Semiconducting to metallic transition with outstanding optoelectronic properties of CsSnCl3 perovskite under pressure

Abstract

inorganic non-toxic metal halide perovskites have taken the dominant place in commercialization of the optoelectronic devices. The first principles simulation has been executed with the help of density functional theory to investigate the structural, optical, electronic and mechanical properties of nontoxic csSncl 3 metal halide under various hydrostatic pressures up to 40 GPa. The analysis of optical functions displays that the absorption edge of CsSnCl 3 perovskite is shifted remarkably toward the low energy region (red shift) with enhanced pressure. The absorptivity, conductivity and the value of dielectric constant also increases with the applied pressure. the investigation of mechanical properties reveals csSncl 3 perovskite is mechanically stable as well as highly ductile and the ductility is increased with increasing pressure. the investigation of electronic properties shows semiconducting to metallic transition occurs in csSncl 3 under elevated pressure. The Physics behind all these changes under hydrostatic pressure has been analyzed and explained in details within the available Scientific theory. In recent years, metal halide perovskite materials of the renowned formula AMX 3 (where, A = a cation, M = a metal ion, and X = a halogen anion) have attracted immense attention of the researchers due to their noticeable solar cell potency with extraordinary optoelectronic characteristics including wide range of absorption spectrum, enhanced optical absorption, tunable band gap, extended charge diffusion, high charge carrier mobility and low carrier effective masses 1,2. The researchers established the application of these semiconducting materials are also wide in the field of electronic devices such as LEDs (Light Emitting Diodes), photodetector, and the devices which are extensively used for solar to fuel energy conversion 3-6. Moreover, these metal halide perovskites are cheap and available in a large quantities on the earth. Consequently, these halide perovskite semiconductors would be more suitable and beneficial in solar cells application compared to the Si-based photovoltaic (PV) technology 1. However, most of the perovskite halides with excellent properties comprise of lead (Pb) which is harmful for the environment 7-9. Due to the environment contamination and worldwide energy crisis, clean and sustainable energy sources have taken great attention. Therefore, a large number of experimental and theoretical works have been performed by replacing Pb with a suitable metal cation in the last few years 10-13. The study of mechanical properties reported by Roknuzzaman et al. 10 demonstrates that the non-toxic CsSnCl 3 perovskite has ductility entity but the halide perovskite semiconductor shows large band gap value (2.8 eV) 11. As a result, the CsSnCl 3 shows medium optical absorption and not appropriate for remarkable efficiency solar cells application. For this purpose, we have reported metal-doped CsSnCl 3 to find a better Pb-free perovskite semiconductor for high potency solar cell application in previous ...

Dimension-Dependent Bandgap Narrowing and Metallization in Lead-Free Halide Perovskite Cs3Bi2X9 (X = I, Br, and Cl) under High Pressure

“…The calculated bandgaps at a pressure of 0 GPa of the Cs 3 Bi 2 I 9 , Cs 3 Bi 2 Br 9 , and Cs 3 Bi 2 Cl 9 are 2.38, 2.60, and 3.08 eV, respectively. The scissor value approach was used to establish the band structure of the Cs 3 Bi 2 X 9 perovskites in order to obtain the accurate value for the Cs 3 Bi 2 X 9 perovskites when they reached the optimal bandgap of the Shockley-Queisser theory and the transition from semiconductor to metal; this methodology overcame the limitations of the GGA-PBE calculation method and has already been applied in the study of the photoelectric properties of the CsSnCl 3 perovskite at HPs [40]. Many experimental studies have been conducted regarding the bandgaps of the Cs 3 Bi 2 I 9 , Cs 3 Bi 2 Br 9 , and Cs 3 Bi 2 Cl 9 perovskites.…”

“…The spin-orbit coupling is not considered due to the high computational cost. Previous studies have shown that higher levels of calculation (including the spin-orbit coupling, the GW method, or hybrid functionals) obtain more accurate bandgaps; However, they induce little change in the band structure of the heavy-metal halide perovskites [40].…”

Lattice Doping of Lanthanide Ions in Cs 2 AgInCl 6 Nanocrystals Enabling Tunable Photoluminescence

“…At this time, leadfree halide perovskites were discovered with lower toxicity and higher stability and have attracted great interests [5][6][7][8][9]. There are many choices for the replacement of Pb 2+ by other benign metal ions, including the incorporation of isovalent Sn 2+ ions [10] and substitution of trivalent Bi 3+ or Sb 3+ ions forming the similar composition as Cs 3 Bi 2 Cl 9 [11][12][13]. However, those materials are either limited by stability challenges [14] or with lower electronic mobility because of the lower symmetry nonperovskite structure [15].…”

Ultra-violet to visible band gap engineering of cubic halide KCaCl3 perovskite under pressure for optoelectronic applications: insights from DFT

“…35 The rst-principle calculations were successfully implemented to cubic perovskite compounds to analyze different physical properties. [35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54] The substitution of element, 35,36 doping, 10,37,38 or applying hydrostatic pressure [39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] can change the physical properties of cubic perovskites.…”

“…[39][40][41][42][43][44] The band gap of halide cubic perovskites CsBX 3 (B ¼ Sn, Ge; X¼ Cl, Br) was decreased to zero by applying external pressure, resulting in a semiconductor to metallic transition. [45][46][47][48][49] The rst-principle investigations under hydrostatic pressure have also been done for Ca based cubic alkali halide perovskites KCaX 3 (X ¼ F, Cl) 50,51 and ACaF 3 (A ¼ Rb, Cs). 52,53 The band gap of KCaF 3 and RbCaF 3 were shied from indirect to direct by applying hydrostatic pressure of 13.5 and $14 GPa, respectively.…”