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This Perspective addresses the design, creation, characterization and control of synthetic quantum materials with strong electronic correlations. We show how emerging synergies between theoretical/computational approaches and materials design/experimental probes are driving recent advances in the discovery, understanding and control of new electronic behaviour in materials systems with interesting and potentially technologically important properties. The focus here is on transition metal oxides, where electronic correlations lead to a myriad of functional properties including superconductivity, magnetism, Mott transitions, multiferroicity and emergent behaviour at picoscale-designed interfaces. Current opportunities and challenges are also addressed, including possible new discoveries of non-equilibrium phenomena and optical control of correlated quantum phases of transition metal oxides. This Perspective addresses the properties of strongly correlated materials, with a particular focus on computational, synthetic and spectroscopic approaches.

The ability to control the dispersion of RuO2 monolayers on a range of perovskite- and corundum-structured oxide substrates was investigated using complementary experiment and theory. Controlled deposition under UHV conditions and subsequent in situ characterization by x-ray photoelectron spectroscopy (XPS), ion scattering spectroscopy (ISS), reflection high energy electron diffraction (RHEED) and low energy electron diffraction (LEED) was used to follow the chemical state, dispersion and structure of the RuO2 layers as a function of growth and post-growth processing conditions. The experimental results reveal that monolayer RuO2 on ferroelectric PbxZr1-xTiO3(001) and non-polar SrTiO3(001) α-Al2O3 ( 1 1 ¯ 02 ) tends to dewet the surface to form three-dimensional clusters, though some kinetic stability of dispersed RuO2 monolayers was achieved on the SrTiO3 surface. Although an RuO2 termination is not favored for SrRuO3(001), deposition onto SrRuO3(001) yields a stable RuO2 surface which ISS suggests is capped by chemisorbed oxygen. The complementary density functional theory modeling and ab initio thermodynamics indicate that Ru oxide monolayers on the perovskite substrates tend to be unstable under the low oxygen pressure experimental conditions; however, either lower temperatures or higher oxygen pressures can lead to a kinetic and even thermodynamic stability. The theoretical findings also provide guidance on how the instability of dispersed RuO2 monolayers can be overcome by inserting buffer layers and increasing the partial pressure of molecules that selectively, strongly adsorb at coordinatively unsaturated Ru sites on the oxide surface.

The ability to synthesize two-dimensional (2D) oxide layers with nonbulk structures on transition-metal surfaces has attracted attention as a method to expand the range of 2D structures and propert...

Two-dimensional (2D) materials can have multiple phases close in energy but with distinct properties, with the phases that form during growth dependent on experimental conditions and the growth substrate. Here, the competition between 2D van der Waals (VDW) silica and 2D Ni silicate phases on NixPd1-x(111) alloy substrates was systematically investigated experimentally as a function of Si surface coverage, annealing time and temperature, O2 partial pressure, and substrate composition and the results were compared with thermodynamic predictions based on density functional theory (DFT) calculations and thermochemical data for O2. Experimentally, 2D Ni silicate was exclusively observed at higher O2 pressures (∼10-6 Torr), higher annealing temperatures (1000 K), and more prolonged annealing (10 min) if the substrate contained any Ni and for initial Si coverages up to 2 monolayers. In contrast, decreasing the O2 pressure to ∼10-8 Torr and restricting the annealing temperature and time enabled 2D VDW silica formation. Amorphous 2D VDW silica was observed even when the substrate composition was tuned to lattice match crystalline 2D VDW silica. The trend of decreased O2 pressure favoring 2D VDW silica was consistent with the theoretical predictions; however, theory also suggested that sufficient Si coverage could avoid Ni silicate formation. The effect of epitaxial strain on 2D Ni silicate was investigated by modifying the solid solution alloy substrate composition. It was found that 2D Ni silicate will stretch to match the substrate lattice constant up to 1.12% tensile strain. When the lattice mismatch was over 1.40%, incommensurate crystalline domains were observed, indicating relaxation of the overlayer to its favored lattice constant. The limited epitaxial strain that could be applied was attributed to a combination of the 2D silicate stiffness, the insensitivity of its bonding to the substrate to its alignment with the substrate, and its lack of accessible structural rearrangements that can reduce the strain energy. The results demonstrate how the resulting 2D material can be manipulated through the growth conditions and how a solid solution alloy substrate can be used to maximize the epitaxial strain imparted to the 2D system.

