi(PO3)(3), 80Pb(PO3)(2). The glass samples were investigated to determine the density, the thermal expansion coefficients and the chemical stability. The magnetic measurements for Bi and Pb-single doped glasses revealed a diamagnetic behavior and those of Bi-Pb-containing glass disclosed a diamagnetic behavior superposed a small paramagnetic contribution, observed in low magnetic fields that can be attributed to the impurities presented in the matrix. The Verdet constant for the analyzed glasses appeared to have positive values proving a diamagnetic behavior of the investigated material. (C) 2016 Published by Elsevier B.V.
94
Effect of in-plane ordering on dielectric properties of highly {111}-oriented bismuth-zinc-niobate thin films
Le Febvrier, A; Deputier, S; Demange, V; Bouquet, V; Galca, AC; Iuga, A; Pintilie, L; Guilloux-Viry, M
OCT 2017, JOURNAL OF MATERIALS SCIENCE, 52, 11313
DOI: 10.1007/s10853-017-1297-x
Show abstract
Bi1.5-xZn0.92-yNb1.5O6.92-delta (BZN) thin films were grown by pulsed laser deposition on two different Pt-covered substrates, namely textured {111} Pt/TiO2/SiO2/(100) Si substrate (Pt/Si) and epitaxial {111} Pt/R-plane sapphire substrate (Pt/sapphire). In both cases, the BZN films present {111} and {100} out-of-plane orientations, in relative ratios of 65: 35 on Pt/Si and 80: 20 on Pt/sapphire, respectively. The film grown on Pt/Si is textured, while the film deposited on Pt/sapphire presents epitaxial-like relationships with the substrate, for both out-of-plane orientations. Dielectric measurements were taken on both types of thin films, using Pt/BZN/Pt planar capacitor structures. The BZN/Pt/sapphire film presents higher dielectric constant (245 at 100 kHz) and higher tunability (12% at 600 kV/cm) than the BZN/Pt/Si film (200; 6%), while the dielectric losses values are nearly same (similar to 0.05).
95
Epitaxial La0.67Ba0.33Ti0.02Mn0.98 O-3 oxide thin films
Marouan, O; Galca, AC
2017, ACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES, 73, C222
DOI: 10.1107/S2053273317093512
96
TEMPERATURE INFLUENCE ON THE CAPACITANCE-VOLTAGE HYSTERESIS OF TRANSPARENT a-IGZO/PZT/FTO MFS-HETEROSTRUCTURE
Trinca, LM; Besleaga, C; Stancu, V; Radu, R; Iuga, A; Boni, AG; Galca, AC; Pintilie, L
2017, ROMANIAN REPORTS IN PHYSICS, 69
Show abstract
Capacitance-voltage (C-V) hysteresis of metal-ferroelectric-semiconductor (MFS) structure based on a-In2GaZnO5.5 and Pb0.2Zr0.8TiO3 layers are recorded in the 350-470 K range. The structure is grown on FTO/glass to obtain a transparent MFS. The memory functionality of the heterostructure is proved through C-V and P-V characteristics. The memory window is dependent on the temperature, the largest value of 2.5 V being obtained at 470 K, where the contribution of the ferroelectric-semiconductor interface defect states is minimized. The direction of C-V hysteresis is clockwise at 350 K, and it turns counterclockwise at higher temperatures where the ferroelectric polarization has the main contribution.
97
Structure, transition temperature, and magnetoresistance of titanium-doped lanthanum barium manganite epilayers onto STO 001 substrates
Galca, AC; Oumezzine, M; Leca, A; Chirila, CF; Kuncser, V; Kuncser, A; Ghica, C; Pasuk, I; Oumezzine, M
OCT 30 2017, APPLIED PHYSICS LETTERS, 111
DOI: 10.1063/1.4998011
Show abstract
We have developed a thin film structure with a maximum magnetoresistance effect (MRE) at room temperature, which is one of the operating requirements for many applications. It is shown that La0.67Ba0.33Ti0.02Mn0.98O3 epilayers obtained by pulsed laser deposition onto (001) SrTiO3 single crystal substrates exhibit the highest MRE, Delta R/R(H) approximate to 150% or Delta R/R(0) approximate to 60% under 5 T, at 300 K, a temperature near to the corresponding Curie temperature (T-C). Both doping with a tiny amount of titanium and induced stress due to lattice mismatch between the thin film and the substrate contribute to a decrease in T-C as compared to the pristine compound and therefore to the decrease in the temperature where the highest MRE is recorded. Published by AIP Publishing.
98
Structural, magnetic and magnetocaloric effects in epitaxial La0.67Ba0.33Ti0.02Mn0.98O3 ferromagnetic thin films grown on 001-oriented SrTiO3 substrates
Oumezzine, M; Galca, AC; Pasuk, I; Chirila, CF; Leca, A; Kuncser, V; Tanase, LC; Kuncser, A; Ghica, C; Oumezzine, M
2016, DALTON TRANSACTIONS, 45, 15040
DOI: 10.1039/c6dt01914e
Show abstract
Epitaxial La0.67Ba0.33Ti0.02Mn0.98O3 (denoted as LBTMO hereafter) thin films of approximately 95 nm thickness were deposited by a pulsed laser deposition technique onto SrTiO3 (STO) (001) substrates. High-resolution X-ray diffraction (HRXRD) and transmission electron microscopy (TEM) investigations revealed that the films are epilayers with a four-fold symmetry around the [001] direction. Cross-sectional TEM and the presence of Pendellosung fringes in the XRD profiles demonstrate smooth interfaces. The STO substrate induces an in-plane compressive strain, which leads to a slight tetragonality of the film structure. The epilayers exhibit paramagnetic-to-ferromagnetic phase transitions at the Curie temperature T-C (286 K), close to room temperature. The magnetization easy axis lies in the film plane along the [100] direction of the (001) substrate. The magnetic entropy change (Delta S-M) associated with the second-order magnetic phase transition was determined via magnetization measurements in the temperature range between 210 and 350 K under different magnetic fields. The relative cooling power (RCP) of this film is about 220 J kg(-1), somewhat lower than that of bulk Gd (410 J kg(-1)) for a 50 kOe field change, making the LBTMO ferromagnetic thin films a promising candidate for micro/nanomagnetic refrigeration around room temperature. The proposed universal curve provides a simple method for extrapolating Delta S-M in a wide range of fields and temperatures, thus confirming the order of the magnetic transition in this system. The magnetic entropy (Delta S-M)(max) around T-C is proportional to (mu H-0/T-C)(2/3) in agreement with the mean-field theory, indicating the existence of long-range ferromagnetic interactions in epitaxial LBTMO thin films.
99
On the growth of conductive aluminum doped zinc oxide on 001 strontium titanate single crystals
Trinca, LM; Galca, AC; Aldica, G; Radu, R; Mercioniu, I; Pintilie, L
FEB 28 2016, APPLIED SURFACE SCIENCE, 364, 370
DOI: 10.1016/j.apsusc.2015.12.106
Show abstract
Aluminum doped zinc oxide (AZO) thin films were obtained by pulsed laser deposition on (001) SrTiO3 (STO) on a range of substrate temperatures during ablation between 300 degrees C and 600 degrees C. A hexagonal system lying on a cubic one should be difficult to be obtained in epitaxial form. The geometrical selection of the AZO growth on (001) STO is not giving a unique preferential orientation. Two orientations, c-axis (along [001]) and 110, have been observed experimentally with different ratios at different substrate temperature. Discussions are made with respect to the temperature dependence of lattice mismatch between the two cases and the cubic surface of the substrate, and to the substrate surface morphology and terminating atomic layer composition. The 110 AZO is the main phase at deposition temperature of 550 degrees C, while for other substrate temperatures the 001 is the preferential orientation. The conductive character of 110 AZO thin film have been inferred from both ellipsometry spectra and current-voltage measurements. Excepting the samples deposited at 300 degrees C, the lowest resistivity is recorded for the samples with 110 AZO as the main phase. (C) 2015 Elsevier B.V. All rights reserved.
100
Gamma irradiation effects on the properties of indium zinc oxide thin films
Craciun, D; Socol, G; Le Caer, S; Trinca, LM; Galca, AC; Pantelica, D; Ionescu, P; Craciun, V
SEP 1 2016, THIN SOLID FILMS, 614, 6
DOI: 10.1016/j.tsf.2016.04.041
Show abstract
Thin films of amorphous and polycrystalline indium zinc oxide (IZO) having various In/(In + Zn) nominal compositions from 0.3 to 0.9 were grown by the pulsed laser deposition technique at room temperature or at 400 degrees C on oxidized Si and quartz substrates. After deposition, the films were gamma irradiated at doses of 10, 20 and 30 kGy under Ar atmosphere. Grazing incidence X-ray diffraction investigations could not find measurable changes of the structure after irradiation. Simulations of the X-ray reflectivity (XRR) and diffuse scattering curves acquired from the films showed a small density decrease after irradiation, accompanied by an increase of the thickness and surface roughness. Spectroscopic ellipsometry investigations confirmed the increase of the IZO films' thickness after irradiation, being in agreement with the XRR results. Small changes in the refractive index, most probably caused by changes in the film density were also observed. Four point probe measurements showed very small resistivity increases after irradiation, with the films containing higher In concentration presenting negligible changes. (C) 2016 Elsevier B.V. All rights reserved.
