We study the formation and evolution of coherent islands on lattice mismatched epitaxially strained films. Faceted islands form in films with aniostropic surface tension. Under annealing, these islands ripen until a stable array is formed, with an island density which increases with film thickness. Under deposition, an island shape transition occurs, which leads to a bimodal island size distribution. In films with isotropic surface tension we observe continual ripening of islands above a certain film thickness. A stable wavy morphology is found in thinner films.
Density functional calculations are performed to study the effect of epitaxial strain on PbZrO3. We find a remarkably small energy difference between the epitaxially strained polar R3c and nonpolar Pbam structures over the full range of experimentally accessible epitaxial strains -3% < η< 4%. While ferroelectricity is favored for all compressive strains, for tensile strains the small energy difference between the nonpolar ground state and the alternative polar phase yields a robust antiferroelectric ground state. The coexistence of ferroelectricity and antiferroelectricity observed in thin fil…
We showed that a wetting layer in epitaxially strained thin films which decreases with increasing lattice mismatch strain arises due to the variation of nonlinear elastic free energy with film thickness. We calculated how and at what thickness a flat film becomes unstable to perturbations of varying size for films with both isotropic and anisotropic surface tension. We showed that anisotropic surface tension gives rise to a metastable enlarged wetting layer. The perturbation amplitude needed to destabilize this wetting layer decreases with increasing lattice mismatch. We also studied the early…
Combining effective Hamiltonian and direct $ab$ $initio$ computation, we obtain the phase diagram of SnTiO$_{3}$ with respect to epitaxial strain and temperature, demonstrating the complex features of the phase diagram and providing insight into the epitaxially strained SnTiO$_{3}$, a presumably simple perovskite. In the phase diagram, two triple points are found, which may be exploited to to achieve high-performance piezoelectric effects. On the other hand, despite the inclusion of the degree of freedoms related to oxygen octahedron tilting, it is found that ferroelectric displacements domina…
The structure and polarization of the as-yet hypothetical Ruddlesden-Popper compound Pb$_2$TiO$_4$ are investigated within density-functional theory. Zone enter phonons of the high-symmetry K$_2$NiF$_4$-type reference structure, space group $I4/mmm$, were calculated. At the theoretical ground-state lattice constants, there is one unstable infrared-active phonon. This phonon freezes in to give the $I2mm$ ferroelectric state. As a function of epitaxial strain, two additional ferroelectric phases are found, with space groups $I4mm$ and $F2mm$ at compressive and tensile strains, respectively.
Using first-principles density functional theory calculations, we discover an anomalously large bi-axial strain-induced octahedral rotation axis reorientation in orthorhombic perovskites with tendency towards rhombohedral symmetry. The transition between crystallographically equivalent (isosymmetric) structures with different octahedral rotation magnitudes originates from strong strain--octahedral rotation coupling available to perovskites and the energetic hierarchy among competing octahedral tilt patterns. By elucidating these criteria, we suggest many functional perovskites would exhibit th…
Using density functional theory within the LSDA + U method, we investigate the effect of strain on the spin state and magnetic ordering in perovskite lanthanum cobaltite, LaCoO3. We show that, while strain-induced changes in lattice parameters are insufficient to stabilize a non-zero spin state, additional heteroepitaxial symmetry constraints -- in particular the suppression of octahedral rotations -- stabilize a ferromagnetic intermediate-spin state. By comparing with experimental data for the bulk material, we calculate an upper bound on the Hubbard U value, and describe the role that the on…
The phase transition behaviour of PbTiO3 and BaTiO3 under (111) epitaxial strain is investigated using density-functional theory calculations. From tensile strains of +0.015 to compressive strains of -0.015, PbTiO3 undergoes phase transitions from C2 through two Cm phases and then to R3m. The total polarisation is found to be almost independent of strain. For the same range of strains BaTiO3 undergoes phase transitions from a single Cm phase, through R3m and then to R-3m. In this case the application of compressive strain inhibits and then completely suppresses the polarisation on transition t…
We propose a physical model which explains the existence of finite thickness wetting layers in epitaxially strained films. The finite wetting layer is shown to be stable due to the variation of the non-linear elastic free energy with film thickness. We show that anisotropic surface tension gives rise to a metastable enlarged wetting layer. The perturbation amplitude needed to destabilize this wetting layer decreases with increasing lattice mismatch. We observe the development of faceted islands in unstable films.
