NIMP| Nicoleta APOSTOL, Author at NIMP

Resume

Nicoleta G. Apostol (b. 1985, other name Gheorghe) earned her PhD degree in Chemistry at the Institute of Physical Chemistry of the Romanian Academy in 2013, is hired since 2009 in the National Institute of Materials Physics (NIMP) Măgurele, in the group of Surfaces and Interfaces. Between March 2014 and March 2015 she obtained a Post-Doctoral position at Elettra - Sincrotrone Trieste in Italy, at the SuperESCA beamline (Dr. Silvano Lizzit).

She earned the "Radu Grigorovici" Prize of the Romanian Academy for 2012, awarded for the group of works "Surface and interface phenomena highlighted by electron spectroscopyies XPS/Auger and other characterization techniques of surfaces and interfaces", date of award 19^th December 2014, is one of the winners of the L'Oréal - UNESCO National scholarship "For Women in Science", section Physical Sciences, 9^th edition, 2018, and she earned the 1^st prize at the “Rada Mihalcea” awards for young researchers in science and engineering, in August 2019. Currently, she is employed as Senior Scientist II, author or co-author for 79 papers published in ISI quoted journals and 7 book chapters, 27 oral presentations or invited to national/international conferences, project manager for 3 national projects: a Post-Doctoral Project and 2 Young Research Team projects. She was a member of the evaluation committee of the Rada Mihalcea competition for Young Researchers in Science and Engineering, is co-responsible within the IOSIN – Special Systems and Objectives of National Interest –programme and is one of the persons responsible for CoSMoS (detached installation at the SuperESCA beamline, from the Elettra Synchrotron, in Trieste, Italy) and co-responsible for XPS spatial resolution in INCDFM. The published works have accumulated about 1080 citations (self-citation excluded) and a Hirsch index of 21. These are elements defining a solid scientific reputation at international level and the ability to extract the maximum information from X-ray Photoelectron Spectroscopy.

Research ID: I-9399-2016

Brainmap UEF – ID: U-1700-039K-3342

ORCID: 0000-0002-8862-9625

View Full CV

Projects

1. Molecular adsorption and reactions under two-dimensional shells

Project Type: TE, Start Date: 2021-01-11 End Date: 2022-12-31

2. Origin of resistance hysteresis in graphene layers on ferroelectric substrates

Project Type: PD, Start Date: 2018-05-02 End Date: 2020-11-30

3. CHEMISTRY AND PHOTOCHEMISTRY ON FERROELECTRIC SURFACES

Project Type: TE, Start Date: 2015-10-01 End Date: 2017-11-30

Publications

1. Reversible oxidation of ethylene on ferroelectric BaTiO3(001): An X-ray photoelectron spectroscopy study

Authors: Iancu, AC; Nicolaev, A; Apostol, NG; Abramiuc, LE; Teodorescu, CM

Published: AUG 15 2024, HELIYON, 10, e35072, DOI: 10.1016/j.heliyon.2024.e35072

Adsorption and desorption of ethylene on BaO-terminated (001) barium titanate are investigated by X-ray photoelectron spectroscopy. Carbon is found in an oxidized state, at a binding energy similar to that resulting from CO adsorption on BaTiO3(001). The amount of carbon adsorbed on the surface is also similar to the case of CO/BaTiO3(001). Upon heating the substrate up to the loss of its ferroelectric polarization, the C 1s signal from the oxidized spectral region vanishes. At the same time, there was no noticeable oxygen depletion of the surface after repeated C2H4 adsorption and desorption. The substrate remains stable after repeated oxidative adsorption and desorption of ethylene. Desorption occurs at different temperatures, depending on the adsorption temperature, which suggests different adsorption geometries: non-dissociated adsorption at high temperature with ethylene bond on two surface oxygen atoms, and locally dissociated adsorption at lower temperatures, in "formaldehyde-like" local configurations.

2. Molecular adsorption-desorption of carbon monoxide on ferroelectric BaTiO₃(001)

Authors: Iancu, AC; Apostol, NG; Nicolaev, A; Abramiuc, LE; Chirila, CF; Popescu, DG; Teodorescu, CM

Published: JUL 15 2024, MATERIALS ADVANCES, 5, DOI: 10.1039/d4ma00389f

Carbon monoxide (CO) is reversibly adsorbed on and desorbed from ferroelectric (001) oriented, BaO-terminated barium titanate. All processes are characterized in real time via photoelectron spectroscopy. Adsorption proceeds on different sites/geometries as a function of substrate temperature. Below room temperature, CO is adsorbed on surface Ba. At room temperature, adsorption proceeds on surface oxygen, whereas at high temperatures, "hollow" site adsorption occurs with carbon coordinated with three oxygens, one oxygen initially belonging to CO and two oxygens from the substrate. The amount of CO adsorbed is about one molecule for 10 surface unit cells, which is slightly increased at low temperatures. CO is desorbed if the substrate is heated above the Curie temperature, which is a sign of the definitory role of ferroelectric polarization. The BaTiO3(001) surface is unaffected by repeated cycles of adsorption-desorption.

3. Composite Photocatalysts with Fe, Co, and Ni Oxides on Supports with Tetracoordinated Ti Embedded into Aluminosilicate Gel during Zeolite Y Synthesis

Authors: Petcu, G; Anghel, EM; Atkinson, I; Culita, DC; Apostol, NG; Kuncser, A; Papa, F; Baran, A; Blin, JL; Parvulescu, V

Published: FEB 2024, GELS, 10, 129, DOI: 10.3390/gels10020129

Ti-aluminosilicate gels were used as supports for the immobilization of Fe, Co, and Ni oxides (5%) by impregnation and synthesis of efficient photocatalysts for the degradation of beta-lactam antibiotics from water. Titanium oxide (1 and 2%) was incorporated into the zeolite network by modifying the gel during the zeolitization process. The formation of the zeolite Y structure and its microporous structure were evidenced by X-ray diffraction and N-2 physisorption. The structure, composition, reduction, and optical properties were studied by X-ray diffraction, H-2-TPR, XPS, Raman, photoluminescence, and UV-Vis spectroscopy. The obtained results indicated a zeolite Y structure for all photocatalysts with tetracoordinated Ti4+ sites. The second transitional metals supported by the post-synthesis method were obtained in various forms, such as oxides and/or in the metallic state. A red shift of the absorption edge was observed in the UV-Vis spectra of photocatalysts upon the addition of Fe, Co, or Ni species. The photocatalytic performances were evaluated for the degradation of cefuroxime in water under visible light irradiation. The best results were obtained for iron-immobilized photocatalysts. Scavenger experiments explained the photocatalytic results and their mechanisms. A different contribution of the active species to the photocatalytic reactions was evidenced.

4. Molecular adsorption-desorption of carbon monoxide on ferroelectric BaTiO₃(001)

Authors: Iancu, AC; Apostol, NG; Nicolaev, A; Abramiuc, LE; Chirila, CF; Popescu, DG; Teodorescu, CM

Published: 2024 JUN 11 2024, MATERIALS ADVANCES, DOI: 10.1039/d4ma00389f

5. Copper-/Zinc-Doped TiO2 Nanopowders Synthesized by Microwave-Assisted Sol-Gel Method

Authors: Predoana, L; Petcu, G; Preda, S; Pandele-Cusu, J; Petrescu, SV; Baran, A; Apostol, NG; Costescu, RM; Surdu, VA; Vasile, BS; Ianculescu, AC

Published: APR 2023, GELS, 9, 267, DOI: 10.3390/gels9040267

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.

6. Silver nanoparticles decorated ZnO-CuO core-shell nanowire arrays with low water adhesion and high antibacterial activity

Authors: Costas, A; Preda, N; Zgura, I; Kuncser, A; Apostol, N; Curutiu, C; Enculescu, I

Published: JUL 3 2023, SCIENTIFIC REPORTS, 13, 10698, DOI: 10.1038/s41598-023-37953-w

Nanostructured surfaces based on silver nanoparticles decorated ZnO-CuO core-shell nanowire arrays, which can assure protection against various environmental factors such as water and bacteria were developed by combining dry preparation techniques namely thermal oxidation in air, radio frequency (RF) magnetron sputtering and thermal vacuum evaporation. Thus, high-aspect-ratio ZnO nanowire arrays were grown directly on zinc foils by thermal oxidation in air. Further ZnO nanowires were coated with a CuO layer by RF magnetron sputtering, the obtained ZnO-CuO core-shell nanowires being decorated with Ag nanoparticles by thermal vacuum evaporation. The prepared samples were comprehensively assessed from morphological, compositional, structural, optical, surface chemistry, wetting and antibacterial activity point of view. The wettability studies show that native Zn foil and ZnO nanowire arrays grown on it are featured by a high water droplet adhesion while ZnO-CuO core-shell nanowire arrays (before and after decoration with Ag nanoparticles) reveal a low water droplet adhesion. The antibacterial tests carried on Escherichia coli (a Gram-negative bacterium) and Staphylococcus aureus (a Gram-positive bacterium) emphasize that the nanostructured surfaces based on nanowire arrays present excellent antibacterial activity against both type of bacteria. This study proves that functional surfaces obtained by relatively simple and highly reproducible preparation techniques that can be easily scaled to large area are very attractive in the field of water repellent coatings with enhanced antibacterial function.

7. Surface charge dynamics on air-exposed ferroelectric Pb(Zr,Ti)O₃(001) thin films

Authors: Abramiuc, LE; Tanase, LC; Prieto, MJ; Caldas, LD; Tiwari, A; Apostol, NG; Husanu, MA; Chirila, CF; Trupina, L; Schmidt, T; Pintilie, L; Teodorescu, CM

Published: AUG 10 2023, NANOSCALE, 15, DOI: 10.1039/d3nr02690f

Probing of the free surface ferroelectric properties of thin polar films can be achieved either by estimating the band bending variance under the top-most layer or by studying the extent of the extrinsic charge accumulated outside the surface. Photoemitted or incoming low-energy electrons can be used to characterize locally both properties in a spectromicroscopic approach. Thin ferroelectric lead zirco-titanate (PZT) is investigated by combining low energy/mirror electron microscopy (LEEM/MEM) with photoemission electron microscopy (PEEM) and high-resolution photoelectron spectroscopy (XPS). Significant extrinsic negative compensation charge is proven to accumulate on the surface of the outward polarized thin film, indicated by high MEM-LEEM transition values, up to 15.3 eV, and is correlated with the surface electrostatic potential, which can be partially screened either by electrons interacting with the sample or by soft X-rays through the ejection of secondary electrons and generation of positive charge under the surface. A radiation-induced surface charge compensation effect is observed. The study indicates that air-exposed high quality ferroelectric thin films show large negative surface potentials, determined locally on the surface, which are nevertheless sensitive to beam damage and molecular desorption. These values represent a confirmation of previously estimated surface potential energy values determined from the LEED data on clean surfaces.

