ABSTRACT
Two-dimensional (2D) hybrid organic-inorganic perovskite (HOIP) crystals show promise as scintillating materials for wide-energy radiation detection, outperforming their three-dimensional counterparts. In this study, we synthesized single crystals of (PEA2-xBZAx)PbBr4 (x ranging from 0.1 to 2), utilizing phenethylammonium (C6H5CH2CH2NH3+) and benzylammonium (C6H5CH2NH3+) cations. These materials exhibit favorable optical and scintillation properties, rendering them suitable for high light yield (LY) and fast-response scintillators. Our investigation, employing various techniques such as X-ray diffraction (XRD), photoluminescence (PL), time-resolved (TR) PL, Raman spectroscopy, radioluminescence (RL), thermoluminescence (TL), and scintillation measurements, unveiled lattice strain induced by dual-organic cations in powder X-ray diffraction. Density functional theory analysis demonstrated a maximal 0.13 eV increase in the band gap with the addition of BZA cation addition. Notably, the largest Stokes shift of 0.06 eV was observed in (BZA)2PbBr4. The dual-organic cation crystals displayed >80% fast component scintillation decay time, which is advantageous for the scintillating process. Furthermore, we observed a dual-organic cations-induced enhancement of electron-hole transfer efficiency by up to 60%, with a contribution of >70% to the fast component of scintillation decay. The crystal with the lowest BZA concentration, (PEA1.9BZA0.1)PbBr4, demonstrated the highest LYs of 14.9 ± 1.5 ph/keV at room temperature. Despite a 55-70% decrease in LY for BZA concentrations >5%, simultaneous reductions in scintillation decay time (12-32%) may work for time-of-flight positron emission tomography and photon-counting computed tomography. Our work underscores the crucial role of dual-organic cations in advancing our understanding of 2D-HOIP crystals for materials science and radiation detection applications.
ABSTRACT
The remarkable brightness and rapid scintillation observed in perovskite single crystals (SCs) become even more striking when they are operated at cryogenic temperatures. In this study, we present advancements in enhancing the scintillation properties of methylammonium lead bromide (MAPbBr3) SCs by optimizing the synthesis process. We successfully synthesized millimeter-sized MAPbBr3 SCs with bright green luminescence under UV light. However, both MAPbBr3 (Control-1M and THF-0.4M) SCs display notable radioluminescence exclusively at low temperatures due to their phase transitions. Notably, the THF-0.4M SCs exhibit a remarkable improvement in radioluminescence light yield, surpassing Control-1M SCs more than 2-fold. Further, THF-0.4M SCs demonstrate an ultrafast decay component of 0.52 ns (82.2%) and a slower component of 1.80 ns (17.8%), contributing to a rapid scintillation response at low temperatures. Therefore, the amalgamation of ultrafast decay components and improved radioluminescence light yield equips THF-0.4M SCs to emerge as a top choice for perovskite scintillators for X-ray timing applications.
ABSTRACT
Two-dimensional hybrid-organic-inorganic perovskite (2D-HOIP) lead bromide perovskite crystals have demonstrated great potential as scintillators with high light yields and fast decay times while also being low cost with solution-processable materials for wide energy radiation detection. Ion doping has been also shown to be a very promising avenue for improvements of the scintillation properties of 2D-HOIP crystals. In this paper, we discuss the effect of rubidium (Rb) doping on two previously reported 2D-HOIP single crystals, BA2PbBr4 and PEA2PbBr4. We observe that doping the perovskite crystals with Rb ions leads to an expansion of the crystal lattices of the materials, which also leads to narrowing of band gaps down to 84% of the pure compounds. Rb doping of BA2PbBr4 and PEA2PbBr4 shows a broadening in the photoluminescence and scintillation emissions of both perovskite crystals. Rb doping also leads to faster γ-ray scintillation decay times, as fast as 4.4 ns, with average decay time decreases of 15% and 8% for Rb-doped BA2PbBr4 and PEA2PbBr4, respectively, compared to those of undoped crystals. The inclusion of Rb ions also leads to a slightly longer afterglow, with residual scintillation still being below 1% after 5 s at 10 K, for both undoped and Rb-doped perovskite crystals. The light yield of both perovskites is significantly increased by Rb doping with improvements of 58% and 25% for BA2PbBr4 and PEA2PbBr4, respectively. This work shows that Rb doping leads to a significant enhancement of the 2D-HOIP crystal performance, which is of particular significance for high light yield and fast timing applications, such as photon counting or positron emission tomography.
