CdS/ZnO纳米线异质结构的制备与性质研究
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摘要
随着现代化工业进程的不断加快,人们对能源的需求进一步加大。太阳能作为一种极其重要的可再生能源受到了人们广泛关注。如何低成本的利用太阳能发电成为人类社会面临的重大挑战之一。为了更加有效的转化和利用太阳能,获得性能稳定、光电转化效率高的极薄窄带隙半导体异质结太阳电池,我们对CdS/ZnO纳米线异质结构光电极进行了制备和性质分析。
本研究主要工作如下:一方面,制备ZnO纳米线阵列,通过对成核和生长条件的控制改变纳米线长度、密度、长径比、取向等形貌。另一方面,在ZnO纳米线阵列上沉积CdS窄带隙半导体薄层,调节窄带隙半导体光吸收层的厚度等进而制备有良好光吸收性质的窄带隙半导体薄层/氧化物半导体纳米线电极。
利用扫描和透射电镜、X-射线衍射技术、紫外-可见吸收光谱、拉曼光谱(Raman)等测试手段表征ZnO纳米线阵列及CdS/ZnO纳米线异质结构的形貌和光学质量等性质;研究沉积条件、退火热处理等因素对CdS薄层的均匀性、厚度、和晶粒尺寸等的影响。利用光电化学等手段研究CdS薄层的厚度以及晶粒尺寸等对其光敏化ZnO纳米线效率的影响。将CdS/ZnO纳米线异质结构进行优化,最终将其应用于I-/I3-电解质体系制成沉积50次的硫化镉薄层敏化长度为2微米的氧化锌纳米线阵列的电池,获得0.51%的光电转换效率。
With the rapid development of modern industry process, the energy requirement of people is further rising. Solar energy, as one of the most important renewable energy sources, has attracted considerable attentions. Exploiting solar energy at a low cost has been a big challenge for the human society. In order to convert and utilize solar energy more efficiently, searching a thin narrow band-gap semiconductor heterojunction solar cell with stable performance and high photoelectric conversion efficiency, we fabricated the CdS/ZnO heterojunction and analyzed its photoelectrochemical properties.
The main content of this study is listed as follows: On one hand, we have synthesized ZnO nanowire array successfully, controlling the morphology of nanowire such as length, density, aspect ratio, orientation etc by changing the conditions of nucleation and growth. On the other hand, ZnO nanowire array was conformally coated with an ultrathin CdS shell layer and then the narrow band-gap semiconductor thin layer/oxide semiconductor nanowire electrode with favorable light absorption property has been prepared successfully by regulating the light absorption layer thickness.
The structure and the optical properties of ZnO nanowire and CdS/ZnO nanowire heterojunction are investigated by XRD,SEM, TEM, Raman, and UV-visible absorption spectra.We have studied the effects of deposition conditions, annealing heat treatment etc on the uniformity, thickness, and grain size of CdS thin layer. Furthermore, we have studied the effect of thickness and grain size of CdS layer on the photosensitizing efficiency of ZnO nanowire by means of photoelectrochemistry. Optimal CdS/ZnO nanowire heterojunction (depositing CdS 50 times on 2 microns-length ZnO nanowire array) was achieved and applied to I/I3- electrolyte system eventually. The cell photoelectric conversion efficiency was 0.51%.
本研究主要工作如下:一方面,制备ZnO纳米线阵列,通过对成核和生长条件的控制改变纳米线长度、密度、长径比、取向等形貌。另一方面,在ZnO纳米线阵列上沉积CdS窄带隙半导体薄层,调节窄带隙半导体光吸收层的厚度等进而制备有良好光吸收性质的窄带隙半导体薄层/氧化物半导体纳米线电极。
利用扫描和透射电镜、X-射线衍射技术、紫外-可见吸收光谱、拉曼光谱(Raman)等测试手段表征ZnO纳米线阵列及CdS/ZnO纳米线异质结构的形貌和光学质量等性质;研究沉积条件、退火热处理等因素对CdS薄层的均匀性、厚度、和晶粒尺寸等的影响。利用光电化学等手段研究CdS薄层的厚度以及晶粒尺寸等对其光敏化ZnO纳米线效率的影响。将CdS/ZnO纳米线异质结构进行优化,最终将其应用于I-/I3-电解质体系制成沉积50次的硫化镉薄层敏化长度为2微米的氧化锌纳米线阵列的电池,获得0.51%的光电转换效率。
With the rapid development of modern industry process, the energy requirement of people is further rising. Solar energy, as one of the most important renewable energy sources, has attracted considerable attentions. Exploiting solar energy at a low cost has been a big challenge for the human society. In order to convert and utilize solar energy more efficiently, searching a thin narrow band-gap semiconductor heterojunction solar cell with stable performance and high photoelectric conversion efficiency, we fabricated the CdS/ZnO heterojunction and analyzed its photoelectrochemical properties.
The main content of this study is listed as follows: On one hand, we have synthesized ZnO nanowire array successfully, controlling the morphology of nanowire such as length, density, aspect ratio, orientation etc by changing the conditions of nucleation and growth. On the other hand, ZnO nanowire array was conformally coated with an ultrathin CdS shell layer and then the narrow band-gap semiconductor thin layer/oxide semiconductor nanowire electrode with favorable light absorption property has been prepared successfully by regulating the light absorption layer thickness.
The structure and the optical properties of ZnO nanowire and CdS/ZnO nanowire heterojunction are investigated by XRD,SEM, TEM, Raman, and UV-visible absorption spectra.We have studied the effects of deposition conditions, annealing heat treatment etc on the uniformity, thickness, and grain size of CdS thin layer. Furthermore, we have studied the effect of thickness and grain size of CdS layer on the photosensitizing efficiency of ZnO nanowire by means of photoelectrochemistry. Optimal CdS/ZnO nanowire heterojunction (depositing CdS 50 times on 2 microns-length ZnO nanowire array) was achieved and applied to I/I3- electrolyte system eventually. The cell photoelectric conversion efficiency was 0.51%.
