The formation of solid-solutions of iodide, bromide, and chloride provides the means to control the structure, band gap, and stability of hybrid halide perovskite semiconductors for photovoltaic ...applications. We report a computational investigation of the CH3NH3PbI3/CH3NH3PbBr3 alloy from density functional theory with a thermodynamic analysis performed within the generalized quasi-chemical approximation. We construct the phase diagram and identify a large miscibility gap, with a critical temperature of 343 K. The observed photoinstability in some mixed-halide solar cells is explained by the thermodynamics of alloy formation, where an initially homogeneous solution is subject to spinodal decomposition with I and Br-rich phases, which is further complicated by a wide metastable region defined by the binodal line.
While the theory of imperfections in solids is firmly established, procedures for first-principles calculations of defect quantities continue to evolve. A plethora of ad hoc correction schemes is ...being replaced by sophisticated self-consistent procedures that will enable more quantitative predictions of the formation energies of defect species and their spectroscopic signatures.
Here we summarize recent progress in machine learning for the chemical sciences. We outline machine-learning techniques that are suitable for addressing research questions in this domain, as well as ...future directions for the field. We envisage a future in which the design, synthesis, characterization and application of molecules and materials is accelerated by artificial intelligence.
We report a model describing the molecular orientation disorder in CH3NH3PbI3, solving a classical Hamiltonian parametrised with electronic structure calculations, with the nature of the motions ...informed by ab initio molecular dynamics. We investigate the temperature and static electric field dependence of the equilibrium ferroelectric (molecular) domain structure and resulting polarisability. A rich domain structure of twinned molecular dipoles is observed, strongly varying as a function of temperature and applied electric field. We propose that the internal electrical fields associated with microscopic polarisation domains contribute to hysteretic anomalies in the current-voltage response of hybrid organic-inorganic perovskite solar cells due to variations in electron-hole recombination in the bulk.
The various phases of tin sulfide have been studied as semiconductors since the 1960s and are now being investigated as potential earth-abundant photovoltaic and photocatalytic materials. Of ...particular note is the recent isolation of zincblende SnS in particles and thin-films. Herein, first-principles calculations are employed to better understand this novel geometry and its place within the tin sulfide multiphasic system. We report the enthalpies of formation for the known phases of SnS, SnS2, and Sn2S3, with good agreement between theory and experiment for the ground-state structures of each. While theoretical X-ray diffraction patterns do agree with the assignment of the zincblende phase demonstrated in the literature, the structure is not stable close to the lattice parameters observed experimentally, exhibiting an unfeasibly large pressure and a formation enthalpy much higher than any other phase. Ab initio molecular dynamics simulations reveal spontaneous degradation to an amorphous phase much lower in energy, as Sn(II) is inherently unstable in a regular tetrahedral environment. We conclude that the known rocksalt phase of SnS has been mis-assigned as zincblende in the recent literature.
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