Epitaxial Thin Films Research Articles

Epitaxial Thin Film Growth on Recycled SrTiO3 Substrates Toward Sustainable Processing of Complex Oxides.

Complex oxide thin films cover a range of physical properties and multifunctionalities that are critical for logic, memory, and optical devices. Typically, the high-quality epitaxial growth of these complex oxide thin films requires single crystalline oxide substrates such as SrTiO3 (STO), MgO, LaAlO3, a-Al2O3, and many others. Recent successes in transferring these complex oxides as free-standing films not only offer great opportunities in integrating complex oxides on other devices, but also present enormous opportunities in recycling the deposited substrates after transfer for cost-effective and sustainable processing of complex oxide thin films. In this work, the surface modification effects introduced on the recycled STO are investigated, and their impacts on the microstructure and properties of subsequently grown epitaxial oxide thin films are assessed and compared with those grown on the pristine substrates. Detailed analyses using high-resolution scanning transmission electron microscopy and geometric phase analysis demonstrate distinct strain states on the surfaces of the recycled STO versus the pristine substrates, suggesting a pre-strain state in the recycled STO substrates due to the previous deposition layer. These findings offer opportunities in growing highly mismatched oxide films on the recycled STO substrates with enhanced physical properties. Specifically, yttrium iron garnet (Y3Fe5O12) films grown on recycled STO present different ferromagnetic responses compared to that on the pristine substrates, underscoring the effects of surface modification. The study demonstrates the feasibility of reuse and redeposition using recycled substrates. Via careful handling and preparation, high-quality epitaxial thin films can be grown on recycled substrates with comparable or even better structural and physical properties toward sustainable process of complex oxide devices.

Resistive Switching Characteristics of NiO Thin Films Influenced by Changes in the Diameter of Nanometer-Scale Top Electrodes.

We investigated the forming, set, and reset voltages affected by the area of the top electrodes of a resistive random access memory (RRAM) capacitor fabricated by epitaxial NiO thin films. NiO RRAM capacitors with Au top electrode with a diameter of 100 μm showed typical unipolar switching characteristics. Au top electrodes with diameters of 10, 20, and 30 nm were formed on the surface of epitaxial NiO thin films by e-beam lithography. The forming, set, and reset voltages tended to decrease as the diameter of NiO RRAM capacitors with nanosized Au top electrodes decreased. As the area of the Au top electrodes increases, the volume of space in which the conductive filaments formed within the NiO RRAM capacitors can be formed becomes larger. This causes the conductive filament to be formed at relatively low energy, giving low forming voltages, while increasing the diversity of paths, causing a wide forming voltage distribution.

A brief review on strain engineering of ferroelectric KxNa1−xNbO3 epitaxial thin films: Insights from phase-field simulations

A brief review on strain engineering of ferroelectric KxNa1−xNbO3 epitaxial thin films: Insights from phase-field simulations

Unraveling the Oxygen Vacancy-Performance Relationship in Perovskite Oxides at Atomic Precision via Precise Synthesis.

Understanding the fundamental effect of the oxygen vacancy atomic structure in perovskite oxides on catalytic properties remains challenging due to diverse facets, surface sites, defects, etc. in traditional powder catalysts and the inherent structural complexity. Through quantitative synthesis of tetrahedral (LaCoO2.5-T), pyramidal (LaCoO2.5-P), and octahedral (LaCoO3) epitaxial thin films as model catalysts, we demonstrate the reactivity orders of active-site geometrical configurations in oxygen-deficient perovskites during the CO oxidation model reaction: CoO4 tetrahedron > CoO6 octahedron > CoO5 pyramid. Ambient-pressure Co L-edge and O K-edge XAS spectra clarify the dynamic evolutions of active-site electronic structures during realistic catalytic processes and highlight the important roles of defect geometrical structures. In addition, in situ XAS and resonant inelastic X-ray scattering spectra and density functional theory calculations directly reveal the nature of high reactivity for CoO4 sites and that the derived shallow-acceptor defect levels in the band structure facilitate the adsorption and activation of reactive gases, resulting in more than 23-fold enhancement for catalytic reaction rates than CoO5 sites.

