Oxide Heteroepitaxy Research Articles

Freestanding oxide membranes: synthesis, tunable physical properties, and functional devices

The study of oxide heteroepitaxy has been hindered by the issues of misfit strain and substrate clamping, which impede both the optimization of performance and the acquisition of a fundamental understanding of oxide systems. Recently, however, the development of freestanding oxide membranes has provided a plausible solution to these substrate limitations. Single-crystalline functional oxide films can be released from their substrates without incurring significant damage and can subsequently be transferred to any substrate of choice. This paper discusses recent advancements in the fabrication, adjustable physical properties, and various applications of freestanding oxide perovskite films. First, we present the primary strategies employed for the synthesis and transfer of these freestanding perovskite thin films. Second, we explore the main functionalities observed in freestanding perovskite oxide thin films, with special attention tothe tunable functionalities and physical properties of these freestanding perovskite membranes under varying strain states. Next, we encapsulate three representative devices based on freestanding oxide films. Overall, this review highlights the potential of freestanding oxide films for the study of novel functionalities and flexible electronics.

A Flexible Magnetic Field Sensor Based on PZT/CFO Bilayer via van der Waals Oxide Heteroepitaxy.

Magnetoelectric (ME) magnetic field sensors utilize ME effects in ferroelectric ferromagnetic layered heterostructures to convert magnetic signals into electrical signals. However, the substrate clamping effect greatly limits the design and fabrication of ME composites with high ME coefficients. To reduce the clamping effect and improve the ME response, a flexible ME sensor based on PbZr0.2Ti0.8O3 (PZT)/CoFe2O4 (CFO) ME bilayered heterostructure was deposited on mica substrates via van der Waals oxide heteroepitaxy. A saturated magnetization of 114.5 emu/cm3 was observed in the bilayers. The flexible sensor exhibited a strong ME coefficient of 6.12 V/cm·Oe. The local ME coupling has been confirmed by the evolution of the ferroelectric domain under applied magnetic fields. The flexible ME sensor possessed a stable response with high sensitivity to both AC and DC weak magnetic fields. A high linearity of 0.9988 and sensitivity of 72.65 mV/Oe of the ME sensor were obtained under flat states. The ME output and limit-of-detection under different bending states showed an inferior trend as the bending radius increased. A flexible proximity sensor has been demonstrated, indicating a promising avenue for wearable device applications and significantly broadening the potential application of the flexible ME magnetic field sensors.

Bicontinuous oxide heteroepitaxy with enhanced photoconductivity

Self-assembled systems have recently attracted extensive attention because they can display a wide range of phase morphologies in nanocomposites, providing a new arena to explore novel phenomena. Among these morphologies, a bicontinuous structure is highly desirable based on its high interface-to-volume ratio and 3D interconnectivity. A bicontinuous nickel oxide (NiO) and tin dioxide (SnO2) heteroepitaxial nanocomposite is revealed here. By controlling their concentration, we fabricated tuneable self-assembled nanostructures from pillars to bicontinuous structures, as evidenced by TEM-energy-dispersive X-ray spectroscopy with a tortuous compositional distribution. The experimentally observed growth modes are consistent with predictions by first-principles calculations. Phase-field simulations are performed to understand 3D microstructure formation and extract key thermodynamic parameters for predicting microstructure morphologies in SnO2:NiO nanocomposites of other concentrations. Furthermore, we demonstrate significantly enhanced photovoltaic properties in a bicontinuous SnO2:NiO nanocomposite macroscopically and microscopically. This research shows a pathway to developing innovative solar cell and photodetector devices based on self-assembled oxides.

Advances in strain engineering on oxide heteroepitaxy

Advances in strain engineering on oxide heteroepitaxy

Remote growth of oxide heteroepitaxy through MoS2

Advanced heterostructures composed of various materials can induce new physical properties and phenomena among existing materials, representing the essential foundation for modern electronics. Recently, many works have been carried out with novel heterostructures combining three-dimensional (3D) and two-dimensional (2D) materials; however, there is a lack of promising methods to fabricate 3D/2D heterostructures due to the poor interfacial quality and the incompatibility of fabrication processes. To further study the interaction between 3D and 2D materials, the fabrication of 3D/2D heterostructures with high-quality interfaces should be attempted. Here, we show the possibility of fabricating high-quality oxide remote epitaxies through layered materials for the exploration on new functionalities. Brand new heterostructures including numerous 3D oxides and MoS2 have been demonstrated and investigated. Our study clarifies a remarkable concept to realize precisely controllable 3D/2D/3D heteroepitaxies for the design and development of next-generation smart devices.

