Fe-O、Fe—N—O薄膜的制备与性能研究
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摘要
近年来，随着科学技术的高速发展，Fe-O、Fe-N薄膜由于其良好的性能，已在各个方面得到了广泛的开发与应用。利用二极溅射的方法在不同衬底上沉积了Fe-O、Fe-N-O薄膜，并对沉积的薄膜在空气的环境下进行了热处理。通过扫描电子显微镜(SEM)、光电子能谱(XPS)、透射电子显微镜(TEM)等现代实验手段分析了热处理前后薄膜形貌、成分和结构特征的变化。应用UV755B型紫外可见分光光度仪和SZ82型四探针测试仪分析了热处理前后薄膜透射率和电阻率的变化。分析结果表明N元素的存在对Fe-O薄膜的性能和结构有一定的影响。热处理前薄膜的主要成分为FeO和少量的Fe_(16)N_2，为纳米晶薄膜，颗粒大小在50nm左右，在生长上存在择优取向。热处理后薄膜的主要成分为Fe_2O_3、Fe_3O_4，颗粒大小在100nm左右，择优取向消失。热处理前后薄膜均对紫外线有较大的吸收；热处理后，薄膜在可见光范围内的透射率明显增加；随着热处理温度的升高，薄膜的导电性明显下降。利用试验测得的参数，理论上分析了薄膜的反射率R、吸收率A以及光学常数k和相对磁导率μ_r。分析结果表明，当薄膜厚度达到一定值时，薄膜的反射率R不再随薄膜厚度的变化而改变，薄膜对不同波长的光均具有较强的吸收。薄膜腐蚀试验的结果表明，薄膜对自然环境具有很高的耐蚀性能，适合在自然环境的条件下长时间使用，热处理后的薄膜还具有一定的抗强酸腐蚀的性能。用称重法测量了薄膜的厚度d，建立了薄膜厚度计算的理论模型，比较并分析了理论值与实测值之间的差别，理论上证明了薄膜的厚度不但与沉积时间和电流有关，还和薄膜的结构和结合状态密切相关。
Recently, with the progress of science and technology, Fe-O and Fe-N thin films have been developed and applied to many fields because of their excellent properties. The Fe-O and Fe-N-O thin films were two-pole sputtered on different substrates. The thin films were treated with different temperature under air environment. The surface morphology, composition and structure character of the Fe-O and Fe-N-O thin films were studied by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The transmittance (T) and resistance of Fe-N-O films were studied by the UV755B ultraviolet-visible spectrometer and SZ82 four-point probe method. The results show that nitrogen in films has influence the optical property and structure of the Fe-N-O film. Before heat treatment, the main phases of Fe-N-O films were FeO and a little Fe16N2. The orientation of the deposited films was found by the results of TEM. The films were nanocrystalline, having crystal size of 50
nm or less. But after heat treatment, the main phases were Fe2O3 and Fe3O4, having crystal size of 100nm or more, the orientation of the deposited films was disappeared. The results have proved the Fe-O and Fe-N-O films can absorb ultraviolet rays. The transmittance and resistance of the films have been increased when the heat treatment temperature increased. The reflectivity (R), absorption (A), the optical constants extinction coefficient (k) and the permeability ( r) were analyzed theoretically. The analytical results show that the R is a constant when the thickness of film is thicker. The films can also absorb all kinds of different wavelength rays. The results of corrosion test showed the films have the highest corrosion resistance against NaCl solution than any other iron materials. So it can be used to for along time under nature environment. But the films can also corrosion resistance against strong sour after heat treatment. The thickness of the films was measured
by the weight gain method. The thickness of the films was analyzed theoretically.
We have proved that the thickness of the films depends on sputtering time,
current, the films structure and binding.