Exploring anti-ferroelectric thin films with high energy storage performance by moderating phase transition

Anti-ferroelectric thin films are renowned for their signature double hysteresis loops and sheds light on the distinguished energy storage capabilities of dielectric capacitors in modern electronic devices. However, anti-ferroelectric capacitors are still facing the dual challenges of low energy density and efficiency to achieve state-of-the-art performance. Their large hysteresis and sharp first-order phase transition usually results in a low energy storage efficiency and easy breakdown, severely obscuring its future application. In this study, we demonstrate that anti-ferroelectric (Pb0.97La0.02)(Zr1−xSnx)O3 epitaxial thin films exhibit enhanced energy storage performance through local structural heterogeneity to moderate the first-order phase transition by calculating the corresponding polarization as a function of switching time for the first time. The films exhibit remarkable enhanced breakdown strength (∼3.47 MV/cm, ∼5 times the value for PbZrO3) and energy storage performance. Our endeavors have culminated in the ingenious formulation of a novel strategy, namely, the postponement of polarization processes, thereby elevating the breakdown strength and total energy storage performance. This landmark achievement has unveiled a fresh vista of investigative opportunities for advancing the energy storage prowess of electric dielectrics.

Atomic structure of self-buffered BaZr(S, Se)3 epitaxial thin film interfaces

Understanding and controlling the growth of chalcogenide perovskite thin films through interface design is important for tailoring film properties. Here, the film and interface structure of BaZr(S,Se)3 thin films grown on LaAlO3 by molecular beam epitaxy and postgrowth anion exchange is resolved using aberration-corrected scanning transmission electron microscopy. Epitaxial films are achieved from self-assembly of an interface “buffer” layer, which accommodates the large film/substrate lattice mismatch of nearly 40% for the alloy film studied here. The self-assembled buffer layer, occurring for both the as-grown sulfide and post-selenization alloy films, is shown to have rock-salt-like atomic stacking akin to a Ruddlesden–Popper phase. These results provide insights into oxide-chalcogenide heteroepitaxial film growth, illustrating a process that yields relaxed, crystalline, epitaxial chalcogenide perovskite films that support ongoing studies of optoelectronic and device properties.

Heteroepitaxial Growth of NiO Thin Films on (‐201) β‐Ga2O3 by Mist Chemical Vapor Deposition

The growth of NiO epitaxial thin films on (‐201) β‐Ga2O3 by mist chemical vapor deposition (CVD) and the effects of carrier gas selection (N2 and O2) and substrate preannealing treatment on the structural and morphological properties on the grown thin films are explored. X‐ray diffraction analysis reveals successful epitaxial growth with the orientation relationship (111) NiO [0‐11] || (‐201) β‐Ga2O3 [010]. As a carrier gas, O2 results in single‐domain NiO films while N2 leads to the formation of rotational domains. Atomic force microscopy and field‐emission scanning electron microscopy confirm the lateral growth of NiO films, thus highlighting the importance of substrate preannealing at 1200 °C in oxygen atmosphere to obtain flat, high‐quality films. The results demonstrate that the method of mist CVD combined with appropriate substrate preparation and carrier gas selection is effective for the growth of high‐quality NiO/β‐Ga2O3 heterostructures. This achievement opens new possibilities for the development of wide‐bandgap p–n heterojunctions, potentially advancing the field of high‐power oxide‐based electronic devices.

Large resistive switching in ultrathin BiFeO3 thin films

Electrically induced resistive switching (RS) effects have been proposed as the basis for future non-volatile memories. In this work, 9 nm-thick BiFeO3 (BFO) epitaxial thin films were deposited on (001)-oriented SrTiO3 substrates by pulsed laser deposition and their resistive switching (RS) behaviors were investigated. A large resistive switching with ON/OFF ratio of ∼106 is observed, surpassing the performance of most resistive random access memories ever reported. The conducting filament is proposed to dominate the RS behavior in the positive voltage region, while the modulation of ferroelectric polarization is suggested to play a significant role in the negative voltage region. Our study significantly deepens the understanding of the physical origin of RS and could provide a reference for designing high-performance memories and memristors based on ultrathin ferroelectric films.

Effects of W alloying on the electronic structure, phase stability, and thermoelectric power factor in epitaxial CrN thin films

CrN-based alloy thin films are of interest as thermoelectric materials for energy harvesting. Ab initio calculations show that dilute alloying of CrN with 3 at. % W substituting Cr induce flat electronic bands and push the Fermi level EF into the conduction band while retaining dispersive Cr 3d bands. These features are conducive for both high electrical conductivity σ and high Seebeck coefficient α and, hence, a high thermoelectric power factor α2σ. To investigate this possibility, epitaxial CrWxNz films were grown on c-sapphire by dc-magnetron sputtering. However, even films with the lowest W content (x = 0.03) in our study contained metallic h-Cr2N, which is not conducive for a high α. Nevertheless, the films exhibit a sizeable power factor of α2σ ∼ 4.7 × 10−4 W m−1 K−2 due to high σ ∼ 700 S cm−1, and a moderate α ∼ − 25 μV/K. Increasing h-Cr2N fractions in the 0.03 < x ≤ 0.19 range monotonically increases σ, but severely diminishes α leading to two orders of magnitude decrease in α2σ. This trend continues with x > 0.19 due to W precipitation. These findings indicate that dilute W additions below its solubility limit in CrN are important for realizing a high thermoelectric power factor in CrWxNz films.

