The local strain distribution in bilayer materials: a multiscale study.

Recent studies show that small geometric changes can result in dramatic changes in physical properties and need to be carefully evaluated. In this regard, we calculate the distribution of local strains in bilayer graphene and two configurations of hexagonal BN (h-BN), which is different from previous studies that focus on homogeneous strains in such materials. We consider a mismatch of one lattice parameter and calculate how strain distributes without external stresses. This problem is equivalent to finding the core structure of a type of dislocation profuse in structural materials. The strain distribution is transformed into the core distribution of a dislocation, which is calculated using a new formulation proposed by us. The new formulation finds new lower-energy states for the 2D materials. Our results show that the strain of one-lattice mismatch in bilayer graphene forms two Lorentz peaks with half widths of 117b-120b (edge component) and 67b-80b (screw component), where b is the lattice constant. The case for bilayer h-BN is slightly more complicated but the results are also presented. Our analytic solutions, which are based on the new formulation with more freedom in structural relaxation, provide the basis for the next-step study of their electronic properties.

Excitation Energies of Localized Correlated Defects via Quantum Monte Carlo: A Case Study of Mn4+-Doped Phosphors.

Accurate excitation energies of localized defects have been a long-standing problem for electronic structure calculation methods. Using Mn4+-doped solids as our proof of principle, we show that diffusion quantum Monte Carlo (DMC) is able to predict phosphorescence emission energies within statistical error. To demonstrate the generality of our DMC approach for other possible localized defects, we conduct charge density analyses using DMC and density functional theory (DFT). We also identify a new material with an emission energy of 1.97(8) eV, which is close to the optimum of 2.03 eV for a red-emitting phosphor. To our knowledge, our work is the first report on studying excitation energies of a transition metal impurity using an ab initio many-body electronic structure method. In contrast, semilocal and hybrid-DFT largely underestimates, and fails to reproduce, some of the trends in the emission energies. Our work underscores the importance of an accurate account of exchange, correlation, and excitonic effects for localized excitations in defective solids.

Formation and Diffusion of Metal Impurities in Perovskite Solar Cell Material CH3NH3PbI3: Implications on Solar Cell Degradation and Choice of Electrode.

Solar cells based on methylammonium lead triiodide (MAPbI3) have shown remarkable progress in recent years and have demonstrated efficiencies greater than 20%. However, the long-term stability of MAPbI3-based solar cells has yet to be achieved. Besides the well-known chemical and thermal instabilities, significant native ion migration in lead halide perovskites leads to current-voltage hysteresis and photoinduced phase segregation. Recently, it is further revealed that, despite having excellent chemical stability, the Au electrode can cause serious solar cell degradation due to Au diffusion into MAPbI3. In addition to Au, many other metals have been used as electrodes in MAPbI3 solar cells. However, how the external metal impurities introduced by electrodes affect the long-term stability of MAPbI3 solar cells has rarely been studied. A comprehensive study of formation energetics and diffusion dynamics of a number of noble and transition metal impurities (Au, Ag, Cu, Cr, Mo, W, Co, Ni, Pd) in MAPbI3 based on first-principles calculations is reported herein. The results uncover important general trends of impurity formation and diffusion in MAPbI3 and provide useful guidance for identifying the optimal metal electrodes that do not introduce electrically active impurity defects in MAPbI3 while having low resistivities and suitable work functions for carrier extraction.

Real-Time Observation of Order-Disorder Transformation of Organic Cations Induced Phase Transition and Anomalous Photoluminescence in Hybrid Perovskites.

A fundamental understanding of the interplay between the microscopic structure and macroscopic optoelectronic properties of organic-inorganic hybrid perovskite materials is essential to design new materials and improve device performance. However, how exactly the organic cations affect the structural phase transition and optoelectronic properties of the materials is not well understood. Here, real-time, in situ temperature-dependent neutron/X-ray diffraction and photoluminescence (PL) measurements reveal a transformation of the organic cation CH3 NH3+ from order to disorder with increasing temperature in CH3 NH3 PbBr3 perovskites. The molecular-level order-to-disorder transformation of CH3 NH3+ not only leads to an anomalous increase in PL intensity, but also results in a multidomain to single-domain structural transition. This discovery establishes the important role that organic cation ordering has in dictating structural order and anomalous optoelectronic phenomenon in hybrid perovskites.

