1
Comparative study of the Cu-TiO2 nanostructures obtained by sol-gel and microwave assisted sol-gel methods
Predoana, L; Pandele-Cusu, J; Atkinson, I; Petrescu, S; Mocioiu, OC; Culiba, DC; Karajz, DA; Odhiambo, VO; Lemago, HH; Gomes, APB; Varady, ZI; Bohus, M; Costescu, RM; Szilágyi, IM; Pokol, G; Zaharescu, M
JUN 2025, JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, 114
DOI: 10.1007/s10971-025-06757-x
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In this study, pristine TiO2 and Copper (Cu)-doped TiO2 nanopowders were synthesized using two sol-gel methods: conventional sol-gel (SG) and microwave-assisted sol-gel (MW). The aim was to investigate the effect of the synthesis route and Cu doping on the structural, optical, and photocatalytic properties of TiO2. X-ray diffraction (XRD) analysis confirmed the formation of anatase TiO2 in all samples, with a minor presence of rutile observed in the samples obtained by the MW method. Scanning electron microscopy (SEM) coupled with energy-dispersive X-ray analysis (EDX) showed that the nanopowders obtained by the MW method exhibited a greater tendency for particle aggregation compared to those obtained through the SG method. The presence of Cu2+/Cu+ species in the samples was confirmed by X-ray photoelectron spectroscopy (XPS). UV-Vis reflectance measurements revealed a shift in the absorption edge of the 5% Cu-doped samples toward the visible light range, significantly reducing the band gap. Evaluation of photocatalytic activity demonstrated that doping TiO2 with 5% Cu enhanced the degradation of Congo Red dye under visible light. [GRAPHICS] .
2
Surface spin asymmetry in Pt(001)-hex induced by electron accumulation
Borcan, LE; Teodorescu, CM; Iancu, AC; Apostol, NG; Nicolaev, A; Costescu, RM; Husanu, MA; Popescu, DG; Lungu, GA; Bianchi, M
JUL 1 2025, JOURNAL OF PHYSICS-MATERIALS, 8, 035010
DOI: 10.1088/2515-7639/aded36
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Spin asymmetry is detected in clean Pt(001)-hex by spin-resolved photoelectron spectroscopy even in absence of external sample magnetization. Magnetization of the sample immediately after preparation yields a consistent remnant spin asymmetry in the direction of the applied magnetic field. The surfaces were also characterized by low energy electron diffraction, scanning tunneling microscopy and high resolution core level x-ray photoelectron spectroscopy, allowing one to quantify the surface component, attributed to the last surface layer enriched in electrons. The explanation of the spin asymmetry induced by electron accumulation into the last monolayer is sketched by using band ferromagnetism criteria. The orientation of the spin asymmetry in the nonmagnetized sample coincides with the direction of the rows of the hex reconstruction, while in the magnetized sample it is aligned with the direction of the external magnetizing field. A strong variation of the spin asymmetry as function of the binding energy near the Fermi level, whose amplitude depends also on the median emission angle, suggests a spin textured state in this energy range or the presence of a Stoner gap
3
Layered Perovskite La2Ti2O7 Obtained by Sol-Gel Method with Photocatalytic Activity
Ilie, A; Predoana, L; Anastasescu, C; Preda, S; Hosu, IS; Costescu, RM; Culita, DC; Bratan, V; Balint, I; Zaharescu, M
JUL 8 2025, APPLIED SCIENCES-BASEL, 15, 7665
DOI: 10.3390/app15147665
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This paper presents the synthesis of La2Ti2O7 nanoparticles by the sol-gel method starting from lanthanum nitrate and titanium alkoxide (noted as LTA). Subsequently, the lanthanum titanium oxide nanoparticles are modified with noble metals (platinum) using the chemical impregnation method, followed by a reduction process with NaBH4. The comparative analysis of the structure and surface characteristics of the nanopowders subjected to thermal treatment at 900 degrees C is conducted using Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray fluorescence (XRF), ultraviolet-visible (UV-Vis) spectroscopy, as well as specific surface area and porosity measurements. The photocatalytic activity is evaluated in the oxidative photodegradation of ethanol (CH3CH2OH) under simulated solar irradiation. The modified sample shows higher specific surfaces areas and improved photocatalytic properties, proving the better conversion of CH3CH2OH than the pure sample. The highest conversion of ethanol (29.75%) is obtained in the case of LTA-Pt after 3 h of simulated solar light irradiation.
4 Open Access
Adsorption-catalysis synergy in the visible-light-driven removal of 17 β-estradiol by (Au)TiO 2 nanotubes-graphene composites
Cosma, DV; Rosu, MC; Socaci, C; Rostas, AM; Urda, A; Radu, T; Turza, A; Dan, MNC; Costescu, R; Gustavsen, KR; Dobroliubov, O; Wang, KY
JUN 2024, JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING, 12, 112885
DOI: 10.1016/j.jece.2024.112885
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Visible light-mediated photodegradation offers a sustainable and environmentally friendly solution for removing emerging contaminants from water sources. Herein, we report on the synergy effect between adsorption and visible-light-driven photo-degradation of 17 fl - estradiol using (Au)TiO 2 nanotubes-graphene composites. The graphene structures (graphene oxide - GO or thermally reduced graphene oxide - trGO) provide a platform for strong adsorption of 17 fl -estradiol molecules and facilitate the charge transfer between plasmonic Au nanoparticles and TiO 2 , leading to an improvement of the overall degradation process. To better understand the effect of Au nanoparticles and TiO 2 separately, three different concentrations of Au (1 %, 2.5 %, and 5 %) were prepared and characterized. The estrogenic molecules preferred GO over trGO, suggesting that hydrogen bonds govern the interaction between GO and 17 fl -estradiol. Consequently, a higher photocatalytic efficiency of GOcontaining composites was observed when removing estrogenic molecules. The role of adsorption proved crucial for capturing and retaining more contaminant molecules on the composite surface, thus increasing the odds of surface reactions with the photogenerated carriers. A total removal of 17 fl -estradiol has been obtained for Au (1 %, 2.5 %, and 5 %) TiO 2 nanotubes-GO. The mechanism behind the adsorption and photo-degradation processes has been discussed.
