CdS、ZnS及Zn_XCd_（1-X）S纳米材料的制备与表征
摘要
近年来,纳米半导体微粒已经吸引了科学家们的广泛关注。作为ⅡB-ⅥA族中重要的半导体纳米材料,CdS、ZnS具有不同于其体相材料的物理和化学性质,在许多领域有潜在的应用。因此,对这些半导体纳米微粒的合成方法的研究在国内外已经成为一个非常活跃的领域。
在本文中,我们用简单经济的化学方法成功地在液相中合成,得到了CdS、ZnS半导体纳米微粒和复合结构ZnXCd1-XS纳米微粒。其合成路线为,以溶剂无水乙醇为反应介质,浓度为0.002 mol·L-1的乙酸镉和乙酸锌、0.004 mol·L-1的硫脲为反应前驱体,不同浓度的聚乙烯吡咯烷酮(PVP)为大分子表面活性剂,整个体系在持续的强磁力搅拌下保持在乙醇回流温度下反应,分别制备得到了CdS和ZnS半导体纳米微粒。改变反应前躯体乙酸锌与乙酸镉的化学计量比,制备得到复合结构的ZnXCd1-XS纳米微粒。在N,N-二甲基甲酰胺为介质的体系中,反应恒温在100℃进行,同样得到了CdS、ZnS纳米半导体及复合结构ZnXCd1-XS纳米微粒。
利用紫外-可见吸收光谱、荧光光谱、透射电子显微镜、X-射线衍射等测试手段对合成的CdS、ZnS半导体纳米微粒及复合结构ZnXCd1-XS纳米微粒样品进行光学性质及结构方面的表征。通过分析其在室温下的紫外-可见吸收光谱图,发现吸收峰值波长明显地朝短波长方向移动,这是由量子尺寸效应引起的“蓝移现象”。用透射电子显微镜观察,结果发现制备得到的纳米微粒的尺寸都在20～60nm的范围内。这些样品在无水.乙醇及N,N-二甲基甲酰胺中有良好的分散性和稳定性。荧光光谱测试结果表明合成的CdS及ZnS半导体纳米微粒可以产生较为明显的表面缺陷态发光。通过改变复合结构ZnXCd1-XS中的化学计量比,可以获得不同颜色的发光光谱。XRD的结果给出了典型的纳米半导体CdS晶体的衍射谱图。
Nanosemiconductor particles have attracted broad attention from scientists in recent years. As importantⅡB-ⅥA semiconductor nanometerials, CdS and ZnS exhibit unique physical and chemical properties that can not be obtained in their bulk corresponding counterpas. They have potential application in many areas. So the investigation for the synthesis ways to nanosemiconductor particles becomes a very active topic home and overseas.
In this paper, CdS, ZnS nanosemiconductors and composite ZnXCd1-XS nanoparticles were obtained successfully through a facile and inexpensive chemical synthesis scheme in solutions respectively. The organic regent ethanol was used as reaction medium, acetic cadmium (0.002mol·L-1), acetic zinc (0.002mol·L-1) and thiourea (0.004mol·L-1) were the reaction precursors, different concentration of Polyvinylpyrrolidone was the macromolecular surfactant. The whole reaction system keep the temperature of ethanol circumfluence under strongly continuous magnetic stirring, a few minutes latter, CdS and ZnS semiconductor particles were obtained respectively. The composite ZnXCd1-XS nanoparticles were also prepared via changing the molar ratios of acetic cadmium and acetic zinc in this mixed ternary. Keep the consistent conditions with the front all the same, foregoing three kinds nanoparticles were gained in the reaction system of N,N-Dimethylformamide(DMF) at 100℃.
UV-Vis absorption spectrum, Transmission electron mirror images, Fluorescence spectra and X-ray diffraction patterns were used to characterize optical properties and crystalloid structures of samples. The UV-Vis absorption spectrum of samples was analyzed. Their spectrums shift evidently to short wavelength. This is so called the phenomenon of blue-shift due to quantum size effect. The transmission electron mirror images showed that the size of particles was the range of 25～60nm. The dispersibility and stability of them were good in ethanol and DMF. Besides, their photoluminescence spectrum was measured. The results indicated CdS and ZnS semiconductor nanoparticals brought obvious surface trap irradiance. Lots of color-tunable emission of the composite ZnXCd1-XS nanoparticles could be watched by changing the composition of particles. X-ray diffraction patterns of nanosemiconductor CdS was obtained and indicated that it was cubic crystalloid.
