Toward Design Rules for Multilayer Ferroelectric Energy Storage Capacitors - A Study Based on Lead-Free and Relaxor-Ferroelectric/Paraelectric Multilayer Devices.

Future pulsed-power electronic systems based on dielectric capacitors require the use of environment-friendly materials with high energy-storage performance that can operate efficiently and reliably in harsh environments. Here, a study of multilayer structures, combining paraelectric-like Ba0.6Sr0.4TiO3 (BST) with relaxor-ferroelectric BaZr0.4Ti0.6O3 (BZT) layers on SrTiO3-buffered Si substrates, with the goal to optimize the high energy-storage performance is presented. The energy-storage properties of various stackings are investigated and an extremely large maximum recoverable energy storage density of ≈165.6 J cm-3 (energy efficiency ≈ 93%) is achieved for unipolar charging-discharging of a 25-nm-BZT/20-nm-BST/910-nm-BZT/20-nm-BST/25-nm-BZT multilayer structure, due to the extremely large breakdown field of 7.5 MV cm-1 and the lack of polarization saturation at high fields in this device. Strong indications are found that the breakdown field of the devices is determined by the outer layers of the multilayer stack and can be increased by improving the quality of these layers. Authors are also able to deduce design optimization rules for this material combination, which can be to a large extend justify by structural analysis. These rules are expected also to be useful for optimizing other multilayer systems and are therefore very relevant for further increasing the energy storage density of capacitors.

Stabilizing Perovskite Pb(Mg0.33Nb0.67)O3-PbTiO3 Thin Films by Fast Deposition and Tensile Mismatched Growth Template.

Because of its low hysteresis, high dielectric constant, and strong piezoelectric response, Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) thin films have attracted considerable attention for the application in PiezoMEMS, field-effect transistors, and energy harvesting and storage devices. However, it remains a great challenge to fabricate phase-pure, pyrochlore-free PMN-PT thin films. In this study, we demonstrate that a high deposition rate, combined with a tensile mismatched template layer can stabilize the perovskite phase of PMN-PT films and prevent the nucleation of passive pyrochlore phases. We observed that an accelerated deposition rate promoted mixing of the B-site cation and facilitated relaxation of the compressively strained PMN-PT on the SrTiO3 (STO) substrate in the initial growth layer, which apparently suppressed the initial formation of pyrochlore phases. By employing La-doped-BaSnO3 (LBSO) as the tensile mismatched buffer layer, 750 nm thick phase-pure perovskite PMN-PT films were synthesized. The resulting PMN-PT films exhibited excellent crystalline quality close to that of the STO substrate.

Thin Films of α-Quartz GeO2 on TiO2-Buffered Quartz Substrates.

α-Quartz (SiO2) is one of the most widely used piezoelectric materials. However, the challenges associated with the control of the crystallization and the growth process limit its production to the hydrothermal growth of bulk crystals. GeO2 can also crystallize into the α-quartz phase, with a higher piezoelectric response and better thermal stability than SiO2. In a previous study, we have found that GeO2 crystallization on nonquartz substrates shows a tendency to form spherulites with a randomized orientation; while epitaxial growth of crystalline GeO2 thin films can take place on quartz (SiO2) substrates. However, in the latter case, the α-ß phase transition that takes place in both substrates and thin films during heating deteriorates the long-range order and, thus, the piezoelectric properties. Here, we report the ousting of spherulitic growth by using a buffer layer. Using TiO2 as a buffer layer, the epitaxial strain of the substrates can be transferred to the growing films, leading to the oriented crystallization of GeO2 in the α-quartz phase. Moreover, since the TiO2 separates the substrates and the thin films, the thermal stability of the GeO2 is kept across the substrate's phase transitions. Our findings reveal the complexity of the crystallization process of quartz thin films and present a way to eliminate the tendency for spherulitic growth of quartz thin films by epitaxial strain.

A broad-spectrum gas sensor based on correlated two-dimensional electron gas.

