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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 towards 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 surfacelayer 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., Y.A.B. and K.S. contributed equally. 30 pages, 4 figures, Supplemental Material (28 pages, 16 figures)

The rapid advent of the piezoelectric microelectromechanical systems (PiezoMEMS) field has created a tremendous demand for low hysteretic piezoelectric thin films on Si. In this work, we present the integration of epitaxial Pb(Mg0.33Nb0.67)O3-PbTiO3 (PMN-PT) thin films with Si to enable device fabrication using state of the art methods. With optimized buffer layers and electronic contacts, high-quality low hysteretic PMN-PT thin films are integrated with Si, which is a significant stride towards employing PMN-PT thin film for PiezoMEMS devices. It is found that the processing of the necessary SrTiO3 buffer layer is crucial to achieve the growth of phase-pure perovskite PMN-PT layers on Si. Furthermore, we propose the engineering of the electronic contact for the PMN-PT-on-Si capacitors to obtain low hysteretic polarization and displacement responses.

The motion of domain walls is a crucial factor in piezoelectric properties and is usually related to the irreversible and hysteretic behaviors. Herein, we report on the investigation of inverse and transverse piezoelectric coefficients of capacitor-based and microcantilever-based Pb(Zr0.52Ti0.48)O3 films with a change in the DC bias and the AC applied voltage. A large inverse piezoelectric strain coefficient of about 350 p.m./V, and a low strain hysteresis of about 7.1%, are achieved in the film capacitors under a low applied voltage of 2 V (20 kV/cm) which can benefit the actuators for motion control in high-precision systems. The field-dependences of the transverse piezoelectric coefficients, obtained from four-point bending and microcantilever displacement, are in good agreement with each other. The results also reveal that the irreversible domain-wall motion is attributed to the nonlinearity in the field-dependent piezoelectric strain and cantilever displacement.

As the employment of halide perovskite films in single-junction and tandem solar cells continues to soar, there is a strong drive -from academia to industry- to produce these films using dry processes, avoiding the use of toxic solvents. Vapor deposition methods such as co-evaporation have shown advantages of solvent-free approaches to produce high-efficiency solar cells. However, co-evaporation requires the use of multiple sources that challenge the deposition rate control of complex halide perovskite compositions. Here, Pulsed Laser Deposition (PLD) is proposed as an alternative method to deposit hybrid halide perovskites films from a single-source and following a fully dry approach. We use the archetypical methylammonium lead iodide (MAPbI3) to demonstrate the formation of high-quality films with optimal optoelectronic properties by PLD on various substrates for single-junction and tandem devices. Furthermore, the important role of the PLD target composition and deposition parameters to achieve control over film microstructure and optoelectronic properties is discussed. The controlled conformal growth provided by PLD demonstrated in this work with MAPbI3 on device-relevant substrates will broaden opportunities to explore PLD of more complex hybrid halide perovskite compositions for efficient, stable, and scalable solar cell devices.

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.

This study reports on the structure, electric, and magnetic properties of Bi0.5(Na0.80,K0.20)0.5TiO3/BaZrO3 (BNKT/BZO) heterolayered films synthesized via chemical solution deposition on Pt/Ti/SiO2/Si substrates. The influence of different heterolayered configurations on the microstructure, electric and magnetic properties of the films was investigated thoroughly. The heterostructures are expected to generate strongly correlated electron systems in the BNKT and BZO layers that cause a magnetic interface effect in the BNKT/BZO conjunction layer. The BZO layer also prevents metal ion evaporation, resulting in a decline in oxygen vacancies and an enhancement in the electric and magnetic properties. The obtained results show that magnetic properties and leakage current density (J) of BNKT/BZO heterolayered films were greatly improved thanks to the heterolayered structure. Heterolayered 4BNKT/2BZO films (M42) yield the highest M s and M r values of 14.4 emu cm−3 and 1.7 emu cm−3, respectively, about three times higher than multilayered BNKT. Thanks to heterolayered structure, J decreases strongly from 16.0 × 10−4 A cm−2 for BNKT films to 1.4 × 10−4 A cm−2 for heterolayered M42 films. It has been verified that the leakage current in BNKT/BZO heterolayered films follows the Schottky barrier mechanism, with the barrier height fluctuating between 0.80 eV and 0.92 eV. The results of the study show that BNKT/BZO heterolayered films may be suitable for use in environmentally friendly multifunction devices.

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.

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.

