Dr. Lucian Dragos FILIP

Despite the promise of high-k dielectrics, inherent limitations persist in transistor scaling and enhancing energy efficiency, including a fundamental threshold of 60 mV/dec for increasing drain current by an order of magnitude. Proposed solutions involve negative capacitance at the gate oxide to overcome this barrier using ferroelectric structures. Efforts to understand and regulate the switching dynamics and intricate electrostatic configurations of ferroelectric structures towards achieving negative capacitance regimes have intensified. While standalone ferroelectric capacitors cannot stabilize negative capacitance without external fields, multilayered thin films offer a promising solution. Typically, ferroelectric layers are paired with dielectrics/insulator, demonstrating steady-state negative capacitance, often at nanoscale or specific temperature domains. This study aims to stabilize negative capacitance in ferroelectric structures by inducing internal electric fields, aligning the system near coercivity, particularly in bilayer structures formed by two ferroelectric layers with slight differences in polarization values, such as p-n heterojunctions using Pb (Zr,Ti)O3 PZT) with different doping as Fe, Nb, Bi. Most of these structures exhibit evident amplification of capacitance compared to the equivalent series-connected capacitance, across a large temperature domain. The complex capacitance-frequency characteristic of these structures indicates a complex equivalent circuit. Analysis of these complex circuits compared with simple component layers concludes that at least one of the FE layers in these bilayer structures is in a negative capacitance (NC) state.

This study focuses on the properties of the BiOi (interstitial Boron-interstitial Oxygen) and CiOi (interstitial Carbon-interstitial Oxygen) defect complexes by 5.5MeV electrons in low resistivity silicon. Two different types of diodes manufactured on p-type epitaxial and Czochralski silicon with a resistivity of about 10 Omega center dot cm were irradiated with fluence values between 1x10(15) cm(-2) and 6x10(15) cm(-2). Such diodes cannot be fully depleted and thus the accurate evaluation of defect concentrations and properties (activation energy, capture cross-section, concentration) from Thermally Stimulated Currents (TSC) experiments alone is not possible. In this study we demonstrate that by performing Thermally Stimulated Capacitance (TS-Cap) experiments in similar conditions to TSC measurements and developing theoretical models for simulating both types of BiOi signals generated in TSC and TS-Cap measurements, accurate evaluations can be performed. The changes of the position-dependent electric field, the effective space charge density N-eff profile as well as the occupation of the BiOi defect during the electric field dependent electron emission, are simulated as a function of temperature. The macroscopic properties (leakage current and..eff) extracted from current-voltage and capacitance-voltage measurements at 20 degrees C are also presented and discussed.

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.

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.

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.

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.

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.

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.

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.

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).

Berry phase (BP) polarization calculations have been investigated for several ferroelectric materials from the point of view of practical calculations. It was shown that interpretation of the results is particular to each case due to the multivalued aspect of polarization in the modern theory. Almost all of the studied examples show ambiguous polarization results which can be difficult to solve especially for super-cells containing large number of atoms. For this reason, a procedure has been proposed to minimize the number of calculations required to produce an unambiguous polarization result from BP polarization investigations.

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.

The fundamental phenomena at ferroelectric interfaces have been the subject of thorough theoretical and computational studies due to their usefulness in a large variety of emergent electronic devices, solar cells and catalysts. Ferroelectricity determines interface band-bending and shifts in electron energies, which can be beneficial or detrimental to device performance. However, the underlying mechanisms are still the subject of debate and investigation, as a deeper understanding of the electrochemistry is required to develop bona fide design principles for functional ferroelectric surfaces and interfaces. Here, using first principles calculations within the GGA + U formalism, we investigate the problem of band alignment in non-defective, asymmetric SrRuO3/PbTiO3/SrRuO3 capacitors with ultra-thin ferroelectric layers. The effects of the dielectric size on the polar distortion stability and interface-specific properties are analyzed. It is shown that the critical size of the dielectric for polarization switching is approximate to 2 nm (5 PbTiO3 u.c.). Below this limit there is no bulk-like region in the dielectric, the space charge accumulated at interfaces leads to the presence of gap states in the whole PbTiO3 layer and ferroelectricity vanishes. We draw the band alignment diagrams as given by the band line-up and band structure terms, as well as by taking Ti 3s semi-core states as reference. In the ferroelectric structures, both approaches predict a strong effect of band-bending on the type of contact, Schottky or Ohmic, at the asymmetric interfaces. The effect of interface states on the interface dipole amplitude and band alignment is discussed.