101
Amorphous thin films in the gallium-chalcogen system
Popescu, M; Sava, F; Lorinczi, A; Velea, A; Simandan, ID; Galca, AC; Matei, E; Socol, G; Gherendi, F; Savastru, D; Miclos, S
JUN 2016, PHYSICA STATUS SOLIDI B-BASIC SOLID STATE PHYSICS, 253, 1037
DOI: 10.1002/pssb.201552551
Show abstract
Thin amorphous films based on gallium-chalcogen (Ga-Ch), namely Ga2S3, Ga2Se3, Ga2Te3, and GaTe have been prepared by pulsed laser deposition (PLD). The films were characterized by X-ray diffraction, extended X-ray absorption fine structure (EXAFS), energy-dispersive X-ray spectroscopy (EDX), optical transmission spectroscopy, ellipsometry, and electrical measurements. Structural measurements showed that Ga is threefold coordinated, except the Te-based alloys were, it seems, only twofold coordinated, while the chalcogen is usually twofold coordinated. In all the compositions, layered and chain-like structures are assumed. The bandgaps range between 1.09 eV for Ga2Te3 and 2.21 eV for Ga2Se3. (C) 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
102
The relationship between magnetism and magneto-optical effects in rare earth doped aluminophosphate glasses
Valeanu, M; Sofronie, M; Galca, AC; Tolea, F; Elisa, M; Sava, B; Boroica, L; Kuncser, V
FEB 25 2016, JOURNAL OF PHYSICS D-APPLIED PHYSICS, 49
DOI: 10.1088/0022-3727/49/7/075001
Show abstract
Aluminophosphate glasses from the Li2O-BaO-Al2O3-P2O5 system with the addition of nonmagnetic and paramagnetic rare earth ions, were prepared using a wet nonconventional method to process the raw materials, followed by a melting-quenching procedure. The glasses obtained were characterized with respect to their magnetic and magneto-optical properties using superconducting quantum interference device magnetometry and spectroscopic ellipsometry. The assumption of a linear dependence of the Verdet constant on the magnetic susceptibility, with a proportionality constant dependent on the type of vitreous matrix and doping ion, is critically discussed. The diamagnetic and paramagnetic contributions to the Faraday rotation were separately analyzed and specific designs for optimal active and passive elements are proposed.
103
Thin films of amorphous Ga2S3 and rare-earth sulphides
Popescu, M; Lorinczi, A; Sava, F; Velea, A; Simandan, ID; Badica, P; Burdusel, M; Galca, AC; Socol, G; Jipa, F; Zamfirescu, M
MAR 1 2015, MATERIALS LETTERS, 142, 231
DOI: 10.1016/j.matlet.2014.12.028
Show abstract
The aim of this research is to prepare amorphous thin films of undoped gallium sulphide and doped with rare-earth sulphides, of rare-earth sulphides and to investigate their physical properties. We have prepared thin amorphous films of Ga2S3, EuS, Er2S3, Gd2S3, and Ga2S3 doped with rare-earth sulphides (Ga2S3:EuS, Ga2S3:Er2S3, Ga2S3:Gd2S3) by Pulsed laser Deposition (PLD). The corresponding targets for preparation of amorphous thin films were obtained by Spark Plasma Sintering (SPS) from commercially available powders of binary sulphides. The structural results for the undoped and doped Ga2S3 thin films indicate a packing of disordered layers similar to that of amorphous As2S3. Femtosecond laser irradiation of the Ga2S3 thin films shows a photoexpansion effect at low laser power (85-100 mW) and an ablation effect at higher laser power (above 105 mW). The threshold between low power and high power pulses is situated at higher value for Ga2S3 (100 mW) in comparison with the case of As2S3 thin films (20 mW). (C) 2014 Elsevier B.V. All rights reserved.
104
In-situ characterization of the optical and electronic properties in GeTe and GaSb thin films
Velea, A; Socol, G; Popescu, M; Galca, AC
OCT 7 2015, JOURNAL OF APPLIED PHYSICS, 118
DOI: 10.1063/1.4932666
Show abstract
GeTe and GaSb thin films obtained by pulsed laser deposition were investigated by spectroscopic ellipsometry at controlled temperatures. The GeTe films were fully amorphous, while the GaSb films were partially crystalized in the as-deposited state. The Tauc-Lorentz model was employed to fit the experimental data. From the temperature study of the optical constants, it was observed the crystallization in the 150-160 degrees C range of GeTe amorphous films and between 230 and 240 degrees C of GaSb amorphous phase. A second transition in the resonance energy and the broadening parameter of the Lorentz oscillator was observed due to the crystallization of Sb after 250 degrees C. The temperatures of 85 degrees C and 130 degrees C are noticed as the start of the relaxation of the amorphous GeTe phase and as-deposited GaSb. The peaks of the imaginary part of the dielectric function red shifted after the phase change, while the variation with temperature of the crystalline phase follows the Varshni law. The electron-phonon coupling constants are 2.88 and 1.64 for c-GeTe and c-GaSb, respectively. An optical contrast up to 60% was obtained for GeTe films and a maximum value of 7.5% is revealed in the case GaSb, which is altered by the partial crystallinity of the as-deposited films. (C) 2015 AIP Publishing LLC.
105
Ceramics and amorphous thin films based on gallium sulphide doped by rare-earth sulphides
Popescu, M; Sava, F; Lorinczi, A; Velea, A; Simandan, ID; Badica, P; Burdusel, M; Galca, AC; Matei, E; Preda, N; Secu, M; Socol, G; Jipa, F; Zamfirescu, M; Balan, A
APR 2015, SEMICONDUCTOR SCIENCE AND TECHNOLOGY, 30
DOI: 10.1088/0268-1242/30/4/044001
Show abstract
Bulk ceramics of Ga2S3 and rare-earth sulfides (EuS, Gd2S3, Er2S3) as well as combinations thereof have been prepared by spark plasma sintering (SPS). The disk-shaped ceramics were used as targets for pulsed laser deposition (PLD) experiments to obtain amorphous thin films. The properties of these new bulks and amorphous thin films have been investigated by x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), optical transmission spectroscopy, and atomic force microscopy (AFM). In order to test the photoexpansion effect in Gd2S3 and the possibility to create planar arrays of microlenses, the film was irradiated with femtosecond laser pulses at different powers. For low laser power pulses (up to 100mW power per pulse) a photoexpansion effect was observed, which leads to formation of hillocks with a height of 40-50 nm. EuS doped Gd2S3 thin film shows luminescence properties, which recommend them for optoelectronic applications.
106
In-situ crystallization of GeTe\GaSb phase change memory stacked films
Velea, A; Borca, CN; Socol, G; Galca, AC; Grolimund, D; Popescu, M; van Bokhoven, JA
DEC 21 2014, JOURNAL OF APPLIED PHYSICS, 116
DOI: 10.1063/1.4904741
Show abstract
Single and double layer phase change memory structures based on GeTe and GaSb thin films were deposited by pulsed laser deposition (PLD). Their crystallization behavior was studied using in-situ synchrotron techniques. Electrical resistance vs. temperature investigations, using the four points probe method, showed transition temperatures of 138 degrees C and 198 degrees C for GeTe and GaSb single films, respectively. It was found that after GeTe crystallization in the stacked films, Ga atoms from the GaSb layer diffused in the vacancies of the GeTe crystalline structure. Therefore, the crystallization temperature of the Sb-rich GaSb layer is decreased by more than 30 degrees C. Furthermore, at 210 degrees C, the antimony excess from GaSb films crystallizes as a secondary phase. At higher annealing temperatures, the crystalline Sb phase increased on the expense of GaSb crystalline phase which was reduced. Extended X-ray absorption fine structure (EXAFS) measurements at the Ga and Ge K-edges revealed changes in their local atomic environments as a function of the annealing temperature. Simulations unveil a tetrahedral configuration in the amorphous state and octahedral configuration in the crystalline state for Ge atoms, while Ga is four-fold coordinated in both as-deposited and annealed samples. (C) 2014 AIP Publishing LLC.