在本文中,我们用简单经济的化学方法成功地在液相中合成,得到了CdS、ZnS半导体纳米微粒和复合结构ZnXCd1-XS纳米微粒。其合成路线为,以溶剂无水乙醇为反应介质,浓度为0.002 mol·L-1的乙酸镉和乙酸锌、0.004 mol·L-1的硫脲为反应前驱体,不同浓度的聚乙烯吡咯烷酮(PVP)为大分子表面活性剂,整个体系在持续的强磁力搅拌下保持在乙醇回流温度下反应,分别制备得到了CdS和ZnS半导体纳米微粒。改变反应前躯体乙酸锌与乙酸镉的化学计量比,制备得到复合结构的ZnXCd1-XS纳米微粒。在N,N-二甲基甲酰胺为介质的体系中,反应恒温在100℃进行,同样得到了CdS、ZnS纳米半导体及复合结构ZnXCd1-XS纳米微粒。
利用紫外-可见吸收光谱、荧光光谱、透射电子显微镜、X-射线衍射等测试手段对合成的CdS、ZnS半导体纳米微粒及复合结构ZnXCd1-XS纳米微粒样品进行光学性质及结构方面的表征。通过分析其在室温下的紫外-可见吸收光谱图,发现吸收峰值波长明显地朝短波长方向移动,这是由量子尺寸效应引起的“蓝移现象”。用透射电子显微镜观察,结果发现制备得到的纳米微粒的尺寸都在20～60nm的范围内。这些样品在无水.乙醇及N,N-二甲基甲酰胺中有良好的分散性和稳定性。荧光光谱测试结果表明合成的CdS及ZnS半导体纳米微粒可以产生较为明显的表面缺陷态发光。通过改变复合结构ZnXCd1-XS中的化学计量比,可以获得不同颜色的发光光谱。XRD的结果给出了典型的纳米半导体CdS晶体的衍射谱图。
Nanosemiconductor particles have attracted broad attention from scientists in recent years. As importantⅡB-ⅥA semiconductor nanometerials, CdS and ZnS exhibit unique physical and chemical properties that can not be obtained in their bulk corresponding counterpas. They have potential application in many areas. So the investigation for the synthesis ways to nanosemiconductor particles becomes a very active topic home and overseas.
In this paper, CdS, ZnS nanosemiconductors and composite ZnXCd1-XS nanoparticles were obtained successfully through a facile and inexpensive chemical synthesis scheme in solutions respectively. The organic regent ethanol was used as reaction medium, acetic cadmium (0.002mol·L-1), acetic zinc (0.002mol·L-1) and thiourea (0.004mol·L-1) were the reaction precursors, different concentration of Polyvinylpyrrolidone was the macromolecular surfactant. The whole reaction system keep the temperature of ethanol circumfluence under strongly continuous magnetic stirring, a few minutes latter, CdS and ZnS semiconductor particles were obtained respectively. The composite ZnXCd1-XS nanoparticles were also prepared via changing the molar ratios of acetic cadmium and acetic zinc in this mixed ternary. Keep the consistent conditions with the front all the same, foregoing three kinds nanoparticles were gained in the reaction system of N,N-Dimethylformamide(DMF) at 100℃.
UV-Vis absorption spectrum, Transmission electron mirror images, Fluorescence spectra and X-ray diffraction patterns were used to characterize optical properties and crystalloid structures of samples. The UV-Vis absorption spectrum of samples was analyzed. Their spectrums shift evidently to short wavelength. This is so called the phenomenon of blue-shift due to quantum size effect. The transmission electron mirror images showed that the size of particles was the range of 25～60nm. The dispersibility and stability of them were good in ethanol and DMF. Besides, their photoluminescence spectrum was measured. The results indicated CdS and ZnS semiconductor nanoparticals brought obvious surface trap irradiance. Lots of color-tunable emission of the composite ZnXCd1-XS nanoparticles could be watched by changing the composition of particles. X-ray diffraction patterns of nanosemiconductor CdS was obtained and indicated that it was cubic crystalloid.
引文
1. 张立德.纳米材料和纳米结构—国家重大基础研究项目新进展[M],北京：化学工业出版社,2005,1-453.
2. Su F H, Fang Z L, Ma B S, et al. Pressure Dependence of Mn2+ Luminescence in Differently Sized ZnS:Mn Nanoparticles [J], Journal of Physical Chemistry B,2003,107, 6991-6996.
3. 炼景先.21世纪的新材料—纳米材料[J],世界有色金属,1999,(1)：34-36.
4. 徐国财.纳米科技导论[M],北京：高等教育出版社,2005,1-365.
5. 朱静.纳米材料和器件[M],北京：清华大学出版社,2003,1-448
6. Joo J, Na H B, Yu T Y, et al. Generalized and Facile Synthesis of Semiconducting Metal Sulfide Nanocrystals [J], Journal of the American Chemical Society,2003,125(36): 11100-11105.
7. 夏建白.半导体纳米材料和物理[J],评述,2003,32(10)：693-699.