Designing a broad-spectrum gas sensor capable of identifying gas components in complex environments, such as mixed atmospheres or extreme temperatures, is a significant concern for various technologies, including energy, geological science, and planetary exploration. The main challenge lies in finding materials that exhibit high chemical stability and wide working temperature range. Materials that amplify signals through non-chemical methods could open up new sensing avenues. Here, we present the discovery of a broad-spectrum gas sensor utilizing correlated two-dimensional electron gas at a delta-doped LaAlO3/SrTiO3 interface with LaFeO3. Our study reveals that a back-gating on this two-dimensional electron gas can induce a non-volatile metal to insulator transition, which consequently can activate the two-dimensional electron gas to sensitively and quantitatively probe very broad gas species, no matter whether they are polar, non-polar, or inert gases. Different gas species cause resistance change at their sublimation or boiling temperature and a well-defined phase transition angle can quantitatively determine their partial pressures. Such unique correlated two-dimensional electron gas sensor is not affected by gas mixtures and maintains a wide operating temperature range. Furthermore, its readout is a simple measurement of electric resistance change, thus providing a very low-cost and high-efficient broad-spectrum sensing technique.

Spatial mapping of photovoltage and light-induced displacement of on-chip coupled piezo/photodiodes by Kelvin probe force microscopy under modulated illumination.

In this work, a silicon photodiode integrated with a piezoelectric membrane is studied by Kelvin probe force microscopy (KPFM) under modulated illumination. Time-dependent KPFM enables simultaneous quantification of the surface photovoltage generated by the photodiode as well as the resulting mechanical oscillation of the piezoelectric membrane with vertical atomic resolution in real-time. This technique offers the opportunity to measure concurrently the optoelectronic and mechanical response of the device at the nanoscale. Furthermore, time-dependent atomic force microscopy (AFM) was employed to spatially map voltage-induced oscillation of various sizes of piezoelectric membranes without the photodiode to investigate their position- and size-dependent displacement.

Signatures of enhanced out-of-plane polarization in asymmetric BaTiO3 superlattices integrated on silicon.

In order to bring the diverse functionalities of transition metal oxides into modern electronics, it is imperative to integrate oxide films with controllable properties onto the silicon platform. Here, we present asymmetric LaMnO3/BaTiO3/SrTiO3 superlattices fabricated on silicon with layer thickness control at the unit-cell level. By harnessing the coherent strain between the constituent layers, we overcome the biaxial thermal tension from silicon and stabilize c-axis oriented BaTiO3 layers with substantially enhanced tetragonality, as revealed by atomically resolved scanning transmission electron microscopy. Optical second harmonic generation measurements signify a predominant out-of-plane polarized state with strongly enhanced net polarization in the tricolor superlattices, as compared to the BaTiO3 single film and conventional BaTiO3/SrTiO3 superlattice grown on silicon. Meanwhile, this coherent strain in turn suppresses the magnetism of LaMnO3 as the thickness of BaTiO3 increases. Our study raises the prospect of designing artificial oxide superlattices on silicon with tailored functionalities.

High-Strain-Induced Local Modification of the Electronic Properties of VO2 Thin Films.

Vanadium dioxide (VO2) is a popular candidate for electronic and optical switching applications due to its well-known semiconductor-metal transition. Its study is notoriously challenging due to the interplay of long- and short-range elastic distortions, as well as the symmetry change and the electronic structure changes. The inherent coupling of lattice and electronic degrees of freedom opens the avenue toward mechanical actuation of single domains. In this work, we show that we can manipulate and monitor the reversible semiconductor-to-metal transition of VO2 while applying a controlled amount of mechanical pressure by a nanosized metallic probe using an atomic force microscope. At a critical pressure, we can reversibly actuate the phase transition with a large modulation of the conductivity. Direct tunneling through the VO2-metal contact is observed as the main charge carrier injection mechanism before and after the phase transition of VO2. The tunneling barrier is formed by a very thin but persistently insulating surface layer of the VO2. The necessary pressure to induce the transition decreases with temperature. In addition, we measured the phase coexistence line in a hitherto unexplored regime. Our study provides valuable information on pressure-induced electronic modifications of the VO2 properties, as well as on nanoscale metal-oxide contacts, which can help in the future design of oxide electronics.

Relaxor-Ferroelectric Films for Dielectric Tunable Applications: Effect of Film Thickness and Applied Electric Field.

