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Lead halide perovskites (LHPs) have attracted considerable attention as promising materials for photovoltaic and optoelectronic applications. Intrinsic point defects play an important role in determining the performance of semiconductor devices. LHPs exhibit strong ionic character and unique electronic structure; thus, their defect properties are quite different from conventional covalent bond semiconductors. Understanding the defect science is crucial to the performance optimization of LHP-based devices. State-of-the-art first-principles calculation methods enable one to explore atomistic mechanisms of various defect-related processes, and tremendous efforts from theoretical simulations have provided invaluable insights to the defect physics and defect control of LHPs. In this review, we summarize recent progress, made with the help of theoretical modeling, on atomic-scale understanding about intrinsic point defects and related processes in LHPs. The fundamental properties of intrinsic point defects in LHPs are first introduced, including defect formation energy, charge transition level, and defect tolerance and its origin. A particular emphasis is given to the effects of band edge position on calculated defect properties. The impact of these defects on structural properties, carrier dynamics, and photoluminescence of LHPs is then presented. Advanced strategies to engineer the defects in LHPs are also reviewed, such as growth condition, defect passivation, and doping. Finally, we discuss open issues and outline directions toward a better understanding of defects of LHPs from a theoretical perspective. The goal of the review is to provide a comprehensive summary of atomic-scale understanding of intrinsic point defects in LHPs and to help further related research in the perovskite community.

Transparent conducting materials (TCMs), which combine high electrical conductivity and high optical transmission in the visible spectral range, are needed in many modern optoelectronic devices such as solar cells, flat-panel displays, touch-screen sensors, light emitting diodes, and transparent thin film transistors. However, many physical properties of the TCMs are still not very well understood. Understanding the band structure and physical origin of the unique properties of the TCMs is, therefore, crucial for the future design of these fascinating materials. In this Perspective, we will first present a brief review of the unique band structure and doping control of TCMs. In particular, we will discuss (i) the fundamental band structures and defect properties for the TCMs and why most of them are oxides (transparent conducting oxides, TCOs); (ii) how to achieve simultaneously high transparency and conductivity in n-type TCMs; (iii) why p-type TCOs are difficult to achieve; (iv) how to modify the band structure or design new materials to achieve p-type TCMs or even bipolarly dopable TCMs. Finally, we will discuss some of the remaining challenges and opportunities for the development of TCMs in the near future.

Recently, CdTe-based solar cells have achieved high power conversion efficiency by alloying with CdSe. Besides the increased photocurrent due to the reduced bandgap, it is also reported that the electron lifetime in the alloyed system is higher than that in the CdTe-based system. However, the origin of the improved lifetime is not clear. In this work, using first-principles calculations and the low energy Σ3 (112) grain boundary (GB) in polycrystalline CdTe as an example, we show that in the alloyed system, Se has the tendency to move toward the Σ3 (112) GB. Consequently, Se at the GBs in CdTe can effectively passivate the deep GB defect levels, thus reducing carrier recombination and improve solar cell performance. More specifically, we find that the Σ3 (112) GB with Te-core has the lowest formation energy among the electronically detrimental GB configurations in polycrystalline CdTe. The Σ3 (112) GB with Te-core introduces a deep defect state in the bandgap of CdTe, which can act as nonradiative recombination center and reduces the carrier lifetime of CdTe. When Se segregates to GB and substitutes the Te atom at the Te dimer site, due to the lower energy of Se 4p orbital and the weak coupling between the dimer elements in the GB core, the deep GB states will shift to shallower states toward the valance band maximum of CdTe. This can increase the carrier lifetime of the CdSeTe layer and thus provide a viable explanation to the improved lifetime and performance of Se-alloyed CdTe solar cells.

