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The permanent ionization damage of semiconductor devices in harsh radiation environments stems from $E'_\gamma$ defect centers generation in the $a$-SiO$_2$ dielectric or isolation layers, but the long-standing "hole transport-trapping" generation mechanism encounters dilemmas to explain recent experiments. In this work, we propose a new "hole capture-structural relaxation" (HCSR) mechanism, based on spin-polarized first-principles calculations of oxygen vacancies ($V_{\rm O}$'s) in $a$-SiO$_2$. It is found that due to an electronic metastability caused by the localization of defect electronic states, the previously suggested puckered precursor, $V_{O\gamma}$, cannot exist in $a$-SiO$_2$, and the $E'_\gamma$ centers can arise from a structural relaxation of dimer $V_{O\delta}$ after nonradiative capture of irradiation-induced valence band holes. We demonstrate that, such an HCSR mechanism can consistently explain the basic but puzzling temperature and electric-field dependences in recent experiments. Moreover, by using reaction rate theory, we derive an analytical formula to uniformly describe the sublinear experimental data over a wide dose and temperature range. This work not only provides a rationale for defect generation in ionizing-irradiated $a$-SiO$_2$, but also offer a general approach to understanding the irradiation physics in alternative dielectrics and wide-band gap semiconductors with intrinsic electronic metastability., Comment: 5 pages, 3 figures

As a popular distributed learning paradigm, federated learning (FL) over mobile devices fosters numerous applications, while their practical deployment is hindered by participating devices' computing and communication heterogeneity. Some pioneering research efforts proposed to extract subnetworks from the global model, and assign as large a subnetwork as possible to the device for local training based on its full computing and communications capacity. Although such fixed size subnetwork assignment enables FL training over heterogeneous mobile devices, it is unaware of (i) the dynamic changes of devices' communication and computing conditions and (ii) FL training progress and its dynamic requirements of local training contributions, both of which may cause very long FL training delay. Motivated by those dynamics, in this paper, we develop a wireless and heterogeneity aware latency efficient FL (WHALE-FL) approach to accelerate FL training through adaptive subnetwork scheduling. Instead of sticking to the fixed size subnetwork, WHALE-FL introduces a novel subnetwork selection utility function to capture device and FL training dynamics, and guides the mobile device to adaptively select the subnetwork size for local training based on (a) its computing and communication capacity, (b) its dynamic computing and/or communication conditions, and (c) FL training status and its corresponding requirements for local training contributions. Our evaluation shows that, compared with peer designs, WHALE-FL effectively accelerates FL training without sacrificing learning accuracy.

Many issues concerning the origin of high-temperature superconductivity (HTS) are still under debate. For example, how the magnetic ordering varies with doping and its relationship with the superconducting temperature; and why the maximal Tc always occurs near the quantum critical point. In this paper, taking hole-doped La2CuO4 as a classical example, we employ the first-principles band structure and total energy calculations and Monte Carlo simulations to explore how the symmetry-breaking magnetic ground state evolves with hole doping and the origin of a dome-shaped superconductivity region in the phase diagram. We demonstrate that the local antiferromagnetic ordering and doping play key roles in determining the electron-phonon coupling, thus Tc. Initially, the La2CuO4 possesses a checkerboard local antiferromagnetic ground state. As the hole doping increases, Tc increases with the increase of the density of states at the Fermi surface. But as the doping increases further, the strength of the antiferromagnetic interaction weakens. At the critical doping level, a magnetic phase transition occurs that reduces the local antiferromagnetism-assisted electron-phonon coupling, thus diminishing the Tc. The superconductivity disappears in the heavily overdoped region when the antiferromagnetic ordering disappears. These observations could account for why cuprates have a dome-shaped superconductivity region in the phase diagram. Our study, thus, contributes to a fundamental understanding of the correlation between doping, local magnetic ordering, and superconductivity of HTS., Comment: 14 pages, 3 figures in the main text; 11 pages, 7 figures in the supplementary materials

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-extracted structural features and physical properties.

