Ag2Se量子点共敏化固态染料敏化太阳能电池光电性能研究

doi:10.15541/jim20180233

无机材料学报 ›› 2019, Vol. 34 ›› Issue (2): 137-144.DOI: 10.15541/jim20180233

所属专题：光伏材料

Ag₂Se量子点共敏化固态染料敏化太阳能电池光电性能研究

杨英^1,2,3,潘德群^1,2,3,张政^1,2,3,陈甜^1,2,3,韩晓敏¹,张力松¹,郭学益^1,2,3

1. 中南大学冶金与环境学院, 长沙 410083;
2. 有色金属资源循环利用湖南省重点实验室, 长沙 410083;
3. 有色金属资源循环利用湖南省工程研究中心, 长沙 410083

收稿日期:2018-05-17 修回日期:2018-09-20 出版日期:2019-02-20 网络出版日期:2019-01-24
作者简介:杨英(1980-),女,副教授.E-mail: muyicaoyang@csu.edu.cn
基金资助:
国家自然科学基金(61774169);中南大学创新驱动计划项目(2016CX022);留学回国基金资助以及湖南省自然科学基金(2016JJ3140);中南大学研究生创新项目(1053320170116, 1053320170565);中南大学本科生创新项目(cx20170271, 201710533300)

Photovoltaic Performance of Ag₂Se Quantum Dots Co-sensitized Solid-state Dye-sensitized Solar Cells

YANG Ying^{1, 2, 3}, PAN De-Qun^{1, 2, 3}, ZHANG Zheng^{1, 2, 3}, CHEN Tian^{1, 2, 3}, HAN Xiao-Min¹, ZHANG Li-Song¹, GUO Xue-Yi^{1, 2, 3}

1. School of Metallurgy and Environment, Central South University, Changsha 410083, China;
2. Hunan Key Laboratory of Nonferrous Metal Resources Recycling, Changsha 410083, China;
3. Hunan Engineering Research Center of Nonferrous Metal Resources Recycling, Changsha 410083, China

Received:2018-05-17 Revised:2018-09-20 Published:2019-02-20 Online:2019-01-24
About author:YANG Ying. E-mail: muyicaoyang@csu.edu.cn
Supported by:
National Natural Science Foundation of China (61774169);Third Innovation Driven Project of Central South University (2016CX022);Scientific Research Foundation for the Returned Overseas Chinese Scholar, Natural Science Foundation of Hunan (2016JJ3140);The Projects of Innovation for Graduate Student of Central South University (1053320170116, 1053320170565);The Projects of Innovation for Undergraduate Student of Central South University (cx20170271, 201710533300)

摘要/Abstract

摘要：

采用水相共沉积法制备Ag₂Se量子点(QDs), 并与染料共敏化制备固态染料敏化太阳能电池(DSSCs)。考察了Ag₂Se量子点不同敏化方式(TiO₂/N719/QDs, TiO₂/QDs/N719)及敏化时间(0~5 h)对DSSCs性能的影响。通过透射电子显微镜(TEM)和紫外-可见光谱图(UV-Vis)对Ag₂Se量子点结构及光学性质进行了表征; 采用光调制光电流/电压谱(IMPS/VS)以及交流阻抗谱(EIS)对器件中载流子传输过程进行了研究。TiO₂/QDs/N719的电池器件比TiO₂/ N719/QDs具有更高的单色光量子转化效率(IPCE)及光电转化效率, 这是由于TiO₂/QDs/N719可以吸附更多的量子点和染料。随着Ag₂Se量子点敏化时间的延长, 光电转化效率先提高后降低, 最高达到3.97%。Ag₂Se量子点在器件中起到了阻挡层作用, 可以促进电子传输, 抑制电子-空穴复合。而随着量子点敏化时间超过2 h, 电子陷入陷阱的几率增加, 导致器件的光伏性能下降。

关键词: Ag₂Se量子点, 水相共沉积法, 共敏化, 染料敏化太阳能电池

Abstract:

Ag₂Se quantum dots (QDs) was synthesized by co-deposition method which was further applied as co-sensitizer in solid-state dye-sensitized solar cells (DSSCs). The effects of different sensitization methods of Ag₂Se QDs (TiO₂/N719/QDs, TiO₂/QDs/N719) and sensitization time (0-5 h) on the performance of QDs/dye co-sensitized solar cells were studied. Structure and optical properties of Ag₂Se QDs were characterized by transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy (UV-Vis). Furthermore, the transmission of charge carriers of solar cell devices was characterized by photo-modulated photocurrent/voltage spectrum (IMPS/VS) and electrochemical impedance spectra (EIS). It was found that the device with TiO₂/QDs/N719 showed higher incident photon-to-current efficiency (IPCE) and photoelectric efficiency than those of TiO₂/N719/QDs, which was due to the fact that TiO₂/QDs/N719 photoanode adsorbed more QDs and dyes. With the extension of Ag₂Se QDs sensitization time, the photovoltaic properties of DSSCs firstly ascended and then descended, achieving the highest photoelectric conversion efficiency 3.97%. The incorporation of Ag₂Se QDs could effectively promote the electron transport and inhibit the electron-hole recombination, which benefited from a blocking layer that QDs served in device. As sensitization time prolonged over 2 h, the photovoltaic performances of device deteriorated, which was attributed to the augmented trap sites in Ag₂Se QDs layer.

Key words: Ag₂Se quantum dots, co-deposition method, co-sensitized, dye-sensitized solar cell

中图分类号:

TM914

杨英,潘德群,张政,陈甜,韩晓敏,张力松,郭学益. Ag₂Se量子点共敏化固态染料敏化太阳能电池光电性能研究[J]. 无机材料学报, 2019, 34(2): 137-144.

YANG Ying, PAN De-Qun, ZHANG Zheng, CHEN Tian, HAN Xiao-Min, ZHANG Li-Song, GUO Xue-Yi. Photovoltaic Performance of Ag₂Se Quantum Dots Co-sensitized Solid-state Dye-sensitized Solar Cells[J]. Journal of Inorganic Materials, 2019, 34(2): 137-144.

图/表 12

图1 Ag2Se量子点的(a)透射电镜照片, (b)粒径分布直方图, (c)高分辨透射电镜照片和(d)放大高分辨透射电镜照片

Fig. 1 (a)Transmission electron microscope (TEM) image, (b) size distribution histogram, (c) HRTEM image, and (d) zoom-in HRTEM image of the Ag2Se quantum dots

图2 (a) Ag2Se量子点乙醇溶液的紫外-可见光谱图; (b)相应的Tauc图谱

Fig. 2 (a) Absorption spectrum and (b) corresponding Tauc plot of the Ag2Se quantum dots in ethanol solution

图3 (a)不同敏化方式光阳极的紫外-可见吸收光谱分析, 插图为光阳极照片; (b)不同敏化方式DSSCs的J-V曲线

Fig. 3 (a) UV-Vis spectra of photoanodes with different Ag2Se QDs sensitization methods with inset showing photographs of photoandes, and (b) J-V curve of DSSCs with different sensitization methods

表1 不同敏化方式的光电参数

Table 1 Photovoltaic parameters of DSSCs with different sensitized methods

Sample	J_sc/(mA∙cm^-2)	V_oc/V	FF	ƞ/%
TiO₂/dye	8.78	0.69	0.50	2.96
TiO₂/dye/QDs	8.08	0.71	0.48	2.74
TiO₂/QDs/dye	9.18	0.74	0.53	3.59

图4 不同敏化方式的太阳能电池IPCE曲线

Fig. 4 IPCE spectra of DSSCs with different sensitization methods

图5 固态基Ag2Se量子点和染料共敏化太阳能电池的(a)结构示意图和(b)能带机理图

Fig. 5 (a) Device structure and (b) energy level diagram of solid-state Ag2Se QDs and dye co-sensitized solar cell

图6 (a)Ag2Se量子点敏化、N719敏化以及Ag2Se/N719共敏化光阳极的紫外-可见吸收光谱图; (b)Ag2Se量子点敏化不同时间的光阳极的紫外-可见吸收光谱图

Fig. 6 (a) UV-Vis absorption spectra of Ag2Se QDs sensitized, N719 sensitized and Ag2Se QDs/N719 co-sensitized photoanodes, and (b) UV-Vis absorption spectra of photoanodes with different sensitization time of Ag2Se QDs