8. 范长宇,李学萍,张振宗,等.硫化物半导体超微粒量子尺寸效应的光谱研究[J],感光科学与光化学,1995,13(2)：97-101.
9. Yi D K, Selvan S, Lee S S, et al. Silica-Coated Nanocomposites of Magnetic Nanoparticles and Quantum Dots [J], Journal of the American Chemical Society,2005, 127(14):4990-4991.
10. Palaniappan K, Xue C H, Arumugam G, et al. Water-Soluble, Cyclodextrin-Modified CdSe-CdS Core-Shell Structured Quantum Dots [J], Chem. Materials,2006,18(5):275-1280.
11. 沈宗华,王安杰,解建国,等.二维硫化锌材料的制备及其研究进展[J],化工进展,2006,25(4)：392-396.
12. 孙宝全,徐咏蓝,衣光舜,等.半导体纳米晶体的光致发光特性及在生物材料荧光标记中的应用[J],分析化学评述与进展,2002,30(9)：1130-1136.
13. Wang Y, Tang Z Y, Correa-Duarte M A, et al. Mechanism of Strong Luminescence Photoactivation of Citrate-Stabilized Water-Soluble Nanoparticles with CdSe Cores [J], The Journal of Physical Chemistry B,2004,108(40):15461-15469.
14. Panda A B, Acharya S, Efrima S, et al. Synthesis, Assembly, and Optical Properties of Shape- and Phase-Controlled ZnSe Nanostructures [J], Journal of the American Chemical Society,2007,23(2):765-770.
15. Rao A P, Pajonk G M, Rao A V. Effect of pH, Aging, and Drying on the Size of CdS Nanocrystallites, Monolithicity, and Transparency of Nanocrystalline CdS-Doped Silica Xerogels [J], Journal of Materials Synthesis and Processing,2001,9(1):11-18.
16.曹维良,张凯华,张敬畅.表面修饰纳米CdS制备中两个重要影响因素及结构表征[J],无机化学学报,2002,10：997-1002.
17. Salata O V, Dobson P J, Sabesan S, et al. Preparation of nanoparticulate CdS films suitable for opto-electronic device applications [J], Thin Solid Films,1996,288(1-2): 235-238.
18. Omura K, Hanahusa A, Arita T, et al. Recent technical advances in thin-film CdS/CdTe solar cells [J], Renewable Energy,1996,8(1-4):405-409.
19. Nanda K K, Sarangi S N, Mohanty S, et al. Optical properties of CdS nanocrystalline films prepared by a precipitation technique [J], Thin Solid Films,1998,322(1-2):21-27.
20. Innocenti M, Cattarin S, Cavallini M, et al. Characterisation of thin films of CdS deposited on Ag(111) by ECALE. A morphological and Photoelectrochemical investigation [J], Journal of Electroanalytiecal Chemistry,2002,532(1-2):219-225.
21. Maldotti A, Andreotti L, Molinari A, et al. Photochemical and photocatalytic reduction of nitrobenzene in the presence of cyclohexene [J], Journal of Photochemistry and Photobiology A:Chemistry,2000,133(1-2):129- 133.
22. Yang Y, Shi J L, Dai S G, et al. High third-order non-resonant optical non- linearities of surface modified CdS quantum dots embedded in BaTiO3 thin film [J], Thin Solid Films, 2003,437(1-2):217-222.
23. Zhao Y W, Zhang Y, Zhu H, et al. Low-Temperature Synthesis of Hexagonal (Wurtzitr) ZnS Nanocrystals [J], Journal of American Chemical Society,2004,126(22):6874-6875.
24.邢德松,石建新,庞起,等.乙醇体系中硫化锌纳米粒子的制备及其光致发光性能研究[J],中山大学学报(自然科学版),2003,42(6)：125-126.
25.李亚玲,王玉红,甄崇礼.纳米硫化锌的制备及光谱分析[J],光谱学与光谱分析,2007,27(9)：1890-1893.
26. Xia B, Lenggoro I W, Okuyama K. Synthesis and Photoluminescence of Spherical ZnS:Mn2+Particles [J], Chemistry of Materials,2002,14(12):4969-4974.
27.常鹏,刘肃,王秀华,等.水热法制备硫化锌纳米线及性能研究[J],人工晶体学报, 2007,36(4):817-820.
28.栾野梅.硫化镉纳米膜的电化学制备方法[J],半导体光电,2007,28(2)：213-217.
29. Ni Y H, Yin G, Hong J M, et al. Rapid fabrication and optical properties of zinc sulfide nanocrystallines in a heterogeneous system [J], Materials Research Bulletin,2004,39 (12):1967-1972.
30. Yang Y, Zhang W J. Preparation and photoluminescence of zinc sulfide nanowires [J], Materials Letters,2004,58(29):3836-3838.
