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Dr. Luminita HRIB

Scientific Researcher III

Laboratory of Complex Heterostructures and Multifunctional Materials

luminita[DOT]hrib[AT]infim[DOT]ro

Resume

Dr. Luminita M. HRIB, Scientific researcher rank III, born in 1983, graduated the Faculty of Physics – Section “Engineering Physics” at “Alexandru Ioan Cuza” University of Iasi (UAIC) (2007), has a MSc degree in Physics − Section “Physics of advanced materials. Nanotechnologies” (UAIC) (2009), and a PhD degree in Physics (UAIC) (2011). Work experience: National Institute of Materials Physics (NIMP) (2011 – to date); Research assistant at Faculty of Physics “Alexandru Ioan Cuza” University of Iasi (UAIC) (2007-2008), Technician at National Institute of Research & Development for Technical Physics, Iasi, Romania (2006-2007), study stage at Laboratoire de Physique des Lasers, Atomes et Molécules, Université Lille 1 Sciences et Technologies, Lille, France. Main areas of interest/expertise: preparation and electrical characterization of ferroelectric and magnetoelectric heterostructures. Publications (last updated November 2022): 28 articles published in Web of Science® (WoS) journals with impact factor; Hirsch index (WoS): 10; Citations (without self-citations): 437, Patents: co-author at 1 OSIM patent (A 2017 00109), Coordinated projects: responsible for 1 national project (MC694/2018 -UEFISCDI). co-authored one book chapter ((John Wiley & Sons,Ltd. 2016). Professional profile web-links: BrainMap: https://www.brainmap.ro/luminita-mirela-hrib, ORCID ID: 0000-0002-1978-3899; WoS ResearcherID: B-8251-2012.

Publications

1. Experimental Band Structure of Pb(Zr,Ti)O-3: Mechanism of Ferroelectric Stabilization
Authors: Popescu, DG; Husanu, MA; Constantinou, PC; Filip, LD; Trupina, L; Bucur, CI; Pasuk, I; Chirila, C; Hrib, LM; Stancu, V; Pintilie, L; Schmitt, T; Teodorescu, CM; Strocov, VN

Published: FEB 2023, ADVANCED SCIENCE, 10, DOI: 10.1002/advs.202205476

Pb(Zr,Ti)O-3 (PZT) is the most common ferroelectric (FE) material widely used in solid-state technology. Despite intense studies of PZT over decades, its intrinsic band structure, electron energy depending on 3D momentum k, is still unknown. Here, Pb(Zr0.2Ti0.8)O-3 using soft-X-ray angle-resolved photoelectron spectroscopy (ARPES) is explored. The enhanced photoelectron escape depth in this photon energy range allows sharp intrinsic definition of the out-of-plane momentum k and thereby of the full 3D band structure. Furthermore, the problem of sample charging due to the inherently insulating nature of PZT is solved by using thin-film PZT samples, where a thickness-induced self-doping results in their heavy doping. For the first time, the soft-X-ray ARPES experiments deliver the intrinsic 3D band structure of PZT as well as the FE-polarization dependent electrostatic potential profile across the PZT film deposited on SrTiO3 and LaxSrMn1-xO3 substrates. The negative charges near the surface, required to stabilize the FE state pointing away from the sample (P+), are identified as oxygen vacancies creating localized in-gap states below the Fermi energy. For the opposite polarization state (P-), the positive charges near the surface are identified as cation vacancies resulting from non-ideal stoichiometry of the PZT film as deduced from quantitative XPS measurements.
2. Experimental Band Structure of Pb(Zr,Ti)O-3: Mechanism of Ferroelectric Stabilization
Authors: Popescu, DG; Husanu, MA; Constantinou, PC; Filip, LD; Trupina, L; Bucur, CI; Pasuk, I; Chirila, C; Hrib, LM; Stancu, V; Pintilie, L; Schmitt, T; Teodorescu, CM; Strocov, VN

