Atomic layer engineering of perovskite oxides for chemically sharp heterointerfaces
Woo Seok Choi, Christopher M. Rouleau, Sung Seok A. Seo, Zhenlin Luo, Hua Zhou, Timothy T. Fister, Jeffrey A. Eastman, Paul H. Fuoss, Dillon D. Fong, Jonathan Z… 展开作者
Woo Seok Choi, Christopher M. Rouleau, Sung Seok A. Seo, Zhenlin Luo, Hua Zhou, Timothy T. Fister, Jeffrey A. Eastman, Paul H. Fuoss, Dillon D. Fong, Jonathan Z. Tischler, Gyula Eres, Matthew F. Chisholm, Ho Nyung Lee
Advances in synthesis techniques and materials understanding have given rise to oxide heterostructures with intriguing physical phenomena that cannot be found in their constituents. In these structures, precise control of interface quality, including oxygen stoichiometry, is critical for unambiguous tailoring of the interfacial properties, with deposition of the first monolayer being the most important step in shaping a well-defined functional interface. Here, we studied interface formation and strain evolution during the initial growth of LaAlO3 on SrTiO3 by pulsed laser deposition, in search of a means for controlling the atomic-sharpness of the interfaces. Our experimental results show that growth of LaAlO3 at a high oxygen pressure dramatically enhances interface abruptness. As a consequence, the critical thickness for strain relaxation was increased, facilitating coherent epitaxy of perovskite oxides. This provides a clear understanding of the role of oxygen pressure during the interface formation, and enables the synthesis of oxide heterostructures with chemically-sharper interfaces.
Electrical transport of a polar heterointerface between two insulating perovskites, KTaO3 and SrTiO3, is studied. It is formed between a thin KTaO3 film deposited on a top of TiO2- terminated (100) SrTiO3 substrate. The resulting (KO)1-(TiO2)0 heterointerface is expected to be hole-doped according to formal valences of K (1+) and Ti (4+). We observed electrical conductivity and mobility in the KTaO3/SrTiO3 similar to values measured earlier in electron-doped LaAlO3/SrTiO3 heterointerfaces. However, the sign of the charge carriers in KTaO3/SrTiO3 obtained from the Hall measurements is negative.…
Perovskite oxide heteroepitaxy receives much attention because of the possibility to com- bine the diverse functionalities of perovskite oxide building blocks. A general boundary con- dition for the epitaxy is the presence of polar discontinuities at heterointerfaces. These polar discontinuities result in reconstructions, often creating new functionalities at the interface. However, for a significant number of materials these reconstructions are unwanted as they alter the intrinsic materials properties at the interface. Therefore, a strategy to eliminate this reconstruction of the polar discon…
The discovery of two-dimensional electron gases (2DEGs) at the heterointerface between two insulating perovskite-type oxides, such as LaAlO3 and SrTiO3, provides opportunities for a new generation of all-oxide electronic and photonic devices. However, significant improvement of the interfacial electron mobility beyond the current value of approximately 1,000 cm2V-1s-1 (at low temperatures), remains a key challenge for fundamental as well as applied research of complex oxides. Here, we present a new type of 2DEG created at the heterointerface between SrTiO3 and a spinel γ-Al2O3 epitaxial film w…
We report charge-transfer up to a single electron per interfacial unit cell across non-polar heterointerfaces from the Mott insulator LaTiO3 to the charge transfer insulator LaCoO3. In high-quality bi- and tri-layer systems grown using pulsed laser deposition, soft X-ray absorption, dichroism and STEM-EELS are used to probe the cobalt 3d-electron count and provide an element-specific investigation of the magnetic properties. The experiments prove a deterministically-tunable charge transfer process acting in the LaCoO3 within three unit cells of the heterointerface, able to generate full conver…