Excellent energy storage performance in combination with a low operating voltage is a very important factor for pulse-power dielectric capacitor devices to achieve miniaturization and integration. Here the heterostructure of the relaxor ferroelectric Pb0.9La0.1(Zr0.52Ti0.48)O3 (PL), with a slim hysteresis loop, on the normal ferroelectric Pb(Zr0.52Ti0.48)0.99Nb0.01O3 (PN), causing a large voltage imprint, is shown to improve the energy-storage performance. A large recoverable energy-storage density of 43.5 J/cm3 and a high energy-storage efficiency of 84.1%, under an electric field of 2450 kV/cm (i.e. a 49 V voltage bias), are obtained in the 180 nm PL/20 nm PN thin film heterostructure. Due to the small total film thickness the excellent energy-storage properties are obtained at a low operating voltage of 49 V. Moreover, the PL/PN heterostructure also exhibits an excellent charge-discharge endurance up to 1010 cycles and good thermal stability in a wide temperature range from room temperature to 200 °C. These performances show that these heterostructures form a promising design for high-temperature pulse-power capacitors, with superior energy-storage performance at low operating voltages.

Interfaces can play an important role in the properties of ferroelectric devices, which effects especially show up in devices with thin ferroelectric layers. Here we describe the measured changes in the slanting, coercive, and self-bias field of the hysteresis loop as function of the thickness of the epitaxially grown PbZr0.52Ti0.48O3 layer in capacitors with SrRuO3 electrodes on (001)-oriented SrTiO3 substrates. Models, available from literature, are discussed that explain the observed features. All observations can be attributed to the presence of a nonswitchable, dielectric and charged, strain-gradient layer at the bottom electrode interface. This study shows experimentally and theoretically the importance of the nature of the ferroelectric–electrode interfaces for the capacitor behavior and the role of strain and strain-relaxation caused by lattice mismatch and growth. We expect that the conclusions drawn from this study can be generalized to other material systems.

In this chapter, examples of the use of reflection high-energy electron diffraction (RHEED) in combination with pulsed laser deposition (PLD) are described. Both the use of RHEED as a real-time rate-monitoring technique as well as methods to study the nucleation and growth during PLD are briefly discussed. After a brief introduction of RHEED, a case will be made for the step-density model to describe the intensity variations encountered during deposition. An overview of the intensity variations, the intensity response during a RHEED experiment because of various initial growth modes, of the LaAlO3/SrTiO3, SrRuO3/SrTiO3, and YBa2Cu3O7/SrTiO3 systems will be given, focusing on the role of the chemical terminations of the starting growth surface. In addition to the growth on oxide single crystal, RHEED was used extensively to study the growth of oxide (buffer) layers on Si and other semiconductors. Finally, RHEED can be used postdeposition to reveal various properties of the as-deposited thin film.

In this work, a transparent and free-standing ionic gel as the dielectric layer for polarization switching in leaky ferroelectric thin films is reported. By applying an electric field over an ionic liquid dielectric layer used as an electrostatic field gated capacitor, one can avoid electronic conduction. The association of the electrical double layer with depolarization at the solid-liquid interface contributes to the reversible switching in PbZrxTi1-xO3 (x = 0.6) (PZT). Using such ionic gels, the anisotropic ferroelastic switching from mono-c-domain toward a-domain is studied in PZT grown on CaF2 substrates. Our results demonstrate that an electrostatic field, induced by the free-standing ionic gel, is an effective and promising way to investigate leaky ferroelectrics.

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.

The interface between the insulators LaAlO$_3$ and SrTiO$_3$ accommodates a two-dimensional electron liquid (2DEL) -- a high mobility electron system exhibiting superconductivity as well as indications of magnetism and correlations. While this flagship oxide heterostructure shows promise for electronics applications, the origin and microscopic properties of the 2DEL remain unclear. The uncertainty remains in part because the electronic structures of such nanoscale buried interfaces are difficult to probe, and is compounded by the variable presence of oxygen vacancies and coexistence of both localized and delocalized charges. These various complications have precluded decisive tests of intrinsic electronic and orbital reconstruction at this interface. Here we overcome prior difficulties by developing an interface analysis based on the inherently interface-sensitive resonant x-ray reflectometry. We discover a high charge density of 0.5 electrons per interfacial unit cell for samples above the critical LaAlO$_3$ thickness, and extract the depth dependence of both the orbital and electronic reconstructions near the buried interface. We find that the majority of the reconstruction phenomena are confined to within 2 unit cells of the interface, and we quantify how oxygen vacancies significantly affect the electronic system. Our results provide strong support for the existence of polarity induced electronic reconstruction, clearly separating its effects from those of oxygen vacancies., Accepted in Physical Review Materials

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.