107
Investigation of DC magnetron-sputtered TiO2 coatings: Effect of coating thickness, structure, and morphology on photocatalytic activity
Daviosdottir, S; Shabadi, R; Galca, AC; Andersen, IHI; Dirscherl, K; Ambat, R
SEP 15 2014, APPLIED SURFACE SCIENCE, 313, 686
DOI: 10.1016/j.apsusc.2014.06.047
Show abstract
The photocatalytic performance of magnetron-sputtered titanium dioxide (TiO2) coatings of different thickness in anatase crystalline structure deposited on aluminium 1050 alloy substrates was investigated using a combination of photo-electrochemistry, methylene blue decomposition, and microscopic and spectroscopic methods, such as high resolution scanning and transmission electron microscopy, atomic force microscopy and ellipsometry. The reaction resistance was measured by AC impedance, while photocurrent measurements were carried out using the zero resistance ammetry (ZRA) method. The results showed that the TiO2 grains grow in dipyramidal columns having a linear increase in surface area with increased coating thickness. The refractive index values indicate also an evolutionary growth. The refractive index values obtained for the thin coatings on aluminium substrate were well below the values reported for monocrystalline anatase. The photocatalytic performance increased with increased coating thickness, though more rapidly over a range of 100-500 nm thickness. The dielectric constant also increased linearly with coating thickness. (C) 2014 Elsevier B.V. All rights reserved.
108
Annealing induced changes in the structure, optical and electrical properties of GeTiO2 nanostructured films
Stavarache, I; Lepadatu, AM; Teodorescu, VS; Galca, AC; Ciurea, ML
AUG 1 2014, APPLIED SURFACE SCIENCE, 309, 174
DOI: 10.1016/j.apsusc.2014.04.212
Show abstract
The GeTiO2 amorphous films were deposited by magnetron sputtering and subsequently annealed at 400, 550, 600 and 700 degrees C for nanostructuring. The structure of annealed films was investigated by X-ray diffraction and transmission electron microscopy. The transmittance spectra of all annealed GeTiO2 films were measured and simulated by using Bruggeman effective medium approximation considering components of TiO2 anatase, crystalline Ge, GeO2 and voids determined from the structure investigations. The electrical behavior of 400, 600 and 700 degrees C annealed films was studied by measuring current-voltage characteristics. We found that by increasing the annealing temperature the films thickness decreases from 330 nm (as-deposited films) to 290 nm (700 degrees C annealed films). The 400 degrees C annealed films are amorphous, while all the others annealed at higher temperatures are crystallized (X-ray diffraction and transmission electron microscopy). In the 550 and 600 degrees C annealed films we found the (TiGe)O-2 rutile structure which is formed by starting from the GeO2 tetragonal structure with high Ti content. Additionally, these films contain TiO2 anatase structure and cubic Ge nanocrystals. At 700 degrees C annealing temperature, a surface layer of GeO2 tetragonal nanocrystals is formed by Ge diffusion and a part of Ge is lost. The experimental transmittance spectra indicate a broadening of the transparency range by increasing the annealing temperature, and the simulated ones also indicate this behavior with the decrease of Ge content, the experimental and simulated spectra being in good agreement. Also, the increase of annealing temperature produces an increase of electrical conductivity. (C) 2014 Elsevier B.V. All rights reserved.
109
Structural Characterization of Impurified Zinc Oxide Thin Films
Trinca, LM; Galca, AC; Stancu, V; Chirila, C; Pintilie, L
2014, ELECTROCERAMICS XIV CONFERENCE, 1627, 128
DOI: 10.1063/1.4901669
Show abstract
Europium doped zinc oxide (Eu:ZnO) thin films have been obtained by pulsed laser deposition (PLD). 002 textured thin films were achieved on glass and silicon substrates, while hetero-epilayers and homo-epilayers have been attained on single crystal SrTiO3 and ZnO, respectively. X-ray Diffraction (XRD) was employed to characterize the Eu:ZnO thin films. Extended XRD studies confirmed the different thin film structural properties as function of chosen substrates.
110
Quantitative analysis of amorphous indium zinc oxide thin films synthesized by Combinatorial Pulsed Laser Deposition
Axente, E; Socol, G; Beldjilali, SA; Mercadier, L; Luculescu, CR; Trinca, LM; Galca, AC; Pantelica, D; Ionescu, P; Becherescu, N; Hermann, J; Craciun, V
OCT 2014, APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING, 117, 236
DOI: 10.1007/s00339-014-8427-y
Show abstract
The use of amorphous and transparent oxides is a key for the development of new thin film transistors and displays. Recently, indium zinc oxide (IZO) was shown to exhibit high transparency in the visible range, low resistivity, and high mobility. Since the properties and the cost of these films depend on the In/(In + Zn) values, the measurement of this ratio is paramount for future developments and applications. We report on accurate analysis of the elemental composition of IZO thin films synthesized using a Combinatorial Pulsed Laser Deposition technique. The monitoring of the thin films elemental composition by Laser-Induced Breakdown Spectroscopy was chosen in view of further in situ and real-time technological developments and process control during IZO fabrication. Our analytical approach is based on plasma modeling, the recorded spectra being then compared to the spectral radiance computed for plasmas in local thermal equilibrium. The cation fractions measured were compared to values obtained by complementary measurements using energy dispersive X-ray spectroscopy and Rutherford backscattering spectrometry. Spectroscopic ellipsometry assisted the scientific discussion. A good agreement between methods was found, independently of the relative fraction of indium and zinc that varied from about 65 to 90 and 35 to 10 at%, respectively, and the measurement uncertainties associated to each analytical method.
111
Nanomechanical characterization of bioglass films synthesized by magnetron sputtering
Popa, AC; Marques, VMF; Stan, GE; Husanu, MA; Galca, AC; Ghica, C; Tulyaganov, DU; Lemos, AF; Ferreira, JMF
FEB 28 2014, THIN SOLID FILMS, 553, 172
DOI: 10.1016/j.tsf.2013.10.104
Show abstract
Bioactive glasses are osteoproductive-type inorganic materials possessing the highest indices of bioactivity in both bulk and thin film forms. The prerequisites for reliable implant-type coatings are both their biological and mechanical performances. Whilst the bioglass films' structural, chemical and biological properties have been studied extensively, information about their mechanical performance is scarce. Here, transmission electron microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, nanoindentation and pull-out measurements were employed to assess the morphological, chemical, structural and mechanical properties of the bioglass films deposited onto Ti substrates by radio-frequency magnetron sputtering (RF-MS). The biological safety of the thin bioglass films was evaluated preliminarily in vitro by investigating the adherence, proliferation and cytotoxicity of fibroblast cells cultivated on their surface. Our study emphasize the versatility of RF-MS, showing how bioglass films' features such as composition, structure, bonding strength, hardness, elastic modulus and biological response can be conveniently adapted by tuning the RF-MS working conditions, and therefore demonstrating the unexplored potential of this deposition technique for preparing quality biomimetic glass coatings. (C) 2013 Elsevier B. V. All rights reserved.
112
Pulsed laser deposition of nanocrystalline SiC films
Socol, G; Galca, AC; Craciun, D; Hanna, M; Taylor, CR; Lambers, E; Craciun, V
JUL 1 2014, APPLIED SURFACE SCIENCE, 306, 69
DOI: 10.1016/j.apsusc.2014.01.201
Show abstract
Thin SiC films were grown on (1 0 0) Si substrates at temperatures from 400 to 1000 degrees C under various CH4 pressures by the pulsed laser deposition (PLD) technique using a KrF excimer laser. After deposition, films were in situ annealed at their deposition temperature under 500 mbar of CH4 for 1.0-1.5h. X-ray reflectivity investigations showed that films exhibited mass densities similar to SiC single crystal samples, while symmetrical and grazing incidence X-ray diffraction investigations found that films deposited at 800 degrees C or higher substrate temperatures were nanocrystalline. Modeling of spectroscopic ellipsometry measurements indicated that the refractive index values were similar to those reported for bulk SiC, while X-ray photoelectron spectroscopy investigations found that films contained in bulk a relatively low oxygen concentration of around 1.0 at.%. Nanoindentation results showed that the deposited SiC films were very hard, with hardness values above 40 GPa for films deposited at temperatures higher than 800 degrees C. (C) 2014 Elsevier B.V. All rights reserved.