A new method for growing epitaxial films on foreign substrates − Bent epitaxy

In recent years, to mitigate the effects of climate change, countries’ transition to the green economy has accelerated, and thereby, the demand of semiconductor industry for wide-gap semiconductors such as SiC and GaN has increased dramatically. These semiconductors are expensive. To reduce the price of the final product, industrial production of thin epitaxial films of sought-after semiconductors on accessible and cheap substrates, such as Si and sapphire, is being developed. When growing epitaxial films on foreign substrates, the resulting heterostructure bends, becomes concave or convex, due to a mismatch between the coefficients of thermal expansion (CTE) of the substrate and the epitaxial film. As a result, the quality of the epitaxial film deteriorates and further processing of the resulting heterostructures in production lines becomes difficult or even impossible. The essence of the proposed new method is that the epitaxial film is grown not on a flat, but on a pre-curved substrate with the expectation that after cooling the fabricated heterostructure to room temperature, the heterostructure will take a flat shape due to the difference in the CTE of the epitaxial film and the substrate. A round bimetallic plate, located under the substrate, bends the substrate in the required direction to the desired value at the growth temperature, and gradually reduces the bend of the fabricated heterostructure during cooling, in proportion to the thermal contraction of the epitaxial film. This allows obtaining qualitative and flat epitaxial films, regardless of the material of the substrate or epitaxial film and the diameter of the substrate or thickness of the epitaxial film, without any buffer layers or carrying out any additional operations and costs.

Rhombohedral R3 Phase of Mn-Doped Hf0.5Zr0.5O2 Epitaxial Films with Robust Ferroelectricity.

HfO2-based ferroelectric materials are emerging as key components for next-generation nanoscale devices, owing to their exceptional nanoscale properties and compatibility with established silicon-based electronics infrastructure. Despite the considerable attention garnered by the ferroelectric orthorhombic phase, the polar rhombohedral phase has remained relatively unexplored due to the inherent challenges in its stabilization. In this study, the successful synthesis of a distinct ferroelectric rhombohedral phase is reported, i.e., the R3 phase, in Mn-doped Hf0.5Zr0.5O2 (HZM) epitaxial thin films, which stands different from the conventional Pca21 and R3m polar phases. These findings reveal that this R3 phase HZM film exhibits a remnant polarization of up to 47 µC cm- 2 at room temperature, along with an exceptional retention capability projected to exceed a decade and an endurance surpassing 109 cycles. Moreover, it is demonstrated that by modulating the concentration of Mn dopant and the film's thickness, it is possible to selectively control the phase transition between the R3, R3m, and Pca21 polar phases. This research not only sheds new light on the ferroelectricity of the HfO2 system but also paves the way for innovative strategies to manipulate ferroelectric properties for enhanced device performance.

Robust resistance switching performance in a Ca3Ti2O7/La0.67Sr0.33MnO3 heterostructure induced by the interface

Ruddlesden–Popper phase oxides, such as Ca3Ti2O7, have been established as hybrid improper ferroelectrics. However, investigations into Ca3Ti2O7 have primarily concentrated on their structural and ferroelectric properties. In this study, we prepared epitaxial Ca3Ti2O7 thin films via magnetron sputtering. Conducting atomic force microscopy was employed to characterize local current variations under an applied bias voltage. Electron paramagnetic resonance measurements of the Ca3Ti2O7/La0.67Sr0.33MnO3 film were conducted to assess its defect characteristics. Interestingly, the Ca3Ti2O7/La0.67Sr0.33MnO3 stacks exhibited remarkable macroscopic resistance switching, with a resistance on/off ratio reaching 100, alongside robust retention (∼2500 s) and endurance (∼2000 cycles) features. Additionally, density functional theory calculations suggest that the resistance switching is attributable to the interface barrier of the Ca3Ti2O7/La0.67Sr0.33MnO3 interface and the efficacy of space charge limitation. This work proposes an avenue for the utilization of Ruddlesden–Popper phase Ca3Ti2O7 in various applications.