31. Bao H B, Gong Y J, Li Z, et al. Enhancement Effect of Illumination on the Photoluminescence of Water-Soluble CdTe Nanocrystals:Toward Highly Fluorescent CdTe/CdS Core-Shell Structure [J], Chemistry of Materials,2004,16(20):3853- 3859.
32.史鸿鑫,王农跃,项斌,等.化学功能材料概论[M],北京：化学工业出版社,2006,8-48.
33.牛俊杰,沙健,马向阳,等.光电子领域中的纳米半导体材料[J],材料导报,2002,16(11)：62-64.
34.宁远.纳米材料的奇异表面效应[J],有色金属,2001,53(3)：9.
35.王占国,陈涌海,叶小玲,等.纳米半导体技术[M],北京：化学工业出版社,2006,4-8.
36.李占双,李芳.纳米半导体的合成现状[J],2005,122(11)：35-37.
37. Lenggoro I W, Okuyama K, de la Mora J F, et al. Preparation of ZnS Nanoparticles by Electrospray Pyrolysis [J], Journal of Aerosol Science,2000,31(1):121-136.
38.李云峰,兰尧中.纳米硫化锌的制备与应用状况[J],湿法冶金,2007,26(3)：123-127.
39. Lu H Y, Chu S Y, Tan S S. The Characteristics of Low-temperature synthesized ZnS and ZnO Nanoparticles [J]. Journal of Crystal Growth,2004,269(2-4):385-391.
40.唐文华,邹洪涛,蒋天智,等.低温固相合成纳米硫化镉的新方法[J],无机盐工业,2006,38(4)：22-24.
41.刘劲松,曹洁明,李子全,等.ZnS纳米粒子的固相合成及其光学性能[J],无机化学学报,2007,23(5)：832-838.
42.张萍,崔海信,李玲玲.纳米TiO2半导体溶胶的光生物学效应[J],无机材料学报,2008,23(1)：55-60.
43.刘辉,魏雨.纳米级铁酸盐粉体材料合成的进展[J],功能材料,2000,31(2)：124-126.
44.彭子飞,汪国忠,王颖,等.化学共沉淀法制备纳米级PbTiO3粉末[J],材料科学与工程,1997,15(1)：26-28.
45.梁丽萍,高荫本.不同干燥工艺制备CaO-ZrO2复合氧化物粉体及粉体性能表征[J],材料科学与工程,1997,15(2)：37-40.
46.苏凌浩,张校刚.脲酶诱发均匀沉淀法室温下制备纳米CdS[J],功能材料与器件学报,2005,11(3)：273-276.
47.俞英,周震涛.核壳纳米晶二硒化镉/硫化镉的合成及荧光法测定溶菌酶[J],分析化学,2005,33(5)：650-652.
48.李兰英,郭峰,古国华,等.水热法制备均分散的硫化锌纳米晶聚集体[J],青岛科技大学学报,2005,26(3)：211-214.
49. Qian Y T, Su Y, Xie Y, et al. Hydrothermal preparation and characterization of nano-crystalline powder of sphalerite [J]. Materials Research Bullletin,1995,30(5):601-605.
50.张莉,刘梅川,程欲晓,等.PVP/CdS量子点修饰电极的制备及其对肌红蛋白的直接电化学研究[J],化学传感器,2005,25(2)：52-56.
51.牛新书,刘艳丽,徐甲强.室温固相合成纳米及其气敏性能研究[J],无机材料学报,2002,17(4)：817-821.
52.邓玉荣,丁晓夏,甘仲惟.化学气相沉积法合成纳米球[J],华中师范大学学报,2002,36(3)：305-307.
53.邵庆辉,古国榜,章莉娟.微乳化技术在纳米材料制备中的应用研究[J],化工新型材料,2001,7：9-12.
54.侯长军,兰作平,霍丹群.微乳法制备超细级纳米材料的研究现状与进展[J],材料导报,2007,21：14-16.
55.刘选明,刘巧玲,萧小鹃,等.微乳液法制备CdSe/CdS核壳纳米粒子及表征[J],湖南大学学报(自然科学版),2006,33(2)：90-94.
56.张鹏,高濂.水热微乳液法合成硫化镉纳米棒晶[J],无机材料学报,2003,18(4)：772-776.
57.聂福德,曾贵玉,尹莉莎,等.硫化锌纳米粒子的微乳液合成[J],材料科学与工艺,2002,10(2)：160-163.
58.曾贵玉,聂福德,尹莉莎,等.硫化锌纳米粒子的乳液合成[J],化学研究与应用,2001,13(4)：442-444.
59.江元汝,崔延青,杨琴,等.乳液法制备纳米硫化锌及表征[J],西安建筑科技大学,2005,37(2)：287-290.
60.何典,周正发,范继贤,等.CdS纳米管合成方法研究进展[J],广东化工,2007,34(1)：49-52.