引文
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[3](美)汉斯S劳申巴赫著,张金熹,廖春发,傅德棣等译.太阳电池阵设计手册[M].北京:宇航出版社,1987,126-132.
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[6] Lori emattlaw, Greene, Justinc, et al. Nanowire dye-sensitized solar cells [J]. nature materials 2005,4(1038):455-458.
[7]申树芳,刘伶俐,徐承天.太阳电池研究及应用[J].化学教学,2007(4):45-47.
[8]刘恩科,朱炳升,罗晋生,等.半导体物理学[M].西安市:西安交通大学出版社,1998,280-283.
[9]苏梦蟾.聚合物有机太阳能电池器件的研究[D]:[硕士学位论文].北京:北京交通大学物理电子学,2006.
[10]朱道本,王佛松.有机固体[M].上海:上海科学技术出版社,1999.89-96.
[11]春兰.独立运行光伏发电系统功率控制研究[D]:[硕士学位论文].内蒙古:内蒙古工业大学物理学院,2004.
[12]SunWen-Tao, Yu Yuan, Pan Hua-Yong,et al. CdS Quantum Dots Sensitized TiO2 Nanotube-Array Photoelectrodes [J]. J Am ChemSoc, 2008, 130 (4), 1124-1125.
[13] Krasina E A,Tveriyanovich E V,Romankevich AV. Optical efficiency of solar engineering Fresnel lenses[J].Applied Solar Energy,1989(6):6-10.
[14] Nayak J, Sahu S N, Kasuya J, et al. CdS-ZnO composite nanorods: Synthesis, characterization and application for photocatalytic degradation of 3,4-dihydroxy benzoic acid[J]. Applied Surface Science, 2008, 254, 7215-7218.
[15]王力衡,黄运添,郑海涛.薄膜技术[M].北京:清华大学出版社,1991.18-19.
[16]田民波.薄膜技术与薄膜材料[M].北京:清华大学出版社,2006.287-289.
[17]Park S M, Ikegami T, Ebihara K, et al. Structure and properties of transparent conductive doped ZnO films by pulsed laser deposition[J]. Appl Surf S,2006,253(3):1522-1527.
[18] Fu Z, Lin B, Zu J.Photoluminescence and structure of ZnO films deposited on Si substrates by-organic chemicaI vapor deposition[J].Thin Sol Fi ,2002,402(1-2):302-306.
[19] Chen Y, Bagnall D, and Yao T. ZnO as a novel photonic material for the UV region. Mater. Sci. Eng. B, 2000, 75(2-3):190-198.
[20] Jolanta Prywer. Explanation of some peculiarities of crystal morphology deduced from the BFDH law . J Cryst Growth 2004, 270:699-710.
[21] Cang H X, Huang W D. and Zhou Y H. Effects of organic solvents on the morphology of themeta-nitroaniline crystal[J].Journal of Crystal Growth, 1998, 192:236-242.
[22] Lokhane C D. Chemical Deposition of Metal Chalcogenide Thin Films [J]. Materials Chemistry and Physics.1991,27:1-43 .
[23] Malle R S, Lokhande C D.Chemical Deposition Method for Metal Chalcogenide Thin Films[J].Materials Chemistry and Physics.2000,65:1-31.
[24] Niesen T P, Guire M R D.Review: Deposition of Ceramic Thin Films at Low Temperatures fix an Aqueous Solutions [J].Solid State Ionics.2002,151:61-68.
[25] Ibanez J G, Gomez F, Konik I,et al. Preparation of Semiconducting Materials in the Laboratory,Part 2:Mieroscale Chemical Bath Deposition of Materials with Band Gap Energies in the UV, VIS, and IR[J].Journal of Chemical Education.1997,74:1205-1207.
[26]Pawar S H, Bhosale P N .Growth of Thin Films by Solution-gas Interface : A New Technique[J].Materials Chemistry and Physics.1984,11:461-479.
[27] Nair P K, Nair M T S , Garcig V M ,et al. Semiconductor thin Films by Chemical Bath Deposition for Solar Energy Related Applications[J].Solar Energy Materials and Solar Ceils.1998,52:313-344.
[28] Nair P K, Nair M T S, Fernandez A, et al. Prospects of Chemically Deposition Metal Chalcogenide Thin Films for Solar Control Applications[J]. Joumal of Physics D:Applied Physics.1989, 22:829-836.
[29]丛秋滋.多晶二维X射线衍射阴.北京:科学出版社,1997,36.
[30]陈治明,王建农.半导体器件的材料物理学基础[M].北京:科学出版社,1999.263.
[31] Ma J G, Liu Y C,Xu C S, et al. Preparation and characterization of ZnO particles embedded in SiO2 matrix by reactive magnetron sputtering[J].J Appl Phys, 2005,97: 103(509) 1-6.
[32]赵藻藩,周性尧,张悟铭,等.仪器分析[M].北京:北京高等教育出版社,1990. 67-75.
[33]白春礼.扫描隧道显微术及其应用[M].上海:上海科学技术出版社,1992.
[34]周玉,武高辉.材料分析测试技术-材料X射线与电子显微分析[M].哈尔滨:哈尔滨工业大学出版社,1998.
[35]常铁军,祁欣.材料近代分析测试方法[M].哈尔滨:哈尔滨工业大学出版社, 1999.
[36]方容川.固体光谱学[M].合肥:中国科学技术大学出版社,2003.282-285.
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