Spin fluctuations have a substantial influence on the electron and lattice behaviors in magnetic materials, which, however, is difficult to be tracked properly by prevalent first-principles methods. We propose a versatile self-adaptive spin-constrained density functional theory formalism. Applying it to the simulation of itinerant ferromagnetic Fe, we present the potential energy surface comprising longitudinal and transverse variations of magnetization. Moreover, this method enables us to identify the delicate coupling between the magnetic moments and other degrees of freedom by following energy variation. As manifestations, magnetic interaction, electronic band structure, and phonon dispersion curves are illustrated for single-layered CrI$_3$ with excited magnetic configuration. All the above information can be obtained not only for spin fluctuations but also for non-collinear spin configurations with arbitrarily modulations; thus, it holds promise for future applications in condensed-matter physics research.

Inter-twisted bilayers of two-dimensional (2D) materials can host low-energy flat bands, which offer opportunity to investigate many intriguing physics associated with strong electron correlations. In the existing systems, ultra-flat bands only emerge at very small twist angles less than a few degrees, which poses challenge for experimental study and practical applications. Here, we propose a new design principle to achieve low-energy ultra-flat bands with increased twist angles. The key condition is to have a 2D semiconducting material with large energy difference of band edges controlled by stacking. We show that the interlayer interaction leads to defect-like states under twisting, which forms a flat band in the semiconducting band gap with dispersion strongly suppressed by the large energy barriers in the moire superlattice even for large twist angles. We explicitly demonstrate our idea in bilayer alpha-In2Se3 and bilayer InSe. For bilayer alpha-In2Se3, we show that a twist angle -13.2 degree is sufficient to achieve the band flatness comparable to that of twist bilayer graphene at the magic angle -1.1 degree. In addition, the appearance of ultra-flat bands here is not sensitive to the twist angle as in bilayer graphene, and it can be further controlled by external gate fields. Our finding provides a new route to achieve ultra-flat bands other than reducing the twist angles and paves the way towards engineering such flat bands in a large family of 2D materials.

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., Comment: 30 pages, 5 figures

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.

Most oscillating reactions (ORs) happen in solutions. Few existing solid-based ORs either happen on solid/gas (e.g., oxidation or corrosion) or solid/liquid interfaces, or at the all-solid interfaces neighboring to metals or ionic conductors (e.g., electrolysis or electroplate). We report in this paper a new type of all-solid based OR that happens at the insulator (amorphous SiO$_2$)/semiconductor (Si) interface with the interfacial point defects as the oscillating species. This OR is the first example of the point-defect coupled ORs (PDC-ORs) proposed by H. Schmalzried et al. and J. Janek et al. decades ago. We use proton implantation as the driving force of the oscillation, and employ techniques common in semiconductor device characterization to monitor the oscillation in situ. This approach not only overcomes the difficulties associated with detecting reactions in solids, but also accurately measure the oscillating ultra-low concentration ($10^{10}\sim10^{11}$ cm$^{-2}$) of the interfacial charged point-defects. We propose a mechanism for the reported PDC-OR based on the Brusselator model by identifying the interfacial reactions., Comment: 57 pages, 12 figures

Materials with ultralow thermal conductivity are of great interest for efficient energy conversion and thermal barrier coating. Copper-based semiconductors such as copper chalcogenides and copper halides are known to possess extreme low thermal conductivity, whereas the fundamental origin of the low thermal conductivity observed in the copper-based materials remains elusive. Here, we reveal that s-d coupling induced giant phonon anharmonicity is the fundamental mechanism responsible for the ultralow thermal conductivity of copper compounds. The symmetry controlled strong coupling of high-lying occupied copper 3d orbital with the unoccupied 4s state under thermal vibration remarkably lowers the lattice potential barrier, which enhances anharmonic scattering between phonons. This understanding is confirmed by temperature-dependent Raman spectra measurements. Our study offers an insight at atomic level connecting electronic structures with phonon vibration modes, and thus sheds light on materials properties that rely on electron-phonon coupling, such as thermoelectricity and superconductivity.