We use first principles density functional theory calculations to investigate the effect of biaxial strain in the low-temperature structural and ferroelectric properties of [111]-oriented SrTiO$_3$. We find that [111] biaxial strain, achievable by coherent epitaxial growth along the [111] direction, induces structural distortions in SrTiO$_3$ that are not present in either bulk or [001]-oriented SrTiO$_3$. Under [111] biaxial strain, SrTiO$_3$ displays ferroelectricity at tensile strain, and paraelectricity at compressive strain. We compute the phonon spectrum and macroscopic polarization of S…
First-principles calculations of the epitaxial-strain phase diagram of perovskite SrCoO$_{3}$ are presented. Through combination of the large spin-phonon coupling with polarization-strain coupling and coupling of the band gap to the polar distortion, both tensile and compressive epitaxial strain are seen to drive the bulk ferromagnetic-metallic (FM-M) phase to antiferromagnetic-insulating-ferroelectric (AFM-I-FE) phases, the latter having unusually low elastic energy. At these coupled magnetic-ferroelectric metal-insulator phase boundaries, cross responses to applied electric and magnetic fiel…
The effect of layer-by-layer heterostructuring and epitaxial strain on lattice instabilities and related ferroelectric properties is investigated from first principles for the [001]-(PbTiO$_3$)$_1$(PbZrO$_3$)$_1$ superlattice and pure PbTiO$_3$ on a cubic substrate. The results for the superlattice show an enhancement of the stability of the monoclinic r-phase with respect to pure PbTiO$_3$. Analysis of the lattice instabilities of the relaxed centrosymmetric reference structure computed within density functional perturbation theory suggests that this results from the presence of two unstable …
We have investigated the effect of epitaxial strain on the magnetic properties and $B$-site cation ordering in multiferroic Bi$_2$FeCrO$_6$ (001) thin films using a density-functional theory approach. We find that in thin films with rock-salt ordering of Fe and Cr the ground state is characterised by C-type anti-ferromagnetic (AFM) order. This is in contrast to the bulk form of the material which was predicted to be a ferrimagnet with G-type AFM order. Furthermore, the cation ordered thin-films undergo a transition with epitaxial strain from C to A-type AFM order. Other magnetic orders appear …
After decades of searching for robust nanoscale ferroelectricity that could enable integration into the next generation memory and logic devices, hafnia-based thin films have appeared as the ultimate candidate because their ferroelectric (FE) polarization becomes more robust as the size is reduced. This exposes a new kind of ferroelectricity, whose mechanism still needs to be understood. Towards this end, thin films with increased crystal quality are needed. We report the epitaxial growth of Hf0.5Zr0.5O2 (HZO) thin films on (001)-oriented La0.7Sr0.3MnO3/SrTiO3 (STO) substrates. The films, whic…
Zirconia and hafnia based thin films have attracted tremendous attention in the last decade due to their unexpected ferroelectric behavior at the nanoscale, which facilitates the downscaling of ferroelectric devices. The present work reports a novel ferroelectric rhombohedral phase of ZrO2 that can be achieved in thin films grown on (111)- Nb:SrTiO3 substrates by ion-beam sputtering. Structural and ferroelectric characterizations reveal that the (111)-oriented ZrO2 films are under epitaxial compressive strain and display a switchable ferroelectric polarization of about 20.2 μC/cm2 with a coerc…
Multiferroics with the coexistence of ferroelectric and ferromagnetic orders are ideal candidates for magnetoelectric applications. Unfortunately, only very few ferroelectric-ferromagnetic multiferroics (with low magnetic critical temperature) were discovered. Here we perform first principles calculations to investigate the effects of the epitaxial strain on the properties of BiMnO3 films grown along the pseudocubic [001] direction. Unlike the ground state with the centrosymmetric C2/c space group in bulk, we reveal that the tensile epitaxial strain stabilizes the ferromagnetic and ferroelectr…
The effect of in-plane strain on the nonlinear dielectric properties of SrTiO3 epitaxial thin films is calculated using density-functional theory within the local-density approximation. Motivated by recent experiments, the structure, zone-center phonons, and dielectric properties with and without an external electric field are evaluated for several misfit strains within +-3% of the calculated cubic lattice parameter. In these calculations, the in-plane lattice parameters are fixed, and all remaining structural parameters are permitted to relax. The presence of an external bias is treated appro…
