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Cuprous halides (CuX; X = Cl, Br, or I) have been extensively investigated in the literature, but many of their fundamental properties are still not very well understood. For example, debate about their crystal stability, i.e., whether the ground-state structures of CuX are zinc-blende, still exists. By performing rigorous first-principles calculations for CuX using an accurate hybrid functional, we unambiguously demonstrate that CuX are indeed stable in the zinc-blende structure, but their accurate description requires careful treatment of the exchange interaction. Previous calculations based on local or semilocal density functionals underestimated the important contributions from exchange interactions and thus underestimated the energy separation between the unoccupied 4s and occupied 3d orbitals in Cu, resulting in an overestimation of the s-d coupling and the energy reduction of distorted CuX. Our study clarifies a long-standing and highly debated issue with regard to ground-state structures of CuX and advances the physics of phase stability and the importance of s-d coupling in semiconductors.

Structural search and feature extraction are a central subject in modern materials design, the efficiency of which is currently limited, but can be potentially boosted by machine learning (ML). Here, we develop an ML-based prediction-analysis framework, which includes a symmetry-based combinatorial crystal optimization program (SCCOP) and a feature additive attribution model, to significantly reduce computational costs and to extract property-related structural features. Our method is highly accurate and predictive, and extracts structural features from desired structures to guide materials design. As a case study, we apply our new approach to a two-dimensional B-C-N system, which identifies 28 previously undiscovered stable structures out of 82 compositions; our analysis further establishes the structural features that contribute most to energy and bandgap. Compared to conventional approaches, SCCOP is about 10 times faster while maintaining a comparable accuracy. Our new framework is generally applicable to all types of systems for precise and efficient structural search, providing new insights into the relationship between ML-tracted structural features and physical properties.

Materials genome engineering and first principle calculations are used to systematically investigate the optical properties of AB2X4 (X = O, S and Se) spinel compounds and to provide insight into the design of stable candidates with high absorption coefficients.

In its lowest-energy three-dimensional (3D) hexagonal crystal structure (γ phase), In

Ferroelectricity of group-IV chalcogenides MX (M = Ge, Sn; X = Se, S) monolayers has been extensively investigated. However, how the ferroelectricity evolves in their one-dimensional nanotubes remains largely unclear. Employing an accurate deep-learning interatomic potential of first-principles precision, we uncover a general stepwise mechanism for polarization switching in zigzag and chiral GeS nanotubes, which has an energy barrier that is substantially lower than the one associated with the conventional one-step switching mechanism. The switching barrier (per atom) gradually decreases with increasing the number of intermediate steps and converges to a value that is almost independent of the tube diameter. In the chiral GeS nanotubes, the switching path of polarization with chirality coupling is preferred at less intermediate steps. This study unveils novel ferroelectric switching behaviors in one-dimensional nanotubes, which is critical to coupling ferroelectricity and chirality.

Activation of O2 is a critical step in heterogeneous catalytic oxidation. Here, the concept of increased electron donors induced by nitrogen vacancy is adopted to propose an efficient strategy to develop highly active and stable catalysts for molecular O2 activation. Carbon nitride with nitrogen vacancies is prepared to serve as a support as well as electron sink to construct a synergistic catalyst with Pt nanoparticles. Extensive characterizations combined with the first-principles calculations reveal that nitrogen vacancies with excess electrons could effectively stabilize metallic Pt nanoparticles by strong p-d coupling. The Pt atoms and the dangling carbon atoms surround the vacancy can synergistically donate electrons to the antibonding orbital of the adsorbed O2. This synergistic catalyst shows great enhancement of catalytic performance and durability in toluene oxidation. The introduction of electron-rich non-oxide substrate is an innovative strategy to develop active Pt-based oxidation catalysts, which could be conceivably extended to a variety of metal-based catalysts for catalytic oxidation.

Polymorphism is universal in energetic materials (EMs), and polymorphic transition may lead to variations of structure and performance. This work exemplifies such variations by revealing the polymo...