8. Co- and Ni-Doped TiO₂ Nanoparticles Supported on Zeolite Y with Photocatalytic Properties

Authors: Petcu, G; Papa, F; Atkinson, I; Baran, A; Apostol, NG; Petrescu, S; Richaudeau, L; Blin, JL; Parvulescu, V

Published: AUG 2023, NANOMATERIALS, 13, 2200, DOI: 10.3390/nano13152200

Zeolite Y samples with microporous and hierarchical structures containing Ti-Ni and Ti-Co oxides were obtained as active photocatalysts. Different Ti amounts (5, 10% TiO2) were supported, followed by the loading of Ni or Co oxides (5%). X-ray diffraction evidenced the presence of TiO2 as an anatase. N-2 adsorption-desorption results showed type IV isotherms for hierarchical zeolite Y samples, and a combination of type IV and I isotherms for zeolite Y samples. UV-Vis diffuse reflectance spectra showed a shift in the absorption band to visible with increasing Ti loading and especially after Co and Ni addition. A significant effect of the support was evidenced for Ti and its interaction with Co/Ni species. The zeolite Y support stabilized Ti in the 4+ oxidation state while hierarchical zeolite Y support favored the formation of Ti3+ species, Ni-0 and Ni2+ and the oxidation of Co to 3+ oxidation state. Photocatalytic activity, under UV and visible light irradiation, was evaluated by the degradation of amoxicillin, used as a model test. The photocatalytic mechanism was investigated using ethanol, p-benzoquinone and KI as & BULL;OH and & BULL;O-2(-) radicals and hole (h(+)) scavengers. The best results were obtained for the immobilized Ni-Ti species on the hierarchical zeolite Y support.

9. Copper-/Zinc-Doped TiO₂ Nanopowders Synthesized by Microwave-Assisted Sol-Gel Method

Authors: Predoana, L; Petcu, G; Preda, S; Pandele-Cusu, J; Petrescu, SV; Baran, A; Apostol, NG; Costescu, RM; Surdu, VA; Vasile, BS; Ianculescu, AC

Published: APR 2023, GELS, 9, 267, DOI: 10.3390/gels9040267

10. Monodispersed nanoplatelets of samarium oxides for biosensing applications in biological fluids

Authors: Leote, RJB; Matei, E; Apostol, NG; Enculescu, M; Enculescu, I; Diculescu, VC

Published: JAN 10 2022, ELECTROCHIMICA ACTA, 402, 139532, DOI: 10.1016/j.electacta.2021.139532

A nanostructured samarium oxide electrode was constructed by electrodeposition onto the surface of a gold electrode on SiO2/Si wafer. The samarium oxides electrode's surface morphology was investigated by scanning electron microcopy showing a quasi-monodispersed nanoplatelets like structure. X-rays diffraction analysis demonstrated a mixture of monoclinic and hexagonal phases while the X-rays photoelectron spectroscopy indicated the co-existence of both Sm2+ and Sm3+ species in a 1:3 proportion. Cyclic voltammetry and electrochemical impedance spectroscopy were used to investigate the charge transfer processes at the surface of the samarium oxide electrode in the absence and in the presence of redox probes. A roughness factor of 2.5 was determined from the samarium oxide electrode while the charge transfer constant was almost double when compared to the planar gold electrode. Then, the samarium oxide electrode was used for the H2O2 detection by fixed potential amperometry at -0.20 V (vs. Ag/AgCl) with a linear region between 0.01 and 1.00 mM, a sensitivity of 153 mu A cm(-2) mM(-1) and a LoD = 2.70 mu M. Glucose oxidase was used as a model enzyme in order to test the capacity of the samarium oxides electrode for biosensing. The enzyme was immobilized by physical adsorption and the optimum conditions for glucose analysis investigated. The biosensor showed a linear range for glucose detection between 0.10 and 1.20 mM with a sensitivity of 8.40 mu A cm(-2) mM(-1) and a LoD = 8.00 mu M. Selectivity was tested toward common interfering species, and the results revealed the lack of biosensor response. The glucose biosensor on samarium oxides was tested for glucose detection in serum samples with a recovery factor of 90%, and the result validated with a commercial glucometer. (C) 2021 Elsevier Ltd. All rights reserved.

11. CO adsorption and oxidation at room temperature on graphene synthesized on atomically clean Pt(001)

Authors: Apostol, NG; Bucur, IC; Lungu, GA; Tache, CA; Teodorescu, CM

Published: APR 15 2021, CATALYSIS TODAY, 366, DOI: 10.1016/j.cattod.2020.02.006

Carbon monoxide is adsorbed at room temperature on graphene formed on atomically clean Pt(001)-hex by chemical vapor deposition, starting with ethylene, in ultrahigh vacuum. The graphene formation is characterized in situ by high resolution photoelectron spectroscopy (HRPES), by low energy electron diffraction (LEED) and by near-edge X-ray absorption fine structure (NEXAFS). The formation of graphene destroys the hex reconstruction of Pt(001) and graphene exhibits totally in-plane sp(2) bonding. CO adsorption is characterized by HRPES and a rigid shift towards higher binding energies by about 96 meV is experienced by Pt 4f core levels, together with a shift towards lower binding energy by 36 meV of the C 1s level corresponding to graphene, while the amplitude analysis of carbon and platinum peaks suggests the intercalation of carbon oxide between graphene and the metal substrate. The presence of oxidized carbon is evidenced by a separate component in the C 1s spectrum (attributed to carbon bond to oxygen) and by the occurrence of the O 1s signal. The coverage expressed in terms of the ratio of the integral amplitudes of the carbon bond to oxygen to the amplitude of the carbon from graphene approaches 3 %, yielding a CO coverage of Pt(001) of about 0.12 monolayer. The derived atomic ratio (O 1s):(C 1s bond to O) is initially close to 1, then evolves in time towards values close to 2, which means that CO is progressively oxidized upon adsorption and irradiation with soft X-rays. The relative amount of oxygen and oxidized carbon decreases in time under irradiation with soft X-rays. Weakly bound graphene on incommensurate metal surfaces may be used as atomic scale nanoreactors for trapping and immediate oxidation of carbon monoxide.

12. THERMAL BEHAVIOR OF Cu-DOPED TiO2 GELS SYNTHESIZED BY THE SOL-GEL METHOD

Authors: Pandele-Cusu, J; Atkinson, I; Rusu, A; Apostol, N; Teodorescu, V; Predoana, L; Szilagyi, IM; Pokol, G; Zaharescu, M

Published: MAR 2021, REVUE ROUMAINE DE CHIMIE, 66, 229, DOI: 10.33224/rrch.2021.66.3.01

The thermal behavior of Cu-doped TiO2 gels obtained by the sol-gel method was investigated by thermogravimetric and differential thermal analysis (TG/DTG/DTA) and differential scanning calorimetry (DSC) measurements. The comparative investigation of the structure and morphology of the as-prepared gels and of the nanopowders obtained by annealing them was realized by transmission electron microscopy (TEM), Fourier transmission infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Significant differences were noticed depending on the amount of dopant (0.5 or 2.0 mol % CuO). A higher dopant concentration resulted in a more complex decomposition of the sample. This behavior was associated with the formation of various molecular species in the sol-gel solutions before gelation, determined by the different amount of the dopant used.

13. Influence of Ce addition and Pt loading upon the catalytic properties of modified mesoporous PtTi-SBA-15 in total oxidation reactions

Authors: Ciobanu, M; Petcu, G; Anghel, EM; Papa, F; Apostol, NG; Culita, DC; Atkinson, I; Todorova, S; Shopska, M; Naydenov, A; Velinova, R; Parvulescu, V

Published: JUN 5 2021, APPLIED CATALYSIS A-GENERAL, 619, DOI: 10.1016/j.apcata.2021.118123

A series of PtCeTi-SBA-15 catalysts, with different concentrations of Pt (0.25 %, 0.5 %, 1.0 %), were synthesized. New Ti-SBA-15 material was obtained by direct synthesis and used as support in successive immobilization of Pt and Ce precursors, changing their order of addition. The characterization of the catalysts has been achieved taking an ensemble of techniques which showed preservation of the support porous structure, high dispersion of the amorphous metal oxides and Pt?, the formation of metal crystals for samples with 1wt% Pt and variation of Pt? content on surface in condition of ceria addition. The best conversion (100 %) was obtained in oxidation of hydrocarbons (CH4, C3H8 and C6H14) for the samples with 1% Pt and a significant diminish of activity was obtained for catalyst in which Ce was added on PtTi-SBA-15 sample. Differently of these, CO oxidation was totally irrespective of the catalyst composition.

14. CO adsorption, reduction and oxidation on Pb(Zr,Ti)O-3(001) surfaces associated with negatively charged gold nanoparticles

Authors: Apostol, NG; Husanu, MA; Lizzit, D; Hristea, IA; Chirila, CF; Trupina, L; Teodorescu, CM

Published: APR 15 2021, CATALYSIS TODAY, 366, 154, DOI: 10.1016/j.cattod.2020.02.042

Gold is deposited on atomically clean, inwards polarized, ferroelectric lead zirco-titanate deposited by pulsed laser deposition on strontium titanate (001) single crystal, then carbon monoxide adsorption and desorption experiments are investigated by in situ fast photoelectron spectroscopy using synchrotron radiation. Atomic force microscopy and high resolution photoelectron spectroscopy are consistent with the formation of 50?100 nm nanoparticles, and their Au 4f core levels point to a negative charge state of gold. As compared with a similar experiment performed on ferroelectric lead zirco-titanate with similar polarization state and without gold, the saturation coverage after exposure to carbon monoxide increases by about 68 %, and also most of the additional carbon is found in oxidized state. Desorption experiments with in situ follow-up by photoelectron spectroscopy are performed as function of temperature, and the neutral carbon intensity decreases when the ferroelectric polarization decreases, while the components corresponding to oxidized carbon remain unchanged. It looks that neutral carbon adsorption is strictly related to the polarization of the ferroelectric film, while carbon still found in molecular form is related to its carbonyl bonding on metal nanoparticles, independent of the polarization state of the substrate. Desorbed carbon at higher temperature uptakes oxygen from the substrate.