Published: JAN 2023, ADVANCED SCIENCE, DOI: 10.1002/advs.202205476

Pb(Zr,Ti)O-3 (PZT) is the most common ferroelectric (FE) material widely used in solid-state technology. Despite intense studies of PZT over decades, its intrinsic band structure, electron energy depending on 3D momentum k, is still unknown. Here, Pb(Zr0.2Ti0.8)O-3 using soft-X-ray angle-resolved photoelectron spectroscopy (ARPES) is explored. The enhanced photoelectron escape depth in this photon energy range allows sharp intrinsic definition of the out-of-plane momentum k and thereby of the full 3D band structure. Furthermore, the problem of sample charging due to the inherently insulating nature of PZT is solved by using thin-film PZT samples, where a thickness-induced self-doping results in their heavy doping. For the first time, the soft-X-ray ARPES experiments deliver the intrinsic 3D band structure of PZT as well as the FE-polarization dependent electrostatic potential profile across the PZT film deposited on SrTiO3 and LaxSrMn1-xO3 substrates. The negative charges near the surface, required to stabilize the FE state pointing away from the sample (P+), are identified as oxygen vacancies creating localized in-gap states below the Fermi energy. For the opposite polarization state (P-), the positive charges near the surface are identified as cation vacancies resulting from non-ideal stoichiometry of the PZT film as deduced from quantitative XPS measurements.
3. Influence of Grain Size on Dielectric Behavior in Lead-Free 0.5 Ba(Zr0.2Ti0.8)O3-0.5 (Ba0.7Ca0.3)TiO3 Ceramics
Authors: Ene, VL; Lupu, VR; Condor, CV; Patru, RE; Hrib, LM; Amarande, L; Nicoara, AI; Pintilie, L; Ianculescu, AC

Published: NOV 2023, NANOMATERIALS, 13, 2934, DOI: 10.3390/nano13222934

Fine-tuning of grain sizes can significantly influence the interaction between different dielectric phenomena, allowing the development of materials with tailored dielectric resistivity. By virtue of various synthesis mechanisms, a pathway to manipulate grain sizes and, consequently, tune the material's dielectric response is revealed. Understanding these intricate relationships between granulation and dielectric properties can pave the way for designing and optimizing materials for specific applications where tailored dielectric responses are sought. The experimental part involved the fabrication of dense BCT-BZT ceramics with different grain sizes by varying the synthesis (conventional solid-state reaction route and sol-gel) and consolidation methods. Both consolidation methods produced well-crystallized specimens, with Ba0.85Ca0.15O3Ti0.9Zr0.1 (BCTZ) perovskite as the major phase. Conventional sintering resulted in microstructured and submicron-structured BCT-BZT ceramics, with average grain sizes of 2.35 mu m for the solid-state sample and 0.91 mu m for the sol-gel synthesized ceramic. However, spark plasma sintering produced a nanocrystalline specimen with an average grain size of 67.5 nm. As the grain size decreases, there is a noticeable decrease in the maximum permittivity, a significant reduction in dielectric losses, and a shifting of the Curie temperature towards lower values.
4. Experimental Band Structure of Pb(Zr,Ti)O3: Mechanism of Ferroelectric Stabilization
Authors: Popescu, DG; Husanu, MA; Constantinou, PC; Filip, LD; Trupina, L; Bucur, CI; Pasuk, I; Chirila, C; Hrib, LM; Stancu, V; Pintilie, L; Schmitt, T; Teodorescu, CM; Strocov, VN