The dielectric properties, tunability and figure-of-merit (FOM) of relaxor Pb0.9La0.1(Zr0.52Ti0.48)O3 (PLZT) films have been investigated. Dielectric measurements indicated that the dielectric constant (at zero-bias field), tunability and FOM are enhanced as the film thickness increases, which are mainly attributed to the presence of an interfacial layer near the film-electrode interface. Experimental results illustrated that a slight reduction is observed in both dielectric constant and tunability (-2%) in a wide-frequency range (10 kHz-1 MHz); meanwhile, the FOM value decreases significantly (-17%) with increasing frequency, arising from the higher dielectric loss value. The 1000-nm PLZT film shows the largest tunability of 94.6% at a maximum electric-field of 1450 kV/cm, while the highest FOM factor is 37.6 at 1000 kV/cm, due to the combination of medium tunability (88.7%) and low dielectric loss (0.0236). All these excellent results indicated that the relaxor PLZT films are promising candidates for specific applications in microwave devices.

Growth and Crystallization of SiO2/GeO2 Thin Films on Si(100) Substrates.

The growth of α-quartz-based piezoelectric thin films opens the door to higher-frequency electromechanical devices than those available through top-down approaches. We report on the growth of SiO2/GeO2 thin films by pulsed laser deposition and their subsequent crystallization. By introducing a devitrifying agent uniformly within the film, we are able to obtain the α-quartz phase in the form of platelets with lateral sizes above 100 µm at accessible temperatures. Films containing different amounts of devitrifying agent are investigated, and their crystallinity is ascertained with X-ray diffraction and electron back-scatter diffraction. Our work highlights the difficulty in crystallization when competing phases arise that have markedly different crystalline orientation.

Influence of Excess Potassium on Structural and Ferroelectric Properties of Lead-Free Bi0.5K0.5TiO3 Thin Films.

Lead-free Bi0.5K0.5TiO3 (BKT) ferroelectric films were synthesized on Pt/Ti/SiO2/Si substrates via the chemical solution deposition. The influence of the excess potassium on the microstructures and the ferroelectric properties of the films was investigated in detail. The results showed that the BKT films have reached the well-crystallized state in the single-phase perovskite structure with 20 mol.% excess amount of potassium. For this film, the ferroelectric properties of the films were significantly enhanced. The remnant polarization (Pr) and maximum polarization (Pm) reached the highest values of 9.4 µC/cm2 and 32.2 µC/cm2, respectively, under the electric field of 400 kV/cm.

Spatially Controlled Octahedral Rotations and Metal-Insulator Transitions in Nickelate Superlattices.

The properties of correlated oxides can be manipulated by forming short-period superlattices since the layer thicknesses are comparable with the typical length scales of the involved correlations and interface effects. Herein, we studied the metal-insulator transitions (MITs) in tetragonal NdNiO3/SrTiO3 superlattices by controlling the NdNiO3 layer thickness, n in the unit cell, spanning the length scale of the interfacial octahedral coupling. Scanning transmission electron microscopy reveals a crossover from a modulated octahedral superstructure at n = 8 to a uniform nontilt pattern at n = 4, accompanied by a drastically weakened insulating ground state. Upon further reducing n the predominant dimensionality effect continuously raises the MIT temperature, while leaving the antiferromagnetic transition temperature unaltered down to n = 2. Remarkably, the MIT can be enhanced by imposing a sufficiently large strain even with strongly suppressed octahedral rotations. Our results demonstrate the relevance for the control of oxide functionalities at reduced dimensions.

Strain-Engineered Metal-to-Insulator Transition and Orbital Polarization in Nickelate Superlattices Integrated on Silicon.

Epitaxial growth of SrTiO3 (STO) on silicon greatly accelerates the monolithic integration of multifunctional oxides into the mainstream semiconductor electronics. However, oxide superlattices (SLs), the birthplace of many exciting discoveries, remain largely unexplored on silicon. In this work, LaNiO3 /LaFeO3 SLs are synthesized on STO-buffered silicon (Si/STO) and STO single-crystal substrates, and their electronic properties are compared using dc transport and X-ray absorption spectroscopy. Both sets of SLs show a similar thickness-driven metal-to-insulator transition, albeit with resistivity and transition temperature modified by the different amounts of strain. In particular, the large tensile strain promotes a pronounced Ni 3 d x 2 - y 2 orbital polarization for the SL grown on Si/STO, comparable to that reported for LaNiO3 SL epitaxially strained to DyScO3 substrate. Those results illustrate the ability to integrate oxide SLs on silicon with structure and property approaching their counterparts grown on STO single crystal, and also open up new prospects of strain engineering in functional oxides based on the Si platform.

Integration of Single Oriented Oxide Superlattices on Silicon Using Various Template Techniques.