As a wide bandgap semiconductor, SiC holds great importance for high temperature and high power devices. It is known that the intrinsic defects play key roles in determining the overall electronic properties of semiconductors; however, a comprehensive understanding of the intrinsic defect properties in the prototype 4H-SiC is still lacking. In this study, we have systematically investigated the electronic properties and kinetic behaviors of intrinsic point defects and defect complexes in 4H-SiC using advanced hybrid functional calculations. Our results show that all the point defects in 4H-SiC have relatively high formation energies, i.e., low defect concentrations even at high growth temperatures. Interestingly, it is found that the migration barriers are very high for vacancies (>3 eV) but relatively low for interstitial defects (∼1 eV) in SiC. Meanwhile, the diffusion energy barriers of defects strongly depend on their charge states due to the charge-state-dependent local environments. Furthermore, we find that VSi in SiC, a key defect for quantum spin manipulation, is unstable compared to the spin-unpolarized VC–CSi complex in terms of the total energy (under p-type conditions). Fortunately, the transformation barrier from VSi to VC–CSi is as high as 4 eV, which indicates that VSi could be stable at room (or not very high) temperature.

Among transition-metal nitrides, the mononitride γ-MoN with a rock-salt structure has drawn particular attention because it has been predicted to possess excellent mechanical and electronic properties, especially the high superconducting temperature around 30 K. However, synthesis of bulk γ-MoNx with the nitrogen concentration, x, more than 0.5 is still challenging, leading to contradictions on its phase stability and properties. In this work, we formulated a high-pressure synthesis reaction for the formation of single-crystal γ-MoNx with a remarkably high nitrogen concentration value of x ≈ 0.67. This nitride possesses a high asymptotic hardness of ∼24 GPa, which is so far the second hardest among metal nitrides. Impressively, the expected superconductivity is absent in the as-synthesized product. We further performed density functional theory calculations to clarify the structural stability and the absence of superconductivity in stoichiometric γ-MoN. We find that the ground state of γ-MoN is theoretically explored to be a Mott insulator with an antiferromagnetic phase, while a paramagnetic configuration is adopted at the ambient conditions. Such magnetic properties would explain the structural stability and the absence of superconductivity in the as-synthesized γ-MoNx with a high nitrogen concentration.

Transparent conducting oxides such as the bixbyite In2O3 and rutile SnO2 systems have large disparities between the optical and fundamental bandgaps, ΔEgOF, because selection rules forbid dipolar transitions from the top of the valence band to the conduction-band minimum; however, the optical gaps of multi-cation compounds with the same chemical species often coincide with their fundamental gaps. To explain this conundrum, we have employed density-functional theory to compute the optical properties of multi-cation compounds, In2ZnO4 and In4Sn3O12, in several crystal structures. We show that a recently proposed mechanism to explain the disparity between the optical and fundamental gaps of M2O3 (M = Al, Ga, and In) applies also to other binary systems and to multi-compounds. Namely, a gap disparity will arise if the following three conditions are satisfied: (i) the crystal structure has inversion symmetry; (ii) the conduction-band minimum is formed by the cation and O s-orbitals; and (iii) there is strong p...

Equilibrium geometries, stabilities, and electronic properties of TinAl (n=1-13) clusters have been studied by using density-functional theory with local spin density approximation and generalized gradient approximation. The ground-state structures of TinAl clusters have been obtained. The resulting geometries show that the aluminum atom remains on the surface of clusters for n

Double perovskites Cs2AgSbCl6 have been synthesized via the solution state for applications as a promising photovoltaic absorber. Considering TiO2 as an electron transport layer (ETL), Cs2AgSbCl6/TiO2 heterojunction nanoparticles have also been prepared by the hydrothermal process to study the interface effect. Experimental measurements show that Cs2AgSbCl6 has a cubic structure with the lattice constant of 10.699 A. The absorption peaks in the optical spectrum of the Ag and Sb-based double perovskites agree well with our density functional theory calculations. The Cs2AgSbCl6/TiO2 heterostructure exhibits enhanced optical absorption in the visible-light region compared to that of Cs2AgSbCl6, which is caused by the formation of the interface states and the decreased bandgap, thus facilitating the photo-induced optical transition in the visible-light region. From the charge transfer analysis of two interfaces (Ag2Sb2Cl8/TiO2 and Cs4Cl4/TiO2 interfaces), we find that the efficient separation of photo-induced...

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.

