Zero-dimensional Sb3+ doped Rb7Bi3Cl16 metal halides with triplet self-trapped exciton emission

Yan Jun; Wang Zi-Yi; Zeng Ruo-Sheng; Zou Bing-Suo

doi:10.7498/aps.70.20211024

Abstract

Low-dimensional metal halides have attracted extensive attention due to their excellent optical properties, especially zero-dimensional metal halides, which can improve the radiation recombination probability due to the characteristics of their isolated octahedral structures. In this paper, we report a zero-dimensional metal halide Sb³⁺ doped Rb₇Bi₃Cl₁₆ with a broadband orange-yellow emission at 613 nm. When the Sb³⁺ doping concentration is 30%, the highest photoluminescence quantum yield of the system reaches 30.7%. This high-efficiency luminescence is derived from the self-trapped excitons generated by the strong interaction between electrons and the crystal lattice. The specific physical mechanism and energy transfer process of self-trapped exciton luminescence are further studied through characterizing the optical performances. The electronic states in the singlet ¹P₁level are relaxed to the triplet ³P₁via an intersystem crossing process, and the strong orange-yellow emission comes from the triplet state ³P₁→¹S₀ radiation recombination process. In addition, Sb³⁺ doped Rb₇Bi₃Cl₁₆ has satisfactory environmental stability, the Sb³⁺:Rb₇Bi₃Cl₁₆-based light-emitting diodes (LED) are fabricated here in this work, and the color coordinates and correlated color temperature of the LED are (0.4886, 0.4534) and 2641 K, respectively. The highly efficient and stable Sb³⁺ doped Rb₇Bi₃Cl₁₆ is expected to be used in solid-state lighting and display fields.

Keywords:

Authors and contacts

School of Physical Science and Technology, Guangxi University, Nanning 530004, China

Corresponding author: Zeng Ruo-Sheng, zengrsh@guet.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 22175043, 52162021) and the Guangxi Natural Science Foundation, China (Grant No. 2017GXNSFGA198005).

[1]	Akkerman Q A, Rainò G, Kovalenko M V, Manna L 2018 Nat. Mater. 17 394 Google Scholar
[2]	Protesescu L, Yakunin S, Bodnarchuk M I, Krieg F, Caputo R, Hendon C H, Yang R X, Walsh A, Kovalenko M V 2015 Nano Lett. 15 3692 Google Scholar
[3]	Wu Y, Li X, Zeng H 2019 Acs Energy Lett. 4 673 Google Scholar
[4]	陈永亮, 唐亚文, 陈沛润, 张力, 刘琪, 赵颖, 黄茜, 张晓丹 2020 物理学报 69 138401 Google Scholar Chen Y L, Tang Y W, Chen P R, Zhang L, Liu Q, Zhao Y, Huang Q, Zhang X D 2020 Acta Phys. Sin. 69 138401 Google Scholar
[5]	樊钦华, 祖延清, 李璐, 代锦飞, 吴朝新 2020 物理学报 69 118501 Google Scholar Fan Q H, Zu Y Q, Li L, Dai J F, Wu C X 2020 Acta Phys Sin. 69 118501 Google Scholar
[6]	Yao M M, Wang L, Yao J S, Wang K H, Chen C, Zhu B S, Yang J N, Wang J J, Xu W P, Zhang Q, Yao H B 2020 Adv. Opt. Mater. 8 1901919 Google Scholar
[7]	Liu Y, Jing Y, Zhao J, Liu Q, Xia Z 2019 Chem. Mater. 31 3333 Google Scholar
[8]	Zhou J, Rong X, Zhang P, Molokeev M S, Wei P, Liu Q, Zhang X, Xia Z 2019 Adv. Opt. Mater. 7 1801435 Google Scholar
[9]	Yang S, Huang S, Wang Q, Wu R, Han Q, Wu W 2019 Opt. Mater. 98 109444 Google Scholar
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[11]	Ke B, Zeng R, Zhao Z, Wei Q, Xue X, Bai K, Cai C, Zhou W, Xia Z, Zou B 2019 J. Phys. Chem. Lett. 11 340 Google Scholar
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[13]	Shi W, Cai T, Wang Z, Chen O 2020 J. Chem. Phys. 153 141101 Google Scholar
[14]	Tailor N K, Satapathi S 2021 J. Phys. Chem. C. 125 5243 Google Scholar
[15]	Han P, Luo C, Yang S, Yang Y, Deng W, Han K 2020 Angew. Chem. Int. Ed. 59 12709 Google Scholar
[16]	Huang J, Chang T, Zeng R, Yan J, Wei Q, Zhou W, Cao S, Zou B 2021 Adv. Opt. Mater. 9 2002267 Google Scholar
[17]	Pradhan A, Sahoo S C, Sahu A K, Samal S L 2020 Cryst. Growth Des. 20 3386 Google Scholar
[18]	Wang X, Ali N, Bi G, Wang Y, Shen Q, Rahimi-Iman A, Wu H 2020 Inorg. Chem. 59 15289 Google Scholar
[19]	Jing Y, Liu Y, Jiang X, Molokeev M S, Lin Z, Xia Z 2020 Chem. Mater. 32 5327 Google Scholar
[20]	Liu M, Ali Löytty H, Hiltunen A, Sarlin E, Qudsia S, Smått J H, Valden M, Vivo P 2021 Small 17 2100101 Google Scholar
[21]	Liu X, Xu X, Li B, Liang Y, Li Q, Jiang H, Xu D 2020 CCS Chemistry 2 216 Google Scholar
[22]	Xie J, Huang Z, Wang B, Chen W, Lu W, Liu X, Song J 2019 Nanoscale 11 6719 Google Scholar
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[24]	Jing Y, Liu Y, Li M, Xia Z 2021 Adv. Opt. Mater. 8 2002213 Google Scholar
[25]	Jing Y, Liu Y, Zhao J, Xia Z 2019 J. Phys. Chem. Lett. 10 7439 Google Scholar
[26]	Li J, Tan Z, Hu M, Chen C, Luo J, Li S, Gao L, Xiao Z, Niu G, Tang J 2019 Frontiers of Optoelectronics 12 352 Google Scholar
[27]	Zeng R, Bai K, Wei Q, Chang T, Yan J, Ke B, Huang J, Wang L, Zhou W, Cao S, Zhao J, Zou B 2021 Nano Res. 14 1551 Google Scholar

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图 1 (a) Rb₇Bi₃Cl₁₆单晶的晶体结构及[XCl₆]^3–八面体和[X₂Cl₁₀]^4–共边二聚体的结构图; (b) 不同Sb³⁺掺杂浓度Rb₇Bi₃Cl₁₆样品的XRD图谱

Figure 1. (a) Crystal structure of Rb₇Bi₃Cl₁₆ single crystals and the unit cell structure diagram of [XCl₆]^3– octahedra and [X₂Cl₁₀]^4– edge-sharing dimers; (b) XRD patterns of Sb:Rb₇Bi₃Cl₁₆ powders with representative Sb content.

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图 2 (a) 纯Rb₇Bi₃Cl₁₆晶体和30%Sb³⁺擦杂的Rb₇Bi₃Cl₁₆晶体的XPS图谱; (b) Rb 3d, Bi 4f, Cl 2p和Sb 3d的高分辨率XPS光谱; (c) Sb³⁺掺杂的Rb₇Bi₃Cl₁₆晶体的SEM表征和Rb, Bi, Sb, Cl元素的EDS

Figure 2. (a) XPS spectra of pure Rb₇Bi₃Cl₁₆ and 30% Sb³⁺:Rb₇Bi₃Cl₁₆; (b) high-resolution XPS spectra of Rb 3d, Bi 4f, Cl 2p and Sb 3d; (c) SEM characterization of 30% Sb³⁺:Rb₇Bi₃Cl₁₆ and EDS mappings of Rb, Bi, Sb, Cl element.

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图 3 30%Sb³⁺离子掺杂Rb₇Bi₃Cl₁₆样品的光学性能　(a) 吸收光谱; (b) PLE光谱(发射波长613 nm); (c) PL光谱(激发波长380 nm); (d) 光致发光强度和峰位随Sb³⁺离子掺杂浓度的变化关系; (e) 不同发射波长下测得的PLE光谱; (f) 不同激发波长测得的PL峰位变化图

Figure 3. Optical properties of 30%Sb³⁺doped Rb₇Bi₃Cl₁₆: (a) Absorption spectra; (b) PLE spectra (emission wavelength 613 nm); (c) PL spectra (excitation wavelength 380 nm); (d) relationship between PL intensity and peak position with Sb³⁺ ion doping concentration; (e) PLE spectra for different PL positions; (f) changes of PL peak position measured at different excitation wavelengths.