Synthesis, Crystal and Electronic Structures, and Optical Properties of (CH3NH3)2CdX4 (X = Cl, Br, I).

We report the synthesis, crystal and electronic structures, as well as optical properties of the hybrid organic-inorganic compounds MA2CdX4 (MA = CH3NH3; X = Cl, Br, I). MA2CdI4 is a new compound, whereas, for MA2CdCl4 and MA2CdBr4, structural investigations have already been conducted but electronic structures and optical properties are reported here for the first time. Single crystals were grown through slow evaporation of MA2CdX4 solutions with optimized conditions yielding mm-sized colorless (X = Cl, Br) and pale yellow (X = I) crystals. Single crystal and variable temperature powder X-ray diffraction measurements suggest that MA2CdCl4 forms a 2D layered perovskite structure and has two structural transitions at 283 and 173 K. In contrast, MA2CdBr4 and MA2CdI4 adopt 0D K2SO4-derived crystal structures based on isolated CdX4 tetrahedra and show no phase transitions down to 20 K. The contrasting crystal structures and chemical compositions in the MA2CdX4 family impact their air stabilities, investigated for the first time in this work; MA2CdCl4 is air-stable, whereas MA2CdBr4 and MA2CdI4 partially decompose when left in air. Optical absorption measurements suggest that MA2CdX4 have large optical band gaps above 3.9 eV. Room temperature photoluminescence spectra of MA2CdX4 yield broad peaks in the 375-955 nm range with full width at half-maximum values up to 208 nm. These PL peaks are tentatively assigned to self-trapped excitons in MA2CdX4 following the crystal and electronic structure considerations. The bands around the Fermi level have small dispersions, which is indicative of high charge localization with significant exciton binding energies in MA2CdX4. On the basis of our combined experimental and computational results, MA2CdX4 and related compounds may be of interest for white-light-emitting phosphors and scintillator applications.

Bulk assembly of organic metal halide nanotubes.

The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C6H13N4)3Pb2Br7. In a metal halide nanotube, six face-sharing metal halide dimers (Pb2Br95-) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C6H13N4+). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resulting in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ∼7%. Having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials.

Observation of Nanoscale Morphological and Structural Degradation in Perovskite Solar Cells by in Situ TEM.

High-resolution in situ transmission electron microscopy (TEM) and electron energy loss spectroscopy were applied to systematically investigate morphological and structural degradation behaviors in perovskite films during different environmental exposure treatments. In situ TEM experiment indicates that vacuum itself is not likely to cause degradation in perovskites. In addition, these materials were found to degrade significantly when they were heated to ∼50-60 °C (i.e., a solar cell's field operating temperature) under illumination. This observation thus conveys a critically important message that the instability of perovskite solar cells at such a low temperature may limit their real field commercial applications. It was further unveiled that oxygen most likely attacks the CH3NH3+ organic moiety rather than the PbI6 component of perovskites during ambient air exposure at room temperature. This finding grants a deeper understanding of the perovskite degradation mechanism and suggests a way to prevent degradation of perovskites by tailoring the organic moiety component.

First-Principles Prediction of Thermodynamically Stable Two-Dimensional Electrides.

Two-dimensional (2D) electrides, emerging as a new type of layered material whose electrons are confined in interlayer spaces instead of at atomic proximities, are receiving interest for their high performance in various (opto)electronics and catalytic applications. Experimentally, however, 2D electrides have been only found in a couple of layered nitrides and carbides. Here, we report new thermodynamically stable alkaline-earth based 2D electrides by using a first-principles global structure optimization method, phonon spectrum analysis, and molecular dynamics simulation. The method was applied to binary compounds consisting of alkaline-earth elements as cations and group VA, VIA, or VIIA nonmetal elements as anions. We revealed that the stability of a layered 2D electride structure is closely related to the cation/anion size ratio; stable 2D electrides possess a sufficiently large cation/anion size ratio to minimize electrostatic energy among cations, anions, and anionic electrons. Our work demonstrates a new avenue to the discovery of thermodynamically stable 2D electrides beyond experimental material databases and provides new insight into the principles of electride design.

Formation of Ideal Rashba States on Layered Semiconductor Surfaces Steered by Strain Engineering.

Spin splitting of Rashba states in two-dimensional electron system provides a promising mechanism of spin manipulation for spintronics applications. However, Rashba states realized experimentally to date are often outnumbered by spin-degenerated substrate states at the same energy range, hindering their practical applications. Here, by density functional theory calculation, we show that Au one monolayer film deposition on a layered semiconductor surface ß-InSe(0001) can possess "ideal" Rashba states with large spin splitting, which are completely situated inside the large band gap of the substrate. The position of the Rashba bands can be tuned over a wide range with respect to the substrate band edges by experimentally accessible strain. Furthermore, our nonequilibrium Green's function transport calculation shows that this system may give rise to the long-sought strong current modulation when made into a device of Datta-Das transistor. Similar systems may be identified with other metal ultrathin films and layered semiconductor substrates to realize ideal Rashba states.

sd(2) Graphene: Kagome band in a hexagonal lattice.

Graphene, made of sp^{2} hybridized carbon, is characterized with a Dirac band, representative of its underlying 2D hexagonal lattice. The fundamental understanding of graphene has recently spurred a surge in the search for 2D topological quantum phases in solid-state materials. Here, we propose a new form of 2D material, consisting of sd^{2} hybridized transition metal atoms in hexagonal lattice, called sd^{2} "graphene." The sd^{2} graphene is characterized by bond-centered electronic hopping, which transforms the apparent atomic hexagonal lattice into the physics of a kagome lattice that may exhibit a wide range of topological quantum phases. Based on first-principles calculations, room-temperature quantum anomalous Hall states with an energy gap of ∼0.1 eV are demonstrated for one such lattice made of W, which can be epitaxially grown on a semiconductor surface of 1/3 monolayer Cl-covered Si(111), with high thermodynamic and kinetic stability.

Formation of quantum spin Hall state on Si surface and energy gap scaling with strength of spin orbit coupling.

For potential applications in spintronics and quantum computing, it is desirable to place a quantum spin Hall insulator [i.e., a 2D topological insulator (TI)] on a substrate while maintaining a large energy gap. Here, we demonstrate a unique approach to create the large-gap 2D TI state on a semiconductor surface, based on first-principles calculations and effective Hamiltonian analysis. We show that when heavy elements with strong spin orbit coupling (SOC) such as Bi and Pb atoms are deposited on a patterned H-Si(111) surface into a hexagonal lattice, they exhibit a 2D TI state with a large energy gap of ≥ 0.5 eV. The TI state arises from an intriguing substrate orbital filtering effect that selects a suitable orbital composition around the Fermi level, so that the system can be matched onto a four-band effective model Hamiltonian. Furthermore, it is found that within this model, the SOC gap does not increase monotonically with the increasing strength of SOC. These interesting results may shed new light in future design and fabrication of large-gap topological quantum states.

Quantum size effect on dielectric function of ultrathin metal film: a first-principles study of Al(1 1 1).

Using first-principles calculations, we show manifestations of the quantum size effect in the dielectric function ε(2) of free-standing Al(1 1 1) ultrathin films of 1 monolayer to 20 monolayers, taking into account size dependent contributions from both interband and intraband electronic transitions. Overall the in-plane components (interband transition) of ε(2) increase with film thickness at all frequencies, converging towards a constant value. However, the out-of-plane components of ε(2) show a more complex behavior, and, only at frequencies less than 0.75 eV, increase with film thickness without convergence. This suggests that ultrathin films can possibly be used for low-loss plasmonics devices in the visible and ultraviolet range. Our findings may shed light on searching for low-loss plasmonic materials via quantum size effect.

Epitaxial growth of large-gap quantum spin Hall insulator on semiconductor surface.

Formation of topological quantum phase on a conventional semiconductor surface is of both scientific and technological interest. Here, we demonstrate epitaxial growth of 2D topological insulator, i.e., quantum spin Hall state, on Si(111) surface with a large energy gap, based on first-principles calculations. We show that the Si(111) surface functionalized with one-third monolayer of halogen atoms [Si(111)-√3 x √3 -X (X = Cl, Br, I)] exhibiting a trigonal superstructure provides an ideal template for epitaxial growth of heavy metals, such as Bi, which self-assemble into a hexagonal lattice with high kinetic and thermodynamic stability. Most remarkably, the Bi overlayer is atomically bonded to but electronically decoupled from the underlying Si substrate, exhibiting isolated quantum spin Hall state with an energy gap as large as ∼ 0.8 eV. This surprising phenomenon originates from an intriguing substrate-orbital-filtering effect, which critically selects the orbital composition around the Fermi level, leading to different topological phases. In particular, the substrate-orbital-filtering effect converts the otherwise topologically trivial freestanding Bi lattice into a nontrivial phase; and the reverse is true for Au lattice. The underlying physical mechanism is generally applicable, opening a new and exciting avenue for exploration of large-gap topological surface/interface states.

Quasiparticle dynamics in reshaped helical Dirac cone of topological insulators.

Topological insulators and graphene present two unique classes of materials, which are characterized by spin-polarized (helical) and nonpolarized Dirac cone band structures, respectively. The importance of many-body interactions that renormalize the linear bands near Dirac point in graphene has been well recognized and attracted much recent attention. However, renormalization of the helical Dirac point has not been observed in topological insulators. Here, we report the experimental observation of the renormalized quasiparticle spectrum with a skewed Dirac cone in a single Bi bilayer grown on Bi(2)Te(3) substrate from angle-resolved photoemission spectroscopy. First-principles band calculations indicate that the quasiparticle spectra are likely associated with the hybridization between the extrinsic substrate-induced Dirac states of Bi bilayer and the intrinsic surface Dirac states of Bi(2)Te(3) film at close energy proximity. Without such hybridization, only single-particle Dirac spectra are observed in a single Bi bilayer grown on Bi(2)Se(3), where the extrinsic Dirac states Bi bilayer and the intrinsic Dirac states of Bi(2)Se(3) are well separated in energy. The possible origins of many-body interactions are discussed. Our findings provide a means to manipulate topological surface states.

Creation of helical Dirac fermions by interfacing two gapped systems of ordinary fermions.

Topological insulators are a unique class of materials characterized by a Dirac cone state of helical Dirac fermions in the middle of a bulk gap. When the thickness of a three-dimensional topological insulator is reduced, however, the interaction between opposing surface states opens a gap that removes the helical Dirac cone, converting the material back to a normal system of ordinary fermions. Here we demonstrate, using density function theory calculations and experiments, that it is possible to create helical Dirac fermion state by interfacing two gapped films-a single bilayer Bi grown on a single quintuple layer Bi(2)Se(3) or Bi(2)Te(3). These extrinsic helical Dirac fermions emerge in predominantly Bi bilayer states, which are created by a giant Rashba effect with a coupling constant of ~4 eV·Å due to interfacial charge transfer. Our results suggest that this approach is a promising means to engineer topological insulator states on non-metallic surfaces.

First-principles study of the electronic, vibrational, electron-phonon interaction and thermodynamics properties of ZrNi(2)Ga.

Using first-principles calculation, we investigate systematically the properties of ZrNi(2)Ga with fcc L 2(1) Heusler structure, including the electronic structure, phonon dispersion, electron-phonon interaction and thermodynamics. The calculated electron-phonon coupling constant λ and the logarithmically averaged frequency [Formula: see text] are 0.747 and 68.48 cm(-1), respectively, giving the superconducting transition temperature T(c) = 3.15 K according to the Allen-Dynes formula. It is in good agreement with the corresponding experimental T(c) and ZrNi(2)Ga therefore can be explained as a conventional phonon-mediated superconductor.