We use density-functional theory with the local-density approximation to study the structural and ferroelectric properties of SrTiO$_3$ under misfit strains. Both the antiferrodistortive (AFD) and ferroelectric (FE) instabilities are considered. The rotation of the oxygen octahedra and the movement of the atoms are fully relaxed within the constraint of a fixed in-plane lattice constant. We find a rich misfit strain-induced phase transition sequence and is obtained only when the AFD distortion is taken into account. We also find that compressive misfit strains induce ferroelectricity in the te…
Motivated by the puzzling report of the observation of a ferromagnetic insulating state in LaMnO$_3$/SrTiO$_3$ heterostructures, we calculate the electronic and magnetic state of LaMnO$_3$, coherently matched to a SrTiO$_3$ square substrate within a "strained-bulk" geometry. We employ three different density functional theory based computational approaches: (a) density functional theory (DFT) supplemented with Hubbard U (DFT+U), (b) DFT + dynamical mean field theory (DMFT), and (c) a hybrid functional treatment of the exchange-correlation functional. While the first two approaches include loca…
The equilibrium shapes and energies of coherent strained InP islands grown on GaP have been investigated with a hybrid approach that has been previously applied to InAs islands on GaAs. This combines calculations of the surface energies by density functional theory and the bulk deformation energies by continuum elasticity theory. The calculated equilibrium shapes for different chemical environments exhibit the {101}, {111}, {\=1\=1\=1} facets and a (001) top surface. They compare quite well with recent atomic-force microscopy data. Thus in the InP/GaInP-system a considerable equilibration of t…
The effect of epitaxial strain on the structural and electronic properties of LaVO_3 is investigated through density functional theory (DFT) and dynamical mean field theory (DMFT). Two different growth orientations of the crystal are considered, one preserving the bulk Pbnm space-group symmetry and another giving rise to a symmetry lowering to P2_1/m. In the nonmagnetic DFT structures, the two growth orientations are equally favored for all tensile strains considered here, as well as for compressive strains weaker than -3%. For stronger compressive strains, the P2_1/m orientation is favored an…
BiFeO3 thin films with various thicknesses were grown epitaxially on (001) LaSrAlO4 single crystal substrates using pulsed laser deposition. High resolution x-ray diffraction measurements revealed that a tetragonal-like phase with c-lattice constant ~4.65 Å is stabilized by a large misfit strain. Besides, a rhombohedral-like phase with c-lattice constant ~3.99 Å was also detected at film thickness of ~50 nm and above to relieve large misfit strains. In-plane piezoelectric force microscopy studies showed clear signals and self-assembled nanoscale stripe domain structure for the tetragonal-like …
Observation of mirror-odd and mirror-even spin texture in ultrathin epitaxially strained RuO2 films
University of Minnesota-Twin Cities（明尼苏达大学双城分校）；Kyung Hee University（庆熙大学）；Rice University（莱斯大学）；Paul Scherrer Institute（保罗谢勒研究所）；Gwangju Institute of Science and Technology (GIST)（光州科学技术院）
Strain is known to greatly influence low temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. However, its catalytic impact on transition metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional c…
We have synthesized 20 nm thick films of tetragonally strained interstitial Fe-Co-B alloys epitaxially grown on Au55Cu45 buffer layer. The strained axis is perpendicular to the film plane and the corresponding lattice constant c is enlarged with respect to the in-plane lattice parameter a. By adding the interstitial boron with different concentrations 0, 4, and 10 at.% we were able to stabilize the tetragonal strain in 20 nm Fe-Co films with different c/a ratios of 1.013, 1.034 and 1.02, respectively. Using ferromagnetic resonance (FMR) and x-ray magnetic circular dichroism (XMCD) we found tha…
We examine the structure and the evolution of Ge islands epitaxially grown on vicinal Si(111) surfaces by scanning tunneling microscopy. Contrary to what is observed on the singular surface, three-dimensional Ge nanoislands form directly through the elastic relaxation of step-edge protrusions during the unstable step-flow growth. As the substrate misorientation is increased, the islands undergo a shape transformation which is driven by surface energy minimization and controlled by the miscut angle. Using finite element simulations, we show that the dynamics of islanding observed in the experim…
