Engineering topics

Klepov, Vladislav

Publications and source records attributed to Klepov, Vladislav.

3 records

DOE OSTI2024

Structural Evolution and Photoluminescence Quenching across the FASnI 3– x Br x ( x = 0–3) Perovskites

One of the primary methods for band gap tuning in metal halide perovskites has been halide (I/Br) mixing. Despite widespread usage of this type of chemical substitution in perovskite photovoltaics, there is still little understanding of the structural impacts of halide alloying, with the assumption being the formation of ideal solid solutions. The FASnI 3–x Br x (x = 0–3) family of compounds provides the first example where the assumption breaks down, as the composition space is broken into two unique regimes (x = 0–2.9; x = 2.9–3) based on their average structure with the former having a 3D and the latter having an extended 3D (pseudo 0D) structure. Pair distribution function (PDF) analyses further suggest a dynamic 5s 2 lone pair expression resulting in increasing levels of off-centering of the central Sn as the Br concentration is increased. These antiferroelectric distortions indicate that even the x = 0–2.9 phase space behaves as a nonideal solid-solution on a more local scale. Solid-state NMR confirms the difference in local structure yielding greater insight into the chemical nature and local distributions of the FA + cation. In contrast to the FAPbI 3–x Br x series, a drastic photoluminescence (PL) quenching is observed with x ≥ 1.9 compounds having no observable PL. In conclusion, our detailed studies attribute this quenching to structural transitions induced by the distortions of the [SnBr 6 ] octahedra in response to stereochemically expressed lone pairs of electrons. This is confirmed through density functional theory, having a direct impact on the electronic structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Investigation of defects in melt and solution grown perovskite CsPbBr 3 single crystals

Recently, there has been considerable interest in x-ray and gamma ray detectors with large volume and high energy resolution that operate at room temperature. To improve detector energy resolution, the carrier mobility-lifetime product needs to be increased, and the electronic trap state concentration needs to be minimized. Defect concentrations in the part per billion range can alter the charge transport and carrier recombination lifetime. In this work, thermally stimulated current spectroscopy measurements were systematically carried out in bulk halide perovskite single crystals of CsPbBr 3 over a temperature range of 80–320 K. The origins and trap parameters of CsPbBr 3 crystals from the solution growth and melt growth procedures were determined and compared. Trap concentrations were ranged from 1 × 10 11 to 1 × 10 16 cm –3 . Appreciable detector performance was observed for CsPbBr3 crystals with trap concentrations less than 1 × 10 14 cm –3 . The comparison of spectral responses of crystal samples grown using two different methods shows that, after purification, solution-grown crystals are comparable to melt-grown crystals in terms of low defect concentration and improved detector performance. Finally, for an improved mobility-lifetime product and enhanced spectral response to high energy radiation from fissile materials, trap states in either type of a crystal ingot must be reduced closer to 10 11 cm –3 .

36 MATERIALS SCIENCE↗

DOE OSTI2022

Gamma-ray Spectra from a 3x3 CsPbBr 3 Array

CsPbBr 3 is a promising semiconductor material for X- and γ-ray detection at room temperature due to a wide bandgap of 2.3eV, high stopping power, and relatively high mobility-lifetime products of electrons and holes, and the capability of growing large crystals. In this paper we report on fabrication and testing of a 3.8 mm thick, 3 X 3 array with 1.2 mm pitch. Raw 137 Cs spectra were acquired with applied bias of 400 V, 500 V, and 600 V. Energy resolution of between 2 and 3 % FWHM at 662 keV was obtained from most pixels without any correction at room temperature. After 15 days under continuous bias at 600 V, no polarization effects were observed.

36 MATERIALS SCIENCE↗