物理化学学报 >> 2023, Vol. 39 >> Issue (1): 2209007.doi: 10.3866/PKU.WHXB202209007

论文 上一篇    

新型(4-HBA)SbX5∙H2O类钙钛矿单晶及其卤素结构对发光特性的调控

庄必浩1,2, 靳子骢1,2, 田德华3,4, 朱遂意1,2, 曾琳茜1,2, 范建东1,2,4,*(), 娄在祝3,4,*(), 李闻哲1,2,*()   

  1. 1 暨南大学, 信息科学与技术学院电子科学与工程系, 新能源技术研究院, 广州 510632
    2 暨南大学, 新型半导体与器件广东省高等学校重点实验室, 广州 510632
    3 暨南大学, 纳米光子学研究院, 广州 511443
    4 山东大学, 晶体材料国家重点实验室, 济南 250100
  • 收稿日期:2022-09-05 录用日期:2022-09-20 发布日期:2022-09-29
  • 通讯作者: 范建东,娄在祝,李闻哲 E-mail:jdfan@jnu.edu.cn;zzlou@jnu.edu.cn;li_wz16@jnu.edu.cn
  • 基金资助:
    国家自然科学基金(22075103);国家自然科学基金(22175076);广东省基础与应用基础研究基金杰出青年项目(2019B151502030);广东省基础与应用基础研究基金杰出青年项目(2018B030306004);广东省自然科学基金(2022A1515010489);广州市科技计划项目(202002030159);中央高校基础研究基金(21621112);山东大学晶体材料国家重点实验室经费(KF21-03);广东省青年珠江学者(2017GC010424)

Halogen Regulation for Enhanced Luminescence in Emerging (4-HBA)SbX5∙H2O Perovskite-Like Single Crystals

Bihao Zhuang1,2, Zicong Jin1,2, Dehua Tian3,4, Suiyi Zhu1,2, Linqian Zeng1,2, Jiandong Fan1,2,4,*(), Zaizhu Lou3,4,*(), Wenzhe Li1,2,*()   

  1. 1 Institute of New Energy Technology, Department of Electronic Science and Engineering, College of Information Science and Technology, Jinan University, Guangzhou 510632, China
    2 Key Laboratory of New Semiconductors and Devices of Guangdong Higher Education Institutes, Jinan University, Guangzhou 510632, China
    3 Institute of Nanophotonics, Jinan University, Guangzhou 511443, China
    4 State Key Laboratory for Crystal Materials, Shandong University, Ji'nan 250100, China
  • Received:2022-09-05 Accepted:2022-09-20 Published:2022-09-29
  • Contact: Jiandong Fan,Zaizhu Lou,Wenzhe Li E-mail:jdfan@jnu.edu.cn;zzlou@jnu.edu.cn;li_wz16@jnu.edu.cn
  • About author:Email: li_wz16@jnu.edu.cn (W.L.)
    Email: zzlou@jnu.edu.cn(Z.L.)
    Email: jdfan@jnu.edu.cn (J.F.)
  • Supported by:
    the National Natural Science Foundation of China(22075103);the National Natural Science Foundation of China(22175076);the Guangdong Basic and Applied Basic Research Foundation for Distinguished Young Scholar(2019B151502030);the Guangdong Basic and Applied Basic Research Foundation for Distinguished Young Scholar(2018B030306004);the Natural Science Foundation of Guangdong Province(2022A1515010489);the Science and Technology Plan Project of Guangzhou(202002030159);the Fundamental Research Funds for the Central Universities(21621112);the State Key Laboratory of Crystal Materials, Shandong University(KF21-03);the "Young Top Talents" in the Pearl River Talent Project of Guangdong Province(2017GC010424)