For thin film synthesis of complex oxides, one of the most important issues has always been how to oxidise the material. For a technique like pulsed laser deposition, a key benefit is the relatively high oxygen background pressure one can operate at, and therefor oxidation should be relatively straightforward. However, understanding the microscopic oxidation mechanisms turns out to be rather difficult. In this perspective, we give a brief overview of the sources of oxidation for complex oxide thin films grown by pulsed laser deposition. While it is clear what these sources are, their role in the kinetics of the formation of the crystal structure and oxygen stoichiometry is not fully understood.

Thin PbZrO3 (PZO) antiferroelectric films with (001)-preferred orientation were deposited on SrRuO3/Ca2Nb3O10-nanosheet/Si substrates using pulsed laser deposition. Variation of the deposition temperature was found to play a key role in the control of the microstructure and strongly influence the energy storage performance of the thin film. The critical phase switching field, where the aligned antiferroelectric (AFE) domains start to transform into the ferroelectric (FE) state, decreased with increasing temperature. On the other hand, the content of the FE phase in the AFE PZO thin films increased with increasing deposition temperature. A large recoverable energy-storage density of 16.8 J/cm3 and high energy-storage efficiency of 69.2% under an electric field of 1000 kV/cm were achieved in the films deposited at 525 °C. This performance was due to the high forward switching field and backward switching field values and the low difference between these two fields. Moreover, the PZO thin films showed great charge-discharge cycling life with fatigue-free performance up to 1010 cycles and good thermal stability from room temperature to 100 °C.

Polarization fatigue, i.e., the loss of polarization of ferroelectric capacitors upon field cycling, has been widely discussed as an interface related effect. However, mechanism(s) behind the development of fatigue have not been fully identified. Here, we study the fatigue mechanisms in Pt/PbZr0.52Ti0.48O3/SrRuO3 (Pt/PZT/SRO) capacitors in which all layers are fabricated by pulsed laser deposition without breaking the vacuum. With scanning transmission electron microscopy, we observed that in the fatigued capacitor, the Pt/PZT interface becomes structurally degraded, forming a 5 nm–10 nm thick non-ferroelectric layer of crystalline ZrO2 and diffused Pt grains. We then found that the fatigued capacitors can regain the full initial polarization switching if the externally applied field is increased to at least 10 times the switching field of the pristine capacitor. These findings suggest that polarization fatigue is driven by a two-step mechanism. First, the transient depolarization field that repeatedly appears during the domain switching under field cycling causes decomposition of the metal/ferroelectric interface, resulting in a non-ferroelectric degraded layer. Second, this interfacial non-ferroelectric layer screens the external applied field causing an increase in the coercive field beyond the usually applied maximum field and consequently suppresses the polarization switching in the cycled capacitor. Our work clearly confirms the key role of the electrode/ferroelectric interface in the endurance of ferroelectric-based devices.

Lead-free Bi

The phenomena of hysteresis, ferroelectric loss, and nonlinearity are investigated for the strain and polarization of a monoclinic, epitaxial Pb(Zr,Ti)O3 film over the 70 Hz to 5 kHz frequency range at sub-coercive excitation fields and zero electrical bias. For the strain, a linear hysteretic behavior is found, whereas the polarization shows a strongly nonlinear hysteretic behavior. In contrast to polycrystalline structures (for instance in ceramics or chemical solution deposited thin films), the commonly referred Rayleigh model cannot explain the observed behavior. A new model is presented, based on the rotation of the polarization vector within the monoclinic or rhombohedral unit cell under an applied electric field, with the viscous interaction of domains accompanying the unit cell deformation. The model explains the amplitude and frequency scaling of the strain, polarization, and loss tangent as well as the observed higher harmonics of polarization in the measured epitaxial Pb(Zr,Ti)O3 films. It is concluded that the nonlinear response and the hysteretic loss originate from two separate physical processes. The nonlinear response is attributed to the nonlinear angular rotation of the polarization vector, whereas the hysteresis and ferroelectric loss are due to a viscous interaction of domains while the polarization vector is rotating.