Published: FEB 2023, ADVANCED SCIENCE, 10, DOI: 10.1002/advs.202205476

Pb(Zr,Ti)O-3 (PZT) is the most common ferroelectric (FE) material widely used in solid-state technology. Despite intense studies of PZT over decades, its intrinsic band structure, electron energy depending on 3D momentum k, is still unknown. Here, Pb(Zr0.2Ti0.8)O-3 using soft-X-ray angle-resolved photoelectron spectroscopy (ARPES) is explored. The enhanced photoelectron escape depth in this photon energy range allows sharp intrinsic definition of the out-of-plane momentum k and thereby of the full 3D band structure. Furthermore, the problem of sample charging due to the inherently insulating nature of PZT is solved by using thin-film PZT samples, where a thickness-induced self-doping results in their heavy doping. For the first time, the soft-X-ray ARPES experiments deliver the intrinsic 3D band structure of PZT as well as the FE-polarization dependent electrostatic potential profile across the PZT film deposited on SrTiO3 and LaxSrMn1-xO3 substrates. The negative charges near the surface, required to stabilize the FE state pointing away from the sample (P+), are identified as oxygen vacancies creating localized in-gap states below the Fermi energy. For the opposite polarization state (P-), the positive charges near the surface are identified as cation vacancies resulting from non-ideal stoichiometry of the PZT film as deduced from quantitative XPS measurements.
5. Ferroelectricity modulates polaronic coupling at multiferroic interfaces
Authors: Husanu, MA; Popescu, DG; Bisti, F; Hrib, LM; Filip, LD; Pasuk, I; Negrea, R; Istrate, MC; Lev, L; Schmitt, T; Pintilie, L; Mishchenko, A; Teodorescu, CM; Strocov, VN

Published: AUG 15 2022, COMMUNICATIONS PHYSICS, 5, 209, DOI: 10.1038/s42005-022-00983-3

A deeper understanding of the coupling at the interface of multiferroics heterostructures is being achieved by the use of synchrotron radiation techniques. Here, the authors use k-resolved soft X-ray photoemission spectroscopy and first principles calculations to investigate the band structure of several multiferroic heterostructures, isolating the distinct signature of the interface. Physics of the multiferroic interfaces is currently understood mostly within a phenomenological framework based on screening of the polarization field and depolarizing charges. Additional effects still unexplored are the band dependence of the interfacial charge modulation and the associated changes of the electron-phonon interaction, coupling the charge and lattice degrees of freedom. Here, multiferroic heterostructures of the colossal-magnetoresistance manganite La1-xSrxMnO3 buried under ferroelectric BaTiO3 and PbZrxTi1-xO3 are investigated using soft-X-ray angle-resolved photoemission. The experimental band dispersions from the buried La1-xSrxMnO3 identify coexisting two-dimensional hole and three-dimensional electron charge carriers. The ferroelectric polarization modulates their charge density, affecting the coupling of the 2D holes and 3D electrons with the lattice which forms large Frohlich polarons inherently reducing mobility of the charge carriers. Our k-resolved results on the orbital occupancy, band filling and electron-lattice interaction in multiferroic oxide heterostructures modulated by the ferroelectric polarization disclose most fundamental physics of these systems needed for further progress of beyond-CMOS ferro-functional electronics.
6. Influence of Thickness on the Magnetic and Magnetotransport Properties of Epitaxial La0.7Sr0.3MnO3 Films Deposited on STO (001)
Authors: Greculeasa, SG; Stanciu, AE; Leca, A; Kuncser, A; Hrib, L; Chirila, C; Pasuk, I; Kuncser, V

Published: DEC 2021, NANOMATERIALS, 11, DOI: 10.3390/nano11123389

Epitaxial La0.7Sr0.3MnO3 films with different thicknesses (9-90 nm) were deposited on SrTiO3 (0 0 1) substrates by pulsed laser deposition. The films have been investigated with respect to morpho-structural, magnetic, and magneto-transport properties, which have been proven to be thickness dependent. Magnetic contributions with different switching mechanisms were evidenced, depending on the perovskite film thickness. The Curie temperature increases with the film thickness. In addition, colossal magnetoresistance effects of up to 29% above room temperature were evidenced and discussed in respect to the magnetic behavior and film thickness.
7. Polarization Switching and Negative Capacitance in Epitaxial PbZr0.2Ti0.8O3 Thin Films
Authors: Pintilie, L; Boni, GA; Chirila, C; Hrib, L; Trupina, L; Filip, LD; Pintilie, I

