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在传统逆温差结晶法基础上, 通过引入高质量籽晶, 采用籽晶诱导逆温差结晶法生长出尺寸为11 mm ×11 mm × 2 mm的CH3NH3PbCl3钙钛矿单晶. X射线衍射和Rietveld精修结果表明, 室温下CH3NH3PbCl3单晶是立方相, 其空间群为Pm
$\bar{3}$ m, 晶格常数a = 0.56877 nm. 偏光显微镜研究结果表明, CH3NH3PbCl3单晶的生长机理遵循光滑界面的台阶横向长大机制, 并沿着台阶的外法线方向长大. 变温拉曼光谱研究表明CH3NH3PbCl3单晶在温度160 K发生了正交-四方相转变, 但四方相结构不稳定, 存在的温度区间非常狭窄, 故再次转变为立方相(Pm$\bar{3}$ m). 紫外-可见-近红外吸收光谱和光致发光谱研究表明, CH3NH3PbCl3单晶的吸收截止边约在波长442 nm, 光致发光峰为450 nm, 通过拟合计算得到其带隙值约为2.93 eV, 稍大于第一性原理计算的理论帯隙值(2.55 eV), 分析认为这与籽晶的引入有关, 因为籽晶作为异质形核的核心被引入晶体生长过程中, 使晶格对称性下降, 引起CH3NH3PbCl3帯隙增大.-
关键词:
- CH3NH3PbCl3单晶 /
- 籽晶诱导逆温差结晶法 /
- 台阶横向长大机制 /
- 第一性原理计算
According to the phenomenon that the solubility of CH3NH3PbCl3 decreases with the increase of temperature in different solvents, CH3NH3PbCl3 perovskite single crystal with a maximum dimension of 11 mm × 11 mm × 2 mm is grown by introducing a high-quality seed crystal via the seed-induced inverse temperature crystallization method in this work. X-ray diffraction and Rietveld refinements show that the full widths at half maximum (FWHM) of CH3NH3PbCl3 single crystal diffraction peaks are 0.1527°, 0.1353°, 0.2295° and 0.3452°, corresponding to the crystal plane indices of (100), (200), (300) and (400), respectively. And there are no miscellaneous peaks, indicating a good crystal quality. As a result, CH3NH3PbCl3 single crystal is of cubic phase at room temperature, its space group belongs to Pm$ \bar{3} $ m, and the lattice constant is a = 0.56877 nm. The surface morphology and growth mechanism of CH3NH3PbCl3 crystal are investigated by using a polarizing microscope. It is found that its growth mechanism follows the step horizontal growing mechanism of smooth interface, and its growth direction (that is, step movement direction) is along the outward normal direction of the step. The structural symmetry of CH3NH3PbCl3 crystal is studied by variable temperature Raman spectroscopy, which reveals an orthogonal-tetragonal phase transition at 160 K. But the tetragonal phase structure is not stable, and its temperature range is very narrow. As temperature rises gradually, the tetragonal phase again transforms into a cubic phase (Pm$\bar{3}$ m). Results of UV-Vis-NIR absorption and photoluminescence spectra show that the absorption cutoff of CH3NH3PbCl3 crystal is about 442 nm, and the photoluminescence peak is 450 nm. Thereupon, its band gap is obtained to be about 2.93 eV by a linear fit of Tauc formula, which is slightly higher than the theoretical value of 2.55 eV calculated by first principles simulation. We believe that it is related to the seed crystal, which is introduced into the crystal growth process as the core of heterogeneous nucleation and thus making the lattice more distorted. The lower the lattice symmetry of CH3NH3PbCl3, the larger the band gap is, that is, the lattice symmetry determines the degree of distortion for inorganic PbCl6 octahedral frameworks, resulting in an increase of band gap for CH3NH3PbCl3.-
Keywords:
- CH3NH3PbCl3 single crystal /
- seed-induced inverse temperature crystallization method /
- step horizontal growing mechanism /
- first-principles calculations
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图 1 籽晶诱导逆温差结晶法生长CH3NH3PbCl3单晶 (a)原理示意图; (b) CH3NH3PbCl3在DMF和DMSO混合溶剂中的溶解度曲线
Fig. 1. CH3NH3PbCl3 single crystal grown by seed-induced inverse temperature crystallization method: (a) Schematic diagram of principle; (b) temperature-dependent solubility curve of CH3NH3PbCl3 in DMF+DMSO mixed solution.
