两步法在硅衬底上制备银薄膜
摘要
在例如大规模集成电路制造和超大规模集成电路制造等半导体工业中,硅是一种非常重要的原材料。同样,它也被广泛应用在微机电系统和太阳能电池制造中。而金属银作为太阳能电池的正面电极材料和集成电路工业中的连接金属,都有着广泛的应用,所以在硅表面制备金属银薄膜有着重要意义,而电化学沉积技术是一种安全,可控,成本低,容易操作且节约能源环境友好的制备工艺,所以本论文中采用化学和电化学法两步法寻找一种简单易行的在P型硅片表面生长银薄膜的方法。
采用两步法制备P型硅表面微米级银薄膜,第一步将硅片置于含AgNO3的HF溶液中,利用在HF环境中Ag+离子能被还原成Ag原子并沉积于硅片表面的特性形成不连续Ag纳米粒子的种子层,第二步用电化学恒电流法将已形成Ag种子层的硅片作为工作电极在含AgNO3和KNO3的溶液中进行电沉积银,生成所需要的银薄膜。分别为硅表面银种子层生长和微米级银膜的形成找寻适合的条件。
为分析种子层生长情况和银薄膜的结构,晶粒大小,表面形貌以及薄膜厚度,分别使用X射线衍射谱(XRD),扫描电子显微镜(SEM)进行分析研究,发现第一步中在0.02g/L AgNO3的5%HF的溶液中Ag种子层的沉积情况较好,第二步中在电流为-1.5mA的0.1mol/LAgNO3和0.1mol/LKNO3的溶液中电沉积银3小时成膜情况较好。
In such as large scale integrated circuit manufacturing and very large scale integrated circuit manufacturing semiconductor industry, silicon is a very important raw materials. Also, it can be widely used in microelectromechanical system and solar battery manufacturing. And silver as the positive electrode materials of the solar cells and the connection metal in the integrated circuit industry, all has the widespread application, so the preparation of silver thin film on silicon surface has important significance. Electrochemical deposition is a safe, controllable, low cost and easy way to operate and also is a preparation process which is saving energy and environment friendly, so in this thesis using the chemical and electrochemical two-step method to looking for a simple and easy way to make the silver thin film on P type silicon surface.
Using the two-step method to fabricate micron-grade silver thin film on P type silicon surface, in the first step silicon substrate was placed in HF solution with AgNO3, in HF environment Ag+ions were reduced to Ag and then deposit on the surface of silicon to form the discontinuous Ag nanoparticles seed layer. In the second step the silicon with Ag seed layer was used as the anode in AgNO3and KNO3solution to electrodeposit silver thin film by electrochemistry constant current method to get the silver thin film which we need. Respectively finding the suitable conditions for the preparation of silver nanoparticles seed layer and micron-grade silver thin film on silicon surface.
In order to analyze the structure of silver thin film, the size of crystal particle, surface morphology and the thickness of the film, X-ray diffraction spectrum (XRD) and scanning electron microscopy (SEM) were used separately for study, finding that in the first step the deposition of silver seed layer in0.02g/L AgNO3and5%HF solution was well and in second step the silver thin film performed well at the current of-1.5mA in0.1mol/L AgNO3and0.1mol/L KNO3solution for3hours.
采用两步法制备P型硅表面微米级银薄膜,第一步将硅片置于含AgNO3的HF溶液中,利用在HF环境中Ag+离子能被还原成Ag原子并沉积于硅片表面的特性形成不连续Ag纳米粒子的种子层,第二步用电化学恒电流法将已形成Ag种子层的硅片作为工作电极在含AgNO3和KNO3的溶液中进行电沉积银,生成所需要的银薄膜。分别为硅表面银种子层生长和微米级银膜的形成找寻适合的条件。
为分析种子层生长情况和银薄膜的结构,晶粒大小,表面形貌以及薄膜厚度,分别使用X射线衍射谱(XRD),扫描电子显微镜(SEM)进行分析研究,发现第一步中在0.02g/L AgNO3的5%HF的溶液中Ag种子层的沉积情况较好,第二步中在电流为-1.5mA的0.1mol/LAgNO3和0.1mol/LKNO3的溶液中电沉积银3小时成膜情况较好。
In such as large scale integrated circuit manufacturing and very large scale integrated circuit manufacturing semiconductor industry, silicon is a very important raw materials. Also, it can be widely used in microelectromechanical system and solar battery manufacturing. And silver as the positive electrode materials of the solar cells and the connection metal in the integrated circuit industry, all has the widespread application, so the preparation of silver thin film on silicon surface has important significance. Electrochemical deposition is a safe, controllable, low cost and easy way to operate and also is a preparation process which is saving energy and environment friendly, so in this thesis using the chemical and electrochemical two-step method to looking for a simple and easy way to make the silver thin film on P type silicon surface.