113
Physical properties of AlxIn1-xN thin film alloys sputtered at low temperature
Besleaga, C; Galca, AC; Miclea, CF; Mercioniu, I; Enculescu, M; Stan, GE; Mateescu, AO; Dumitru, V; Costea, S
OCT 21 2014, JOURNAL OF APPLIED PHYSICS, 116
DOI: 10.1063/1.4898565
Show abstract
In this paper, we report on the structural, optical, and electrical properties of a wide compositional range of AlxIn1-xN thin layers deposited on glass and polyethylene terephthalate substrates. AlxIn1-xN layers of controlled composition were obtained by a simple reactive magnetron co-sputtering protocol, using a single aluminium target with indium insets, by varying the Al/In target surface area ratio, and the composition of the deposition atmosphere. The relevant physical properties were investigated and discussed. It is shown that the texture of the thin films is dependent on the cation ratio, while the bowing parameters of lattice constants and band gap values are larger than those of epitaxial layers. (C) 2014 AIP Publishing LLC.
114
Strong bonding between sputtered bioglass-ceramic films and Ti-substrate implants induced by atomic inter-diffusion post-deposition heat-treatments
Stan, GE; Popa, AC; Galca, AC; Aldica, G; Ferreira, JMF
SEP 1 2013, APPLIED SURFACE SCIENCE, 280, 538
DOI: 10.1016/j.apsusc.2013.05.022
Show abstract
Bioglasses (BG) are the inorganic materials exhibiting the highest indices of bioactivity. Their appliance as films for bio-functionalization of metallic implant surfaces has been regarded as an optimal solution for surpassing their limited bulk mechanical properties. This study reports on magnetron sputtering of alkali-free BG thin films by varying the target-to-substrate working distance, which proved to play an important role in determining the films' properties. Post deposition heat-treatments at temperatures slightly above the glass transformation temperature were then applied to induce inter-diffusion processes at the BG/titanium substrate interface and strengthening the bonding as determined by pull-out adherence measurements. The morphological and structural features assessed by SEM-EDS, XRD, and FTIR revealed a good correlation between the formations of inter-metallic titanium silicide phases and the films' bonding strength. The highest mean value of pull-out adherence (60.3 +/- 4.6 MPa), which is adequate even for load-bearing biomedical applications, was recorded for films deposited at a working distance of 35 mm followed by a heat-treatment at 750 degrees C for 2 h in air. The experimental findings are explained on the basis of structural, compositional and thermodynamic considerations. (C) 2013 Elsevier B.V. All rights reserved.
115
InN Based Water Condensation Sensors on Glass and Flexible Plastic Substrates
Dumitru, V; Costea, S; Brezeanu, M; Stan, GE; Besleaga, C; Galca, AC; Ionescu, G; Ionescu, O
DEC 2013, SENSORS, 13, 16949
DOI: 10.3390/s131216940
116
Stoichiometry dependence of the optical properties of amorphous-like Inx-wGawZn1-xO1+0.5x-delta thin films
Galca, AC; Socol, G; Trinca, LM; Craciun, V
SEP 15 2013, APPLIED SURFACE SCIENCE, 281, 99
DOI: 10.1016/j.apsusc.2013.01.176
Show abstract
The paper investigates the dependence of the optical properties on cation concentration of amorphous-like indium gallium zinc oxide thin films (Inx-wGawZn1-xO1+0.5x-delta) with various (In + Ga)/(In + Ga + Zn) and Ga/(In + Ga) ratios obtained by pulsed laser deposition. X-ray reflectivity and spectroscopic ellipsometry thickness results were in good agreement. The proportionality between density and the refractive index in the transparency range is evidenced. The extracted physical parameters are clearly influenced by the variation of cation concentration. (C) 2013 Elsevier B. V. All rights reserved.
117
Structural, Optical, and Dielectric Properties of Bi1.5-xZn0.92-yNb1.5O6.92-delta Thin Films Grown by PLD on R-plane Sapphire and LaAlO3 Substrates
Le Febvrier, A; Galca, AC; Corredores, Y; Deputier, S; Bouquet, V; Demange, V; Castel, X; Sauleau, R; Lefort, R; Zhang, LY; Tanne, G; Pintilie, L; Guilloux-Viry, M
OCT 2012, ACS APPLIED MATERIALS & INTERFACES, 4, 5233
DOI: 10.1021/am301152r
Show abstract
Bi1.5-xZn0.92-yNb1.5O6.92-delta thin films have the potential to be implemented in microwave devices. This work aims to establish the effect of the substrate and of the grain size on the optical and dielectric properties. Bi1.5-xZn0.92-yNb1.5O6.92-delta thin films were grown at 700 degrees C via pulsed-laser deposition on R-plane sapphire and (100)(pc) LaAlO3 substrates at various oxygen pressures (30, 50, and 70 Pa). The structure, morphology, dielectric and optical properties were investigated. Despite bismuth and zinc deficiencies, with respect to the Bi1.5Zn0.92Nb1.5O6.92 stoichiometry, the films show the expected cubic pyrochlore structure with a (100) epitaxial-like growth. Different morphologies and related optical and dielectric properties were achieved, depending on the substrate and the oxygen pressure. In contrast to thin films grown on (100)(pc) LaAlO3, the films deposited on R-plane sapphire are characterized by a graded refractive index along the layer thickness. The refractive index (n) at 630 nm and the relative permittivity (epsilon(t)) measured at 10 GHz increase with the grain size: on sapphire, n varies from 2.29 to 2.39 and epsilon(r) varies from 85 to 135, when the grain size increases from 37 nm to 77 nm. On the basis of this trend, visible ellipsometry can be used to probe the characteristics in the microwave range quickly, nondestructively, and at a low cost.
118
TILT c AXIS CRYSTALLITE GROWTH OF ALUMINIUM NITRIDE FILMS BY REACTIVE RF-MAGNETRON SPUTTERING
Stan, GE; Pasuk, I; Trinca, LM; Galca, AC; Enculescu, M; Miculescu, F
JAN-MAR 2012, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 7, 50
Show abstract
The article reports on the tilted growth of textured aluminium nitride thin films obtained by radio-frequency magnetron sputtering onto 50 mm diameter Si (111) wafers, in reactive atmosphere, in a planar sputtering system without tilting the substrate and with no additional sputtering geometry alterations. The films were investigated using, X-ray diffraction, spectroscopic ellipsometry and scanning electronic microscopy, done by local measurements on the wafer surface, at different distances from the centre. A progressive increase of the tilt angle when moving away from the sample centre has been found. The maximum tilt angle of the columnar AlN crystallites, obtained near the edges of the wafer, is about 7 degrees. The results showed also that tilting is associated with smaller thickness and larger dispersion of the c axis orientation. Synthesizing inclined c axis AlN films should allow the fabrication of surface acoustic wave devices based on shear waves for liquid sensor applications.
119
Double layer structure of ZnO thin films deposited by RF-magnetron sputtering on glass substrate
Besleaga, C; Stan, GE; Galca, AC; Ion, L; Antohe, S
SEP 1 2012, APPLIED SURFACE SCIENCE, 258, 8824
DOI: 10.1016/j.apsusc.2012.05.097
Show abstract
Transparent ZnO films are synthesized by RF-magnetron sputtering (1.78 MHz) onto glass substrates, using a mild-pressed ZnO powder target. The depositions were carried at three inert argon pressures (0.25 Pa, 0.30 Pa, and 0.45 Pa) at two substrate temperatures (100 degrees C and 400 degrees C). The role of the sputtering conditions on ZnO thin films nanostructuring, optical properties and morphology is investigated by Xray diffraction (XRD), X-ray reflectometry (XRR) and Spectroscopic ellipsometry (SE). XRD investigations revealed that ZnO films show a (0 0 l) texture with nanosized crystallites. Right-angle asymmetry of the (0 0 2) diffraction peak is observed. The peak profile analysis using pseudo-Voigt functions unveils a double overlapped peak structure with different coherent zone size values. A double layer structure is evidenced by analyzing the XRR data. Samples prepared at 0.3 Pa at a temperature of 400 degrees C have a similar to 4 nm bottom layer consisting of highly depleted in oxygen ZnO1-x structure, continued by a 53 nm top layer of textured ZnO. Electrical measurements show that the temperature dependence of the conductivity is well described by the Mott variable range hopping (VRH) law. The samples obtained at 400 degrees C have a significantly lower resistivity. (C) 2012 Elsevier B. V. All rights reserved.
120
Morphological, optical and electrical properties of samarium oxide thin films
Constantinescu, C; Ion, V; Galca, AC; Dinescu, M
AUG 1 2012, THIN SOLID FILMS, 520, 6397
DOI: 10.1016/j.tsf.2012.06.049
Show abstract
We present here results on samarium oxide thin films, obtained by pulsed laser deposition and by radio frequency assisted pulsed laser deposition. Three different substrate types were used: silicon, platinum covered silicon and titanium covered silicon. The influence of the deposition parameters (oxygen pressure and laser fluence) on the structure and morphology of the thin films was studied. The substrate-thin film interface zone was investigated; the optical and electrical properties (the losses, dielectric constant and leakage currents) were also determined. (C) 2012 Elsevier B.V. All rights reserved.