We propose experimental verification and theoretical explanation of magnetic anomalies in the complex Fe-contained double perovskite multiferroics like PbFe$_{1/2}$Nb$_{1/2}$O$_3$. The theoretical part is based on our model of coexistence of long-range magnetic order and spin glass in the above substances. In our model, the exchange interaction is anisotropic, coupling antiferromagnetically $z$ spin components of Fe$^{3+}$ ions. At the same time, the $xy$ components are coupled by much weaker exchange interaction of ferromagnetic sign. In the system with spatial disorder (half of corresponding…
The two-dimensional electron gas (2DEG) at the non-isostructural interface between spinel gamma-Al2O3 and perovskite SrTiO3 is featured by a record electron mobility among complex oxide interfaces in addition to a high carrier density up to the order of 1E15 cm-2. Herein, we report on the patterning of 2DEG at the gamma-Al2O3/SrTiO3 interface grown at 650 °C by pulsed laser deposition using a hard mask of LaMnO3. The patterned 2DEG exhibits a critical thickness of 2 unit cells of gamma-Al2O3 for the occurrence of interface conductivity, similar to the unpatterned sample. However, its maximum c…
Halide double perovskites with alternating silver and pnictogen cations are an emerging family of photoabsorber materials with robust stability and band gaps in the visible range. However, the nature of optical excitations in these systems is not yet well understood, limiting their utility. Here, we use ab initio many-body perturbation theory within the $GW$ approximation and the Bethe-Salpeter equation approach to calculate the electronic structure and optical excitations of the double perovskite series Cs$_2$AgBX$_6$, with B=Bi$^{3+}$, Sb$^{3+}$, X = Br$^-$, Cl$^-$. We find that these materi…
Single phase polycrystalline sample of perovskite Sr2TiMnO6 (STMO) has been successfully synthesized via solid state reaction route. Its detailed structural and physical properties have been studied using x-ray diffraction, transmission electron microscopy, magnetization, specific heat, and dielectric measurements. Rietveld analysis of the powder XRD data and transmission electron microscopy studies confirm that STMO is not a double perovskite structure with Fm-3m space group. But it is a disordered perovskite structure with Pm-3m space group where Ti4+ and Mn4+ ions are randomly distributed a…
We perform first-principles density functional calculations to explore the role of substrate proximity effects on the octahedral rotation patterns in perovskite oxide superlattices. With cubic perovskite SrFeO$_3$ as our model film and tetragonal SrTiO$_3$ as the substrate, we show that in most cases the substrate octahedral rotation patterns propagate into the film across the heterointerface. We also identify elastic boundary conditions for which the enforced structural coherence induces atomic displacement patterns that are not found in the bulk phase diagram of either individual constituent…
We have investigated the structural phase transitions of the transition metal oxide perovskites SrTiO$_{3}$, LaAlO$_{3}$ and LaTiO$_{3}$ using the screened hybrid density functional of Heyd, Scuseria and Ernzerhof (HSE06). We show that HSE06-computed lattice parameters, octahedral tilts and rotations, as well as electronic properties, are significantly improved over semilocal functionals. We predict the crystal field splitting ($Δ_{CF}$) resulting from the structural phase transition in SrTiO$_{3}$ and LaAlO$_{3}$ to be 3 meV and 10 meV, respectively, in excellent agreement with experimental r…
Transparent conducting oxides (TCOs) and transparent oxide semiconductors (TOSs) have become necessary materials for a variety of applications in the information and energy technologies, ranging from transparent electrodes to active electronics components. Perovskite barium stannate (BaSnO3), a new TCO or TOS system, is a potential platform for realizing optoelectronic devices and observing novel electronic quantum states due to its high electron mobility, excellent thermal stability, high transparency, structural versatility, and flexible doping controllability at room temperature. This artic…