A single layer of Fe silicate was grown on Pd(111) and analyzed experimentally and theoretically. Following sequential deposition of SiO and Fe and annealing above 900 K in O2, an incommensurate but well-ordered, low-defect density layer was observed with low-energy electron diffraction and scanning tunneling microscopy (STM). The STM images revealed a moire pattern due to the lattice mismatch between the relaxed oxide layer and the substrate, while high-resolution images showed a honeycomb structure consistent with a silicate layer with six-membered rings of corner-sharing SiO4 tetrahedra at its surface. Reflection-absorption infrared spectroscopy revealed a single peak at 1050 cm−1 due to Si–O–Fe linkages, while x-ray photoelectron spectroscopy data indicated a Si/Fe ratio of one, that the Fe were all 3+, and that the Si atoms were closest to the surface. Consistent with these experimental observations, first principles theory identified a layer with an overall stoichiometry of Fe2Si2O9 with the six-membered rings of SiO4 tetrahedra at the surface. One of the oxygen atoms appears as a chemisorbed atom on the Pd surface, and, thus, the layer is better described as Fe2Si2O8 atop an oxygen-covered Pd surface. The Fe2Si2O8 is chemically bound to the Pd surface through its oxygen atoms; and the passivation of these bonds by hydrogen was investigated theoretically. Upon hydrogenation, the adsorbed O atom joins the Fe silicate layer and thermodynamic analysis indicates that, at room temperature and H2 pressures below 1 atm, Fe2Si2O9H4 becomes favored. The hydrogenation is accompanied by a substantial increase in the equilibrium distance between the oxide layer and the Pd surface and a drop in the adhesion energy to the surface. Together the results indicate that a highly ordered 2D Fe silicate can be grown on Pd(111) and that subsequent hydrogenation of this layer offers potential to release the 2D material from the growth substrate.

A single atomic layer of ZrO2 exhibits ferroelectric switching behavior when grown with an atomically abrupt interface on silicon. Hysteresis in capacitance–voltage measurements of a ZrO2 gate stack demonstrate that a reversible polarization of the ZrO2 interface structure couples to the carriers in the silicon. First-principles computations confirm the existence of multiple stable polarization states and the energy shift in the semiconductor electron states that result from switching between these states. This monolayer ferroelectric represents a new class of materials for achieving devices that transcend conventional complementary metal oxide semiconductor (CMOS) technology. Significantly, a single atomic layer ferroelectric allows for more aggressively scaled devices than bulk ferroelectrics, which currently need to be thicker than 5–10 nm to exhibit significant hysteretic behavior (Park, et al. Adv. Mater. 2015, 27, 1811).

Through a combination of experimental measurements and theoretical modeling, we describe a strongly orbital-polarized insulating ground state in an ${({\mathrm{LaTiO}}_{3})}_{2}/{({\mathrm{LaCoO}}_{3})}_{2}$ oxide heterostructure. X-ray absorption spectra and ab initio calculations show that an electron is transferred from the titanate to the cobaltate layers. The charge transfer, accompanied by a large octahedral distortion, induces a substantial orbital polarization in the cobaltate layer of a size unattainable via epitaxial strain alone. The asymmetry between in-plane and out-of-plane orbital occupancies in the high-spin cobaltate layer is predicted by theory and observed through x-ray linear dichroism experiments. Manipulating orbital configurations using interfacial coupling within heterostructures promises exciting ground-state engineering for realizing new emergent electronic phases in metal oxide superlattices.

We use density functional theory and Monte Carlo lattice simulations to investigate the structure of ZrO$_{2}$ monolayers on Si(001). Recently, we have reported on the experimental growth of amorphous ZrO$_{2}$ monolayers on silicon and their ferroelectric properties, marking the achievement of the thinnest possible ferroelectric oxide [M. Dogan et al. Nano Lett., 18 (1) (2018)]. Here, we first describe the rich landscape of atomic configurations of monocrystalline ZrO$_{2}$ monolayers on Si and determine the local energy minima. Because of the multitude of low-energy configurations we find, we consider the coexistence of finite-sized regions of different configurations. We create a simple nearest-neighbor lattice model with parameters extracted from DFT calculations, and solve it numerically using a cluster Monte Carlo algorithm. Our results suggest that up to room temperature, the ZrO$_{2}$ monolayer consists of small domains of two low-energy configurations with opposite ferroelectric polarization. This explains the observed ferroelectric behavior in the experimental films as a collection of crystalline regions, which are a few nanometers in size, being switched with the application of an external electric field.

A monolayer of ZrO$_{2}$ has recently been grown on the Si(001) surface and shown to have ferroelectric properties, which signifies the realization of the lowest possible thickness in ferroelectric oxides [M. Dogan et al., Nano Lett., 18 (1) (2018)]. In our previous computational study, we reported on the multiple (meta)stable configurations of ZrO$_{2}$ monolayers on Si, and how switching between a pair of differently polarized configurations may explain the observed ferroelectric behavior of these films [M. Dogan and S. Ismail-Beigi, arXiv:1902.01022 (2019)]. In the current study, we conduct a DFT-based investigation of (i) the effect of oxygen content on the ionic polarization of the oxide, and (ii) the role of zirconia monolayers as buffer layers between silicon and a thicker oxide film that is normally paraelectric on silicon, e.g. SrTiO$_{3}$. We find that (i) total energy-vs-polarization behavior of the monolayers, as well as interface chemistry, is highly dependent on the oxygen content; and (ii) SrTiO$_{3}$/ZrO$_{2}$/Si stacks exhibit multiple (meta)stable configurations and polarization profiles, i.e. zirconia monolayers can induce ferroelectricity in oxides such as SrTiO$_{3}$ when used as a buffer layer. This may enable a robust non-volatile device architecture where the thickness of the gate oxide (here strontium titanate) can be chosen according to the desired properties.

