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Dr. Andra-Georgia Boni

Scientific Researcher III

Laboratory of Complex Heterostructures and Multifunctional Materials

andra[DOT]boni[AT]infim[DOT]ro

Publications

1. Resistive-like Behavior of Ferroelectric p-n Bilayer Structures Based on Epitaxial Pb(Zr0.2Ti0.8)O-3 Thin Films
Authors: Boni, AG; Chirila, C; Trupina, L; Radu, C; Filip, LD; Moldoveanu, V; Pintilie, I; Pintilie, L

Published: 2023 JAN 25 2023, ACS APPLIED ELECTRONIC MATERIALS, DOI: 10.1021/acsaelm.2c01497

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.
2. Resistive-like Behavior of Ferroelectric p-n Bilayer Structures Based on Epitaxial Pb(Zr0.2Ti0.8)O3 Thin Films
Authors: Boni, AG; Chirila, C; Trupina, L; Radu, C; Filip, LD; Moldoveanu, V; Pintilie, I; Pintilie, L

Published: 2023 JAN 25 2023, ACS APPLIED ELECTRONIC MATERIALS, DOI: 10.1021/acsaelm.2c01497

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.
3. Resistive-like Behavior of Ferroelectric p-n Bilayer Structures Based on Epitaxial Pb(Zr0.2Ti0.8)O-3 Thin Films
Authors: Boni, AG; Chirila, C; Trupina, L; Radu, C; Filip, LD; Moldoveanu, V; Pintilie, I; Pintilie, L

Published: JAN 2023, ACS APPLIED ELECTRONIC MATERIALS, DOI: 10.1021/acsaelm.2c01497

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.
4. Negative Capacitance and Switching Dynamics Control Via Non-Ferroelectric Elements
Authors: Boni, AG; Patru, R; Filip, LD; Chirila, C; Pasuk, I; Pintilie, I; Pintilie, L

Published: MAR 15 2022, ACS APPLIED ENERGY MATERIALS, 5, DOI: 10.1021/acsaem.1c03890

Complex ferroelectric structures with dielectric interlayers may become possible alternatives for neuromorphic computing and low-power field-effect transistors since they exhibit multiple polarization states and negative capacitance. However, the effects on the switching characteristics due to the electric properties of the nonferroelectric circuit element have not been clearly evaluated so far. A high-resistance or low-capacitance element is usually associated with an increased depolarization field and eventually with suppression of polarization but without further consideration of the electrostatic differences. Therefore, we show that switching behavior is dramatically changed if the non-FE element is a resistive component or a capacitive one. This is reflected by either an increased apparent coercive field or imprint, respectively. A negative capacitance regime was observed at different moments but strongly depends on the nature of the nonferroelectric element. The voltage on the ferroelectric component remains constant during switching, which is a fingerprint of the system passing through non-equilibrium states. Therefore, we propose an algorithm to recover the S-shape of polarization dependence on the ferroelectric internal voltage during the slowed transition between the two stable states of polarization.
5. Controlling polarization direction in epitaxial Pb(Zr0.2Ti0.8)O-3 films through Nb (n-type) and Fe (p-type) doping
Authors: Chirila, CF; Stancu, V; Boni, GA; Pasuk, I; Trupina, L; Filip, LD; Radu, C; Pintilie, I; Pintilie, L

Published: JAN 14 2022, SCIENTIFIC REPORTS, 12, 755, DOI: 10.1038/s41598-022-04802-1