Published: JUL 27 2020, PHYSICAL REVIEW APPLIED, 14, DOI: 10.1103/PhysRevApplied.14.014080

The negative-capacitance effect in devices based on combined ferroelectric-dielectric gate oxides is thought to be a potential solution to break free from the so-called Boltzmann tyranny. To lower the power consumption in field-effect transistors, the subthreshold swing factor S should be reduced below the ther-modynamic limit of 60 mV per decade. Yet, despite numerous studies dedicated to this effect in the past decade, its origin in ferroelectric capacitors or ferroelectric-based superlattices remains unclear, being considered either a transitory product of polarization switching or an intrinsic phenomenon related to the presence of ferroelectric polarization. In this study it is shown, starting from simple electrostatic con-siderations, that negative capacitance is present during polarization switching and is accompanied by a significant increase of the current flowing through the ferroelectric capacitor. Coupled with piezo-force microscopy results, it is shown that the polarization orientation suddenly changes at the coercive voltage, accompanied by a complete reconfiguration of the potential barriers at the Schottky-like contacts present at the electrode-ferroelectric interfaces. A method to estimate the polarization-switching time, as the time associated with the presence of the negative-capacitance effect, is proposed. Values in the range from 100 to 1000 ns are obtained for epitaxial PbZr0.2Ti0.8O3 films. These findings suggest that negative capacitance may be an intrinsic effect in ferroelectrics but that it is a transitory effect, present only when ferroelectric polarization passes through zero (switching).
8. Complex exchange coupling mechanisms in SRO/BFO/Fe heterostructures
Authors: Greculeasa, SG; Schinteie, G; Hrib, LM; Stancu, V; Pasuk, I; Kuncser, A; Kuncser, V

Published: JAN 30 2019, JOURNAL OF ALLOYS AND COMPOUNDS, 773, 345, DOI: 10.1016/j.jallcom.2018.09.208

Temperature dependent interfacial coupling mechanisms in SRO/BFO/Fe layered structures were investigated. The BFO/Fe heterostructures were prepared by PLD and sputtering, respectively, on the STO(0 0 1) substrate with a 20 nm SRO buffer layer. An annealing treatment in external magnetic field was further applied. Complex characterizations with X-ray diffraction, atomic force microscopy, Transmission Electron Microscopy, Mossbauer spectroscopy, magneto-optic Kerr effect and SQUID magnetometry were performed. Before annealing, the films show good crystallization and epitaxy of the SRO and BFO layers with smooth interfaces. Two coupling mechanisms of the ferromagnetic layers (top Fe and bottom SRO, respectively) to the epitaxial BFO film with mainly antiferromagnetic structure were evidenced in the as deposited samples at low temperatures. Negative exchange bias fields of up to 67(10) Oe and 37(5) Oe at low temperatures were observed for the two ferromagnetic components, respectively, depending on the thickness of the Fe layer. The field annealing treatments induce a specific morphology and magnetic spin structure at both interfaces of the BFO spacer layer, giving rise to a long range magnetostatic coupling between the two ferromagnetic films, in addition to the interfacial couplings. Moreover, the experimentally evidenced Fe clusters penetrating the BFO/Fe interface toward the BFO layer give support for this interaction. As an additional consequence, a considerable enhancement of both uniaxial and unidirectional anisotropies as well as an increased blocking temperature of exchange bias were obtained. The involved exchange coupling mechanisms were discussed in detail. (C) 2018 Elsevier B.V. All rights reserved.
9. EXPERIMENTAL STUDY OF TERAHERTZ RESPONSE FROM SOME FERROELECTRIC AND DIELECTRIC MATERIALS
Authors: Banciu, MG; Nedelcu, L; Furuya, T; Hrib, L; Geambasu, DC; Trupina, L; Pantelica, D; Mihai, MD; Tani, M

Published: OCT-DEC 2019, PROCEEDINGS OF THE ROMANIAN ACADEMY SERIES A-MATHEMATICS PHYSICS TECHNICAL SCIENCES INFORMATION SCIENCE, 20, 360, DOI:

Barium strontium titanate (BST) ferroelectric layers were deposited on high resistivity Si substrates by Pulsed Laser Deposition and Radio Frequency sputtering. The stoichiometry was measured by using the Rutherford Backscattering technique at 3.041 MeV. For sub-THz measurements of Si samples, a new resonant method placing the sample between two flanged waveguides is proposed. In the THz range, the Time Domain Spectroscopy proved to be a reliable method. Both methods show effects due to the dielectric losses of BST in that frequency range.
10. Memcomputing and Nondestructive Reading in Functional Ferroelectric Heterostructures
Authors: Boni, GA; Filip, LD; Chirila, C; Iuga, A; Pasuk, I; Hrib, L; Trupina, L; Pintilie, I; Pintilie, L

Published: AUG 26 2019, PHYSICAL REVIEW APPLIED, 12, DOI: 10.1103/PhysRevApplied.12.024053

Multiple nonvolatile and well-separated capacitive states can be obtained in a two-terminal ferroelectric capacitor setup by fine tuning the polarization switching process. This approach allows for the implementation of memcomputing (same platform for storage and computing) capable ferroelectric structures. Digital and analog storage modes are exemplified in this work together with an algorithm for simple binary computation functions such as OR/NOR and AND/NAND for data processing on the same device. Results are obtained by controlling the polarization switching process in ferroelectric multi-layers such as Pb (Zr0.2Ti0.8)O-3/SrTiO3/Pb (Zr0.2Ti0.8)O-3 and Pb (Zr0.2Ti0.8)O-3/BaTiO3/Pb (Zr0.2Ti0.8)O-3. Besides memcomputing, these results can be used for nondestructive capacitive reading of information in simple ferroelectric capacitors or can open the way toward applications such as neuromorphic and chaotic circuits.
11. Structural, electric and pyroelectric properties of up and down graded PZT multilayers
Authors: Botea, M; Hrib, L; Pasuk, I; Iuga, A; Trupina, L; Negrea, R; Becherescu, N; Pintilie, L

Published: JUL 2019, CURRENT APPLIED PHYSICS, 19, 810, DOI: 10.1016/j.cap.2019.04.010

Multi-layered structures, composed of thin films from materials with different compositions or physical properties, represents a way to obtain enhanced properties or even new functionalities. In this work, lead zirconate titanate PbZrxTi1-xO3 (PZT; x = 0.20, 0.52, 0.80) multilayers were grown by pulsed laser deposition (PLD) on a single crystal strontium titanate (SrTiO3, STO) substrate, using a strontium ruthenate (SrRuO3, SRO) film as buffer layer for epitaxial growth, and also as back electrode. Up and down multi-layers were grown and their physical and structural properties were compared, up being the structure in which Zr concentration was varied from 20% near the STO substrate to 80% at the surface, while down is for the structure in which the Zr concentration starts with 80% near the substrate and ends with 20% at the surface. It was found that the electric and pyroelectric properties of the two graded structures are significantly different. The up structure presents electric properties that are comparable with those of single composition PZT films while the properties of the down structure are deteriorated, especially in terms of the leakage current magnitude. Pyroelectric signal could be measured only for the up structure. These differences were attributed to larger density of structural defects in the down structure compared to the up one. This is due to the different growth sequence: Lop structure starts with tetragonal PZT on cubic substrate (lower lattice mismatch, 1.1%) while down structure starts with rhombohedral PZT on cubic substrate (larger lattice mismatch, almost 5%).
12. Low value for the static background dielectric constant in epitaxial PZT thin films
Authors: Boni, GA; Chirila, CF; Hrib, L; Negrea, R; Filip, LD; Pintilie, I; Pintilie, L