15. Resistance hysteresis correlated with synchrotron radiation surface studies in atomic sp(2) layers of carbon synthesized on ferroelectric (001) lead zirconate titanate in an ultrahigh vacuum

Authors: Apostol, NG; Lizzit, D; Lungu, GA; Lacovig, P; Chirila, CF; Pintilie, L; Lizzit, S; Teodorescu, CM

Published: JAN 8 2020, RSC ADVANCES, 10, DOI: 10.1039/c9ra09131a

Carbon layers are deposited on 100 nm thick atomically clean (001) lead zirconate titanate (PZT) in ultrahigh vacuum, ruling out the presence of any contaminants. X-ray photoelectron spectroscopy is used to assess the substrate surface or interface composition, substrate polarization and the thickness of carbon layers, which ranges from less than one monolayer (1 ML) of graphene to several monolayers. Atomically clean PZT(001) exhibit inwards polarization, and this polarization reverses the sign upon carbon deposition. Cationic vacancies are detected near the PZT surface, consistent with heavy p doping of these films near the surface. The carbon layers exhibited a consistent proportion of atoms forming in-plane sp(2) bonds, as detected by near-edge absorption fine structure (NEXAFS) analysis and confirmed partially by scanning tunneling microscopy (STM). In situ poling with simultaneous in-plane transport measurements revealed the presence of resistance anti-hysteresis versus the polarization orientation for films with less than 1 ML carbon amount, evolving towards 'normal' hysteresis for thicker carbon films. The anti-hysteresis is explained in terms of a mixed screening mechanism, involving charge carriers from the sp(2) carbon layers together with holes or ionized acceptors in PZT(001) near the interface. For thicker films, the compensation mechanism becomes extrinsic, involving mostly electrons and holes from carbon, yielding the expected hysteresis.

16. Functionalization of eggshell membranes with CuO-ZnO based p-n junctions for visible light induced antibacterial activity against Escherichia coli

Authors: Preda, N; Costas, A; Beregoi, M; Apostol, N; Kuncser, A; Curutiu, C; Iordache, F; Enculescu, I

Published: DEC 1 2020, SCIENTIFIC REPORTS, 10, DOI: 10.1038/s41598-020-78005-x

Biopolymers provide versatile platforms for designing naturally-derived wound care dressings through eco-friendly pathways. Eggshell membrane (ESM), a widely available, biocompatible biopolymer based structure features a unique 3D porous interwoven fibrous protein network. The ESM was functionalized with inorganic compounds (Ag, ZnO, CuO used either separately or combined) using a straightforward deposition technique namely radio frequency magnetron sputtering. The functionalized ESMs were characterized from morphological, structural, compositional, surface chemistry, optical, cytotoxicity and antibacterial point of view. It was emphasized that functionalization with a combination of metal oxides and exposure to visible light results in a highly efficient antibacterial activity against Escherichia coli when compared to the activity of individual metal oxide components. It is assumed that this is possible due to the fact that an axial p-n junction is created by joining the two metal oxides. This structure separates into components the charge carrier pairs promoted by visible light irradiation that further can influence the generation of reactive oxygen species which ultimately are responsible for the bactericide effect. This study proves that, by employing inexpensive and environmentally friendly materials (ESM and metal oxides) and fabrication techniques (radio frequency magnetron sputtering), affordable antibacterial materials can be developed for potential applications in chronic wound healing device area.

17. Direct Immobilization of Biomolecules through Magnetic Forces on Ni Electrodes via Ni Nanoparticles: Applications in Electrochemical Biosensors

Authors: Barsan, MM; Enache, TA; Preda, N; Stan, G; Apostol, NG; Matei, E; Kuncser, A; Diculescu, VC

Published: JUN 5 2019, ACS APPLIED MATERIALS & INTERFACES, 11, 19877, DOI: 10.1021/acsami.9b04990

The present work describes a new simple procedure for the direct immobilization of biomolecules on Ni electrodes using magnetic Ni nanoparticles (NiNPs) as biomolecule carriers. Ni electrodes were fabricated by electroplating, and NiNPs were chemically synthesized. The chemical composition, crystallinity, and granular size of Ni electrodes, NiNP, and NiNP-modified Ni electrodes (NiNP/Ni) were determined by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS). The electrochemical characterization of Ni electrodes by cyclic voltammetry and electrochemical impedance spectroscopy confirmed the existence of nickel oxides, hydroxides, and oxohydroxide films at the surface of Ni. Magnetic characterization and micromagnetic simulations were performed in order to prove that the magnetic force is responsible for the immobilization process. Further, Ni electrodes were employed as amperometric sensors for the detection of hydrogen peroxide because it is an important performance indicator for a material to be applied in biosensing. The working principle for magnetic immobilization of the enzyme-functionalized NiNP, without the use of external magnetic sources, was demonstrated for glucose oxidase (GOx) as a model enzyme. XPS results enabled to identify the presence of GOx attached to the NiNP (GOx-NiNP) on Ni electrodes. Finally, glucose detection and quantification were evaluated with the newly developed GOx-NiNP/Ni biosensor by amperometry at different potentials, and control experiments at different electrode materials in the presence and absence of NiNP demonstrated their importance in the biosensor architecture.

18. Room temperature ferromagnetism and its correlation to ferroelectricity of manganese embedded in lead zirco-titanate

Authors: Bucur, IC; Apostol, NG; Abramiuc, LE; Tanase, LC; Tache, CA; Lungu, GA; Costescu, RM; Chirila, CF; Trupina, L; Pintilie, L; Teodorescu, CM

Published: JAN 1 2019, THIN SOLID FILMS, 669, DOI: 10.1016/j.tsf.2018.11.018

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.

19. Core-shell nanowire arrays based on ZnO and CuxO for water stable photocatalysts

Authors: Florica, C; Costas, A; Preda, N; Beregoi, M; Kuncser, A; Apostol, N; Popa, C; Socol, G; Diculescu, V; Enculescu, I

Published: NOV 21 2019, SCIENTIFIC REPORTS, 9, DOI: 10.1038/s41598-019-53873-0

Staggered gap radial heterojunctions based on ZnO-CuxO core-shell nanowires are used as water stable photocatalysts to harvest solar energy for pollutants removal. ZnO nanowires with a wurtzite crystalline structure and a band gap of approximately 3.3 eV are obtained by thermal oxidation in air. These are covered with an amorphous CuxO layer having a band gap of 1.74 eV and subsequently form core-shell heterojunctions. The electrical characterization of the ZnO pristine and ZnO-CuxO core-shell nanowires emphasizes the charge transfer phenomena at the junction and at the interface between the nanowires and water based solutions. The methylene blue degradation mechanism is discussed taking into consideration the dissolution of ZnO in water based solutions for ZnO nanowires and ZnO-CuxO core-shell nanowires with different shell thicknesses. An optimum thickness of the CuxO layer is used to obtain water stable photocatalysts, where the ZnO-CuxO radial heterojunction enhances the separation and transport of the photogenerated charge carriers when irradiating with UV-light, leading to swift pollutant degradation.

20. Efficient glucose dehydration to HMF onto Nb-BEA catalysts

Authors: Candu, N; El Fergani, M; Verziu, M; Cojocaru, B; Jurca, B; Apostol, N; Teodorescu, C; Parvulescu, VI; Coman, SM

Published: MAR 15 2019, CATALYSIS TODAY, 325, 116, DOI: 10.1016/j.cattod.2018.08.004

The one-pot production of HMF from glucose was investigated in pure hot water and biphasic water/methyli-sobutylketone (MIBK) solvent using mesoporous Nb(0.02 and 0.05 mol%)-Beta zeolites obtained by a post synthesis methodology. The mesoporous Nb-Beta zeolites present residual framework Al-acid sites, extra-framework isolated Nb(V) and Nb2O5 pore-encapsulated clusters in which Nb(V) O-H exhibit moderate strength Bronsted acidity. After optimization, the dehydration of glucose onto the Nb-modified Beta-zeolites occurred with a selectivity of 84.3% in HMF for a glucose conversion of 97.4%. This result has been obtained in a biphasic water/ MIBK solvent and in the presence of NaCl, at 180 degrees C, after 12 h.

21. Radial heterojunction based on single ZnO-CuxO core-shell nanowire for photodetector applications

Authors: Costas, A; Florica, C; Preda, N; Apostol, N; Kuncser, A; Nitescu, A; Enculescu, I

Published: APR 3 2019, SCIENTIFIC REPORTS, 9, DOI: 10.1038/s41598-019-42060-w

ZnO-CuxO core-shell radial heterojunction nanowire arrays were fabricated by a straightforward approach which combine two simple, cost effective and large-scale preparation methods: (i) thermal oxidation in air of a zinc foil for obtaining ZnO nanowire arrays and (ii) radio frequency magnetron sputtering for covering the surface of the ZnO nanowires with a CuxO thin film. The structural, compositional, morphological and optical properties of the high aspect ratio ZnO-CuxO core-shell nanowire arrays were investigated. Individual ZnO-CuxO core-shell nanowires were contacted with Pt electrodes by means of electron beam lithography technique, diode behaviour being demonstrated. Further it was found that these n-p radial heterojunction diodes based on single ZnO-CuxO nanowires exhibit a change in the current under UV light illumination and therefore behaving as photodetectors.