Fe (acceptor) and Nb (donor) doped epitaxial Pb(Zr0.2Ti0.8)O-3 (PZT) films were grown on single crystal SrTiO3 substrates and their electric properties were compared to those of un-doped PZT layers deposited in similar conditions. All the films were grown from targets produced from high purity precursor oxides and the doping was in the limit of 1% atomic in both cases. The remnant polarization, the coercive field and the potential barriers at electrode interfaces are different, with lowest values for Fe doping and highest values for Nb doping, with un-doped PZT in between. The dielectric constant is larger in the doped films, while the effective density of charge carriers is of the same order of magnitude. An interesting result was obtained from piezoelectric force microscopy (PFM) investigations. It was found that the as-grown Nb-doped PZT has polarization orientated upward, while the Fe-doped PZT has polarization oriented mostly downward. This difference is explained by the change in the conduction type, thus in the sign of the carriers involved in the compensation of the depolarization field during the growth. In the Nb-doped film the majority carriers are electrons, which tend to accumulate to the growing surface, leaving positively charged ions at the interface with the bottom SrRuO3 electrode, thus favouring an upward orientation of polarization. For Fe-doped film the dominant carriers are holes, thus the sign of charges is opposite at the growing surface and the bottom electrode interface, favouring downward orientation of polarization. These findings open the way to obtain p-n ferroelectric homojunctions and suggest that PFM can be used to identify the type of conduction in PZT upon the dominant direction of polarization in the as-grown films.
6. Accidental Impurities in Epitaxial Pb(Zr0.2Ti0.8)O-3 Thin Films Grown by Pulsed Laser Deposition and Their Impact on the Macroscopic Electric Properties
Authors: Boni, GA; Chirila, CF; Stancu, V; Amarande, L; Pasuk, I; Trupina, L; Istrate, CM; Radu, C; Tomulescu, A; Neatu, S; Pintilie, I; Pintilie, L

Published: MAY 2021, NANOMATERIALS, 11, DOI: 10.3390/nano11051177

Structural and electrical properties of epitaxial Pb(Zr0.2Ti0.8)O-3 films grown by pulsed laser deposition from targets with different purities are investigated in this study. One target was produced in-house by using high purity precursor oxides (at least 99.99%), and the other target was a commercial product (99.9% purity). It was found that the out-of-plane lattice constant is about 0.15% larger and the a domains amount is lower for the film grown from the commercial target. The polarization value is slightly lower, the dielectric constant is larger, and the height of the potential barrier at the electrode interfaces is larger for the film deposited from the pure target. The differences are attributed to the accidental impurities, with a larger amount in the commercial target as revealed by composition analysis using inductive coupling plasma-mass spectrometry. The heterovalent impurities can act as donors or acceptors, modifying the electronic characteristics. Thus, mastering impurities is a prerequisite for obtaining reliable and reproducible properties and advancing towards all ferroelectric devices.
7. Ultrafast nondestructive pyroelectric reading of FeRAM memories
Authors: Iuga, AR; Lindfors-Vrejoiu, I; Boni, GA

Published: AUG 2021, INFRARED PHYSICS & TECHNOLOGY, 116, DOI: 10.1016/j.infrared.2021.103766

FeRAM memories constitute themselves as a robust counterpart to the mainstream NVRAM memories. Their unique properties, such as radiation resilience and low voltage operation, together with high speed writing and reading, high and long lasting remanence and very good endurance to cycling endorse them in the data storage domain. However price, poor scalability, the destructive way of reading and the necessary consequent re-writing represent technical drawbacks that diminish their practical value. This paper presents a new paradigm of completing previous efforts towards fast nondestructive reading of FeRAMs. An intermittent low intensity IR (infrared) laser diode generates a pyroelectric signal in the ferroelectric material. The amplitude and phase of this response depends on the state of polarisation of the ferroelectric. Comparing the phase of the electric response with the phase of the illuminating radiation (on/off), a decisive indication of the poling sense in the ferroelectric is given. Aiming to circumvent the notorious slowness of the pyroelectric response the array is continuously illuminated with the pulsating laser, which ensures a prompt answer from every bit of memory. The reading speed is, practically, limited by the electronics.
8. Effect of strain and stoichiometry on the ferroelectric and pyroelectric properties of the epitaxial Pb(Zr0.2Ti0.8)O-3 films deposited on Si wafers
Authors: Chirila, C; Boni, GA; Filip, LD; Husanu, M; Neatu, S; Istrate, CM; Le Rhun, G; Vilquin, B; Trupina, L; Pasuk, I; Botea, M; Pintilie, I; Pintilie, L