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.

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.

The substantial increase in the power conversion efficiency of hybrid perovskite solar cells, to date reaching more than 20% in the laboratory, has strongly motivated research on this class of organic-inorganic materials and related devices, particularly based on CH3NH3PbI3-xXx/TiO2 heterostructures (X = Cl,Br). Taking under consideration that a ferroelectric substrate may act as an efficient electron transporter, positively influencing charge collection across the interface and allowing the tuning of the halide perovskite (HP) - ferroelectric junction, we performed extensive density functional theory calculations on CH3NH3PbI3-xClx layers deposited on tetragonal PbTiO3 (PTO) (001) surfaces, to study their structural and electronic properties. The main findings of this study are as follows. (i) A ferroelectric polarization pointing from the PTO/HP interface to the PTO is favorable for the photogenerated electrons transfer across the interface and their transport to the collecting electrode. (ii) The PTO internal electric field leads to a position dependent energy levels diagram. (iii) The HP gap may be tuned by chlorine concentration at the interface, as well as the by the surface terminations of PbTiO3 and hybrid perovskite layers. (iv) The presence of the PTO ferroelectric surface is likely to have just a slight orientational effect on the (CH3NH3)(+) dipoles.

Some of the modern aspects of field emission based electron sources have been collated in a short and comprehensive review. The usually overlooked peculiar aspects in this research field have been particularly emphasized in order to increase the interest in further fundamental studies and technological applications. The vast material was roughly split in two main branches which occasionally overlap: the electron emission devices based on chemically homogeneous nanostructured surfaces and the more complex nanocomposite emitting surfaces.

A model for current voltage characteristics of a thin film metal-ferroelectric-metal structure is constructed by combining the electrostatics of a polarized ferroelectric film with the balanced flow of charge through its interfaces. Using a set of fitting parameters, good agreement with several sets of experimental data is obtained for different system temperatures. The influence of model parameters on the current-voltage characteristic is discussed. Best fit values of some of these parameters correlate well with ab initio calculations in the literature, supporting the idea of low dielectric permittivity of the interface transition layers in the ferroelectric.

The leakage current for a thin film metal-ferroelectric-metal device was modelled using an electron tunnelling approach. The potential energy through the device was obtained from an electrostatic argument and a balance equation was imposed for the incoming and outgoing currents. Using the obtained leakage current, experimental data was fitted in order to obtain qualitative values for the model parameters. Good agreement between the obtained dielectric constant and numerical calculations performed in the literature.

The current-voltage (C-V) characteristic of epitaxial ferroelectric films is simulated assuming the presence of Schottky-type contacts at the two electrode interfaces. The model assumes that the overall capacitance of the metal-ferroelectric-metal (MFM) structure is composed of two parts: (i) one associated with the Schottky contacts, in which the ferroelectric polarization is saturated, the dielectric constant is independent on the voltage and only the linear response to the applied electric field is taken into account; (ii) one related to the ferroelectric volume, where the dielectric constant is voltage dependent through the hysteresis response of the ferroelectric polarization. Themost important result of the model is that it can simulate the experimentally observed thickness dependence of the dielectric constant without considering a so-called "dead layer" at the electrode interface. The model renders C-V characteristics in good qualitative agreement with the experimental ones in the case of an MFM structure based on epitaxial PZT films. The quantitative fit suggests that the behaviour of the ferroelectric polarization during the C-V measurement may be very different from its behaviour during the hysteresis measurement. This is explained by the fact that the two measurements have very different principles. It is also found that the dielectric constant of the ferroelectric volume has a different voltage dependence compared to the one derived from the hysteresis loop or from the experimental C-V characteristic. This is also related to the different measurement principles and to the fact that the measured capacitance of the MFM structure includes, besides the ferroelectric volume, the voltage dependent capacitance of the Schottky contacts. (C) 2015 Elsevier B.V. All rights reserved.

Oxide materials are becoming of increasing interest due to their large variety of physical properties such as dielectric, magnetism, superconductivity, conductivity, ferroelectricity, multiferroism, etc. In addition, interfacing oxides with other materials is conferring new or better device functionalities. The main physical properties of oxides interfaces and their impact on the electrical properties of interest for microelectronic applications are presented. Further on, this subchapter is also devoted to the investigation and understanding of interface effects observed in heterostructures containing linear (SiO2) and non-linear (ferroelectrics) dielectrics in combination with wide-band gap semiconductor materials (e.g. ZnO and SiC) with special emphasis on size effects, interface quality and the opportunity to control the emergent phenomena in Metal-Oxide-Semiconductor (MOS) and Metal-Ferroelectric-Semiconductor (MFS) materials systems.