22. Palladium/palladium oxide coated electrospun fibers for wearable sweat pH-sensors

Authors: Diculescu, VC; Beregoi, M; Evanghelidis, A; Negrea, RF; Apostol, NG; Enculescu, I

Published: JUN 20 2019, SCIENTIFIC REPORTS, 9, DOI: 10.1038/s41598-019-45399-2

The work describes the development of a flexible, hydrogel embedded pH-sensor that can be integrated in inexpensive wearable and non-invasive devices at epidermal level for electrochemical quantification of H+ ions in sweat. Such a device can be useful for swift, real time diagnosis and for monitoring specific conditions. The sensors' working electrodes are flexible poly(methyl methacrylate) electrospun fibers coated with a thin gold layer and electrochemically functionalized with nanostructured palladium/palladium oxide. The response to H+ ions is investigated by cyclic voltammetry and electrochemical impedance spectroscopy while open circuit potential measurements show a sensitivity of aprox. -59 mV per pH unit. The modification of the sensing interface upon basic and acid treatment is characterized by scanning and transmission electron microscopy and the chemical composition by X-ray photoelectron spectroscopy. In order to demonstrate the functionality of the pH-sensor at epidermal level, as a wearable device, the palladium/palladium oxide working electrode and silver/silver chloride reference electrode are embedded within a pad of polyacrylamide hydrogel and measurements in artificial sweat over a broad pH range were performed. Sensitivity up to -28 mV/pH unit, response time below 30 s, temperature dependence of approx. 1 mV/degrees C as well as the minimum volume to which the sensor responses of 250 nanoliters were obtained for this device. The proposed configuration represents a viable alternative making use of low-cost and fast fabrication processes and materials.

23. Physical properties of the ferroelectric capacitors based on Al-doped HfO2 grown via Atomic Layer Deposition on Si

Authors: Vulpe, S; Nastase, F; Dragoman, M; Dinescu, A; Romanitan, C; Iftimie, S; Moldovan, A; Apostol, N

Published: JUL 31 2019, APPLIED SURFACE SCIENCE, 483, 333, DOI: 10.1016/j.apsusc.2019.03.166

Ferroelectric capacitors based on aluminium (Al) doped hafnium oxide (HfO2) thin films grown on silicon substrates were fabricated by Atomic Layer Deposition (ALD), taking into account two methods. The first one involved the growth of a binary oxide, in a laminar way, by alternating the ALD cycles of HfO2 and Al2O3, and the second, the two precursors were sequentially mixed on the surface. The composition and structure of deposited aluminium doped hafnium oxide (Al: HfO2) thin films have been studied using X-ray photoelectron spectroscopy (XPS) and grazing incidence X-ray diffraction (GIXRD). XPS measurements show the formation of opposite ferroelectric polarization areas. Via GIXRD, it was found that the Al: HfO2 films deposited on Si have a structure with polycrystalline domains. Recording and investigation of ferroelectric domains were performed by Piezoresponse Force Microscopy (PFM), while the electrical performances of obtained devices were analysed by capacitance-voltage (C-V) and current-voltage (I-V) characteristics. The PFM measurements show there is a mechanical non-zero response even outside the written area and for an appropriate value of the electrical stress the difference in phase between successive areas is saturated to a value close to 180 degrees. The atomic force microscopy (AFM) analyses indicate a very low value of roughness average, for all grown thin films, similar to 0.2 nm, for a thickness of similar to 7 nm. From C-V characteristics, the memory window was extracted and the calculated values were found to be 0.8 V for the device obtained by the first ALD method, and 0.44 V for the second one, respectively. Moreover, in the case of the device based on the ferroelectric layer grown by the second ALD method, the memory window extends over a much wider applied voltage domain, in the range (+/- 4 V; +/- 8 V), at a signal of 100 kHz.

24. Growth of Ag(111) on Si(111) with nearly flat band and abrupt interface

Authors: Bocirnea, AE; Costescu, RM; Apostol, NG; Teodorescu, CM

Published: APR 15 2019, APPLIED SURFACE SCIENCE, 473, 441, DOI: 10.1016/j.apsusc.2018.12.167

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.

25. Epitaxial growth of single-orientation high-quality MoS2 monolayers

Authors: Bana, H; Travaglia, E; Bignardi, L; Lacovig, P; Sanders, CE; Dendzik, M; Michiardi, M; Bianchi, M; Lizzit, D; Presel, F; De Angelis, D; Apostol, N; Das, PK; Fujii, J; Vobornik, I; Larciprete, R; Baraldi, A; Hofmann, P; Lizzit, S

Published: JUL 2018, 2D MATERIALS, 5, DOI: 10.1088/2053-1583/aabb74

We present a study on the growth and characterization of high-quality single-layer MoS2 with a single orientation, i.e. without the presence of mirror domains. This single orientation of the MoS2 layer is established by means of x-ray photoelectron diffraction. The high quality is evidenced by combining scanning tunneling microscopy with x-ray photoelectron spectroscopy measurements. Spin-and angle-resolved photoemission experiments performed on the sample revealed complete spin-polarization of the valence band states near the K and -K points of the Brillouin zone. These findings open up the possibility to exploit the spin and valley degrees of freedom for encoding and processing information in devices that are based on epitaxially grown materials.

26. The adsorption of silicon on an iridium surface ruling out silicene growth

Authors: Satta, M; Lacovig, P; Apostol, N; Dalmiglio, M; Orlando, F; Bignardi, L; Bana, H; Travaglia, E; Baraldi, A; Lizzit, S; Larciprete, R

Published: APR 21 2018, NANOSCALE, 10, 7094, DOI: 10.1039/c8nr00648b

The adsorption of Si atoms on a metal surface might proceed through complex surface processes, whose rate is determined differently by factors such as temperature, Si coverage, and metal cohesive energy. Among other transition metals, iridium is a special case since the Ir(111) surface was reported first, in addition to Ag(111), as being suitable for the epitaxy of silicene monolayers. In this study we followed the adsorption of Si on the Ir(111) surface via high resolution core level photoelectron spectroscopy, starting from the clean metal surface up to a coverage exceeding one monolayer, in a temperature range between 300 and 670 K. Density functional theory calculations were carried out in order to evaluate the stability of the different Si adsorption configurations as a function of the coverage. Results indicate that, at low coverage, the Si adatoms tend to occupy the hollow Ir sites, although a small fraction of them penetrates the first Ir layer. Si penetration of the Ir surface can take place if the energy gained upon Si adsorption is used to displace the Ir surface atoms, rather then being dissipated differently. At a Si coverage of similar to 1 monolayer, the Ir 4f spectrum indicates that not only the metal surface but also the layers underneath are perturbed. Our results point out that the Si/Ir(111) interface is unstable towards Si-Ir intermixing, in agreement with the silicide phase formation reported in the literature for the reverted interface.

27. Triggering surface ferroelectric order in Pb(Zr, Ti)O-3(001) by deposition of platinum

Authors: Bucur, IC; Tanase, LC; Abramiuc, LE; Lungu, GA; Chirila, C; Trupina, L; Apostol, NG; Costescu, RM; Negrea, RF; Pintilie, L; Teodorescu, CM

Published: FEB 28 2018, APPLIED SURFACE SCIENCE, 432, DOI: 10.1016/j.apsusc.2017.04.238

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.

28. Polarization Orientation in Lead Zirconate Titanate (001) Thin Films Driven by the Interface with the Substrate

Authors: Tanase, LC; Abramiuc, LE; Popescu, DG; Trandafir, AM; Apostol, NG; Bucur, IC; Hrib, L; Pintilie, L; Pasuk, I; Trupina, L; Teodorescu, CM

Published: SEP 11 2018, PHYSICAL REVIEW APPLIED, 10, DOI: 10.1103/PhysRevApplied.10.034020

We investigate the effect of the nature of the substrate and the bottom interface on the out-of-plane polarization orientation of ultrathin (10-nm) lead zirconate titanate (PZT) thin films of (001) orientation by photoelectron spectroscopy of samples without surface contamination. The substrate nature is varied between insulator (strontium titanate, STO) and semiconductor (Nb-doped STO, STON) and finally to a metal with a work function lower than that of PZT (strontium ruthenate, SRO). Outward polarization is obtained for PZT/STON(001) and inward polarization is obtained for PZT/STO(001) and PZT/SRO(001). Explanations are given for all these typical cases, the main elements being charge accumulation for compensation of the depolarization field, self-doping of PZT films, and the interface electric field driving the orientation of the polarization of the ferroelectric films. We find p-type self-doping is correlated with the inward polarization, and the driving field is formed between a negatively charged region with negatively ionized acceptors near the interface with the substrate and the p-type degenerate region with holes accumulated inside, toward the surface. This mechanism may be reversed under the assumption of n-type self-doping, positively ionized donors near the interface, and accumulated electrons toward the surface in the case of an interface with a substrate with a higher work function, being in line with recent data (PZT/Pt or BaTiO3/SRO).

29. Highly Efficient, Easily Recoverable, and Recyclable Re-SiO2-Fe3O4 Catalyst for the Fragmentation of Lignin

Authors: Tudorache, M; Opris, C; Cojocaru, B; Apostol, NG; Tirsoaga, A; Coman, SM; Parvulescu, VI; Duraki, B; Krumeich, F; van Bokhoven, JA

Published: AUG 2018, ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 6, 9618, DOI: 10.1021/acssuschemeng.7b04294

A series of Fe3O4@SiO2@Re catalysts were prepared by deposition of rhenium by means of the precipitation-deposition and impregnation procedures. Characterization of the catalysts confirmed that the deposition of silica protected the magnetite nanoparticles, resulting in a stable SiO(2)pFe(3)O(4) composite, which was not affected by the treatments during the further deposition of rhenium. Rhenium was silent in XRD over the range of concentrations, at which it was deposited. Furthermore, XPS detected rhenium, only in the impregnation series; this may confirm that dispersion was high. As expected, rhenium was not reduced to the metallic state and generated weakly acidic Bronsted-type centers as detected by NH3-TPD. H-2-TPD and chemisorption experiments demonstrate the capacity of these catalysts to chemisorb hydrogen. In line with these properties, rhenium catalyzed both C-C hydrogenolysis and C-O hydrolysis in successive steps. The performance of these catalysts was checked for a series of lignins of different origin and by means of different separation procedures. A very important finding is that these catalysts were highly stable and easy to recover.

