PbS量子点能级结构的尺寸和配体依赖性及其对异质结电池性能的影响

doi:10.15541/jim20160017

无机材料学报 ›› 2016, Vol. 31 ›› Issue (9): 915-922.DOI: 10.15541/jim20160017

PbS量子点能级结构的尺寸和配体依赖性及其对异质结电池性能的影响

王恒^{1, 2}, 翟光美^{1, 2}, 张继涛¹, 杨永珍¹, 刘旭光^{1, 3}, 李学敏¹, 许并社¹

(1. 太原理工大学新材料界面科学与工程教育部和山西省重点实验室, 新材料工程技术研究中心, 太原 030024; 2. 电子科技大学电子薄膜与集成器件国家重点实验室, 成都 610054; 3. 太原理工大学化学与化工学院, 太原 030024)

收稿日期:2016-01-06 修回日期:2016-03-18 出版日期:2016-09-20 网络出版日期:2016-08-29
作者简介:王恒(1989–), 男, 硕士研究生. E-mail: whtyut@foxmail.com
基金资助:
电子薄膜与集成器件国家重点实验室开放课题(KFJJ201406);国家自然科学基金(21471111, 21176169, 61475110, 61404089, 61504090);山西省科技创新重点团队(2015013002-10);山西省基础研究计划项目(2014011016-6, 2014021019-1, 2015021103)

PbS Quantum Dots: Size, Ligand Dependent Energy Level Structures and Their Effects on the Performance of Heterojunction Solar Cells

WANG Heng^{1, 2}, ZHAI Guang-Mei^{1, 2}, ZHANG Ji-Tao¹, YANG Yong-Zhen¹, LIU Xu-Guang^{1, 3}, LI Xue-Min¹, XU Bing-She¹

(1. Key Laboratory of Interface Science and Engineering in Advanced Materials of Ministry of Education and Shanxi Province; Research Centre of Advanced Materials Science and Technology of Taiyuan University of Technology, Taiyuan 030024, China; 2. State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of China, Chengdu 610054, China; 3. College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China)

Received:2016-01-06 Revised:2016-03-18 Published:2016-09-20 Online:2016-08-29
About author:WANG Heng. E-mail: whtyut@foxmail.com
Supported by:
The Open Foundation of State Key Laboratory of Electronic Thin Films and Integrated Devices (KFJJ201406);National Natural Science Foundation of China (21471111, 21176169, 61475110, 61404089, 61504090);Shanxi Provincial Key Innovative Research Team in Science and Technology (2015013002-10);Basic Research Projects of Shanxi Province (2014011016-6, 2014021019-1, 2015021103)

摘要/Abstract

摘要：

通过电化学循环伏安测试和吸收光谱测试, 确定了有机配体(油酸)和原子配体(四正丁基碘化铵, TBAI)钝化的不同粒径(2.6~4.5 nm)PbS量子点的导带和价带能级, 并研究了量子点尺寸对PbS/TiO₂异质结电池(空气气氛中制备)性能的影响。结果表明：PbS量子点的能级结构受其粒径大小和表面配体特性的影响。当PbS量子点尺寸从2.6 nm增加至4.5 nm时, 油酸包覆PbS量子点的导带底从-3.67 eV减小到-4.0 eV, 价带顶从-5.19 eV增加到-4.97 eV; 而对于TBAI配体置换的PbS量子点, 其导带底和价带顶则分别从-4.15 eV和-5.61 eV变化至-4.51 eV和-5.46 eV。粒径为3.9 nm的PbS量子点所制备的电池性能最优, 其能量转化效率达到2.32%, 这可归因于其适宜的禁带宽度、结晶质量和良好的PbS/TiO₂界面能级匹配度。

关键词: PbS量子点, 循环伏安, 能级结构, 太阳能电池

Abstract:

The conduction band minimum and valence band maximum of colloidal PbS quantum dots with different sizes (2.6-4.5 nm) and different surface ligands (oleic acid or tetrabutylammonium iodide, TBAI) were determined by cyclic voltammetry and absorption measurements. Furthermore, the effect of quantum dot sizes on the performance of PbS quantum dots/TiO₂ heterojunction solar cells prepared in air was also studied. The results show that energy level structures of PbS quantum dots strongly depend on the size and ligand on the surface. As the quantum dot size increases from 2.6 nm to 4.5 nm, the conduction band minimum of pristine PbS quantum dots with oleic acid ligands decreases from -3.67 eV to -4.0 eV, while their valence band maximum increases from -5.19 eV to -4.97 eV. However, for PbS quantum dots passivated by TBAI ligands, their conduction band minimum and valence band maximum change from -4.15eV and -5.61 eV to -4.51eV and -5.46 eV, respectively. Devices made of the PbS quantum dots with size of 3.9 nm show the highest power conversion efficiency of 2.32%, which can be ascribed to their proper bandgap, crystal quality and favorable energy-level alignment at the PbS quantum dot /TiO₂ interface.

