CVD金刚石膜化学机械抛光液的研制
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摘要
金刚石具有优异的机械性能、热力学性能、光学性能、声学性能、半导体性能及化学惰性,作为一种全方位的多功能材料,在诸多领域具有非常广阔的应用前景。尽管CVD金刚石膜的问世缓解了天然金刚石储量极少和价格昂贵的问题,但它表面质量太差,很多情况下难以直接使用。因此金刚石膜的抛光技术已成为扩大金刚石膜应用的关键技术之一。
在过去的近二十年中,大量的学者和工程人员对金刚石膜的抛光进行了深入的研究,探讨了多种抛光方法,建立了多种理论模型,取得了丰硕的研究成果。但这些抛光方法所能达到的表面粗糙度Ra停留在亚微米级,比如:电火花抛光、热化学抛光等,而且容易对金刚石膜的表面造成损伤,缺少一种超精密低损伤的抛光技术。因此学者们对于CVD金刚石膜的抛光技术的研究从未间断,不断涌现出新的理论和方法。
本文采用一种化学机械抛光方法对CVD金刚石膜的抛光进行了研究,主要的研究内容和结论如下:
(1)根据氧化还原电位选择10种氧化剂进行了抛光试验,研究了不同氧化剂对金刚石膜的材料去除率和表面粗糙度Ra的影响。根据试验结果,优选出了高锰酸钾作为抛光液的氧化剂。
(2)选用硫酸、磷酸、三氯化铁等化学试剂作为添加剂进行了抛光对比试验,选择了材料去除率及表面粗糙度Ra均比较好的磷酸作为抛光液的添加剂。通过对磷酸的浓度进行优选,发现当磷酸的浓度为磷酸:去离子水=115ml:35ml时抛光效果最佳。
(3)在确定了氧化剂和添加剂的基础上,对磨料的硬度、粒径进行了优选,试验结果表明:在粗加工时,采用粒径10μm的金刚石作为磨料,精加工时采用粒径2μm的碳化硼磨料可以获得最佳的效果。
(4)对抛光盘的材料进行了优选,研究结果表明:在粗加工时宜采用耐磨损的碳化硼盘,而在精加工时宜采用硬度适中、载料能力强的玻璃盘。
(5)最后通过正交试验研究了抛光的主要工艺参数,优化出了最佳工艺参数:抛光压力为0.35MPa,抛光盘转速为50r/min,配重块转速为70r/min,抛光温度为50℃。
(6)采用优化工艺抛光后的金刚石膜表面,没有出现变质层或其他杂质,表面品质良好。
Diamond has excellent mechanical properties, thermodynamic properties, optical properties, acoustic properties, semiconductor performance and chemical inertness. As a full range of multi-functional material in many fields it has very broad application prospects. Although the advent of CVD diamond film has eased the matter of natural diamond's few reserves and valuableness, its poor surface quality makes it difficult to be used directly in many cases. So the diamond film's polishing has become one of the key technologies to expand its application.
In the past nearly two decades, a large number of scholars and engineers have in-depth studied on the polishing diamond films, researched various polishing methods, established a wide range of theoretical models and yielded fruitful results of research. However, these methods such as: electrical discharge polishing thermo-chemical polishing, can achieve the polished surface roughness remaining in the sub-micron. And they are easy to cause damage layers on the diamond films" surface. It is lack of an ultra-precision and low-injury polishing method, so the scholars CVD have never stopped probing the diamond films' polishing technicses. There are emerging plenty of new theories and methods.
In this paper, a CMP method has been studied, the main contents and conclusions of the study are as follows:
(1) According to the oxidation-reduction potential, 10 kinds of antioxidants are used to polishing experiments. The effects of different oxidizer on the diamond films' materials removal and surface roughness have shown that potassium permanganate as the oxidizer is the best choice.
(2) Some chemical reagents such as sulfuric acid, phosphoric acid, ferric chloride as the additive have been experimentized. Phosphoric acid has been as the additive for its better material removal rate and surface roughness. And the additive concentration is optimized, the experiment found that the best concentration is phosphoric acid phosphate: deionized water = 115ml: 35ml at the best polishing.
(3) After the oxidizer and additives has been determined, the abrasive hardness and particle size are optimized, the results show that: in the rough machining process, 10μm diamond used as abrasive, in the finish machining process, 2μm boron carbide used as abrasive can get the best effect.
(4) The lap material is optimized, and the results show that: in the rough machining process it should use the wear-resistant boron carbide dish, and in the finish machining process it should use glass dish which has moderate hardness, the ability of the material contained in.