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图 4 (a) 30%Sb³⁺:Rb₇Bi₃Cl₁₆的激发和光致发光光谱(E_x = 380 nm); (b) 30%Sb³⁺:Rb₇Bi₃Cl₁₆粉末(E_x = 380 nm, E_m = 613 nm)的PL衰减曲线, 橙色曲线以单指数衰减函数拟合实验数据; (c) 30%Sb³⁺:Rb₇Bi₃Cl₁₆的激发光谱和光致发光光谱(E_x = 307 nm); (d) 30%Sb³⁺:Rb₇Bi₃Cl₁₆粉末(E_x = 307 nm, E_m = 595 nm)的PL衰减曲线, 紫色曲线以双指数衰减函数拟合实验数据

Figure 4. (a) Excitation and photoluminescence (E_x = 380 nm) spectra of 30%Sb³⁺:Rb₇Bi₃Cl₁₆; (b) PL decay curves of the 30%Sb³⁺:Rb₇Bi₃Cl₁₆ powders (E_x = 380 nm, E_m = 613 nm), orange curve is a fit to the experimental data with a single exponential decay function; (c) excitation and photoluminescence (E_x = 307 nm) spectra of 30%Sb³⁺:Rb₇Bi₃Cl₁₆; (d) PL decay curves of the 30%Sb³⁺:Rb₇Bi₃Cl₁₆ powders (E_x = 307 nm, E_m = 595 nm), purple curve is a fit to the experimental data with a double exponential decay function.

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图 5 (a) 跃迁和发光过程示意图; (b) 自陷激子发射示意图; (c) 能量传递模型的示意图

Figure 5. (a) Schematic diagram of the potential energy curves as well as the transition and luminescence processes in a configuration space; (b) schematic diagram of self-trapping exciton emission; (c) schematic diagram of proposed energy-transfer model.

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图 6 (a) LED器件通/关电的示意图; (b) 与发射光谱对应的CIE色度图; (c) 基于30%Sb³⁺:Rb₇Bi₃Cl₁₆的LED的发射光谱

Figure 6. (a) Packaging of LED device of power on/off; (b) CIE chromaticity diagram corresponding to emission spectrum; (c) emission spectrum of the LED based on 30%Sb³⁺:Rb₇Bi₃Cl_16.

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表 1 样品的时间分辨光致发光衰减曲线拟合数据

Table 1. Fitting date of time-resolved PL decay curve of sample

Sample E_m/nm E_x/nm τ₁/μs A₁ τ₂/μs A₂

Sb/(Bi+Sb) = 30% 613 380 6.38
595 307 3.39 0.9139 9.82 0.1479
Sb/(Bi+Sb) = 100% 570 380 1.52 1.0905 13.72 0.0722

