Chlorine-additive-promoted incorporation of Mn2+ dopants into CsPbCl3 perovskite nanocrystals

Su Zhou; Yiwen Zhu; Jiasong Zhong; Feifan Tian; Hai Huang; Jiangkun Chen; Daqin Chen

doi:10.1039/c9nr04663a

Chlorine-additive-promoted incorporation of Mn²⁺ dopants into CsPbCl₃ perovskite nanocrystals

Nanoscale. 2019 Jul 14;11(26):12465-12470. doi: 10.1039/c9nr04663a. Epub 2019 Jun 20.

Authors

Su Zhou¹, Yiwen Zhu¹, Jiasong Zhong¹, Feifan Tian², Hai Huang², Jiangkun Chen², Daqin Chen³

Affiliations

¹ College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou, Zhejiang 310018, P. R. China. jiasongzhong@hdu.edu.cn dqchen@hdu.edu.cn.
² College of Physics and Energy, Fujian Normal University, Fuzhou, Fujian 350117, China. dqchen@fjnu.edu.cn and Fujian Provincial Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Xiamen, Fujian 361005, China.
³ College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou, Zhejiang 310018, P. R. China. jiasongzhong@hdu.edu.cn dqchen@hdu.edu.cn and College of Physics and Energy, Fujian Normal University, Fuzhou, Fujian 350117, China. dqchen@fjnu.edu.cn and Fujian Provincial Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Xiamen, Fujian 361005, China.

PMID: 31219129
DOI: 10.1039/c9nr04663a

Abstract

Effective Mn²⁺ doping in a CsPbCl₃ lattice utilizing manganese acetate and trimethylchlorosilane is achieved via a one-pot hot-injection synthesis method. This strongly contrasts to the previous case, where only the MnCl₂ precursor was suitable for Mn²⁺ doping by considering the matching of bond dissociation energies between Mn-Cl and Pb-Cl. The Mn doping concentration and luminescence quantum yield are highly dependent on trimethylchlorosilane content. A new doping mechanism is proposed, where the incorporation of Mn²⁺ into CsPbCl₃ is achieved via directly inserting [MnCl₆]^4- octahedra into the perovskite structure during the nucleation/growth processes instead of Mn-to-Pb cation exchange. Accordingly, increasing Cl^- content in the reaction solution indeed promotes the doping of other divalent transition metal ions such as Ni²⁺, Cu²⁺ and Zn²⁺ in CsPbCl₃ and improve the quantum yield of CsPbCl₃ nanocrystals up to ∼20% compared to the undoped counterparts (∼1%).