(5) Finally, the main technical parameters has been through the studied by Orthogonal experiment. The best technical parameters which have been optimized are that: the pressure is 0.35MPa, the speed of lap is 50r/min, the speed of up disk is 70r/min, the temperature is 50℃.
(6) There is a good surface quality and no metamorphic layer deterionration or other impurities after polished by optimization of process.
在过去的近二十年中,大量的学者和工程人员对金刚石膜的抛光进行了深入的研究,探讨了多种抛光方法,建立了多种理论模型,取得了丰硕的研究成果。但这些抛光方法所能达到的表面粗糙度Ra停留在亚微米级,比如:电火花抛光、热化学抛光等,而且容易对金刚石膜的表面造成损伤,缺少一种超精密低损伤的抛光技术。因此学者们对于CVD金刚石膜的抛光技术的研究从未间断,不断涌现出新的理论和方法。
本文采用一种化学机械抛光方法对CVD金刚石膜的抛光进行了研究,主要的研究内容和结论如下:
(1)根据氧化还原电位选择10种氧化剂进行了抛光试验,研究了不同氧化剂对金刚石膜的材料去除率和表面粗糙度Ra的影响。根据试验结果,优选出了高锰酸钾作为抛光液的氧化剂。
(2)选用硫酸、磷酸、三氯化铁等化学试剂作为添加剂进行了抛光对比试验,选择了材料去除率及表面粗糙度Ra均比较好的磷酸作为抛光液的添加剂。通过对磷酸的浓度进行优选,发现当磷酸的浓度为磷酸:去离子水=115ml:35ml时抛光效果最佳。
(3)在确定了氧化剂和添加剂的基础上,对磨料的硬度、粒径进行了优选,试验结果表明:在粗加工时,采用粒径10μm的金刚石作为磨料,精加工时采用粒径2μm的碳化硼磨料可以获得最佳的效果。
(4)对抛光盘的材料进行了优选,研究结果表明:在粗加工时宜采用耐磨损的碳化硼盘,而在精加工时宜采用硬度适中、载料能力强的玻璃盘。
(5)最后通过正交试验研究了抛光的主要工艺参数,优化出了最佳工艺参数:抛光压力为0.35MPa,抛光盘转速为50r/min,配重块转速为70r/min,抛光温度为50℃。
(6)采用优化工艺抛光后的金刚石膜表面,没有出现变质层或其他杂质,表面品质良好。
Diamond has excellent mechanical properties, thermodynamic properties, optical properties, acoustic properties, semiconductor performance and chemical inertness. As a full range of multi-functional material in many fields it has very broad application prospects. Although the advent of CVD diamond film has eased the matter of natural diamond's few reserves and valuableness, its poor surface quality makes it difficult to be used directly in many cases. So the diamond film's polishing has become one of the key technologies to expand its application.
In the past nearly two decades, a large number of scholars and engineers have in-depth studied on the polishing diamond films, researched various polishing methods, established a wide range of theoretical models and yielded fruitful results of research. However, these methods such as: electrical discharge polishing thermo-chemical polishing, can achieve the polished surface roughness remaining in the sub-micron. And they are easy to cause damage layers on the diamond films" surface. It is lack of an ultra-precision and low-injury polishing method, so the scholars CVD have never stopped probing the diamond films' polishing technicses. There are emerging plenty of new theories and methods.
In this paper, a CMP method has been studied, the main contents and conclusions of the study are as follows:
(1) According to the oxidation-reduction potential, 10 kinds of antioxidants are used to polishing experiments. The effects of different oxidizer on the diamond films' materials removal and surface roughness have shown that potassium permanganate as the oxidizer is the best choice.
(2) Some chemical reagents such as sulfuric acid, phosphoric acid, ferric chloride as the additive have been experimentized. Phosphoric acid has been as the additive for its better material removal rate and surface roughness. And the additive concentration is optimized, the experiment found that the best concentration is phosphoric acid phosphate: deionized water = 115ml: 35ml at the best polishing.
(3) After the oxidizer and additives has been determined, the abrasive hardness and particle size are optimized, the results show that: in the rough machining process, 10μm diamond used as abrasive, in the finish machining process, 2μm boron carbide used as abrasive can get the best effect.
(4) The lap material is optimized, and the results show that: in the rough machining process it should use the wear-resistant boron carbide dish, and in the finish machining process it should use glass dish which has moderate hardness, the ability of the material contained in.