5 Open Access
Spin asymmetry of O 2p-related states in SrTiO3(001)
Popescu, DG; Nicolaev, A; Costescu, RM; Borcan, LE; Lungu, GA; Tache, CA; Husanu, MA; Teodorescu, CM
OCT 1 2024, PHYSICA SCRIPTA, 99, 105925
DOI: 10.1088/1402-4896/ad732c
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Atomically clean SrTiO3(001) is characterized by low energy electron diffraction, core level and valence band photoelectron spectroscopy, the latter also with spin resolution. Samples prepared by a sputtering-annealing procedure exhibited in-gap states in the valence band spectra, Ti3+ components in Ti 2p core level spectra and a noticeable spin asymmetry in the 3-9 eV binding energy range, which corresponds to valence states of mainly O 2p character. Upon annealing in oxygen, the spin asymmetry vanishes, accompanied by the intensity decrease of the contribution of titanium low ionization states and of in-gap states, indicating that these three phenomena are mutually connected. The observed spin asymmetry may be generated by indirect exchange mediated by the in-gap states between O 2p orbitals, or by the partial Ti 3d character of these states, which acquire non-zero spin in case of incomplete oxygen coordination.
6 Open Access
Copper-/Zinc-Doped TiO2 Nanopowders Synthesized by Microwave-Assisted Sol-Gel Method
Predoana, L; Petcu, G; Preda, S; Pandele-Cusu, J; Petrescu, SV; Baran, A; Apostol, NG; Costescu, RM; Surdu, VA; Vasile, BS; Ianculescu, AC
APR 2023, GELS, 9, 267
DOI: 10.3390/gels9040267
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Using the microwave-assisted sol-gel method, Zn- and Cu-doped TiO2 nanoparticles with an anatase crystalline structure were prepared. Titanium (IV) butoxide was used as a TiO2 precursor, with parental alcohol as a solvent and ammonia water as a catalyst. Based on the TG/DTA results, the powders were thermally treated at 500 degrees C. XRD and XRF revealed the presence of a single-phase anatase and dopants in the thermally treated nanoparticles. The surface of the nanoparticles and the oxidation states of the elements were studied using XPS, which confirmed the presence of Ti, O, Zn, and Cu. The photocatalytic activity of the doped TiO2 nanopowders was tested for the degradation of methyl-orange (MO) dye. The results indicate that Cu doping increases the photoactivity of TiO2 in the visible-light range by narrowing the band-gap energy.
7 Open Access
Antimicrobial Properties of TiO2 Microparticles Coated with Ca- and Cu-Based Composite Layers
Bucuresteanu, R; Ionita, M; Chihaia, V; Ficai, A; Trusca, RD; Ilie, CI; Kuncser, A; Holban, AM; Mihaescu, G; Petcu, G; Nicolaev, A; Costescu, RM; Husch, M; Parvulescu, V; Ditu, LM
JUL 2022, INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES, 23, 6888
DOI: 10.3390/ijms23136888
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The ability of TiO2 to generate reactive oxygen species under UV radiation makes it an efficient candidate in antimicrobial studies. In this context, the preparation of TiO2 microparticles coated with Ca- and Cu-based composite layers over which Cu(II), Cu(I), and Cu(0) species were identified is presented here. The obtained materials were characterized by a wide range of analytical methods, such as X-ray diffraction, electron microscopy (TEM, SEM), X-ray photoelectron (XPS), and UV-VIS spectroscopy. The antimicrobial efficiency was evaluated using qualitative and quantitative standard methods and standard clinical microbial strains. A significant aspect of this composite is that the antimicrobial properties were evidenced both in the presence and absence of the light, as result of competition between photo and electrical effects. However, the antibacterial effect was similar in darkness and light for all samples. Because no photocatalytic properties were found in the absence of copper, the results sustain the antibacterial effect of the electric field (generated by the electrostatic potential of the composite layer) both under the dark and in light conditions. In this way, the composite layers supported on the TiO2 microparticles' surface can offer continuous antibacterial protection and do not require the presence of a permanent light source for activation. However, the antimicrobial effect in the dark is more significant and is considered to be the result of the electric field effect generated on the composite layer.
8 Open Access
Photocatalytic and Antibacterial Properties of Doped TiO2 Nanopowders Synthesized by Sol-Gel Method
Preda, S; Pandele-Cusu, J; Petrescu, SV; Ciobanu, EM; Petcu, G; Culita, DC; Apostol, NG; Costescu, RM; Raut, I; Constantin, M; Predoana, L
OCT 2022, GELS, 8, 673
DOI: 10.3390/gels8100673
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For environmental applications, nanosized TiO2-based materials are known as the most important photocatalyst and are intensively studied for their advantages such as their higher activity, lower price, and chemical and photoresist properties. Zn or Cu doped TiO2 nanoparticles with anatase crystalline structure were synthesized by sol-gel process. Titanium (IV) butoxide was used as a TiO2 precursor, with parental alcohol as a solvent, and a hydrolysing agent (ammonia-containing water) was added to obtain a solution with pH 10. The gels were characterized by TG/DTA analysis, SEM, and XPS. Based on TG/DTA results, the temperature of 500 degrees C was chosen for processing the powders in air. The structure of the samples thermally treated at 500 degrees C was analysed by XRD and the patterns show crystallization in a single phase of TiO2 (anatase). The surface of the samples and the oxidation states was investigated by XPS, confirming the presence of Ti, O, Zn and Cu. The antibacterial activity of the nanoparticle powder samples was verified using the gram-positive bacterium Staphylococcus aureus. The photocatalytic efficiency of the doped TiO2 nanopowders for degradation of methyl orange (MO) is here examined in order to evaluate the potential applications of these materials for environmental remediation.