To benefit from the diverse functionalities of perovskite oxides in silicon-based complementary metal oxide semiconductor (CMOS) technology, integrating oxides into a silicon platform has become one of the major tasks for oxide research. Using the deposition of LaMnO3/SrTiO3 (STO) superlattices (SLs) as a case study, we demonstrate that (001) single oriented oxide SLs can be integrated on Si using various template techniques, including a single-layer buffer of STO prepared by molecular beam epitaxy (MBE) and pulsed laser deposition, a multilayer buffer of Y-stabilized zirconia/CeO2/LaNiO3/STO, and STO-coated two-dimensional nanosheets of Ca2Nb3O10 (CNO) and reduced graphene oxide. The textured SL grown on STO-coated CNO nanosheets shows the highest crystallinity, owing to the small lattice mismatch between CNO and STO as well as less clamping from a Si substrate. The epitaxial SL grown on STO buffer prepared by MBE suffers the largest thermal strain, giving rise to a strongly suppressed saturation magnetization but an enhanced coercive field, as compared to the reference SL grown on an STO single crystal. These optional template techniques used for integrating oxides on Si are of significance to fulfill practical applications of oxide films in different fields.

Growing a LaAlO3/SrTiO3 heterostructure on Ca2Nb3O10 nanosheets.

The two-dimensional electron liquid which forms between the band insulators LaAlO3 (LAO) and SrTiO3 (STO) is a promising component for oxide electronics, but the requirement of using single crystal SrTiO3 substrates for the growth limits its applications in terms of device fabrication. It is therefore important to find ways to deposit these materials on other substrates, preferably Si, or Si-based, in order to facilitate integration with existing technology. Interesting candidates are micron-sized nanosheets of Ca2Nb3O10 which can be used as seed layers for perovskite materials on any substrate. We have used low-energy electron microscopy (LEEM) with in-situ pulsed laser deposition to study the subsequent growth of STO and LAO on such flakes which were deposited on Si. We can follow the morphology and crystallinity of the layers during growth, as well as fingerprint their electronic properties with angle resolved reflected electron spectroscopy. We find that STO layers, deposited on the nanosheets, can be made crystalline and flat; that LAO can be grown in a layer-by-layer fashion; and that the full heterostructure shows the signature of the formation of a conducting interface.

Nanoscale piezoelectric surface modulation for adaptive extreme ultraviolet and soft x-ray optics.

Extreme ultraviolet and soft x-ray wavelengths have ever-increasing applications in photolithography, imaging, and spectroscopy. Adaptive schemes for wavefront correction at such a short wavelength range have recently gained much attention. In this Letter we report, to the best of our knowledge, the first demonstration of a functional actuator based on piezoelectric thin films. We introduce a new approach that allows producing a gradually varying surface deformation. White light interferometery is used to show the level of control in generating arbitrary surface profiles at the nanoscale.

Tandem Si Micropillar Array Photocathodes with Conformal Copper Oxide and a Protection Layer by Pulsed Laser Deposition.

This work demonstrates the influence of high-quality protection layers on Si-Cu2O micropillar arrays created by pulsed laser deposition (PLD), with the goal to overcome photodegradation and achieve long-term operation during photoelectrochemical (PEC) water splitting. Sequentially, we assessed planar and micropillar device designs with various design parameters and their influence on PEC hydrogen evolution reaction. On the planar device substrates, a Cu2O film thickness of 600 nm and a Cu2O/CuO heterojunction layer with a 5:1 thickness ratio between Cu2O to CuO were found to be optimal. The planar Si/Cu2O/CuO heterostructure showed a higher PV performance (Jsc = 20 mA/cm2) as compared to the planar Si/Cu2O device, but micropillar devices did not show this improvement. Multifunctional overlayers of ZnO (25 nm) and TiO2 (100 nm) were employed by PLD on Si/Cu2O planar and micropillar arrays to provide a hole-selective passivation layer that acts against photocorrosion. A micropillar Si/ITO-Au/Cu2O/ZnO/TiO2/Pt stack was compared to a planar device. Under optimized conditions, the Si/Cu2O photocathode with Pt as a HER catalyst displayed a photocurrent of 7.5 mA cm-2 at 0 V vs RHE and an onset potential of 0.85 V vs RHE, with a stable operation for 75 h.

Spin chirality fluctuation in two-dimensional ferromagnets with perpendicular magnetic anisotropy.