Published: OCT 11 2019, SCIENTIFIC REPORTS, 9, DOI: 10.1038/s41598-019-51312-8

Ferroelectrics are intensively studied materials due to their unique properties with high potential for applications. Despite all efforts devoted to obtain the values of ferroelectric material constants, the problem of the magnitude of static dielectric constant remains unsolved. In this article it is shown that the value of the static dielectric constant at zero electric field and with negligible contribution from the ferroelectric polarization (also called static background dielectric constant, or just background dielectric constant) can be very low (between 10 and 15), possibly converging towards the value in the optical domain. It is also found that the natural state of an ideal, mono-domain, epitaxial ferroelectric is that of full depletion with constant capacitance at voltages outside the switching domain. The findings are based on experimental results obtained from a new custom method designed to measure the capacitance-voltage characteristic in static conditions, as well from Rayleigh analysis. These results have important implications in future analysis of conduction mechanisms in ferroelectrics and theoretical modeling of ferroelectric-based devices.
13. 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).
14. Millimeter wave and Terahertz investigations on some dielectric materials
Authors: Banciu, MG; Furuya, T; Geambasu, DC; Nedelcu, L; Pantelica, D; Dracea, MD; Ionescu, P; Iuga, A; Chirila, C; Hrib, L; Trupina, L; Tani, M

Published: 2018, CAS 2018 PROCEEDINGS: 2018 INTERNATIONAL SEMICONDUCTOR CONFERENCE, 290, DOI:

Investigations of barium strontium titanate (BST) layers deposited on MgO and Si substrates are presented. Since the Sr content determines the dielectric and optical properties of the BST layers at room temperature, accurate compositional analysis was performed by using Rutherford Backscattering technique at 3.041 Mev.
15. 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.
16. Electrical properties of NiFe2O4 epitaxial ultra-thin films
Authors: Boni, GA; Hrib, L; Porter, SB; Atcheson, G; Pintilie, I; Rode, K; Pintilie, L

Published: JAN 2017, JOURNAL OF MATERIALS SCIENCE, 52, 803, DOI: 10.1007/s10853-016-0376-8

Epitaxial thin films of NiFe2O4 are fabricated by pulsed laser deposition on SrTiO3 substrate. Symmetrical capacitor-like structures are formed using SrRuO3 as bottom and top electrodes. Electrical characterizations, including current-voltage, capacitance-voltage and capacitance-frequency measurement, reveal a hysteresis-like behaviour for current and capacitance as function of voltage. This could be assigned to a resistive and/or capacitive switching. A "degradation" process takes place after repeated voltage cycling or after heating the sample to 400 K, leading to the stabilization of different resistive states. These features can be related to the changes observed in the capacitance-frequency characteristics, suggesting the presence of a relaxation mechanism at low frequencies, and can be associated with the presence of a deep donor-type level in the band-gap of the NiFe2O4 layer.
17. Magnetocapacitance in La0.7Sr0.3MnO3/Pb(Zr0.2Ti0.8)O-3/La0.7Sr0.3MnO3 multiferroic heterostructures
Authors: Hrib, LM; Pintilie, L; Alexe, M

Published: JUL 26 2017, SCIENTIFIC REPORTS, 7, DOI: 10.1038/s41598-017-06487-3

Measurements of the magnetocapacitance effect in epitaxial La0.7Sr0.3MnO3/Pb(Zr0.2Ti0.8)O-3/La0.7Sr0.3MnO3 heterostructures have been performed using a quasi-static method. Through capacitance-voltage measurements carried out under variable magnetic field it has been found that the magneto-capacitance depends on the orientation of the ferroelectric polarization. The value of magneto-capacitance can be as high as 1% in the voltage range near the ferroelectric coercive field. This has been attributed to a variation of the apparent built-in voltage of the PZT-LSMO Schottky barriers on applied magnetic field.
18. 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.
19. 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.
20. Spectro-microscopic photoemission evidence of charge uncompensated areas in Pb(Zr,Ti)O-3(001) layers
Authors: Popescu, DG; Husanu, MA; Trupina, L; Hrib, L; Pintilie, L; Barinov, A; Lizzit, S; Lacovig, P; Teodorescu, CM

Published: 2015, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 17, 520, DOI: 10.1039/c4cp04546g