Two-dimensional (2D) layered inorganic nanomaterials have attracted huge attention due to their unique electronic structures, as well as extraordinary physical and chemical properties for use in electronics, optoelectronics, spintronics, catalysts, energy generation and storage, and chemical sensors. Graphene and related layered inorganic analogues have shown great potential for gas-sensing applications because of their large specific surface areas and strong surface activities. This review aims to discuss the latest advancements in the 2D layered inorganic materials for gas sensors. We first elaborate the gas-sensing mechanisms and introduce various types of gas-sensing devices. Then, we describe the basic parameters and influence factors of the gas sensors to further enhance their performance. Moreover, we systematically present the current gas-sensing applications based on graphene, graphene oxide (GO), reduced graphene oxide (rGO), functionalized GO or rGO, transition metal dichalcogenides, layered II...

Design and preparation of photosensitive materials is important for a wide range of applications in solar cells, photocatalysts, photodetectors, and other optoelectronics devices. In recent decades, many photosensitive devices based on the polymer-functionalized metal compound semiconductors have attracted extensive attention and research. These devices combine the advantages of both polymers and metal compounds, and they show tremendously enhanced photosensitive performance compared with the individual components, even exhibiting some optoelectronic properties that are absent for the constituents. In this paper, we review recent developments including mechanisms of photosensitivity, various approaches to obtaining the polymer-functionalized metal compound semiconductors, the properties that are created or enhanced through the functionalization, and some of their applications.

The atomic structures and electronic properties of small Ti-N (N=2-10) clusters have been studied by using the density-functional theory with a local spin density approximation. We find that the inner-shells (3s3p) of the titanium atom plays an important role in the formation of the small clusters. We have obtained the ground state of titanium clusters, Ti-7 is found to be a magic cluster, which is in good agreement with the experimental results. Starting with Ti-8 cluster some features of the electronic structure of the titanium bulk have been developed. The ionization potentials and magnetic moments for these small titanium clusters are also presented. (C) 2000 American Institute of Physics. [S0021- 9606(00)30544-X].

Using first principles band structure theory we have calculated (i) the alloy bowing coefficients, (ii) the alloy mixing enthalpies, and (iii) the interfacial valence band offsets for three Cd-based (CdS, CdSe, CdTe) compounds. We have also calculated defect formation energies and defect transition energy levels of Cd vacancy VCd and CuCd substitutional defect in CdS and CdTe, as well as the isovalent defect TeS in CdS. The calculated results are compared with available experimental data.

We found theoretically that Na has three effects on CuInSe2: (1) If available in stoichiometric quantities, Na will replace Cu, forming a more stable NaInSe2 compound having a larger band gap (higher open-circuit voltage) and a (112)tetra morphology. The ensuing alloy NaxCu1−xInSe2 has, however, a positive mixing enthalpy, so NaInSe2 will phase separate, forming precipitates. (2) When available in small quantities, Na will form defect on Cu site and In site. Na on Cu site does not create electric levels in the band gap, while Na on In site creates acceptor levels that are shallower than CuIn. The formation energy of Na(InCu) is very exothermic, therefore, the major effect of Na is the elimination of the InCu defects and the resulting increase of the effective hole densities. The quenching of InCu as well as VCu by Na reduces the stability of the (2VCu−+InCu2+), thus suppressing the formation of the “Ordered Defect Compounds.” (3) Na on the surface of CuInSe2 is known to catalyze the dissociation of O2 int...

Semiconductors differ widely in their ability to be doped. As their band gap increases, it is usually possible to dope them either n or p type, but not both. This asymmetry is documented here, and explained phenomenologically in terms of the “doping pinning rule.”

We investigate whether the electric field gradient (EFG) at an atomic site in the unit cell of a periodic solid can be modeled via the electrostatic field gradient set up by atomic point charges outside that site. To test this approach we contrast the EFG predicted by such point-ion models for long-range ordered GaInP2 alloys with the results obtained from self-consistent all-electron calculations in the local density approximation (LDA). We first tested our LDA approach for ZnAl2O4, for which experimental data exist, finding the quadrupole coupling constant Qcc(27Al)=3.94 MHz, compared with the measured value of |Q|=3.68 MHz. Applying next the LDA approach to perfectly ordered GaInP2 (for which experimental data do not exist), we find the LDA quadrupole coupling constant Qcc=−4.83, −2.84, and 13.08 MHz for 69Ga, 71Ga, and 115In, respectively. We further find that more than 95% of these EFGs originate from the anisotropic electron charge distribution within a small sphere of radius ∼0.2 A about the respec...

