Two-dimensional (2D) layered lead iodide (PbI2) is an important precursor and common residual species during the synthesis of lead-halide perovskites. There currently exist some debates and uncertainties about the effect of excess PbI2 on the efficiency and stability of the solar cell with respect to its energy alignment and energetics of defects. Herein, by applying the first-principles calculations, we investigate the energetics, changes of work function and the defective levels associated with the iodine vacancy (VI) and interstitial iodine (II) defects of monolayer PbI2 (ML-PbI2). We find that the PbI2 has a very low formation energy of VI of 0.77 and 0.19 eV for dilute and high concentration, respectively, reflecting coalescence tendency of isolated VI, much lower than that of vacancies in other 2D materials like phosphorene. Similar to VI, a low formation energy of II of 0.65 eV is found, implying a high population of such defects. Both defects generate in-gap defective levels which are mainly due to the unsaturated chemical bonds of p-orbitals of exposed Pb or inserted I. Such rich defective levels allow the VI and II as the reservoir or sinks of electron/hole carriers in PbI2. Our results suggest that the remnant PbI2 in perovskite MAPbI3 (or FAPbI3) would play dual opposite roles in affecting the efficiency of the perovskite: (1) Forming Schottky-type interface with MAPbI3 (or FAPbI3) in which the built-in potential would facilitate the electron-hole separation and prolong the carrier lifetime; (2) Acting as the recombination centers due to the deep defective levels. To promote the efficiency by the Schottky effect, our work reveals that the II defect is favored, and to reduce the recombination centers the VI defect should be suppressed. Our results shall be beneficial in improving strategies for the related optoelectronics applications.
Titanium dioxide materials have been studied intensively and extensively due to photocatalytic applications. A long-standing open question is the energy band alignment of rutile and anatase TiO2 phases, which can affect the photocatalytic process in the composite system. There are basically two contradictory viewpoints about the alignment of these two TiO2 phases supported by respective experiments: 1) straddling type and 2) staggered type. In this work, our DFT plus U calculations find that the perfect rutile (110) and anatase (101) surfaces have the straddling type band alignment, whereas th…
Formation and excitation energies as well charge transition levels, are determined forthe substitutional nitrogen (Ns),the vacancy (V) and related point defects (NV, NVH, N2, N2V and V2) by screened non-local hybrid density functional supercell plane wave calculations in bulk diamond. In additionthe activation energy for V and NV diffusion is calculated.We find good agreement between theory and experiment for the previously well-establisheddata, and predict missing ones. Based on the calculated properties of these defects, the formation of the negatively charged nitrogen-vacancy center is stud…
Finite-size corrections for charged defect supercell calculations typically consist of image-charge and potential alignment corrections. A wide variety of schemes for both corrections have been proposed for decades. Regarding the image-charge correction, Freysoldt, Neugebauer, and Van de Walle (FNV) recently proposed a novel method that enables us to accurately estimate the correction energy a posteriori through alignment of the defect-induced potential to the model charge potential [Freysoldt et al., Phys. Rev. Lett. 102, 016402 (2009)]. This method, however, still has two issues in practice.…
This paper provides an accurate theoretical defect energy database for pure and Bi-containing III-V (III-V:Bi) materials and investigates efficient methods for high-throughput defect calculations based on corrections of results obtained with local and semi-local functionals. Point defects as well as nearest-neighbor and second-nearest-neighbor pair defects were investigated in charge states ranging from -5 to 5. Ga-V:Bi systems (GaP:Bi, GaAs:Bi, and GaSb:Bi) were thoroughly investigated with significantly slower, higher fidelity hybrid Heyd-Scuseria-Ernzerhof (HSE) and significantly faster, lo…
Alignment of electrostatic potential between different atomic configurations is necessary for first-principles calculations of band offsets across interfaces and formation energies of charged defects. However, strong oscillations of this potential at the atomic scale make alignment challenging, especially when atomic geometries change considerably from bulk to the vicinity of defects and interfaces. We introduce a method to suppress these strong oscillations by eliminating the deep wells in the potential at each atom. We demonstrate that this method considerably improves the system-size conver…
We perform optical, surface anchoring, and textural studies of an organo-siloxane tetrapode material in the broad temperature range of the nematic phase. The optical, structural, and topological features are compatible with the uniaxial nematic order rather than with the biaxial nematic order, in the entire nematic temperature range -25C < T < 46C studied. For homeotropic alignment, the material experiences surface anchoring transition, but the director can be realigned into an optically uniaxial texture by applying a sufficiently strong electric field. The topological features of textures in …