Heteroepitaxial Hexagonal (00.1) CuFeO2 Thin Film Grown on Cubic (001) SrTiO3 Substrate Through Translational and Rotational Domain Matching

Heteroepitaxy of complex oxide thin films is a significant challenge when a large mismatch in the lattice parameters (>8%) and difference in the crystallographic symmetry coexist between the film and substrate. Herein, the heteroepitaxial growth of a hexagonal delafossite CuFeO2 thin film with (00.1) orientation on a cubic perovskite (001) SrTiO3 substrate through translational and rotational domain matching epitaxy is reported. The rotational in‐plane domain orientation relationships are CuFeO2 [11.0]//SrTiO3 [110] and CuFeO2 [2.0]//SrTiO3 [110] with about 10% in‐plane lattice mismatch. The 14.8 nm‐thick (00.1) CuFeO2 thin film shows high‐crystalline quality with a full width at half maximum of rocking curve of about 0.24° and exhibits a possible indirect optical bandgap of 1.43 eV or direct optical bandgap of 1.94 eV. Herein, not only a model system demonstrating translational and rotational domain matching heteroepitaxy of complex oxides is reported, but also a way to thin‐film heterostructures integrating hexagonal delafossite with cubic perovskite materials for functional oxide devices is opened.

Empirical approach to measuring interface energies in mixed-phase bismuth ferrite

In complex oxide heteroepitaxy, strain engineering is a powerful tool to obtain phases in thin films that may be otherwise unstable in bulk. A successful example of this approach is mixed phase bismuth ferrite (BiFeO3) epitaxial thin films. The coexistence of a tetragonal-like (T-like) matrix and rhombohedral-like (R-like) striations provides an enhanced electromechanical response, along with other attractive functional behaviors. In this paper, we compare the energetics associated with two thickness dependent strain relaxation mechanisms in this system: domain walls arising from monoclinic distortion in the T-like phase, and the interphase boundary between the host T-like matrix and tilted R-like phases. Combining x-ray diffraction measurements with scanning probe microscopy, we extract quantitative values using an empirical energy balance approach. The domain wall and phase boundary energies are found to be 113 $\pm$ 21 and 426 $\pm$ 23 mJ.m$^{-2}$, respectively. These numerical estimates will help us realize designer phase boundaries in multiferroics, which possess colossal responses to external stimuli, attractive for a diverse range of functional applications.

Strain-induced room-temperature ferroelectricity in SrTiO3 membranes

Advances in complex oxide heteroepitaxy have highlighted the enormous potential of utilizing strain engineering via lattice mismatch to control ferroelectricity in thin-film heterostructures. This approach, however, lacks the ability to produce large and continuously variable strain states, thus limiting the potential for designing and tuning the desired properties of ferroelectric films. Here, we observe and explore dynamic strain-induced ferroelectricity in SrTiO3 by laminating freestanding oxide films onto a stretchable polymer substrate. Using a combination of scanning probe microscopy, optical second harmonic generation measurements, and atomistic modeling, we demonstrate robust room-temperature ferroelectricity in SrTiO3 with 2.0% uniaxial tensile strain, corroborated by the notable features of 180° ferroelectric domains and an extrapolated transition temperature of 400 K. Our work reveals the enormous potential of employing oxide membranes to create and enhance ferroelectricity in environmentally benign lead-free oxides, which hold great promise for applications ranging from non-volatile memories and microwave electronics.

Giant Resistivity Change of Transparent ZnO/Muscovite Heteroepitaxy.