Epitaxially strained SrRuO3 films have been a model system for understanding the magnetic anisotropy in metallic oxides. In this paper, we investigate the anisotropy of the Ru 4d and O 2p electronic structure and magnetic properties using high-quality epitaxially strained (compressive and tensile) SrRuO3 films grown by machine-learning-assisted molecular beam epitaxy. The element-specific magnetic properties and the hybridization between the Ru 4d and O 2p orbitals were characterized by Ru M2,3-edge and O K-edge soft X-ray absorption spectroscopy and X-ray magnetic circular dichroism measureme…
Ba(Fe1-xCox)2As2 superconducting thin films have been grown on SrTiO3, (La,Sr)(Al,Ta)O3, LaAlO3 and YAlO3 (YAO) single crystal substrates by pulsed laser deposition. All the films, except on YAO, have been grown epitaxially without buffer layers. The films deposited on YAO contained 45 degree in-plane rotated grains and showed a broad superconducting transition. The onset Tc of the films is observed to increase from 16.2 K to 24.5 K with increasing c/a, mainly due to a slight distortion of the AsFe4 tetrahedron. From this correlation, we expect that higher superconducting transition temperatur…
Layered perovskite La2CuO4+delta(LCO) thin films were epitaxially grown on SrTiO3 (STO) and LaSrAlO4 (LSAO) substrates by atomic-layer-by-layer molecular beam epitaxy. The lattice de-fects and residual strain in these films were investigated by means of transmission electron mi-croscopy and electron energy loss spectroscopy. The LCO films showed a high epitaxial quality with flat interfaces and top surfaces. Misfit dislocations with Burgers vector a<010> and shear defects were frequently observed at or near the film/substrate interfaces and in the films, respec-tively, for all the LCO films. I…
We report on an angular resolved X-ray Absorption Spectroscopy study of $La_{0.7}Sr_{0.3}MnO_{3}$ thin films epitaxially grown by pulsed laser deposition on slightly mismatched substrates which induce tensile or compressive strains. XANES spectra give evidence of tetragonal distortion within the $MnO_{6}$ octahedra, with opposite directions for tensile and compressive strains. Quantitative analysis has been done and a model of tetragonal distortion reflecting the strain has been established. EXAFS data collected in plane for tensile substrate confirm the change in the $Mn-O$ average bond dista…
Orthorhombic SrIrO3 is a typical spin-orbit-coupling correlated metal that shows diversified physical properties under the external stimuli. Here nonlinear Hall effect and weakly temperature-dependent resistance are observed in a SrIrO3 film epitaxially grown on SrTiO3 substrate. It infers that orthorhombic SrIrO3 is a semimetal oxide. However, linear Hall effect and insensitive-temperature-dependent resistance are observed in SrIrO3 films grown on (La,Sr)(Al,Ta)O3 (LSAT) substrates, suggesting a tunable semimetallic state due to band structure change in SrIrO3 films under different compressiv…
Epitaxially strained LaCoO3 (LCO) thin films were grown with different film thickness, t, on (001) oriented (LaAlO3)0.3(SrAl0.5Ta0.5O3)0.7 (LSAT) substrates. After initial pseudomorphic growth the films start to relieve their strain partly by the formation of periodic nano-twins with twin planes predominantly along the <100> direction. Nano-twinning occurs already at the initial stage of growth, albeit in a more moderate way. Pseudomorphic grains, on the other hand, still grow up to a thickness of at least several tenths of nanometers. The twinning is attributed to the symmetry lowering of the…
Manipulating the orbital occupation of valence electrons via epitaxial strain in an effort to induce new functional properties requires considerations of how changes in the local bonding environment affect the band structure at the Fermi level. Using synchrotron radiation to measure the x-ray linear dichroism of epitaxially strained films of the correlated oxide CaFeO3, we demonstrate that the orbital polarization of the Fe valence electrons is opposite from conventional understanding. Although the energetic ordering of the Fe 3d orbitals is confirmed by multiplet ligand field theory analysis …
We study the morphological evolution of strained islands in growing crystal films by use of a continuum description including wetting, elasticity and deposition flux. Wetting breaks translational invariance, allowing the flux to tune different nonlinear regimes. Increasing the flux, we find first an annealing-like dynamics, then a slower but non-conventional ripening followed by a steady regime, while the island density continuously increases. The islands develop spatial correlations and ordering with a narrow two-peaked distance distribution and ridge-like clusters of islands for high flux.