The optimization of band alignment at the buffer/absorber interface is realized by tuning compositions of Cd and Zn chalcogenides as the buffer layer toward high-efficiency Cu(In,Ga)Se2 (CIGS) solar cells. Using the special quasi-random structure (SQS) approach, we construct randomly disordered ZnxCd1-xSySe1-y alloys and ZnSxO1-x alloys as alternatives to the traditional CdS buffer layer. The compositional dependence of formation energies, lattice parameters, band-gap energies, and band alignments of ZnxCd1-xSySe1-y and ZnSxO1-x alloys is investigated by first-principles density functional theory calculations. For quaternary ZnxCd1-xSySe1-y alloys, we find that the miscibility temperatures and the bandgap bowing coefficients are proportional to the lattice mismatch between the mixing elements. The linear dependence of lattice parameters, trinomial dependence of band-gap energies and band-edge positions on the alloy-composition of ZnxCd1-xSySe1-y alloys are established. For ZnSxO1-x alloys, we find the lattice parameters also exhibit a linear dependence on its composition. Because of the large lattice mismatch and the chemical disparity between ZnO and ZnS, the bowing coefficient for the bandgap energies of ZnSxO1-x alloys is composition dependent, and is larger for dilute ZnSxO1-x alloys. With the optimization criteria of moderate spike-like conduction band offset, large valance band offset, sufficiently wide bandgap, and lattice match with respect to the CIGS absorber, we illustrate the optimal composition range of both ZnxCd1-xSySe1-y alloys and ZnSxO1-x alloys as the buffer layer of the CIGS solar cells. Our work demonstrates that ZnxCd1-xSySe1-y alloys and ZnSxO1-x alloys are promising buffer layers for high-efficiency CIGS solar cells.

The practical damage of silicon bipolar devices subjected to mixed ionization and displacement irradiations is usually evaluated by the sum of separated ionization and displacement damages. However...

The lifetime of non-equilibrium electrons and holes in semiconductors is crucial for solar cell and optoelectronic applications. Non-adiabatic molecular dynamics (NAMD) simulations based on time-dependent density functional theory (TDDFT) are widely used to study excited-state carrier dynamics. However, the calculated carrier lifetimes are often different from experimental results by orders of magnitude. In this work, by revisiting the definition of carrier lifetime and considering different recombination mechanisms, we report a systematic procedure for calculating the effective carrier lifetime in realistic semiconductor crystals that can be compared directly to experimental measurements. The procedure shows that considering all recombination mechanisms and using reasonable densities of carriers and defects are crucial in calculating the effective lifetime. When NAMD simulations consider only Shockey-Read-Hall (SRH) defect-assisted and band-to-band non-radiative recombination while neglect band-to-band radiative recombination, and the densities of non-equilibrium carriers and defects in supercell simulations are much higher than those in realistic semiconductors under solar illumination, the calculated lifetimes are ineffective and thus differ from experiments. Using our procedure, the calculated effective lifetime of the halide perovskite CH3NH3PbI3 agrees with experiments. It is mainly determined by band-to-band radiative and defect-assisted non-radiative recombination, while band-to-band non-radiative recombination is negligible. These results indicate that it is possible to calculate carrier lifetimes accurately based on NAMD simulations, but the directly calculated values should be converted to effective lifetimes for comparison to experiments. The revised procedure can be widely applied in future carrier lifetime simulations., 30 pages, 5 figures

Irradiation damage is a key issue for the reliability of semiconductor devices under extreme environments. For decades, the ionizing-irradiation-induced damage in transistors with silica-silicon (SiO

Phase transitions are a common phenomenon in condensed matter and act as a critical degree of freedom that can be employed to tailor the mechanical or electronic properties of materials. Understanding the fundamental mechanisms of the thermodynamics and kinetics of phase transitions is, thus, at the core of modern materials design. Conventionally, studies of phase transitions have, to a large extent, focused on pristine bulk phases. However, realistic materials exist in a complex form; their microstructures consist of different point and extended defects. The presence of defects impacts the thermodynamics and kinetics of phase transitions, but has been commonly ignored or treated separately. In recent years, with the significant advances in theoretical and experimental techniques, there has been an increasing research interest in modeling and characterizing how defects impact or even dictate phase transitions. The present review systematically discusses the recent progress in understanding the kinetics of defect-characterized phase transitions, derives the key mechanisms underlying these phase transitions, and envisions the remaining challenges and fruitful research directions. We hope that these discussions and insights will help to inspire future research and development in the field.