The piezoresistive effect has shown a remarkable potential for mechanical sensor applications and been sought for its excellent performance. A great attention was paid to the giant piezoresistive effect and sensitivity delivered by silicon-based nanostructures. However, low thermal stability and complicated fabrication process hinder their practical applications. To overcome these issues and enhance the functionalities, we envision the substantial piezopotential in a zinc oxide (ZnO)/muscovite (mica) heteroepitaxy system based on theoretical consideration and realize it in practice. High piezoresistive effect with giant change of resistivity (-80 to 240%) and large gauge factor (>1000) are demonstrated through mechanical bending. The detailed features of heteroepitaxy, electrical transport, and strain are probed to understand the mechanism of such a giant resistivity change. In addition, a bending model is established to reveal the distribution of strain. Finally, we demonstrate a flex sensor featuring high sensitivity, optical transparency, and two-segment sensing with a great potential toward practical applications. Such an oxide heteroepitaxy exhibits excellent piezoresistive properties and mechanical flexibility. In the near future, the importance of flex sensors will emerge because of the precise control in the automation industries, and our results lead to a new design in the field of flex sensors.

Mechanically controllable nonlinear dielectrics.

Strain-sensitive Ba x Sr1-x TiO3 perovskite systems are widely used because of their superior nonlinear dielectric behaviors. In this research, new heterostructures including paraelectric Ba0.5Sr0.5TiO3 (BSTO) and ferroelectric BaTiO3 (BTO) materials were epitaxially fabricated on flexible muscovite substrate. Through simple bending, the application of mechanical force can regulate the dielectric constant of BSTO from -77 to 36% and the channel current of BTO-based ferroelectric field effect transistor by two orders. The detailed mechanism was studied through the exploration of phase transition and determination of band structure. In addition, the phase-field simulations were implemented to provide theoretical support. This research opens a new avenue for mechanically controllable components based on high-quality oxide heteroepitaxy.

Encapsulation of Metal Oxide Nanoparticles by Oxide Supports during Epitaxial Growth

The traditional view of complex oxide heteroepitaxy is that the substrate is merely a passive bystander. Here we show that this is not always the case, in particular for a metal oxide/metal oxide interface during the synthesis of epitaxial nickel oxide (NiO) nanoislands on (001) strontium titanate (SrTiO3–STO) single crystal substrates. We find that the substrate atoms are driven to encapsulate the metal oxide nanocrystal islands—a phenomenon more commonly reported for metal/metal oxide heterogeneous catalysis where the migration of atoms from the support onto the functional nanoparticle system is driven by strong metal–support interactions (SMSI). High-resolution transmission electron microscopy (HRTEM), high angle angular dark field (HAADF) scanning transmission electron microscopy (STEM), and electron tomography (ET) are used to reveal a clear physical displacement of the interface; the atoms from the STO substrate climb and cover the bottom facets of NiO nanoparticles during the synthesis process duri...

Oxide Heteroepitaxy-Based Flexible Ferroelectric Transistor.

With the rise of Internet of Things, the presence of flexible devices has attracted significant attention owing to design flexibility. A ferroelectric field-effect transistor (FeFET), showing the advantages of high speed, nondestructive readout, and low-power consumption, plays a key role in next-generation technology. However, the performance of these devices is restricted since conventional flexible substrates show poor thermal stability to integrate traditional ferroelectric materials, limiting the compatibility of wearable devices. In this study, we adopt flexible muscovite mica as a substrate due to its good thermal properties and epitaxial integration ability. A flexible FeFET composed of oxide heteroepitaxy on muscovite is realized by combining an aluminum-doped zinc oxide film as the semiconductor channel layer and a Pb(Zr0.7Ti0.3)O3 film as the ferroelectric gate dielectric. The excellent characteristics of the transistor together with superior thermal stability and mechanical flexibility are demonstrated through various mechanical bending and temperature measurements. The on/off current ratio of the FeFET is higher than 103, which based on the field effect in the transfer curve. The smallest bending radius that can be achieved is 5 mm with a cyclability of 300 times and a retention of 100 h. This study opens an avenue to use oxide heteroepitaxy to construct a FeFET for next-generation flexible electronic systems.

Transparent Antiradiative Ferroelectric Heterostructure Based on Flexible Oxide Heteroepitaxy.