30. High hexitols selectivity in cellulose hydrolytic hydrogenation over platinum (Pt) vs. ruthenium (Ru) catalysts supported on micro/mesoporous carbon

Authors: Lazaridis, PA; Karakoulia, SA; Teodorescu, C; Apostol, N; Macovei, D; Panteli, A; Delimitis, A; Coman, SM; Parvulescu, VI; Triantafyllidis, KS

Published: OCT 5 2017, APPLIED CATALYSIS B-ENVIRONMENTAL, 214, 14, DOI: 10.1016/j.apcatb.2017.05.031

The "one-pot" hydrolyltic hydrogenation of cellulose towards C2-C6 sugar alcohols has been recognized as one of the most promising biomass valorization routes for the production of high added-value chemicals. In this work, we studied the performance of Ru and Pt catalysts supported on micro/mesoporous activated carbon, in the hydrolytic hydrogenation of microcrystalline and ball-milled cellulose, in neat water, at 180 C and at relatively low hydrogen pressure of 2 MPa. The impact of metal loading (1-5 wt.%), metal reduction method (H2 at 350 C or NaBH4) and acidification (sulfonation) of the AC support on cellulose conversion and selectivity to the various products were systematically addressed. It was shown that Pt is significantly more selective towards hexitols (sorbitol and mannitol) compared to Ru, in glucose rich reaction media, such as those offered by the easily hydrolyzed ball-milled cellulose. For example, the 5wt%PtIAC-SO3H catalyst afforded hexitols yield of 69.5 wt.% (at 96.1% conversion) compared to 10.9 wt.% (at 95.2% wt.% conversion) obtained by the corresponding Ru catalyst, the latter being also selective towards glycerol and propane-1,2-diol (propylene glycol). A relatively moderate metal loading, such as in 3 wt.%Ru/AC-SO3H, was more favorable for hexitols production (44.5 wt.% yield, at 94.8 wt.% conversion) with Ru catalysts. These results were also verified by glucose hydrogenation experiments that were conducted at the same experimental conditions. Both Pt and Ru exhibited relatively high glucose hydrogenation activity towards hexitols, versus retro-aldol reactions that lead directly to smaller C2-C4 compounds, while the difference in the final product yields between the two metals was attributed to the higher hexitols hydrogenolysis (C C cleavage) reactivity of Ru. HRTEM data showed the formation of metallic crystalline Pt and Ru nanoparticles (<= 4 nm, depending on loading) as well as of amorphous oxygen-rich M(O)(x)(delta+) phases, which were also confirmed by the XPS data. The presence of these phases which may be a source of acidity, as well as the bacisity of the parent AC used in this study, were mainly responsible for inducing isomerization, retro-aldol and dehydration reactions leading eventually to increased glycerol and propylene glycol selectivity, as was observed for both low-metal catalysts, i.e. 1 wt.% Pt or Ru/AC. (C) 2017 Elsevier B.V. All rights reserved.

31. Low-energy electron diffraction from ferroelectric surfaces: Dead layers and surface dipoles in clean Pb(Zr, Ti)O-3(001)

Authors: Teodorescu, CM; Pintilie, L; Apostol, NG; Costescu, RM; Lungu, GA; Hrib, L; Trupina, L; Tanase, LC; Bucur, IC; Bocirnea, AE

Published: SEP 19 2017, PHYSICAL REVIEW B, 96, 115438, DOI: 10.1103/PhysRevB.96.115438

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.

32. Long-range magnetic interaction in MnxGe1-x: structural, spectromicroscopic and magnetic investigations

Authors: Tanase, LC; Lungu, GA; Abramiuc, LE; Bucur, IC; Apostol, NG; Costescu, RM; Tache, CA; Macovei, D; Barinov, A; Teodorescu, CM

Published: MAR 2017, JOURNAL OF MATERIALS SCIENCE, 52, DOI: 10.1007/s10853-016-0618-9

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.

33. Polarization landscape effects in soft X-ray-induced surface chemical decomposition of lead zirco-titanate, evidenced by photoelectron spectromicroscopy

Authors: Abramiuc, LE; Tanase, LC; Barinov, A; Apostol, NG; Chirila, C; Trupina, L; Pintilie, L; Teodorescu, CM

Published: AUG 21 2017, NANOSCALE, 9, 11067, DOI: 10.1039/c7nr03003g

The stability of thin films of lead zirco-titanate (PZT) under intense soft X-ray beams is investigated by time-resolved photoelectron spectromicroscopy with a lateral resolution below 1 micrometer. Surface dissociation is observed when samples are irradiated with intense (5 x 10(23) photons per s per m(2)) soft X-rays, with promotion of reduced lead on the surface. On areas exhibiting outwards polarization (P(+)), the reduced lead is formed at the expense of P(+)-PZT. On areas presenting co-existing P(+) states with areas without out-of-plane polarization (P-(0)), the reduced lead is formed at the expense of the P-(0)-PZT component, while the P(+)-PZT remains constant. The main dissociation mechanism was found to be triggered by 'hot' electrons in the conduction band, with energies exceeding the surface dissociation energies. Dissociation occurs basically when the electron affinity is larger than the dissociation energy of PbO (for P(+) areas) or PbO- (for P-(0) areas). Such mechanisms may be adapted for dissociation of other molecules on surfaces of ferroelectric thin films or for quantifying the stability of ferroelectric surfaces interacting with other radiation, with applications in the fields of photocatalysis or photovoltaic devices.

34. Aging phenomena and wettability control of plasma deposited carbon nanowall layers

Authors: Vizireanu, S; Ionita, MD; Ionita, ER; Stoica, SD; Teodorescu, CM; Husanu, MA; Apostol, NG; Baibarac, M; Panaitescu, D; Dinescu, G

Published: NOV 2017, PLASMA PROCESSES AND POLYMERS, 14, DOI: 10.1002/ppap.201700023

This paper reports on the aging of carbon nanowalls (CNW) and modification of their wettability by the storage time, growth conditions, and post-fabrication plasma treatments. The as-deposited CNW initially exhibit marked hydrophilic behavior (fresh CNW), but within a few days they become highly hydrophobic (aged CNW). Their final hydrophobicity is closely related to their topography which is controlled by the deposition parameters. In addition, subsequent fluorinated plasma treatments result in super-hydrophobic CNW layers, irrespective of the hydrophilic or hydrophobic character of the pre-treated samples. To explain this, we show that the CNW edges contain many defects initially, but such defects become passivated in time. As a result, the surfaces become highly hydrophobic after aging or fluorination, having inert stable terminations.

35. Band bending at magnetic Ni/Ge(001) interface investigated by X-ray photoelectron spectroscopy

Authors: Bocirnea, AE; Tanase, LC; Costescu, RM; Apostol, NG; Teodorescu, CM

Published: DEC 1 2017, APPLIED SURFACE SCIENCE, 424, 274, DOI: 10.1016/j.apsusc.2017.04.168

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.

36. Oriented Au nanoplatelets on graphene promote Suzuki-Miyaura coupling with higher efficiency and different reactivity pattern than supported palladium

Authors: Candu, N; Dhakshinamoorthy, A; Apostol, N; Teodorescu, C; Corma, A; Garcia, H; Parvulescu, VI

Published: AUG 2017, JOURNAL OF CATALYSIS, 352, 66, DOI: 10.1016/j.jcat.2017.04.034

Facet 111 oriented Au nanoplatelets (20-40 nm wide, 3-4 nm height) grafted on graphene ((Au) over bar /fl-G) are about three orders of magnitude more efficient than Pd nanoparticles supported on graphene to promote Suzuki-Miyaura coupling. In contrast to Pd catalysis, it is shown here that the product yields in Suzuki-Miyaura coupling catalyzed by Au nanoparticles follow the order chlorobenzene > bromobenzene > iodobenzene. Kinetic studies show that this reactivity order is the result of the poisoning effect of halides for Au that is much higher for I- than Br- and much higher than for Cl-, due to adsorption. This strong iodide adsorption leading to Au catalyst deactivation was predicted by DFT calculations of Au clusters. (Au) over bar /fl-G are about one order of magnitude more efficient than small Au nanoparticles (4-6 nm) obtained by the polyol method supported on graphene. Our results can have impact in organic synthesis, showing the advantage of (Au) over bar /fl-G as catalyst for Suzuki-Miyaura couplings. (C) 2017 Elsevier Inc. All rights reserved.

37. Ferroelectric triggering of carbon monoxide adsorption on lead zirco-titanate (001) surfaces

Authors: Tanase, LC; Apostol, NG; Abramiuc, LE; Tache, CA; Hrib, L; Trupina, L; Pintilie, L; Teodorescu, CM

Published: OCT 14 2016, SCIENTIFIC REPORTS, 6, DOI: 10.1038/srep35301

Atomically clean lead zirco-titanate PbZr0.2Ti0.8O3 (001) layers exhibit a polarization oriented inwards P(-), visible by a band bending of all core levels towards lower binding energies, whereas as introduced layers exhibit P(+) polarization under air or in ultrahigh vacuum. The magnitude of the inwards polarization decreases when the temperature is increased at 700 K. CO adsorption on P(-) polarized surfaces saturates at about one quarter of a monolayer of carbon, and occurs in both molecular (oxidized) and dissociated (reduced) states of carbon, with a large majority of reduced state. The sticking of CO on the surface in ultrahigh vacuum is found to be directly related to the P(-) polarization state of the surface. A simple electrostatic mechanism is proposed to explain these dissociation processes and the sticking of carbon on P(-) polarized areas. Carbon desorbs also when the surface is irradiated with soft X-rays. Carbon desorption when the polarization is lost proceeds most probably in form of CO2. Upon carbon desorption cycles, the ferroelectric surface is depleted in oxygen and at some point reverses its polarization, owing to electrons provided by oxygen vacancies which are able to screen the depolarization field produced by positive fixed charges at the surface.

38. Non-interacting, sp(2) carbon on a ferroelectric lead zirco-titanate: towards graphene synthesis on ferroelectrics in ultrahigh vacuum

Authors: Apostol, NG; Lungu, GA; Bucur, IC; Tache, CA; Hrib, L; Pintilie, L; Macovei, D; Teodorescu, CM

Published: 2016, RSC ADVANCES, 6, DOI: 10.1039/c6ra12910b

Carbon layers grown on lead zirco-titanate (PZT) weakly interact with the substrate and exhibit a nearly two dimensional character, up to a carbon surface density approaching that of graphene. The first feature is evidenced by X-ray photoelectron spectroscopy, and the second by angle resolved near-edge-absorption spectroscopy (NEXAFS). The binding energies and lineshape parameters of C 1s are similar to that of graphene. The dichroism of C K-edge NEXAFS shows the prevalence of in-plane sp(2) bonds for layers whose effective coverage is below the graphene surface density. The polarization state of the substrate, oriented outwards, is preserved upon carbon deposition. The surface Pb content is strongly affected by the carbon ad-layers.