图7 纯Ag2Se量子点敏化太阳能电池和Ag2Se量子点敏化不同时间的共敏化太阳能电池J-V曲线

Fig. 7 J-V curves of pure Ag2Se quantum dot sensitized solar cell and co-sensitized solar cells with different Ag2Se QDs sensitization time

表2 Ag2Se量子点敏化不同时间的共敏化太阳能电池光电参数

Table 2 Photovoltaic parameters of co-sensitized solar cells with different Ag2Se QDs sensitization time

Sample	J_sc/(mA∙cm^-2)	V_oc/V	FF	ƞ /%
TiO₂/QDs(2 h)	0.44	0.41	0.55	0.10
TiO₂/dye	8.78	0.69	0.50	2.96
TiO₂/QDs(1 h)/dye	9.18	0.74	0.53	3.59
TiO₂/QDs(2 h)/dye	9.53	0.75	0.55	3.97
TiO₂/QDs(3 h)/dye	9.46	0.73	0.55	3.82
TiO₂/QDs(4 h)/dye	8.69	0.75	0.56	3.68
TiO₂/QDs(5 h)/dye	7.69	0.74	0.55	3.10

图8 (a) Ag2Se量子点敏化不同时间的共敏化太阳能电池器件的交流阻抗图谱, 插图为等效电路图; (b) R2随Ag2Se量子点敏化时间的变化曲线

Fig. 8 (a) Electrochemical impedance plots of co-sensitized solar cells with different Ag2Se QDs sensitization time with inset showing the equivalent circuit, and (b) the recombination resistance R2 of DSSCs as a function of different Ag2Se QDs sensitization time

图9 Ag2Se量子点敏化不同时间的共敏化太阳能电池器件的(a) IMPS/VS和(b)IMVS图谱

Fig. 9 (a) IMPS and (b) IMVS plots of co-sensitized solar cells with different Ag2Se QDs sensitization time

表3 Ag2Se量子点敏化不同时间的共敏化太阳能电池器件的IMPS/VS动力学参数

Table 3 IMPS/VS kinetic parameters of co-sensitized solar cells with different Ag2Se QDs sensitization time

Sample	τ_d/ms	τ_c/ms	D_n/ (cm²·s^-1)	L_n/μm	η_cc
TiO₂/dye	31.77	8.45	7.25	15.18	0.73
TiO₂/QDs(1 h)/dye	33.65	8.45	7.25	15.62	0.75
TiO₂/QDs(2 h)/dye	42.37	7.98	7.68	18.04	0.81
TiO₂/QDs(3 h)/dye	42.37	8.45	7.25	17.52	0.80
TiO₂/QDs(4 h)/dye	31.77	7.53	8.14	16.07	0.76
TiO₂/QDs(5 h)/dye	23.83	8.45	7.25	13.14	0.65