121
Structural, optical, and electric properties of BNT-BT0.08 thin films processed by sol-gel technique
Cernea, M; Trupina, L; Dragoi, C; Galca, AC; Trinca, L
OCT 2012, JOURNAL OF MATERIALS SCIENCE, 47, 6971
DOI: 10.1007/s10853-012-6646-1
Show abstract
Thin films with the composition [(Bi0.5Na0.5)TiO3](0.92)-[BaTiO3](0.08) (hereafter BNT-BT0.08) were deposited on Pt-Si by spin-coating from a stable sol precursor. The BNT-BT0.08 film, crystallized on the Bi0.5Na0.5TiO3 rhombohedral lattice, was obtained after annealing the film-gel at 700 A degrees C. The films have a smooth surface (Rms = 2.76 nm) and grains with ferroelectric domains. The film showed a bandgap of 3.25 eV and a refractive index of 2.20 at a wavelength of 630 nm. The dielectric characteristics of BNT-BT0.08 thin films were measured at room temperature and 10 kHz the dielectric constant (epsilon (r)) was 243 and the loss tangent (tan delta) was 0.38. The remnant polarization (P (r)) was 0.87 mu C/cm(2) and the coercive field (E (c)) was 220 kV/cm at 10 kHz and room temperature. The current density was approximately 2.7 x 10(-5) A/cm(2) at low electric fields (100 kV/cm). BNT-BT0.08 thin films shown piezoelectric properties (d (33eff) = 100 pm/V) comparable to those of PZT thin films.
122
Pulsed laser deposition of transparent conductive oxide thin films on flexible substrates
Socol, G; Socol, M; Stefan, N; Axente, E; Popescu-Pelin, G; Craciun, D; Duta, L; Mihailescu, CN; Mihailescu, IN; Stanculescu, A; Visan, D; Sava, V; Galca, AC; Luculescu, CR; Craciun, V
NOV 1 2012, APPLIED SURFACE SCIENCE, 260, 46
DOI: 10.1016/j.apsusc.2012.02.148
Show abstract
The influence of target-substrate distance during pulsed laser deposition of indium zinc oxide (IZO), indium tin oxide (ITO) and aluminium-doped zinc oxide (AZO) thin films grown on polyethylene terephthalate (PET) substrates was investigated. It was found that the properties of such flexible transparent conductive oxide (TCO)/PET electrodes critically depend on this parameter. The TCO films that were deposited at distances of 6 and 8 cm exhibited an optical transmittance higher than 90% in the visible range and electrical resistivities around 5 x 10(-4) Omega cm. In addition to these excellent electrical and optical characteristics the films grown at 8 cm distance were homogenous, smooth, adherent, and without cracks or any other extended defects, being suitable for opto-electronic device applications. (C) 2012 Elsevier B. V. All rights reserved.
123
Ferroelectric and dielectric multilayer heterostructures based on KTa0.65Nb0.35O3 and Bi1.5-xZn0.92-yNb1.5O6.92-1.5x-y grown by pulsed laser deposition and chemical solution deposition for high frequency tunable devices
Le Febvrier, A; Deputier, S; Bouquet, V; Demange, V; Ollivier, S; Galca, AC; Dragoi, C; Radu, R; Pintilie, L; Guilloux-Viry, M
MAY 1 2012, THIN SOLID FILMS, 520, 4567
DOI: 10.1016/j.tsf.2011.10.142
Show abstract
Epitaxial growth of Bi1.5-xZn0.92-yNb1.5O6.92-1.5x-y (BZN) thin films was achieved on (100)(pc) LaAlO3 substrate by pulsed laser deposition (PLD) and by chemical solution deposition based on Pechini process. Effect of bismuth and zinc deficiency on the BZN thin films obtained by PLD was discussed, in relation with the starting target composition. Dielectric permittivity and bandgap values were determined from electrical and spectroscopic ellipsometry measurements performed on randomly oriented films grown on Pt/Si substrate. BZN thin films obtained by PLD exhibit, at 100 kHz, a dielectric constant of epsilon(r) = 203 and quite low dielectric losses of tan delta = 5 x 10(-2). Epitaxial ferroelectric - dielectric KTa0.65Nb0.35O3 (KTN) -Bi1.5-xZn0.92-yNb1.5O6.92-1.5x-y (KTN on BZN and BZN on KIN) bilayers were obtained by PLD on (100)(pc) LaAlO3 with the insertion of a suitable buffer layer of KNbO3 in the case of KTN on BZN. Such multilayer heterostructures with an epitaxial growth control of each layer are promising candidates for potential integration in microwave devices. (C) 2011 Elsevier B.V. All rights reserved.
124
Spectroscopic ellipsometry investigations of Eu-doped oxy-fluoride glass and glass-ceramics
Galca, AC; Preda, N; Secu, CE; Luculescu, CR; Secu, M
JUN 2012, OPTICAL MATERIALS, 34, 1496
DOI: 10.1016/j.optmat.2012.03.015
Show abstract
Oxyfluoride glass-ceramics in the system SiO2-Al2O3-CaF2-EuF3 containing Eu3+-doped CaF2 nanocrystals were produced by using controlled crystallization of melt-quenched glass. X-ray diffraction and scanning electron microscopy data have revealed the formation of CaF2 nanocrystals of about 50 nm size. The Eu3+-dopant ions act as the nucleating agent necessary to initiate the crystallization process. The refractive index is higher in the glass ceramics than in the initial glass and varies as the annealing time increases. Two competitive processes are responsible for this behavior, the crystallization of the CaF2 phase and the decrease of the glass ceramic mass density. (C) 2012 Elsevier B.V. All rights reserved.
125
Structural and optical properties of c-axis oriented aluminum nitride thin films prepared at low temperature by reactive radio-frequency magnetron sputtering
Galca, AC; Stan, GE; Trinca, LM; Negrila, CC; Nistor, LC
DEC 1 2012, THIN SOLID FILMS, 524, 333
DOI: 10.1016/j.tsf.2012.10.015
Show abstract
Spectroscopic ellipsometry, X-ray diffraction and transmission electron microscopy experiments are employed to characterize aluminum nitride (AlN) thin films obtained by radio-frequency magnetron sputtering at low temperature (approximate to 50 degrees C). To understand the growth mechanism and to get in depth information of such films by using ex situ characterization techniques, the AlN thin film sample series were prepared for different sputtering times, while keeping constant all the other deposition conditions. The diffraction studies reveal a [002] oriented growth of the AlN thin films. The misorientation of this crystallographic axis to the normal to the surface reduces progressively with film growth. A nonmonotonic behavior of the AlN pseudo-refractive index versus deposition time indicates a complex depth profile of the AlN thin films optical properties. The difference in orientation dispersion of the [002] crystallite axis, the variation of defects concentration and each constituent atom density influence the refractive index evolution. Our interpretation validity was verified by producing and characterizing samples obtained at intermediate deposition time. The AlN thin films show also very good pull-out adherence values. (C) 2012 Elsevier B. V. All rights reserved.
126
Optical properties of amorphous-like indium zinc oxide and indium gallium zinc oxide thin films
Galca, AC; Socol, G; Craciun, V
MAY 1 2012, THIN SOLID FILMS, 520, 4725
DOI: 10.1016/j.tsf.2011.10.194
Show abstract
The paper presents the optical properties of amorphous-like indium zinc oxide and indium gallium zinc oxide thin films with various In/(In + Zn) ratios obtained by Pulsed Laser Deposition. Thickness results obtained from simulations of X-ray Reflectivity and Spectroscopic Ellipsometry data were very similar. The dependence of density on stoichiometry resembles the corresponding dependence of the refractive index in the transparency range. A free carrier absorption was noted in the visible spectral range, leading to a weak absorbing thin transparent conductive oxide. On the other hand, the refractive index is smaller than those of based oxides (ZnO and In2O3), and counterbalance therefore the weak light absorption. (C) 2011 Elsevier B.V. All rights reserved.
127
Carbon layers cleaning from inside of narrow gaps by a RF glow discharge
Stancu, C; Teodorescu, M; Galca, AC; Dinescu, G
JUL 25 2011, SURFACE & COATINGS TECHNOLOGY, 205, S438
DOI: 10.1016/j.surfcoat.2011.03.090
Show abstract
The paper focuses on the utilization of radiofrequency discharges at intermediate pressures for plasma removal of carbon residuals or layers from narrow gaps and channels. It is shown that by proper handling of the discharge power and pressure it is possible to control the development of plasma inside narrow gaps, in the proximity of surfaces to be cleaned. The discharge operation inside gaps having the width in the range 0.6-2 mm was demonstrated. The cleaning effectiveness is exemplified for castellated surfaces having rectangular gaps coated with hydrogenated amorphous carbon layers. Cleaning of large surfaces can be approached with a movable "plasma shower" type device. (C) 2011 Elsevier B.V. All rights reserved.