Using the two-step method to fabricate micron-grade silver thin film on P type silicon surface, in the first step silicon substrate was placed in HF solution with AgNO3, in HF environment Ag+ions were reduced to Ag and then deposit on the surface of silicon to form the discontinuous Ag nanoparticles seed layer. In the second step the silicon with Ag seed layer was used as the anode in AgNO3and KNO3solution to electrodeposit silver thin film by electrochemistry constant current method to get the silver thin film which we need. Respectively finding the suitable conditions for the preparation of silver nanoparticles seed layer and micron-grade silver thin film on silicon surface.
In order to analyze the structure of silver thin film, the size of crystal particle, surface morphology and the thickness of the film, X-ray diffraction spectrum (XRD) and scanning electron microscopy (SEM) were used separately for study, finding that in the first step the deposition of silver seed layer in0.02g/L AgNO3and5%HF solution was well and in second step the silver thin film performed well at the current of-1.5mA in0.1mol/L AgNO3and0.1mol/L KNO3solution for3hours.
引文
[1]杨金焕,于化从,葛亮.太阳能光伏发电应用技术[M].北京：电子工业出版社,2009
[2]王少南.太阳能建筑技术在国内外的发展[J].新型建筑材料,2006,10：44-46.
[3]赵争鸣.太阳能光伏发电及其应用[M].北京：科学出版社,2005.
[4]杨德仁.太阳能电池材料[M].北京：化学工业出版社,2006.
[5]刘鉴民.太阳能利用原理·技术·工程[M].北京：电子工业出版社,2010
[6]赵富鑫,魏彦章主编.太阳能电池及其应用[M].北京：国防工业出版社,1985
[7]R.M.怀特.太阳电池[M].北京：北京大学出版社,1990.
[8]Shengjuan Huo, Qiaoxia Li.Yangang Yan, et al. Tunable Surface-Enhanced Infrared Absorption on Au Nanofilms on Si Fabricated by Self-Assembly and Growth of Colloidal Particles[J]. The journal of physical chemistry,2005,109 (33),15985-15991
[9]Miyake Hiroto,Ye Shen, Osawa Masatoshi. Electroless deposition of gold thin films on silicon for surface-enhanced infrared spectroelectrochemistry[J]. Electrochemistry Communications,2002,4(12),973-977.