Based on first-principles calculations, we show that chemically active metal ns2 lone pairs play an important role in exciton relaxation and dissociation in low-dimensional halide perovskites. We studied excited-state properties of several recently discovered luminescent all-inorganic and hybrid organic-inorganic zero-dimensional (0D) Sn and Pb halides. The results show that, despite the similarity in ground-state electronic structure between Sn and Pb halide perovskites, the chemically more active Sn2+ lone pair leads to stronger excited-state structural distortion and larger Stokes shift in …
A novel 2-dimensional electron gas (2DEG) system with high-mobility was discovered at the interface of two perovskite oxides, a polar orthorhombic perovskite LaScO3 (LSO) and a nonpolar cubic perovskite BaSnO3 (BSO). Upon depositing the LSO film on the BSO film, the conductance enhancement and the resulting 2DEG density (n2D) was measured. Comparing the results with the previously reported LaInO3/BaSnO3 (LIO/BSO) polar interface, we applied the interface polarization model to the LSO/BSO system, in which the polarization exists only over 4 pseudocubic unit cells in LSO from the interface and v…
Organic-inorganic halide perovskite solar cells have recently attracted much attention due to their low-cost fabrication, flexibility, and high-power conversion efficiency. The reduction from three- to two-dimension (2D) promises an exciting opportunity to tune the electronic properties of organic-inorganic halide perovskites. Here, we propose first-principles density-functional theory based route to study the effect of reduced dimensionality, impurity doping, and heterostructure engineering on energy stability, band-gap and transport properties of 2D hybrid organic-inorganic halide perovskite…
At interfaces between polar and nonpolar perovskite oxides, an unusual electron-doping has been previously observed, due to electronic reconstructions. We report on remote hole-doping at an interface composed of only polar layers, revealed by high-resolution hard x-ray core-level photoemission spectroscopy. In LaAlO3/LaVO3/LaAlO3 trilayers, the vanadium valence systematically evolves from the bulk value of V3+ to higher oxidation states with decreasing LaAlO3 cap layer thickness. These results provide a synthetic approach to hole-doping transition metal oxide heterointerfaces without invoking …
We present an ab initio study of the (001) interfaces between two insulating perovskites, the polar LaAlO3 and the nonpolar SrTiO3. We observe an insulating-to-metallic transition above a critical LaAlO3 thickness. We explain that the high conductivity observed at the TiO2 /LaO interface and the lack of similar conductivity at the SrO/AlO2 interface are inherent in the atomic geometry of the system. A large interfacial hopping matrix element between cations causes the formation of a bound electron state at the TiO2 /LaO interface. This mechanism for the formation of interfacial bound states su…
Lead (Pb) halide perovskites have achieved great success in recent years due to their excellent optoelectronic properties, which is largely attributed to the lone-pair s orbital-derived antibonding states at the valence band edge. Guided by the key band-edge orbital character, a series of ns2-containing (i.e., Sn2+, Sb3+, Bi3+) Pb-free perovskite alternatives have been explored as potential photovoltaic candidates. On the other hand, based on the band-edge orbital components (i.e., M2+ s and p/X- p orbitals), a series of strategies have been proposed to optimize their optoelectronic properties…
ABO3 oxides with the perovskite-related structures are attracting significant interest due to their promising physical and chemical properties for many applications requiring tunable chemistry, including fuel cells, catalysis, and electrochemical water splitting. Here we report on the crystal structure of the entire family of perovskite oxides with ABO3 stoichiometry, where A and B are Ba, Sr, Mn, Ce. Given the vast size of this chemically complex material system, exploration for stable perovskite-related structures with respect to its constituent elements and annealing temperature is performe…
We develop a probabilistic machine learning model and use it to screen for new hybrid organic-inorganic perovskites (HOIPs) with targeted electronic band gap. The data set used for this work is highly diverse, containing multiple atomic structures for each of 192 chemically distinct HOIP formulas. Therefore, any property prediction on a given formula must be associated with an irreducible "uncertainty" that comes from its unknown atomic details. As a result, dozens of new HOIP formulas with band gap falling between 1.25 and 1.50 eV were identified and validated against suitable first-principle…