Photoelectron spectroscopy studies of (001) oriented PbTi0.8Zr0.2O3 (PZT) single crystal layers with submicron resolution revealed areas with different Pb 5d binding energies, attributed to the different charge and polarization states of the film surface. Two novel effects are evidenced by using intense synchrotron radiation beam experiments: (i) the progressive increase of a low binding energy component for the Pb core levels (evidenced for both 5d and 4f, on two different measurement setups), which can be attributed to a partial decomposition of the PZT film at its surface and promoting the growth of metallic Pb during the photoemission process, with the eventuality of the progressive formation of areas with downwards ferroelectric polarization; (ii) for films annealed in oxygen under clean conditions (in an ultrahigh vacuum installation) a huge shift of the Pb 5d core levels (by 8-9 eV) towards higher binding energies is attributed to the formation of areas with depleted mobile charge carriers, whose surface density is insufficient to screen the depolarization field. This shift is attenuated progressively with time, as the sample is irradiated with high flux soft X-rays. The formation of these areas with strong internal electric field promotes these films as good candidates for photocatalysis and solar cells, since in the operation of these devices the ability to perform charge separation and to avoid electron-hole recombination is crucial.
21. 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.
22. STUDY OF THE LEAKAGE CURRENT IN EPITAXIAL FERROELECTRIC Pb(Zr0.52Ti0.48)O-3 LAYER WITH SrRuO3 BOTTOM ELECTRODE AND DIFFERENT METALS AS TOP CONTACTS
Authors: Boni, AG; Chirila, C; Hrib, L; Pintilie, I; Pintilie, L

Published: OCT-DEC 2015, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 10, 1265, DOI:

The leakage current was studies in epitaxial ferroelectric Pb(Zr0.52Ti0.48)O-3 layer with common SrRuO3 bottom electrode and different metals as top contacts (SrRuO3, Pt, Ir, Ru). It was found that the dominant conduction mechanism in the 200-350 K temperature range and for voltages significantly larger than the coercive value is the thermionic emission governed by the Schottky-Simmons equation. The height of the potential barriers was estimated and was found that this is about the same for negative and positive voltage polarities. No correlation was found between the height of the potential barriers for different top contacts and the work function difference between the bottom and top electrodes. The results suggest that the potential barrier is controlled by the polarization charges in a similar way to the one reported for Pb(Zr0.2Ti0.8)O-3 and BaTiO3 epitaxial films with bottom SrRuO3 electrode and different metals as top contacts. It was also found that above 350 K the conduction mechanism changes to ohmic and/or space charge limited currents.
23. 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.
24. General equivalent circuit derived from capacitance and impedance measurements performed on epitaxial ferroelectric thin films
Authors: Pintilie, L; Hrib, L; Pasuk, I; Ghica, C; Iuga, A; Pintilie, I

Published: JUL 28 2014, JOURNAL OF APPLIED PHYSICS, 116, DOI: 10.1063/1.4891255

Voltage and frequency dependent capacitance measurements were performed on epitaxial BaTiO3 and Pb(Zr0.2Ti0.8)O-3 thin films deposited on single crystal SrTiO3 substrates with (001) and (111) orientations. The measured capacitors have common bottom SrRuO3 contact and different metals as top electrodes: SrRuO3, Pt, Cu, Al, and Au. The capacitance-voltage characteristics were used to extract information regarding the density of the free carriers and the linear contribution to the static dielectric constant. The frequency dependent impedance was used to develop a suitable equivalent circuit for the epitaxial ferroelectric capacitors. It was found that the frequency dependence of the imaginary part of the impedance can be well simulated, in all cases, using a circuit composed of Schottky-type capacitance related to electrode interfaces, contact resistance, and the R-C parallel connection related to the ferroelectric volume of the film. Values for the components of the equivalent circuit were obtained by fitting the experimental data with the simulated curves. These were then used to extract quantities such as dielectric constant in the ferroelectric volume, the width of the depletion layers, and the apparent built-in potential. It was found that, although the investigated capacitors are of different ferroelectric materials, grown on substrates with different orientations, and having different metals as top electrodes, the values for the capacitance associated with the Schottky contacts and the apparent built-in potential are not very different. The results suggest a strong influence of ferroelectric polarization on the electrode interface properties in the case of epitaxial ferroelectric films. (C) 2014 AIP Publishing LLC.
25. Structural, electric and magnetic properties of Pb(Zr0.2Ti0.8)O-3-CoFe2O4 heterostructures
Authors: Chirila, C; Ibanescu, G; Hrib, L; Negrea, R; Pasuk, I; Kuncser, V; Pintilie, I; Pintilie, L