Recently, with the progress of science and technology, Fe-O and Fe-N thin films have been developed and applied to many fields because of their excellent properties. The Fe-O and Fe-N-O thin films were two-pole sputtered on different substrates. The thin films were treated with different temperature under air environment. The surface morphology, composition and structure character of the Fe-O and Fe-N-O thin films were studied by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The transmittance (T) and resistance of Fe-N-O films were studied by the UV755B ultraviolet-visible spectrometer and SZ82 four-point probe method. The results show that nitrogen in films has influence the optical property and structure of the Fe-N-O film. Before heat treatment, the main phases of Fe-N-O films were FeO and a little Fe16N2. The orientation of the deposited films was found by the results of TEM. The films were nanocrystalline, having crystal size of 50
nm or less. But after heat treatment, the main phases were Fe2O3 and Fe3O4, having crystal size of 100nm or more, the orientation of the deposited films was disappeared. The results have proved the Fe-O and Fe-N-O films can absorb ultraviolet rays. The transmittance and resistance of the films have been increased when the heat treatment temperature increased. The reflectivity (R), absorption (A), the optical constants extinction coefficient (k) and the permeability ( r) were analyzed theoretically. The analytical results show that the R is a constant when the thickness of film is thicker. The films can also absorb all kinds of different wavelength rays. The results of corrosion test showed the films have the highest corrosion resistance against NaCl solution than any other iron materials. So it can be used to for along time under nature environment. But the films can also corrosion resistance against strong sour after heat treatment. The thickness of the films was measured
by the weight gain method. The thickness of the films was analyzed theoretically.
We have proved that the thickness of the films depends on sputtering time,
current, the films structure and binding.
引文
[1] 田民波，刘德令．薄膜科学与技术手册(上)．机械工业出版社，1991：1-55
[2] 张为民，侯英兰．氧化铁在玻璃中的着色．玻璃．1994，24(6)：22-26
[3] 贺宏胜，徐廷献，安建军等．化学法合成Fe_3O_4薄膜．材料研究学报．1997，11(4)：387-391
[4] 娄向东，杨秀清，李靖华．α-Fe_2O_3／SnO_2气敏薄膜的结构与性质．应用化学．1995，12(1)：77-79
[5] 梁振斌，郑顺镟，郭斯金．Fe_2O_3：SnO_2薄膜的气敏透射光学特性．激光杂志．1997，8(3)：23-27
[6] 袁洪春，王强春，王巍等．α-Fe_2O_3纳米薄膜的超声喷雾热解制备及其表征．淮北煤师院学报．2002，23(1)：29-31
[7] T. Stenberg, P. Vuoristo, J. Keranen. Thin Solid Films. 1998, (312): 46-60
[8] V. S. Speriosu, M. M. Chen, T. Suzuki. IEEE Transactions on Magnetics. 1989, 25(5): 3875-3877
[9] Wemer Weiss, Wolfgang Ranke, Surface Chemistry and Catalysis on Well-defined Epitaxial Iron-oxide Layers. Progress in Surface and Science 2002, (70): 1-151