Pulsed laser deposition is widely used to synthesize complex oxide thin films with advanced functional properties because of the versatility of the process, although the actual processes and mechanisms that take place are highly dynamic and nontrivial. Detailed understanding of the plume dynamics is required to achieve enhanced control of the growth of complex oxide thin films. However, analytical models of the plasma plume proposed in previous studies, the so-called shockwave model, drag model, and adiabatic thermalization model, only apply to a specific pressure regime and only focus on the propagation of the plasma front. Numerical modeling of the plasma dynamics has previously been pursued for the one-dimensional propagation of a Si plasma plume in a noble background gas. Here we have explored a more generalized numerical model for the dynamics of a ${\mathrm{TiO}}_{2}$ plasma plume by extending to three dimensions, multiple elements in the plasma plume, and including chemical reactions in an oxygen environment without the use of adaptive parameters, other than used for the description of the initial plume shape. Comparison between the simulations and the self-emission measurements of the ${\mathrm{TiO}}_{2}$ plasma plume shows good agreement. Our model enables detailed simulation of the oxidation state of the arriving particles (Ti, TiO, and ${\mathrm{TiO}}_{2}$) on the substrate surface depending on oxygen background pressure. Interestingly, low pressures of about 0.02 mbar result in fast oxygen particles arriving prior to the slower titanium particles, which could significantly influence the oxidation state of the initial substrate surface. The enhanced number of collisions for higher pressures of about 0.1 mbar leads to a large amount of the low-mass oxygen particles coming to a standstill 1--2 cm away from the ablated target. Furthermore, the three-dimensional nature of our model has enabled simulation of the lateral variations in composition of the deposited particles on the substrate surface. Although negligible variations in the Ti:TiO and Ti:${\mathrm{TiO}}_{2}$ ratios are present for high pressures over deposition areas with diameters up to 5 cm, significant variations can be observed for low pressures. These insights could play an important role in upscaling pulsed laser deposition from a scientific laboratory-based scale to an industrial large-area scale.

Magnetic domain engineering in ferromagnetic thin films is a very important route toward the rational design of spintronics and memory devices. Although the magnetic domain formation has been extensively studied, artificial control of magnetic domain remains challenging. Here, we present the control of magnetic domain formation in paradigmatic SrRuO3/SrTiO3 heterostructures via structural domain engineering. The formation of structural twin domains in SrRuO3 films can be well controlled by breaking the SrTiO3 substrate symmetry through engineering miscut direction. The combination of x-ray diffraction analysis of structural twin domains and magnetic imaging of reversal process demonstrates a one-to-one correspondence between structural domains and magnetic domains, which results in multi-step magnetization switching and anomalous Hall effect in films with twin domains. Our work sheds light on the control of the magnetic domain formation via structural domain engineering, which will pave a path toward desired properties and devices applications.

Reflection high-energy electron diffraction is a widely used tool to study the growth dynamics of thin films, in situ and operando. Here it is applied after deposition, revealing that the morphological state of the surface is connected to the amount of material underneath. We focus on the growth of ${\mathrm{LaAlO}}_{3}$ thin films on a ${\mathrm{SrTiO}}_{3}$ substrate by pulsed laser deposition, utilizing a geometrically anisotropic plasma plume. After deposition, oscillations in the intensity and width of the specular spot as a function of position are observed along the short axis of the plasma plume. Each complete oscillation represents a unit-cell difference in film thickness, as confirmed by local x-ray reflectivity measurements. We apply this approach to demonstrate the critical thickness for conductivity at the ${\mathrm{LaAlO}}_{3}/{\mathrm{SrTiO}}_{3}$ interface on a single sample. Our results introduce a straightforward method to engineer and study thickness-dependent properties of epitaxial thin films on a highly detailed level.

Pure perovskite phase, (001)-oriented, epitaxial thin films of (Pb(Mg1/3Nb2/3)O3)0.67-(PbTiO3)0.33 (PMN-PT) were fabricated on single crystal, (001)-oriented SrTiO3 substrates using a hard (Fe-doped) and soft doped (Nb-doped) PZT(52/48) interfacial layer. The effect of different interface layers on the structural and ferroelectric properties of the PMN-PT films was investigated in detail. A significant self-bias voltage in the PMN-PT films can be introduced by using an appropriate interfacial layer. There are significant differences in polarization for different types of doped and undoped interface layers and a doubling of the relative dielectric constant was observed for the Nb-doped interfacial layer. Device properties remain stable up to at least 108 cycles.