39. Self-Assembly of Graphene Nanoblisters Sealed to a Bare Metal Surface

Authors: Larciprete, R; Colonna, S; Ronci, F; Flammini, R; Lacovig, P; Apostol, N; Politano, A; Feulner, P; Menzel, D; Lizzit, S

Published: MAR 2016, NANO LETTERS, 16, 1817, DOI: 10.1021/acs.nanolett.5b04849

The possibility to intercalate noble gas atoms below epitaxial graphene monolayers coupled with the instability at high temperature of graphene on the surface of certain metals has been exploited to produce Ar-filled graphene nanosized blisters evenly distributed on the bare Ni(111) surface. We have followed in real time the self-assembling of the nanoblisters during the thermal annealing of the Gr/Ni(111) interface loaded with Ar and characterized their morphology and structure at the atomic scale. The nanoblisters contain Ar aggregates compressed at high pressure arranged below the graphene monolayer skin that is decoupled from the Ni substrate and sealed only at the periphery through stable C-Ni bonds. Their in-plane truncated triangular shapes are driven by the crystallographic directions of the Ni surface. The nonuniform strain revealed along the blister profile is explained by the inhomogeneous expansion of the flexible graphene lattice that adjusts to envelop the Ar atom stacks.

40. Unveiling the Mechanisms Leading to H-2 Production Promoted by Water Decomposition on Epitaxial Graphene at Room Temperature

Authors: Politano, A; Cattelan, M; Boukhvalov, DW; Campi, D; Cupolillo, A; Agnoli, S; Apostol, NG; Lacovig, P; Lizzit, S; Farias, D; Chiarello, G; Granozzi, G; Larcipretev, R

Published: APR 2016, ACS NANO, 10, 4549, DOI: 10.1021/acsnano.6b00554

By means of a combination of surface-science spectroscopies and theory, we investigate the mechanisms ruling the catalytic role of epitaxial graphene (Gr) grown on transition-metal substrates for the production of hydrogen from water. Water decomposition at the Gr/metal interface at room temperature provides a hydrogenated Gr sheet, which is buckled and decoupled from the metal substrate. We evaluate the performance of Gr/metal interface as a hydrogen storage medium, with a storage density in the Gr sheet comparable with state-of-the-art materials (1.42 wt %). Moreover, thermal programmed reaction experiments show that molecular hydrogen can be released upon heating the water-exposed Gr/metal interface above 400 K. The Gr hydro/dehydrogenation process might be exploited for an effective and eco-friendly device to produce (and store) hydrogen from water, i.e., starting from an almost unlimited source.

41. Study of formation of LiCoO2 using a modified Pechini aqueous sol-gel process

Authors: Predoana, L; Jitianu, A; Voicescu, M; Apostol, NG; Zaharescu, M

Published: MAY 2015, JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, 74, 418, DOI: 10.1007/s10971-014-3611-2

In the present study the formation of lithium cobaltite using a modified Pechini aqueous sol-gel process was investigated. The gelling processes in the lithium-cobalt-citric acid system in 1.1:1:1 molar ratio was performed at 80 A degrees C using aqueous solutions of 0.25 mol/dm(3) of Co(NO3)(2)center dot 6H(2)O with Li(NO3)center dot 6H(2)O or Co(CH3COO)(2)center dot 6H(2)O with Li(CH3COO)center dot 2H(2)O, respectively. The study of the mechanism of gelling of transition metal ion Co(II) in aqueous medium in the presence of lithium ions and citric acid as chelating agents was approached using mainly UV-Vis and FTIR spectroscopic methods. The UV-Vis spectroscopy indicated that the Co(II) ions are in a tetragonal distorted geometry characteristic to a D-4h group symmetry in the solutions in the early steps of the gels formation. After gelling at 80 A degrees C it was observed that the symmetry of the Co(II) ions becomes octahedral (O-h). From the FTIR spectra based on the frequency separation between the antisymmetric stretching nu(as)(COO-) and symmetric stretching nu(sym)(COO-) vibrations, it was identified that the carboxylic groups are bond as a bridging ligands. Using X-ray photoelectron spectroscopy it was identified that the cobalt is present in both final gels as Co(II) ions and the citrate ions are covalently bonded to the cobalt ions. The thermogravimetric/differential thermal analysis showed the thermal stability of the studied gels is higher in the low temperature range for the gels prepared using acetates. Based on the thermal analysis the Li-Co-CA gels were calcinated at 700 A degrees C for 6 h and for each gel a monophasic LiCoO2 was obtained.

42. Band bending at copper and gold interfaces with ferroelectric Pb(Zr,Ti)O-3 investigated by photoelectron spectroscopy

Authors: Apostol, NG; Stoflea, LE; Tanase, LC; Bucur, IC; Chirila, C; Negrea, RF; Teodorescu, CM

Published: NOV 1 2015, APPLIED SURFACE SCIENCE, 354, 468, DOI: 10.1016/j.apsusc.2015.02.167

Interfaces formed by gold and copper on single crystal layers of (0 0 1) PbZr0.2Ti0.8O3 (PZT) produced by pulsed laser deposition and exhibiting outwards polarization are analyzed by X-ray photoelectron spectroscopy. The stoichiometry of the layers reproduces reasonably that of the PZT target. The band bending occurring at the interface between PZT and the metals is investigated by analyzing the core level shifts as function on the metal deposition. It is found that for Au/PZT(0 0 1) the gold layer is not continuous and the observed band bendings can be attributed to a Schottky mechanism, whereas for Cu/PZT(0 0 1) the copper layer is continuous; in this latter case, the observed band bendings towards higher energies (lower binding energies) can be attributed to a concomitant bending due to the Schottky effect together with the disappearance of the initial bending due to the outwards polarization of the samples. Metal Pb is observed to segregate only in the case of Cu/PZT(0 0 1), therefore the surface self-reduction might also be connected to the presence of a metal with lower work function, which for larger coverage forms a continuous metal layer, able to provide electrons to the surface. High resolution transmission electron spectroscopy yielded the disappearance of the tetragonal distortion in the case of Cu/PZT(0 0 1), in line with the assumption of disappearance of the polarization-induced band bending. (C) 2015 Elsevier B.V. All rights reserved.

43. Polarization induced self-doping in epitaxial Pb(Zr0.20Ti0.80)O-3 thin films

Authors: Pintilie, L; Ghica, C; Teodorescu, CM; Pintilie, I; Chirila, C; Pasuk, I; Trupina, L; Hrib, L; Boni, AG; Apostol, NG; Abramiuc, LE; Negrea, R; Stefan, M; Ghica, D

Published: OCT 8 2015, SCIENTIFIC REPORTS, 5, DOI: 10.1038/srep14974

The compensation of the depolarization field in ferroelectric layers requires the presence of a suitable amount of charges able to follow any variation of the ferroelectric polarization. These can be free carriers or charged defects located in the ferroelectric material or free carriers coming from the electrodes. Here we show that a self-doping phenomenon occurs in epitaxial, tetragonal ferroelectric films of Pb(Zr0.2Ti0.8)O-3, consisting in generation of point defects (vacancies) acting as donors/acceptors. These are introducing free carriers that partly compensate the depolarization field occurring in the film. It is found that the concentration of the free carriers introduced by selfdoping increases with decreasing the thickness of the ferroelectric layer, reaching values of the order of 10(26) m(-3) for 10 nm thick films. One the other hand, microscopic investigations show that, for thicknesses higher than 50 nm, the 2O/(Ti+Zr+Pb) atomic ratio increases with the thickness of the layers. These results suggest that the ratio between the oxygen and cation vacancies varies with the thickness of the layer in such a way that the net free carrier density is sufficient to efficiently compensate the depolarization field and to preserve the outward direction of the polarization.

44. Photoelectron spectroscopy and spectro-microscopy of Pb(Zr,Ti)O-3 (111) thin layers: Imaging ferroelectric domains with binding energy contrast

Authors: Husanu, MA; Popescu, DG; Tache, CA; Apostol, NG; Barinov, A; Lizzit, S; Lacovig, P; Teodorescu, CM

Published: OCT 15 2015, APPLIED SURFACE SCIENCE, 352, 81, DOI: 10.1016/j.apsusc.2015.01.153

The ability of photoelectron spectro-microscopy with sub-micrometer lateral resolution to identify ferroelectric domains by analysis of surface band bendings is demonstrated on lead zirco-titanate PZT(1 1 1) thin films grown by pulsed laser deposition. Conventional synchrotron radiation X-ray photoelectron spectroscopy allowed one to derive the surface composition of the sample and evidenced shifts toward higher binding energy when the sample is subject to intense soft X-ray beam. A basic model is developed which supposes that photogenerated carriers reduce the depolarization field, yielding a lower torque applied to the ferroelectric polarization. As a consequence, the out-of-plane component of the polarization increases. Domain migration during irradiation with soft X-ray is inferred from the relative amplitude of the components with different binding energy. When the flux density of soft X-ray is on the order of 1011 photons/(s mu m(2)), metal Pb clusters are formed at the surface on areas with the out-of-plane component of the polarization pointing outwards only. (C) 2015 Elsevier B.V. All rights reserved.

45. Polarization-Control of the Potential Barrier at the Electrode Interfaces in Epitaxial Ferroelectric Thin Films

Authors: Pintilie, I; Teodorescu, CM; Ghica, C; Chirila, C; Boni, AG; Hrib, L; Pasuk, I; Negrea, R; Apostol, N; Pintilie, L

Published: FEB 26 2014, ACS APPLIED MATERIALS & INTERFACES, 6, 2939, DOI: 10.1021/am405508k

Electrode interface is a key element in controlling the macroscopic electrical properties of the ferroelectric capacitors based on thin films. In the case of epitaxial ferroelectrics, the electrode interface is essential in controlling the leakage current and the polarization switching, two important elements in the read/write processes of nonvolatile memories. However, the relation between the polarization bound charges and the electronic properties of the electrode interfaces is not yet well understood. Here we show that polarization charges are controlling the height of the potential barriers at the electrode interfaces in the case of Pb(Zr,Ti)O-3 and BaTiO3 epitaxial films. The results suggest that the height is set to a value allowing rapid compensation of the depolarization field during the polarization switching, being almost independent of the metals used for electrodes. This general behavior open a new perspective in engineering interface properties and designing new devices based on epitaxial ferroelectrics.