Non-coplanar spin textures with scalar spin chirality can generate an effective magnetic field that deflects the motion of charge carriers, resulting in a topological Hall effect (THE)1-3. However, spin chirality fluctuations in two-dimensional ferromagnets with perpendicular magnetic anisotropy have not been considered so far. Here, we report evidence of spin chirality fluctuations by probing the THE above the Curie temperature in two different ferromagnetic ultra-thin films, SrRuO3 and V-doped Sb2Te3. The temperature, magnetic field, thickness and carrier-type dependence of the THE signal, along with Monte Carlo simulations, suggest that spin chirality fluctuations are a common phenomenon in two-dimensional ferromagnets with perpendicular magnetic anisotropy. Our results open a path for exploring spin chirality with topological Hall transport in two-dimensional magnets and beyond4-7.

Metal-insulator-transition engineering by modulation tilt-control in perovskite nickelates for room temperature optical switching.

In transition metal perovskites ABO3, the physical properties are largely driven by the rotations of the BO6 octahedra, which can be tuned in thin films through strain and dimensionality control. However, both approaches have fundamental and practical limitations due to discrete and indirect variations in bond angles, bond lengths, and film symmetry by using commercially available substrates. Here, we introduce modulation tilt control as an approach to tune the ground state of perovskite oxide thin films by acting explicitly on the oxygen octahedra rotation modes-that is, directly on the bond angles. By intercalating the prototype SmNiO3 target material with a tilt-control layer, we cause the system to change the natural amplitude of a given rotation mode without affecting the interactions. In contrast to strain and dimensionality engineering, our method enables a continuous fine-tuning of the materials' properties. This is achieved through two independent adjustable parameters: the nature of the tilt-control material (through its symmetry, elastic constants, and oxygen rotation angles), and the relative thicknesses of the target and tilt-control materials. As a result, a magnetic and electronic phase diagram can be obtained, normally only accessible by A-site element substitution, within the single SmNiO3 compound. With this unique approach, we successfully adjusted the metal-insulator transition (MIT) to room temperature to fulfill the desired conditions for optical switching applications.

Growth mechanism of epitaxial YSZ on Si by Pulsed Laser Deposition.

The epitaxial growth of yttria-stabilized zirconia (YSZ) on silicon with native oxide was investigated in order to gain more insight in the growth mechanism. Specifically, attention was paid to the possibilities to control the chemical interactions between YSZ, silicon and oxygen during initial growth. The sources of oxygen during growth proved to play an important role in the growth process, as shown by individual manipulation of all sources present during Pulsed Laser Deposition. Partial oxidation of the YSZ plasma and sufficient delivery of oxygen to the growing film were necessary to prevent silicide formation and obtain optimal YSZ crystalline qualities. In these conditions, thickness increase of the silicon native oxide before growth just started to occur, while a much faster regrowth of silicon oxide at the YSZ-Si interface occurred during growth. Control of all these contributions to the growth process is necessary to obtain reproducible growth of high quality YSZ.

Large piezoelectric strain with ultra-low strain hysteresis in highly c-axis oriented Pb(Zr0.52Ti0.48)O3 films with columnar growth on amorphous glass substrates.

Thin films of PbZr0.52Ti0.48O3 (PZT) with largely detached columnar grains, deposited by pulsed laser deposition (PLD) on amorphous glass substrates covered with Ca2Nb3O10 nanosheets as growth template and using LaNiO3 electrode layers, are shown to exhibit very high unipolar piezoelectric strain and ultra-low strain hysteresis. The observed increase of the piezoelectric coefficient with increasing film thickness is attributed to the reduction of clamping, because of the increasingly less dense columnar microstructure (more separation between the grains) with across the film thickness. A very large piezoelectric coefficient (490 pm/V) and a high piezoelectric strain (~0.9%) are obtained in 4-µm-thick film under an applied electric field of 200 kV/cm, which is several times larger than in usual PZT ceramics. Further very low strain hysteresis (H≈2-4%) is observed in 4 to 5 µm thick films. These belong to the best values demonstrated so far in piezoelectric films. Fatigue testing shows that the piezoelectric properties are stable up to 1010 cycles. The growth of high quality PZT films with very large strain and piezoelectric coefficients, very low hysteresis and with long-term stability on a technologically important substrate as glass is of great significance for the development of practical piezo driven microelectromechanical actuator systems.