(5) Finally, the main technical parameters has been through the studied by Orthogonal experiment. The best technical parameters which have been optimized are that: the pressure is 0.35MPa, the speed of lap is 50r/min, the speed of up disk is 70r/min, the temperature is 50℃.
(6) There is a good surface quality and no metamorphic layer deterionration or other impurities after polished by optimization of process.
引文
[1]顾长志,金曾孙.金刚石膜的性质、应用及国内外研究现状.功能材料,1997,28(3):232-236.
[2]匡同春,王晓初.CVD金刚石道具的研究进展与应用现状.金刚石与磨料磨具工程,2000,116(2):27-30.
[3]张铮.CVD金刚石薄膜抛光技术的研究进展.真空科学与技术学报,2000,20(4):270-273.
[4]S.Jin,.E.Graebner,M.McCormack et al.Shaping of diamond films by etching with molten rear-earth metals.Nature,1993,362:822-824.
[5]M.Yoshikawa.Development and performance of a diamond film polishing apparatus with hot metals.Diamond Optics,SPIE,1990,(1325):210-221.
[6]A.Hirata.Smoothing of chemically vapor deposited diamond films by ion beam irradiation.Thin Solid Films,1992,(212):43-48.
[7]Victor GRalchenko,Sergej M.Pimenov.Processing of Diamond Films.Diamond Films and Technology,1997,7(1):15-50.
[8]陈启瑾.异质基底上化学气相沉积金刚石形核与生长研究:(硕士论文).上海:中国学院物理研究所,1995.06.
[9]Tankala K.Modeling of the role of atomic hydrogen in heat transfer during hot filament assisted deposition of diamond.Appl Phys,1992,72(2):712-718.
[10]方向阳.直流电弧等离子体喷射CVD金刚石膜的制备工艺探讨.宁夏工程技术,2002,1(3):246-249.
[11]黄树涛,姚英学.金刚石膜的加工技术.新技术新工艺,1996,(1):13-14.
[12]李伯民,赵波.实用磨削技术.北京:机械工业出版社,1996.
[13]袁巨龙.功能陶瓷的超精密加工技术.哈尔滨:哈尔滨工业大学出版社,2000.
[14]B.H.Ethob.钻石加工工艺学.史恩泽译.广州:广东科技出版社,1991.
[15]C.D.Ollison,W.D.Brown,A.P.Malshe.A comparison of mechanical lapping versus chemical-assisted mechnical polishing and planarization of chemical vapor deposited diamond.Diamond and Related Materials,1999,(8):1083-1090.
[16]徐锋.CVD金刚石厚膜的加工技术研究:(硕士学位论文).南京:南京航空航天大学,2002.
[17]余忠民,匡同春.CVD金刚石膜的机械抛光加工研究.硬质合金,2000,(9):151-155.
[18]Masanori Yoshikawa,Fuminori Okuzumi.Hot-iron-metal polishing machine for CVD diamond films and characteristics of the polished surfaces.Surface and Coating Technology,1996,(8):197-203.
[19]A.P.Mslshe,B.S.Park.A Review of technology for polishing and planarizing chemically vapor-deposited(CVD) diamond films and substrates.Diamond and Releted Materials,1999,(8):198-121.
[20]S.Jin,W.Zhu.Diamond Shaping and Polishing by Chemical Reactions.Electrochemical Society Proceedings,1995,(4):261-270.
[21]A.M.Zaitsev,GKosaca,B.Richarz et al.Thermochemical polishing of CVD diamond films.Diamond and Related Materials,1999,(8):108-117.
[22]Hitoshi Tokura,Masanori Yoshikawa.Polishing of CVD Diamond Film.Applications of Diamond Films and Related Materials,1991,103(2):241-248.
[23]Masanori Yoshikawa,Fuminori Okuzumi.Hot-iron Metal Polishing Machine for CVD Diamond Films and Characteristics of the Polished Surfaces.Surface and Coating Techology,1996,(88):197-203.
[24]S.K.Choi,D.Y.Jung,S.Y.Kweon et al.Surface Characterization of Diamond Films Polished by Thermomechnical Polishing Method.Thin Solid Films,1996,(279):110-114.
[25]Chao C.L,J.Hung J.Y.Investigation of the thermal-Chemical Polishing and Laser Ablation of CVD Diamond Film,Progress of machining technology with some topic in Advanced Manufacturing Technology Aviation Industry Press,Xian,2002:236-241Pr.,1978.
[26]A.Hirata.Smoothing of chemically vapor deposited diamond films by ion beam irradiation Thin Solid Films,1992,(212):43-48.