In the era of Internet of Things, the demand for flexible and transparent electronic devices has shifted to the forefront of materials science research. However, the radiation damage to key performance of transparent devices under radiative environment remains as a critical issue. Here, we present a promising technology for nonvolatile transparent electronic devices based on flexible oxide heteroepitaxy. A direct fabrication of epitaxial lead lanthanum zirconate titanate on transparent flexible mica substrate with indium tin oxide electrodes is presented. The transparent flexible ferroelectric heterostructures not only retain their superior performance, thermal stability, reliability, and mechanical durability, but also exhibit remarkably robust properties against to a strong radiation exposure. Our study demonstrates an extraordinary concept to realize transparent flexible nonvolatile electronic devices for the design and development of next-generation smart devices with potential application in electronics, automotive, aerospace, and nuclear systems.

Electrostatic Force-Driven Oxide Heteroepitaxy for Interface Control.

Oxide heterostructure interfaces create a platform to induce intriguing electric and magnetic functionalities for possible future devices. A general approach to control growth and interface structure of oxide heterostructures will offer a great opportunity for understanding and manipulating the functionalities. Here, it is reported that an electrostatic force, originating from a polar ferroelectric surface, can be used to drive oxide heteroepitaxy, giving rise to an atomically sharp and coherent interface by using a low-temperature solution method. These heterostructures adopt a fascinating selective growth, and show a saturation thickness and the reconstructed interface with concentrated charges accumulation. The ferroelectric polarization screening, developing from a solid-liquid interface to the heterostructure interface, is decisive for the specific growth. At the interface, a charge transfer and accumulation take place for electrical compensation. The facile approach presented here can be extremely useful for controlling oxide heteroepitaxy and producing intriguing interface functionality via electrostatic engineering.

(Invited) Oxide Heteroepitaxy for Soft Technology

A new world is being formed based on the technologies composed of artificial intelligence, Internet of Things (IoT), and robot systems. Especially, in the research fields of IoT and robot systems, a device with mechanical flexibility can deliver more degrees of freedom on design of the systems. Therefore, the development of soft and flexible electronics becomes an important research direction for wearable and IoT devices. Due to the mechanical flexibility, polymers materials and thin foils made of metals are commonly used in the fabrication of flexible electronic systems. However, the reliability issue under practical operation hinders the applications of these flexible electronics, especially those on polymer substrates. This is attributed to a mismatch of thermal expansion coefficient between substrate and functional materials or low thermal and chemical endurance of polymers and organic materials. A lot of researchers are working hard and together to expand the applicability of current flexible devices. However, new pathway to flexible electronics can also be developed in parallel to provide more subtle solutions, thus needing new platform to integrate functional materials with good thermal and chemical stabilities together with mechanical flexibility. Recently, due to the quick rise of growth facilities, various techniques are employed to acquire flexible oxide heteroepitaxy. In this talk, I will highlight the methods to develop oxide heteroepitaxy with mechanical flexibility, including direct and indirect approaches. I will also provide an overview that classifies the application fields where flexible oxide heteroepitaxy have been adopted and the approach which has been used to develop particular oxide with the emphasis on electronic and photonic devices.

Controlling the structure and ferroic properties of strained epitaxial NiTiO3 thin films on sapphire by post-deposition annealing

Ferroelectrically induced weak ferromagnetism had been predicted earlier in metal titanate compounds MTiO3 (M = Fe, Mn, Ni) with the lithium niobate-type (LiNbO3) structure. In order to stabilize this metastable structure by oxide heteroepitaxy, we attempted to grow epitaxial nickel titanate (NiTiO3) films on the nonpolar, non-magnetic sapphire substrate by pulsed laser deposition. As a follow-up to our earlier work, we investigated the effect of post-synthesis annealing in order to improve physical properties. Our structural data from x-ray diffraction and electron microscopy suggest that the crystalline quality of the NiTiO3 films was greatly improved by annealing the films at 600 and 1000 °C, with new phase formation along the interface at 1000 °C. Our physical property characterization indicates increased ferromagnetism and polarization after 600 °C, but a change in the magnetic state to likely ferrimagnetism, and a loss of polarization after the 1000 °C treatment. Our results suggest that the ferroic domain properties of the NiTiO3 films can be favorably altered by post-synthesis heat treatment at the proper temperature to manipulate interfacial strain and enhance the multiferroic properties.