9
Polarization-dependent magnetism of the Ni/BaTiO3 interface
Bocirnea, AE; Popescu, DG; Chirila, C; Costescu, RM; Kuncser, V; Stancu, V; Trupina, L; Pasuk, I; Vlaicu, AM; Husanu, MA
MAR 4 2020, PHYSICAL REVIEW MATERIALS, 4, 034402
DOI: 10.1103/PhysRevMaterials.4.034402
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We explore the cross coupling between the ferroelectric and ferromagnetic phases in Ni/BaTiO3(001) heterostructures and demonstrate the modulation of the magnetism and incidence of exchange bias in the ultrathin metallic Ni overlayer, depending on the ferroelectric state of the bottom layer. We establish that 5-nm-thick monocrystalline Ni film deposited on BaTiO3 with ferroelectric polarization pointing towards the surface (P+) favors the organization of Ni into uniform ferromagnetic domains. Ni grown on BaTiO3 with opposite ferroelectric polarization is featured by emerging exchange-bias coupling between the ferromagnetic Ni top layers and the antiferromagnetic reacted interface, as theoretically explained by first-principles calculations. We explicitly obtain the morphology of the magnetic domains of the crystalline Ni layer in atomic and magnetic force microscopy measurements (AFM/MFM). The resemblance of AFM and MFM images indicate that, although with radically different morphologies, in both cases all spins orient in the Ni plane. Consequently, the distinct signature of the ferroelectric-ferromagnetic coupling extracted from the magneto-optical Kerr effect measurements encodes all the information of sample magnetism. The peculiar magnetic coupling depending on the ferroelectric state indicates new ways of engineering the functionality of metal/ferroelectric interfaces.
10
Magnetic properties of BaNi x Fe 12-x O 19 (x=0.0-1.0) hexaferrites, synthesized by citrate -gel auto -combustion and sintered by conventional and spark plasma methods
Cernea, M; Greculeasa, SG; Radu, R; Aldica, G; Ganea, P; Surdu, VA; Tanasa, ET; Cioangher, M; Iacob, N; Costescu, RM
AUG 5 2020, JOURNAL OF ALLOYS AND COMPOUNDS, 831
11
Room temperature ferromagnetism and its correlation to ferroelectricity of manganese embedded in lead zirco-titanate
Bucur, IC; Apostol, NG; Abramiuc, LE; Tanase, LC; Tache, CA; Lungu, GA; Costescu, RM; Chirila, CF; Trupina, L; Pintilie, L; Teodorescu, CM
JAN 1 2019, THIN SOLID FILMS, 669
DOI: 10.1016/j.tsf.2018.11.018
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Manganese is deposited at high temperature on (001) oriented ferroelectric lead zirco-titanate prepared in two different ways: sputter-annealed or just simply annealed in ultrahigh vacuum. Room temperature ferromagnetism (FM) is obtained for Mn deposited on sputter-annealed substrates, while for the other sample preparation a paramagnetic behaviour is obtained. Also, for the first case a clear inwards component of the polarization P( - ) is observed by X-ray photoelectron spectroscopy and piezoresponse force microscopy. Composition analysis evidenced formation of Pb vacancies in the case of FM - P(( - ) )sample, consistent with hole formation near the surface, needed both to stabilize the inwards polarization state and to intermediate ferromagnetism between Mn2+ ions. The indirect exchange ferromagnetism mediated by holes is stronger, most probably because the interaction energy is proportional with the carrier effective mass. Also, whereas in the case of unsputtered substrate a stable surface Mn oxide is formed, defect formation by sputtering seems to favor Mn migration inside the sample. This also induces the formation of a thin film where ferromagnetism and the orientation of ferroelectric polarization might have the same origin, i. e. holes accumulated near the outer surface.
12
Growth of Ag(111) on Si(111) with nearly flat band and abrupt interface
Bocirnea, AE; Costescu, RM; Apostol, NG; Teodorescu, CM
APR 15 2019, APPLIED SURFACE SCIENCE, 473, 441
DOI: 10.1016/j.apsusc.2018.12.167
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Growth of Ag films of up to 30 nm thickness on Si(1 1 1) 7 x 7 at room temperature is investigated by low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). LEED revealed the coexistence of Ag and Si spots starting with 1 monolayer (ML) of Ag deposited. The Ag lattice constant, starting with 25 ML, is slightly higher than for bulk Ag and increase linearly with Ag thickness, reaching about 4.2 nm for the thickest films. The average terrace widths detected from LEED spot profile analysis are about 30 nm for clean Si(1 1 1) 7 x 7 and about 5.5 nm for the thickest Ag(1 1 1) film, in agreement with STM observations. The intensity variation of core levels analyzed by XPS is taken into account by a model assuming the initial formation of Ag islands with linear variation of coverage vs. the amount of Ag deposited, followed by growth in a quasi layer-by-layer mode. The interface barrier is in the range of 0.4 eV, lower than all values reported previously. Ag deposited on Si(1 1 1) 7 x 7 at room temperature provides flat Ag(1 1 1) for synthesis of 2D materials, and may be used for low barrier Schottky diodes.