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摘要：

发光材料因其在照明、显示、成像等方面的广泛应用而备受关注。作为新兴发光材料之一，钙钛矿类材料的研究及报道较多。其中，铅基钙钛矿的研究取得了巨大进展，光致发光量子产率(PLQY)几乎达到了100%。然而，基于铅基钙钛矿化学毒性和低稳定性，在实际应用过程中需要特殊的封装，因而提高了生产成本并限制了其实际应用领域。被广泛关注的锡基钙钛矿的荧光量子产率几乎能达到90%，但Sn2+易氧化成Sn4+，在空气中极不稳定。相较于铅基钙钛矿和锡基钙钛矿，锑基钙钛矿的低化学毒性、高热稳定性等优点突出。此外，锑基钙钛矿的光学性能在过去几年中也取得了很大的进展，有望突破传统钙钛矿应用的局限。在此，我们报道了一系列新型单晶(4-HBA)SbX5∙H2O (4-HBA为4-羟基苄胺缩写，X为Cl或Br)。利用溶剂热法可制备高质量的(4-HBA)SbBr5∙H2O、(4-HBA)SbBr3Cl2∙H2O和(4-HBA)SbCl5∙H2O单晶，以上三个材料均为P-1空间群，Sb5+离子与卤素离子和4-羟基苄胺中的羟基离子形成畸变八面体结构。(4-HBA)SbX5∙H2O单晶随着Cl−离子浓度的提高，带隙逐渐增大，光致发光波长从618 nm蓝移到595 nm。随着Cl−的引入，激发态电子由八面体中心的Sb5+离子向羟基的复合路径逐渐被向卤素离子的复合路径取代。Sb5+离子向卤素离子的复合大大提高了发光效率，将荧光寿命从12 ns延长到22 ns，光致发光量子产率(PLQY)提高了近40倍。

关键词: 单晶, 光致发光, 锑基钙钛矿, 光物理性质, 卤素调控

Abstract:

Luminescent materials have attracted considerable attention because of their extensive applications, for example, in lighting, display, and imaging. As one of the emerging luminescent materials, perovskites have been widely studied and reported. Among them, Pb-based perovskites have shown great promise as their photoluminescence quantum yield (PLQY) is almost 100%. However, the high chemical toxicity and low stability of Pb-based perovskites increase their production costs and limit their practical applications. Sn-based perovskites are also widely studied and their PLQY can reach approximately 90%; however, Sn2+ easily oxidizes to Sn4+ especially upon air exposure. When compared with Pb- and Sn-based perovskites, Sb-based perovskites have the advantages of low chemical toxicity and high thermal stability. Furthermore, the optical properties of Sb-based perovskites have been improved in recent years and are expected to surpass those of Pb- and Sn-based perovskites. Herein, we report a novel series of (4-HBA)SbX5∙H2O single crystals (where 4-HBA is short for 4-hydroxybenzylamine, and X is Cl or Br). High quality single crystals of (4-HBA)SbBr5∙H2O, (4-HBA)SbBr3Cl2∙H2O, and (4-HBA)SbCl5∙H2O with Sb5+ can be prepared via the solvothermal method. The abovementioned three materials belong to the P-1 space group. The halide and hydroxyl ions surrounded by Sb5+ ions in 4-hydroxybenzylamine formed distorted octahedral structures. Based on the results of steady-state fluorescence spectroscopy, excitation spectroscopy, transient fluorescence spectroscopy, fluorescence lifetime imaging, and density functional theory, it was found that the (4-HBA)SbBr5∙H2O single crystal has a direct band gap, whereas the single crystals of (4-HBA)SbBr3Cl2∙H2O and (4-HBA)SbCl5∙H2O have an indirect band gap. When the concentration of Cl− in (4-HBA)SbX5∙H2O increased, the band gap increased from 2.99 to 3.58 eV and the photoluminescence wavelength decreased from 618 to 595 nm. The obtained results also showed that the emission of the (4-HBA)SbX5∙H2O single crystal originated from the self-trapping exciton effect. With the introduction of Cl−, the size of the [SbX5O]2− octahedron decreased, the exciton shielding reduced, and the exciton absorption was enhanced. Additionally, after replacing Br− with Cl−, the radiation recombination process of the excited electrons from the Sb5+ ions surrounding the halide ions gradually replaced the electron recombination of the hydroxyl ions, which extended the fluorescence lifetime from 12 to 22 ns and improved the PLQY by a factor of approximately 40.

Key words: Single crystal, Photoluminescence, Sb-based perovskite, Photophysical property, Halogen regulation