参考文献 43

[1]	XIE Y S, TANG Y Y, WU W J,et al. Porphyrin cosensitization for a photovoltaic efficiency of 11.5%: a record for non-ruthenium solar cells based on iodine electrolyte. J. Am. Chem. Soc., 2015, 137(44): 14055-14058.
[2]	MATHEW S, YELLA A, GAO P,et al. Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers. Nat. Chem., 2014, 6(3): 242-247.
[3]	OZAWA H, YU O, ARAKAWA H.Dependence of the efficiency improvement of black-dye based dye-sensitized solar cells on alkyl chain length of quaternary ammonium cations in electrolyte solutions.Chem. Phys. Chem., 2014, 15(6): 1201-1206.
[4]	KAKIAGE K, AOYAMA Y, YANO T,et al. Fabrication of a high-performance dye-sensitized solar cell with 12.8% conversion efficiency using organic silyl-anchor dyes. Chem. Commun., 2015, 51(29): 6315-6317.
[5]	YU W W, PENG X G.Formation of high quality CdS and other II-VI semiconductor nanocrystals in noncoordinating solvents: tunable reactivity of monomers.Angew. Chem. Int. Ed., 2002, 41(13): 2368-2371.
[6]	SARMA D D, NAG A, SANTRA P K,et al. Origin of the enhanced photoluminescence from semiconductor CdSeS nanocrystals. J. Phys. Chem. Lett., 2010, 1(14): 2149-2153.
[7]	SEOL M, KIM H, TAK Y,et al. Novel nanowire array based highly efficient quantum dot sensitized solar cell. Chem. Commun., 2010, 46(30): 5521-5523.
[8]	ELLINGSON R J, BEARD M C, JOHNSON J C,et al. Highly efficient multiple exciton generation in colloidal PbSe and PbS quantum dots. Nano Lett., 2005, 5(5): 865-871.
[9]	SCHALLER R D, AGRANOVICH V M, KLIMOV V I.High-efficiency carrier multiplication through direct photogeneration of multi-excitons via virtual single-exciton states. Nat. Phys., 2005, 1(3): 189-194.
[10]	DU J, DU Z, HU J S,et al. Zn-Cu-In-Se quantum dot solar cells with a certified power conversion efficiency of 11.6%. J. Am. Chem. Soc., 2016, 138(12): 4201-4209.
[11]	JI G, LIU Z, GUAN D,et al. Ag2S quantum dots and N3 dye co-sensitized TiO2, nanotube arrays for a solar cell. Appl. Surf. Sci., 2013, 282(10): 695-699.
[12]	LIU Y, WANG J.Co-sensitization of TiO2, by PbS quantum dots and dye N719 in dye-sensitized solar cells.Thin Solid Films., 2010, 518(24): E54-E56.
[13]	YANG Y, GAO J, ZHANG Z,et al. Black phosphorus based photocathodes in wide band bifacial dye-sensitized solar cells. Adv. Mater., 2016, 28(40): 8937-8944.
[14]	GUO X Y, GAO J, ZHANG Z,et al. Highly efficient interfacial layer using SILAR derived Ag2S quantum dots for solid-state bifacial dye-sensitized solar. Mater. Today Energy, 2017, 5: 320-330.
[15]	GIMENEZ S, LANA-VILLARREAL T, GOMEZ R, et al. Determination of limiting factors of photovoltaic efficiency in quantum dot sensitized solar cells: correlation between cell performance and structural properties. J. Appl. Phys., 2010, 108(6): 064310-1-7.
[16]	SCHOEN D T, XIE C, CUI Y.Electrical switching and phase transformation in silver selenide nanowires.J. Am. Chem. Soc., 2007, 129(14): 4116-4117.
[17]	SAHU A, BRAGA D, WASER O,et al. Solid-phase flexibility in Ag2Se semiconductor nanocrystals. Nano Lett., 2014, 14(1): 115-121.
[18]	ZHU C N, JIANG P, ZHANG Z L,et al. Ag2Se quantum dots with tunable emission in the second near-infrared window. ACS Appl. Mater. Interfaces, 2013, 5(4): 1186-1189.
[19]	ZHANG Z, YANG Y, GAO J,et al. Highly efficient Ag2Se quantum dots blocking layer for solid-state dye-sensitized solar cells: size effects on device performances. Mater. Today Energy, 2018, 7: 27-36.
[20]	YANG Y, YI P, ZHOU C,et al. Magnetic field processed solid- state dye-sensitized solar cells with nickel oxide modified agarose electrolyte. J. Power Sources, 2013, 243(6): 919-924.
[21]	YANG Y, ZHANG Z, GAO J,et al. Metal-organic materials as efficient additives in polymer electrolytes for quasi-solid-state dye-sensitized solar cells. J. Alloy. Compd., 2017, 726: 1286-1294.
[22]	TIAN Q, DENG D, ZHANG Z,et al. Facile synthesis of Ag2Se quantum dots and their application in dye/Ag2Se co-sensitized solar cells. J. Mater. Sci., 2017, 52(20): 12131-12140.
[23]	GU Y P, CUI R, ZHANG Z L,et al. Ultrasmall near-infrared Ag2Se quantum dots with tunable fluorescence for in vivo imaging. J. Am. Chem. Soc., 2012, 134(1): 79-82.
[24]	PEJOVA B, NAJDOSKI M, GROZDANOV I,et al. Chemical bath deposition of nanocrystalline (111) textured Ag2Se thin films. Mater. Lett., 2000, 43(5/6): 269-273.
[25]	ANTHONY, PHILIP S.Synthesis of Ag2S and Ag2Se nanoparticles in self assembled block copolymer micelles and nano-arrays fabrication.Mater Lett., 2009, 63(9): 773-776.
[26]	SIBIYA P N, MOLOTO M J.Effect of precursor concentration and pH on the shape and size of starch capped silver selenide (Ag2Se) nanoparticles.Chalcogenide Lett., 2014, 11(11): 577-588.
[27]	LEE K E, GOMEZ M A, ELOUATIK S,et al. Further understanding of the adsorption mechanism of N719 sensitizer on anatase TiO2 films for DSSC applications using vibrational spectroscopy and confocal Raman imaging. Langmuir, 2010, 26(12): 9575-9583.
[28]	LUO J, WEI H, HUANG Q,et al. Highly efficient core-shell CuInS-Mn doped CdS quantum dot sensitized solar cells. Chem. Comm., 2013, 49(37): 3881-3883.
[29]	HU X, ZHANG Q X, HUANG X M,et al. Aqueous colloidal CuInS2 for quantum dot sensitized solar cells. J. Mater. Chem., 2011, 21(40): 15903-15905.
[30]	CUI C, QIU Y W, ZHAO J H,et al. A comparative study on the quantum-dot-sensitized, dye-sensitized and co-sensitized solar cells based on hollow spheres embedded porous TiO2 photoanodes. Electrochim. Acta, 2015, 173: 551-558.
[31]	REN F M, LI S J, HE C L.Electrolyte for quantum dot-sensitized solar cells assessed with cyclic voltammetry.Sci. China-Mater., 2015, 58(6): 490-495.
[32]	SHALOM M, DOR S, RUHLE S,et al. Core CdS quantum dot/shell mesoporous solar cells with improved stability and efficiency using an amorphous TiO2 coating. J. Phys. Chem. C, 2009, 11(9): 3895-3898.
[33]	SERO I M, BISQUERT J.Breakthroughs in the development of semiconductor-sensitized solar cells.J. Phys. Chem. Lett., 2010, 1(20): 3046-3052.
[34]	LAN Z, WU W X, ZHANG S,et al. An efficient method to prepare high-performance dye-sensitized photoelectrodes using ordered TiO2 nanotube arrays and TiO2 quantum dot blocking layers. J. Phys. Chem. C., 2016, 20(10): 2643-2650.
[35]	LI J, LI Z, WANG S,et al. Great improvement of photoelectric property from co-sensitization of TiO2 electrodes with CdS quantum dots and dye N719 in dye-sensitized solar cells. Mater. Res. Bull., 2013, 48(7): 2566-2570.
[36]	XU B, WU J H, ZHANG X K,et al. The influence of blocking layer on the photovoltaic properties of dye-sensitized solar cells. Journal of Function Materials, 2008, 39: 1703-1709.
[37]	LELII C, BAWENDI M G, BIAGINI P,et al. Enhanced photovoltaic performance with co-sensitization of quantum dots and an organic dye in dye-sensitized solar cells. J. Mater. Chem. A, 2014, 2: 18375-18382.
[38]	GAO J, YANG Y, ZHANG Z,et al. Bifacial quasi-solid-state dye-sensitized solar cells with poly (vinyl pyrrolidone)/polyaniline transparent counter electrode. Nano Energy, 2016, 26: 123-130.
[39]	ELBOHY H, THAPA A, POUDEL P,et al. Vanadium oxide as new charge recombination blocking layer for high efficiency dye-sensitizedsolar cells. Nano Energy, 2015, 13: 368-375.
[40]	YANG Y, WANG W.Effects of incorporating PbS quantum dots in perovskite solar cells based on CH3NH3PbI3.J. Power Sources, 2015, 293: 577-584.
[41]	LAGEMAAT J V D, FRANK A J. Nonthermalized electron transport in dye-sensitized nanocrystalline TiO2 films: transient photocurrent and random-walk modeling studies.J. Phys. Chem. B, 2001, 105(45): 11194-11205.
[42]	OEKERMANN T, ZHANG D, YOSHIDA T,et al. Electron transport and back reaction in nanocrystalline TiO2 films prepared by hydrothermal crystallization. J. Phys. Chem. B, 2004, 108(7): 2227-2235.
[43]	ZHU K, NEALE N R, MIEDANER A,et al. Enhanced charge-collection efficiencies and light scattering in dye-sensitized solar cells using oriented TiO2 nanotubes arrays. Nano Lett., 2007, 7(1): 69-74.

Ag₂Se量子点共敏化固态染料敏化太阳能电池光电性能研究

Photovoltaic Performance of Ag₂Se Quantum Dots Co-sensitized Solid-state Dye-sensitized Solar Cells

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 43

相关文章 15

编辑推荐

Metrics

本文评价

[1]	吕喜庆, 张环宇, 李瑞, 张梅, 郭敏. Nb₂O₅包覆对TiO₂纳米阵列/上转换发光复合结构柔性染料敏化太阳能电池性能的影响[J]. 无机材料学报, 2019, 34(6): 590-598.
[2]	程厚燕, 罗俊, 黄丽群, 李家科, 杨志胜, 郭平春, 王艳香, 张琦锋. 基于ZnO纳米片多级结构的柔性染料敏化太阳能电池的制备[J]. 无机材料学报, 2018, 33(5): 507-514.
[3]	刘永强, 黄浩, 翟进生, 马梦君, 范佳杰. 石墨烯量子点/CdS/CdSe共敏化太阳能电池[J]. 无机材料学报, 2017, 32(10): 1042-1048.
[4]	冉慧丽, 黄浩, 马梦君, 翟进生, 范佳杰. 性能增强的双层TiO₂复合膜染料敏化太阳能电池[J]. 无机材料学报, 2017, 32(10): 1049-1054.
[5]	杨英, 张政, 高菁, 林泽华, 严靖园, 郭学益. 基于低共熔溶剂聚合物电解质染料敏化太阳能电池研究[J]. 无机材料学报, 2017, 32(1): 25-32.
[6]	尹月锋, 梁桂杰, 张强, 潘峥, 李望南, 李在房. 基于Pechini溶胶-凝胶法的染料敏化太阳能电池的优化[J]. 无机材料学报, 2016, 31(7): 739-744.
[7]	张陈乐, 张培新, 云斯宁, 李永亮, 何挺树. 染料敏化太阳能电池过渡金属化合物对电极制备方法研究进展[J]. 无机材料学报, 2016, 31(2): 113-122.
[8]	谢寿东, 王刚, 陈慧媛, 林红, 闫志男, 张慧. 黑枸杞与石墨烯纳米片在染料敏化太阳能电池中的应用[J]. 无机材料学报, 2016, 31(10): 1117-1122.
[9]	陈盎然，赵伟，崔厚磊，支键，黄富强. 基于介孔TiO₂/石墨烯修饰的TiO₂纳米线光阳极的染料敏化太阳能电池[J]. 无机材料学报, 2015, 30(8): 891-896.
[10]	陈蔚, 刘阳桥, 罗建强, 靳喜海, 孙静, 高濂. 柔性染料敏化太阳能电池TiO₂光阳极的制备[J]. 无机材料学报, 2014, 29(6): 561-570.
[11]	唐蓓蓓, 郭明星, 姜维, 尹淑慧, 张曼霞, 王亮, 张艺鸣, 郑磊, 孟悦琦. 钼酸锌-碳复合材料在染料敏化太阳能电池对电极中的应用[J]. 无机材料学报, 2014, 29(11): 1133-1138.
[12]	王桂强, 王德龙, 况帅, 禚淑萍. 染料敏化太阳能电池用过渡金属化合物对电极的研究进展[J]. 无机材料学报, 2013, 28(9): 907-915.
[13]	罗华明, 刘志勇, 白传易, 鲁玉明, 蔡传兵. 基于二氧化钛纳米管的染料敏化电池光阳极研究[J]. 无机材料学报, 2013, 28(5): 521-526.
[14]	孟凡宁, 王春雷, 武明星, 林逍, 王同华, 马廷丽. 染料敏化太阳能电池无FTO煤基炭对电极的研究[J]. 无机材料学报, 2013, 28(3): 273-277.
[15]	崔旭梅, 左承阳, 蓝德均, 王军. TiO₂/SnO₂纳米晶膜的制备及其电学性能研究[J]. 无机材料学报, 2013, 28(11): 1233-1236.