Over the last decade, field emission miniature x-ray tubes emerged as cutting-edge applications of nanotechnology, possessing massive potential for use in various important fields, including that of precision medical therapy. The article essentially presents a review of such new devices reported in the literature. Additional discussions on the necessity of stabilizing the electron beam that generates x-rays are also included, and a simple technique for minimizing the current fluctuations is described. It is also pointed out that further miniaturization of field emission x-ray sources may need new concepts in designing the tube in shapes acting as "self focusing" structures for the electron beams.

In this work, anomalous discontinuities observed in Capacitance-Voltage (C-V) characteristics on non-nitridated n-4H-SiC/SiO2 capacitors at low temperature are addressed. The appearance of abrupt capacitance minima, always at the same gate voltages (4V and 8V) and independent on probe frequency, led us to consider a resonant electron tunneling process from neutral donor states present at the SiC/SiO2 interface into two well defined energy levels in the oxide layer. Results of numerical simulations based on this model describe quantitatively the experimentally observed discontinuities at 4V and 8V and provide strong evidence for the presence resonant tunneling.

As-grown n-4H-SiC/SiO2 capacitors exhibit anomalous capacitance-vs.-voltage (C-V) characteristics at low temperatures. Abrupt minima appear in the C-V curves at specific values of the gate voltages independent of the sample temperature, strongly suggesting the presence of resonant electron tunneling. We put forward a qualitative model where neutral donor states present at the SiC/SiO2 interface enable electron tunneling into distinct energy levels in the oxide. Numerical simulations based on this model show close agreement with the anomalous C-V characteristics observed experimentally. The model implies that under given conditions, i.e., the existence of a sufficient density of neutral donors at the semiconductor/oxide interface and empty electron states in the oxide layer, abrupt minima are in general to be expected during C-V measurements of metal-oxide-semiconductor capacitors. (C) 2013 Elsevier B. V. All rights reserved.

The hysteretic behavior of the epitaxial Pb(Zr,Ti)O-3 thin films with different top metal electrodes is studied, with emphasis on the influence of the leakage current and trap generation current on the shape of the loop as well as on the magnitude of the measured polarization. Cu, Pt, and SrRuO3 were used as top contacts and important differences were observed for measurements performed in both dynamic and static modes, although the contacts were deposited on the same epitaxial Pb(Zr,Ti)O-3 film grown on SrRuO3/SrTiO3 substrate. A peculiar behavior was observed especially for the static hysteresis loops where, depending of the top contact, the loop is influenced mainly by the leakage current (Pt) or by the trap generation current (Cu and SrRuO3). The last one can contribute with an additive charge, having a linear dependence on the applied voltage, as suggested by the simple model developed to explain the abnormally high values of the dielectric constant extracted from the linear part of the static hysteresis loop. It is concluded that the properties of the top electrode interface can significantly impact the hysteretic behavior of the ferroelectric films. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4754318]

The electronic properties of two-dimensional toroidal surfaces of nanometer size have been investigated by approximately solving the time-independent Schrodinger equation. The effects of the quantum confinement on the electron population of these structures were shown by studying the average electron density on the surface of the torus. The unique electron spread that resulted from such computations encouraged further study on the field emission properties of this two-dimensional manifold. The Wentzel-Kramers-Brillouin approximate approach was used for a preliminary study of the field emission properties of the nanotori for various geometrical parameters. (c) 2011 American Vacuum Society. [DOI: 10.1116/1.3531935]

A general method for mapping the equipotential profile surrounding a conductive cylindrically symmetric high aspect ratio structure, such as a carbon nanotube or a Spindt tip, is devised. The surface of the object is replaced by a discrete set of charges located on the symmetry axis. The overall electrostatic potential must satisfy a set of boundary conditions imposed on the original surface. The optimum number of charges is determined through an iterative self-validating process such that the obtained equipotential mimics the surface of the object. The method is exemplified by calculating the electric field enhancement factor for rounded cones and cylinders resembling Spindt tips and carbon nanotubes, respectively. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3582141]