13
Nanostructured palladium doped nickel electrodes for immobilization of oxidases through nickel nanoparticles
Barsan, MM; Matei, E; Enculescu, M; Costescu, R; Preda, N; Enache, TA; Enculescu, I; Diculescu, VC
AUG 20 2019, ELECTROCHIMICA ACTA, 315, 113
DOI: 10.1016/j.electacta.2019.04.143
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The present investigation deals with the development, characterization and application of nano-structured Pd doped Ni electrodes (Pd@Ni), which uses the electrochemical properties of Pd in synergy with the magnetic properties of Ni for biosensors development. The Pd@Ni electrodes have been characterized by X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. It has been shown that palladium presented spherical assemblies ranging 150-200 nm medium diameter size that covers large areas of the electrode surface while metallic nickel, which confers magnetic properties, showed a uniform granular structure with sizes between 20 and 50 nm. Cyclic voltammetry and electrochemical impedance spectroscopy were performed to understand the electrochemical process at the Pd@Ni electrodes in neutral media. The Pd@Ni electrodes were applied for the electrochemical detection of H2O2. Finally, Ni nanoparticles (NiNP) functionalized with the model enzyme glucose oxidase (GOx-NiNP) have been attached to the Pd@Ni electrode solely through magnetic interactions, and the obtained GOx-NiNP/Pd@Ni biosensor applied for glucose determination in aqueous solutions by fixed potential amperometry at -0.05 V (vs Ag/AgCl) with reduced interferences. (C) 2019 Elsevier Ltd. All rights reserved.
14
Triggering surface ferroelectric order in Pb(Zr, Ti)O-3(001) by deposition of platinum
Bucur, IC; Tanase, LC; Abramiuc, LE; Lungu, GA; Chirila, C; Trupina, L; Apostol, NG; Costescu, RM; Negrea, RF; Pintilie, L; Teodorescu, CM
FEB 28 2018, APPLIED SURFACE SCIENCE, 432
DOI: 10.1016/j.apsusc.2017.04.238
Show abstract
By platinum deposition on a 150 nm thick film of lead zirco-titanate oriented PZT(001), grown on strontium titanate (001) single crystals with a strontium ruthenate buffer layer, which did not show initial preferential out-of-plane orientation of its ferroelectric polarization, a band bending near the interface towards lower energies is observed using photoelectron spectroscopy, by following all core levels from the substrate (Pb 4f, Zr 3d, Ti 2p, O 1s). This is unexpected given the fact that platinum has a larger work function than PZT and a rectifying contact for electrons is expected to be built at the interface. This observation may have two explanations: (i) platinum forms an alloy with elements from PZT yielding a metal with considerable lower work function; (ii) platinum provides electrons to the substrate which are able to compensate the depolarization field generated by the outwards polarization state. Several arguments are brought in favor of the second hypothesis, especially the attenuation of core levels from the substrate which is well described by exponential functions with reasonable values of the photoelectron inelastic mean free path, suggesting the formation of a sharp interface. High resolution transmission electron microscopy confirmed the sharpness of the interface. (C) 2017 Elsevier B.V. All rights reserved.
15
Structural and magnetic properties of Ni nanofilms on Ge(001) by molecular beam epitaxy
Bocirnea, AE; Costescu, RM; Pasuk, I; Lungu, GA; Teodorescu, CM
DEC 1 2017, APPLIED SURFACE SCIENCE, 424
DOI: 10.1016/j.apsusc.2017.03.034
Show abstract
Ni films of 20 nm nominal thickness were grown on Ge(001) substrates by molecular beam epitaxy at several different temperatures from room temperature up to 400 C. X-ray diffraction and X-ray photoelectron spectroscopy reveal the nucleation of Ni-Ge compounds (NiGe, Ni2Ge, Ni5Ge2) as well as a departure from the fcc Ni structure exhibited by the films at and beyond a temperature of 100 C. The binding energy of the Ni 2p peak increases from the RT value (852.7 eV) by 0.51.1 eV for the Ni/Ge(001) samples, while the Ge 2p binding energy changes by 0.60.7 eV after Ni growth compared to a clean Ge(001) substrate (there is only a +/- 0.15 eV shift among the samples grown on substrates at higher temperatures). By increasing substrate temperature, we obtained higher intermixing of Ni and Ge, but rather than both Ni and Ge interdiffusing, we find that Ni diffuses further into the germanium with higher substrate temperature, forming increasingly Ni-rich Ni-Ge compounds diluted into the Ge matrix. Based on Magneto-optic Kerr Effect measurements, Ni/Ge(001) grown on substrates at 100 and 200 C does not exhibit a hysteresis loop, while the samples on 300 and 400 C substrates show magnetic behavior, which we attribute to the magnetic character of hexagonal Ni5Ge2 (which is determined here for the first time to be a ferromagnetic phase). (c) 2017 Elsevier B.V. All rights reserved.