[10] Nilgun Ozer, Fatma Tepehan. Optical and electrochemical characteristics of sol-gel deposited iron oxide films. Solar Energy Materials and Solar Cells 1999, (56): 141-152
[11] Kim T K, Takahashi M M. Appl Phys Lett. 1972, 20:492
[12] Kim, YK, Minerals, Metals and Materials Society/AIME(USA). 1994, pp: 105-120
[13] 詹倩，贺连龙，李斗星．磁控溅射Fe-N薄膜的微结构研究．电子显微学报．2002，21(5)：645-646
[14] 姜恩永，孙多春，林川等．高饱和磁化强度Fe_(16)N_2单晶薄膜．科学通报．1996；41(4)：370-373
[15] 张振涛，成正维，蒋龙等．Fe-N薄膜磁性能的研究．金属功能材料．1997(6)：274-276
[16] 王合英，姜恩永，白海力等．掺杂Ti对Fe-N薄膜结构与磁性的影响．金属学报．1996，32(11)：1199-1203
[17] Dong-Liang Peng, Kenji Sumiyama, Kenji Suzuki. Journal of Alloys and Compounds. 1997, (259): 1-6
[18] S.L. Roberson, D. Finello, A.D. Banks, R.F. Davis. Growth of Fe_3N films via chemical vapor deposition of iron acctylacetonate and anhydrous ammonia. Thin Solid Films. 1998, (326): 47-50
[19] Milton Ohring. Materials Science of Thin Films. Second Edition. Academic Press, 2002:60-100
[20] 唐伟忠．薄膜材料制备原理、技术及应用．冶金工业出版社，2003：1-102
[21] 李强勇．纳米薄膜研究的进展．真空与低温．1994，13(3)：162～167
[22] 李林．薄膜科学研究进展．科技导报．1997，(2)：9～19
[23] 赵文轸．材料表面工程导轮．西安交通大学出版社，西安，1998：301
[24] 程守洙，江之永．普通物理学．高等教育出版社，1992：55-75
[25] 吴自勤，王兵．薄膜生长．科学出版社，2001：21-25
[26] 李铁藩．金属高温氧化和热腐蚀．化学工业出版社，2003：102-115
[27] 王建祺，吴文辉，冯大明．电子能谱学(XPS/XAES/UPS)引论．国防工业出版社，1992：513-559
[28] 陈光华，邓金祥等．新型电子薄膜材料．化学工业出版社，2002：1-64
[29] 漆睿，戎泳华．X射线衍射与电子显微分析．上海交通大学出版社，1992．
[30] 陈世朴，王永瑞．金属电子显微分析．西安交通大学出版社，1989：65-105
[31] 王长安．半导体物理学．上海科学技术出版社，1985：127-130
[32] 唐晋发，郑权．应用薄膜光学。上海科学技术出版社，1984．
[33] 吕维刚，杨得全，力虎林．AFM研究表面活性剂对Fe_2O_3纳米薄膜形貌的影响．功能材料．2000，31(5)：558-559
[34] 周剑平，李丹，顾有松等．Fe-N软磁薄膜的结构与性能．中国科学．2002，32(2)：132-140
[35] Santanu Beta, S. Rangarajan, S.V. Narasimhan. Corrosion Science. 2000, (42): 1709-1724
[36] Masayuki Okoshi, Takashi Maniwa, Mitsugu Hanabusa. Applied Surface Science. 1998, (127-129): 462-465
[37] 顾培夫．薄膜厚度分布的测试．浙江大学学报．1989，23(3)：399-406
[38] 王其祥，潘海斌，宋宝珍等．XPS研究纳你粒子表面包覆无机膜．无机材
料学报．2002，17(4)：783-786
[39] 王学华，薛亦渝，赵利．新型光学薄膜研究及发展现状．武汉理工大学学报．2002，24(2)：20-23
[40] E. Yagasaki, K. Kishi. Journal of Electron Spectroscopy and Related Phenomena. 1994, (69): 133-140
[41] V. S. Speriosu, M. M. Chen, T. Suzuki. IEEE TRANSACTIONS ON MAGNETICS, 1989, 25(5): 1221
[42] 陈国均，吕键，陈殿金等．HDD用磁头材料的发展现状．信息记录材料．2002，3(1)：25-35
[43] 张随新，陈国平．阳光控制膜玻璃的光学特性及膜系设计．真空科学与技术．1995，15(1)：36-44
[44] 诸葛兰剑，姚伟国，吴雪梅．基片及基片温度对薄膜的形成及其特性的影响．功能材料．2002，33(5)：477-478
[45] 张三慧．电磁学．清华大学出版社，1999．
[46] T. Stenberg, P. Vuoristo, J. Kenranen. Thin Solid Films. 1998, (312): 46-60
[2] 张为民，侯英兰．氧化铁在玻璃中的着色．玻璃．1994，24(6)：22-26
[3] 贺宏胜，徐廷献，安建军等．化学法合成Fe_3O_4薄膜．材料研究学报．1997，11(4)：387-391
[4] 娄向东，杨秀清，李靖华．α-Fe_2O_3／SnO_2气敏薄膜的结构与性质．应用化学．1995，12(1)：77-79
[5] 梁振斌，郑顺镟，郭斯金．Fe_2O_3：SnO_2薄膜的气敏透射光学特性．激光杂志．1997，8(3)：23-27
[6] 袁洪春，王强春，王巍等．α-Fe_2O_3纳米薄膜的超声喷雾热解制备及其表征．淮北煤师院学报．2002，23(1)：29-31