Key words: PbS quantum dot, cyclic voltammetry, energy level structure, solar cell

中图分类号:

TQ174

王恒, 翟光美, 张继涛, 杨永珍, 刘旭光, 李学敏, 许并社. PbS量子点能级结构的尺寸和配体依赖性及其对异质结电池性能的影响[J]. 无机材料学报, 2016, 31(9): 915-922.

WANG Heng, ZHAI Guang-Mei, ZHANG Ji-Tao, YANG Yong-Zhen, LIU Xu-Guang, LI Xue-Min, XU Bing-She. PbS Quantum Dots: Size, Ligand Dependent Energy Level Structures and Their Effects on the Performance of Heterojunction Solar Cells[J]. Journal of Inorganic Materials, 2016, 31(9): 915-922.

图/表 8

图1 (a)PbS量子点的吸收光谱图, (b)PbS量子点薄膜(TBAI配体)的吸收光谱图, (c)平均粒径4.5 nm的单分散PbS量子点TEM照片, 插图为量子点的高分辨TEM照片和(d)平均粒径4.5 nm PbS量子点的动态光散射粒径分布图

Fig. 1 Absorption spectra and morphology of PbS QDs (a) Absorption spectra of PbS QDs with different sizes; (b) Absorption spectra of PbS QD-films after TBAI ligand exchange; (c) TEM image of colloidal PbS QDs with average size of 4.5 nm; (d) Size distribution of PbS QDs with an average size of 4.5 nm measured by dynamic light scattering

图2 (a) TBAI配体置换前后PbS薄膜的FT-IR图谱和(b) TBAI配体置换后量子点的XPS图谱(I 3d)

Fig. 2 (a) FT-IR spectra of PbS QDs film before and after TBAI ligand-exchange, and (b) XPS spectrum (I3d) of the TBAI-exchanged PbS QDs

图3 (a)油酸包覆的PbS量子点和(b)TBAI配体置换后量子点的TEM照片

Fig. 3 TEM images of (a) PbS QDs capped with oleic acid and (b) PbS QDs after ligand exchange with TBAI

图4 (a)二茂铁在乙腈溶液中的循环伏安曲线; (b)3.9 nm PbS量子点薄膜配体处理前后的循环伏安曲线; (c)和(d)分别为计算得到的油酸配体及TBAI配体置换后PbS量子点的能级图

Fig. 4 (a) Cyclic voltammetry curve of ferrocene in acetonitrile solution, (b) Cyclic voltammetry curves of 3.9 nm PbS QDs capped by OA and TBAI; The energy level diagrams of (c) as-synthesized PbS QDs with OA ligands and (d) PbS QDs after ligand exchange with TBAI

图5 (a) PbS/TiO2异质结电池结构示意图, (b) TiO2致密层的AFM图, (c) TiO2介孔层的AFM图和(d) TBAI配体钝化后PbS量子点薄膜的AFM图

Fig. 5 Schematic diagram (a) of the PbS/TiO2 heterojunction solar cell, AFM images of (b) TiO2 compact layer, (c) mesoporous TiO2 nanoparticle layer and (d) PbS QD film passivated by TBAI

图6 不同粒径PbS量子点/TiO2异质结电池的(a)亮态电流密度-电压曲线和(b) 暗态电流密度-电压曲线

Fig. 6 (a) Light current density-voltage curves and (b) dark current density-voltage curves of the PbS QDs/TiO2 heterojunction solar cells made of different sizes of QDs

表1 TBAI处理的不同粒径PbS量子点电池性能参数

Table 1 Parameters of solar cells made of different sizes of PbS QDs with TBAI ligands

Size/nm	V_oc/V	J_sc/(mA·cm^-2)	FF/%	η/%
2.6	0.43	11.0	25	1.18
3.1	0.37	13.7	29	1.47
3.9	0.35	15.4	43	2.32
4.5	0.33	6.93	35	0.80

图7 (a)PbS/TiO2异质结器件中所用材料的能级结构示意图, (b)3.9 nm 异质结器件中能带弯曲示意图和(c)4.5 nm异质结器件中能带弯曲示意图

Fig. 7 Energy level diagram (a) of the materials used in PbS/TiO2 heterojunction solar cells and schematic diagram of the energy levels in the heterojunction devices made of (b) 3.9 nm PbS QDs and (c) 4.5 nm PbS QDs.

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PbS量子点能级结构的尺寸和配体依赖性及其对异质结电池性能的影响

PbS Quantum Dots: Size, Ligand Dependent Energy Level Structures and Their Effects on the Performance of Heterojunction Solar Cells

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