Q-CdS/聚合物纳米复合膜的制备、表征和光电性能
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摘要
本文综述了国内外CdS/聚合物纳米复合膜的研究与发展现状,合成了一系列不同粒径、不同聚合物基体、不同Q-CdS含量的Q-CdS/聚合物纳米复合膜,通过透射电子显微镜对其形态、结构和粒径进行了表征,通过紫外吸收光谱、荧光发射光谱及导电率等测试手段对其光电性能进行了研究,具体如下:
     1.通过改变硫化氢的加入量,反应中硫醇与镉离子的比例含量以及分步沉降的次数制备出几种不同粒径的Q-CdS。通过讨论分步沉降过程中沉降剂的类型、用量以及沉降次数等因素分离出单分散性的Q-CdS。通过改变硫醇的碳链和加入量,对比有氧无氧合成环境的影响,研究了Q-CdS的表面修饰效应,结果表明这种表面经过修饰的Q-CdS荧光强度明显增大,并且可以发出两种不同颜色的荧光。
     2.将制备好的Q-CdS溶液与聚合物溶液通过机械搅拌共混,挥发溶剂成膜,制备出一系列不同粒径、不同聚合物、不同Q-CdS含量的Q-CdS/聚合物纳米复合膜,通过透射电子显微镜对其形态进行了表征,发现Q-CdS与聚合物想互作用,有效阻止了Q-CdS粒子间的团聚,通过紫外可见吸收光谱的研究,发现这些纳米复合膜具有明显的量子尺寸效应。
     3.研究了不同粒径、不同Q-CdS含量的Q-CdS/聚合物纳米复合膜的荧光光谱性质,并且对不同聚合物基体的Q-CdS/聚合物纳米复合膜荧光光谱性质进行了比较。发现不同粒径的Q-CdS/聚合物纳米复合膜具有明显的荧光量子尺寸效应,并且这种以聚合物为基体的纳米复合膜,由于聚合物与Q-CdS之间的相互作用,表现出与单一相组分完全不同的特征荧光发射峰,而Q-CdS的含量对Q-CdS/聚合物纳米复合膜的荧光发光强度具有重要的影响。
     4.将导电聚苯胺和Q-CdS溶液采用共混法复合,通过紫外可见光谱表征,电导率测定以及荧光光谱性能测定,发现Q-CdS/聚苯胺因Q-CdS特殊的纳米结构和聚苯胺的掺杂特性,表现出特殊的导电性和荧光发光性能。
In this thesis, the studies on the synthesis, analysis means, the properties and applications of CdS/polymer nanocomposite films have been reviewed in detail. A series of Q-CdS/polymer nanocomposite films with different polymer materials, different sizes or different content of Q-CdS were prepared and their morphological structure and sizes were observed in TEM images. Photoelectronic properties of these nanocomposites were studied by UV-vis spectra, fluorescent spectra and conductivity measurement, etc.
    1. Several kinds of Q-CdS nanoparticles with different sizes were prepared by changing the content of H2S, the radio of the reactants and the times of size-selective precipitation. In addition, Q-CdS nanoparticles with narrow disperse were obtained by changing the type and volume of precipitating agent and times of precipitation, etc. The effect of surface modification of Q-CdS was studied by changing carbon chain and content of mercaptan and environment of synthesis. The results showed that the intensities of the samples would increase more greatly than that of the un-modified in fluorescence spectra and two kind of fluorescence with different color would be observed.
    2. Some kinds of Q-CdS/polymer nanocomposite films were successfully prepared by mixing Q-CdS with polymer under different conditions such as particle sizes, the ratio of the Q-CdS/polymer and the kind of polymer matrix, etc. Their morphological structures were observed in TEM image. The results indicate that the strong interaction between Q-CdS particles and polymers had the obvious effect on preventing the particles from aggregating. At the same time, the size quantization effect was observed on their UV-vis spectra.
    3. Size quantization effect was also observed on fluorescent spectra of different sizes Q-CdS/polymer nanocomposite films. Compared to Q-CdS nanoparticles or single matrix, these nanocomposite films have the capability to show special fluorescent properties due to the strong interaction between them and the intensity
    
    
    would change with the content of the Q-CdS nanoparticle.