DownLoad: CSV

[1]	Akkerman Q A, Rainò G, Kovalenko M V, Manna L 2018 Nat. Mater. 17 394 Google Scholar
[2]	Protesescu L, Yakunin S, Bodnarchuk M I, Krieg F, Caputo R, Hendon C H, Yang R X, Walsh A, Kovalenko M V 2015 Nano Lett. 15 3692 Google Scholar
[3]	Wu Y, Li X, Zeng H 2019 Acs Energy Lett. 4 673 Google Scholar
[4]	陈永亮, 唐亚文, 陈沛润, 张力, 刘琪, 赵颖, 黄茜, 张晓丹 2020 物理学报 69 138401 Google Scholar Chen Y L, Tang Y W, Chen P R, Zhang L, Liu Q, Zhao Y, Huang Q, Zhang X D 2020 Acta Phys. Sin. 69 138401 Google Scholar
[5]	樊钦华, 祖延清, 李璐, 代锦飞, 吴朝新 2020 物理学报 69 118501 Google Scholar Fan Q H, Zu Y Q, Li L, Dai J F, Wu C X 2020 Acta Phys Sin. 69 118501 Google Scholar
[6]	Yao M M, Wang L, Yao J S, Wang K H, Chen C, Zhu B S, Yang J N, Wang J J, Xu W P, Zhang Q, Yao H B 2020 Adv. Opt. Mater. 8 1901919 Google Scholar
[7]	Liu Y, Jing Y, Zhao J, Liu Q, Xia Z 2019 Chem. Mater. 31 3333 Google Scholar
[8]	Zhou J, Rong X, Zhang P, Molokeev M S, Wei P, Liu Q, Zhang X, Xia Z 2019 Adv. Opt. Mater. 7 1801435 Google Scholar
[9]	Yang S, Huang S, Wang Q, Wu R, Han Q, Wu W 2019 Opt. Mater. 98 109444 Google Scholar
[10]	Chu L, Ahmad W, Liu W, Yang J, Zhang R, Sun Y, Yang J, Li X A 2019 Nano-Micro Lett. 11 16 Google Scholar
[11]	Ke B, Zeng R, Zhao Z, Wei Q, Xue X, Bai K, Cai C, Zhou W, Xia Z, Zou B 2019 J. Phys. Chem. Lett. 11 340 Google Scholar
[12]	Igbari F, Wang Z K, Liao L S 2019 Adv. Energy Mater. 9 1803150 Google Scholar
[13]	Shi W, Cai T, Wang Z, Chen O 2020 J. Chem. Phys. 153 141101 Google Scholar
[14]	Tailor N K, Satapathi S 2021 J. Phys. Chem. C. 125 5243 Google Scholar
[15]	Han P, Luo C, Yang S, Yang Y, Deng W, Han K 2020 Angew. Chem. Int. Ed. 59 12709 Google Scholar
[16]	Huang J, Chang T, Zeng R, Yan J, Wei Q, Zhou W, Cao S, Zou B 2021 Adv. Opt. Mater. 9 2002267 Google Scholar
[17]	Pradhan A, Sahoo S C, Sahu A K, Samal S L 2020 Cryst. Growth Des. 20 3386 Google Scholar
[18]	Wang X, Ali N, Bi G, Wang Y, Shen Q, Rahimi-Iman A, Wu H 2020 Inorg. Chem. 59 15289 Google Scholar
[19]	Jing Y, Liu Y, Jiang X, Molokeev M S, Lin Z, Xia Z 2020 Chem. Mater. 32 5327 Google Scholar
[20]	Liu M, Ali Löytty H, Hiltunen A, Sarlin E, Qudsia S, Smått J H, Valden M, Vivo P 2021 Small 17 2100101 Google Scholar
[21]	Liu X, Xu X, Li B, Liang Y, Li Q, Jiang H, Xu D 2020 CCS Chemistry 2 216 Google Scholar
[22]	Xie J, Huang Z, Wang B, Chen W, Lu W, Liu X, Song J 2019 Nanoscale 11 6719 Google Scholar
[23]	Benin B M, Mccall K M, Wörle M, Morad V, Aebli M, Yakunin S, Shynkarenko Y, Kovalenko M V 2020 Angew. Chem. Int. Ed. 59 14490 Google Scholar
[24]	Jing Y, Liu Y, Li M, Xia Z 2021 Adv. Opt. Mater. 8 2002213 Google Scholar
[25]	Jing Y, Liu Y, Zhao J, Xia Z 2019 J. Phys. Chem. Lett. 10 7439 Google Scholar
[26]	Li J, Tan Z, Hu M, Chen C, Luo J, Li S, Gao L, Xiao Z, Niu G, Tang J 2019 Frontiers of Optoelectronics 12 352 Google Scholar
[27]	Zeng R, Bai K, Wei Q, Chang T, Yan J, Ke B, Huang J, Wang L, Zhou W, Cao S, Zhao J, Zou B 2021 Nano Res. 14 1551 Google Scholar

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Zero-dimensional Sb³⁺ doped Rb₇Bi₃Cl₁₆ metal halides with triplet self-trapped exciton emission

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Corresponding author: Zeng Ruo-Sheng, zengrsh@guet.edu.cn

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Sample	E_m/nm	E_x/nm	τ₁/μs	A₁	τ₂/μs	A₂
Sb/(Bi+Sb) = 30%	613	380	6.38
Sb/(Bi+Sb) = 30%	595	307	3.39	0.9139	9.82	0.1479
Sb/(Bi+Sb) = 100%	570	380	1.52	1.0905	13.72	0.0722

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