异价阳离子替代实现的金属卤化物CsCdCl3的明亮宽带绿色发光

人工晶体学报 ›› 2023, Vol. 52 ›› Issue (2): 307-314.

异价阳离子替代实现的金属卤化物CsCdCl₃的明亮宽带绿色发光

宋妍^1,2, 王录^1,2, 陈明星³, 魏荣敏², 李新慧², 贾贞^1,2, 夏明军⁴

1.中北大学化学工程与技术学院,太原 038507;
2.德州学院化学化工学院,德州 253023;
3.北京大学分析测试中心,北京 100871;
4.中国科学院理化技术研究所,人工晶体研究发展中心,中国科学院功能晶体与激光技术重点实验室,北京 100190

收稿日期:2022-12-06 出版日期:2023-02-15 发布日期:2023-03-08
通信作者: 贾贞,博士,教授。E-mail:jiazhen@dzu.edu.cn
作者简介:宋妍(1999—),女,河北省人,硕士研究生。E-mail:songyan202203@163.com
基金资助:
山东省自然科学基金(ZR2020MF128,ZR2021MB059)

Bright Broadband Green Photoluminescence of CsCdCl₃ Metal Halides Achieved by Heterovalent Cation Substitution

SONG Yan^1,2, WANG Lu^1,2, CHEN Mingxing³, WEI Rongmin², LI Xinhui², JIA Zhen^1,2, XIA Mingjun⁴

1. School of Chemical Engineering and Technology, North University of China, Taiyuan 038507, China;
2. College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023, China;
3. Analytical Instrumentation Center of Peking University, Peking University, Beijing 100871, China;
4. Key Laboratory of Functional Crystals and Laser Technology, Beijing Center for Crystal Research and Development, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Received:2022-12-06 Online:2023-02-15 Published:2023-03-08

摘要/Abstract

摘要： 全无机金属卤化物灵活多变的结构及优异的发光性能使其在固态光电子领域显示出重要的应用前景。本研究采用异价阳离子取代策略,用三价锑离子部分取代CsCdCl₃中的二价镉离子,促进自陷激子的产生,使CsCdCl₃∶Sb³⁺产生了明亮的宽带绿色发光,中心波长为530 nm。机理研究结果表明,CsCdCl₃∶Sb³⁺ 中相邻SbCl₆八面体被孤立,形成了低维电子构型,促进了Sb³⁺ 局域化,实现了量子效率最高为95.5%的高效发光。此外,尽管CsCdCl₃和RbCdCl₃均属于ACdCl₃(A为碱金属家族),但它们的晶体结构明显不同。RbCdCl₃属于正交晶系,空间群为Pnma;CsCdCl₃属于六方晶系,空间群为P6₃/mmc。CsCdCl₃的结构对称性大于RbCdCl₃,其晶体结构偏离立方相的扭曲程度比RbCdCl₃小,导致CsCdCl₃∶Sb³⁺比RbCdCl₃∶Sb³⁺有较小的斯托克斯位移,并造成发射光谱的蓝移。本工作不仅为异价阳离子取代设计新的发光材料提供了方法,而且为通过晶体结构对称调控金属卤化物的发光性能提供了思路。

关键词: 金属卤化物, 异价阳离子取代, 自陷激子, 高量子效率, 镉, 绿色发光

Abstract: All-inorganic metal halides have shown significant applications in solid-state optoelectronics because of their flexible structures and impressive fluorescence emissions. In this study, a heterovalent cation substitution strategy was used to partially replace the divalent cadmium ions in CsCdCl₃ with trivalent antimony ions to promote the production of self-trapped excitons, resulting in a bright broadband green photoluminescence of CsCdCl₃∶Sb³⁺ with a central wavelength of 530 nm. Mechanism researches results show that the adjacent SbCl₆ octahedra in CsCdCl₃∶Sb³⁺ are isolated, forming a low-dimensional electronic configuration that promotes Sb³⁺ localization and achieves efficient photoluminescence with a quantum efficiency of up to 95.5%. Furthermore, although both CsCdCl₃ and RbCdCl₃ belong to ACdCl₃ (A is an alkali metal family), they have distinctly different crystal structures. RbCdCl₃ crystallizes in the orthorhombic crystal system with space group of Pnma; while CsCdCl₃ crystallizes in the hexagonal phase crystal system with space group of P6₃/mmc. The structural symmetry of CsCdCl₃ is higher than that of RbCdCl₃, indicating that its crystal structure is less distorted away from the cubic phase than that of RbCdCl₃, resulting in a smaller Stokes shift and corresponding blue shift of the emission spectrum in CsCdCl₃∶Sb³⁺ than in RbCdCl₃∶Sb³⁺. This work not only provides a method for designing new photoluminescence materials by heterovalent cation substitution but also paves an avenue for modulating the luminescent properties of metal halides through crystal structure symmetry.

Key words: metal halide, heterovalent cation substitution, self-trapped exciton, high quantum efficiency, cadmium, green photoluminescence

中图分类号:

O641

宋妍, 王录, 陈明星, 魏荣敏, 李新慧, 贾贞, 夏明军. 异价阳离子替代实现的金属卤化物CsCdCl₃的明亮宽带绿色发光[J]. 人工晶体学报, 2023, 52(2): 307-314.

SONG Yan, WANG Lu, CHEN Mingxing, WEI Rongmin, LI Xinhui, JIA Zhen, XIA Mingjun. Bright Broadband Green Photoluminescence of CsCdCl₃ Metal Halides Achieved by Heterovalent Cation Substitution[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(2): 307-314.

参考文献

[1] MCCALL K M, MORAD V, BENIN B M, et al. Efficient lone-pair-driven luminescence: structure-property relationships in emissive 5s² metal halides[J]. ACS Materials Letters, 2020, 2(9): 1218-1232.
[2] KESHAVARZ M, DEBROYE E, OTTESEN M, et al. Tuning the structural and optoelectronic properties of Cs₂AgBiBr₆ double-perovskite single crystals through alkali-metal substitution[J]. Advanced Materials, 2020, 32(40): e2001878.
[3] LI M Z, XIA Z G. Recent progress of zero-dimensional luminescent metal halides[J]. Chemical Society Reviews, 2021, 50(4): 2626-2662.
[4] LIU R X, ZHANG W J, LI G J, et al. An ultraviolet excitation anti-counterfeiting material of Sb³⁺ doped Cs₂ZrCl₆ vacancy-ordered double perovskite[J]. Inorganic Chemistry Frontiers, 2021, 8(17): 4035-4043.
[5] LIU L, NIU G D, ZHANG G D, et al. Lead-free halide perovskite Cs₃Bi₂Br₉ single crystals for high-performance X-ray detection[J]. Science China Materials, 2021, 64(6): 1427-1436.
[6] ZHANG P, HUA Y Q, XU Y D, et al. Ultrasensitive and robust 120 keV hard X-ray imaging detector based on mixed-halide perovskite CsPbBr_3-nI_n single crystals[J]. Advanced Materials, 2022, 34(12): e2106562.
[7] 赫世辉, 赵静, 刘泉林. 高效、宽带发射有机-无机金属卤化物荧光材料[J]. 无机化学学报, 2022, 38(7): 1209-1225.
HE S H, ZHAO J, LIU Q L. High-efficiency and broad-spectrum emitting organic-inorganic metal halide photoluminescent materials[J]. Chinese Journal of Inorganic Chemistry, 2022, 38(7): 1209-1225(in Chinese).
[8] YU H Q, CHEN W J, FANG Z B, et al. Alkalis-doping of mixed tin-lead perovskites for efficient near-infrared light-emitting diodes[J]. Science Bulletin, 2022, 67(1): 54-60.
[9] 张欣雷, 王涛, 查钢强. CsPbBr₃单晶薄膜制备及其X射线探测性能研究[J]. 人工晶体学报, 2021, 50(10): 1900-1906.
ZHANG X L, WANG T, ZHA G Q. Fabrication of CsPbBr₃ single-crystal film and its X-ray detection performance[J]. Journal of Synthetic Crystals, 2021, 50(10): 1900-1906(in Chinese).
[10] LI X F, WANG S S, ZHAO S G, et al. Mixing halogens to assemble an all-inorganic layered perovskite with warm white-light emission[J]. Chemistry, 2018, 24(37): 9243-9246.
[11] QIU Y X, MA Z M, DAI G K, et al. All-inorganic luminescent ternary cadmium halide Cs₇Cd₃Br₁₃ with two types of Cd-centered polyhedrons[J]. Inorganic Chemistry, 2022, 61(7): 3288-3295.
[12] XU H P, DONG X H, ZHANG Z Z, et al. Three-dimensional all-inorganic dual halogen emitter Cs₂Cd₂BrCl₅ exhibiting broadband white-light emission[J]. Journal of Materials Chemistry C, 2022, 10(37): 13844-13850.
[13] JIN J C, PENG Y H, XU Y T, et al. Bright green emission from self-trapped excitons triggered by Sb³⁺ doping in Rb₄CdCl₆[J]. Chemistry of Materials, 2022, 34(12): 5717-5725.
[14] MENG X F, WEI Q L, LIN W C, et al. Efficient yellow self-trapped exciton emission in Sb³⁺-doped RbCdCl₃ metal halides[J]. Inorganic Chemistry, 2022, 61(18): 7143-7152.
[15] LI X T, HOFFMAN J M, KANATZIDIS M G. The 2D halide perovskite rulebook: how the spacer influences everything from the structure to optoelectronic device efficiency[J]. Chemical Reviews, 2021, 121(4): 2230-2291.
[16] 陈婷, 刘晓霖. 零维金属卤化物钙钛矿的A、B、X位对其光物理性质的调控[J]. 半导体技术, 2022, 47(10): 761-773.
CHEN T, LIU X L. Regulation of A, B and X sites of zero-dimensional metal halide perovskites on their photophysical properties[J]. Semiconductor Technology, 2022, 47(10): 761-773(in Chinese).
[17] CHEN B, GUO Y, WANG Y, et al. Multiexcitonic emission in zero-dimensional Cs₂ZrCl₆∶Sb³⁺ perovskite crystals[J]. Journal of the American Chemical Society, 2021, 143(42): 17599-17606.
[18] HAN P G, LUO C, YANG S Q, et al. All-inorganic lead-free 0D perovskites by a doping strategy to achieve a PLQY boost from <2% to 90[J]. Angewandte Chemie, 2020, 59(31): 12709-12713.
[19] 王谦, 王京康, 成双良, 等. 零维钙钛矿结构Cs₃Cu₂Br₅单晶的生长和X射线探测性能[J]. 人工晶体学报, 2021, 50(10): 1919-1924.
WANG Q, WANG J K, CHENG S L, et al. Crystal growth and X-ray detection performance of 0D Cs₃Cu₂Br₅ single crystal perovskite[J]. Journal of Synthetic Crystals, 2021, 50(10): 1919-1924(in Chinese).
[20] SIEGEL S, GEBERT E. The structures of hexagonal CsCdCl₃ and tetragonal Cs₂CdCl₄[J]. Acta Crystallographica, 1964, 17(6): 790.
[21] HAMZAOUI F, NOIRET I, ODOU G, et al. A new investigation of rubidium cadmium trichloride[J]. Journal of Solid State Chemistry, 1996, 124(1): 39-42.
[22] JACOBS P W M. Alkali halide crystals containing impurity ions with the ns² ground-state electronic configuration[J]. Journal of Physics and Chemistry of Solids, 1991, 52(1): 35-67.
[23] 吴新栋, 张潮, 刘晓霖. 钙钛矿及类钙钛矿热致变色单晶材料的研究进展[J]. 人工晶体学报, 2022, 51(6): 1099-1109.
WU X D, ZHANG C, LIU X L. Research progress on the perovskite and perovskite-like thermochromic single crystal materials[J]. Journal of Synthetic Crystals, 2022, 51(6): 1099-1109(in Chinese).
[24] LUO J J, WANG X M, LI S R, et al. Efficient and stable emission of warm-white light from lead-free halide double perovskites[J]. Nature, 2018, 563(7732): 541-545.
[25] LIAN L Y, ZHENG M Y, ZHANG P, et al. Photophysics in Cs₃Cu₂X₅ (X = Cl, Br, or I): highly luminescent self-trapped excitons from local structure symmetrization[J]. Chemistry of Materials, 2020, 32(8): 3462-3468.
[26] LIAN L Y, ZHENG M Y, ZHANG W Z, et al. Efficient and reabsorption-free radioluminescence in Cs₃Cu₂I₅ nanocrystals with self-trapped excitons[J]. Advanced Science, 2020, 7(11): 2000195.
[27] LOCARDI F, SAMOLI M, MARTINELLI A, et al. Cyan emission in two-dimensional colloidal Cs₂CdCl₄∶Sb³⁺ ruddlesden-popper phase nanoplatelets[J]. ACS Nano, 2021, 15(11): 17729-17737.
[28] BARANOWSKI M, PLOCHOCKA P. Excitons in metal-halide perovskites[J]. Advanced Energy Materials, 2020, 10(26): 1903659.