16
Low-energy electron diffraction from ferroelectric surfaces: Dead layers and surface dipoles in clean Pb(Zr, Ti)O-3(001)
Teodorescu, CM; Pintilie, L; Apostol, NG; Costescu, RM; Lungu, GA; Hrib, L; Trupina, L; Tanase, LC; Bucur, IC; Bocirnea, AE
SEP 19 2017, PHYSICAL REVIEW B, 96, 115438
DOI: 10.1103/PhysRevB.96.115438
Show abstract
The positions of the low energy electron diffraction (LEED) spots from ferroelectric single crystal films depend on its polarization state, due to electric fields generated outside of the sample. Onemay derive the surface potential energy, yielding the depth where the mobile charge carriers compensating the depolarization field are located (delta). On ferroelectric Pb(Zr, Ti)O-3(001) samples, surface potential energies are between 6.7 and 10.6 eV, and d values are unusually low, in the range of 1.8 +/- 0.4 angstrom. When delta is introduced in the values of the band bending inside the ferroelectric, a considerably lower value of the dielectric constant and/or of the polarization near the surface than their bulk values is obtained, evidencing either that the intrinsic 'dielectric constant' of the material has this lower value or the existence of a 'dead layer' at the free surface of clean ferroelectric films. The inwards polarization of these films is explained in the framework of the present considerations by the formation of an electron sheet on the surface. Possible explanations are suggested for discrepancies between the values found for surface potential energies from LEED experiments and those derived from the transition between mirror electron microscopy and low energy electron microscopy.
17
Long-range magnetic interaction in MnxGe1-x: structural, spectromicroscopic and magnetic investigations
Tanase, LC; Lungu, GA; Abramiuc, LE; Bucur, IC; Apostol, NG; Costescu, RM; Tache, CA; Macovei, D; Barinov, A; Teodorescu, CM
MAR 2017, JOURNAL OF MATERIALS SCIENCE, 52
DOI: 10.1007/s10853-016-0618-9
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We report the structural, electronic and magnetic investigation using extended X-ray absorption fine structure spectroscopy (EXAFS), photoelectron microscopy, spin-resolved photoemission and magneto-optical Kerr effect on the properties of MnGe systems obtained by molecular beam epitaxy deposition of manganese on Ge(001) wafers annealed on temperatures between 50 and 450 C. Magnetic ordering can be achieved when the substrate temperature is higher than 250 C, when the manganese tends to diffuse into the Ge matrix and segregate in MnGe-like compounds, as proved by EXAFS. High spatial resolution photoelectron spectroscopy reveals Mn inhomogeneities in the 5-10 m range, even though Mn is found mostly in the same chemical state all over the surface.
18
Band bending at magnetic Ni/Ge(001) interface investigated by X-ray photoelectron spectroscopy
Bocirnea, AE; Tanase, LC; Costescu, RM; Apostol, NG; Teodorescu, CM
DEC 1 2017, APPLIED SURFACE SCIENCE, 424, 274
DOI: 10.1016/j.apsusc.2017.04.168
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We report the molecular beam epitaxy growth of Ni on a clean Ge(001) surface with an intermediate NiGe layer forming at the interface at room temperature. The crystallinity of the substrate is lost after the deposition of more than 2 Ni monolayers. The Schottky barrier formation is investigated by X-ray photoelectron spectroscopy. The method allows us to infer a 0.39-0.45 eV band bending at the interface between the compound and Ge(001). Magneto-optical Kerr effect measurements were conclusive in detecting the ferromagnetic ordering of Ni outermost layers. (C) 2017 Elsevier B.V. All rights reserved.
19
Growth mechanisms and band bending in Cu and Pt on Ge(001) investigated by LEED and photoelectron spectroscopy
Tanase, LC; Bocirnea, AE; Serban, AB; Abramiuc, LE; Bucur, IC; Lungu, GA; Costescu, RM; Teodorescu, CM
NOV 2016, SURFACE SCIENCE, 653
DOI: 10.1016/j.susc.2016.06.006
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We investigate band bending effects occurring at the interface between atomically clean Ge(001) and molecular beam epitaxy (MBE) deposited copper and platinum. Low energy electron diffraction(LEED) confirmed the crystallinity of the surface, evidenced the formation of (2 x 1) and (1 x 2) reconstructions, and revealed that it is strongly affected with metal deposition. X-ray photoelectron spectroscopy (XPS) data let us assume a Stranski-Krastanov growth mechanism and confirmed that the observed band bending is associated to an ohmic contact in both cases. For the platinum contact, the high values of the apparent inelastic mean free path (IMFP) derived from the evolution of the XPS intensities indicate a prevalence of mixture of Pt with Ge nearby the interface. Pt deposited on Ge(001) does not behave like a Schottky contact, as one may have expected due to the higher work function of platinum. The observed effect is similar to the ease where interfacial Pt had a lower work function by 2.25/1.96 eV than that of metallic Pt. We propose a model to explain this fact by the effective mass variation or to the conduction band broadening due to the strong intermixing of platinum with germanium under the surface. (C) 2016 Elsevier B.V. All rights reserved.
20
Structure, reactivity, electronic configuration and magnetism of samarium atomic layers deposited on Si(001) by molecular beam epitaxy
Gheorghe, NG; Lungu, GA; Husanu, MA; Costescu, RM; Macovei, D; Teodorescu, CM
FEB 15 2013, APPLIED SURFACE SCIENCE, 267
DOI: 10.1016/j.apsusc.2012.08.016
Show abstract
The surface structure, interface reactivity, electron configuration and magnetic properties of Sm layers deposited on Si(0 0 1) at various temperatures are investigated by low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS) and magneto-optical Kerr effect (MOKE). It is found that metal Sm is present on samples prepared at low temperature, with an interface layer containing SmSi2 and Sm4Si3. When samples are prepared at high temperature, much less metal Sm is found, with an increasing amount of SmSi2. Room temperature ferromagnetism is observed for all prepared layers, with a decrease of the saturation magnetization when samples are prepared at high temperature. It is found that ferromagnetism implies mostly a compound with approximate stoichiometry Sm4Si3. Also, the decrease in the intensity of the XAS 2p(3/2) -> 3d white lines with the corresponding increasing amount of SmSi2 may be explained by assuming a higher occupancy of Sm 5d orbitals (5d(2) configuration), most probably due to hybridation effects. (C) 2012 Elsevier B. V. All rights reserved.