46. Selective adsorption of contaminants on Pb(Zr,Ti)O-3 surfaces shown by X-ray photoelectron spectroscopy

Authors: Stoflea, LE; Apostol, NG; Trupina, L; Teodorescu, CM

Published: 2014, JOURNAL OF MATERIALS CHEMISTRY A, 2, 14392, DOI: 10.1039/c4ta02660h

X-ray photoelectron spectroscopy (XPS) analyses of lead zirco-titanate Pb(Zr,Ti)O-3(001) single crystal thin layers as a function of the time spent between sample preparation by pulsed laser deposition and introduction in to a ultrahigh vacuum revealed the fact that freshly prepared samples showed a shift of the C 1s towards a higher binding energy, together with shifts of core levels originating from the substrate (particularly Ti 2p and O 1s) towards a lower binding energy. This behaviour is explained by considering that the molecules of contaminants (fatty acids, alcohols, esters) are adsorbed preferentially on areas exhibiting outwards polarization P(+). Thus, photoelectrons originating from contaminants will have larger binding energies because of the charge state of the P(+) areas, whereas the substrate XPS signals from these P(+) areas are attenuated by the contaminants, with the consequence of a prevalence of XPS substrate signals originating from the P(-) areas, shifted towards lower binding energies. Piezoresponse force microscopy confirmed the assumptions derived from XPS results and suggests the existence of an interplay between the adsorption of contaminants and the surface polarization state.

47. Evidence of A-B site cooperation in the EuFeO3 perovskite from Eu-151 and Fe-57 Mossbauer spectroscopy, EXAFS, and toluene catalytic oxidation

Authors: Florea, M; Alifanti, M; Kuncser, V; Macovei, D; Apostol, N; Granger, P; Parvulescu, VI

Published: JUL 2014, JOURNAL OF CATALYSIS, 316, 140, DOI: 10.1016/j.jcat.2014.04.016

EuFeO3 perovskite was considered as a case study of the cooperative effects of the rare earth and transition metal elements in the total catalytic oxidation of aromatic hydrocarbons. For this purpose, a EuFeO3 perovskite was prepared using the citrate route. Extensive characterization was performed via ex situ and in situ methods. EXAFS revealed that oxygen vacancies are formed in the nearest neighborhood of Fe and next-nearest neighborhood of Eu. Combining Eu-151 and Fe-57 Mossbauer experiments also suggested local oxygen defects in the proximity of the Eu cations during the reaction, as well as cooperative electron delocalization effects between Eu and Fe. XPS has shown the +3 oxidation state of both Eu and Fe cations and the relatively strong ionicity of the Fe-O chemical bonds, as suggested by the weakened 2p(3/2) satellite in the Fe2p spectrum. A systematic change of this satellite with the A cation in AFeO(3) perovskites was also discussed. The thermal treatment of the catalyst at 623 K, in air or toluene, was accompanied by a partial reduction of Fe and a partial oxidation of Eu, respectively. The interaction between the two elements appeared to be influenced mainly by the temperature and only slightly by the sample environment during further treatments. Catalytic oxidation of toluene on this perovskite led only to the production of carbon dioxide and water with no side-product formation from partial oxidation reactions. All the characterization and catalytic results preferably agree with a Volkenstein mechanism. (C) 2014 Elsevier Inc. All rights reserved.

48. Schottky barrier versus surface ferroelectric depolarization at Cu/Pb(Zr, Ti)O-3 interfaces

Authors: Stoflea, LE; Apostol, NG; Chirila, C; Trupina, L; Negrea, R; Pintilie, L; Teodorescu, CM

Published: MAY 2014, JOURNAL OF MATERIALS SCIENCE, 49, 3351, DOI: 10.1007/s10853-014-8041-6

The band bending at Cu/PZT(001) interfaces is investigated by X-ray photoelectron spectroscopy (XPS) for a PZT(001) layer which exhibits initial outwards ferroelectric polarization. Two competitive processes are identified: (a) formation of the Schottky barrier between the ferroelectric and unconnected Cu islands, and (b) coalescence of the Cu islands, realisation of an electrical contact to the ground of the system, inducing the apparent loss of the component of the ferroelectric polarization perpendicular to the sample surface, at least as it manifests in band bending. Three mechanisms are proposed to explain this loss of band bending when a full metal layer connected to ground is formed on the surface: (i) over-compensation of depolarization field in the sub-surface region, (ii) formation of domains with in-plane orientation of the polarization vector and (iii) loss of polarization in the near-surface layers of the ferroelectric due to electrons provided by the metal. These result in a non-monotonous variation of binding energies with the amount of Cu deposited. High resolution transmission electron microscopy and piezoresponse force microscopy confirmed these hypotheses. The XPS data allowed also to derive the surface PZT composition, its evolution with the deposition of copper and the formation of surface compounds.

49. Structural, down- and phase selective up-conversion emission properties of mixed valent Pr doped into oxides with tetravalent cations

Authors: Tiseanu, C; Parvulescu, V; Avram, D; Cojocaru, B; Apostol, N; Vela-Gonzalez, AV; Sanchez-Dominguez, M

Published: 2014, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 16, 5802, DOI: 10.1039/c3cp54899f

We report on structure-property relationships in Pr-doped CeO2 and ZrO2 using X-ray diffraction (XRD), Raman, UV to Vis Diffuse Reflectance (DR-UV/Vis), X-ray Photoelectron (XPS), and luminescence (PL) spectroscopies. Both 3+ and 4+ valence states of Pr are evidenced, irrespective of the host and calcination temperature, T (T = 500 and 1000 degrees C) with consequences on absorption, surface, vibrational and luminescence properties. Only zirconia represents a suitable host for Pr3+ luminescence. The distinct trivalent Pr centers and their excitation mechanism are identified in relation to the tetragonal and monoclinic phases of ZrO2. A near-infrared to visible up-conversion (UPC) emission of Pr3+ is observed upon excitation at 959 nm which occurs, most probably, via a two-photon excited state process. By using a multi-wavelength, time-gated excitation, the UPC process is established as phase selective, i.e. only Pr3+ located in the monoclinic sites of the mixed phase, monoclinic and tetragonal ZrO2 (T = 1000 degrees C) contribute to the UPC emission. We believe that, besides the local symmetry, a key role in phase selective UPC is played by the presence of Pr3+ low-lying 4f 5d levels. To the best of our knowledge, this is the first report of phase selective up-conversion emission in a lanthanide doped multi-phase host.

50. Band Bending at Ferroelectric Surfaces and Interfaces Investigated by X-ray Photoelectron Spectroscopy

Authors: Apostol, NG

Published: 2014, TIM 2013 PHYSICS CONFERENCE, 1634, 88, DOI: 10.1063/1.4903018

This work reports on the use of X-ray photoelectron spectroscopy to quantify band bending at ferroelectric free surfaces and at their interfaces with metals. Surfaces exhibiting out-of-plane ferroelectric polarization are characterized by a band bending, due to the formation of a dipole layer at the surface, composed by the uncompensated polarization charges (due to ionic displacement) and to the depolarization charge sheet of opposite sign, composed by mobile charge carriers, which migrate near surface, owing to the depolarization electric field. To this surface band bending due to out-of-plane polarization states, metal-semiconductor Schottky barriers must be considered additionally when ferroelectrics are covered by metal layers. It is found that the net band bending is not always an algebraic sum of the two effects discussed above, since sometimes the metal is able to provide additional charge carriers, which are able to fully compensate the surface charge of the ferroelectric, up to the vanishing of the ferroelectric band bending. The two cases which will be discussed in more detail are Au and Cu deposited by molecular beam epitaxy on PbZr0.2Ti0.8O3(001) single crystal thin layers, prepared by pulsed laser deposition. Gold forms unconnected nanoparticles, and their effect on the band bending is the apparition of a Schottky band bending additional to the band bending due to the out-of-plane polarization. Copper, starting with a given thickness, forms continuous metal layers connected to the ground of the system, and provide electrons in sufficient quantity to compensate the band bending due to the out-of-plane polarization.

51. Epitaxial Growth of a Single-Domain Hexagonal Boron Nitride Mono layer

Authors: Orlando, F; Lacovig, P; Omiciuolo, L; Apostol, NG; Larciprete, R; Baraldi, A; Lizzit, S

Published: DEC 2014, ACS NANO, 8, 12070, DOI: 10.1021/nn5058968

We investigate the structure of epitaxially grown hexagonal boron nitride (h-BN) on Ir(111) by chemical vapor deposition of borazine. Using photoelectron diffraction spectroscopy, we unambiguously show that a single-domain h-BN monolayer can be synthesized by a cyclic dose of high-purity borazine onto the metal substrate at room temperature followed by annealing at T = 1270 K, this method giving rise to a diffraction pattern with 3-fold symmetry. In contrast, high-temperature borazine deposition (T = 1070 K) results in a h-BN monolayer formed by domains with opposite orientation and characterized by a 6-fold symmetric diffraction pattern. We identify the thermal energy and the binding energy difference between fcc and hcp seeds as key parameters in controlling the alignment of the growing h-BN clusters during the first stage of the growth, and we further propose structural models for the h-BN monolayer on the Ir(111) surface.

52. Surface Reactivity and Magnetism at Metal-Semiconductor Interfaces

Authors: Apostol, NG; Teodorescu, CM

Published: 2014, SIZE EFFECTS IN NANOSTRUCTURES: BASICS AND APPLICATIONS, 205, 292, DOI: 10.1007/978-3-662-44479-5_8

The interplay between magnetic properties and structure and interdifussion at interfaces is analyzed mainly by surface science methods and by core level spectroscopies (based on X-ray absorption XAS and X-ray photoelectron spectroscopy XPS) on model systems implying deposition of magnetic metals (Fe, Co, Sm) on usual semiconductors (Si, GaAs, InAs). The Chapters begins with a review of the core level spectroscopies and of derived techniques, such as X-ray photoelectron diffraction (XPD) from XPS and X-ray magnetic circular dichroism (XMCD) from XAS, together with a brief description of other surface science techniques employed, such as low energy electron diffraction (LEED), reflection high energy electron diffraction (RHEED), magneto-optical Kerr effect (MOKE), and with some basics of the molecular beam epitaxy (MBE) method. The examples are organized in pairs, namely one analyzes comparatively (i) interfaces formed by Fe or by Sm on Si(001), (ii) by Fe on GaAs(001) and on InAs(001), (iii) and by Co on bare GaAs(011) and on GaAs(011) passivated with Sb, in order to outline how small changes of the nature of the metal deposited, of the substrate (though identical from the chemical point of view) and of its initial state may result in strong deviations concerning both the quality of structures obtained and their magnetic properties. For instance, it is shown that Sb/Si(001) yields better properties than Fe/Si(001), Fe/InAs(001) exhibits lower reactivity and enhanced Fe magnetic moments than Fe/GaAs(001), and that passivation with antimony of GaAs(011) substrates yields to a reduced As out-diffusion into the metal layer, yielding lower tetragonal distortion and enhanced Co magnetic moments.