128
High quality amorphous indium zinc oxide thin films synthesized by pulsed laser deposition
Socol, G; Craciun, D; Mihailescu, IN; Stefan, N; Besleaga, C; Ion, L; Antohe, S; Kim, KW; Norton, D; Pearton, SJ; Galca, AC; Craciun, V
DEC 1 2011, THIN SOLID FILMS, 520, 1277
DOI: 10.1016/j.tsf.2011.04.196
Show abstract
Indium zinc oxide films were grown from targets with two different In atomic concentration [In/(In+Zn)] of 40% and 80% by the pulsed laser deposition technique on glass substrates from room temperature up to 100 degrees C. X-ray diffraction and reflectometry investigations showed that films were amorphous and dense. Thin films (thickness1000 nm), probably caused by a significant decrease of oxygen vacancies due to atmosphere exposure. Films deposited from the In rich target under an oxygen pressure of 1 Pa exhibited optical transmittance higher than 85%, resistivities around 5-7x10(-4) Omega cm and mobilities in the 47-54 cm(2)/V s range. (C) 2011 Elsevier B. V. All rights reserved.
129
Tailoring the optical properties of Mg (x) Zn1-x O thin films by nitrogen doping
Epurescu, G; Birjega, R; Galca, AC
SEP 2011, APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING, 104, 893
DOI: 10.1007/s00339-011-6433-x
Show abstract
Thin films of Mg (x) Zn1-x O and Mg (x) Zn1-x O doped with nitrogen were deposited by Radio Frequency plasma beam assisted Pulsed Laser Deposition (RF-PLD) in oxygen or oxygen-nitrogen discharge with different nitrogen/oxygen ratios. A Nd:YAG laser working at a wavelength of 266 nm, having a 10 Hz repetition rate was used for the depositions. The energy density of the incident beam was 3 J/cm(2) and the RF power was set to 100 W for all the samples. X-ray Diffraction (XRD) and Spectroscopic Ellipsometry (SE) were employed to investigate the samples. The degree of crystallinity is fount to decrease with increasing the Mg concentration, while the solubility of Mg in ZnO increases by 30% in the N-doped Mg (x) Zn1-x O thin films grown by RF-PLD. Segregation of MgO phase at a Mg concentration of 30% for Mg (x) Zn1-x O thin film is detected both by XRD and SE. The band gap of the samples increases from 3.37 up to 3.57 eV with increasing the Mg concentration and the nitrogen/oxygen ratio for each Mg concentration. A dependence of the dielectric function (refractive index) on both stoichiometry and degree of crystalinity is also found, the refractive index having values between 1.7 and 2 in visible spectral range.
130
Band-gap correlations in Bi4Ge3O12 amorphous and glass-ceramic materials
Polosan, S; Galca, AC; Secu, M
JAN 2011, SOLID STATE SCIENCES, 13, 53
DOI: 10.1016/j.solidstatesciences.2010.10.007
Show abstract
The Bi4Ge3O12 (BGO) glass materials were sintered from a mixture of oxides powders, rapidly heated and melted at 1323 K and poured on the graphite plates heated at different temperatures. Their optical properties are compared with BGO single crystals being strongly dependent by the experimental conditions, which influence the further stability of the samples. The dielectric functions of the samples reveal a clear difference between the two phases (amorphous and crystalline). The refractive index of the amorphous phase has lower values which indicate that the density of the material is diminishes. Also, a sign of disorder is seen in optical absorption (extinction coefficient). From the optical band gap determinations of those two phases, it is confirmed the disorder structure and red-shifts of the band gap value compared with crystalline phase. The absorption spectra are in good agreement with the ellipsometric measurements, regarding the transparency and the edge of the band gap. (C) 2010 Elsevier Masson SAS. All rights reserved.
131
Substrate-target distance dependence of structural and optical properties in case of Pb(Zr,Ti)O-3 films obtained by pulsed laser deposition
Galca, AC; Stancu, V; Husanu, MA; Dragoi, C; Gheorghe, NG; Trupina, L; Enculescu, M; Vasile, E
MAR 1 2011, APPLIED SURFACE SCIENCE, 257, 5943
DOI: 10.1016/j.apsusc.2011.01.056
Show abstract
The paper presents the influence of pulsed laser deposition (PLD) parameters on the structural and optical properties of PZT thin films grown on platinum substrate. X-ray diffraction (XRD), spectroscopic ellipsometry (SE) and X-ray photoelectron spectroscopy (XPS) are used to determine the thin film properties. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) are employed to get additional information. By changing the distance between target and substrate, different crystalline orientations of PZT are obtained. The thin film thickness and its roughness, as well as the refractive index are also influenced by the chosen distance. (C) 2011 Elsevier B.V. All rights reserved.
132
Piezoelectric BNT-BT0.11 thin films processed by sol-gel technique
Cernea, M; Galca, AC; Cioangher, MC; Dragoi, C; Ioncea, G
SEP 2011, JOURNAL OF MATERIALS SCIENCE, 46, 5627
DOI: 10.1007/s10853-011-5512-x
Show abstract
0.89(Na0.5Bi0.5)TiO3-0.11BaTiO(3), (BNT-BT0.11) thin film was fabricated by sol-gel/spin coating process, on platinized silicon wafer. Perovskite structure with random orientation of crystallites has been obtained at 700 A degrees C. Piezoelectric activity of BNT-BT0.11 thin film was detected using piezoresponse force microscopy (PFM). Effective piezoelectric coefficient d (33eff) of such film, recorded at 5 V applied dc voltage, was similar to 29 pm/V, which is similar to other BNT-BT (x) thin films. The complex refractive index and dielectric function of BNT-BT0.11 thin films were also investigated. The high leakage current density significantly influences the dielectric, ferroelectric, and piezoelectric properties of the BNT-BT0.11 films.
133
TAILORING OF OPTICAL, COMPOSITIONAL AND ELECTRICAL PROPERTIES OF THE InxZn1-xO THIN FILMS OBTAINED BY COMBINATORIAL PULSED LASER DEPOSITION
Socol, G; Galca, AC; Luculescu, CR; Stanculescu, A; Socol, M; Stefan, N; Axente, E; Duta, L; Mihailescu, CM; Craciun, V; Craciun, D; Sava, V; Mihailescu, IN
JAN-MAR 2011, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 6, 115
Show abstract
Indium Zinc Oxide compositional libraries were fabricated by combinatorial pulsed laser deposition technique on glass substrate at room temperature. Two pairs of targets with In atomic concentrations, In/(In+Zn), of 28 at.% and 56 at.% or 42 at.% and 70 at.% were employed. A high transparency was observed for all the coatings with transmittance values better than 95%. The maximum thicknesses of the samples, inferred by spectroscopic ellipsometry, were within the 174-310 nm range for the simple PLD films, whereas in case of combinatorial PLD coatings were 341 or 467 nm. Energy dispersive X-ray spectroscopy revealed that In content in the combinatorial films was in the 27-52 at. % range. From atomic force microscopy histograms we evidenced a decrease of the RMS roughness down to 1 nm with the increase of the In content. As a result of the compositional library studies two minimum values of the electrical resistivity were identified at 2.3x10(-3) Omega.cm and 8.6 x 10(-4) Omega.cm, which correspond to 28.8-29.5 at.% and 44-49 at% range of Indium content.
134
INFLUENCE OF THE DEPOSITION CONDITIONS ON THE PROPERTIES OF TiO2-Ge NANOCOMPOSITE FILMS SYNTHESIZED BY MAGNETRON CO-SPUTTERING
Slav, A; Stan, GE; Galca, AC
2010, 2010 INTERNATIONAL SEMICONDUCTOR CONFERENCE (CAS), VOLS 1 AND 2, 340
Show abstract
A growing need for eco-friendly energy sources have led recently to a frantic search of new compositional systems for photovoltaic applications. The nanocomposite titania-germanium (TiO2-Ge) systems represent a new viable family of optoelectronic materials. Their structural, optical and electronic properties can be easily tailored by customizing the density and size of Ge dots in the TiO2 matrix. Early studies on TiO2-Ge nanocomposites have shown promises for their use as an alternative in photovoltaic applications. In this study we report the TiO2-Ge films synthesis by reactive magnetron co-sputtering. Their properties were evaluated by compositional (EDS), structural (XRD, FTIR) and optical (UV-Vis) characterizations.