    4. A series of Q-CdS/PANi nanaocomposite solution were successfully prepared by mixing Q-CdS with PANi and characterized by UV-spectra, fluorescent spectra and conductivity measurement etc. The special fluorescent and conductive properties can be observed due to the nanostructure of Q-CdS and the ability of intermingle for
    PANi.
引文
[1] 张立德,牟季美主编.纳米材料和纳米结构[M].北京:科学出版社,2002.
    [2] J.H.芬德勒等著,项金钟,吴兴惠译.纳米粒子与纳米结构薄膜[M].北京:化学工业出版社,2003.
    [3] 朱屯,王福明,王习东等编著.国外纳米材料技术进展与应用[M].北京:化学工业出版社,2002.
    [4] 陈德文,王素华.纳米级CdS粒子尺寸量子化的化学效应研究[J].中国科学(B辑),1996,26(3),262~267
    [5] Y. Wang, N. Herron. Nanometer-Sized Semiconductor Clusters: Materials synthesis, quantum size effects, and photophysical properties[J]. J. Phys. Chem., 1991, 95, 525~532
    [6] Y. Wang, A. Suna, J. McHugh. Optical transient bleaching of quantum-confined CdS clusters: The effects of surface-trapped electron-hole pairs[J], J. Chem. Phys., 1990, 92(11), 6927~6938
    [7] 章伟光,范军,钟昀等.Q态硫化镉纳米晶的制备、形态、量子尺寸效应与光催化性能[J].中国科学(B辑),2003,33(1),66~73
    [8] 徐国财,张立德编著.纳米复合材料[M].北京:化学工业出版社,2002
    [9] 柯扬船,皮特.斯壮主编.聚合物-无机纳米复合材料[M].北京:化学工业出版社,2003
    [10] 李玲,向航编著.纳米技术与功能材料[M].北京:化学工业出版社,2002
    [11] T. B. Liu, L. Z. Liu, B. Chu. Nanofabrication in polymer solutions[J]. 应用化学, 2001, 18(5), 259~266
    [12] D. Meissner, R. Memming, B. Kastening. Light-induced generation of hydrogen at CdS-monograin membranes[J]. Chem. Phys. Letters, 1983, 96(1), 34~37
    [13] M. Krishnan, J. R. White, A. J. Bard, et al. Inregrated Chemical Systems: Photocatalysis at semiconductors incorporated into polymer(Nafion)/mediator systems[J], J. Am. Chem. Soc., 1983, 105, 7002~7003
    [14] W. H. Mau, A. J. Bard, E. Webber, et al. H_2 Photoproduction by Nafion/CdS/Pt Films in H_2O/S~(2-) Solutions[J]. J. Am. Chem. Soc., 1984, 106, 6537~6542
    [15] Y. Wang, N. Herron. Photoconductivity of CdS nanocluster-doped polymers[J]. Chemical
    
    Physics Letters, 1992, 200(1, 2), 71~75
    [16] J. G. Winiarz, L. M. Zhang, M. Lal, et al. Observation of the photorefractive effect in a hybrid organic-inorganiv nanocomposite[J]. J. Am. Chem., 1999, 121, 5287~5295
    [17] S. H. Wang, S. H. Yang, C. L. Yang, el al. Poly(N-vinylcarbazole)(PVK) Photoconductivity enhancement induced by doping with CdS nanocrystals through chemical hybridization[J]. J. Phys. Chem. B, 2000, 104(50), 11853~11858
    [18] K. R. Choudhury, J. G. Winiarz, M. Samoc, et al. Charge carrier mobility in an organic-inorganic hybrid nanocomposite[J]. Applied Physics Letters, 2003, 82(3), 406~408
    [19] S. Pethkar, R. C. Partil, J. A. Kher, et al. Deposition and characterization of CdS nanoparticles/polyaniline composite films[J]. Thin Solid Film, 1999, 349, 105~109
    [20] D. Yu. Codovsky, A. E. Varfolomeev, D. F. Zaretsky, et al. Prepartion of nanocomposites of polyaniline and inorganic semiconductors[J]. J. Mater Chem., 2001, 11, 2465~2469
    [21] 李东升,吕功煊.制备导电聚合物-半导体纳米颗粒自组装膜[J].物理化学学报,2001,17(3),252~256
    [22] 李东升,吕功煊.导电聚合物-半导体纳米颗粒自组装膜(Ⅱ)光电化学性质[J].高等学校化学学报,2002,23(4),685~689
    [23] X. Y. Ma, G. X. Lu, B. J. Yang. Study of the luminescence characteristics of cadmium sulfide quantum dots in a sulfonic group polyaniline(SPAn) film, Applied Surface Science[J], 2002, 187: 235-238