Atomically precise tailoring of graphene can enable unusual transport pathways and new nanometer-scale functional devices. Here we describe a recipe for the controlled production of highly regular "5-5-8" line defects in graphene by means of simultaneous electron irradiation and Joule heating by applied electric current. High-resolution transmission electron microscopy reveals individual steps of the growth process. Extending earlier theoretical work suggesting valley-discriminating capabilities of a graphene 5-5-8 line defect, we perform first-principles calculations of transport and find a s…
Control of the crystalline orientation of nitrogen-vacancy (NV) defects in diamond is here demonstrated by tuning the temperature of chemical vapor deposition (CVD) growth on a (113)-oriented diamond substrate. We show that preferential alignment of NV defects along the [111] axis is significantly improved when the CVD growth temperature is decreased. This effect is then combined with temperature-dependent incorporation of NV defects during the CVD growth to obtain preferential alignment over dense ensembles of NV defects spatially localized in thin diamond layers. These results demonstrate th…
Van der Waals heterostructures are the ideal material platform for tunnel field effect transistors (TFETs) because a band-to-band tunneling (BTBT) dominant current is feasible at room temperature (RT) due to ideal, dangling bond free heterointerfaces. However, achieving subthreshold swing (SS) values lower than 60 mVdec-1 of the Boltzmann limit is still challenging. In this work, we systematically studied the band alignment and heterointerface quality in n-MoS2 channel heterostructure TFETs. By selecting a p+-MoS2 source with a sufficiently high doping level, stable gate modulation to a type I…
The dielectric breakdown at metal-oxide interfaces is a critical electronic device failure mechanism. Electronic tunneling through dielectric layers is a well-accepted explanation for this phenomenon. Theoretical band alignment studies, providing information about tunneling, have already been conducted in the literature for metal-oxide interfaces. However, most of the time materials were assumed defect free. Oxygen vacancies being very common in oxides, their effect on band lineup is of prime importance in understanding electron tunneling in realistic materials and devices. This work explores …
Hybrid halide perovskites such as methylammonium lead iodide (CH3NH3PbI3) exhibit unusually low free carrier concentrations despite being processed at low-temperatures from solution. We demonstrate, through quantum mechanical calculations, that the origin of this phenomenon is a prevalence of ionic over electronic disorder in stoichiometric materials. Schottky defect formation provides a mechanism to self-regulate the concentration of charge carriers through ionic compensation of charged point defects. The equilibrium charged vacancy concentration is predicted to exceed 0.4% at room temperatur…
The Dirac point gap at the surface of the antiferromagnetic topological insulator MnBi$_2$Te$_4$ is a highly debated issue. While the early photoemission measurements reported on large gaps in agreement with theoretical predictions, other experiments found vanishingly small splitting of the MnBi$_2$Te$_4$ Dirac cone. Here, we study the crystalline and electronic structure of MnBi$_2$Te$_4$(0001) using scanning tunneling microscopy/spectroscopy (STM/S), micro($μ$)-laser angle resolved photoemission spectroscopy (ARPES), and density functional theory (DFT) calculations. Our topographic STM image…
Impact of interface defects on the band alignment and performance of TiO$_2$/MAPI/Cu$_2$O perovskite solar cells
Faculty of Physics, University of Bucharest（布加勒斯特大学物理学院）；Horia Hulubei National Institute for Physics and Nuclear Engineering（霍里亚·胡利贝伊核物理与核工程国家研究所）；National Institute of Materials Physics（材料物理国家研究所）；Department of Engineering, School of Technology, Reykjavik University（雷克雅未克大学技术学院工程系）
Endowed with a multitude of exquisite properties such as rich electrochemistry, superb topology and eccentric electromagnetic phenomena, honeycomb layered oxides have risen to the top echelons of science with applications in diverse fields ranging from condensed matter physics, solid-state chemistry, materials science, solid-state ionics to electrochemistry. However, these oxides are vastly underutilised as their underlying atomistic mechanisms remain unexplored. Therefore, in this study, atomic-resolution imaging on pristine $\rm K_2Ni_2TeO_6$ along multiple zone axes was conducted using sphe…
Plasma engineered Hydroxyl Defects in NiO a DFTSupported-Spectroscopic Analysis of Oxygen Hole States and Implications for Water Oxidation
Technical University of Darmstadt（达姆施塔特工业大学）；Dutch Institute for Fundamental Energy Research（荷兰基础能源研究所）；Università degli studi di Milano（米兰大学）；Max Planck Institute for Chemical Energy Conversion（马克斯·普朗克化学能转换研究所）；Diamond Light Source（钻石光源）