[10]A Rodes J. M Orts,J. M Perez, J. M Feliu,A Aldaz. Sulphate adsorption at chemically deposited silver thin film electrodes:time-dependent behaviour as studied by internal reflection step-scan infrared spectroscopy[J]. Electrochemistry Communications,2003, 56-60
[11]Bright Robin M, Walter Daniel G, Musick Michael D, Jackson Michael A, Allison Keith J, Natan Michael J. Chemical and Electrochemical Ag Deposition onto Preformed Au Colloid Monolayers:Approaches to Uniformly-Sized Surface Features with Ag-Like Optical Properties[J]. Langmuir,1996,12(3),810-17
[12]Delgado Jose Manuel, Orts Jose Manuel, Rodes Antonio. ATR-SEIRAS Study of the Adsorption of Acetate Anions at Chemically Deposited Silver Thin Film Electrodes[J]. Langmuir,2005,21(19),8809-8816
[13]Miyake Hiroto, Osawa Masatoshi. Surface-enhanced infrared spectrum of CO adsorbed on Cu electrodes in solution[J]. Chemistry Letters,2004,33(3),278-279
[14]Yuxia Diao, Meijuan Han, Li jun Wan, Itaya Kingo, Uchida, Taro, Miyake Hiroto, Yamakata Akira, Osawa Masatoshi. Adsorbed Structures of 4,4-Bipyridine on Cu(111) in Acid Studi ed by STM and IR[J].Langmuir,2006,22(8),3640-3646
[15]Shengjuan Huo, Xiaokang Xue, Qiaoxia Li.Sufan Xu, and Wenbin Ca. Seeded-Growth Approach to Fabrication of Silver Nanoparticle Films on Silicon for Electrochemical ATR Surface-Enhanced IR Absorption Spectroscopy[J]. J. Phys. Chem.B 2006,110,25721-25728
[16]Chia Lung Lee,Shinsuke Tsuru, Yuji Kanda, Shigeru Ikeda, and Michio. Matsumura Formation of 100 N Deep Vertical Pores in Si Wafers by Wet[J]. Journal of The Electrochemical Society,2009,156 (12),543-547
[17]Bright Robin M., Walter Daniel G.,Musick Michael D., Jackson Michael A..Allison Keith J., Natan Michael J. Chemical and Electrochemical Ag Deposition onto Preformed Au Colloid Monolayers:Approaches to Uniformly-Sized Surface Features with Ag-Like Optical Properties[J].Langmuir,1996,12(3),810-17
[18]安茂忠.电镀工艺学[M].哈尔滨：哈尔滨工业大学出版社,2001
[19]冯立明,王玥,孙华,马希聘.电镀工艺与设备[M].北京：化学工业出版社,2005
[20]刘仁志.电子电镀技术[M]北京：化学工业出版社,2008
[21]姜传海,杨传铮.材料射线衍射和散射分析[M].北京：高等教育出版社,2010
[22]谷亦杰,宫声凯.材料分析检测技术[M].长沙：中南大学出版社,2009
[23]廖晓玲,周安若,蔡苇.材料现代测试技术[M].北京：冶金工业出版社,2010
[24]祁景玉.现代分析测试技术[M].上海：同济大学出版社,2006
[25]F.C.Walsh, M. E. Herron. Electrocrystallization and Electrochemical Control of Crystal Growth:Fundamental Considerations and Electro-deposition of Metals[J]. J. Phys. D:Appl. Phys.1991,24:217-225
[26]Tong, Hao;Zhu, Li;Li, Mengke;Wang, Chunming. Electroless silver deposition on Si (100) substrate based on the seed layer of silver itself Electrochimica[J]. Acta.2003,48(17), 2473-2477
[27]He R, Qian X F,Yin J, Zhu Z K. Formation of silver dendrites under microwave irradiation[J]. Chem. Phys. Lett.2003,369:454-458.
[28]周伟舫.电化学测量[M].上海：上海科学技术出版社,1985
[2]王少南.太阳能建筑技术在国内外的发展[J].新型建筑材料,2006,10：44-46.
[3]赵争鸣.太阳能光伏发电及其应用[M].北京：科学出版社,2005.
[4]杨德仁.太阳能电池材料[M].北京：化学工业出版社,2006.
[5]刘鉴民.太阳能利用原理·技术·工程[M].北京：电子工业出版社,2010
[6]赵富鑫,魏彦章主编.太阳能电池及其应用[M].北京：国防工业出版社,1985
[7]R.M.怀特.太阳电池[M].北京：北京大学出版社,1990.
[8]Shengjuan Huo, Qiaoxia Li.Yangang Yan, et al. Tunable Surface-Enhanced Infrared Absorption on Au Nanofilms on Si Fabricated by Self-Assembly and Growth of Colloidal Particles[J]. The journal of physical chemistry,2005,109 (33),15985-15991
[9]Miyake Hiroto,Ye Shen, Osawa Masatoshi. Electroless deposition of gold thin films on silicon for surface-enhanced infrared spectroelectrochemistry[J]. Electrochemistry Communications,2002,4(12),973-977.
