Ultrafast Study of Exciton Transfer in Sb(III)-Doped Two-Dimensional [NH₃(CH₂)₄NH₃]CdBr₄ Perovskite

Abstract

Antimony-based metal halide hybrids have attracted enormous attention due to the stereoactive 5s2 electron pair that drives intense triplet broadband emission. However, energy/charge transfer has been rarely achieved for Sb3+-doped materials. Herein, Sb3+ ions are homogeneously doped into 2D [NH3(CH2)4NH3]­CdBr4 perovskite (Cd-PVK) using a wet-chemical method. Compared to the weak singlet exciton emission of Cd-PVK at 380 nm, 0.01% Sb3+-doped Cd-PVK exhibits intense triplet emission located at 640 nm with a near-unity quantum yield. Further increasing the doping concentration of Sb3+ completely quenches singlet exciton emission of Cd-PVK, concurrently with enhanced Sb3+ triplet emission. Delayed luminescence and femtosecond-transient absorption studies suggest that Sb3+ emission originates from exciton transfer (ET) from Cd-PVK host to Sb3+ dopant, while such ET cannot occur with Pb2+-doped Cd-PVK because of the mismatch of energy levels. In addition, density function theory calculations indicate that the introduced Sb3+ likely replace the Cd2+ ions along with the deprotonation of butanediammonium for charge balance, instead of generating Cd2+ vacancies. This work provides a deeper understanding of the ET of Sb3+-doped Cd-PVK and suggests an effective strategy to achieve efficient triplet Sb3+ emission beyond 0D Cl-based hybrids.

Cyan Emission in Two-Dimensional Colloidal Cs2CdCl4:Sb3+Ruddlesden–Popper Phase Nanoplatelets

“…The photoluminescence excitation (PLE) spectrum consists of two different bands around 290 and 340 nm (Figure a). Typically, Sb 3+ possesses an allowed 1 S 0 – 1 P 1 and a partially allowed 1 S 0 – 3 P 1 transition named C and A bands, respectively, − which reportedly split into a triplet and a doublet due to a pseudo-Jahn–Teller effect. ,, The PLE spectrum of Cs 2 CdCl 4 :Sb 3+ follows this predicted behavior, with the A band evidenced by the features at ∼350 and 333 nm and the C band evidenced by the signals at 293 and ∼280 nm (Figure S9), mostly resembling the bulk material . The third peak of the triplet, which is expected to be around 270 nm, might be partially shadowed by other features.…”

Antimony and bismuth cooperation to enhance the broad yellow photoluminescence of zero-dimensional hybrid halide

“…15 In addition, Luo's group reported that upon doping Sb 3+ into a 2D-structured [NH 3 (CH 2 ) 4 NH 3 ]CdBr 4 perovskite, a PLQY of close to 1 was achieved. 16 Other studies have shown that Sb 3+ is an excellent luminescent center. 11,17 Therefore, further studies on the relationship between the emission intensity and the structural distortion of Sb 3+ -doped OIMHs are required.…”

Controlled Modulation of the Structure and Luminescence Properties of Zero-Dimensional Manganese Halide Hybrids through Structure-Directing Metal-Ion (Cd2+ and Zn2+) Centers

“…In order to devise a rational strategy to demonstrate synthetic control over modulation of the structure and luminescence properties of 0D Mn­(II) halide hybrids, we turned our attention to d 10 transition metal halide-based hybrids as a potential host material. Recently, many have reported on 0D Cd­(II) and Zn­(II) halide hybrids that show broadband emission arising due to the significant emission contribution by the organic ligand. ,, Zn­(II) halide-based 0D hybrids typically crystallize with the [ZnX 4 ] 2– tetrahedral unit as a building block. ,,, Noteworthy, Cd­(II) halide-based 0D hybrids can show the [CdX 6 ] 4– octahedral − or [CdX 4 ] 2– tetrahedral − coordination environment depending upon the nature of the organic ligand and the halide type. , Such transition metal halide-based 0D hybrids are known to adopt a variety of structures that can potentially be exploited as a host material/starting framework. These host materials can further be doped with Mn­(II) ions to exert synthetic control on modulating the local structure and emissive properties of 0D Mn­(II) halide hybrids.…”