Published: APR 2021, MATERIALS SCIENCE AND ENGINEERING B-ADVANCED FUNCTIONAL SOLID-STATE MATERIALS, 266, DOI: 10.1016/j.mseb.2021.115042

Properties of epitaxial PbZr0.2Ti0.8O3 (PZT) films deposited on Si substrates were investigated for integration in the present CMOS technology. Polarization is downward oriented, in association with the presence of an internal electric field, and has a lower value compared to the PZT films deposited on single crystal perovskite SrTiO3 (STO) substrates (40 mu C/cm(2) versus 80 mu C/cm(2)), while the dielectric constant is larger (180 versus 120). Large value for the pyroelectric coefficient was also found, 1.22 x 10(-3)C/m(2)K, as for PZT grown on single crystal STO. The macroscopic ferroelectric and pyroelectric properties appear to be affected by the structural quality and stoichiometry of the PZT film. The changes in the electric properties are an effect of the strain gradients induced by the large difference between the thermal expansion coefficients of PZT and Si substrate, leading in turn to Pb oxidation and antisite defect formation compared to PZT films deposited on STO substrates.
9. Negative capacitance in epitaxial ferroelectric capacitors evidenced by dynamic dielectric characterization
Authors: Boni, GA; Chirila, C; Filip, LD; Pintilie, I; Pintilie, L

Published: MAR 2021, MATERIALS TODAY COMMUNICATIONS, 26, DOI: 10.1016/j.mtcomm.2021.102076

A simple dynamic method was developed to evaluate the components in the equivalent circuit of a ferroelectric capacitor. The method is based on the application of short trapezoidal voltage pulses of variable amplitude and the analysis of the resulting current by considering the ferroelectric capacitor as a parallel R-p-C-p equivalent circuit. The values of R-p and C-p components are obtained in relation to different stages of polarization switching as the amplitude of the applied pulses increases. The most important result obtained by applying the present method is the evidence of an abrupt decrease of the R-p value (about 2 orders of magnitude) at the coercive voltage, while the equivalent C-p does not present a dramatic variation during polarization switching. This is interpreted in the context of negative capacitance obtained for ferroelectrics when polarization passes through zero value. The results obtained by using the proposed dynamic characterization method that will be referred to as "dynamic dielectric characterization", are in good agreement with those obtained by classic capacitance-voltage measurements. A method to stabilize the negative capacitance for longer periods of time is also presented by adding an external resistance in series with the ferroelectric capacitor.
10. The Role of Interface Defect States in n- and p-Type Ge Metal-Ferroelectric-Semiconductor Structures with Hf0.5Zr0.5O2 Ferroelectric
Authors: Boni, GA; Istrate, CM; Zacharaki, C; Tsipas, P; Chaitoglou, S; Evangelou, EK; Dimoulas, A; Pintilie, I; Pintilie, L

Published: FEB 2021, PHYSICA STATUS SOLIDI A-APPLICATIONS AND MATERIALS SCIENCE, 218, DOI: 10.1002/pssa.202000500

The discovery of ferroelectricity in doped HfO2 represents an excellent opportunity to overcome the obstacles in manufacturing reliable ferroelectric field effect transistors (FeFET) for nonvolatile memory applications, considering that HfO2 is compatible with Si and Ge and it is already used in semiconductor industry. The presence of interface defects may have detrimental effects on the operation of FeFETs, so their role is systematically investigated in this study in correlation with the substrate doping. Metal-ferroelectric-semiconductor (MFS) structures are fabricated by depositing Hf0.5Zr0.5O2 (HZO) layers on n-type Ge substrate. Their electric properties are compared with those of MFS structures obtained by depositing HZO on p-type Ge, to study the influence of the doping. It is found that, although the ferroelectric properties of HZO are similar, the capacitance and impedance of the MFS structures behave differently. For n-Ge, the occupation probability of a large number of low-lying interface defect acceptor states, charges the interface negatively which adversely affects the C-V response of the MFS, albeit without harming the ferroelectric (P-V) hysteresis. Although the interface defects do not harm ferroelectricity, they could inhibit inversion in p-type Ge or accumulation in n-type Ge so they should be taken into account when designing Ge FeFET devices.
11. Homogeneous versus Inhomogeneous Polarization Switching in PZT Thin Films: Impact of the Structural Quality and Correlation to the Negative Capacitance Effect
Authors: Pintilie, L; Boni, GA; Chirila, CF; Stancu, V; Trupina, L; Istrate, CM; Radu, C; Pintilie, I

