溶液法CH3NH3PbCl3单晶的生长与性能研究

doi:10.15541/jim20160150

无机材料学报 ›› 2016, Vol. 31 ›› Issue (10): 1063-1067.DOI: 10.15541/jim20160150

溶液法CH₃NH₃PbCl₃单晶的生长与性能研究

王万富¹, 苏静¹, 雷勇¹, 仲坤¹, 王迪²

(1. 南京信息工程大学物理与光电工程学院, 南京 210044; 2. 固体微结构物理国家重点实验室, 人工微结构科学与技术协同创新中心, 南京 210093)

收稿日期:2016-03-15 修回日期:2016-03-25 出版日期:2016-10-20 网络出版日期:2016-09-23
作者简介:王万富(1993–), 男, 硕士研究生. E-mail: 572088876@qq.com
基金资助:
国家自然科学基金(51472123;51302268;51502142);江苏省高等学校大学生实践创新训练计划重点项目

Solution Growth and Performance of CH₃NH₃PbCl₃Single Crystal

WANG Wan-Fu¹, SU Jing¹, LEI Yong¹, ZHONG Kun¹, WANG Di²

(1. School of Physics and Optoelectronic Engineering, Nanjing University of Information Science & Technology, Nanjing 210044, China; 2. National Laboratory of Solid State Microstructures and Department of Physics and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China)

Received:2016-03-15 Revised:2016-03-25 Published:2016-10-20 Online:2016-09-23
About author:WANG Wan-Fu. E-mail: 572088876@qq.com
Supported by:
National Natural Science Foundation of China (51472123;1302268;51502142);Jiangsu Province Practice and Innovation Training Program for College Students(201410300014Z);'Qing Lan' Project Foundation of Jiangsu Province

摘要/Abstract

摘要：

分别采用蒸发结晶法和逆温结晶法生长尺寸约为4 mm×3 mm×3 mm的CH₃NH₃PbCl₃单晶。对两种方法生长的单晶粉体的XRD分析结果显示, 单晶具有立方晶系结构, 其晶格常数分别为0.56833、0.56891 nm。实验测量了CH₃NH₃PbCl₃单晶的红外光谱(FT-IR)和拉曼光谱, 并对谱峰进行了指认; 使用UV-VIS-NIR分光光度计、荧光光度计对CH₃NH₃PbCl₃单晶的光学性能进行了测试。结果表明: CH₃NH₃PbCl₃晶体的吸收边约为423 nm, 光致发光峰为433 nm, 带隙值为2.97 eV, 与CH₃NH₃PbCl₃薄膜的光学特性相比, CH₃NH₃PbCl₃单晶更具潜在的应用前景。最后, 结合第一性原理研究了CH₃NH₃PbCl₃晶体的能带结构, 计算得出带隙值2.428 eV, 与实验值吻合较好。

关键词: CH₃NH₃PbCl₃单晶, 蒸发结晶法, 逆温结晶法, 光谱

Abstract:

Perovskite-type organic-inorganic hybrids CH₃NH₃PbX₃(X= halogen) are good application materials for solid-state solar cell devices. To study the basic performances of these perovskite compounds, growth and optical-electrical properties of the large single crystals with high quality are of great necessity. In present study, CH₃NH₃PbCl₃ single crystals with dimension of about 4 mm×3 mm×3 mm were grown by evaporation and inversion crystallization method. Powder X-ray diffraction (PXRD) of the obtained crystals powder showed that the crystals were of cubic structure, and their lattice constants were 0.56833 nm and 0.56891 nm, respectively. Fourier transform-infrared (FT-IR) and Raman spectra of the crystals were measured and the peaks were assigned. The optical properties were characterized by UV-VIS-NIR and photoluminescence spectroscopy. The results showed that the absorption edge of CH₃NH₃PbCl₃ crystal was about 423 nm, with the photoluminescence peak at 433 nm, the band gap at 2.97 eV. As compared with the optical properties of CH₃NH₃PbCl₃ thin films, CH₃NH₃PbCl₃ single crystal has application advantages in solar cell. Finally, the band structure of CH₃NH₃PbCl₃ crystal was studied by the first principle, and the band gap value was calculated to be 2.428 eV, which was in good agreement with the present experimental result.

Key words: CH₃NH₃PbCl₃ single crystal, evaporation crystallization, inversion crystallization, spectroscopy

中图分类号:

O782

王万富, 苏静, 雷勇, 仲坤, 王迪. 溶液法CH₃NH₃PbCl₃单晶的生长与性能研究[J]. 无机材料学报, 2016, 31(10): 1063-1067.

WANG Wan-Fu, SU Jing, LEI Yong, ZHONG Kun, WANG Di. Solution Growth and Performance of CH₃NH₃PbCl₃Single Crystal[J]. Journal of Inorganic Materials, 2016, 31(10): 1063-1067.