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, recent experiments show clear difference between the practical and summed damages, indicating significant irradiation synergistic effects (ISEs). Understanding the behaviors and mechanisms of ISEs is essential to predict the practical damages. In this work, we first make a brief review on the state of the art, critically emphasizing on the difficulty encountered in previous models to understand the dose rate dependence of the ISEs. We then introduce in detail our models explaining this basic phenomenon, which can be described as follows. Firstly, we show our experimental works on PNP and NPN transistors. A variable neutron fluence and $\gamma$-ray dose setup is adopted. Fluence-dependent `tick'-like and sublinear dose profiles are observed for PNP and NPN transistors, respectively. Secondly, we describe our theoretical investigations on the positive ISE in NPN transistors. We propose an atomistic model of transformation and annihilation of $\rm V_2$ displacement defects in p-type silicon under ionization irradiation, which is totally different from the traditional picture of Coulomb interaction of oxide trapped charges in silica on charge carriers in irradiated silicon. The predicted novel dose and fluence dependences are fully verified by the experimental data. Thirdly, the mechanism of the observed negative ISE in PNP transistors is investigated in a similar way as in the NPN transistor case. The difference is that in n-type silicon, VO displacement defects also undergo an ionization-induced transformation and annihilation process. Our results show that, the evolution of displacement defects due to carrier-enhanced defect diffusion and reaction is the dominating mechanism of the ISEs., Comment: 11 pages, 10 figures; accepted by ACS Applied Electronic Materials

In$_2$Se$_3$ in the three-dimensional (3D) hexagonal crystal structure with space group $P6_1$ ($\gamma$-In$_2$Se$_3$) has a direct band gap of $\sim$1.8 eV and high absorption coefficient, making it a promising semiconductor material for optoelectronics. Incorporating Te allows for tuning the band gap, adding flexibility to device design and extending the application range. Here we report the growth and characterization of $\gamma$-In$_2$Se$_3$ thin films, and results of hybrid density functional theory calculations to assess the electronic and optical properties of $\gamma$-In$_2$Se$_3$ and $\gamma$-In$_2$(Se$_{1-x}$Te$_x$)$_3$ alloys. The calculated band gap of 1.84 eV for $\gamma$-In$_2$Se$_3$ is in good agreement with data from the absorption spectrum, and the absorption coefficient is found to be as high as that of direct band gap conventional III-V and II-VI semiconductors. Incorporation of Te in the form of $\gamma$-In$_2$(Se$_{1-x}$Te$_x$)$_3$ alloys is an effective way to tune the band gap from 1.84 eV down to 1.23 eV, thus covering the optimal band gap range for solar cells. We also discuss band gap bowing and mixing enthalpies, aiming at adding $\gamma$-In$_2$Se$_3$ and $\gamma$-In$_2$(Se$_{1-x}$Te$_x$)$_3$ alloys to the available toolbox of materials for solar cells and other optoelectronic devices.

Enhancing the dopability of semiconductors via strain engineering is critical to improving their functionalities, which is, however, largely hindered by the lack of fundamental rules. In this Letter, for the first time, we develop a unified theory to understand the total energy changes of defects (or dopants) with different charge states under strains, which can exhibit either parabolic or superlinear behaviors, determined by the size of defect-induced local volume change ({\Delta}V). In general, {\Delta}V increases (decreases) when an electron is added (removed) to (from) the defect site. Consequently, in terms of this unified theory, three fundamental rules can be obtained to further understand or predict the diverse strain-dependent doping behaviors, i.e., defect formation energies, charge-state transition levels, and Fermi pinning levels, in semiconductors. These three fundamental rules could be generally applied to improve the doping performance or overcome the doping bottlenecks in various semiconductors.

Irradiation damage is a key physics issue for semiconductor devices under extreme environments. For decades, the ionization-irradiation-induced damage in transistors with silica-silicon structures under constant dose rate is modeled by a uniform generation of $E'$ centers in the bulk silica region and their irreversible conversion to $P_b$ centers at the silica-silicon interface. But, the traditional model fails to explain experimentally observed dependence of the defect concentrations on dose, especially at low dose rate. Here, we propose that, the generation of $E'$ is decelerated due to the dispersive diffusion of induced holes in the disordered silica and the conversion of $P_b$ is reversible due to recombination-enhanced defect reactions under irradiation. It is shown that the derived analytic model based on these new understandings can consistently explain the fundamental but puzzling dependence of the defect concentrations on dose and dose rate in a wide range., Comment: 5 pages, 1 page of supplementary materials

