射频磁控反应溅射法制备Y_2O_3薄膜的研究
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摘要
金刚石具有优异的力学、电学、热学和光学性能,是用于长波红外波段(8～12μm)理想的窗口和头罩材料。然而,当温度超过750℃时金刚石很容易发生氧化,导致透过率急剧下降。为了满足在高速、高温下应用的要求,需要在金刚石表面制备抗氧化、增透保护涂层。三氧化二钇(Y_2O_3)具有优良的物理、化学性能,抗高温氧化能力强,可用作金刚石抗氧化保护涂层。在国外,Y_2O_3用作金刚石抗氧化涂层的研究已经展开,并取得进展;在国内,有关Y_2O_3光学保护涂层的研究还未见报道。本文主要研究制备Y_2O_3薄膜的制备工艺和薄膜的成分、结构及红外透过性能,为金刚石应用于高速红外窗口和头罩提供工艺技术基础。论文的主要工作及研究成果如下:
利用OPFCAD软件在金刚石衬底上设计了Y_2O_3增透膜系,并对所设计的膜系进行了结构敏感因子及结构偏差分析。膜系设计结果表明,在金刚石衬底上镀Y_2O_3或Y_2O_3/AlN膜系后在8-12μm波段的红外透过率可达90%,最大增透效果可达21%。
在JGP560C型磁控溅射镀膜机上优化出了制备Y_2O_3薄膜的工艺参数,揭示了射频功率、溅射气压、衬底温度和Ar/O_2气体流量比对薄膜沉积速率的影响规律。正交试验设计结果表明,溅射气压和射频功率是影响Y_2O_3薄膜沉积速率的主要因素,并由此确定了获得薄膜最大沉积速率的工艺参数。
对制备的Y_2O_3薄膜进行了X射线光电子谱(XPS)、X射线衍射(XRD)和FTIR红外透过光谱分析。XPS分析结果表明,沉积态薄膜中Y和O原子结合形成了Y_2O_3化合物;XRD分析结果表明,沉积态薄膜中Y_2O_3主要以非晶状态存在,在800℃下退火后Y_2O_3薄膜向多晶转变;红外透过光谱分析结果表明,Si衬底上镀Y_2O_3膜后,在2000～3000cm~(-1)波数范围的平均透过率可达90%以上,Y_2O_3薄膜的折射率约为1.93。
Diamond is an ideal material for airborne LWIR (8~12μm) windows and domes with excellent properties in mechanics, electrics, calorifics and optics. However, diamond is easily subject to oxidation in air at temperatures higher than 750℃, and the optical transmittance is hence degraded greatly. In order to meet the requirements of the applications under high-speed or high-temperature, anti-oxidation and anti-reflective films must be prepared on the diamond surface. Yttrium oxide (Y2O3) is a promising anti-oxidation material for diamond with good physical, chemical and anti-oxidation properties. Great progresses have been made in the researches on Y_2O_3 anti-oxidation films overseas. But no domestic work has yet been done. Researches of this paper concentrate mostly on the preparations, components, structures and infrared transmission properties of Y_2O_3 films, which will establish a technical foundation for using diamond for high-speed IR windows and domes. The main research works and results are as follows:Anti-reflective films containing Y2O3 are designed on diamond substrates with OPFCAD software and the sensitive factor and deviation of the films' structure are analyzed. The designed results show that the average transmittances of both Y_2O_3//Diamond and Y_2O_3/AIN//Diamond systems over 8~11.5μm waveband exceed 90%, and the maximal increased transmittance is up to 21%.Y_2O_3 films are prepared on silicon substrates through JGP560C magnetron sputtering apparatus in order to research the influences of the main depositing parameters, such as the RF power, gas pressure, Ar/O_2 gas flow ratio, and substrate temperature, on the film depositing rates, and thus the optimized parameters are obtained. The orthogonal experiment results show that the effects of RF power and gas pressure on the deposition rates is most significant, and the parameters to get high deposition rate are decided.
XPS and XRD analyses as well as FTIR transmission spectrum tests are carried out. XPS analysis confirms the formation of the compound of Y2O3 XRD results show that the as-deposited Y2O3 films are mainly amorphous and after annealed at 800 °C become polycrystalline. FTIR results show that the average transmittance over 2000-3 000cm"1 of silicon substrate with Y2O3 films coated on both sides exceeds 90%, and the refractive indexes of the film are about 1.93.