图/表 6

图1 (a)蒸发结晶法和(b)逆温结晶法生长的CH3NH3PbCl3晶体照片

Fig. 1 CH3NH3PbCl3 crystal grown by (a) evaporation crystallization method (T=85℃) and (b) inversion crystallization method (Heated from room temperature and kept at 50℃)

图2 蒸发结晶法(HCl)和逆温结晶法(DMF-DMSO)制备的CH3NH3PbCl3单晶粉体的XRD图谱

Fig. 2 Powder XRD patterns of the CH3NH3PbCl3 crystal grown by evaporation (HCl method) and inversion crystallization (DMF-DMSO method)

图3 CH3NH3PbCl3的红外(a)和拉曼(b)光谱图

Fig. 3 FT-IR (a) and Raman (b) spectra of CH3NH3PbCl3

表1 红外光谱和拉曼光谱的谱峰归属结果

Table 1 Peak assignments of FT-IR and Raman spectra

FT-IR / cm^-1	Raman / cm^-1	Assignment
3113	3177, 3122	N-H symmetric stretching
2993	2972	C-H asymmetric stretching
2908, 2838	2833	C-H symmetric stretching
2399		H-C-N stretching
1581, 1481, 1436	1591, 1487	C-N stretching, C-H bending
1315, 1254		H-C-N bending
986, 922	977	C-N bending
710	470	N-H bending
	122	Pb-Cl stretching

图4 CH3NH3PbCl3单晶粉末的吸收光谱和荧光光谱(a)及其带隙图谱(b)

Fig. 4 Absorption and fluorescence spectra (a) and band gap (b) of CH3NH3PbCl3 crystal

图5 第一性原理计算CH3NH3PbCl3能带图谱(a)和态密度图(b)

Fig. 5 First principles calculation of CH3NH3PbCl3 band pattern (a) and PDOS (b)

参考文献 20

[1]	ZHANG D, EATON SW, YU Y, et al.solution-Phase synthesis of cesium lead halide perovskite nanowires. J. Am. Chem. Soc., 2015, 137(29): 9230-9233.
[2]	WANG Y, LI X, ZHAO X, et al.Nonlinear absorption and low- threshold multiphoton pumped stimulated emission from all-inorganic perovskite nanocrystals.Nano Lett., 2016, 16(1): 448-453.
[3]	SONG J, LI J, LI X, et al.Quantum dot light-emitting diodes based on inorganic perovskite cesium lead halides (CsPbX3). Adv. Mater., 2015, 27(44): 7162-7167.
[4]	YANG W S, NOH J H, JEON N J, et al.High-performance photo voltaic perovskite layers fabricated through intramolecular exchange.Science, 2015, 348(6240): 1234-1237.
[5]	SHI D, ADINOLFI V, COMIN R, et al.Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals.Science, 2015, 347(6221): 519-522.
[6]	SAIDAMINOV M I, ABDELHADY A L, MURALI B, et al.High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization. Nat. Commun. 2015, 6: 7586-7592.
[7]	SU J, CHEN D P, LIN C T.Growth of large CH3NH3PbX3 (X= I, Br) single crystals in solution.J. Cryst. Growth, 2015, 422: 75-79.
[8]	LIU Y, YANG Z, CUI D, et al.Two-inch-sized perovskite CH3NH3PbX3 (X = Cl, Br, I) crystals: growth and characterization. Adv. Mater., 2015, 27(35): 5176-5183.
[9]	MANSER J S, SAIDAMINOV M I, CHRISTIANS J A, et al.Making and breaking of lead halide perovskites.Acc. Chem. Res., 2016, 49(2): 330-338.
[10]	LIU YUNXIA.Study on PbCl2 Solubility under different conditions of HCl concentration, Sb3+ concentration and temperature.Rare Metals, 2000, 24(4): 270-272.
[11]	WU Y, ISLAM A, YANG X, et al.Retarding the crystallization of PbI2 for highly reproducible planar-structured perovskite solar cells via sequential deposition.Energ. Environ. Sci., 2014, 7(9): 2934-2938.
[12]	STAMPLECOSKIE K G, MANSER J S, KAMAT P V.Dual nature of the excited state in organic-inorganic lead halide perovskites.Energ. Environ. Sci., 2015, 8(1): 208-215.
[13]	JEON N J, NOH J H, KIM Y C, et al.Solvent engineering for high-performance inorganic-organic hybrid perovskite solar cells.Nat. Mater., 2014, 13(9): 897-903.
[14]	ONODA-YAMAMURO N, MATSUO T, SUGA H.Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II)†.J. Phys. Chem. Solids, 1990, 51(12): 1383-1395.
[15]	DIMESSO L, DIMAMY M, HAMBURGER M, et al.Properties of CH3NH3PbX3 (X= I, Br, Cl) powders as precursors for organic/inorganic solar cells.Chem. Mater., 2014, 26(23): 6762-6770.
[16]	CARABATOS-NÉDELEC C, BRÉHAT F, WYNCKE B. Lattice vibrations in lead bromide and chloride.Infrared Phys. Technol., 1991, 31(6): 611-619.
[17]	VALERIO D, AJAY RAM S K, MICHELE D B, et al. Tuning the light emission properties by band gap engineering in hybrid lead halide perovskite.J. Am. Chem. Soc., 2014, 136(51): 17730-17733.
[18]	KITAZAWA N, WATANABE Y, NAKAMURA Y.Optical proper ties of CH3NH3PbX3 (X= halogen) and their mixed-halide crystals.J. Mater. Sci., 2002, 37(17): 3585-3587.
[19]	MASHIYAMA H, KURIHARA Y, AZETSU T.Disordered cubic perovskite structure of CH3NH3PbX3 (X= Cl, Br, I).J. Koren. Phys. Soc., 1998, 32: S156-S158.
[20]	EVEN J, PEDESSEAU L, JANCU J M, et al.Importance of spin-orbit coupling in hybrid organic/inorganic perovskites for photovoltaic applications.J. Phys. Chem. Lett., 2013, 4(17): 2999-3005.

溶液法CH₃NH₃PbCl₃单晶的生长与性能研究

Solution Growth and Performance of CH₃NH₃PbCl₃Single Crystal

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