There is widespread interest in finding sustainable replacements for fossil fuels, and hence hydrogen production via water splitting has received much attention. However, finding efficient water splitting methods remains a challenge. We use first principles theory to design a catalytic cycle for water splitting that employs the pyroelectric effect in ferroelectrics. Taking PbTiO3 as an example, we show that actively controlling the ferroelectric polarization via cyclic temperature modulations can catalyze the splitting of H2O into O2 and H2. In practice, the energy needed to drive this cycle may be provided by low/intermediate grade heat. Since no precious metals are used in this catalytic cycle, this approach may lead to viable water-splitting methods that employ earth-abundant elements.

Synthesizing monolayers and heterostructures is an enabling approach to extract new physical phenomena from bulk materials. Among the structures amenable to this approach is stanene, which is a monolayer of tin, similar to graphene, and has been predicted to host one-dimensional topological states at its edges. Stanene can be tuned by decorating with different adatoms, which makes it a promising platform on which to engineer topological devices. Here, we deposit Sn on Bi2Te3 and characterize the growth using anomalous synchrotron x-ray scattering and x-ray photoelectron spectroscopy (XPS). X-ray diffraction data reveal the formation of epitaxial Sn-based structures, along with penetration of Sn into the Bi2Te3, with Sn intercalating between the upper 10 Bi2Te3 quintuple layers. Additionally, XPS data show deposited Sn reacting to form SnTe and Bi at the Bi2Te3 surface. The calculated heat of reaction for Sn and Bi2Te3 is consistent with an exothermic reaction to SnTe and Bi. Using thermodynamic calculations as a guide, we identify several candidate substrates that can stabilize the stanene phase.

We demonstrate the integration of a two-dimensional electron gas (2DEG) oxide structure composed of $\mathrm{LaTi}{\mathrm{O}}_{3}/\mathrm{SrTi}{\mathrm{O}}_{3}$ (LTO/STO) on undoped Si(001) that possesses the attractive attributes of high charge density from the oxide and high mobility of silicon. Key to this approach is modification of the oxygen content at the STO-Si interface, which tunes the band alignment and induces electron carriers to move from the oxide 2DEG to form a 2DEG in the silicon substrate. As a consequence, the overall mobility of the heterostructure increases by two orders of magnitude compared to that in the oxide 2DEG to up to $100\phantom{\rule{0.28em}{0ex}}\mathrm{c}{\mathrm{m}}^{2}{\mathrm{V}}^{\ensuremath{-}1}{\mathrm{s}}^{\ensuremath{-}1}$ at room temperature, with a carrier density of $\ensuremath{\sim}1\ifmmode\times\else\texttimes\fi{}{10}^{13}\phantom{\rule{0.28em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}2}$. This approach can be applied to technologies that require both high carrier and high carrier mobility for applications in plasmonics and high power electronics.

We investigate the (surface) bonding of a class of industrially and biologically important molecules in which the chemically active orbital is a 2 p electron lone pair located on an N or O atom bound via single bonds to H or alkyl groups. This class includes water, ammonia, alcohols, ethers, and amines. Using extensive density functional theory (DFT) calculations, we discover scaling relations (correlations) among molecular binding energies of different members of this class: the bonding energetics of a single member can be used as a descriptor for other members. We investigate the bonding mechanism for a representative (H2O) and find the most important physical surface properties that dictate the strength and nature of the bonding through a combination of covalent and noncovalent electrostatic effects. We describe the importance of surface intrinsic electrostatic, geometric, and mechanical properties in determining the extent of the lone-pair-surface interactions. We study systems including ionic materials in which the surface positive and negative centers create strong local surface electric fields, which polarize the dangling lone pair and lead to a strong "electrostatically driven bond". We emphasize the importance of noncovalent electrostatic effects and discuss why a fully covalent picture, common in the current first-principles literature on surface bonding of these molecules, is not adequate to correctly describe the bonding mechanism and energy trends. By pointing out a completely different mechanism (charge transfer) as the major factor for binding N- and O-containing unsaturated (radical) adsorbates, we explain why their binding energies can be tuned independently from those of the aforementioned species, having potential implications in scaling-driven catalyst discovery.

The maximum efficiency of a fixed catalytic surface occurs when the adsorbate–surface interaction strength is optimal as per the Sabatier principle: strong enough to drive the reactions forward but weak enough to permit the products’ desorption. Such a compromise can fundamentally limit catalytic activity. One solution is to create a surface with switchable activity between strong binding (rapid dissociation) and weak binding (easy desorption). On the basis of first-principles theory, we describe a class of catalysts comprising an epitaxial monolayer of a transition metal oxide on an oxide ferroelectric substrate in which reversing the ferroelectric polarization state switches the surface activity between these two limits. As an example, a CrO2 monolayer on ferroelectric PbTiO3 permits direct NOx decomposition and CO oxidation while circumventing oxygen and sulfur poisoning. Our computed binding energy trends are explained by a generalization of the canonical d-band model for transition metals to metal ox...