利用OPFCAD软件在金刚石衬底上设计了Y_2O_3增透膜系,并对所设计的膜系进行了结构敏感因子及结构偏差分析。膜系设计结果表明,在金刚石衬底上镀Y_2O_3或Y_2O_3/AlN膜系后在8-12μm波段的红外透过率可达90%,最大增透效果可达21%。
在JGP560C型磁控溅射镀膜机上优化出了制备Y_2O_3薄膜的工艺参数,揭示了射频功率、溅射气压、衬底温度和Ar/O_2气体流量比对薄膜沉积速率的影响规律。正交试验设计结果表明,溅射气压和射频功率是影响Y_2O_3薄膜沉积速率的主要因素,并由此确定了获得薄膜最大沉积速率的工艺参数。
对制备的Y_2O_3薄膜进行了X射线光电子谱(XPS)、X射线衍射(XRD)和FTIR红外透过光谱分析。XPS分析结果表明,沉积态薄膜中Y和O原子结合形成了Y_2O_3化合物;XRD分析结果表明,沉积态薄膜中Y_2O_3主要以非晶状态存在,在800℃下退火后Y_2O_3薄膜向多晶转变;红外透过光谱分析结果表明,Si衬底上镀Y_2O_3膜后,在2000～3000cm~(-1)波数范围的平均透过率可达90%以上,Y_2O_3薄膜的折射率约为1.93。
Diamond is an ideal material for airborne LWIR (8~12μm) windows and domes with excellent properties in mechanics, electrics, calorifics and optics. However, diamond is easily subject to oxidation in air at temperatures higher than 750℃, and the optical transmittance is hence degraded greatly. In order to meet the requirements of the applications under high-speed or high-temperature, anti-oxidation and anti-reflective films must be prepared on the diamond surface. Yttrium oxide (Y2O3) is a promising anti-oxidation material for diamond with good physical, chemical and anti-oxidation properties. Great progresses have been made in the researches on Y_2O_3 anti-oxidation films overseas. But no domestic work has yet been done. Researches of this paper concentrate mostly on the preparations, components, structures and infrared transmission properties of Y_2O_3 films, which will establish a technical foundation for using diamond for high-speed IR windows and domes. The main research works and results are as follows:Anti-reflective films containing Y2O3 are designed on diamond substrates with OPFCAD software and the sensitive factor and deviation of the films' structure are analyzed. The designed results show that the average transmittances of both Y_2O_3//Diamond and Y_2O_3/AIN//Diamond systems over 8~11.5μm waveband exceed 90%, and the maximal increased transmittance is up to 21%.Y_2O_3 films are prepared on silicon substrates through JGP560C magnetron sputtering apparatus in order to research the influences of the main depositing parameters, such as the RF power, gas pressure, Ar/O_2 gas flow ratio, and substrate temperature, on the film depositing rates, and thus the optimized parameters are obtained. The orthogonal experiment results show that the effects of RF power and gas pressure on the deposition rates is most significant, and the parameters to get high deposition rate are decided.
XPS and XRD analyses as well as FTIR transmission spectrum tests are carried out. XPS analysis confirms the formation of the compound of Y2O3 XRD results show that the as-deposited Y2O3 films are mainly amorphous and after annealed at 800 °C become polycrystalline. FTIR results show that the average transmittance over 2000-3 000cm"1 of silicon substrate with Y2O3 films coated on both sides exceeds 90%, and the refractive indexes of the film are about 1.93.
引文
1.赵秀丽.红外光学系统设计.北京:机械出版社,1986,
2.张贵峰.新型红外增透膜与保护膜.红外技术,1995.17(5):23
3. Daniel C. Harris. Materials for Infrared Windows and Domes. SPIE Optical Engineering Press. 1999.
4.彭鸿雁,赵立新.类金刚石膜的制备、性能与应用.北京:科学出版社,2004
5. Jane Yuan Howe. The Oxidation of Diamond. Thesis for Doctor Degree. Alfred University, New York(February, 2001)
6. Chang Q Sun. model of bonding and band-forming for oxides and nitrides. Appl. Phys. Lett, 1998, 72: 1706
7. Chang Q Sun et al. Preferential Oxidation of Diamond {111}. J. Phys. D: Appl. Phys, 2000, 33: 2196
8. P. John et al. The Oxidation of (100) Textured Diamond. Diamond and Related Materials, 2002, 11: 862
9. K. P. Loh et al. Surface oxygenation studies on (100)-oriented diamond using an atom beam source and local anodic oxidation. Surface Science, 2002, 11: 862
10. Chen J et al. Graphitization of nano diamond powder annealed in argon ambient. Appl. Phys. Lett, 1999, 74: 3651
11.巨志高.金刚石衬底上红外增透及抗氧化膜系的制备与性能研究.西北工业大学硕士学位论文,2005年
12. Grannen K J, Tsu D V, Meliunas R Jet al. Oxidation studies of fluorine containing diamond films [J]. Applied Physics Letters, 1991, 59(6): 745-747
13. Miyata K, Kobashi K. Air oxidation of undoped and B-doped polycrystalline diamond films at high temperature [J]. Journal of Material Research, 1996, 11: 296-305
14. Yoshihito Hara. ALN formation and enhancement of high-temperature oxidation resistance by plasma-based ion implantation. Surface and Coatings Technology, 169-170(2003) 359
15. V. N. Inkin. Properties of aluminum nitride coating obtained by vacuum arc discharge method with plasma flow separation. Diamond and Related Materials, 2001, 10: 1314
16. S. P. McGeoch EM. Waddell, et al. Aluminum Nitride Coatings for Protection of Diamond at High Temperature in Air. Proc. SPIE1999, 3705: 163～169
17.乔保卫.磁控反应溅射AlN薄膜的制备工艺与性能研究.西北工业大学硕士学位论文,2003年
18.刘金声.离子束沉积薄膜技术及应用.北京:国防工业出版社,2003.
19. T P Mollart, K L lewis, CJK Wort and CSJ Pickles. Coating Technology for CVD diamond Optics. Window and Dome Technologies and Materials Ⅶ.SPIE, Vol.4375(2001).
20. Ken-ichi Onisawa, Moriaki Fuyama, et al. Dielectric properties of rf-sputtered Y_2O_3 thin films. J. Appl. Phys. 68(2), 15 July 1990
21.周玉.陶瓷材料学.哈尔滨工业大学出版社.1995
22. K. A. