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Physical Properties of Candidate X-ray Detector Material Rb 4 Ag 2 BiBr 9

Recently, metal halide perovskites have emerged as promising semiconductor candidates for sensitive X-ray photon detection due to their suitable band gap energies, excellent charge transport properties, and low material cost afforded by their low-temperature solution-processing preparation. Furthermore, we report an improved methodology for single crystal growth and thermal and electrical properties of a two-dimensional (2D) layered halide material Rb 4 Ag 2 BiBr 9 , which has been identified as a potential candidate for X-ray radiation detection applications. The measured heat capacity for Rb 4 Ag 2 BiBr 9 implies that there are no structural phase transitions upon cooling. Temperature dependence of thermal transport measurements further suggests remarkably low thermal conductivities of Rb 4 Ag 2 BiBr 9 that are comparable to the lowest reported in literature. The bulk crystal resistivity is determined to be 2.59 × 10 9 Ω·cm from the current–voltage (I–V) curve. Density of trap states is estimated to be ~10 10 cm –3 using the space-charge-limited-current measurements. The fabricated Rb 4 Ag 2 BiBr 9 -based X-ray detector shows good operational stability with no apparent current drift, which may be ascribed to the 2D crystal structure of Rb 4 Ag 2 BiBr 9 . Finally, by varying the X-ray tube current to change the corresponding dose rate, the Rb4Ag2BiBr9 X-ray detector sensitivity is determined to be 222.03 μC Gy –1 cm –2 (at an electric field of E = 24 V/mm).

36 MATERIALS SCIENCE↗

Materials Data on BiBr by Materials Project

BiBiBr2 crystallizes in the monoclinic C2/m space group. The structure is one-dimensional and consists of eight bismuth molecules and eight BiBr2 ribbons oriented in the (0, 1, 0) direction. In each BiBr2 ribbon, Bi1+ is bonded in a square co-planar geometry to four Br1- atoms. There are two shorter (2.94 Å) and two longer (2.95 Å) Bi–Br bond lengths. There are two inequivalent Br1- sites. In the first Br1- site, Br1- is bonded in an L-shaped geometry to two equivalent Bi1+ atoms. In the second Br1- site, Br1- is bonded in an L-shaped geometry to two equivalent Bi1+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ga(BiBr)4 by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗

Crystal structure and luminescence properties of lead-free metal halides (C 6 H 5 CH 2 NH 3 ) 3 MBr 6 (M = Bi and Sb)

Organic–inorganic hybrid metal halides have received extensive attention owing to their versatile structures and optoelectronic properties. Herein, we report two lead-free metal halides, (PMA) 3 BiBr 6 and (PMA) 3 SbBr 6 [PMA + : (C 6 H 5 CH 2 NH 3 ) + , as the abbreviation of phenylmethylammonium], which possess iso-structural zero-dimensional structures and crystallize in the monoclinic space group P2 1 /c. (PMA) 3 BiBr 6 and (PMA) 3 SbBr 6 exhibit optical band gaps of ~3.50 and 3.40 eV, respectively, and density functional theory calculations reveal their indirect bandgap behaviors. Upon 350 and 425 nm excitation, (PMA) 3 BiBr 6 and (PMA) 3 SbBr 6 exhibit broadband emission peaking at 510 nm and 625 nm with wide full-widths at half-maximum of ~153 and 175 nm, respectively. The emission mechanism of the metal halides is attributed to self-trapped exciton emission. The relationship between the crystal structure and luminescence intensity is also discussed. Lastly, both metal halides have high decomposition temperatures and are stable for long-term storage under ambient conditions, demonstrating their potential for optoelectronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Octahedral Distortion and Excitonic Behavior of Cs 3 Bi 2 Br 9 Halide Perovskite at Low Temperature

The metal halide ionic octahedron, represented as [MX 6 ] $n$- (M = metal cation, X = halide anion), serves as the basic structural unit in halide perovskites and plays a crucial role in determining their optoelectronic and chemical properties. Thus, it is possible to correlate the responses of metal halide perovskites to various environmental stimuli with the dynamic behaviors of the [MX 6 ] $n$- octahedra. In this study, with the temperature-dependent single-crystal X ray diffraction (SCXRD) measurements on Cs 3 Bi 2 Br 9 2D halide perovskites, we can identify two classes of distortions through the lowering of temperature: intraoctahedral distortion, which is the off-centering of Bi 3+ cation within a [BiBr 6 ] 3– octahedron due to the Bi 3+ 6s 2 lone pair electrons, and interoctahedral distortion, which is the collective misalignments among the [BiBr 6 ] 3– building blocks. Free exciton (FE) and self-trapped exciton (STE) models are used to study the relationship between the distortion of octahedra in Cs 3 Bi 2 Br 9 and the corresponding changes in its optoelectronic properties, which transform from dominating blue emission above 100 K to red emission at 4 K. In conclusion, this work provides new insights into the excitonic behaviors of perovskites and suggests a possibility that we can design and rationalize the optical properties of halide perovskites by regulating the environmental stimuli based on the knowledge of behaviors of the individual [MX 6 ] $n$- building blocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spin-resolved topology and partial axion angles in three-dimensional insulators

Abstract Symmetry-protected topological crystalline insulators (TCIs) have primarily been characterized by their gapless boundary states. However, in time-reversal- ( $${{{{{{{\mathcal{T}}}}}}}}$$ T -) invariant (helical) 3D TCIs—termed higher-order TCIs (HOTIs)—the boundary signatures can manifest as a sample-dependent network of 1D hinge states. We here introduce nested spin-resolved Wilson loops and layer constructions as tools to characterize the intrinsic bulk topological properties of spinful 3D insulators. We discover that helical HOTIs realize one of three spin-resolved phases with distinct responses that are quantitatively robust to large deformations of the bulk spin-orbital texture: 3D quantum spin Hall insulators (QSHIs), “spin-Weyl” semimetals, and $${{{{{{{\mathcal{T}}}}}}}}$$ T -doubled axion insulator (T-DAXI) states with nontrivial partial axion angles indicative of a 3D spin-magnetoelectric bulk response and half-quantized 2D TI surface states originating from a partial parity anomaly. Using ab-initio calculations, we demonstrate that β -MoTe 2 realizes a spin-Weyl state and that α -BiBr hosts both 3D QSHI and T-DAXI regimes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