Exploring Cs2AgInxBi1−xCl6 double perovskites for optoelectronics: insights from theoretical and photophysical approaches

Abstract

Lead-free halide double perovskites (HDPs) have become attractive materials for optoelectronic applications owing to their nontoxicity, structural stability, and germane photoelectric properties. In this work, we report the synthesis of high-quality In-alloyed Cs₂AgIn_xBi_1−xCl₆ nanocrystals (NCs) using the antisolvent recrystallization method and comprehensively investigate the effects of In alloying on the structural, morphological, optoelectronic, and temperature-dependent photoluminescence (TDPL) properties using the state-of-the-art experimental and computational tools. Both XRD and Raman spectroscopy analyses confirmed the synthesis of highly crystalline Cs₂AgIn_xBi_1−xCl₆ materials, which exhibited cubic morphology, as confirmed by TEM analysis. Room-temperature photoluminescence (PL) measurements revealed a drastic increase in the intensity above 75% In concentration with dual emission, whereas the time-resolved PL (TR-PL) results show an increase in the average lifetime values with an increase in In content, suggesting that the materials have excellent optical properties and hence are suitable candidates for optoelectronics. The TDPL measurements revealed the smallest Huang–Rhys factor (18.6) for the Cs₂AgIn_xBi_(1−x)Cl₆ (x = 0.9) sample, indicating weak exciton–phonon coupling in this composition. When deployed in the fabrication of a photodetector device, the Cs₂AgIn_xBi_(1−x)Cl₆ (x = 0.9) sample exhibited significantly enhanced photoresponsivity and a faster response time, confirming its potential for photodetector applications. Complementary DFT calculations showed that In alloying modifies the band structure of Cs₂AgIn_xBi_(1−x)Cl₆. Our results provide valuable insights for designing multifunctional Cs₂AgIn_xBi_(1−x)Cl₆-based materials for next-generation energy and optoelectronic devices.