纳米ZnFe_2O_4的制备及其光生电荷行为的研究
摘要
本文利用固相反应法和水热合成法分别制备出不同粒径的纳米ZnFe_2O_4材料,并且利用表面光电压谱(SPS)和场诱导表面光电压谱(FISPS)进行了测试分析,分析了光激发电子-空穴对的运动状态以及它们对表面光电压带来的各种响应。得到了当ZnFe_2O_4材料尺寸接近或小于它的载流子德布罗意波长时,将会出现光伏响应峰蓝移现象。结合拉曼光谱的分析了尖晶石结构铁酸锌的振动模式,表明了ZnFe_2O_4在光照和外电场的共同作用下,都会使得它的一阶振动模增强,初步认为造成的原因是材料中无序的阳离子Fe~(3+)和Zn~(2+)占据了八面体和四面体中氧原子位置引起的。
ZnFe_2O_4, one of the most important ferrite binary oxides with the spinel structure, has been of great interest for a long time because of its importance in many technological applications. Surface Photovoltage Spectra (SPS) is a sensitive tool for detecting the photogenerated charge at the surface of semiconductor materials. However, SPS is little employed to study ZnFe_2O_4, especially its corresponding nanostructure.
Applied external electric field can promote the separation of photogenerated electron-hole pairs, and thus influence the transfer, capture, and recombination of photogenerated carriers. Therefore, field-induced surface photovoltage spectra (FISPS), which is normally considered as the steady state SPS, can detect the nice change of photogenerated charge at the surface of semiconductor materials. In this thesis, we use SPS and FISPS to obtain the surface photovoltage spectra of ZnFe_2O_4, and study the effects of illumination, sample size, and field on its surface voltage. Well-crystallized ZnFe_2O_4 with ultrafine sizes was prepared by a hydrothermal reaction. When the size of ZnFe_2O_4 sample is less than 10 nm, FISPS allows us to observe its blue-shift phenomena. This blue shift, corresponding to the excition transition, occurs in the presence of an electric field. With the effect of both field and illumination, all the five first-order Raman active modes increase, which is attributed to the existence of non-order Fe3 and Zn2+ in the structure of octahedron and tetrahedral of samples,and their sites are changed with Oxygen.
ZnFe_2O_4, one of the most important ferrite binary oxides with the spinel structure, has been of great interest for a long time because of its importance in many technological applications. Surface Photovoltage Spectra (SPS) is a sensitive tool for detecting the photogenerated charge at the surface of semiconductor materials. However, SPS is little employed to study ZnFe_2O_4, especially its corresponding nanostructure.
Applied external electric field can promote the separation of photogenerated electron-hole pairs, and thus influence the transfer, capture, and recombination of photogenerated carriers. Therefore, field-induced surface photovoltage spectra (FISPS), which is normally considered as the steady state SPS, can detect the nice change of photogenerated charge at the surface of semiconductor materials. In this thesis, we use SPS and FISPS to obtain the surface photovoltage spectra of ZnFe_2O_4, and study the effects of illumination, sample size, and field on its surface voltage. Well-crystallized ZnFe_2O_4 with ultrafine sizes was prepared by a hydrothermal reaction. When the size of ZnFe_2O_4 sample is less than 10 nm, FISPS allows us to observe its blue-shift phenomena. This blue shift, corresponding to the excition transition, occurs in the presence of an electric field. With the effect of both field and illumination, all the five first-order Raman active modes increase, which is attributed to the existence of non-order Fe3 and Zn2+ in the structure of octahedron and tetrahedral of samples,and their sites are changed with Oxygen.
引文
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[*1] 张立德,牟季美,纳米材料和纳米结构
[*2] 李子亨,吉林大学博士论文(2005)
[2] L. D. Tung, V. Kolesnichenko, G. Caruntu, D. Caruntu, Y. Remond, V. O. Golub, C. J. O’Connor, L. Spinu. Physica B, 319 (2002) 116.
[3] X. S. Niu, W. P. Du, W. M. Du, Sensors and Actuators B, 99 (2004) 405.
[4] J. L. Li,X. Y. Li,W. Z. Li, Journal of Nanchang University (Natural Science), 21 (1997).
[5] S. H. Yu, T. Fujino, Masahiro Yoshimura, Journal of Magnetism and Magnetic Materials 256 (2003) 420.
[6] L. Kronik, Y. Shapira, Surface Science Reports, 37 (1999) 1.
[7] L.J. Brillson, Surface Science Reports, 2 (1982) 123.
[8] H. Luèth, Appl. Phys., 8 (1975) 1.
[9] H. Luèth, G. Heiland, Il Nuovo Cimento, 39 (1977) 748.
[10] W. Moènch, R. Vanselow, R. Howe (Eds), Chem . Phys. Solid Surfaces, 35 V (1984).