Using first‐principles band‐structure theory we have systematically calculated the (i) alloy bowing coefficients, (ii) alloy mixing enthalpies, and (iii) interfacial valence‐ and conduction‐band offsets for three mixed‐anion (CuInX2, X=S, Se, Te) and three mixed‐cation (CuMSe2, M=Al, Ga, In) chalcopyrite systems. The random chalcopyrite alloys are represented by special quasirandom structures (SQS). The calculated bowing coefficients are in good agreement with the most recent experimental data for stoichiometric alloys. Results for the mixing enthalpies and the band offsets are provided as predictions to be tested experimentally. Comparing our calculated bowing and band offsets for the mixed‐anion chalcopyrite alloys with those of the corresponding Zn chalcogenide alloys (ZnX, X=S, Se, Te), we find that the larger p−d coupling in chalcopyrite alloys reduces their band offsets and optical bowing. Bowing parameters for ordered, Zn‐based II‐VI alloys in the CuAu, CuPt, and chalcopyrite structures are present...

We investigated the stability and electronic properties of defects in CdTe1−xSx that can be formed at the CdS/CdTe interface. As the anions mix at the interface, the defect properties are significantly affected, especially those defects centered at cation sites like Cd vacancy, VCd, and Te on Cd antisite, TeCd, because the environment surrounding the defect sites can have different configurations. We show that at a given composition, the transition energy levels of VCd and TeCd become close to the valence band maximum when the defect has more S atoms in their local environment, thus improving the device performance. Such beneficial role is also found at the grain boundaries when the Te atom is replaced by S in the Te-Te wrong bonds, reducing the energy of the grain boundary level. On the other hand, the transition levels with respect to the valence band edge of CdTe1−xSx increases with the S concentration as the valence band edge decreases with the S concentration, resulting in the reduced p-type doping e...

Dislocations are essentially lines of point defects which can act as recombination centers in semiconductor devices. These point defects do not behave as isolated defects. Their spatial proximity enables them to hybridize into a one-dimensional band, and the distribution of resulting defect-band states is determined by both the position of the band and its dispersion. In the case of glissile 90° partial dislocations in III-V semiconductors, the dislocation core can adopt a variety of different reconstructions. Each of these reconstructions has a different arrangement of point defects, which affects the hybridization into defect bands and their associated dispersion. Here, we illustrate these principles by performing first-principles calculations for InAs and find that some defect levels for InAs dislocations lie outside of the band gap where they cannot act as recombination centers. To provide some insight into the electronic structure of dislocations in ternary alloys, some examples relevant to InGaAs an...

Cu and Cl treatments are important processes to achieve high efficiency polycrystalline cadmium telluride (CdTe) solar cells, thus it will be beneficial to understand the roles they play in both bulk CdTe and CdTe grain boundaries (GBs). Using first-principles calculations, we systematically study Cu and Cl-related defects in bulk CdTe. We find that Cl has only a limited effect on improving p-type doping and too much Cl can induce deep traps in bulk CdTe, whereas Cu can enhance p-type doping of bulk CdTe. In the presence of GBs, we find that, in general, Cl and Cu will prefer to stay at GBs, especially for those with Te-Te wrong bonds, in agreement with experimental observations.

Deep level defects are usually harmful to solar cells. Here we show that incorporation of selected deep level defects in the carrier-collecting region, however, can be utilized to improve the efficiency of optoelectronic devices. The designed defects can help the transport of the majority carriers by creating defect levels that are resonant with the band edge state, and/or reduce the concentration of minority carriers through Coulomb repulsion, thus suppressing the recombination at the carrier-collecting region. The selection process is demonstrated by using Si solar cell as an example. Our work enriches the understanding and utilization of the semiconductor defects.