    [24] V. L. Colvin, M. C. Schlamp, A. P. Alivsatos. Light-emitting diodes made from cadmium selenide nanocrystals and a semiconducting polymer[J]. Letters to Nature, 1994, 370(4), 354~356
    [25] G. Leo, M. L Curri, A. Cola, et al. Preparation and characterization of organic-inorganic heterojunction based on BDA-PPV/CdS nanocrystals[J]. Materials Science and Engineering, 2000, B74, 175~179
    [26] X. K. Zhao, S. Q, Xu, J. H. Fendler. Semiconductor particles formed at monolayer surfaces[J]. Langmuir, 1991, 7, 520~524
    [27] L. Spanhel, E. Arpac, H. Schmidt. Semiconductor clusters in the sol-gel process: synthesis and properties of CdS nanocomposites[J]. J. Non-Crystalline Solids, 1992, 147~148, 657~602
    
    
    [28] N. A. Kotov, I. Dekany, J. H. Fendler. Layer-by-layer self-assembly of polyelectrolyte-semiconductor nanoparticles composite[J]. J. Phys. Chem., 1995, 99, 13065~13069
    [29] M. Y. Gao, X. Zhang, B. Yang, et al. Assembly of modified CdS particles/cationc polymer based on electrostatic interactions[J]. Thin Solid Films, 1996, 284~285, 242~245
    [30] H. M. Xiong, Z. Zhou, Z. Q. Wang, et al. A new approach to fabrication of a self-organizing film of heterostructured polymer/CdS nanoparticles[J]. Supramolecular Science, 1998, 5(5~6), 623~626
    [31] A. S. Susha, F. Caruso, A. L. Rogach, G. B. Sukhorukov, et al. Formation of luminescent spherical core-shell particles by the consecutive adsorption of polyeletrolyte and CdTe(S) nanocrystals on latex colloids[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2000, 163, 39~44
    [32] F. Grohn, E. J. Amis, B. J. Bauer, et al. Nanoparticle formation within dendrimer-containing polymer networks: route to new organic-inorganic hybrid materials[J], Macromolecules, 2001, 34, 2179~2185
    [33] A. Chevreau, B. Phillips, B. G. Higgins, et al. Processing and optical properties of spin-coated polystyrene films containing CdS nanoparticles[J]. J. Mater. Chem., 1996, 6(10), 1643~1647
    [34] S. H. Yu, M. Yoshimura, J.M.C. Moreno, et al. In situ fabrication and optical properties of a novel polystyrene/semiconductor nanocomposite embedded with CdS nanowires by a soft solution processing route[J]. Langmuir, 2001, 17, 1700~1707
    [35] H. Du, G. Q. Xu, W. S. Chin. Synthesis, characterization, and nonlinear optical properties of hybridized CdS-polystyrene nanocomposites. Chem. Mater., 2002, 14, 4473~4479
    [36] M. Moffitt, A. Eisenberg. Size control of nanoparticles in multiplet aggregation numbers in styrene-based random ionomers[J]. Chem. Mater., 1995, 7, 1178~1184
    [37] M. Moffitt, H. Vaili, A. Eisenberg. Spherical assemblies of semiconductor nanoparticles in water-soluble block copolymer aggregates. Chem. Mater., 1998, 10, 1021~1028
    [38] D. Wang, Y. Cao, X. T. Zhang, et al. Size control of CdS nanocrystals in bolck copolymer micelle[J]. Chem. Mater., 1999, 11, 392~398
    [39] H. Y. Zhao, E. P. Douglas, B. S. Harrison, et al. Preparation of CdS Nanoparticles in
    
    Salt-Induced Block Copolymer Micelles[J]. Langmuir, 2001, 17, 8428~8433
    [40] H. Y. Zhao, E. P. Douglas. Preparation of Corona-Embedded CdS Nanoparticles[J]. Chem. Mater., 2002, 14, 1418~1423
    [41] 陈慧文,李军荣,章明秋等.纳米CdS的表面修饰及其与嵌段共聚物的复合材料[J].全国高分子学术论文报告会,2003,F65~F66