Anisotropic Superconductivity with Enhanced Critical Field in Strained RuO2
The Ohio State University（俄亥俄州立大学）；Cornell University（康奈尔大学）；Williams College（威廉姆斯学院）；Kavli Institute at Cornell for Nanoscale Science, Cornell University（康奈尔大学卡弗里纳米科学研究所）；Leibniz-Institut für Kristallzüchtung（莱布尼茨晶体生长研究所）
We report a comparative study of the properties of very thin films of La0.67Ca0.33MnO3 grown epitaxially under strain on flat SrTiO3 (STO) and on 1 deg miscut STO. For the films on flat STO the transport properties show well-known behavior, namely values of the metal-insulator transition temperature which are strongly reduced with respect to the bulk value. The reduction in films on miscut STO is significantly less strong than in films on flat STO, even though they appear similar as to strain state. Moreover, the residual resistance at low temperatures is lower than for the case of flat films.…
While structure refinement is routinely achieved for simple bulk materials, the accurate structural determination still poses challenges for thin films due on the one hand to the small amount of material deposited on the thicker substrate and, on the other hand, to the intricate epitaxial relationships that substantially complicate standard X-ray diffraction analysis. Using a combined approach, we analyze the crystal structure of epitaxial LaVO$_3$ thin films grown on (100)-oriented SrTiO$_3$. Transmission electron microscopy study reveals that the thin films are epitaxially grown on SrTiO$_3$…
Transport and magnetic properties of LSMO manganite thin films and bicrystal junctions were investigated. Manganite films were epitaxially grown on STO, LAO, NGO and LSAT substrates and their magnetic anisotropy were determined by two techniques of magnetic resonance spectroscopy. Compare with cubic substrates a small (about 0.3 persentage), the anisotropy of the orthorhombic NGO substrate leads to a uniaxial anisotropy of the magnetic properties of the films in the plane of the substrate. Samples with different tilt of crystallographic basal planes of manganite as well as bicrystal junctions …
We investigate the stress-driven morphological instability of epitaxially growing multilayer films, which are coherent and dislocation-free. We construct a direct elastic analysis, from which we determine the elastic state of the system recursively in terms of that of the old states of the buried layers. In turn, we use the result for the elastic state to derive the morphological evolution equation of surface profile to first order of perturbations, with the solution explicitly expressed by the growth conditions and material parameters of all the deposited layers. We apply these results to two…
Gray tin, also known as $α$-Sn, can be turned into a three-dimensional topological insulator (3D-TI) by strain and finite size effects. Such room temperature 3D-TI is peculiarly interesting for spintronics due to the spin-momentum locking along the Dirac cone (linear dispersion) of the surface states. Angle resolved photoemission spectroscopy (ARPES) has been used to investigate the dispersion close to the Fermi level in thin (0\,0\,1)-oriented epitaxially strained films of $α$-Sn, for different film thicknesses as well as for different capping layers (Al, AlO$_x$ and MgO). Indeed a proper cap…
The interaction of Mn with Ge quantum dots (QD), which are bounded by {105} facets, and the strained Ge wetting layer (WL), terminated by a (001) surface, is investigated with scanning tunneling microscopy (STM). Mn is deposited on the Ge QD and WL surface in sub-monolayer concentrations, and subsequently annealed up to temperature of 400 C. Bonding and surface topography were measured with STM during the annealing process. Mn forms flat islands on the Ge {105} facet, whose shape and position is guided by the rebonded step reconstruction. The images show a hybridization of Mn-d band and empty …