Published: OCT 31 2013, THIN SOLID FILMS, 545, 7, DOI: 10.1016/j.tsf.2013.06.033

Electric and magnetic properties of symmetric and asymmetric Pb(Zr-0.2 Ti-0.8)O-3-CoFe2O4 (PZT/CFO) heterostructures, grown by pulsed laser deposition on SrTiO3 (100) substrates with a 25 nm SrRuO3 (SRO) buffer layer as bottom electrode, were investigated by using hysteresis and capacitance measurements. X-ray diffraction, and transmission electron microscopy investigations reveal the high quality crystalline structure and the epitaxial relationship between SRO, PZT and CFO. The electric polarization-voltage hysteresis reveals that the remnant polarization and the coercive field are significantly affected by the CFO layer. The frequency dependence of capacitance suggests a Maxwell-Wagner type relaxation at low frequencies and is also affected by the presence of the PZT/CFO interface(s). The magnetic hysteresis measurements infer the possible presence of another spinel phase (Co3O4) in the CFO film, due to the lattice mismatch at the PZT/CFO interfaces, and with direct influence on the magnetic response of the structure. According to the electric and magnetic characterization, better room temperature multiferroic properties would be expected for the symmetric heterostructure. (C) 2013 Published by Elsevier B. V.
26. Electrode interface control of the Schottky diode-like behavior in epitaxial Pb(Zr0.2Ti0.8)O-3 thin films: A critical analysis
Authors: Hrib, LM; Boni, AG; Chirila, C; Pasuk, I; Pintilie, I; Pintilie, L

Published: JUN 7 2013, JOURNAL OF APPLIED PHYSICS, 113, DOI: 10.1063/1.4808464

Metal-ferroelectric-metal structures based on epitaxial Pb(Zr0.2Ti0.8)O-3 thin films are prepared by pulsed laser deposition on single crystal SrTiO3 substrates ((001) orientation) with buffer SrRuO3 layer as bottom electrode. Pt, Cu, and SrRuO3 are used as top contacts. The current-voltage (I-V) measurements reveal a strong influence of the top electrode interface on the magnitude of the leakage current and the shape of the I-V characteristics. The lowest current values are obtained for top Cu and the highest for top Pt. Diode-like behavior is obtained for top Cu and Pt, but the forward and reverse biases are opposite in sign. Contrary to the case of BiFeO3 layers deposited on the same type of substrates, it was found that the diode-like behavior is not switchable with the polarization reversal although the polarization values are comparable. It is also shown that the metal-ferroelectric-metal (MFM) structure based on Pb(Zr,Ti)O-3 (PZT) can be simulated and modeled as a back-to-back connection of two Schottky diodes. The diode-like behavior of the MFM structure can be induced by a slight asymmetry of the potential barriers at the electrode interfaces behaving as Schottky contacts. The study ends with a critical discussion of the MFM structures based on PZT and BiFeO3 (BFO) layers. It is shown that the switchable diode-like behavior is not uniquely determined by the polarization reversal and is not a general characteristic for MFM structures. Such behavior may be present only if the polarization induced band-bending at the interface is generating an accumulation layer at the interface. This could be possible in BiFeO3 based MFM structures due to the lower band gap compared to Pb(Zr0.2Ti0.8)O-3 thin films. (C) 2013 AIP Publishing LLC.
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