Defects are crucial in determining the overall physical properties of semiconductors. Generally, the charge-state transition level (TEL), one of the key physical quantities that determines the dopability of defects in semiconductors, is temperature dependent. However, little is known about the temperature dependence of TEL, and, as a result, almost all existing defect theories in semiconductors are built on a temperature-independent approximation. In this article, by deriving the basic formulas for temperature-dependent TEL, we have established two fundamental rules for the temperature dependence of TEL in semiconductors. Based on these rules, surprisingly, it is found that the temperature dependences of TEL for different defects are rather diverse: it can become shallower, deeper, or stay unchanged. This defect-specific behavior is mainly determined by the synergistic or opposing effects between free energy corrections (determined by the local volume change around the defect during a charge-state transition) and band edge changes (which differ for different semiconductors). These basic formulas and rules, confirmed by a large number of state-of-the-art temperature-dependent defect calculations in GaN, may potentially be widely adopted as guidelines for understanding or optimizing doping behaviors in semiconductors at finite temperatures.

Energetic cocrystallization is thriving now and presents a promising perspective to create new energetic materials (EMs). In comparison with the single-component EMs, the creation of energetic cocr...

The intrinsic material instability and toxicity of organic-inorganic hybrid perovskite CH3NH3PbI3 are the main challenges for the large-scale deployment of perovskite solar cells, propelling the se...

The chemistry of trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPt(CH3)3), a platinum organometallic compound often used for the chemical deposition of Pt films, on nickel oxide surfaces was in...

Recently, the structural stability of all-inorganic halide perovskite nanocrystals has been significantly enhanced. To understand the enhancement, we developed surface-passivation models for cubic CsPbBr3 nanocrystals with anionic (oleate) and cationic (oleylammonium) organic ligands based on first-principles calculations and nuclear magnetic resonance investigations. We propose that the (100) surface is initially terminated with oleate ligand complexes on PbBr2(100) surfaces. Also, the ligand transition to oleylammonium on the Pb-rich surfaces is expected due to the addition of metal halides (ZnBr2) during colloidal synthesis. The significant improvement in the structural stability of the cationic ligand-passivated CsPbBr3 nanocrystals was attributed to the suppressed exposure of the merging-vulnerable (110) surface, caused by the large difference in formation energy between the ligand-passivated (100) and Br-passivated (110) surfaces.

The performance of Gamma-ray irradiated silicon devices usually deteriorates due to the total ionizing dose (TID) effect. The common belief is that the TID mainly involves the change of charge states of existing point defects or defect complexes and their subsequent evolution, especially at the widely used amorphous SiO2(a-SiO2)/Si interface, but the TID is not expected to induce new structural defects and change the interface structures. We show in this paper that, contrary to the common belief, gamma-ray irradiation can lead to remarkable structural changes characterized by oxidation and disproportionation of the a-SiO2/Si interface. We present both experimental evidence and theoretical verification of the structural changes. The effective modulation of interfacial structures further suggests the “defective” gamma-ray to be a “constructive” defect engineering method by post-synthesis tuning of the physical performance.

Searching for half-metals in low dimensional materials is not only of scientific importance, but also has important implications for the realization of spintronic devices on a small scale. In this work, we show theoretically that simple bending can induce spin-splitting in bilayer silicene. For bilayer silicene with Bernal stacking, the monolayer has a long range ferromagnetic spin order and between the two monolayers, the spin orders are opposite, giving rise to an antiferromagnetic configuration for the ground state of the bilayer silicene. Under bending, the antiferromagnetic spin order is retained but the energetic degeneracy of opposite spin states is lifted. Due to the unusual deformation potentials of the conduction band minimum (CBM) and valence band maximum (VBM) as revealed by density-functional theory calculations and density-functional tight-binding calculations, this spin-splitting is nearly proportional to the degree of bending deformation. Consequently, the spin-splitting can be significant and the desired half-metallic state may emerge when the bending increases, which has been verified by direct simulation of the bent bilayer silicene using the generalized Bloch theorem. Our results hint that bilayer silicene may be an excellent candidate for half-metallicity.