First-principles calculations of charged defects have become a cornerstone of research in semiconductors and insulators by providing insights into their fundamental physical properties. But current standard approach using the so-called jellium model has encountered both conceptual ambiguity and computational difficulty, especially for low-dimensional semiconducting materials. In this Communication, we propose a physical, straightforward, and dimension-independent universal model to calculate the formation energies of charged defects in both three-dimensional (3D) bulk and low-dimensional semiconductors. Within this model, the ionized electrons or holes are placed on the realistic host band-edge states instead of the virtual jellium state, therefore, rendering it not only naturally keeps the supercell charge neutral, but also has clear physical meaning. This realistic model reproduces the same accuracy as the traditional jellium model for most of the 3D semiconducting materials, and remarkably, for the low-dimensional structures, it is able to cure the divergence caused by the artificial long-range electrostatic energy introduced in the jellium model, and hence gives meaningful formation energies of defects in charged state and transition energy levels of the corresponding defects. Our realistic method, therefore, will have significant impact for the study of defect physics in all low-dimensional systems including quantum dots, nanowires, surfaces, interfaces, and 2D materials.

The existence of Bloch flat bands provides an facile pathway to realize strongly correlated phenomena in materials. Using density-functional theory and tight-binding approach, we show that the flat bands can form in twisted bilayer of hexagonal boron nitride ($h$BN). However, unlike the twisted graphene bilayer where a magic angle is needed to form the flat band, for the polar $h$BN, the flat bands can appear as long as the twisted angle is less than certain critical values. Our simulations reveal that the valence band maximum (conduction band minimum) states are predominantly resided in the regions of the moir\'{e} supperlattice where the anion N (cation B) atoms in both layers are on top of each other. The preferential localization of these valence and conduction states originate from the chemical potential difference between N and B and is enhanced by the stacking effects of N and B in both layers, respectively, as demonstrated by an analysis of the energy level order of the $h$BN bilayers with different stacking patterns. When these states are spatially localized because regions with a specific stacking pattern are isolated for moir\'{e} supperlattices at sufficient small twist angle, completely flat bands will form. This mechanism is applicable to other twisted bilayers of two-dimensional polar crystals., Comment: 5 pages, 4 figures

Gallium oxide (Ga2O3) is a wide-band-gap semiconductor promising for UV sensors and high power transistor applications, with Baliga's figure of merit that far exceeds those of GaN and SiC, second only to diamond. Engineering its band structure through alloying will broaden its range of applications. Using hybrid density functional calculations we study the effects on adding Bi to Ga2O3. While in III-V semiconductors, such as GaAs and InAs, Bi tend to substitute on the pnictide site, we find that in Ga2O3, Bi prefers to substitute on the Ga site, resulting in dilute (Ga_{1-x}Bi_{x})2O3 alloys with unique electronic structure properties. Adding a few percent of Bi reduces the band gap of Ga2O3 by introducing an intermediate valence band that is significantly higher in energy than the valence band of the host material. This intermediate valence band is composed mainly of Bi 6s and O 2p orbitals, and it is sufficiently high in energy to provide opportunity for p-type doping.

The synergistic effects of neutron and gamma ray radiated PNP transistors are systematically investigated as functions of the neutron fluence, gamma ray dose, and dose rate. We find that the damages show a `tick'-like dependence on the gamma ray dose after the samples are radiated by neutrons. Two negative synergistic effects are derived, both of which have similar magnitudes as the ionization damage (ID) itself. The first one depends linearly on the gamma ray dose, whose slope depends quadratically on the initial displacement damage (DD) and can be attributed to the healing of neutron-radiation-induced defects in silicon. The second one has an exponential decay with the gamma ray dose, whose amplitude shows a rather strong enhanced low-dose-rate sensitivity (ELDRS) effect and can be attributed to the passivation of neutron-induced defects near the silica/silicon interface by the gamma-ray-generated protons in silica, which can penetrate the silica/silicon interface to passivate the neutron-induced defects in silicon. The simulated results based on the proposed model match the experimental data very well, but differ from previous model, which does not assume annihilation or passivation of the displacement defects. The unraveled defect annealing mechanism is important because it implies that displacement damages can be repaired by gamma ray radiation or proton diffusion, which can have important device applications in the space or other extreme environments., Comment: 10 pages with 9 figures