Suppression of cracking induced by epitaxial strain relaxation using a relaxation absorber during the transfer of epitaxial thin films of anatase-type Nb:TiO2

This work developed a technique for fabricating flexible epitaxial thin films of anatase-type Nb:TiO2 (epitaxial TNO) via a transfer process. In our prior work, epitaxial TNO deposited on LaAlO3 (001) single crystal substrates was lifted off and affixed to flexible polymeric sheets. However, many cracks occurred on the surfaces of the transferred thin films, such that the conductivity of the epitaxial TNO was drastically decreased. This loss of conductivity was attributed to the interruption of current paths by the cracks. These numerous cracks were linear and in most cases were oriented either parallel to the [100]anatase∥[100]LAO direction or parallel to the [010]anatase∥[010]LAO direction (where the subscripts anatase and LAO represent the materials for each Miller index). Therefore, cracking likely occurred as a consequence of the relaxation of epitaxial strain and a return to the original axial lengths of the TNO during the transfer process. In the present work, the surface of epitaxial TNO was coated with the ductile polymer SU-8 3050 as a relaxation absorber prior to the transfer. This modified transfer process greatly reduced crack formation in the TNO such that the conductivity of the thin film was improved by two orders of magnitude. Thus, pre-coating with a ductile relaxation absorber was shown to effectively suppress the cracking of flexible epitaxial TNO.

Strain-oxygen vacancies coupling in topotactic (La,Sr)CoO3-δ thin films

Oxygen defect engineering is a widely used approach for tuning physical properties in oxides. Multivalent transition metal oxide La0.7Sr0.3CoO3-δ (LSCO) shows oxygen vacancy-driven metal-to-insulator transition (MIT) due to topotactic phase transition and its high oxygen vacancy tolerance. Here, we introduce strain as a new degree of freedom to study the strain-oxygen vacancy coupling effects and elucidate its impact on the electronic property in oxygen-deficient LSCO epitaxial thin films grown on SrTiO3 (100) single crystal. By combining the experimental results with density functional theory plus U (DFT+U) calculations, we reveal that 2.1 % in-plane tensile strain can stabilize the insulating state of LSCO with a surprisingly low concentration of oxygen vacancies, <0.5 %. This study reveals that the MIT in LSCO is governed by the combination of oxygen vacancies and strain, offering the potential for additional tuning knob of the material's electronic properties.

Superior Piezo-/Ferro-Electricity in Antiferroelectric AgxNbO3-δ Thin Films by Nanopillar Local Structure Design.

Antiferroelectrics are fundamental mother compounds critical in developing innovative lead-free piezoelectrics and ferroelectrics and hold great promise for wide-ranging applications in energy conversion and electronic devices. However, harnessing their superior properties presents a significant challenge due to the delicate balance required between their various states. In this study, through the unique design of nanopillar structures to alleviate the local polar heterogeneity, we have achieved significantly improved piezo-/ferro-electricity in classic lead-free antiferroelectric AgxNbO3-δ (x = 1, 0.9, and 0.8) epitaxial thin films. The effective piezoelectric coefficient reaches 440 pm V-1, 1 order of magnitude larger than the stoichiometric AgNbO3, rivaling classic lead zirconate titanate piezoelectrics. Atomic-scale electron microscopy investigations unravel the underlying mechanisms. The nanopillars, characterized by antisite occupancy of both Ag and Nb atoms and forming out-of-phase boundaries with the matrix, reduce the local crystal symmetry via interphase strain. This leads to the creation of flexible multinanodomain structures that significantly facilitate polarization rotation, thus substantially enhancing the piezoelectric performance. This study demonstrates the feasibility of engineering local heterogeneity through nanopillar design, offering a generally applicable method for property improvement of a wide range of antiferroelectrics.

Controlling Bi/Fe ratio in bismuth iron garnet thin films deposited by confocal magnetron sputtering for enhanced Faraday rotation

We have successfully deposited high-quality bismuth-iron-garnet (BIG; Bi3Fe5O12) epitaxial thin films on single crystal gadolinium-gallium-garnet (GGG; Gd3Ga5O12) (111) substrates through Radio frequency (RF) confocal sputtering, utilizing separate bismuth and iron oxide sputtering targets and optimized thermal treatments. The Bi/Fe ratio in the deposited BIG thin films can be varied by controlling the sputter process parameters. These deposited thin films exhibit homogeneity and surface root mean square (rms) roughness of less than 2 nm. The epitaxial film quality is confirmed by X-ray diffraction (XRD) and Transmission electron microscopy (TEM). Moreover, the films demonstrate low optical loss and a magneto-optical Faraday rotation as high as −34o±1o /μm at a wavelength of 535 nm for a BIG thin film with a Bi/Fe ratio 0.7 and annealing temperature of 510oC. Additionally, the coercivity of the deposited films is lower than that of those deposited via RF sputtering using a single composite target. This co-sputtering approach provides real-time flexibility for the deposition of high-quality BIG films.