异价阳离子替代实现的金属卤化物CsCdCl₃的明亮宽带绿色发光

Bright Broadband Green Photoluminescence of CsCdCl₃ Metal Halides Achieved by Heterovalent Cation Substitution

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	吴忠航, 孙斌, 黄钢, 屈骞, 唐懿文, 孙九爱. 碲锌镉器件技术进展及其在SPECT中的应用[J]. 人工晶体学报, 2023, 52(2): 196-207.
[2]	李振兴, 柏伟, 王琰璋, 刘江高, 张瑛侠, 折伟林. 大尺寸非规则碲锌镉晶片双面抛光技术[J]. 人工晶体学报, 2023, 52(2): 244-251.
[3]	田娜, 刘英才, 杨远航, 肖晨希, 朱建宇, 段博峰, 张强, 宋娟. 一例吡嗪羧酸镉配合物的合成、结构及荧光性质研究[J]. 人工晶体学报, 2023, 52(2): 322-326.
[4]	金敏. 晶体人生丨介万奇:辐射探测半导体晶体拓荒者[J]. 人工晶体学报, 2022, 51(9-10): 1523-1526.
[5]	肖友鹏. GeSe基薄膜太阳电池模拟研究[J]. 人工晶体学报, 2022, 51(7): 1270-1274.
[6]	张嘉泓, 张继军, 王林军, 徐哲人, 曹祥智, 卢伟. 移动加热器法生长碲锌镉晶体的组分输运与界面形貌研究[J]. 人工晶体学报, 2022, 51(6): 973-985.
[7]	任锦涛, 陈青, 霍宇, 吴治昕, 余春燕, 翟光美. 钝化剂乙酰水杨酸对钙钛矿太阳能电池性能影响的研究[J]. 人工晶体学报, 2022, 51(6): 1042-1050.
[8]	肖建敏, 袁吉仁, 王鹏, 邓新华, 黄海宾, 周浪. 铅基卤化物钙钛矿太阳电池的模拟研究[J]. 人工晶体学报, 2022, 51(6): 1051-1058.
[9]	张静, 师倩莹, 龚浩, 郭雨菲, 张卫珂. MCNOs/CdS双效光催化剂的制备及其性能研究[J]. 人工晶体学报, 2021, 50(8): 1485-1495.
[10]	刘艺蕊, 段敏娜, 顾希煊, 高艳红, 何勇, 宋娟. 一例镉(Ⅱ)配合物的合成、结构及发光性质研究[J]. 人工晶体学报, 2021, 50(6): 1044-1048.
[11]	徐衡, 桂乃成, 严达, 熊志, 黄荣谊. 新型镉(Ⅱ)配合物荧光探针的合成及性能[J]. 人工晶体学报, 2021, 50(6): 1049-1055.
[12]	成双良, 任国浩, 吴云涛. Cs₂HfCl₆和Cs₂HfCl₆∶Tl晶体的生长、光学和闪烁性能研究[J]. 人工晶体学报, 2021, 50(5): 803-808.
[13]	张晓勇, 张琰春, 张晓玉, 张森. 化学水浴沉积法制备硫化镉薄膜的微结构和性能[J]. 人工晶体学报, 2021, 50(2): 310-317.
[14]	杜园园, 姜维春, 陈晓, 雒涛. Te溶剂Bridgman法CdMnTe晶体核辐射探测器的制备和表征[J]. 人工晶体学报, 2021, 50(10): 1892-1899.
[15]	孙啟皓, 郝莹莹, 张鑫, 肖宝, 介万奇, 徐亚东. Cs₃Bi₂I₉晶体的生长及辐射探测性能[J]. 人工晶体学报, 2021, 50(10): 1907-1912.