We use first-principles methods to investigate the effects of collective lattice excitations on the formation of oxygen vacancies in perovskite thin films. We find that phonons play a crucial role on the strain-mediated control of defect chemistry at finite temperatures. In particular, zero-temperature oxygen vacancy formation trends deduced as a function of epitaxial strain can be fully reversed near room temperature. Our first-principles calculations evidence a direct link between the lattice contribution to the oxygen vacancy free energy and the volume expansion that the system undergoes wh…
We investigate the structure--property relationships in $AB$O$_3$ perovskites exhibiting octahedral rotations and cooperative octahedral breathing distortions (CBD) using group theoretical methods. Rotations of octahedra are ubiquitous in the perovskite family, while the appearance of breathing distortions -- oxygen displacement patterns that lead to approximately uniform dilation and contraction of the $B$O$_6$ octahedra -- are rarer in compositions with a single, chemically unique $B$-site. The presence of a CBD relies on electronic instabilities of the $B$-site cations, either orbital degen…
The discovery of two-dimensional electron gases (2DEGs) in SrTiO3-based heterostructures provides new opportunities for nanoelectronics. Herein, we create a new type of oxide 2DEG by the epitaxial-strain-induced polarization at an otherwise nonpolar perovskite-type interface of CaZrO3/SrTiO3. Remarkably, this heterointerface is atomically sharp, and exhibits a high electron mobility exceeding 60,000 cm2V-1s-1 at low temperatures. The 2DEG carrier density exhibits a critical dependence on the film thickness, in good agreement with the polarization induced 2DEG scheme.
The discovery of two-dimensional electron gas (2DEG) at well-defined interfaces between insulating complex oxides provides the opportunity for a new generation of all-oxide electronics. Particularly, the 2DEG at the interface between two perovskite insulators represented by the formula of ABO3, such as LaAlO3 and SrTiO3, has attracted significant attention. In recent years, progresses have been made to decipher the puzzle of the origin of interface conduction, to design new types of oxide interfaces, and to improve the interfacial carrier mobility significantly. These achievements open the doo…
Variable resistors were constructed from epitaxial SrRuO3 (SRO), La0.67Sr0.33MnO3 (LSMO) and SrTiO3 layers with perovskite crystal structure. Each layer was patterned separately by lithographic methods. Optimized wet chemical etchants and several polishing steps in organic solvents allowed good epitaxy of subsequent layers, comparable to epitaxy on pristine substrates. Periodate as the oxidizing agent for SRO and iodide with ascorbic acid as the reducing agents for LSMO were used to attack these chemically resistant oxides. The final devices changed their conductance in a similar manner to pre…
Understanding Graphene-Perovskite Interactions: From Flake Chemistry to Crystallisation and Solar Cell Performance
CIC nanoGUNE（纳米材料中心）；Fisika Saila, Centro Fı́sica Materiales CSIC-UPV/EHU（巴斯克国家研究委员会-巴斯克国立大学物质物理中心物理系）；Centre for Advanced Materials and Technologies (CEZAMAT), Warsaw University of Technology（华沙理工大学先进材料与技术中心）；Key Laboratory for Special Functional Materials of Ministry of Education, School of Nanoscience and Materials Engineering, Henan University（河南大学纳米科学与工程学部委部省共建特殊功能材料重点实验室）；Instituto de Ciencia de los Materiales (ICMUV), Universitat de Valencia（瓦伦西亚大学材料科学研究所）；Donostia International Physics Center（圣塞巴斯蒂安国际物理中心）；Ikerbasque, Basque Foundation for Science（伊克尔巴斯科，巴斯克科学基金会）；Polymat, University of the Basque Country UPV/EHU（巴斯克国立大学聚合物材料研究中心）；BCMaterials, Basque Center for Materials, Applications and Nanostructures, UPV/EHU Science Park（巴斯克材料、应用与纳米结构中心）