61.唐文华,张艾飞,邹洪涛,等.CdS纳米材料合成方法研究进展[J],贵州师范大学学报(自然科学版),2006,24(2)：119-124.
62.张言波,邵华峰,钱雪峰,等.单分散球形硫化镉粒子的制备及其形貌控制[J],无机材料学报,2005,20(3)：575-579.
63.王世铭,刘萍,付贤智.离子交换膜中CdS单分散纳米晶的合成及其光学性质[J],物理化学学报,2005,21(10)：1151-1155.
64.余红英.半导体CdS1-XSeX纳米材料的制备及其光吸收性能研究[D],江苏南京理工大学,2007.
65.沈学础.半导体光谱和光学性质[M],北京：科学出版社,2002,1-85.
66.白冰.硫化镉纳米粒子的形貌控制合成研究[D],湖南中南大学,2007.
67.杨洋.乙酸分子缔合结构的荧光光谱分析[D],江苏南京理工大学,2006.
68.刘粤惠,刘平安.X射线衍射分析原理与应用[M],北京：化学工业出版社,2003,1-150.
69.张小琴,谭镜明.纳米材料的应用进展[J],河北化工,2006,29(10)：55-57.
70.田明原,施尔畏,郭景坤.纳米陶瓷与纳米陶瓷粉末[J],无机材料学报,1998,1(32)：129-137.
71.胡安正.纳米科技与纳米材料的应用研究[J],郧阳师范高等专科学校学报,2005,25(6)：39-43.
72. Bogomolov V N, Feoktistov N A, Golubev V G, et al. Three-dimensional array of silicon nanoscale elements in artificial SiO2 opal host [J], Journal of non-crystalline solids,2000, 266-269:1021-1024.
73.王德禧.2006年纳米材料应用技术进展[J],国外塑料,2007,125(1-2)：38-43.
74.唐辉.催化领域中纳米材料的利用[J],科技信息,35-36.
75. Vinodgopal K, Wynkoop D E, Kamat P V. Environmental photochemistry on semicon-ductor surfaces:photosensitized degradation of a textile azdye, acid orange 7, on TiO2 particles using visible light [J], Environmental Science and Technology,1996,30(5): 1660-1666.
76.吴鸣,李文钊,顾婉贞,等.主客体结构纳米半导体光催化的界面钉住效应[J],催化学报,1999,20(3)：297-300.
77.徐宝财.日用化学品—性能、制备、配方(第二版)[M],北京：化学工业出版社,2008,106-109.
78.韩慧芳,崔英德,蔡立彬.聚乙烯吡咯烷酮的应用[J],精细石油化工进展,2003,4 (11)：43-48.
79.马婷芳,史铁钧.聚乙烯吡咯烷酮的性能、合成及应用[J],应用化工,2002,31(3)：16-19.
80. Sun Y G, Xia Y N. Shape-Controlled Synthesis of Gold and Silver Nanoparticles [J], Science,2002,298:2176-2179.
81. Peng Z A, Peng X G. Nearly Monodisperse and Shape-Controlled CdSe Nanocrystals via Alternative Routes:Nucleation and Growth [J], Journal of the American Chemical Society,2002,124 (13):3343-3353.
82.唐文华,邹洪涛,刘吉平,等.纳米硫化镉液相合成及其研究进展[J],无机盐工业,2006,38(7)：9-13.
83. Murray C B, Norris D J, Bawendi M G. Synthesis and characterization of nearly mono-disperse CdE (E=S, Se, Te) Semiconductor Nanocrystallites [J], Journal of American Chemical Society,1993,115(19):8706-8715.
84.刘引烽,贺英,刘丽,等.电致发光聚合物/纳米半导体材料及其双功能器件[J],高分子通报,2006,(5)：79-85.
85. Empedocles S A, Neuhauser R, Shimizu K, et al. Photoluminescence from Single Semiconductor Nanostructures [J], Advanced Materials,1999,11(15):1243-1256.
86. Zhong X H, Feng Y Y, Wolfgang K, et al. Alloyed ZnXCd1-XS Nanocrystals with Highly Narrow Luminescence Spectral Width [J], Journal of American Chemical Society,2003, 125(44):13559- 13563.
87.秦竹丽.纳米硫化锌复合半导体的制备及性能研究[D],陕西西安建筑科技大学,2007.
2. Su F H, Fang Z L, Ma B S, et al. Pressure Dependence of Mn2+ Luminescence in Differently Sized ZnS:Mn Nanoparticles [J], Journal of Physical Chemistry B,2003,107, 6991-6996.
3. 炼景先.21世纪的新材料—纳米材料[J],世界有色金属,1999,(1)：34-36.
4. 徐国财.纳米科技导论[M],北京：高等教育出版社,2005,1-365.