135
Optical properties of zinc oxide thin films doped with aluminum and lithium
Galca, AC; Secu, M; Vlad, A; Pedarnig, JD
JUN 1 2010, THIN SOLID FILMS, 518, 4606
DOI: 10.1016/j.tsf.2009.12.041
Show abstract
Aluminum doped Zinc Oxide (AZO) and Lithium doped Zinc Oxide (LZO) thin films are obtained by Pulsed Laser Deposition (PLD) method. These films are characterized by using Spectroscopic Ellipsometry (SE), X-ray Diffraction (XRD) and Photoluminescence (PL). By modeling the ellipsometry spectra we get the dielectric functions, the optical band gap E(g), and the electrical properties. Our results show the influence of the processing parameters on the optical and structural properties of doped ZnO thin films. The post-annealing treatment applied to AZO thin films, changes strongly the optical properties, by lowering the resistivity and red-shifting the band gap. (C) 2009 Elsevier B.V. All rights reserved.
136
Optical and structural studies on Ba(Mg1/3Ta2/3)O-3 thin films obtained by radiofrequency assisted pulsed plasma deposition
Scarisoreanu, ND; Galca, AC; Nedelcu, L; Ioachim, A; Toacsan, MI; Morintale, E; Stoica, SD; Dinescu, M
SEP 1 2010, APPLIED SURFACE SCIENCE, 256, 6530
DOI: 10.1016/j.apsusc.2010.04.041
Show abstract
Single-phase Ba(Mg1/3Ta2/3)O-3 thin films were prepared by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) starting from a bulk ceramic target synthesized by solid state reaction. Atomic force microscopy, X-ray diffraction and spectroscopic ellipsometry were used for morphological, structural and optical characterization of the BMT thin films. The X-ray diffraction spectra show that the films exhibit a polycrystalline cubic structure. From spectroscopic ellipsometry analysis, the refractive index varies with the thin films deposition parameters. By using the transmission spectra and assuming a direct band to band transition a band gap value of approximate to 4.72 eV has been obtained. (C) 2010 Elsevier B.V. All rights reserved.
137
The study of the silicon oxide thickness on crystalline Si by X-ray photoelectron spectroscopy and spectroscopic ellipsometry
Cotirlan, C; Galca, AC; Ciobanu, CS; Logofatu, C
MAY 2010, JOURNAL OF OPTOELECTRONICS AND ADVANCED MATERIALS, 12, 1097
Show abstract
The to study of the total oxide (SiO2+SiOx) thickness, SiO2 and SiOx (e.g. Si2O, SiO, Si2O3) thicknesses on Si(100) crystalline substrate with take-off angles ranging from 30 degrees to 80 degrees has been carried out by spectrometric method. The d(s) X-ray Photoelectron Spectroscopy (XPS) thicknesses were compared with d(EL) thicknesses obtained by fitting the Spectroscopic Ellipsometry (SE) spectra. A qualitatively good correlation is revealed. However, from these estimations of film thicknesses it results that ellipsometry analysis cannot be as accurate as in XPS evaluation. This is due to uncertainty of used optical constants as well due to very thin oxide films used in this work.
138
Nanostructured gold layers. II. Gold deposition onto polystyrene substrate
Zgura, I; Beica, T; Frunza, S; Rasoga, O; Galca, A; Frunza, L; Moldovan, A; Dinescu, M; Zaharia, C
FEB 2010, JOURNAL OF OPTOELECTRONICS AND ADVANCED MATERIALS, 12, 359
Show abstract
In the aim to improve the adherence of the nanostructured gold layers onto glass substrate, gold deposition has been first time performed onto a polystyrene (PS) layer. The PS layer of ca. 50nm was spin-coated onto glass plates from a toluene solution. Gold layers of 10-20nm were vacuum deposited at small incidence angle. We found that at variance from the plates with gold deposited directly on the glass, the plates with an intermediate PS layer do not peel under overnight treatment in ethanol solution. The layers were characterized by several methods. X-ray diffraction (XRD) measurements showed that gold peaks have the position corresponding to the face-centered cubic structure: However, the crystallites on the sample with PS layer seem to be a little bit smaller than those with gold deposited directly onto the glass. XR reflectometry measurements have given the thickness of the gold layer in good agreement with the value estimated from quartz monitor readings and with the ellipsometric data as well, Liquid crystal cells were obtained to observe the molecular alignment imposed by the nanostructured gold layer deposited onto PS film. A rather strong interaction of gold atoms with the substrate molecules can be considered on the basis of the XRD and ellipsometry measurements.
139
HIGHLY TEXTURED (001) AlN NANOSTRUCTURED THIN FILMS SYNTHESIZED BY REACTIVE MAGNETRON SPUTTERING FOR SAW AND FBAR APPLICATIONS
Stan, GE; Pasuk, I; Galca, AC; Dinescu, A
OCT-DEC 2010, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 5, 1054
Show abstract
Highly oriented (001) AlN (wurtzite type) thin films have been successfully deposited on silicon, platinized silicon and glass substrates by reactive radio-frequency magnetron sputtering at low temperature (150 degrees C). X-ray diffraction, spectroscopic ellipsometry and scanning electron microscopy techniques have been employed to asses the structural characteristics of the AlN films. We have investigated both the influence of AlN film's thickness and of the substrate nature on crystallinity. The thicker films present a better c axis alignment, a minimum orientation dispersion of 3.5. being reached for 1 mu m AlN on silicon. The micro-and macrostrain of the AlN lattice relaxes as the film thickness increases. The film deposited onto platinum has the maximum value of tensile strain along c axis. The film on glass exhibited the poorest texturing and the highest defect concentration. From an optical point of view the film deposited on Pt is the denser one and that deposited on glass is the most rarefied. One can conclude that when using a low deposition temperature and a base pressure of similar to 10(-4) Pa the increase of film thickness leads to improved AlN structure on Si or Pt supports.
140
Polymer-like thin films obtained by RF plasma polymerization of pentacyclic monomers
Satulu, V; Mitu, B; Galca, AC; Aldica, GV; Dinescu, G
MAR 2010, JOURNAL OF OPTOELECTRONICS AND ADVANCED MATERIALS, 12, 636
Show abstract
Plasma polymerization has been carried out in a parallel plate RF discharge reactor in mixtures of argon with pentacyclic precursors, namely thiophene, furan and pyrrole. The plasma characterization showed the presence of emission bands peculiar to each monomer. The deposition of highly transparent films with partial conservation of the pentacyclic structure, inclusion of various oligomers, roughness and surface energy depending on the precursor nature was demonstrated by material investigations results. The material conductivity is significantly improved upon iodine doping in the case of polythiophene and polypyrrole-like films, while an opposite behavior was observed for the polyfuran-like films.
141
Radiofrequency plasma beam deposition of various forms of carbon based thin films and their characterization
Vizireanu, S; Stoica, SD; Mitu, B; Husanu, MA; Galca, A; Nistor, L; Dinescu, G
MAR 1 2009, APPLIED SURFACE SCIENCE, 255, 5381
DOI: 10.1016/j.apsusc.2008.08.042
Show abstract
The characteristics of carbonic materials obtained by downstream deposition in a low pressure argon plasma beam injected with acetylene are reported. The influence of substrate temperature, presence of Ni catalyst and hydrogen in gas composition on the material properties is described. By increasing the substrate temperature, an enhanced order in the material is revealed by Raman spectroscopy, while FTIR measurements show a decreasing of the hydrogen content and the disappearing of sp(1) hybridized carbon in the deposit. The SEM and Raman investigation show a clear tendency of crystalline phases formation when hydrogen is assisting the deposition. (C) 2008 Elsevier B. V. All rights reserved.
142
Pulsed-laser deposition of smooth thin films of Er, Pr and Nd doped glasses
Epurescu, G; Vlad, A; Bodea, MA; Vasiliu, C; Dumitrescu, O; Niciu, H; Elisa, M; Siraj, K; Pedarnig, JD; Bauerle, D; Filipescu, M; Nedelcea, A; Galca, AC; Grigorescu, CEA; Dinescu, M
MAR 1 2009, APPLIED SURFACE SCIENCE, 255, 5298
DOI: 10.1016/j.apsusc.2008.10.038
Show abstract
Thin films of complex oxides have been obtained by pulsed-laser deposition (PLD) from glass targets belonging to the system Li2O-Al2O3-P2O5-(RE)(2)O-3, with RE = Nd, Pr, Er. The films were deposited on quartz, silicon and ITO/glass substrates using a F-2 laser (lambda = 157 nm, iota approximate to 20 ns) for ablation in vacuum. The structural, morphological and optical properties of the oxide films were investigated through IR and UV-VIS spectroscopy, Atomic Force Microscopy (AFM), Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy (SEM-EDX) and Spectroscopic Ellipsometry. The laser wavelength was found to be the key parameter to obtain thin films with very smooth surface. In this way new possibilities are opened to grow multilayer structures for photonic applications. (C) 2008 Elsevier B. V. All rights reserved.