Oxide heterointerfaces constitute a rich platform for realizing novel functionalities in condensed matter. A key aspect is the strong link between structural and electronic properties, which can be modified by interfacing materials with distinct lattice symmetries. Here we determine the effect of the cubic-tetragonal distortion of $\text{SrTiO}_3$ on the electronic properties of thin films of $\text{SrIrO}_3$, a topological crystalline metal hosting a delicate interplay between spin-orbit coupling and electronic correlations. We demonstrate that below the transition temperature at 105 K, $\tex…
Two-dimensional electron gas (2DEG) formed at the interface between two insulating oxides offers an opportunity for fundamental research and device applications. Binary alkaline earth metal oxides possess compatible lattice constants with both silicon and perovskite oxides, exhibiting an enormous potential to bridging those two materials classes for multifunctionalities. Here we report the formation of 2DEG at the interface between the rock-salt BaO and SrTiO3. The highest electron mobility reaches 69000 cm^2 V.S^-1 at 2 K, leading to the typical Shubniko de Haas (SdH) oscillations under the h…
Designing heterostructures to control oxygen stoichiometry in helimagnetic perovskite strontium ferrite
Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory（斯坦福材料能源科学研究所，SLAC国家加速器实验室）；Department of Applied Physics, Stanford University（斯坦福大学应用物理系）；Department of Materials Science and Engineering, Northwestern University（西北大学材料科学与工程系）；Catalan Institute of Nanoscience and Nanotechnology (ICN2)（加泰罗尼亚纳米科学与纳米技术研究所（ICN2））；School of Applied and Engineering Physics, Cornell University（康奈尔大学应用与工程物理学院）；Center for Nanophase Materials Sciences, Oak Ridge National Laboratory（橡树岭国家实验室纳米材料科学中心）；Department of Material Science Engineering, Pusan National University（釜山大学材料科学与工程系）；Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory（SLAC国家加速器实验室斯坦福同步辐射光源）
Understanding muon diffusion in perovskite oxides below room temperature based on harmonic transition state theory
Advanced Science Research Center, Japan Atomic Energy Agency（日本原子能机构先进科学研究中心）；Department of Physics, Tokyo Institute of Technology（东京工业大学物理系）；Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK)（高能加速器研究机构物质结构科学研究所）
Double-perovskite A2BB'O6 oxides with magnetic B and B' ions and E*-type antiferromagnetic order (E*-AFM, i.e. the ++-- structure) are believed to exhibit promising multiferroic properties, and Y2CoMnO6 (YCMO) is one candidate in this category. However, the microscopic origins for magnetically induced ferroelectricity in YCMO remain unclear. In this work, we perform detailed symmetry analysis on the exchange striction effect and lattice distortion, plus the first-principles calculations on YCMO. The E*-AFM state as the ground state with other competing states such as ferromagnetic and A-antife…
To achieve high quality epitaxial thin films and heterostructures of transition metal oxides with atomically controlled interfaces, one critical requirement is the use of atomically flat single terminated oxide substrates since the atomic arrangements and the reaction chemistry of the topmost surface layer of substrates determine the growth and consequent properties of the overlying films. Achieving the atomically flat and chemically single terminated surface state of commercially available substrates, however, requires judicious efforts because the surface of as-received substrates is of chem…
Complex oxide heterostructures display some of the most chemically abrupt, atomically precise interfaces, which is advantageous when constructing new interface phases with emergent properties by juxtaposing incompatible ground states. One might assume that atomically precise interfaces result from stoichiometric growth, but here we show that the most precise control is obtained for non-stoichiometric growth where differing surface energies can be compensated by surfactant-like effects. For the precise growth of Sr$_{n+1}$Ti$_n$O$_{3n+1}$ Ruddlesden-Popper (RP) phases, stoichiometric deposition…
Establishing Atomic Coherence in Twisted Oxide Membranes Containing Volatile Elements
Oak Ridge National Laboratory（橡树岭国家实验室）；North Carolina State University（北卡罗来纳州立大学）；Sungkyunkwan University（成均馆大学）；Institute for Basic Science（基础科学研究院）；Duke University（杜克大学）