[10]A Rodes J. M Orts,J. M Perez, J. M Feliu,A Aldaz. Sulphate adsorption at chemically deposited silver thin film electrodes:time-dependent behaviour as studied by internal reflection step-scan infrared spectroscopy[J]. Electrochemistry Communications,2003, 56-60
[11]Bright Robin M, Walter Daniel G, Musick Michael D, Jackson Michael A, Allison Keith J, Natan Michael J. Chemical and Electrochemical Ag Deposition onto Preformed Au Colloid Monolayers:Approaches to Uniformly-Sized Surface Features with Ag-Like Optical Properties[J]. Langmuir,1996,12(3),810-17
[12]Delgado Jose Manuel, Orts Jose Manuel, Rodes Antonio. ATR-SEIRAS Study of the Adsorption of Acetate Anions at Chemically Deposited Silver Thin Film Electrodes[J]. Langmuir,2005,21(19),8809-8816
[13]Miyake Hiroto, Osawa Masatoshi. Surface-enhanced infrared spectrum of CO adsorbed on Cu electrodes in solution[J]. Chemistry Letters,2004,33(3),278-279
[14]Yuxia Diao, Meijuan Han, Li jun Wan, Itaya Kingo, Uchida, Taro, Miyake Hiroto, Yamakata Akira, Osawa Masatoshi. Adsorbed Structures of 4,4-Bipyridine on Cu(111) in Acid Studi ed by STM and IR[J].Langmuir,2006,22(8),3640-3646
[15]Shengjuan Huo, Xiaokang Xue, Qiaoxia Li.Sufan Xu, and Wenbin Ca. Seeded-Growth Approach to Fabrication of Silver Nanoparticle Films on Silicon for Electrochemical ATR Surface-Enhanced IR Absorption Spectroscopy[J]. J. Phys. Chem.B 2006,110,25721-25728
[16]Chia Lung Lee,Shinsuke Tsuru, Yuji Kanda, Shigeru Ikeda, and Michio. Matsumura Formation of 100 N Deep Vertical Pores in Si Wafers by Wet[J]. Journal of The Electrochemical Society,2009,156 (12),543-547
[17]Bright Robin M., Walter Daniel G.,Musick Michael D., Jackson Michael A..Allison Keith J., Natan Michael J. Chemical and Electrochemical Ag Deposition onto Preformed Au Colloid Monolayers:Approaches to Uniformly-Sized Surface Features with Ag-Like Optical Properties[J].Langmuir,1996,12(3),810-17
[18]安茂忠.电镀工艺学[M].哈尔滨：哈尔滨工业大学出版社,2001
[19]冯立明,王玥,孙华,马希聘.电镀工艺与设备[M].北京：化学工业出版社,2005
[20]刘仁志.电子电镀技术[M]北京：化学工业出版社,2008
[21]姜传海,杨传铮.材料射线衍射和散射分析[M].北京：高等教育出版社,2010
[22]谷亦杰,宫声凯.材料分析检测技术[M].长沙：中南大学出版社,2009
[23]廖晓玲,周安若,蔡苇.材料现代测试技术[M].北京：冶金工业出版社,2010
[24]祁景玉.现代分析测试技术[M].上海：同济大学出版社,2006
[25]F.C.Walsh, M. E. Herron. Electrocrystallization and Electrochemical Control of Crystal Growth:Fundamental Considerations and Electro-deposition of Metals[J]. J. Phys. D:Appl. Phys.1991,24:217-225
[26]Tong, Hao;Zhu, Li;Li, Mengke;Wang, Chunming. Electroless silver deposition on Si (100) substrate based on the seed layer of silver itself Electrochimica[J]. Acta.2003,48(17), 2473-2477
[27]He R, Qian X F,Yin J, Zhu Z K. Formation of silver dendrites under microwave irradiation[J]. Chem. Phys. Lett.2003,369:454-458.
[28]周伟舫.电化学测量[M].上海：上海科学技术出版社,1985