5. 朱静.纳米材料和器件[M],北京：清华大学出版社,2003,1-448
6. Joo J, Na H B, Yu T Y, et al. Generalized and Facile Synthesis of Semiconducting Metal Sulfide Nanocrystals [J], Journal of the American Chemical Society,2003,125(36): 11100-11105.
7. 夏建白.半导体纳米材料和物理[J],评述,2003,32(10)：693-699.
8. 范长宇,李学萍,张振宗,等.硫化物半导体超微粒量子尺寸效应的光谱研究[J],感光科学与光化学,1995,13(2)：97-101.
9. Yi D K, Selvan S, Lee S S, et al. Silica-Coated Nanocomposites of Magnetic Nanoparticles and Quantum Dots [J], Journal of the American Chemical Society,2005, 127(14):4990-4991.
10. Palaniappan K, Xue C H, Arumugam G, et al. Water-Soluble, Cyclodextrin-Modified CdSe-CdS Core-Shell Structured Quantum Dots [J], Chem. Materials,2006,18(5):275-1280.
11. 沈宗华,王安杰,解建国,等.二维硫化锌材料的制备及其研究进展[J],化工进展,2006,25(4)：392-396.
12. 孙宝全,徐咏蓝,衣光舜,等.半导体纳米晶体的光致发光特性及在生物材料荧光标记中的应用[J],分析化学评述与进展,2002,30(9)：1130-1136.
13. Wang Y, Tang Z Y, Correa-Duarte M A, et al. Mechanism of Strong Luminescence Photoactivation of Citrate-Stabilized Water-Soluble Nanoparticles with CdSe Cores [J], The Journal of Physical Chemistry B,2004,108(40):15461-15469.
14. Panda A B, Acharya S, Efrima S, et al. Synthesis, Assembly, and Optical Properties of Shape- and Phase-Controlled ZnSe Nanostructures [J], Journal of the American Chemical Society,2007,23(2):765-770.
15. Rao A P, Pajonk G M, Rao A V. Effect of pH, Aging, and Drying on the Size of CdS Nanocrystallites, Monolithicity, and Transparency of Nanocrystalline CdS-Doped Silica Xerogels [J], Journal of Materials Synthesis and Processing,2001,9(1):11-18.
16.曹维良,张凯华,张敬畅.表面修饰纳米CdS制备中两个重要影响因素及结构表征[J],无机化学学报,2002,10：997-1002.
17. Salata O V, Dobson P J, Sabesan S, et al. Preparation of nanoparticulate CdS films suitable for opto-electronic device applications [J], Thin Solid Films,1996,288(1-2): 235-238.
18. Omura K, Hanahusa A, Arita T, et al. Recent technical advances in thin-film CdS/CdTe solar cells [J], Renewable Energy,1996,8(1-4):405-409.
19. Nanda K K, Sarangi S N, Mohanty S, et al. Optical properties of CdS nanocrystalline films prepared by a precipitation technique [J], Thin Solid Films,1998,322(1-2):21-27.
20. Innocenti M, Cattarin S, Cavallini M, et al. Characterisation of thin films of CdS deposited on Ag(111) by ECALE. A morphological and Photoelectrochemical investigation [J], Journal of Electroanalytiecal Chemistry,2002,532(1-2):219-225.
21. Maldotti A, Andreotti L, Molinari A, et al. Photochemical and photocatalytic reduction of nitrobenzene in the presence of cyclohexene [J], Journal of Photochemistry and Photobiology A:Chemistry,2000,133(1-2):129- 133.
22. Yang Y, Shi J L, Dai S G, et al. High third-order non-resonant optical non- linearities of surface modified CdS quantum dots embedded in BaTiO3 thin film [J], Thin Solid Films, 2003,437(1-2):217-222.
23. Zhao Y W, Zhang Y, Zhu H, et al. Low-Temperature Synthesis of Hexagonal (Wurtzitr) ZnS Nanocrystals [J], Journal of American Chemical Society,2004,126(22):6874-6875.
24.邢德松,石建新,庞起,等.乙醇体系中硫化锌纳米粒子的制备及其光致发光性能研究[J],中山大学学报(自然科学版),2003,42(6)：125-126.
25.李亚玲,王玉红,甄崇礼.纳米硫化锌的制备及光谱分析[J],光谱学与光谱分析,2007,27(9)：1890-1893.
26. Xia B, Lenggoro I W, Okuyama K. Synthesis and Photoluminescence of Spherical ZnS:Mn2+Particles [J], Chemistry of Materials,2002,14(12):4969-4974.
27.常鹏,刘肃,王秀华,等.水热法制备硫化锌纳米线及性能研究[J],人工晶体学报, 2007,36(4):817-820.
28.栾野梅.硫化镉纳米膜的电化学制备方法[J],半导体光电,2007,28(2)：213-217.
