The photophysical properties of lead halide perovskite nanocrystals (NCs) are critical to their potential application in light emitting devices and other optoelectronics, and are typically characterized using optical spectroscopies. Measurements of nuclei and nascent NC photophysics during synthesis provide insight into how the reaction can be changed to control the properties of the resulting NCs. However, these measurements are typically only performed ex situ after growth is halted by centrifuging the reaction mixture for several minutes. Here, a method is reported to rapidly sample the reaction mixture during a solvation-limited synthesis to enable multiple spectroscopic measurements during nucleation and NC growth. Absorbance and fluorescence measurements of a reaction mixture during the formation of methylammonium lead triiodide perovskite NCs are reported. The changing positions of spectral features as a function of reaction time show the expected weakening of exciton confinement during NC growth. The evolving fluorescence spectra demonstrate that the capping and surface passivation of nascent NCs changes during the reaction. The species in the reaction mixture, particularly during the early stages of the synthesis, are shown to be unstable. This indicates that, even for a relatively slow solvation-limited reaction, the photophysics of the reaction mixture can only be accurately captured if spectroscopic measurements are completed within seconds of sampling. The common use of centrifugation to quench NC syntheses prior to spectroscopic measurement biases the NC population towards more stable, well-capped NCs and does not accurately report on the full NC population in a reaction mixture.

Using first-principles calculation, we investigate water-dissociation dynamics in a Σ5 tilt grain boundary (GB) of Methyl-Ammonium Lead Triiodide (MAPbI3) perovskite. We find that the water dissociation process undergoes with two-step reaction at the GB: one of H ions of a water molecule that segregates into the GB is dissociated, migrates along the GB, and is attracted by an N atom in the MAPbI3, following the H-ion release from the ammonium. The process thereby generates OH− ion and, in turn, leads to possible initiation of the degradation for crystallinity in the perovskite.

Cesium lead iodide perovskite (CsPbI3) with excellent optical and electrical properties have attracted numerous academic attentions. Specifically, the black cubic phase CsPbI3 with a direct band gap of 1.74 eV has been most appropriate materials for various optoelectronic applications, especially for photovoltaic (PV), Light-Emitting Diodes (LED) and photodetector applications1. However, the preferred cubic phase of bulk CsPbI3 (α-CsPbI3) is usually only stable at high temperatures and it will undergo an immediate phase transformation to orthorhombic phase (δ-CsPbI3) after fabrication at room temperature. In this work, we have discovered a convenient CVD method to investigate the growth behavior of the cubic α-CsPbI3 film on the porous alumina substrate. The lead iodide and cesium iodide were used as the precursors for the deposition of CsPbI3. The porous alumina with high surface area and large pore volume was used as growth substrate. It was shown that the porous alumina promoted the growth of CsPbI3 film by absorbing the precursor and increasing the nucleation density. The prepared CsPbI3 film emitted strong and stable red light under ultraviolet light excitation at room temperature and ambient atmosphere. The lead iodide was absorbed on the surface of the porous alumina firstly then reacted with cesiumiodide to form the CsPbI3. The successful preparation of the CsPbI3 by the direct CVD method paves the way for its large scale growth and application in optoelectronic devices.

Fully inorganic lead halide perovskite nanocrystals (NCs) are of interest for photovoltaic and light emitting devices due to optoelectronic properties. Understanding the surface chemistry of these materials is of importance as surface defects can introduce trap-states which reduce their functionality. Here we use Density Functional Theory (DFT) to model surface defects introduced by Pb2+ on a CsPbBr3 NC atomistic model. Two types of defects are studied: (i) an under-coordinated Pb2+ surface atom and (ii) Pb2+ atomic or molecular adsorbents to the NC surface. From the DFT calculations we compute the density of states (DOS) and absorption spectra of the defect models to the pristine fully-passivated NC model. We observe that for the low surface defect regime explored here that neither (i) or (ii) produce trap-states inside of the bandgap and exhibit bright optical absorption for the lowest energy transition. From the models studied, it was found that the Pb2+ atomic absorbent provides broadening of the conduction band edge, which implies chemisorption of Pb2+ to the NC surface. At higher defect densities it would be expected that Pb2+ atomic absorbents would introduce trap-states and degrade the opto-electronic properties of these materials.