143
Structural investigations of ITO-ZnO films grown by the combinatorial pulsed laser deposition technique
Craciun, D; Socol, G; Stefan, N; Miroiu, M; Mihailescu, IN; Galca, AC; Craciun, V
MAR 1 2009, APPLIED SURFACE SCIENCE, 255, 5291
DOI: 10.1016/j.apsusc.2008.07.120
Show abstract
Mixtures of transparent and conductive oxides such as ITO-ZnO have been grown by a combinatorial pulsed laser deposition technique from two targets that were located 15 mm apart. The films were deposited on (1 0 0) Si and quartz substrates that were heated at temperatures from 300 to 500 degrees C. Measurements of the In to Zn ratios along the transversal axis of the substrates, which passes through the maximum thickness points corresponding to each target position were performed using energy dispersive X-ray spectroscopy and spectroscopic ellipsometry. From simulations of the X-ray reflectivity spectra, collected with a 2 mm mask on different locations along the transversal axis of the samples, the density and thickness of the deposited films were calculated and then the In to Zn ratios. The crystalline structure and electrical properties of the deposited films were also investigated along the same axis. Changes in the ratio of In/Zn along this axis resulted in changes of the film lattice constant and texture. (C) 2008 Elsevier B. V. All rights reserved.
144
Field induced phase segregation in ferrofluids
Kooij, ES; Galca, AC; Poelsema, B
NOV 1 2008, JOURNAL OF COLLOID AND INTERFACE SCIENCE, 327, 265
DOI: 10.1016/j.jcis.2008.08.029
Show abstract
We study the phase segregation in magnetite ferrofluids under the influence of an external magnetic field. A phase with lower nanoparticle density and corresponding higher optical transmission is formed in the bottom of a glass cell in the presence of only a very modest magnetic field gradient (smaller than 25 T/m). The flux density in our magnetic configuration is simulated using finite element methods. Upon switching off the external magnetic field, the low-density phase develops into a 'bubble'-like feature. The kinetics of this 'bubble' in the absence and presence of a magnetic field are described and analyzed in terms of a simple model, which takes into account buoyancy and drag forces. (C) 2008 Elsevier Inc. All rights reserved.
145
SBN thin films growth by RF plasma beam assisted pulsed laser deposition
Scarisoreanu, ND; Dinescu, G; Birjega, R; Dinescu, M; Pantelica, D; Velisa, G; Scintee, N; Galca, AC
NOV 2008, APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING, 93, 800
DOI: 10.1007/s00339-008-4753-2
Show abstract
SBN thin films were grown on MgO and Silicon substrates by PLD and RF-PLD (radiofrequency assisted PLD) starting from single crystal Sr0.6Ba0.4Nb2O6 and ceramic Sr0.5Ba0.5Nb2O6 stoichiometric targets. Morphological and structural analyses were performed on the SBN layers by AFM and XRD and optical properties were measured by spectroellipsometry. The films composition was determined by Rutherford Backscattering Spectrometry. The best set of experimental conditions for obtaining crystalline, c-axis preferential texture and with dominant 31 degrees in-plane orientation relative to the MgO (100) axis is identified.
146
Optica and structural properties of polythiophene-like films deposited by plasma polymerization
Galca, AC; Satulu, V; Ionita, MD; Bercu, M; Barna, E; Dumitru, M; Mitu, B; Dinescu, G
AUG 2008, JOURNAL OF OPTOELECTRONICS AND ADVANCED MATERIALS, 10, 2037
Show abstract
Polymer-like organic thin films obtained by plasma techniques are of wide interest for various applications. Polythiophene-like thin films were deposited by plasma polymerization in a parallel plate radiofrequency reactor starting from thiophene vapors. The optical properties of the films were obtained from spectroscopic ellipsometry, in the 250-1250 nm range. The calculated band gap is in agreement with a polythiophene-like material consisting of cross-linking of oligomers. The presence of functional groups and film stability against oxidation is analyzed by FTIR spectrometry. The monitoring of functional groups incorporation during the film deposition was done by analyzing the integral intensities of specific absorption bands and led to the conclusion that homogeneous films are obtained whatever the process duration.
147
Spectroscopic ellipsometry study of amorphous SrxBa1-xNb2O6 thin films obtained by pulsed laser deposition
Ion, V; Galca, AC; Scarisoreanu, ND; Filipescu, M; Dinescu, M
2008, PHYSICA STATUS SOLIDI C - CURRENT TOPICS IN SOLID STATE PHYSICS, VOL 5, NO 5, 5, +
DOI: 10.1002/pssc.200777818
Show abstract
Optical properties of amorphous Strontium Barium Niobate (a-SBN) thin film are investigated using spectroscopic ellipsometry. Since the SBN can be applied to optoelectronic devices, the dispersion of refractive index is desirable. The films are obtained by Pulsed Laser Deposition (PLD) onto MgO and Si substrates by targeting a SBN:60 monocrystal: The dielectric function of a-SBN is approximated using a single Tauc-Lorentz oscillator model. Thicknesses of the films and of their rough layer are in agreement with SEM and AFM results. The dispersion of the refractive index is presented in the 1 - 5 eV range.
148
Combinatorial pulsed laser deposition of thin films
Craciun, V; Craciun, D; Mihailescu, IN; Socol, G; Stefan, N; Miroiu, M; Galca, AC; Bourne, G
2008, HIGH-POWER LASER ABLATION VII, PTS 1-2, 7005
DOI: 10.1117/12.782589
Show abstract
Pulsed Laser Deposition (PLD) is an ideal technique to be used for combinatorial approaches. By simply changing the deposition targets one can obtain alternating layers with different periodicities both vertically and laterally, along the substrate surface. By changing the laser impact area location and the number of pulses on each target used for ablation, one can grow films with a continuous variation of the chemical composition, which will be a function of the location on the substrate. To illustrate the advantages and versatility of this Combinatorial PLD (C-PLD) technique, several examples of films used in applications where more than one property should be tailored or optimized are presented. Investigations of thermo-chemical stability, chemical bonding and crystalline structure of thin films of mixtures of HfO2 and Al2O3 that are used as high-k dielectric layers in advanced C-MOS transistors is the first example, followed by a study of structural, mechanical, optical and electrical properties of mixtures of indium tin oxide and doped or pure zinc oxide that are used as transparent and conductive layers. The third example is from the deposition of multilayers of ZrC and ZrN with variable thicknesses to obtain hard coatings.
149
Multilevel Memristive GeTe Devices
Velea, A; Dumitru, V; Sava, F; Galca, AC; Mihai, C
, PHYSICA STATUS SOLIDI-RAPID RESEARCH LETTERS, 2000475
DOI: 10.1002/pssr.202000475
Show abstract
Phase-change memories have reached an advanced degree of maturity, although, to be able to meet the increasing storage demand, multilevel capability is needed. A GeTe memristor is obtained in an amorphous state and it is subjected to a specific thermal treatment which initiates the transition toward the crystalline state. It is found that this crystalline state initialization process is highly beneficial for subsequently obtaining a large number of intermediate resistive states between the high and low resistive states. Multiple resistance levels are achieved by operating the devices in both DC sweeps and rectangular pulse modes in the low-voltage subthreshold regime. The conduction is modeled using a space charge limited conduction model, showing three distinct conduction regions in the high resistive state which merge toward a single conduction region as the low resistive state is approached. The obtained memristors can be used as multilevel nonvolatile memories or as synapses in neuromorphic computing.
150
Argon pressure dependent optoelectronic characteristics of amorphous tin oxide thin films obtained by non-reactive RF sputtering process
Ziani, N; Galca, AC; Belkaid, MS; Stavarache, I
, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
DOI: 10.1007/s10854-021-05861-2
Show abstract
In this work, amorphous tin oxide thin films were deposited by non-reactive radio frequency magnetron sputtering. A ceramic SnO2 target was used, while different working pressures were employed. The target to substrate distance was fixed to 17 cm, and the substrate was not intentionally heated. The properties of SnO2 (thickness, refractive index dispersion, optical band gap, resistivity, free carriers concentration, carriers mobility, carriers majority type and their scattering time) have been inferred from spectroscopic ellipsometry, conventional UV-Vis spectroscopy and specific Hall electrical measurements. Thickness and refractive index are slightly dependent on the deposition conditions, while the optical band gap, free carriers concentration and their mobilities are changing from sample to sample. The evolution of the optical band gap and carriers concentration is correlated to the active defects concentration. Amorphous SnO2 films grown at 0.4 Pa have the lowest resistivity of 0.86 Omega cm, a carrier concentration of 1.05x10(18)cm(-3) Vs. The average optical transmittance in visible spectrum is 76%.