Formation of twin boundaries during the growth of semiconductor nanowires is very common. However, the effects of such planar defects on the electronic and optical properties of nanowires are not very well understood. Here, we use a combination of ab initio simulation and experimental techniques to study these effects. Twin boundaries in GaP are shown to act as an atomically-narrow plane of wurtzite phase with a type-I homostructure band alignment. Twin boundaries and stacking faults (wider regions of the wurtzite phase) lead to the introduction of shallow trap states observed in photoluminesc…
Calculations of formation energies and charge transition levels of defects routinely rely on density functional theory (DFT) for describing the electronic structure. Since bulk band gaps of semiconductors and insulators are not well described in semilocal approximations to DFT, band-gap correction schemes or advanced theoretical models which properly describe band gaps need to be employed. However, it has become apparent that different methods that reproduce the experimental band gap can yield substantially different results regarding charge transition levels of point defects. We investigate t…
The dependencies of the B$_{i}$O$_{i}$ defect concentration on doping, irradiation fluence and particle type in p-type silicon diodes have been investigated. We evidenced that large data scattering occurs for fluences above $10^{12}$ 1 MeV neutrons/cm$^2$, becoming significant larger for higher fluences. We show that the B$_{i}$O$_{i}$ defect is metastable, with two configurations A and B, of which only A is detected by Deep Level Transient Spectroscopy and Thermally Stimulated Currents techniques. The defect's electrical activity is influenced by the inherent variations in ambient and procedu…
We consider the Br vacancy in CsPbBr3 as a prototype for the impact of structural dynamics on defect energetics in halide perovskites (HaPs). Using first-principles molecular dynamics based on density functional theory, we find that the static picture of defect energetics breaks down; the energy of the Br vacancy level is found to be intrinsically dynamic, oscillating by as much as 1 eV on the ps time scale at room temperature. These significant energy fluctuations are correlated with the distance between the neighboring Pb atoms across the vacancy and with the electrostatic potential at these…
We unveil the nature of the structural disorder in bottom-up zigzag graphene nanoribbons along with its effect on the magnetism and electronic transport on the basis of scanning probe microscopies and first-principles calculations. We find that edge-missing m-xylene units emerging during the cyclodehydrogenation step of the on-surface synthesis are the most common point defects. These "bite'' defects act as spin-1 paramagnetic centers, severely disrupt the conductance spectrum around the band extrema, and give rise to spin-polarized charge transport. We further show that the electronic conduct…
The formation and field-induced switching of defect dipoles in acceptor doped lead titanate is described by a kinetic model representing an extension of the well established Arlt-Neumann model [Ferroelectrics {\bf 76}, 303 (1987)]. Energy barriers for defect association and reorientation of oxygen vacancy-dopant (Cu and Fe) complexes are obtained from first-principles calculations and serve as input data for the kinetic coefficients in the rate equation model. The numerical solution of the model describes the time evolution of the oxygen vacancy distribution at different temperatures and dopan…
In order to perform automated calculations of defect and dopant properties in semiconductors and insulators, we developed a software package, Defect and Dopant ab-initio Simulation Package (DASP), which is composed of four modules for calculating: (i) elemental chemical potentials, (ii) defect (dopant) formation energies and transition energy levels, (iii) defect and carrier densities and (iv) carrier dynamics properties of high-density defects. DASP uses the materials genome database for quick determination of competing secondary phases and calculation of the energy above convex hull when cal…
The mechanical, structural and functional properties of crystals are determined by their defects and the distribution of stresses surrounding these defects has broad implications for the understanding of transport phenomena. When the defect density rises to levels routinely found in real-world materials, transport is governed by local stresses that are predominantly nonlinear. Such stress fields however, cannot be measured using conventional bulk and local measurement techniques. Here, we report direct and spatially resolved experimental measurements of the nonlinear stresses surrounding collo…
The possible symmetries of the biaxial nematic phase are examined against the implications of the presently available experimental results. Contrary to the widespread notion that biaxial nematics have orthorhombic symmetry, our study shows that a monoclinic ($C_{2h}$) symmetry is more likely to be the case for the recently observed phase biaxiality in thermotropic bent-core and calamitc tetrapode nematic systems. The methodology for differentiating between the possible symmetries of the biaxial nematic phase by NMR and by IR spectroscopy measurements is presented in detail. The manifestations …