[7] T. Stenberg, P. Vuoristo, J. Keranen. Thin Solid Films. 1998, (312): 46-60
[8] V. S. Speriosu, M. M. Chen, T. Suzuki. IEEE Transactions on Magnetics. 1989, 25(5): 3875-3877
[9] Wemer Weiss, Wolfgang Ranke, Surface Chemistry and Catalysis on Well-defined Epitaxial Iron-oxide Layers. Progress in Surface and Science 2002, (70): 1-151
[10] Nilgun Ozer, Fatma Tepehan. Optical and electrochemical characteristics of sol-gel deposited iron oxide films. Solar Energy Materials and Solar Cells 1999, (56): 141-152
[11] Kim T K, Takahashi M M. Appl Phys Lett. 1972, 20:492
[12] Kim, YK, Minerals, Metals and Materials Society/AIME(USA). 1994, pp: 105-120
[13] 詹倩，贺连龙，李斗星．磁控溅射Fe-N薄膜的微结构研究．电子显微学报．2002，21(5)：645-646
[14] 姜恩永，孙多春，林川等．高饱和磁化强度Fe_(16)N_2单晶薄膜．科学通报．1996；41(4)：370-373
[15] 张振涛，成正维，蒋龙等．Fe-N薄膜磁性能的研究．金属功能材料．1997(6)：274-276
[16] 王合英，姜恩永，白海力等．掺杂Ti对Fe-N薄膜结构与磁性的影响．金属学报．1996，32(11)：1199-1203
[17] Dong-Liang Peng, Kenji Sumiyama, Kenji Suzuki. Journal of Alloys and Compounds. 1997, (259): 1-6
[18] S.L. Roberson, D. Finello, A.D. Banks, R.F. Davis. Growth of Fe_3N films via chemical vapor deposition of iron acctylacetonate and anhydrous ammonia. Thin Solid Films. 1998, (326): 47-50
[19] Milton Ohring. Materials Science of Thin Films. Second Edition. Academic Press, 2002:60-100
[20] 唐伟忠．薄膜材料制备原理、技术及应用．冶金工业出版社，2003：1-102
[21] 李强勇．纳米薄膜研究的进展．真空与低温．1994，13(3)：162～167
[22] 李林．薄膜科学研究进展．科技导报．1997，(2)：9～19
[23] 赵文轸．材料表面工程导轮．西安交通大学出版社，西安，1998：301
[24] 程守洙，江之永．普通物理学．高等教育出版社，1992：55-75
[25] 吴自勤，王兵．薄膜生长．科学出版社，2001：21-25
[26] 李铁藩．金属高温氧化和热腐蚀．化学工业出版社，2003：102-115
[27] 王建祺，吴文辉，冯大明．电子能谱学(XPS/XAES/UPS)引论．国防工业出版社，1992：513-559
[28] 陈光华，邓金祥等．新型电子薄膜材料．化学工业出版社，2002：1-64
[29] 漆睿，戎泳华．X射线衍射与电子显微分析．上海交通大学出版社，1992．
[30] 陈世朴，王永瑞．金属电子显微分析．西安交通大学出版社，1989：65-105
[31] 王长安．半导体物理学．上海科学技术出版社，1985：127-130
[32] 唐晋发，郑权．应用薄膜光学。上海科学技术出版社，1984．
[33] 吕维刚，杨得全，力虎林．AFM研究表面活性剂对Fe_2O_3纳米薄膜形貌的影响．功能材料．2000，31(5)：558-559
[34] 周剑平，李丹，顾有松等．Fe-N软磁薄膜的结构与性能．中国科学．2002，32(2)：132-140
[35] Santanu Beta, S. Rangarajan, S.V. Narasimhan. Corrosion Science. 2000, (42): 1709-1724
[36] Masayuki Okoshi, Takashi Maniwa, Mitsugu Hanabusa. Applied Surface Science. 1998, (127-129): 462-465
[37] 顾培夫．薄膜厚度分布的测试．浙江大学学报．1989，23(3)：399-406
[38] 王其祥，潘海斌，宋宝珍等．XPS研究纳你粒子表面包覆无机膜．无机材
料学报．2002，17(4)：783-786
[39] 王学华，薛亦渝，赵利．新型光学薄膜研究及发展现状．武汉理工大学学报．2002，24(2)：20-23
[40] E. Yagasaki, K. Kishi. Journal of Electron Spectroscopy and Related Phenomena. 1994, (69): 133-140
[41] V. S. Speriosu, M. M. Chen, T. Suzuki. IEEE TRANSACTIONS ON MAGNETICS, 1989, 25(5): 1221
[42] 陈国均，吕键，陈殿金等．HDD用磁头材料的发展现状．信息记录材料．2002，3(1)：25-35
[43] 张随新，陈国平．阳光控制膜玻璃的光学特性及膜系设计．真空科学与技术．1995，15(1)：36-44
[44] 诸葛兰剑，姚伟国，吴雪梅．基片及基片温度对薄膜的形成及其特性的影响．功能材料．2002，33(5)：477-478
[45] 张三慧．电磁学．清华大学出版社，1999．
[46] T. Stenberg, P. Vuoristo, J. Kenranen. Thin Solid Films. 1998, (312): 46-60
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