Using first-principles calculations based on density functional theory, we study the energetics and charge transfer effects in ${\mathrm{MgB}}_{x}$ nanotubes and two-dimensional (2D) sheets. The behavior of adsorbed Mg on 2D boron sheets is found to depend on the amount of electron transfer between the two subsystems. The amount is determined by both the density of adsorbed Mg as well as the atomic-scale structure of the boron subsystem. The degree of transfer can lead to repulsive or attractive Mg-Mg interactions. In both cases, model ${\mathrm{MgB}}_{x}$ nanotubes built from 2D ${\mathrm{MgB}}_{x}$ sheets can display negative curvature energy: a relatively unusual situation in nanosystems where the energy cost to curve the parent 2D sheet into a small-diameter nanotube is negative. Namely, the small-diameter nanotube is energetically preferred over the corresponding flat sheet. We also discuss how these findings may manifest themselves in experimentally synthesized ${\mathrm{MgB}}_{x}$ nanotubes.

The surface chemistry and physics of oxide ferroelectric surfaces with a fixed polarization state have been studied experimentally for some time. Here, we discuss the possibility of using these materials in a different mode, namely under cyclically changing polarization conditions achievable via periodic perturbations by external fields (e.g., temperature, strain or electric field). We use Density Functional Theory (DFT) and electronic structure analysis to understand the polarization-dependent surface physics and chemistry of ferroelectric oxide PbTiO3 as an example of this class of materials. This knowledge is then applied to design catalytic cycles for industrially important reactions including NOx direct decomposition and SO2 oxidation into SO3. The possibility of catalyzing direct partial oxidation of methane to methanol is also investigated. More generally, we discuss how using ferroelectrics under cyclically changing polarization conditions can help overcome some of the fundamental challenges facing the catalysis community such as the limitations imposed by the Sabatier principle and scaling relations.

Resonant inelastic x-ray scattering is used to investigate the electronic origin of orbital polarization in nickelate heterostructures taking $\mathrm{LaTiO_3-LaNiO_3-3x(LaAlO_3)}$, a system with exceptionally large polarization, as a model system. We find that heterostructuring generates only minor changes in the Ni $3d$ orbital energy levels, contradicting the often-invoked picture in which changes in orbital energy levels generate orbital polarization. Instead, O $K$-edge x-ray absorption spectroscopy demonstrates that orbital polarization is caused by an anisotropic reconstruction of the oxygen ligand hole states. This provides an explanation for the limited success of theoretical predictions based on tuning orbital energy levels and implies that future theories should focus on anisotropic hybridization as the most effective means to drive large changes in electronic structure and realize novel emergent phenomena., Accepted for publication in Physical Review Letters. 6 pages, 4 figures

The strong interaction at an interface between a substrate and thin film leads to epitaxy and provides a means of inducing structural changes in the epitaxial film. These induced material phases often exhibit technologically relevant electronic, magnetic, and functional properties. The 2×1 surface of a Ge(001) substrate applies a unique type of epitaxial constraint on thin films of the perovskite oxide BaTiO_{3} where a change in bonding and symmetry at the interface leads to a non-bulk-like crystal structure of the BaTiO_{3}. While the complex crystal structure is predicted using first-principles theory, it is further shown that the details of the structure are a consequence of hidden phases found in the bulk elastic response of the BaTiO_{3} induced by the symmetry of forces exerted by the germanium substrate.

Crystalline metal oxides display a large number of physical functionalities such as ferroelectricity, magnetism, superconductivity, and Mott transitions. High quality heterostructures involving metal oxides and workhorse semiconductors such as silicon have the potential to open new directions in electronic device design that harness these degrees of freedom for computation or information storage. This review describes how first-principles theoretical modeling has informed current understanding of the growth mechanisms and resulting interfacial structures of crystalline, coherent, and epitaxial metal oxide thin films on semiconductors. Two overarching themes in this general area are addressed. First, the initial steps of oxide growth involve careful preparation of the semiconductor surface to guard against amorphous oxide formation and to create an ordered template for epitaxy. The methods by which this is achieved are reviewed, and possibilities for improving present processes to enable the epitaxial growth of a wider set of oxides are discussed. Second, once a heterointerface is created, the precise interfacial chemical composition and atomic structure is difficult to determine unambiguously from experiment or theory alone. The current understanding of the structure and properties of complex oxide/semiconductor heterostructures is reviewed, and the main challenges to prediction—namely, (i) are these heterostructures in thermodynamic equilibrium or kinetically trapped, and (ii) how do the interfaces modify or couple to the degrees of freedom in the oxide?—are explored in detail for two metal oxide thin films on silicon. Finally, an outlook of where theoretical efforts in this field may be headed in the near future is provided., National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Grant DMR-1119826), National Science Foundation (U.S.). (Yale University. Biomedical High Performance Computing Center. Grant CNS 08-21132)

The ability to understand and predict the phase diagrams of surface phases from first principles can be valuable for developing processes for growth of epitaxial structures. In the growth of epitaxial oxides on Si (0 0 1), a submonolayer phase of Sr plays a key role. The physical structure for this phase, which has 2 × 3 symmetry and occurs at 1/6 monolayer Sr coverage, was recently elucidated using both first principles theory and diffraction experiments [J.W. Reiner, K.F. Garrity, F.J. Walker, S. Ismail-Beigi, C.H. Ahn, Role of strontium in oxide epitaxy on silicon (0 0 1), Phys. Rev. Lett. 101 (10) (2008) 105503.]. Our approach to understanding the broader Sr/Si phase diagram combines density functional theory with a thermodynamic analysis of the phase equilibrium between a Sr lattice gas and the 2 × 3 structure. We use reflection high energy electron diffraction (RHEED) to experimentally determine the phase diagram, finding good agreement with theoretical predictions.

We provide a closer look into the diameter and chirality dependences of exciton properties in carbon nanotubes, using a variational methodology based on the effective mass and envelope function approximations, supported by ab initio parameters. Experimental measurements of the binding energy are reproduced within 0.02 eV for a large variety of tubes. We also report on the singlet-triplet energy splittings, which show a 1/d 2 diameter dependence.

The maximum efficiency of a fixed catalytic surface occurs when the adsorbate–surface interaction strength is optimal as per the Sabatier principle: strong enough to drive the reactions forward but weak enough to permit the products’ desorption. Such a compromise can fundamentally limit catalytic activity. One solution is to create a surface with switchable activity between strong binding (rapid dissociation) and weak binding (easy desorption). On the basis of first-principles theory, we describe a class of catalysts comprising an epitaxial monolayer of a transition metal oxide on an oxide ferroelectric substrate in which reversing the ferroelectric polarization state switches the surface activity between these two limits. As an example, a CrO2 monolayer on ferroelectric PbTiO3 permits direct NOx decomposition and CO oxidation while circumventing oxygen and sulfur poisoning. Our computed binding energy trends are explained by a generalization of the canonical d-band model for transition metals to metal ox...

First principles theory and methodology have made rapid advances in their ability to describe electronic excitations and optical properties from first principles. Here we present an overview of the progress in this field. We illustrate with results for three systems that exhibit interesting excitonic behavior: single-walled carbon nanotubes, single-walled gallium nitride nanotubes, and self-trapped excitons in silica. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

We present a first-principles study of the effects of many-electron interactions on the optical properties of single-walled carbon nanotubes. Motivated by recent experiments, we have carried out ab initio calculations on the single-walled carbon nanotubes (3, 3), (5, 0) and (8, 0). The calculations are based on a many-body Green’s function approach in which both the quasiparticle (single-particle) excitation spectrum and the optical (electron–hole excitation) spectrum are determined. We show that the optical spectrum of both the semiconducting and metallic nanotubes studied exhibits important excitonic effects due to their quasi-one-dimensional nature. Binding energies for excitonic states range from zero for the metallic (5, 0) tube to nearly 1 eV for the semiconducting (8, 0) tube. Moreover, the metallic (3, 3) tube possesses exciton states bound by nearly 100 meV. Our calculated spectra explain quantitatively the observed features found in the measured spectra.

Typical logic elements utilizing the field effect rely on the change in carrier concentration due to the field in the channel region of the device. Ferroelectric-field-effect devices provide a nonvolatile version of this effect due to the stable polarization order parameter in the ferroelectric. In this study, we describe an oxide/oxide ferroelectric heterostructure device based on (001)-oriented PbZr₀.₂Ti₀.₈O₃-LaNiO₃ where the dominant change in conductivity is a result of a significant mobility change in the interfacial channel region. The effect is confined to a few atomic layers at the interface and is reversible by switching the ferroelectric polarization. More interestingly, in one polarization state, the field effect induces a 1.7 eV shift of the interfacial bands to create a new conducting channel in the interfacial PbO layer of the ferroelectric.

There is considerable interest in the controlled p-type and n-type doping of carbon nanotubes (CNT) for use in a range of important electronics applications, including the development of hybrid CNT/silicon (Si) photovoltaic devices. Here, we demonstrate that easy to handle metallocenes and related complexes can be used to both p-type and n-type dope single-walled carbon nanotube (SWNT) thin films, using a simple spin coating process. We report n-SWNT/p-Si photovoltaic devices that are >450 times more efficient than the best solar cells of this type currently reported and show that the performance of both our n-SWNT/p-Si and p-SWNT/n-Si devices is related to the doping level of the SWNT. Furthermore, we establish that the electronic structure of the metallocene or related molecule can be correlated to the doping level of the SWNT, which may provide the foundation for controlled doping of SWNT thin films in the future.

Based on {\em ab initio} calculation, we propose a new structure for the fundamental excitation of the reconstructed 30$^\circ$ partial dislocation in silicon. This soliton has a rare structure involving a five-fold coordinated atom near the dislocation core. The unique electronic structure of this defect is consistent with the electron spin resonance signature of the hitherto enigmatic thermally stable R center of plastically deformed silicon. We present the first {\em ab initio} determination of the free energy of the soliton, which is also in agreement with the experimental observation. This identification suggests the possibility of an experimental determination of the density of solitons, a key defect in understanding the plastic flow of the material.

Based on ab initio calculation, we propose a new structure for the fundamental excitation of the reconstructed 30$^\circ$ partial dislocation in silicon. This soliton has a rare structure involving a five-fold coordinated atom near the dislocation core. The unique electronic structure of this defect is consistent with the electron spin resonance signature of the hitherto enigmatic thermally stable R center of plastically deformed silicon. This identification suggests the possibility of an experimental determination of the density of solitons, a key defect in understanding the plastic flow of the material., 5 pages, 4 figures

Phenomenological models suggest that thin epitaxial SrTiO${}_{3}$ films on silicon will exhibit ferroelectric behavior as a result of compressive strain. However, such models do not include atomic-scale interface effects, which can dramatically alter the predicted behavior. In this paper, we use density functional theory computations to systematically elucidate the effects of the interface atomic structure and composition on the properties of SrTiO${}_{3}$/Si heterostructures. We show that while the band alignment and metallicity of the heterostructure are highly sensitive to the chemical composition and geometry of the interface, the system also exhibits several important features that are universal to all compositions. These universal features, which include an electronic dipole across the interface and a large cation-oxygen displacement in the interfacial oxide layer, conspire to induce a net positive polarization in ultrathin SrTiO${}_{3}$ films. We demonstrate that, due to its origin in the chemical bonds at the interface, this polarization is pinned in a single direction. Our results provide a fundamental understanding of the important role played by interfacial chemical bonds within the general class of atomically abrupt, oxide-semiconductor heterostructures and, furthermore, suggest guidelines for the future design of coupled functional oxide-semiconductor devices.

We use SrTiO₃/Si as a model system to elucidate the effect of the interface on ferroelectric behavior in epitaxial oxide films on silicon. Using both first-principles computations and synchrotron x-ray diffraction measurements, we show that structurally imposed boundary conditions at the interface stabilize a fixed (pinned) polarization in the film but inhibit ferroelectric switching. We demonstrate that the interface chemistry responsible for these phenomena is general to epitaxial silicon-oxide interfaces, impacting on the design of silicon-based functional oxide devices.

A number of intriguing properties emerge upon the formation of the epitaxial interface between the insulating oxides LaAlO 3 and SrTiO 3 . These properties, which include a quasi two-dimensional conducting electron gas, low temperature superconductivity, and magnetism, are not present in the bulk materials, generating a great deal of interest in the fundamental physics of their origins. While it is generally accepted that the novel behavior arises as a result of a combination of electronic and atomic reconstructions and growth-induced defects, the complex interplay between these effects remains unclear. In this report, we review the progress that has been made towards unraveling the complete picture of the SrTiO 3 /LaAlO 3 interface, focusing primarily on present ab initio theoretical work and its relation to the experimental data. In the process, we highlight some key unresolved issues and discuss how they might be addressed by future experimental and theoretical studies.

Based on first-principles calculations, we present various properties of single- and double-layered boron sheets, along with single- and double-walled boron nanotubes. Single-layered boron sheets, made of hexagons and triangles, have buckled ground-state geometries if the ratio of triangles to hexagons is large and stay flat otherwise. We demonstrate that this asymmetric behavior of buckling cannot be explained by a simple chemical picture based on $\ensuremath{\sigma}\text{\ensuremath{-}}\ensuremath{\pi}$ mixing. Instead, reduction in the electronic kinetic energy is the driving force for buckling. In addition, we show that double-layered boron sheets can form strong interlayer bonds between two layers only if the precursor single-layered sheet itself prefers a buckled ground-state structure. The optimal double-layered boron sheet in our library is semiconducting and is more stable than any single-layered sheet. Next, we discuss the curvature energies, buckling behavior and soliton structural fluctuations for single-walled boron nanotubes and the implications for the electronic properties of these nanotubes: our main finding is that the semiconducting nature of small-diameter single-walled nanotubes is robust under various perturbations and fluctuations. We end by showing that due to strong bonds forming between walls, the optimal double-walled boron nanotubes have different wall structures from single-walled ones. Such double-walled nanotubes are always more stable than any single-walled nanotube and are furthermore metallic for the likely experimentally relevant diameter range. We conclude with the implications of these results for fabricated nanotube systems.

This review outlines developments in the growth of crystalline oxides on the ubiquitous silicon semiconductor platform. The overall goal of this endeavor is the integration of multifunctional complex oxides with advanced semiconductor technology. Oxide epitaxy in materials systems achieved through conventional deposition techniques is described first, followed by a description of the science and technology of using atomic layer-by-layer deposition with molecular beam epitaxy (MBE) to systematically construct the oxide-silicon interface. An interdisciplinary approach involving MBE, advanced real-space structural characterization, and first-principles theory has led to a detailed understanding of the process by which the interface between crystalline oxides and silicon forms, the resulting structure of the interface, and the link between structure and functionality. Potential applications in electronics and photonics are also discussed.

