All-Inorganic Lead-Free Heterometallic Cs4MnBi2Cl12 Perovskite Single Crystal with Highly Efficient Orange Emission

Abstract

A luminescent all-inorganic manganese-bismuth heterometallic Cs 4 MnBi 2 Cl 12 perovskite single crystal has been synthesized with a [BiCl 6 ] 3À -[MnCl 6 ] 4À -[BiCl 6 ] 3À triple-layered two-dimensional structure. Benefit from the effective energy transfer from [BiCl 6 ] 3À octahedron donor to luminescent [MnCl 6 ] 4À acceptor, Cs 4 MnBi 2 Cl 12 shows a photoluminescence quantum yield (PLQY) of up to 25.7% (~610 nm), 51-fold higher than the Bi unalloyed CsMnCl 3 $2H 2 O counterpart. Suggested by the theoretical calculations, Bi and Mn exhibit hybridization in conduction and valence band, which further results in a favorable low activation energy for exciton transfer (~23 meV). By virtue of all-inorganic chemical composition, Cs 4 MnBi 2 Cl 12 exhibits impressive stability toward moisture, light, and heat. Furthermore, Cs 4 MnBi 2 Cl 12 features strong soft X-ray attenuation and bright radiative luminescence under X-ray excitation, which pave a way for its application in medical flat-panel X-ray digital radiography. This work presents a new avenue toward fabrication of function-directed material with tailored photoelectric properties.

Efficient Luminescent Halide Quadruple‐Perovskite Nanocrystals via Trap‐Engineering for Highly Sensitive Photodetectors

“…[ 3 ] Subsequently, A 3 M ‘ 2 X 9 ‐type layer perovskite, A 2 MM ‘ X 6 ‐type, and A 2 BX 6 ‐type double perovskite (where A denotes alkali‐metal ions; M, M‘ and B denotes monovalent‐, trivalent‐, and tetravalent‐ cations; X denotes halogen ions) with high stability have been reported. [ 9–20 ] However, optoelectronic devices based on these lead‐free perovskite NCs have made limited progress. Such as, photodetectors based on lead‐free perovskite NCs exhibited low responsivity (typically <1 A W −1 ).…”

Lead‐Free Halide Double Perovskites: Structure, Luminescence, and Applications

“…Vacancy‐ordered layered HDPs are suitable hosts for bivalent substitution, which covers the shortage for limited bivalent doping in HDPs, such as Cu 2+ , Mn 2+ , and Cd 2+ . [ 119,125–127 ] Recently, Cai et al synthesized Cs 4 Cu x Ag 2−2 x Sb 2 Cl 12 (0 ≤ x ≤ 1) NCs with a uniform sphere‐like shape for the first time. [ 123 ] The vacancy‐ordered HDP NCs have electronic band structural transition from a wide indirect bandgap to a narrow direct bandgap with increased Cu content.…”

“…[ 137,138 ] Bi‐based metal halides have strong light absorption, benefiting from the 6s 2 to 6s 1 p 1 transition in Bi 3+ . [ 127 ] It is worth expecting Bi‐based HDPs to possess a direct bandgap and large absorption coefficient. Cs 2 NaBiI 6 thin films converted from Cs 3 Bi 2 I 9 · x Na 2 S have a direct bandgap of ≈1.81 eV.…”

“…[ 185 ] Layered quadruple HDP Cs 4 MnBi 2 Cl 12 SCs show enhanced orange–red emission of Mn 2+ with a PL QY up to 25.7% (Figure 12 d) benefiting from efficient energy transfer from adjacent BiCl 6 3− to the MnCl 6 4− octahedral in which the activation energy for this favorable energy transfer process is as low as 23 meV. [ 127 ] Incorporating Cd 2+ into Cs 4 MnBi 2 Cl 12 SCs further enhances the PL QY to 56.6%. Cs 4 Cd 1‐ x Mn x Bi 2 Cl 12 SCs are grown using hydrothermal synthesis routes via slow cooling the saturated HCl and H 3 PO 2 solution.…”

Mn2+‐Doped Metal Halide Perovskites: Structure, Photoluminescence, and Application

“…Therefore, in this article, these low‐dimensional systems are included within the broad category of metal halide perovskites. The structural diversity makes them widely applied for diverse optoelectronic applications including solar cells, [ 19–25 ] light‐emitting diodes (LEDs), [ 26–32 ] photodetectors, [ 33–39 ] display, [ 40–42 ] and lasers. [ 43–45 ] Notably, the power conversion efficiency in solar cells has been improved from 3.8% to above 25% by using the metal halides in the short period of ten years, which is equivalent to the commercialized crystalline silicon solar cell.…”