Flexible Heteroepitaxy Photoelectrode for Photo-electrochemical Water Splitting

MICAtronics represents a new research direction by taking the advantages of good mechanical flexibility and optical transparency of muscovite mica, leading to a new platform to use oxide heteroepitaxy for novel transparent soft technology. Here we report a model flexible photoelectrode for photo-electrochemical (PEC) water splitting based on Fe2O3/ZnO/mica heteroepitaxy. The heteroepitaxy was confirmed by a combination of X-ray diffraction and transmission electron microscopy. The PEC performance of this flexible and semitransparent photoelectrode under various bending states was investigated. We found that the photocurrent of the heteroepitaxial system was enhanced by three times relative to pure ZnO and Fe2O3 under visible-light irradiation, and the heteroepitaxial photoelectrodes retain their photocurrent after continuous bending in cycling (>3000 cycles) with a smallest bending radius of 3.5 mm. The energy band alignment and charge dynamics under light excitation were characterized to understand the m...

Development of oxide heteroepitaxy for soft technology

Soft technology has been an emerging field since flexible and wearable electronics started flourishing.

Local Enhancement of Polarization at PbTiO3/BiFeO3 Interfaces Mediated by Charge Transfer.

Ferroelectrics hold promise for sensors, transducers, and telecommunications. With the demand of electronic devices scaling down, they take the form of nanoscale films. However, the polarizations in ultrathin ferroelectric films are usually reduced dramatically due to the depolarization field caused by incomplete charge screening at interfaces, hampering the integrations of ferroelectrics into electric devices. Here, we design and fabricate a ferroelectric/multiferroic PbTiO3/BiFeO3 system, which exhibits discontinuities in both chemical valence and ferroelectric polarization across the interface. Aberration-corrected scanning transmission electron microscopic study reveals an 8% elongation of out-of-plane lattice spacing associated with 104%, 107%, and 39% increments of δTi, δO1, and δO2 in the PbTiO3 layer near the head-to-tail polarized interface, suggesting an over ∼70% enhancement of polarization compared with that of bulk PbTiO3. Besides that in PbTiO3, polarization in the BiFeO3 is also remarkably enhanced. Electron energy loss spectrum and X-ray photoelectron spectroscopy investigations demonstrate the oxygen vacancy accumulation as well as the transfer of Fe3+ to Fe2+ at the interface. On the basis of the polar catastrophe model, FeO2/PbO interface is determined. First-principles calculation manifests that the oxygen vacancy at the interface plays a predominate role in inducing the local polarization enhancement. We propose a charge transfer mechanism that leads to the remarkable polarization increment at the PbTiO3/BiFeO3 interface. This study may facilitate the development of nanoscale ferroelectric devices by tailing the coupling of charge and lattice in oxide heteroepitaxy.

Epitaxy on Demand

Perovskite oxide heteroepitaxy is realized on the top of inorganic nanosheets that are covering the amorphous oxide surfaces of Si substrates. Utilizing pulsed laser deposition, thin films of SrRuO3 in a (001)pc and (110)pc orientation on nanosheets of Ca2Nb3O10 and Ti0.87O2 are grown, respectively. The two types of nanosheets are patterned to locally tailor the crystallographic orientation and properties of SrRuO3. The success of our approach is demonstrated by electron backscatter diffraction and spatial magnetization maps. An unprecedented control of perovskite film growth on arbitrary substrates is illustrated in this work, and the methods that are developed to deposit SrRuO3 thin films are a viable starting point for growth of artificial heteroepitaxial thin films that require a bottom electrode. Control is not just reached in the direction of film growth, as the crystal orientation and film properties are regulated laterally on the surface of micropatterned nanosheets. Local control of magnetic properties is illustrated, which holds out prospects for the fabrication of next‐generation devices like noncollinear magnetic random access memories.