Published: AUG 2021, NANOMATERIALS, 11, DOI: 10.3390/nano11082124

Polarization switching in ferroelectric films is exploited in many applications, such as non-volatile memories and negative capacitance field affect transistors. This can be inhomogeneous or homogeneous, depending on if ferroelectric domains are forming or not during the switching process. The relation between the polarization switching, the structural quality of the films and the negative capacitance was not studied in depth. Here, Pb(Zr0.2Ti0.8)O-3 (PZT) layers were deposited by pulse laser deposition (PLD) and sol-gel (SG) on single crystal SrTiO3 (STO) and Si substrates, respectively. The structural quality was analyzed by X-ray diffraction and transmission electron microscopy, while the electric properties were investigated by performing hysteresis, dynamic dielectric measurements, and piezo-electric force microscopy analysis. It was found that the PZT layers grown by PLD on SRO/STO substrates are epitaxial while the layers deposited by SG on Pt/Si are polycrystalline. The polarization value decreases as the structure changes from epitaxial to polycrystalline, as well as the magnitude of the leakage current and of the differential negative capacitance, while the switching changes from homogeneous to inhomogeneous. The results are explained by the compensation rate of the depolarization field during the switching process, which is much faster in epitaxial films than in polycrystalline ones.
12. Electro-active properties of nanostructured films of cytosine and guanine nucleobases
Authors: Socol, M; Trupina, L; Galca, AC; Chirila, C; Stan, GE; Vlaicu, AM; Stanciu, AE; Boni, AG; Botea, M; Stanculescu, A; Pintilie, L; Borca, B

Published: OCT 8 2021, NANOTECHNOLOGY, 32, DOI: 10.1088/1361-6528/ac10e4

The discovery of multifunctional properties related to electro-activity of organic systems of biomolecules is important for a variety of applications, especially for devices in the realm of biocompatible sensors and/or bioactuators. A further step towards such applications is to prepare thin films with the required properties. Here, the investigation is focused on the characterization of films of guanine and cytosine nucleobases, prepared by thermal evaporation-an industrial accessible deposition technique. The cytosine films have an orthorhombic non-centrosymmetric structure and grow in two interconnected nanostructured fractal patterns, of nearly equal proportion. Piezoresponse force microscopy images acquired at room temperature on the cytosine films display large zones with antiparallel alignment of the vertical components of the polarization vector. Guanine films have a dense nano-grained morphology. Our studies reveal electrical polarization switching effects which can be related to ferroelectricity in the films of guanine molecules. Characteristic ferroelectric polarization-electric-field hysteresis loops showing large electrical polarization are observed at low temperatures up to 200 K. Above this temperature, the guanine films have a preponderant paraelectric phase containing residual or locally induced nano-scopic ferroelectric domains, as observed by piezoresponse force microscopy at room temperature.
13. 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).
14. Carbon-based sprayed electrodes for pyroelectric applications
Authors: Chirila, C; Botea, M; Iuga, A; Tomulescu, AG; Balescu, L; Galca, AC; Boni, AG; Leonat, L; Pintilie, I; Pintilie, L

Published: AUG 15 2019, PLOS ONE, 14, DOI: 10.1371/journal.pone.0221108

A carbon-based layer was deposited by spraying on top of a ferroelectric layer grown by sol-gel on Si (001) substrate and its properties as electrode and absorber for pyroelectric detection were tested. It was found that the electric properties of the ferroelectric capacitor with top carbon-based sprayed electrode (CBSE) are comparable with those of the capacitors with standard top SrRuO3 (SRO)/Au electrode. Pyroelectric measurements show that the pyroelectric signal recorded on ferroelectric capacitors with top CBSE electrode is 2.5 times greater than for top SRO/Au electrode for low frequency range. The value of the pyroelectric coefficient was estimated to 9.73.10(-4) C/m(2)K for CBSE electrodes and 3.36.10(-4) C/m(2)K for SRO/Au respectively. The fabrication process of CBSE is of low cost, easy to implement and with high throughput making it attractive for manufacturing various devices like pyroelectric detector, thermal imaging, solar cells, etc.
15. 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.
16. 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.
17. Effect of Li doping on the electric and pyroelectric properties of ZnO thin films
Authors: Trinca, LM; Galca, AC; Boni, AG; Botea, M; Pintilie, L