21
Room Temperature Ferromagnetic, Anisotropic, Germanium Rich FeGe(001) Alloys
Lungu, GA; Apostol, NG; Stoflea, LE; Costescu, RM; Popescu, DG; Teodorescu, CM
FEB 2013, MATERIALS, 6
DOI: 10.3390/ma6020612
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Ferromagnetic FexGe1-x with x = 2%-9% are obtained by Fe deposition onto Ge(001) at high temperatures (500 degrees C). Low energy electron diffraction (LEED) investigation evidenced the preservation of the (1 x 1) surface structure of Ge(001) with Fe deposition. X-ray photoelectron spectroscopy (XPS) at Ge 3d and Fe 2p core levels evidenced strong Fe diffusion into the Ge substrate and formation of Ge-rich compounds, from FeGe3 to approximately FeGe2, depending on the amount of Fe deposited. Room temperature magneto-optical Kerr effect (MOKE) evidenced ferromagnetic ordering at room temperature, with about 0.1 Bohr magnetons per Fe atom, and also a clear uniaxial magnetic anisotropy with the in-plane [110] easy magnetization axis. This compound is a good candidate for promising applications in the field of semiconductor spintronics.
22
Epitaxial ferromagnetic samarium and samarium silicide synthesized on Si(001)
Costescu, RM; Gheorghe, NG; Husanu, MA; Lungu, GA; Macovei, D; Pintilie, I; Popescu, DG; Teodorescu, CM
OCT 2012, JOURNAL OF MATERIALS SCIENCE, 47
DOI: 10.1007/s10853-012-6672-z
Show abstract
Samarium is deposited on Si(001) at various temperatures (room temperature to 400 A degrees C), and the surface structure, interface reactivity, electron configuration, and magnetic properties are investigated by low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and magneto-optical Kerr effect (MOKE), respectively. It is found that metal Sm is present on samples prepared at room temperature with an interface layer containing mostly Sm2+ and a lower amount of Sm3+. When samples are prepared at high temperature, much less Sm-0 is found with an increasing amount of Sm2+. Freshly prepared Sm-0 and SmSi2 layers react strongly with oxygen from the residual gas, promoting formation of Sm2O3 at the expense of both metal Sm and SmSi2. Room temperature ferromagnetism is observed for all prepared layers with a decrease of the saturation magnetisation when samples are prepared at high temperature. It is found that ferromagnetism implies mostly Sm3+ and Sm metal. In addition to these findings, this work proposes a new assignment of the Sm 3d chemically shifted components. Also, a noticeable variation of the XPS Sm 3d spin-orbit splitting is found as a function of the Sm ionization state.
23
Atomic structure and reactivity of ferromagnetic Fe deposited on Si(001)
Gheorghe, NG; Husanu, MA; Lungu, GA; Costescu, RM; Macovei, D; Teodorescu, CM
FEB 2012, JOURNAL OF MATERIALS SCIENCE, 47
DOI: 10.1007/s10853-011-5963-0
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This study presents a correlated study of structural, reactivity, and magnetic properties of ultrathin Fe layers grown on Si(001) by molecular beam epitaxy in ultrahigh vacuum. The interface reactivity is characterized by Auger electron spectroscopy. The surface structure is characterized by low electron energy diffraction with spot profile analysis. The magnetism of the synthesized layers is investigated by magneto-optical Kerr effect. At room temperature, metal Fe layers with poor long-range order are synthesized; these layers are ferromagnetic with an extremely low coercitive field (below 1 Oe). The reactivity with Si is low in this case, with formation of an interface layer of about 8 angstrom Fe equivalent thickness with about 7 at.% Si diffused. Samples synthesized at higher temperatures (500 degrees C) exhibit better long-range order, though the Fe reactivity with Si is higher and leads to the formation of an interface compound whose approximate stoichiometry is very close to Fe(3)Si. Once this compound is formed (for an equivalent Fe thickness of about 14 monolayers), disordered metal Fe islands are developing with subsequent Fe deposition, which contain also about 8 at.% Si diffused. These structures exhibit a much lower ferrimagnetism, with saturation magnetization about one order of magnitude lower than in the case of the room temperature synthesis. In this case of high temperature synthesis, two phases are observed, a ferrimagnetic one and a superparamagnetic one.
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ATOMIC STRUCTURE AND MAGNETISM OF PLD DEPOSITED Tio(2):Fe
Costescu, RM; Lungu, GA; Socol, G; Gheorghe, NG; Macovei, D; Negrila, CC; Logofatu, C; Husanu, MA; Popescu, DG; Tache, CA; Teodorescu, CM
JAN-MAR 2012, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 7
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TiO2:Fe thin films prepared by pulsed laser deposition exhibit in some case light dependent saturation magnetization, as determined from Kerr magnetometry measurements performed in dark or by illuminating the sample. This phenomenon is studied in correlation with local atomic structure investigated by extended X-ray absorption fine structure, composition and chemical state analyzed by X-ray photoelectron spectroscopy and by X-ray absorption near-edge structure. It is found that light-controllable magnetism is a property of a mixture of Fe and oxidized Fe clusters embedded in the anatase TiO2 matrix.