This review outlines developments in the growth of crystalline oxides on the ubiquitous silicon semiconductor platform. The overall goal of this endeavor is the integration of multifunctional complex oxides with advanced semiconductor technology. Oxide epitaxy in materials systems achieved through conventional deposition techniques is described first, followed by a description of the science and technology of using atomic layer-by-layer deposition with molecular beam epitaxy (MBE) to systematically construct the oxide-silicon interface. An interdisciplinary approach involving MBE, advanced real-space structural characterization, and first-principles theory has led to a detailed understanding of the process by which the interface between crystalline oxides and silicon forms, the resulting structure of the interface, and the link between structure and functionality. Potential applications in electronics and photonics are also discussed.

Based on first-principles methods, we present a self-doping picture in atomically thin boron sheets: this shows that for two-dimensional boron nanostructures, adding or removing boron atoms is essentially equivalent to simply adding or removing electrons from a fixed electronic structure. This picture allows us to propose a general design rule for pure boron nanostructures and explains the occurrence of known stable nanostructures. In addition, self-doping provides a powerful tool for finding stable metal boride nanostructures. We illustrate this last point by showing an unexpectedly stable ${\text{MgB}}_{2}$ sheet structure which is likely the precursor of ${\text{MgB}}_{2}$ nanotubes. Our results are easily generalized to other stoichiometries and other choices of metals.

The best known method for growing epitaxial oxides on silicon requires the deposition of 1/2 monolayer of an alkaline earth metal, usually Sr, as the first step; however, the details of this process are not well understood. Using first-principles density functional theory calculations, we compute the total energies and vibrational free energies of several classes of Sr on Si(001) structures. These structures, in particular those with submonolayer Si reconstructions, allow us to explain the observed phase diagram of submonolayer Sr on Si(001). We analyze the electronic states of key structures using maximally localized Wannier functions and present simulated scanning tunneling microscopy images of key structures and find that they compare well with recent experiments. Our results clarify the role of temperature in epitaxial oxide growth on silicon, predict an experimentally verified low temperature path to epitaxy, and may be important in finding pathways to epitaxy between silicon and other oxides.

We present an ab initio study of the (001) interfaces between two insulating perovskites, the polar ${\text{LaAlO}}_{3}$ and the nonpolar ${\text{SrTiO}}_{3}$. We observe an insulating-to-metallic transition above a critical ${\text{LaAlO}}_{3}$ thickness. We explain that the high conductivity observed at the ${\text{TiO}}_{2}/\text{LaO}$ interface and the lack of similar conductivity at the $\text{SrO}/{\text{AlO}}_{2}$ 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 ${\text{TiO}}_{2}/\text{LaO}$ interface. This mechanism for the formation of interfacial bound states suggests a robust means for tuning conductivities at various oxide heterointerfaces.

We present the structure of the interface responsible for epitaxy of crystalline oxides on silicon. Using synchrotron x-ray diffraction, we observe a 2 x 1 unit cell reconstruction at the interface of BaO grown on Si(001) terminated with 1/2 ML of Sr. Since this symmetry is not present in bulk BaO or Si, only the interface contributes to diffracted intensity. First principles calculations accurately predict the observed diffraction and identify the structure of the BaO/Si interface, including the elemental composition and a sub-{angstrom} rumpling due to epitaxial strain of the 7 adjacent BaO and Si layers.

Epitaxial oxide-Si heterostructures, which integrate the functionality of crystalline oxides with Si technology, are made possible by a submonolayer of Sr deposited on Si (001). We find by electron diffraction studies using single termination Si wafers that this Sr submonolayer replaces the top layer of Si when deposited at 650 degrees C. Supported by first-principles calculations, we propose a model for the reaction dynamics of Sr on the Si surface and its effect on oxide epitaxy. This model predicts, and we experimentally confirm, an unexplored 25 degrees C pathway to crystalline oxide epitaxy on Si.

We present the first ab initio predictions of electronic and excitonic states in gallium nitride nanotubes. Electron-hole interactions dramatically affect optical properties. Low-energy excitons are dark (dipole forbidden) in all nanotubes with key ramifications for applications. We describe an unusual decrease of energy gaps with decreasing nanotube diameter, opposing expectations from quantum confinement. This stems from a combination of nanoscale curvature and gallium chemistry, should apply to other systems, and furnishes an interesting way to reduce excitation energies with decreasing dimension.

We present a new class of boron sheets, composed of triangular and hexagonal motifs, that are more stable than structures considered to date and thus are likely to be the precursors of boron nanotubes. We describe a simple and clear picture of electronic bonding in boron sheets and highlight the importance of three-center bonding and its competition with two-center bonding, which can also explain the stability of recently discovered boron fullerenes. Our findings call for reconsideration of the literature on boron sheets, nanotubes, and clusters., Comment: 4 pages, 4 figures, 1 table

Semiconductor materials are being used in an increasingly diverse array of applications, with new device concepts being proposed each year for solar cells, flat-panel displays, sensors, memory, and spin transport. This rapid progress of invention outpaces the development of new semiconductor materials with the required properties and performance. In many applications, high carrier mobility at room temperature is required in addition to specific functional properties critical to the device concept. We review recent developments on high mobility stannate perovskite oxide materials and devices.