图 2 CH3NH3PbCl3单晶生长 (a)单晶生长温度工艺曲线; (b)单晶宏观形貌图(尺寸为11 mm × 11 mm × 2 mm)
Fig. 2. CH3NH3PbCl3 single crystal growth: (a) Temperature control curve of single crystal growth; (b) macroscopic morphology of single crystal (Size: 11 mm × 11 mm × 2 mm).
图 3 籽晶诱导逆温差结晶法生长CH3NH3PbCl3单晶 (a) 单晶XRD图谱; (b)粉末XRD与Material studio模拟的标准XRD图谱; (c) 粉末XRD Rietveld精修结果(Rp = 12.6%, Rwp = 18.5%)
Fig. 3. CH3NH3PbCl3 single crystal grown by seed-induced inverse temperature crystallization method: (a) XRD pattern of single crystal; (b) powder XRD and standard XRD pattern simulated by Material studio; (c) Rietveld result of powder XRD pattern (Rp = 12.6%, Rwp = 18.5%).
图 4 CH3NH3PbCl3单晶的偏光显微形貌图 (a)单晶整体; (b)单晶局部放大图
Fig. 4. Polarizing micromorphology of CH3NH3PbCl3 single crystal: (a) Whole crystal; (b) partial magnification of single crystal.
图 5 (a) CH3NH3PbCl3单晶的UV-Vis-NIR吸收光谱和PL光谱; (b) 通过拟合得到的帯隙值(蓝色散点是实验数据, 黑色实线是拟合结果Eg = 2.93 eV)
Fig. 5. (a) UV-Vis-NIR absorption and PL spectra of CH3NH3PbCl3 single crystal; (b) band gap obtained by fitting (Blue scatter dots are the experimental data, and the black solid line is the fitting result of Eg = 2.93 eV).
图 6 CH3NH3PbCl3单晶的变温拉曼光谱 (a), (b) 80—300 K; (c), (d) 150—170 K; (e) 158 K; (f) 160 K; (g) 不同温度下CH3NH3PbCl3晶体结构(立方/四方/正交)的拉曼谱
Fig. 6. Temperature-dependent Raman spectra of CH3NH3PbCl3 single crystal: (a), (b) 80–300 K; (c), (d) 150–170 K; (e) 158 K; (f) 160 K; (g) Raman spectra of CH3NH3PbCl3 crystal structures (cubic/tetragonal/orthogonal) at different temperatures.
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[1] Turedi B, Lintangpradipto M N, Sandberg O J, Yazmaciyan A, Matt G J, Alsalloum A Y, Almasabi K, Sakhatskyi K, Yakunin S, Zheng X, Naphade R, Nematulloev S, Yeddu V, Baran D, Armin A, Saidaminov M I, Kovalenko M V, Mohammed O F, Bakr O M 2022 Adv. Mater. 34 2202390
Google Scholar
[2] Xing G, Mathews N, Sun S, Lim S S, Lam Y M, Grätzel M, Mhaisalkar S, Sum T C 2013 Science 342 344
Google Scholar
[3] Wang S, Yang F, Zhu J, Cao Q, Zhong Y, Wang A, Du W, Liu X 2020 Sci. China Mater. 63 1438
Google Scholar
[4] Stranks S D, Eperon G E, Grancini G, Menelaou C, Alcocer M J P, Leijtens T, Herz L M, Petrozza A, Snaith H J 2013 Science 342 341
Google Scholar
[5] Zhang Y, Liu Y, Liu S 2022 Adv. Funct. Mater. 32 2210335
Google Scholar
[6] Chen H, Ye F, Tang W, He J, Yin M, Wang Y, Xie F, Bi E, Yang X, Grätzel M, Han L 2017 Nature 550 92
Google Scholar
[7] Li M, Zhao C, Wang Z, Zhang C, Lee H K H, Pockett A, Barbé J, Tsoi W C, Yang Y, Carnie M J, Gao X, Yang W, Durrant J R, Liao L, Jain S M 2018 Adv. Energy Mater. 8 1801509
Google Scholar
[8] Wang Y, Chen W, Wang L, Tu B, Chen T, Liu B, Yang K, Koh C W, Zhang X, Sun H, Chen G, Feng X, Woo H Y, Djurišic´ A B, He Z, Guo X 2019 Adv. Mater. 31 1902781
Google Scholar