[11] J. Lagowski, P. Edelman, M. Dexter, W. Henley, Semicond. Sci. Technol, 7 (1992) A185.
[12] R. J. Hamers, K. Markert, Phys. Rev. Lett., 64 (1990) 1051.
[13] Y. Kuk, R. S. Becker, P. J. Silverman, G. P. Kochanski, Phys. Rev. Lett., 65 (1990) 456.
[14] J. M. R. Weaver, H . K. Wickramasinghe, J. Vac. Sci. Technol. B, 9 (1991) 1562.
[15] W. G. Adams, R. E. Day, Proc. R. Soc. A, 25 (1976) 113.
[16] E. V. Ostroumova, Sov. Phys. Semicond., 3 (1970) 926.
[17] M. Buèchel, H. Luèth, Surf. Sci., 50 (1975) 451.
[18] Y. Lubianiker, I. Balberg, E. Fefer, Y. Shapira, J. Non-Cryst. Solids, 309 (1996) 198.
[19] B. Wang, D. Wang, Y. Cao, X. Chai, X. Geng, T. Li, Thin Solid Films, 284 (1996) 588.
[20] L. Burstein, Y. Shapira, J. Partee, J. Shinar, Y. Lubianiker, I. Balberg, Phys. Rev. B, 55 (1997) R1930.
[21] B. Mishori, Y. Shapira, A. Belu. Marian, M. Manciu, A. Devenyi, Chem. Phys. Lett., 264 (1997) 163.
[22] I. P. Koutzarov, C. H. Edirisinghe, H. E. Ruda, L. Z. Jedral, Q. Liu, Proc. MRS. Symp., 421 (1996) 93.
[23] N. Kinrot, Y. Shapira, M. A. Bica de Moraes, Appl. Phys. Lett., 70 (1997) 3011.
[24] S. Lehr, H. Pagnia, Phys. Stat. Sol., 49 (1978) 83.
[25] B. Adamowicz, J. Szuber, Surf. Sci., 247 (1991) 94.
[26] I. Shalish, L. Kronik, G. Segal, Y. Shapira, Y. Rosenwaks, U. Tisch, J. Salzman, Phys. Rev. B, 59 (1999) 9748.
[27] L. J. Brillson, Surf. Sci., 69 (1977) 62.
[28] S. Kuzminski, K. Pater, A. T. Szaynok, Vacuum, 46 (1995) 501.
[29] M. S. El-Dessouki, V. A. Attia, J. Phys. Chem. Solids, 44 (1983) 939.
[30] M.S. El-Dessouki, F. El-Kabbany, V. A. Attia, Annalen derPhysik, 46 (1989) 615.
[31] J. Lagowski, H. C. Gatos, C. L. Balestra, J. Appl. Phys., 49 (1978) 2821.
[32] D. Gal, J. Beier, E. Moons, Proc. AIP., 353 (1995) 453.
[33] E. Moons, D. Gal, J. Beier, G. Hodes, D. Cahen, L. Kronik, L. Burstein, Sol. Ener. Mater. Sol. Cells, 43 (1996) 73.
[34] L. Kronik, B. Mishori, E. Fefer, Y. Shapira, W. Riedl, Sol. Ener. Mater. Sol. Cells, 51 (1998) 21.
[35] J. Zhang, D. Wang, Y. Chen, T. Li, H. Mao, H. Tian, Q. Zhou, H. Xu, Thin Solid Films, 300 (1997) 208.
[36] N. Mirowska, J. Misiewicz, Semicond. Sci. Tech.. 7 (1992) 1332.
[37] H. M. Yang, X. C. Zhang, C.H. Huang, W.G. Yang, J. Phys. Chem of Solids., 65 (2004) 1329.
[38] M. Veith, M. Haas, V. Huch . Chem. Mater., 17 (2005) 95.
[39] Leeor. Kronik, Yoram. Shapira. Surface Interface Anal, 31 (2001) 954.
[40] L. Burstlln, Y. Shapira, Phys. Rev. B., 15 (1997) 1930.
[41] T. K. Sharma, S. Porwal, Rev. of Sci. Ins., 73 (2002) 1835.
[42] F. F. Volkenshtein, The Electronic Theory of Catalysis on Semiconductors, (1963).
[43] W. M. H. Sachtler, P. Van der Plank, Surface Sci., 18 (1969) 62.
[44] O. Johnson, J. Catal., 28 (1973) 503.
[45] Z. Knor, Adv. Catal., 22 (1972) 51.
[46] Z.W. Wang, P. Lazor, S.K. Saxena, G. Artioli, J. Solid State Chem., 165 (2002) 165.
[47] H.S.C. O’Neill, Eur. J. Mineral., 4 (1992) 571.
[*1] 张立德,牟季美,纳米材料和纳米结构
[*2] 李子亨,吉林大学博士论文(2005)