Published: JAN 1 2018, APPLIED SURFACE SCIENCE, 427, 37, DOI: 10.1016/j.apsusc.2017.08.009

Un-doped ZnO (UDZO) and Li-doped ZnO (LZO) polycrystalline thin films were grown on platinized silicon by pulsed laser deposition (PLD). The electrical properties were investigated on as-grown and annealed UDZO and LZO films with capacitor configuration, using top and bottom platinum electrodes. In the case of the as-grown films it was found that the introduction of Li increases the resistivity of ZnO and induces butterfly shape in the C-V characteristic, suggesting ferroelectric-like behavior in LZO films. The properties of LZO samples does not significantly changes after thermal annealing while the properties of UDZO samples show significant changes upon annealing, manifested in a butterfly shape of the C-V characteristic and resistive-like switching. However, the butterfly shape disappears if long delay time is used in the C-V measurement, the characteristic remaining non-linear. Pyroelectric signal could be measured only on annealed films. Comparing the UDZO results with those obtained in the case of Li: ZnO, it was found that the pyroelectric properties are considerably enhanced by Li doping, leading to pyroelectric signal with about one order of magnitude larger at low modulation frequencies than for un-doped samples. Although the results of this study hint towards a ferroelectric-like behavior of Li doped ZnO, the presence of real ferroelectricity in this material remains controversial. (C) 2017 Elsevier B.V. All rights reserved.
18. Strong composition dependence of resistive switching in Ba1-xSrxTiO3 thin films on semiconducting substrates and its thermodynamic analysis
Authors: Mohammadmoradi, O; Sen, C; Boni, AG; Pintilie, L; Misirlioglu, IB

Published: APR 15 2018, ACTA MATERIALIA, 148, 431, DOI: 10.1016/j.actamat.2018.02.015

In this work, we report on the variability of the Schottky effect in solution processed Ba1-xSrxTiO3 films (BST, x = 0, 0.5) grown on 0.5% Nb doped SrTiO3 substrates with top Pt electrodes (NSTO/BST/Pt). The films display leakage currents accompanied by varying degrees of hystereses in the current-voltage measurements. The magnitude of the leakage and hystereses depend on the Sr content. We focus on the current-voltage (I-V) behavior of our samples in the light of thermodynamic theory of ferroelectrics coupled with equations of semiconductors. Our calculations allowed us to unambigously determine the electronic character of the defects and related band bending effects in our samples. The extent of asymmetry and the hystereses in the I-V curves for x = 0 and 0.5 are shown to be controlled by the polarization in qualitative agreement with our calculations. Amplitude of the ferroelectric polarization, which is a function of composition here, has a strong impact on leakage currents in forward bias while this effect is much weaker under negative bias. The latter occurs as polarization pointing away from the NSTO semiconducting substrate causes depletion of carriers at the NSTO side of the NSTO/BST interface, increasing resistance to current flow through the stack. Such an occurence also increases the energy gap between the Fermi level and the conduction bands of the films, thereby reducing the bulk conduction through the film as well. The dependence of leakage currents on polarization direction points out to the possibility of a non-destructive read-out route in ferroelectric films much thicker than tunnel junctions. (c) 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
19. Multiple polarization states in symmetric ferroelectric heterostructures for multi-bit non-volatile memories
Authors: Boni, GA; Filip, LD; Chirila, C; Pasuk, I; Negrea, R; Pintilie, I; Pintilie, L