[9] Quan L N, García de Arquer F P, Sabatini R P, Sargent E H 2018 Adv. Mater. 30 1801996
Google Scholar
[10] Cao Y, Wang N, Tian H, Guo J, Wei Y, Chen H, Miao Y, Zou W, Pan K, He Y, Cao H, Ke Y, Xu M, Wang Y, Yang M, Du K, Fu Z, Kong D, Dai D, Jin Y, Li G, Li H, Peng Q, Wang J, Huang W 2018 Nature 562 249
Google Scholar
[11] Zhang Q, Su R, Liu X, Xing J, Sum T C, Xiong Q 2016 Adv. Funct. Mater. 26 6238
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[12] Wang K, Wang S, Xiao S, Song Q 2018 Adv. Optical Mater. 6 1800278
Google Scholar
[13] Li D, Cheng H, Wang Y, Zhao Z, Wang G, Wu H, He Q, Huang Y, Duan X 2017 Adv. Mater. 29 1601959
Google Scholar
[14] Yu W, Li F, Yu L, Niazi M R, Zou Y, Corzo D, Basu A, Ma C, Dey S, Tietze M L, Buttner U, Wang X, Wang Z, Hedhili M N, Guo C, Wu T, Amassian A 2018 Nat. Commun. 9 5354
Google Scholar
[15] Tian W, Zhou H, Li L 2017 Small 13 1702107
Google Scholar
[16] Pan W, Wei H, Yang B 2020 Front. Chem. 8 268
Google Scholar
[17] Andričević P, Frajtag P, Lamirand V P, Pautz A, Kollár M, Náfrádi B, Sienkiewicz A, Garma T, Forró L, Horváth E 2021 Adv. Sci. 8 2001882
Google Scholar
[18] Ma L, Yan Z, Zhou X, Pi Y, Du Y, Huang J, Wang K, Wu K, Zhuang C, Han X 2021 Nat. Commun. 12 2023
Google Scholar
[19] Shen H, Nan R, Jian Z, Li X 2019 J. Mater. Sci. 54 11596
Google Scholar
[20] Wang W, Meng H, Qi H, Xu H, Du W, Yang Y, Yi Y, Jing S, Xu S, Hong F, Qin J, Huang J, Xu Z, Zhu Y, Xu R, Lai J, Xu F, Wang L, Zhu J 2020 Adv. Mater. 32 2001540
Google Scholar
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Google Scholar
[22] Cheng X, Jing L, Zhao Y, Du S, Ding J, Zhou T 2018 J. Mater. Chem. C 6 1579
Google Scholar
[23] Zheng E, Yuh B, Tosado G A, Yu Q 2017 J. Mater. Chem. C 5 3796
Google Scholar
[24] Liu Y, Yang Z, Cui D, Ren X, Sun J, Liu X, Zhang J, Wei Q, Fan H, Yu F, Zhang X, Zhao C, Liu S 2015 Adv. Mater. 27 5176
Google Scholar
[25] Ding J, Cheng X, Jing L, Zhou T, Zhao Y, Du S 2018 ACS Appl. Mater. Interfaces 10 845
Google Scholar
[26] Mosconi E, Amat A, Nazeeruddin M K, Grätzel M, Angelis F D 2013 J. Phys. Chem. C 117 13902
Google Scholar
[27] Zhang F, Zhong H, Chen C, Wu X, Hu X, Huang H, Han J, Zou B, Dong Y 2015 ACS Nano 9 4533
Google Scholar
[28] Bernasconi A, Page K, Dai Z, Tan L Z, Rappe A M, Malavasi L 2018 J. Phys. Chem. C 122 28265
Google Scholar
[29] Songvilay M, Wang Z, Sakai V G, Guidi T, Bari M, Ye Z G, Xu G, Brown K L, Gehring P M, Stock C 2019 Phys. Rev. Mater. 3 125406
Google Scholar
[30] Ivanovska T, Quarti C, Grancini G, Petrozza A, Angelis F D, Milani A, Ruani G 2016 Chem. Sus. Chem 9 2994
Google Scholar
[31] Wang H, Nan R, Jian Z, Jin C, Wei Y, Bai Y, Li H 2021 Mater. Sci. Semicond. Process. 135 106107
Google Scholar
[32] Singleton J, Rabe K M 2002 Phys. Today 55 61
Google Scholar
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