29. Ni Y H, Yin G, Hong J M, et al. Rapid fabrication and optical properties of zinc sulfide nanocrystallines in a heterogeneous system [J], Materials Research Bulletin,2004,39 (12):1967-1972.
30. Yang Y, Zhang W J. Preparation and photoluminescence of zinc sulfide nanowires [J], Materials Letters,2004,58(29):3836-3838.
31. Bao H B, Gong Y J, Li Z, et al. Enhancement Effect of Illumination on the Photoluminescence of Water-Soluble CdTe Nanocrystals:Toward Highly Fluorescent CdTe/CdS Core-Shell Structure [J], Chemistry of Materials,2004,16(20):3853- 3859.
32.史鸿鑫,王农跃,项斌,等.化学功能材料概论[M],北京：化学工业出版社,2006,8-48.
33.牛俊杰,沙健,马向阳,等.光电子领域中的纳米半导体材料[J],材料导报,2002,16(11)：62-64.
34.宁远.纳米材料的奇异表面效应[J],有色金属,2001,53(3)：9.
35.王占国,陈涌海,叶小玲,等.纳米半导体技术[M],北京：化学工业出版社,2006,4-8.
36.李占双,李芳.纳米半导体的合成现状[J],2005,122(11)：35-37.
37. Lenggoro I W, Okuyama K, de la Mora J F, et al. Preparation of ZnS Nanoparticles by Electrospray Pyrolysis [J], Journal of Aerosol Science,2000,31(1):121-136.
38.李云峰,兰尧中.纳米硫化锌的制备与应用状况[J],湿法冶金,2007,26(3)：123-127.
39. Lu H Y, Chu S Y, Tan S S. The Characteristics of Low-temperature synthesized ZnS and ZnO Nanoparticles [J]. Journal of Crystal Growth,2004,269(2-4):385-391.
40.唐文华,邹洪涛,蒋天智,等.低温固相合成纳米硫化镉的新方法[J],无机盐工业,2006,38(4)：22-24.
41.刘劲松,曹洁明,李子全,等.ZnS纳米粒子的固相合成及其光学性能[J],无机化学学报,2007,23(5)：832-838.
42.张萍,崔海信,李玲玲.纳米TiO2半导体溶胶的光生物学效应[J],无机材料学报,2008,23(1)：55-60.
43.刘辉,魏雨.纳米级铁酸盐粉体材料合成的进展[J],功能材料,2000,31(2)：124-126.
44.彭子飞,汪国忠,王颖,等.化学共沉淀法制备纳米级PbTiO3粉末[J],材料科学与工程,1997,15(1)：26-28.
45.梁丽萍,高荫本.不同干燥工艺制备CaO-ZrO2复合氧化物粉体及粉体性能表征[J],材料科学与工程,1997,15(2)：37-40.
46.苏凌浩,张校刚.脲酶诱发均匀沉淀法室温下制备纳米CdS[J],功能材料与器件学报,2005,11(3)：273-276.
47.俞英,周震涛.核壳纳米晶二硒化镉/硫化镉的合成及荧光法测定溶菌酶[J],分析化学,2005,33(5)：650-652.
48.李兰英,郭峰,古国华,等.水热法制备均分散的硫化锌纳米晶聚集体[J],青岛科技大学学报,2005,26(3)：211-214.
49. Qian Y T, Su Y, Xie Y, et al. Hydrothermal preparation and characterization of nano-crystalline powder of sphalerite [J]. Materials Research Bullletin,1995,30(5):601-605.
50.张莉,刘梅川,程欲晓,等.PVP/CdS量子点修饰电极的制备及其对肌红蛋白的直接电化学研究[J],化学传感器,2005,25(2)：52-56.
51.牛新书,刘艳丽,徐甲强.室温固相合成纳米及其气敏性能研究[J],无机材料学报,2002,17(4)：817-821.
52.邓玉荣,丁晓夏,甘仲惟.化学气相沉积法合成纳米球[J],华中师范大学学报,2002,36(3)：305-307.
53.邵庆辉,古国榜,章莉娟.微乳化技术在纳米材料制备中的应用研究[J],化工新型材料,2001,7：9-12.
54.侯长军,兰作平,霍丹群.微乳法制备超细级纳米材料的研究现状与进展[J],材料导报,2007,21：14-16.
55.刘选明,刘巧玲,萧小鹃,等.微乳液法制备CdSe/CdS核壳纳米粒子及表征[J],湖南大学学报(自然科学版),2006,33(2)：90-94.
56.张鹏,高濂.水热微乳液法合成硫化镉纳米棒晶[J],无机材料学报,2003,18(4)：772-776.
57.聂福德,曾贵玉,尹莉莎,等.硫化锌纳米粒子的微乳液合成[J],材料科学与工艺,2002,10(2)：160-163.
58.曾贵玉,聂福德,尹莉莎,等.硫化锌纳米粒子的乳液合成[J],化学研究与应用,2001,13(4)：442-444.
59.江元汝,崔延青,杨琴,等.乳液法制备纳米硫化锌及表征[J],西安建筑科技大学,2005,37(2)：287-290.
60.何典,周正发,范继贤,等.CdS纳米管合成方法研究进展[J],广东化工,2007,34(1)：49-52.
61.唐文华,张艾飞,邹洪涛,等.CdS纳米材料合成方法研究进展[J],贵州师范大学学报(自然科学版),2006,24(2)：119-124.
62.张言波,邵华峰,钱雪峰,等.单分散球形硫化镉粒子的制备及其形貌控制[J],无机材料学报,2005,20(3)：575-579.
63.王世铭,刘萍,付贤智.离子交换膜中CdS单分散纳米晶的合成及其光学性质[J],物理化学学报,2005,21(10)：1151-1155.
64.余红英.半导体CdS1-XSeX纳米材料的制备及其光吸收性能研究[D],江苏南京理工大学,2007.
65.沈学础.半导体光谱和光学性质[M],北京：科学出版社,2002,1-85.
66.白冰.硫化镉纳米粒子的形貌控制合成研究[D],湖南中南大学,2007.
67.杨洋.乙酸分子缔合结构的荧光光谱分析[D],江苏南京理工大学,2006.
68.刘粤惠,刘平安.X射线衍射分析原理与应用[M],北京：化学工业出版社,2003,1-150.
69.张小琴,谭镜明.纳米材料的应用进展[J],河北化工,2006,29(10)：55-57.
70.田明原,施尔畏,郭景坤.纳米陶瓷与纳米陶瓷粉末[J],无机材料学报,1998,1(32)：129-137.
71.胡安正.纳米科技与纳米材料的应用研究[J],郧阳师范高等专科学校学报,2005,25(6)：39-43.
72. Bogomolov V N, Feoktistov N A, Golubev V G, et al. Three-dimensional array of silicon nanoscale elements in artificial SiO2 opal host [J], Journal of non-crystalline solids,2000, 266-269:1021-1024.
73.王德禧.2006年纳米材料应用技术进展[J],国外塑料,2007,125(1-2)：38-43.
74.唐辉.催化领域中纳米材料的利用[J],科技信息,35-36.
75. Vinodgopal K, Wynkoop D E, Kamat P V. Environmental photochemistry on semicon-ductor surfaces:photosensitized degradation of a textile azdye, acid orange 7, on TiO2 particles using visible light [J], Environmental Science and Technology,1996,30(5): 1660-1666.
76.吴鸣,李文钊,顾婉贞,等.主客体结构纳米半导体光催化的界面钉住效应[J],催化学报,1999,20(3)：297-300.
77.徐宝财.日用化学品—性能、制备、配方(第二版)[M],北京：化学工业出版社,2008,106-109.
78.韩慧芳,崔英德,蔡立彬.聚乙烯吡咯烷酮的应用[J],精细石油化工进展,2003,4 (11)：43-48.
79.马婷芳,史铁钧.聚乙烯吡咯烷酮的性能、合成及应用[J],应用化工,2002,31(3)：16-19.
80. Sun Y G, Xia Y N. Shape-Controlled Synthesis of Gold and Silver Nanoparticles [J], Science,2002,298:2176-2179.
81. Peng Z A, Peng X G. Nearly Monodisperse and Shape-Controlled CdSe Nanocrystals via Alternative Routes:Nucleation and Growth [J], Journal of the American Chemical Society,2002,124 (13):3343-3353.
82.唐文华,邹洪涛,刘吉平,等.纳米硫化镉液相合成及其研究进展[J],无机盐工业,2006,38(7)：9-13.
83. Murray C B, Norris D J, Bawendi M G. Synthesis and characterization of nearly mono-disperse CdE (E=S, Se, Te) Semiconductor Nanocrystallites [J], Journal of American Chemical Society,1993,115(19):8706-8715.
84.刘引烽,贺英,刘丽,等.电致发光聚合物/纳米半导体材料及其双功能器件[J],高分子通报,2006,(5)：79-85.
85. Empedocles S A, Neuhauser R, Shimizu K, et al. Photoluminescence from Single Semiconductor Nanostructures [J], Advanced Materials,1999,11(15):1243-1256.
86. Zhong X H, Feng Y Y, Wolfgang K, et al. Alloyed ZnXCd1-XS Nanocrystals with Highly Narrow Luminescence Spectral Width [J], Journal of American Chemical Society,2003, 125(44):13559- 13563.
87.秦竹丽.纳米硫化锌复合半导体的制备及性能研究[D],陕西西安建筑科技大学,2007.