[27]Atsushi Hirata,Hitoshi Tokura,Masanori Yoshikawa.Smoothing of diamond films by ion beam irradiation.Applications of Diamond Films and Related Materials,1991:227-232.
[28]Akihisa Yoshida,Masahiro Deguchi.Atomic level smoothing of CVD diamond films gas cluster ion beam etching.Nuclear Instruments and Methods in Physics Research B,1996,(112):248-251.
[29]S.Kiyohara,K.Mori,I.Miyamoto.Oxygen ion beam assisted etching of single crystal diamond chips using relative oxygen gas.Journal of Materials Science:Materials in Electronics,2001,12:477-481.
[30]V.N.Tokarev,J.I.B.Wilson,M.G.Jubber.Modeling of self-limiting laser ablation of rough surfaces,diamond and related materials,1995,(4):167-175.
[31]A.M.Ozkan,A.P.Malshe,W.D.Brown.Sequential multiple-laser-assisted polishing of free-standing CVD diamond substrates,diamond and related materials,1997,(6):1789-1798.
[32]S.Gloor,S.M.Pimenov,E.D.Obraztsova.Laser ablation of diamond films in various atmospheres.Diamond and Related Materials,1998,(7):607-61l.
[33]陈启成.化学辅助机械式抛光钻石膜之研磨液作用:(硕士学位论文).台湾:国立清华大学,2006.
[34]陈春林.机械与氧化化学法抛光金刚石膜研究:(硕士学位论文).广州:广东工业大学,2003.
[35]苏建修,康仁科,郭东明.超大规模集成电路制造中硅片化学机械抛光技术分析.半导体技术.2003,28(10):27-32.
[36]苏建修,郭东明,康仁科等.硅片化学机械抛光时硅片运动形式对片内非均匀性的影响分析.中国机械工程.2005,16(9):815-818.
[37]大连理工大学无机化学教研室.无机化学.北京:高等教育出版社,2004.
[38]邢哲,刘玉岭,檀柏梅等.ULSI铜多层布线中钽阻挡层CMP抛光液的研究与优化.半导体学报.2004,(25):1726-1728.
[39]张楷亮,宋志棠,封松林.化学机械抛光的研究与展望.微电子学.2005,(35):226-230.
[40]杨建东.高速研磨技术.北京:国防工业出版社,2003.
[41]刘文卿.实验设计.北京:清华大学出版社,2005.
[42]陈光华,张阳.金刚石膜的制备与应用.北京:化学工业出版社,2004.
[2]匡同春,王晓初.CVD金刚石道具的研究进展与应用现状.金刚石与磨料磨具工程,2000,116(2):27-30.
[3]张铮.CVD金刚石薄膜抛光技术的研究进展.真空科学与技术学报,2000,20(4):270-273.
[4]S.Jin,.E.Graebner,M.McCormack et al.Shaping of diamond films by etching with molten rear-earth metals.Nature,1993,362:822-824.
[5]M.Yoshikawa.Development and performance of a diamond film polishing apparatus with hot metals.Diamond Optics,SPIE,1990,(1325):210-221.
[6]A.Hirata.Smoothing of chemically vapor deposited diamond films by ion beam irradiation.Thin Solid Films,1992,(212):43-48.
[7]Victor GRalchenko,Sergej M.Pimenov.Processing of Diamond Films.Diamond Films and Technology,1997,7(1):15-50.
[8]陈启瑾.异质基底上化学气相沉积金刚石形核与生长研究:(硕士论文).上海:中国学院物理研究所,1995.06.
[9]Tankala K.Modeling of the role of atomic hydrogen in heat transfer during hot filament assisted deposition of diamond.Appl Phys,1992,72(2):712-718.
[10]方向阳.直流电弧等离子体喷射CVD金刚石膜的制备工艺探讨.宁夏工程技术,2002,1(3):246-249.
[11]黄树涛,姚英学.金刚石膜的加工技术.新技术新工艺,1996,(1):13-14.
[12]李伯民,赵波.实用磨削技术.北京:机械工业出版社,1996.
[13]袁巨龙.功能陶瓷的超精密加工技术.哈尔滨:哈尔滨工业大学出版社,2000.
[14]B.H.Ethob.钻石加工工艺学.史恩泽译.广州:广东科技出版社,1991.
[15]C.D.Ollison,W.D.Brown,A.P.Malshe.A comparison of mechanical lapping versus chemical-assisted mechnical polishing and planarization of chemical vapor deposited diamond.Diamond and Related Materials,1999,(8):1083-1090.