It is well known that the DX center is a kind of defect that limits the n-type doping in some tetrahedral coordinated semiconductors. It is a deep negatively charged defect complex converted from a nominal shallow donor defect, which can serve as a trap center of electrons, thus is detrimental to the performance of optoelectronic devices. Similar to the DX center, we find that a donor-yielded complex center (DY center) also exists in six-fold coordinated semiconducting materials. For example, Bi is commonly expected as a shallow n-type dopant in perovskite APbX3. However, our first-principles calculations show that the DY center is formed in Bi-doped MAPbBr3 when the Fermi level is high in the gap, but, interestingly, it does not form in MAPbI3. The reason that the DY center is formed in MAPbBr3 instead of MAPbI3 is attributed to the high conduction band minimum (CBM) of MAPbBr3. Our results are able to explain recent puzzling experiment observations and the thorough discussions of the formation and the properties of the DY center in perovskites provide enlightening insights to the defect study in six-fold coordinated semiconductors., Comment: 15 pages, 4 figures, under review

CdTe is one of the leading materials for low cost, high efficiency thin-film solar cells, because it has a high absorption coefficient and a nearly ideal band gap of 1.48 eV for solar cell according to the Shockley-Queisser limit. However, its solar to electricity power conversion efficiency (PCE) is hindered by the relatively low open circuit voltage (VOC) due to intrinsic defect related issues. Here, we propose the strategy of improving CdTe solar cell performance byr reducing the "ideal" band gap of CdTe to gain more short-circuit current from long-wavelength absorption without sacrificing much VOC. Alloying CdTe with CdSe seems to be the most appropriate approach to reduce the band gap because of the large optical bowing and relatively small lattice mismatch in this system, even though CdSe has larger band gap than CdTe. Using the first principle hybrid functional calculation, we find that the minimum band gap of the CdTe1-xSex alloy can be reduced from 1.48 eV at x=0 to 1.39 eV at x=0.32. We also show that the formation of the alloy can improve the defect property, for example, p-type doping of CdTe by CuCd can be greatly enhanced by the alloying effects., Comment: 13 pages, 4 figures, defects in alloy; 1st edition has been finished on 2018.09.13

In2O3 is a prototype wide-band-gap semiconductor that exhibits metallic conductivity when highly doped with Sn while retaining a high degree of transparency to visible light. It is widely used as a transparent window/electrode in solar cells and LEDs. The functionality of In2O3 would be greatly extended if p-type conductivity could also be achieved. Using electronic structure calculations, we show that adding Bi to In2O3, in the form of dilute (In_{1-x}Bi_{x})_2O3} alloys, leads to a new valence band that is sufficiently higher in energy than the original O-2p valence band to allow for p-type doping. Moreover, the raised valence band in the (In_{1-x}Bi_{x})_2O3} dilute alloys leads to strong optical absorption in the visible spectrum, opening up for new applications such as a wide band gap absorber layer in tandem solar cells.

Although the direct or indirect nature of the bandgap transition is an essential parameter of semiconductors for optoelectronic applications, the understanding why some of the conventional semiconductors have direct or indirect bandgaps remains ambiguous. In this Letter, we revealed that the existence of the occupied cation d bands is a prime element in determining the directness of the bandgap of semiconductors through the s-d and p-d couplings, which push the conduction band energy levels at the X- and L-valley up, but leaves the {\Gamma}-valley conduction state unchanged. This unified theory unambiguously explains why Diamond, Si, Ge, and Al-containing group III-V semiconductors, which do not have active occupied d bands, have indirect bandgaps and remaining common semiconductors, except GaP, have direct bandgaps. Besides s-d and p-d couplings, bond length and electronegativity of anions are two remaining factors regulating the energy ordering of the {\Gamma}-, X-, and L-valley of the conduction band, and are responsible for the anomalous bandgap behaviors in GaN, GaP, and GaAs that have direct, indirect, and direct bandgaps, respectively, despite the fact that N, P, and As are in ascending order of the atomic number. This understanding will shed light on the design of new direct bandgap light-emitting materials., Comment: 15 pages, 4 figures

We experimentally investigated total ionizing dose (TID) response of the input-stage PNP transitor in an operational amplifier LM324N with various initial displacement damage (IDD). We found that, the damage first decreases and then increases with the total dose, which can be exactly described by a dose-rate-dependent linear generation term, an IDD-dependent linear annealing term, and a dose-rate-dependent exponential annealing term. We demonstrate that, the first two terms are the well-known TID and injection annealing effect, respectively, while the third term stems from the reactions between the TID-induced protons diffusing from silica and the defects generated in silicon, which implies the presence of a unexplored proton-defect interaction between TID and DD effects. Moreover, we find that such an interaction is as strong as the injection annealing. Our work show that, beside the well-known Coulomb interaction of trapping charge in silica with carriers in silicon, a strong proton-defect interaction also plays important role in the synergistic damage., Comment: 9 pages, 7 figures

Photoelectrochemical (PEC) water splitting to generate hydrogen is one of the most studied methods for converting solar energy into clean fuel because of its simplicity and potentially low cost. Despite over 40 years of intensive research, PEC water splitting remains in its early stages with stable efficiencies far less than 10%, a benchmark for commercial applications. Here, we revealed that the desired photocorrosion stability sets a limit of 2.48 eV (relative to the normal hydrogen electrode (NHE)) for the highest possible potential of the valence band (VB) edge of a photocorrosion-resistant semiconducting photocatalyst. We further demonstrated that such limitation has a deep root in underlying physics after deducing the relation between energy position of the valence band edge and free-energy for a semiconductor. The disparity between the stability-limited VB potential at 2.48 V and the oxygen evolution reaction (OER) potential at 1.23 V vs NHE reduces the maximum STH conversion efficiency to approximately 8% for long-term stable single-bandgap PEC water splitting cells. Based on this understanding, we suggest that the most promising strategy to overcome this 8% efficiency limit is to decouple the requirements of efficient light harvesting and chemical stability by protecting the active semiconductor photocatalyst surface with a photocorrosion-resistant oxide coating layer., Comment: 19 pages, 4 figures

Triply degenerate points (TDPs) in band structure of a crystal can generate novel TDP fermions without high-energy counterparts. Although identifying ideal TDP semimetals, which host clean TDP fermions around the Fermi level ($E_F$) without coexisting of other quasiparticles, is critical to explore the intrinsic properties of this new fermion, it is still a big challenge and has not been achieved up to now. Here, we disclose an effective approach to search for ideal TDP semimetals via selective band crossing between antibonding $s$ and bonding $p$ orbitals along a line in the momentum space with $C_{3v}$ symmetry. Applying this approach, we have successfully identified the NaCu$_3$Te$_2$ family of compounds to be ideal TDP semimetals, where two and only two pairs of TDPs are located around the $E_F$. Moreover, we reveal an interesting mechanism to modulate energy splitting between a pair of TDPs, and illustrate the intrinsic features of TDP Fermi arcs in these ideal TDP semimetals., Comment: 9 pages, 4 figures

Tuning band gaps in two-dimensional (2D) materials is of great interest in the fundamental and practical aspects of contemporary material sciences. Recently, black phosphorus (BP) consisting of stacked layers of phosphorene was experimentally observed to show a widely tunable band gap by means of the deposition of potassium (K) atoms on the surface, thereby allowing great flexibility in design and optimization of electronic and optoelectronic devices. Here, based on the density-functional theory calculations, we demonstrates that the donated electrons from K dopants are mostly localized at the topmost BP layer and such a surface charging efficiently screens the K ion potential. It is found that, as the K doping increases, the extreme surface charging and its screening of K atoms shift the conduction bands down in energy, i.e., towards higher binding energy, because they have more charge near the surface, while it has little influence on the valence bands having more charge in the deeper layers. This result provides a different explanation for the observed tunable band gap compared to the previously proposed giant Stark effect where a vertical electric field from the positively ionized K overlayer to the negatively charged BP layers shifts the conduction band minimum ${\Gamma}_{\rm 1c}$ (valence band minimum ${\Gamma}_{\rm 8v}$) downwards (upwards). The present prediction of ${\Gamma}_{\rm 1c}$ and ${\Gamma}_{\rm 8v}$ as a function of the K doping reproduces well the widely tunable band gap, anisotropic Dirac semimetal state, and band-inverted semimetal state, as observed by angle-resolved photoemission spectroscopy experiment. Our findings shed new light on a route for tunable band gap engineering of 2D materials through the surface doping of alkali metals., Comment: 7 pages, 5 figures