The relative energies and occupancies of valence orbital states can dramatically influence collective electronic and magnetic phenomena in correlated transition metal oxide systems. We review the current state of research on the modification and control of these orbital properties in rare-earth nickelates, especially LaNiO3, a model degenerate d orbital system where significant recent progress has been made. Theoretical and experimental results on thin films and heterostructures are described, including the influence of electronic correlation effects. We highlight the latest approaches to achieving non-degenerate bands and discuss the outlook and applicability of this body of knowledge to other correlated metal oxide systems.

Irradiating silica produces self-trapped excitons (STEs) that spontaneously create atomic-scale distortions on which they localize themselves. Despite enduring interest in STEs and subsequent defects in this key technological material, the trapping mechanism and geometry remain a mystery. Our ab initio study of STEs in $\ensuremath{\alpha}$-quartz using a many-electron Green's function approach answers both questions. The STE comprises a broken O-Si bond with the hole localized on the defected oxygen and the electron on the defected silicon atom in a planar $s{p}^{2}$ conformation. The results further explain quantitatively the measured STE spectra.

Despite considerable work in the field, the precise mechanism for the photoisomerization of azobenzene, C(12)H(10)N(2), is still an open issue. Early theoretical studies of the problem indicated that isomerization occurs through an in-plane inversion path, and this has been used to explain recent time-resolved UV-visible spectroscopy measurements. On the other hand, a number of recent theoretical studies have concluded that a torsion of the N-N bond ("rotation path") is probably the most favorable mechanism for photoisomerization involving the first excited state. We have performed first-principles calculations using constrained density-functional theory (DFT) and time-dependent DFT in the local-density approximation, with results that also favor the rotation path mechanism. Our results are compared with other analyses, primarily based on configuration interaction.

This manuscript explores the apparent discrepancy between experimental data and theoretical calculations of the lattice resistance of bcc tantalum. We present the first results for the temperature dependence of the Peierls stress in this system and the first ab initio calculation of the zero-temperature Peierls stress to employ periodic boundary conditions, which are those best suited to the study of metallic systems at the electron-structure level. Our ab initio value for the Peierls stress is over five times larger than current extrapolations of experimental lattice resistance to zero-temperature. Although we do find that the common techniques for such extrapolation indeed tend to underestimate the zero-temperature limit, the amount of the underestimation which we observe is only 10-20%, leaving open the possibility that mechanisms other than the simple Peierls stress are important in controlling the process of low temperature slip., Comment: 12 pages and 9 figures

We present an ab initio exploration of the phenomena which will become important for freestanding structures of silicon as they are realized on the nanoscale. We find that not only surface but also edge effects are important considerations in structures of dimensions on the order of 3 nm. Specifically, for long nanoscale silicon bars, we find two competing low-energy reconstructions with a transition from one to the other as the cross section of the bar decreases. We predict that this size-dependent phase transition has a signature in the electronic structure of the bar but little effect on elastic properties.

The free energy of the concerted exchange mechanism for self-diffusion in silicon is estimated using the thermodynamic integration method and Monte Carlo (MC) simulations with an interatomic potential fitted to reproduce local-density-approximation calculations. Anharmonicity and relaxation are fully taken into account in the calculations, since the phase space is extensively explored by the MC simulations. The results indicate that the concerted exchange mechanism can have a significant contribution to the self-diffusion constant in silicon. \textcopyright{} 1996 The American Physical Society.

In this study, the effect of using high-electron-mobility channel materials, such as GaAs, InAs, and InGaAs, on drive current in n-channel metal-oxide-semiconductor (nMOS) and p-channel metal-oxide-semiconductor devices is studied. Relative to silicon, these materials have lower electron effective mass, which leads to lower inversion capacitance (Cinv) due to their lower density of states. Despite their lower Cinv, high-electron mobility channel materials are shown to be promising alternatives to silicon in delivering higher drive current in nMOS devices.

Using electron and synchrotron x-ray diffraction, the authors investigate the reconstructions induced on the Si (001) surface by the presence of a submonolayer of Sr atoms. These Sr surface phases on Si (001) are the first steps in the synthesis of crystalline oxide on silicon heterostructures. Through the use of in situ reflection high energy electron diffraction, the authors observe 2×1→2×3→1×2 transitions in the surface symmetry as 12 monolayer Sr is deposited at 650 °C. Anomalous synchrotron x-ray diffraction studies of the 2×3 structure are consistent with a model where each Sr atom replaces two silicon dimers, resulting in a change in the surface Si stoichiometry. X-ray diffraction from the surface formed when the Sr deposition occurs at room temperature shows a different dependence on x-ray energy and is consistent with a surface phase consisting of Sr adsorbed onto a stoichiometric Si surface.