    [42] 黄金满,杨毅,沈家骢等.硫化镉纳米微粒在聚合物网络中的组装[J].高等学校化学学报,1995,16(12),1976~1977
    [43] J.M. Huang, Y. Yang, J. C. Shen, et al. Synthesis of the CdS nanoparticles in polymer networks[J]. Polymer Bulletin, 1996, 36, 337~340
    [44] H. L. Hu, P. K. Nair. Chemical deposition of photosensitive CdS thin films on polyester foils[J]. J. Crystal Growth, 1995, 152, 150~157
    [45] M. A. Olshavsky, H. R. Allcock. Synthesis of CdS Nanoparticles in Solution and in a Polyphosphazene Matrix[J]. Chem. Mater., 1997, 9, 1367~1376
    [46] Y. Xie, Z. P Qiao, M. Chen, et al. Spherical assemblies of CdS nanofibers in poly(vinyl acetate) by γ-irradiation[J]. Nanostructured Materials, 1999, 11(8), 1165~1169
    [47] Y. Xie, Z. P. Qiao, M. Chen, et al.γ-Irradiation route to semiconductor/polymer nanocable fabrication[J]. Adv. Mater., 1999, 11(18), 1512~1514
    [48] J. H. Zeng, J. Yang, Y. Zhu, et al. Nanocomposite of CdS particles in polymer rods fabricated by a novel hydrothermal polymerization and simultaneous sulfidation technique[J]. Chem. Commun., 2001, 1332~1333
    [49] M. Chen, Y. Xie, H. Y. Chen, et al. Templated synthesis of CdS/PAN composite nanowires under ambient conditions[J]. J. Collid and Interface Science, 2000, 229, 217~221
    [50] P. A. Bianconi, J. Lin, A. R. Strzelecki. Crystallization of an inorganic phase controlled by a polymer matrix[J]. Letters to Nature, 1991, 349(24), 315~317
    [51] J. Lin, E. Cates, P. A. Bianconi. A synthetic analogue of the biomineralization process: controlled crystallization of an inorganic phase by a polymer matrix[J]. J. Am. Chem. Soc., 1994, 116, 4738~4745
    [52] 樊凤秋,胡志国,张瑞云等,聚乙二醇与镉(Ⅱ)离子的配位作用及其对硫化镉结晶的影响[J].无机化学学报,1996,12(1),76~79
    [53] Y. F. Liu, L. Chen, B. Su, et al. Synthesis and characterization of CdS nanocrystals embedded
    
    on solid electrolyte films[J]. J. Applied Polymer Science, 2002, 84, 1263~1268
    [54] S. Yamazaki, Y. Kurokawa. Preparation of non-linear optic polymer films doped with fine particles by a mutual couter diffusion method[J]. Polymer Commun., 1991, 32(17), 524~527
    [55] I. Nosaka, K. Tanaka, N. Fujii. Laser-irradiation effect on poly(vinyl alcohol)films doped with nanometer-sized CdS particles: ablation and third-harmonic generztion[J]. Secience of Applied Polymer, 1993, 47, 1773~1779
    [56] O. V. Salata, P. J. Dobson, P. J. Hull, et al. Fabrication of CdS nanoparticles embedded in a polymer film by gas-aerosol reactive electrostatic deposition technique[J]. Thin Solid Films, 1994, 251, 1~3
    [57] V. S. Gurin, M. V. Artemyev. CdS quantum dots in colloids and polymer matrices: electronic structure and photochemical properties[J]. Journal of Crystal Growth, 1994, 138, 993~997
    [58] M. V. Artemyev, S. V. Gaponenko, I. N. Germanenko, et al. Irreversible photochemical spectral hole burning in quantum-sized CdS nanocrystals embedded in a polymeric film[J]. Chem. Phys. Letters, 1995, 243,450~455
    [59] Z. P. Qiao, Y. Xie, G. Li, et al. Single-step synthesis of nanocrystalline CdS/polyacrylamide composites by γ-irradiation[J]. J. mater, science, 2000, 35, 285~287
    [60] J. H. Zhan, X. G. Yang, S. D. Li, et al. A chemical solution transport mechanism for one-dimensional growth of CdS nanowires[J]. J. Crystal Growth, 2000, 220, 231~234