Bismuth ferrite (BiFeO3) and La-, Nd- and Gd-substituted bismuth ferrite of the Bi1-xLaxFeO3, Bi1-xNdxFeO3, and Bi1-xGdxFeO3 types with the atomic part of the substitution element x equal up to 0.20 were synthesized by the solid-state reaction method using powders of oxides Bi2O3, Fe2O3, and La2O3, or Nd2O3, or Gd2O3 of pure grade quality and investigated using X-ray diffraction analysis. The magnetization was measured in the magnetic field up to 6.5⋅106 A/m at 5 and 300 K. It was found that the total substitution up to 0.20 atomic part of Bi by La, Nd, and Gd leads to the paramagnetic behavior of the doped bismuth ferrite at low temperatures in a wide range of magnetic field. Strong nonlinear dependence of magnetization on the magnetic field was detected and a ferromagnetic-like dependence of magnetization was observed for small magnetic fields. This can be explained by the exchange interaction between doping magnetic ions, as well as by the exchange interaction of these ions with ions of iron. The enhancement of magnetic properties with the increase of the content of the substitution is monotone and is more pronounced for the Bi1-xGdxFeO3 ceramics.

Two benzodifuran (BDF) polymers, PBDF-C and PBDF-S, with alkyl and alkylthio substituted thiophene side-chains and benzodithiophene-4,8-dione (BDD) as the acceptor were designed and synthesized. Their optical, electrochemical properties and photovoltaic performances were systematically investigated. The polymer solar cells (PSCs) with a device structure of ITO/PEDOT:PSS/polymer:PC71BM/Ca/Al were fabricated. The PBDF-C based device showed a power conversion efficiency (PCE) of 3.01% after adding 1 vol% 1,8-diodooctane (DIO) as the solvent additive, and PBDF-S gave an enhanced PCE of 3.48% without any post-treatments. The enhancements were from the higher open-circuit voltage (Voc) and fill factor (FF). The thermal- and solvent-treatment-free processing is more favourable for the large area roll-to-roll manufacturing or printing technology for PSCs.

Silicon nanowires (SiNWs) show unique optoelectronic properties such as band gap, radiative and nonradiative relaxations. In this research, the optoelectronic properties of <211> SiNW are calculated by combining time-dependent density matrix methodology. Description of photo-excited dynamics processes is enabled by computing “on–the–fly” nonadiabatic couplings (NAC) between electronic and nuclear degrees of freedom using density functional theory (DFT). The dynamics of electronic degrees of freedom is propagated by the reduced density matrix with Redfield equation of motion. Oscillator strengths are used to compute radiative relaxation and to generate time resolved photoluminescence (PL) spectrum. Analysis of the simulated nonradiative decay shows that high-energy photoexcitation relaxes to the band gap edge on the order of 1 ps. We also simulate time-resolved emission spectra of the <211> SiNW that reveals optical emissions above the optical band gap. These emission features are attributed to the interband transitions. The results of this study can be useful for the material choice for optoelectronic applications.

Despite the improvements seen in efficiency of GaAs cells over the years, there remains room for improvement for it to approach the theoretical single junction limit posited by Shockley and Quiesser decades ago. One of the more pursued options is the growth of quantum wells within the structure of GaAs to enhance its photon absorption below its bandgap. Multiple Quantum Wells (MQW) have been an ongoing topic of research and discussion for the scientific community with structures like InGaAs/GaAs and InGaP/GaAs quantum wells producing promising results that could potentially improve overall energy conversion. Here, we used WEIN2K, a commercial density functional theory package, to study the ternary compound Ga1-xTlxAs and determine its electronic properties. Using these results combined with experimental confirmation we extend these properties to simulate its application to form a MQW GaAs/ Ga1-xTlxAs solar cell. Ga1-xTlxAs is a tunable ternary compound, with its bandgap being strongly dependent on the concentration of Tl present. Concentrations of Tl as low as 7% can reduce the bandgap of Ga1-xTlxAs to roughly 1.30 eV from GaAs’s 1.45 eV at room temperature with as little as a 1.7% increase in lattice constant. The change in bandgap, accompanied by the relatively small change in lattice constant makes Ga1-xTlxAs a strong candidate for a MQW cell with little to no strain balancing required within the structure to minimize unwanted defects that impede charge collection within the device. Our GaAs photodiode with TlGaAs MQWs shows an expanded absorption band and improved conversion efficiency over the standard GaAs photovoltaic cell with dilute concentrations of Tl incorporated into the compound.