53. Band bending at free Pb(Zr,Ti)O-3 surfaces analyzed spectroscopy by X-ray photoelectron

Authors: Apostol, NG; Stoflea, LE; Lungu, GA; Tache, CA; Popescu, DG; Pintilie, L; Teodorescu, CM

Published: NOV 20 2013, MATERIALS SCIENCE AND ENGINEERING B-ADVANCED FUNCTIONAL SOLID-STATE MATERIALS, 178, DOI: 10.1016/j.mseb.2013.02.007

This paper analyses in detail the core levels evolution of Pb(Zr,Ti)O-3, i.e. Pb 4f, Zr 3d, Ti 2p, O 1s in various conditions: absolutely freshly prepared sample, sample stored under air, and the effects of in vacuum annealing. The aim of the study is to quantify separately the chemical reactivity at the surface and the band bending effects due to the ferroelectric polarization. It is found that freshly prepared samples present mostly inwards (down arrow) polarization. This phenomenon is mostly revealed by the Ti 2p and O 1s spectra, manifested as a distinct component with 1.8 eV lower binding energy in the O 1s binding energy and by 1.1 eV in the Ti 2p binding energy. Sample aging under air suppresses the inwards polarization, and most signal comes from surfaces not presenting ferroelectric permanent polarization perpendicular to the sample surface. This process conducts also to the formation of Pb(CO3)(2) on the surface. Annealing to temperatures up to 400 degrees C stabilizes a surface composed by a main part of surface without polarization perpendicular to the surface, and with some areas presenting outwards (up arrow) polarization. These areas have, most probably, different terminations, the polarized area being (Ti,Zr)O-2 terminated. (C) 2013 Elsevier B.V. All rights reserved.

54. Band bending in Au/Pb(Zr,Ti)O-3 investigated by X-ray photoelectron spectroscopy: Dependence on the initial state of the film

Authors: Apostol, NG; Stoflea, LE; Lungu, GA; Tanase, LC; Chirila, C; Frunza, L; Pintilie, L; Teodorescu, CM

Published: OCT 31 2013, THIN SOLID FILMS, 545, DOI: 10.1016/j.tsf.2013.04.092

This work presents a systematic investigation by X-ray photoelectron spectroscopy of the mechanisms of interface formation and band bending for Au/Pb(Zr,Ti)O-3 (PZT) layers grown on SrTiO3(001) with a SrRuO3 buffer layer, as function on the initial state of the PZT surface. After isolating the chemical effects, such as the formation of metal Pb at some surfaces, the evolution of the core levels with Au deposition allows one to simultaneously investigate the Schottky barrier formation and the built-in potential effects (charging induced by the static ferroelectric polarization). Areas of the sample with outwards P(+) and no polarization perpendicular to the surface P-(0) are identified for all samples. Only the freshly prepared sample exhibited inward polarization areas P(-). The built-in potential is on the order of 0.9 eV, while the Schottky band bending ranges from 0.2 to 0.6 eV towards lower absolute energies, therefore indicating that the work function of PZT exceeds that of Au deposited. We report also a chemically differentiate value of the built-in potential, manifested by a preferential distribution of the charge accumulated at the surface on Ti and O atoms. The O 1s and Ti 2p core levels manifest quite strong variations with the Au thickness for freshly prepared samples, resulting in shifts on the order of 2 eV towards lower binding energies. Au deposited on areas with an outward polarization is positively charged by the same potential as atoms from the PZT film (0.8-0.9 eV), whereas Au deposited on areas with an inward polarization forms a continuous grounded layer, which progressively pumps the accumulated charge and removes the polarization of these areas. (C) 2013 Elsevier B. V. All rights reserved.

55. Charge transfer and band bending at Au/Pb(Zr0.2Ti0.8)O-3 interfaces investigated by photoelectron spectroscopy

Authors: Apostol, NG; Stoflea, LE; Lungu, GA; Chirila, C; Trupina, L; Negrea, RF; Ghica, C; Pintilie, L; Teodorescu, CM

Published: MAY 15 2013, APPLIED SURFACE SCIENCE, 273, DOI: 10.1016/j.apsusc.2013.02.056

The growth of gold layers on Pb(Zr,Ti)O-3 (PZT) deposited on SrTiO3 is investigated by X-ray photoelectron spectroscopy in the Au thickness range 2-100 angstrom. Two phases are identified, with compositions close to nominal PZT. The 'standard' phase is represented by all binding energies (Pb 4f, Ti 2p, Zr 3d, O 1s) sensibly equal to the nominal values for PZT, whereas the 'charged' phase exhibits all core levels are shifted by similar to 1 eV toward higher binding energies. By taking into account also scanning probe microscopy images together with recent photoemission results, the 'charged' phase belongs to P(+) regions of PZT, whereas the 'normal' phase corresponds to regions with no net ferroelectric polarization perpendicular to the surface. Au deposition proceeds in a band bending of Phi(PZT) - Phi(Au) similar to 0.4-0.5 eV for both phases, identified as similar shifts toward higher binding energies of all Pb, Ti, Zr, O core levels with Au deposition. The Au 4f core level exhibits also an unusually low binding energy component 1 eV below the 'nominal' Au 4f binding energy position (metal Au). This implies the existence of negatively charged gold, or electron transfer from PZT to Au, although the 'normal' PZT phase have a higher work function, as it is derived from the band bending. Most probably this charge transfer occurs toward Au nanoparticles, which have even higher ionization energies. High resolution transmission electron microscopy evidenced the formation of such isolated nanoparticles. (C) 2013 Elsevier B.V. All rights reserved.

56. Co environment and magnetic defects in anatase CoxTi1-O-x(2) nanopowders

Authors: Grecu, MN; Macovei, D; Ghica, D; Logofatu, C; Valsan, S; Apostol, NG; Lungu, GA; Negrea, RF; Piticescu, RR

Published: APR 22 2013, APPLIED PHYSICS LETTERS, 102, 161909, DOI: 10.1063/1.4802819

Cobalt environment and magnetic defects nature in hydrothermal synthesized anatase CoxTi1-xO2 nanopowders (0 <= x <= 0.1) are investigated by x-ray diffraction and a variety of spectroscopic techniques. One shows that cobalt is partially inserted in the anatase lattice, as Co2+ ions located on substitutional and interstitial sites. The fraction of the diluted Co is limited to 3 at.% for x >= 0.05, while the rest of the Co atoms gather into Co3O4 clusters. As found by electron paramagnetic resonance, the Co doping brings about hole-and electron-excess defects. (C) 2013 AIP Publishing LLC [http://dx.doi.org/10.1063/1.4802819]

57. Room Temperature Ferromagnetic, Anisotropic, Germanium Rich FeGe(001) Alloys

Authors: Lungu, GA; Apostol, NG; Stoflea, LE; Costescu, RM; Popescu, DG; Teodorescu, CM

Published: FEB 2013, MATERIALS, 6, DOI: 10.3390/ma6020612

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.

58. Manganese-based room temperature ferromagnetism in gallium arsenide

Authors: Vasilache, V; Apostol, NG; Lungu, GA; Macovei, D; Teodorescu, CM

Published: NOV-DEC 2012, OPTOELECTRONICS AND ADVANCED MATERIALS-RAPID COMMUNICATIONS, 6, DOI:

Manganese is deposited onto GaAs(001) substrates in high vacuum conditions (10(-7) hPa), with substrates held at 300 degrees C. It is shown that this procedure yields to the diffusion of magnanese into gallium arsenide and the formation of a layer which exhibits room temperature ferromagnetism, with highly diluted Mn (below 1 atomic percent). X-ray absorption fine structure determinations at the Mn and Ga K-edges evidenced that Mn is not placed into substitutional Ga sites in GaAs. Most probably, Mn forms MnO clusters with rocksalt local structure. These clusters are the origin of the detected ferromagnetism.

59. BAND FERROMAGNETISM IN SYSTEMS WITH LINEAR DENSITY OF STATES

Authors: Lungu, GA; Apostol, NG; Morariu, M; Teodorescu, CM

Published: OCT-DEC 2012, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 7, DOI:

The band (or Stoner) ferromagnetism in systems exhibiting a linear density of states, such as a graphene sheet, where the density of states g(e) is proportional to e, is investigated as function of temperature. The calculations are performed by neglecting spin-wave excitations and some arguments are presented for this approximation. It is found that the occurrence of ferromagnetism becomes easier at finite temperature than in the low temperature limit, especially for systems with low values of carrier density. An almost linear dependence of the magnetization on temperature is predicted; the temperature of vanishing magnetization is linear with the value of the equilibrium Fermi energy, irrespective of the value of the interaction (Hubbard) parameter. Also, for low values of the Hubbard energy an increase in the average value of the polarization with the temperature is predicted in the range of low temperatures. The most important application of such systems consists of control over the onset of magnetization by the charge density (the value of the Fermi energy).

60. Novel Pd heterogeneous catalysts for cycloisomerisation of acetylenic carboxylic acids

Authors: Neatu, F; Protesescu, L; Florea, M; Parvulescu, VI; Teodorescu, CM; Apostol, N; Toullec, PY; Michelet, V

Published: DEC 2010, GREEN CHEMISTRY, 12, 2149, DOI: 10.1039/c0gc00258e

The Pd-TPPTS complex (TPPTS - trisodium salt of 3,3',3 ''-phosphanetriyl benzenesulfonic acid) and PdCl42- salt heterogenised onto Zn2AlNO3 layered double hydroxide (LDH) using an ion-exchange procedure, have been shown to be efficient green catalysts in the cycloisomerisation reaction of acetylenic carboxylic acids to the corresponding 5-membered heterocycles.

Dr. Nicoleta APOSTOL

Scientific Researcher II