[16]徐锋.CVD金刚石厚膜的加工技术研究:(硕士学位论文).南京:南京航空航天大学,2002.
[17]余忠民,匡同春.CVD金刚石膜的机械抛光加工研究.硬质合金,2000,(9):151-155.
[18]Masanori Yoshikawa,Fuminori Okuzumi.Hot-iron-metal polishing machine for CVD diamond films and characteristics of the polished surfaces.Surface and Coating Technology,1996,(8):197-203.
[19]A.P.Mslshe,B.S.Park.A Review of technology for polishing and planarizing chemically vapor-deposited(CVD) diamond films and substrates.Diamond and Releted Materials,1999,(8):198-121.
[20]S.Jin,W.Zhu.Diamond Shaping and Polishing by Chemical Reactions.Electrochemical Society Proceedings,1995,(4):261-270.
[21]A.M.Zaitsev,GKosaca,B.Richarz et al.Thermochemical polishing of CVD diamond films.Diamond and Related Materials,1999,(8):108-117.
[22]Hitoshi Tokura,Masanori Yoshikawa.Polishing of CVD Diamond Film.Applications of Diamond Films and Related Materials,1991,103(2):241-248.
[23]Masanori Yoshikawa,Fuminori Okuzumi.Hot-iron Metal Polishing Machine for CVD Diamond Films and Characteristics of the Polished Surfaces.Surface and Coating Techology,1996,(88):197-203.
[24]S.K.Choi,D.Y.Jung,S.Y.Kweon et al.Surface Characterization of Diamond Films Polished by Thermomechnical Polishing Method.Thin Solid Films,1996,(279):110-114.
[25]Chao C.L,J.Hung J.Y.Investigation of the thermal-Chemical Polishing and Laser Ablation of CVD Diamond Film,Progress of machining technology with some topic in Advanced Manufacturing Technology Aviation Industry Press,Xian,2002:236-241Pr.,1978.
[26]A.Hirata.Smoothing of chemically vapor deposited diamond films by ion beam irradiation Thin Solid Films,1992,(212):43-48.
[27]Atsushi Hirata,Hitoshi Tokura,Masanori Yoshikawa.Smoothing of diamond films by ion beam irradiation.Applications of Diamond Films and Related Materials,1991:227-232.
[28]Akihisa Yoshida,Masahiro Deguchi.Atomic level smoothing of CVD diamond films gas cluster ion beam etching.Nuclear Instruments and Methods in Physics Research B,1996,(112):248-251.
[29]S.Kiyohara,K.Mori,I.Miyamoto.Oxygen ion beam assisted etching of single crystal diamond chips using relative oxygen gas.Journal of Materials Science:Materials in Electronics,2001,12:477-481.
[30]V.N.Tokarev,J.I.B.Wilson,M.G.Jubber.Modeling of self-limiting laser ablation of rough surfaces,diamond and related materials,1995,(4):167-175.
[31]A.M.Ozkan,A.P.Malshe,W.D.Brown.Sequential multiple-laser-assisted polishing of free-standing CVD diamond substrates,diamond and related materials,1997,(6):1789-1798.
[32]S.Gloor,S.M.Pimenov,E.D.Obraztsova.Laser ablation of diamond films in various atmospheres.Diamond and Related Materials,1998,(7):607-61l.
[33]陈启成.化学辅助机械式抛光钻石膜之研磨液作用:(硕士学位论文).台湾:国立清华大学,2006.
[34]陈春林.机械与氧化化学法抛光金刚石膜研究:(硕士学位论文).广州:广东工业大学,2003.
[35]苏建修,康仁科,郭东明.超大规模集成电路制造中硅片化学机械抛光技术分析.半导体技术.2003,28(10):27-32.
[36]苏建修,郭东明,康仁科等.硅片化学机械抛光时硅片运动形式对片内非均匀性的影响分析.中国机械工程.2005,16(9):815-818.
[37]大连理工大学无机化学教研室.无机化学.北京:高等教育出版社,2004.
[38]邢哲,刘玉岭,檀柏梅等.ULSI铜多层布线中钽阻挡层CMP抛光液的研究与优化.半导体学报.2004,(25):1726-1728.
[39]张楷亮,宋志棠,封松林.化学机械抛光的研究与展望.微电子学.2005,(35):226-230.
[40]杨建东.高速研磨技术.北京:国防工业出版社,2003.
[41]刘文卿.实验设计.北京:清华大学出版社,2005.
[42]陈光华,张阳.金刚石膜的制备与应用.北京:化学工业出版社,2004.