With a recently developed unique deep ultraviolet picoseconds time-resolved photoluminescence (PL) spectroscopy system and improved growth technique, we are able to determine the detailed band structure near the Γ point of wurtzite (WZ) AlN with a direct band gap of 6.12 eV. Combined with first-principles band structure calculations we show that the fundamental optical properties of AlN differ drastically from that of GaN and other WZ semiconductors. The discrepancy in energy band gap values of AlN obtained previously by different methods is explained in terms of the optical selection rules in AlN and is confirmed by measurement of the polarization dependence of the excitonic PL spectra.

In the past, codoping by mixing donors with acceptors has been proposed to lower the dopant ionization energy. However, the level repulsion between donor and acceptor states is weak due to symmetry considerations. Here, we propose an innovative approach to lower the donor ionization energy by combining donor with donor. Using first-principles band structure method, we demonstrated this concept with n-type doping in ZnTe. For example, we find that the BrTe–SnZn pair has a binding energy of 0.9 eV and a shallow e(+/0) donor level at 70 meV below the conduction-band minimum, compared to 240 meV for the isolated BrTe impurity.

Electronic and magnetic properties of MnN and MnAs compounds in the hypothetical cubic zinc-blende phase are studied using first-principles band structure method. We show that the high electronegativity and small atomic size of N compared to As lead to interesting consequences: MnN has a low-spin antiferromagnetic ground state, whereas MnAs has a high-spin hole mediated ferromagnetic (FM) ground state. Because the Mn d bands are higher in energy than the N p band, Mn is not efficient to generate free holes in the nitrides. Therefore, previous prediction that undoped Ga1−xMnxN diluted alloy can result in room-temperature FM semiconductor should be reexamined.

The search for the highest quality and efficient spin-polarized electron source (SPES) is of fundamental importance in the investigation of spin-dependent phenomena in atomic, condensed-matter, nuclear, and particle physics. We propose a material, AgGaSe2 in the CuAu phase, as a high-quality SPES. We show that AgGaSe2 in the CuAu phase has an “ideal” band structure that allows the generation of electron beams with 100% polarization: a direct band gap with large and positive spin-orbit splitting and crystal-field splitting. Moreover, we predict that strain-free AgGaSe2 in CuAu phase can be obtained by epitaxial growth on ZnSe substrate.

Using first-principles total energy calculations, we have studied self-doping in the ternary transparent conducting oxide, Cd2SnO4. Formation of the CdO and SnO2 binaries limits the inverse spinel Cd2SnO4 phase into a narrow region in the atomic chemical potential (μ) space. This suggests that μSn is not independent of μCd, so a Cd-rich growth or annealing condition also implies Sn-rich, and vice versa. We found that the widely accepted intrinsic donors such as oxygen vacancy and cadmium interstitial are not responsible for the observed conductivity in Cd2SnO4: both require too much energy to form. In addition, the oxygen vacancy is rather deep. We show instead that the Sn-on-Cd antisite defect is the most probable donor responsible for the n typeness under Cd-rich conditions.

CuInS2 epitaxial films grown on Si(111) substrates at different conditions have been investigated. Transmission electron diffraction shows the coexistence of domains having the Cu–Au and chalcopyrite structure. X-ray diffraction analysis allows the estimation of the relative amount of the phase domains, which is dependent on the growth conditions of the films. The films also present additional modes in the Raman spectra, together with the ones that are chalcopyrite related. The relative intensity of the additional modes directly correlates with the estimated amount of Cu–Au ordered phase. This supports the interpretation that the additional Raman modes are related to Cu–Au ordered domains. Group theory analysis is in agreement with the symmetry of the observed modes. The phonon frequency of the Cu–Au assigned Raman mode is also in excellent agreement with the first-principles frozen-phonon calculations.

We report direct observation of the existence of buried thin wurtzite CdTe layers in nominally pure zinc-blende CdTe thin films using high-resolution transmission electron microscopy. The formation of the buried wurtzite layers is a result of the formation of high density of planar defects in the zinc-blende films—the wurtzite layers are formed by closely spaced lamellar twins. First-principles calculations reveal that the presence of the buried wurtzite layers may be responsible for the poor electrical properties of the polycrystalline zinc-blende CdTe films.