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REACTIVITY, MAGNETISM AND LOCAL ATOMIC STRUCTURE IN FERROMAGNETIC FE LAYERS DEPOSITED ON SI(001)
Gheorghe, NG; Husanu, MA; Lungu, GA; Costescu, RM; Macovei, D; Popescu, DG; Teodorescu, CM
JAN-MAR 2012, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 7
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This work presents recent studies concerning the synthesis of ultrathin ferromagnetic Fe layers on Si(001) and the correlated follow-up measurement of their structural properties, interface reactivity, and magnetism. This study is undertaken as function of the amount of Fe deposited and of substrate temperature. The interface reactivity is characterized by Auger electron spectroscopy. The surface structure is characterized by low electron energy diffraction (LEED). The local order of Fe atoms is investigated by X-ray absorption fine structure (XAFS) and the magnetism by magneto-optical Kerr effect (MOKE). A general trend established is that a higher deposition temperature stabilizes a better surface ordering, but also enhances Fe and Si interdiffusion and therefore decreases the magnetism. A surprising effect obtained by Fe deposition at room temperature is that, despite the rapid disappearance of the long range order with Fe deposition (no LEED pattern is observed for Fe coverage exceeding one monolayer), the material exhibits a significant uniaxial in-plane magnetic anisotropy. When the deposition is performed at high temperature (500 degrees C), a weak ferromagnetism is still observed, with saturation magnetization of about 10 % of the value obtained for room temperature deposition. The combined MOKE and EXAFS studies allowed inferring consistent values for the range of Fe thicknesses where the reaction takes place and the main properties of the distinct formed layers.
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Structural investigations of Ge nanoparticles embedded in an amorphous SiO2 matrix
Stavarache, I; Lepadatu, AM; Gheorghe, NG; Costescu, RM; Stan, GE; Marcov, D; Slav, A; Iordache, G; Stoica, TF; Iancu, V; Teodorescu, VS; Teodorescu, CM; Ciurea, ML
JAN 2011, JOURNAL OF NANOPARTICLE RESEARCH, 13, 232
DOI: 10.1007/s11051-010-0021-4
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Transmission electron microscopy and X-ray photoelectron spectroscopy analyses are performed to investigate Ge nanoparticles embedded in an amorphous SiO2 matrix. GeSiO thin films are prepared by two methods, sol-gel and radio frequency magnetron sputtering. After the deposition, the sol-gel films are annealed in either N-2 (at 1 atm and 800 A degrees C) or H-2 (at 2 atm and 500 A degrees C), and the sputtered films in H-2 (at 2 atm and 500 A degrees C), to allow Ge segregation. Amorphous Ge-rich nanoparticles (3-7 nm size) are observed in sol-gel films. Crystalline Ge nanoparticles in the high pressure tetragonal phase (10-50 nm size) are identified in the sputtered films. The size of the nanoparticles increases with Ge concentration in the volume of the film. At the film surface, the Ge concentration is much larger that in the volume for both sol-gel and sputtered films. At the same time, at the film surface, only oxidized Ge is observed.
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Significantly different contamination of atomically clean Si(001) when investigated by XPS and AES
Gheorghe, NG; Lungu, GA; Costescu, RM; Teodorescu, CM
AUG 2011, PHYSICA STATUS SOLIDI B-BASIC SOLID STATE PHYSICS, 248
DOI: 10.1002/pssb.201147220
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Clean Si(001) single crystal surfaces provided different surface reconstructions: p(1 x 2) and c(n x 2) (n = 4, 6) at room temperature. The in situ oxidation of these surfaces was followed by Auger electron spectroscopy and by X-ray photoelectron spectroscopy. It is found that, in similar ultrahigh vacuum conditions, much faster contamination (about 500 times) occurs when the samples are investigated by AES than by XPS, owing to the interaction of the electron beam with the sample surface. With the sample subject to the AES investigation, the contamination occurs by forming >Si2C=O complexes based on the Si dimers. During XPS, reaction with water molecules from the residual gas should also be taken into account.
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Enhanced contamination of Si(001) when analyzed by AES with respect to XPS
Gheorghe, NG; Lungu, GA; Costescu, RM; Popescu, DG; Teodorescu, CM
MAY 2011, OPTOELECTRONICS AND ADVANCED MATERIALS-RAPID COMMUNICATIONS, 5
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Clean Si(001) single crystal surfaces are obtained by cycles of long (30 mins.) annealings in ultrahigh vacuum (fairly below 1 x 10(-9) mbar). The surface reconstruction is investigated by low energy electron diffraction (LEED). This paper reports, in addition to the well-known p(2 x 1) reconstruction, the first observation of c(4 x 2) at room temperature and also the completely new c(6 x 2) reconstruction. The in situ oxidation of these surfaces was investigated by Auger electron spectroscopy (AES) and by X-ray photoelectron spectroscopy (XPS). It is found that, in similar ultrahigh vacuum conditions (6 x 10(-10) mbar), much faster contamination (about 500 times) occurs when the samples are investigated by AES than by XPS, owing mainly to the interaction of the electron beam with the sample surface. Also, much gentler surface bombardment with electrons, such as in LEED, still enhances sample oxidation. Therefore, XPS proves to be a much more convenient technique for non-destructive assessment of the surface composition. When the surface is subjected to the AES investigation, we found that the contamination occurs by forming >Si2C=O complexes based on the Si dimers.