Hybrid organic-inorganic halide perovskites with the prototype material of CH$_{3}$NH$_{3}$PbI$_{3}$ have recently attracted intense interest as low-cost and high-performance photovoltaic absorbers. Despite the high power conversion efficiency exceeding 20% achieved by their solar cells, two key issues -- the poor device stabilities associated with their intrinsic material instability and the toxicity due to water soluble Pb$^{2+}$ -- need to be resolved before large-scale commercialization. Here, we address these issues by exploiting the strategy of cation-transmutation to design stable inorganic Pb-free halide perovskites for solar cells. The idea is to convert two divalent Pb$^{2+}$ ions into one monovalent M$^{+}$ and one trivalent M$^{3+}$ ions, forming a rich class of quaternary halides in double-perovskite structure. We find through first-principles calculations this class of materials have good phase stability against decomposition and wide-range tunable optoelectronic properties. With photovoltaic-functionality-directed materials screening, we identify eleven optimal materials with intrinsic thermodynamic stability, suitable band gaps, small carrier effective masses, and low excitons binding energies as promising candidates to replace Pb-based photovoltaic absorbers in perovskite solar cells. The chemical trends of phase stabilities and electronic properties are also established for this class of materials, offering useful guidance for the development of perovskite solar cells fabricated with them., Comment: pages 19, 4 figures in main text

Topological phase transition in a single material usually refers to transitions between a trivial band insulator and a topological Dirac phase, but the transition may also occur between different classes of topological Dirac phases. However, it is a fundamental challenge to realize quantum transition between Z2 nontrivial topological insulator (TI) and topological crystalline insulator (TCI) in one material because Z2 TI and TCI are hardly both co-exist in a single material due to their contradictory requirement on the number of band inversions. The Z2 TIs must have an odd number of band inversions over all the time-reversal invariant momenta, whereas, the newly discovered TCIs, as a distinct class of the topological Dirac materials protected by the underlying crystalline symmetry, owns an even number of band inversions. Here, take PbSnTe2 alloy as an example, we show that at proper alloy composition the atomic-ordering is an effective way to tune the symmetry of the alloy so that we can electrically switch between TCI phase and Z2 TI phase when the alloy is ordered from a random phase into a stable CuPt phase. Our results suggest that atomic-ordering provides a new platform to switch between different topological phases., Comment: 3 figures

Defects play important roles in semiconductors for optoelectronic applications. Common intuition is that defects with shallow levels act as carrier providers and defects with deep levels are carrier killers. Here, taking the Cu defects in CdTe as an example, we show that shallow defects can play both roles. Using first-principles calculation methods combined with thermodynamic simulations, we study the dialectic effects of Cu-related defects on hole density and lifetime in bulk CdTe over a wide range of Cu incorporation conditions. Because CuCd can form a relatively shallow acceptor in CdTe, we find that increased Cu incorporation into CdTe indeed can help achieve high hole density; however, too much Cu can cause significant non-radiative recombination. We discuss two strategies to balance the contradictory effects of Cu defects based on the calculated impact of Cd chemical potential, copper defect concentrations, and incorporation temperature on lifetime and hole density. The results indicates that to optimize the Cu doping in CdTe, it is important to control the total amount of Cu incorporated into CdTe and optimize the match between the Cu incorporation temperature and the Cd chemical potential. These findings can help understand the roles of Cu defects in CdTe and the potential complex defect behaviors of relatively shallow defect states in semiconductors for optoelectronic applications.