From weak to strong-coupling superconductivity tuned by substrate in TiN films

Abstract The interplay between substrates and superconducting thin films has attracted increasing attention. Here, we report an in-depth investigation on superconducting properties of the epitaxial TiN thin films grown on three different substrates by dc reactive magnetron sputtering. The TiN films grown on (0001) sapphire exhibit (111) crystal orientation, while that grown on (100) Si and MgO substrates exhibit (100) orientation. Moreover, the samples grown on Si reveal a relatively lower level of disorder, accompanied by the higher critical transition temperature Tc and smaller magnitude of upper critical field slope near Tc. Remarkably, we uncovered a rather high value of superconducting gap (with Δ0/kBTc = 3.05) in TiN film on Si indicating a very strong coupling superconductivity, in sharp contrast to the case using sapphires and MgO as the substrate which reveals a weak-coupling feature. The comprehensive analysis considering the scenarios of the three substrate shows that the grain size of the thin films may be an important factor influencing the superconductivity.

Epitaxial growth of single unit-cell superconducting β-Bi2Pd

Bismuth-based binary alloy β-Bi2Pd has recently been suggested as a connate topological superconductor with immense promise for Majorana zero modes. However, the epitaxial thin films down to the ultimate level of single unit-cell have been challenging. Here, we employed the state-of-the-art molecular beam epitaxy to prepare single unit-cell superconducting β-Bi2Pd films with lateral dimensions of hundreds of nanometers. Utilizing in situ scanning tunneling microscopy/spectroscopy, we uncover evidence of anisotropic superconductivity whose spectra are well fit by anisotropic s-wave gap functions and demonstrate that the epitaxial growth of β-Bi2Pd films relies substantially on the substrate temperature, flux ratio, growth rate, and coverage. The high-quality epitaxial films provide a promising platform to investigate the topological superconductivity at the two-dimensional limit.

Room-Temperature Possible Current-Induced Transition in Ca2RuO4 Thin Films Grown Through Intercalation-Like Cation Diffusion in the A2BO4 Ruddlesden-Popper Structure.

Cation deficiency tuning is a central issue in thin-film epitaxy of functional metal oxides, as it is typically more difficult than anion deficiency tuning, as anions can be readily supplied from gas sources. Here, highly effective internal deficiency compensation of Ru cations is demonstrated for Ca2RuO4 epitaxial films based on diffusive transfer of metal cations in the A2BO4 Ruddlesden-Popper lattice from solid-phase cation sources. Through detailed structural characterization of Ca2RuO4/LaAlO3 (001) thin films grown with external cation sources by solid-phase epitaxy, the occurrence of intercalation-like, interstitial diffusion of La cations (from the substrates) in the A2BO4 structure is revealed, and that of Ru cations is also suggested. Relying on the interstitial-type diffusion, an optimized Ru deficiency compensation method, which does not induce the formation of Can +1RunO3 n +1 Ruddlesden-Popper impurity phases with higher n, is proposed for Ca2RuO4 epitaxial films. In the Ca2RuO4/LaAlO3 (001) thin films grown with Ru deficiency compensation, record-high resistivity values (102-10-1 Ω cm) and a large (more than 200 K) increase in the temperature range of the nonlinear transport properties are demonstrated by transport measurements, demonstrating the possible advantages of this method in the control of the current-induced quantum phase transition of Ca2RuO4.

Producing Freestanding Single-Crystal BaTiO3 Films through Full-Solution Deposition.

Strontium aluminate, with suitable lattice parameters and environmentally friendly water solubility, has been strongly sought for use as a sacrificial layer in the preparation of freestanding perovskite oxide thin films in recent years. However, due to this material's inherent water solubility, the methods used for the preparation of epitaxial films have mainly been limited to high-vacuum techniques, which greatly limits these films' development. In this study, we prepared freestanding single-crystal perovskite oxide thin films on strontium aluminate using a simple, easy-to-develop, and low-cost chemical full-solution deposition technique. We demonstrate that a reasonable choice of solvent molecules can effectively reduce the damage to the strontium aluminate layer, allowing successful epitaxy of perovskite oxide thin films, such as 2-methoxyethanol and acetic acid. Molecular dynamics simulations further demonstrated that this is because of their stronger adsorption capacity on the strontium aluminate surface, which enables them to form an effective protective layer to inhibit the hydration reaction of strontium aluminate. Moreover, the freestanding film can still maintain stable ferroelectricity after release from the substrate, which provides an idea for the development of single-crystal perovskite oxide films and creates an opportunity for their development in the field of flexible electronic devices.