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Successful Cleaning and Study of Contamination of Si(001) in Ultrahigh Vacuum
Gheorghe, NG; Lungu, GA; Husanu, MA; Costescu, RM
2011, PHYSICS CONFERENCE (TIM-10), 1387
DOI: 10.1063/1.3647078
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This paper presents the very first surface physics experiment performed in ultrahigh vacuum (UHV) in Romania, using a new molecular beam epitaxy (MBE) installation. Cleaning of a Si(001) wafer was achieved by using a very simple technique: sequences of annealing at 900-1000 degrees C in ultrahigh vacuum: low 10(-8) mbar, with a base pressure of 1.5 x 10(-10) mbar. The preparation procedure is quite reproducible and allows repeated cleaning of the Si(001) after contamination in ultrahigh vacuum. The Si(001) single crystal surface is characterized by low energy electron diffraction (LEED), reflection high energy electron diffraction (RHEED), and Auger electron spectroscopy (AES). The latter technique is utilized in order to investigate the sample contamination by the residual gas in the UHV chamber, as determined by a residual gas analyzer (RGA). Unambiguous assignment of oxidized and unoxidized silicon is provided; also, an important feature is that the LVV Auger peak at 90-92 eV cannot be solely attributed to clean Si (i.e. Si surrounded only by Si), but also to silicon atoms bounded with carbon. Even with a sum of partial pressures of oxygen and carbon containing molecules in the range of 5 x 10(-10) mbar, the sample is contaminated very quickly, having a (1/e) lifetime of about 76 minutes.
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Fe/Si(001) Ferromagnetic Layers: Reactivity, Local Atomic Structure and Magnetism
Lungu, GA; Costescu, RM; Anu, MAH; Gheorghe, NG
2011, PHYSICS CONFERENCE (TIM-10), 1387
DOI: 10.1063/1.3647075
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Ultrathin ferromagnetic Fe layers on Si(001) have recently been synthesized using the molecular beam epitaxy (MBE) technique, and their structural and magnetic properties, as well as their interface reactivity have been investigated. The study was undertaken as function of the amount of Fe deposited and of substrate temperature. The interface reactivity was characterized by Auger electron spectroscopy (AES). The surface structure was characterized by low-energy electron diffraction (LEED). The magnetism was investigated by magneto-optical Kerr effect (MOKE). A higher deposition temperature stabilizes a better surface ordering, but it also enhances Fe and Si interdiffusion and it therefore decreases the magnetism. Despite the rapid disappearance of the long range order with Fe deposition at room temperature, the material exhibits a significant uniaxial in-plane magnetic anisotropy. For the Fe deposition performed at high temperature (500 degrees C), a weak ferromagnetism is still observed, with saturation magnetization of about 10 % of the value obtained previously. MOKE studies allowed inferring the main properties of the distinct formed layers.
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Illumination-dependent HF Etching of AlAs Sacrificial Layers for the Formation of "Rolled Up" Nanotubes from Strained InGaAs/GaAs Films
Costescu, RM
2011, PHYSICS CONFERENCE (TIM-10), 1387
DOI: 10.1063/1.3647071
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Rolled-up nanostructures formed from lattice mismatched III-V heterojunction films by taking advantage of a strain-induced self-rolling mechanism represent a useful type of building blocks for nanotechnology, with possible applications in high-speed microelectronic and optoelectronic devices. This work investigated the effect of illumination on the hydrofluoric acid etching of AlAs sacrificial layers with systematically varied thicknesses in order to release and roll up MBE grown InGaAs/GaAs bilayers. Based on this "etch suppression effect" (ESE), we propose an illumination-assisted technique that offers an advantage over other methods of rolling up nano-objects on a substrate from inherently strained films because it allows control over the positioning of rolled-up micro- and nanotubes independently from lithographic methods. For thicknesses of AlAs below 10 nm, we found two etching regimes for the area under illumination: one at low illumination intensities, in which the etching and releasing proceeds as expected and one at higher intensities in which the etching and any releasing are completely suppressed. The "etch suppression" area is well defined by the illumination spot, which can be used to realize well-controlled heterogeneously etched regions on the same sample.
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ATOMIC STRUCTURE AND MAGNETIC PROPERTIES OF COBALT DOPED ZnO THIN FILMS PREPARED BY THE SOL-GEL METHOD
Neamtu, J; Georgescu, G; Malaeru, T; Gheorghe, NG; Costescu, RM; Jitaru, I; Ferre, J; Macovei, D; Teodorescu, CM
OCT-DEC 2010, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 5, 885
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The ability of a sol-gel route for the synthesis of cobalt doped ZnO (Zn 1-xCoxO, x = 0.04-0.11) films grown on Si (100) and glass substrates is investigated. A homogeneous and stable Zn (1-x) CoxO sol was prepared by dissolving zinc nitrate hexahydrate and cobalt acetate tetrahydrate in a PVP (polyvinylpyrrolidone) solution, followed by annealing at 800 degrees C. Local structure studies of the Zn1-xCoxO thin films by XANES (X-ray absorption near-edge structure) and EXAFS (extended X-ray absorption fine structure) proved the co-existence of a few amount of small metal cobalt aggregates with Co in non-stoichiometric ConOm aggregates, with n > m, and m similar to 4. Low temperature magneto-optical Kerr effect (Faraday rotation) measurements of the magnetization versus field give a direct proof of a superparamagnetic behavior of the magnetic aggregates and allowed an estimate of the number of magnetically active atoms in Co aggregates, which is close to the number of Co excess atoms inferred from XANES and EXAFS considerations: n - m similar to 3 atoms per aggregate. To this main superparamagnetic phase, a weak ferromagnetic phase with coercitive field of similar to 50 Oe is superimposed, most probably due to metal cobalt nanoclusters.