    [61] T. Hirai, T. Watanabe, I. Komasawa. Preparation of semiconductor nanoparticle-polymer composites by direct reverse micelle polymerization using polymerizable surfactants[J]. J. Phys. Chem. B, 2000,104, 8962~8966
    [62] A. L. Stroyuk, V. M. Granchak, S. Ya. Kuchmii. Polymertization of butylmethylacrylate in isopropanol, Photoinduced by quantumsized CdS particles[J]. Theoretical and Experimental Chemistry, 2001, 37(3), 174~179
    [63] J.G Zhang, N. Coombs, E. Kumacheva. A new approach to hybrid nanocomposite materials with periodc structures[J]. J. Am. Chem. Soc., 2002, 124, 14512~14513
    [64] I. Potapova, R. Mruk, S. Prehi, et al. Semiconductor nanocrystals with multifunctional polymer ligands[J]. J. Am. Chem. Soc, 2003, 125,320~321
    [65] C. S. Yang, D. D. Awschalom, G. D. Stucky. Growth of CdS nanorods in nonionic amphiphilic triblock copolymer systems[J]. Chem. Mater, 2002, 14, 1277~1284
    
    
    [66] T. Torimoto, M. Yamashita, S. Kuwabata, et al. Fabrication of CdS nanoparticle chains along DNA double strands[J]. J. Phys. Chem. B, 1999, 103(42), 8779~8803
    [67] 吴庆生,郑能武,丁亚平等,活体生物膜控制合成纳米半导体硫化镉[J].高等学校化学学报,2000,21(10),1471~1472
    [68] 杨百全,江林,杨文胜等.修饰寡聚DNA包裹的CdS纳米粒子[J].化学学报,2001,59(11),2024~2026
    [69] 杨百全,江林,李铁津等.利用侧链修饰寡聚DNA组装CdS有序纳米结构[J].高等学校化学学报,2002,23(6),1168~1170
    [70] 王姗,房喻,张颖等.壳聚糖-CdS复合膜制备及其对吡啶的传感特性[J].物理化学学报,2003,19(6),514~518
    [71] 赫恩才,杨柏,任晓君等.97全国高分子学术论文报告会论文集,1997,2,20~21
    [72] 黄春辉,李富友,黄岩谊.光电功能超薄膜[M].北京:北京大学出版社,2001
    [73] Y. C. Tian, J. H. Fendler. Langmuir-Blodgett film formation from fluorescence-activated, surfactant-capped, size-selented CdS nanoparticles spread on water surfaces[J]. Chem. Mater., 1996, 8, 969~974
    [74] Y. C. Tian, C. J. Wu, J. H. Fendler. J. Phys. Chem., 1994, 98, 4913~4918
    [75] 吴涛,张希.自组装超薄膜:从纳米层状构筑到功能组装[J].高等学校化学学报,2001,22(6),1057~1065
    [76] L.E. Brus. Electron-electron and electron-hole interactions in small semiconductor crystallites: The size dependence of the lowest excited electronic state[J]. J. Chem. Phys., 1984, 80(9), 4403~4409
    [77] 方容川编著.固体光谱学[M].合肥:中国科学技术大学出版社,2001
    [78] R. Premachandran, S. Banerjee, J. A. Akkara, et al. The enzymatic synthesis of thiol-containing polymers to prepare polymer-CdS nanocomposites[J]. Chem. Mater., 1997, 9(6), 1342-1347
    [79] J. X. Cheng, S. H. Wang, S. H. Yang, et al. Fast interfacial charge separation in chemically hybridized CdS-PVK nanocomposites studied by photoluminescence and photoconductivity measurements[J]. Chem. Phys. Letters, 2001, 333,375~380
    [80] J. G. Winiarz, L. M. Zhang, P. N. Prasad. Photogeneration, charge transport, and photoconductivity of a novel PVK/CdS-nanocrystal polymer composite[J]. Chem. Phys.,
    
    1999, 245, 417~428
    [81] A. Taylor. X-Ray Metallography[M], Publisher: Wiley, New York, 1961, P.259
    [82] N. D. Kumar, M. P. Jashi, C. S. Friend, et al. Organic-inorganic heterojunction light emitting diodes based on poly(p-phenylenevinylene)/cadmium sulfide thin films[J]. Appl. Phys. Lett., 1997, 71(10), 1388~1390
    [83] 平贵臣,席时权,曹立新等.CdS半导体纳米微粒的复合与组装[J].化学通报,2000,2,32~35

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