Published: DEC 28 2017, NANOSCALE, 9, 19278, DOI: 10.1039/c7nr06354g

Here we report a ferroelectric capacitor structure obtained by alternating ferroelectric and insulator thin-film layers which allows an increase of up to 2(n) polarization states, with n the number of ferroelectric layers. Four and up to eight distinct, stable and independently addressed polarization states are experimentally demonstrated in this work. The experimental findings are supported by a theoretical model based on the Landau-Ginzburg-Devonshire theory. The key parameter is the change in the strain conditions of ferroelectric layers induced by the insulating separator. Notably, the 2(n) increase in the storage capacity can be achieved without major changes in the present technology used for FeRAM devices. The test structures demonstrate very good memory characteristics such as retention and fatigue, opening the way towards the design of high density ferroelectric memories.
20. 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.
21. TEMPERATURE INFLUENCE ON THE CAPACITANCE-VOLTAGE HYSTERESIS OF TRANSPARENT a-IGZO/PZT/FTO MFS-HETEROSTRUCTURE
Authors: Trinca, LM; Besleaga, C; Stancu, V; Radu, R; Iuga, A; Boni, AG; Galca, AC; Pintilie, L

Published: 2017, ROMANIAN REPORTS IN PHYSICS, 69, DOI:

Capacitance-voltage (C-V) hysteresis of metal-ferroelectric-semiconductor (MFS) structure based on a-In2GaZnO5.5 and Pb0.2Zr0.8TiO3 layers are recorded in the 350-470 K range. The structure is grown on FTO/glass to obtain a transparent MFS. The memory functionality of the heterostructure is proved through C-V and P-V characteristics. The memory window is dependent on the temperature, the largest value of 2.5 V being obtained at 470 K, where the contribution of the ferroelectric-semiconductor interface defect states is minimized. The direction of C-V hysteresis is clockwise at 350 K, and it turns counterclockwise at higher temperatures where the ferroelectric polarization has the main contribution.
22. Steplike Switching in Symmetric PbZr0.2Ti0.8O3/CoFeO4/PbZr0.2Ti0.8O3 Heterostructures for Multistate Ferroelectric Memory
Authors: Boni, AG; Chirila, C; Pasuk, I; Negrea, R; Pintilie, I; Pintilie, L

Published: SEP 28 2017, PHYSICAL REVIEW APPLIED, 8, DOI: 10.1103/PhysRevApplied.8.034035

A hysteresis loop with three polarization states is obtained in the case of a symmetric epitaxial ferroelectric-interlayer-ferroelectric structure with bottom and top SrRuO3 electrodes. The ferroelectric layers are of PbZr0.2Ti0.8O3, while the interlayer is CoFe2O4. It is shown that the three polarization states can be separately accessed, suggesting that this type of structure can be used as building element for a three-state nonvolatile ferroelectric random-access memory (FERAM). The presence of the three-state memory effect is explained through a simple phenomenological model based on Landau-Ginzburg-Devonshire theory. The findings of this study can pave the way to multistate all-oxide FERAM devices, resulting in a 50% increase in the storage density compared to actual nonvolatile memories.
23. Electrical properties of single CuO nanowires for device fabrication: Diodes and field effect transistors
Authors: Florica, C; Costas, A; Boni, AG; Negrea, R; Ion, L; Preda, N; Pintilie, L; Enculescu, I

Published: JUN 1 2015, APPLIED PHYSICS LETTERS, 106, DOI: 10.1063/1.4921914

High aspect ratio CuO nanowires are synthesized by a simple and scalable method, thermal oxidation in air. The structural, morphological, optical, and electrical properties of the semiconducting nanowires were studied. Au-Ti/CuO nanowire and Pt/CuO nanowire electrical contacts were investigated. A dominant Schottky mechanism was evidenced in the Au-Ti/CuO nanowire junction and an ohmic behavior was observed for the Pt/CuO nanowire junction. The Pt/CuO nanowire/Pt structure allows the measurements of the intrinsic transport properties of the single CuO nanowires. It was found that an activation mechanism describes the behavior at higher temperatures, while a nearest neighbor hopping transport mechanism is characteristic at low temperatures. This was also confirmed by four-probe resistivity measurements on the single CuO nanowires. By changing the metal/semiconductor interface, devices such as Schottky diodes and field effect transistors based on single CuO p-type nanowire semiconductor channel are obtained. These devices are suitable for being used in various electronic circuits where their size related properties can be exploited. (c) 2015 AIP Publishing LLC.
24. Comparison between the ferroelectric/electric properties of the PbZr0.52Ti0.48O3 films grown on Si (100) and on STO (100) substrates
Authors: Chirila, C; Boni, AG; Pasuk, I; Negrea, R; Trupina, L; Le Rhun, G; Yin, S; Vilquin, B; Pintilie, I; Pintilie, L

Published: JUN 2015, JOURNAL OF MATERIALS SCIENCE, 50, 3894, DOI: 10.1007/s10853-015-8907-2

Ferroelectric/electric properties of PbZr0.52Ti0.48O3 (PZT) thin films grown by pulsed laser deposition (PLD) on two different substrates, Si (001) and SrTiO3 (STO) (001), were comparatively analyzed. The structural characterization has revealed the epitaxial relationship between the grown layers and the two types of substrates, with larger density of structural defects for the films deposited on Si (001) with buffer STO layer. The ferroelectric/electric properties are also different, with lower remnant polarization (about half of the value obtained on STO substrate), higher dielectric constant (about two times larger), and lower leakage current (about two orders of magnitude lower) for the PZT films deposited on Si (001) compared to those deposited on (001) STO substrates. Nevertheless, the results show that the use of a STO buffer layer on Si can be a solution to obtain good quality PZT capacitor structures without using expensive single-crystal oxide substrates. In this way, applications based on PZT capacitors (e.g. non-volatile memories, pyroelectric detectors, light switches, etc.) would be more easily integrated directly on Si wafers.
25. Electric and pyroelectric properties of AIN thin films deposited by reactive magnetron sputtering on Si substrate
Authors: Stan, GE; Botea, M; Boni, GA; Pintilie, I; Pintilie, L

Published: OCT 30 2015, APPLIED SURFACE SCIENCE, 353, 1202, DOI: 10.1016/j.apsusc.2015.07.059

Electric and pyroelectric properties of AIN layers deposited on Si substrates with different resistivities were investigated. The dielectric constant was found to be around 12, while the conductance determined from dc current measurements was found to be in the 10(-9) to 10(-19) S range. The pyroelectric measurements were performed in voltage mode using two types of IR sources: a laser diode with 800 nm wavelength and a black body at 700 degrees C. A peculiar behavior was observed for the signal recorded when the laser diode was used as IR source. It was found that the Si substrate is introducing a signal component, due to the photogenerated carriers, which is adding to the pyroelectric signal generated by the AIN layer. This component is strongly dependent on the resistivity of the Si substrate. For strongly doped Si (Si++) the signal generated into the substrate represents only 10% of the recorded pyroelectric voltage. For electronic grade Si the signal generated into the substrate is about 100 times larger than the pyroelectric signal generated in the AIN layer. This effect can be used as an optical amplification of the pyroelectric signal. The frequency dependence observed for the pyroelectric signal recorded when the black body is used as IR source is typical for a pyroelectric detector. A value as large as 12.4 degrees C m(-2) K-1 was obtained for the pyroelectric coefficient using for estimation the constant signal at low modulation frequencies of the IR beam. However, the value of the pyroelectric coefficient is strongly affected by the electrical conductance of the AIN layer. As the conductance is frequency dependent it results that the value of the pyroelectric coefficient is frequency dependent, the value from above being valid only for very small frequencies of the temperature variation. It was also found that the electric and pyroelectric properties are dependent on the crystalline quality of the AIN layer. (C) 2015 Elsevier B.V. All rights reserved.
26. 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.
27. Electrode interface controlled electrical properties in epitaxial Pb(Zr0.52Ti0.48)O-3 films grown on Si substrates with SrTiO3 buffer layer
Authors: Boni, AG; Chirila, C; Pasuk, I; Negrea, R; Trupina, L; Le Rhun, G; Vilquin, B; Pintilie, I; Pintilie, L

Published: OCT 30 2015, THIN SOLID FILMS, 593, 130, DOI: 10.1016/j.tsf.2015.09.028

Electrical properties of ferroelectric capacitors based on PbZr0.52Ti0.48O3 thin films grown by pulsed laser deposition on silicon substrate with SrTiO3 buffer layer grown by molecular beam epitaxy were studied. A SrRuO3 layer was deposited as bottom electrode also by pulse laser deposition and Pt, Ir, Ru, SrRuO3 were used as top contacts. Electrical characterization comprised hysteresis and capacitance-voltage measurements in the temperature range from 150 K to 400 K. It was found that the macroscopic electrical properties are affected by the electrode interface, by the choice of the top electrode. However, even for metals with very different work functions (e.g. Pt and SrRuO3) the properties of the top and bottom electrode interfaces remain fairly symmetric suggesting a strong influence from the bound polarization charges located near the interface. (C) 2015 Elsevier B.V. All rights reserved.
28. 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.
29. 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.
30. Electronic transport in (La,Sr)MnO3-ferroelectric-(La,Sr)MnO3 epitaxial structures
Authors: Boni, AG; Pintilie, I; Pintilie, L; Preziosi, D; Deniz, H; Alexe, M

Published: JUN 14 2013, JOURNAL OF APPLIED PHYSICS, 113, DOI: 10.1063/1.4808335

The leakage current in all oxide epitaxial (La,Sr)MnO3-ferroelectric-(La,Sr)MnO3 structures, where the ferroelectric layer is either BaTiO3 or Pb(Zr0.2Ti0.8)O-3, was analyzed on a broad range of temperatures and for different thicknesses of the ferroelectric layer. It was found that, although the structures are nominally symmetric, the current-voltage (I-V) characteristics are asymmetric. The leakage current depends strongly on the thicknesses of the ferroelectric layer, on temperature and on the polarity of the applied voltage. Simple conduction mechanisms such as space charge limited currents or thermionic emission cannot explain in the same time the voltage, temperature, and thickness dependence of the experimentally measured leakage currents. A combination between interface limited charge injection and bulk controlled drift-diffusion (through hopping in the case of BTO and through band mobility in the case of PZT) is qualitatively explaining the experimental I-V characteristics. (C) 2013 AIP Publishing LLC.
31. 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.
32. The Role of Interface Defect States in n- and p-Type Ge Metal-Ferroelectric-Semiconductor Structures with Hf0.5Zr0.5O2 Ferroelectric
Authors: Boni, GA; Istrate, CM; Zacharaki, C; Tsipas, P; Chaitoglou, S; Evangelou, EK; Dimoulas, A; Pintilie, I; Pintilie, L

Published: , PHYSICA STATUS SOLIDI A-APPLICATIONS AND MATERIALS SCIENCE, 2000500, DOI: 10.1002/pssa.202000500

The discovery of ferroelectricity in doped HfO2 represents an excellent opportunity to overcome the obstacles in manufacturing reliable ferroelectric field effect transistors (FeFET) for nonvolatile memory applications, considering that HfO2 is compatible with Si and Ge and it is already used in semiconductor industry. The presence of interface defects may have detrimental effects on the operation of FeFETs, so their role is systematically investigated in this study in correlation with the substrate doping. Metal-ferroelectric-semiconductor (MFS) structures are fabricated by depositing Hf0.5Zr0.5O2 (HZO) layers on n-type Ge substrate. Their electric properties are compared with those of MFS structures obtained by depositing HZO on p-type Ge, to study the influence of the doping. It is found that, although the ferroelectric properties of HZO are similar, the capacitance and impedance of the MFS structures behave differently. For n-Ge, the occupation probability of a large number of low-lying interface defect acceptor states, charges the interface negatively which adversely affects the C-V response of the MFS, albeit without harming the ferroelectric (P-V) hysteresis. Although the interface defects do not harm ferroelectricity, they could inhibit inversion in p-type Ge or accumulation in n-type Ge so they should be taken into account when designing Ge FeFET devices.
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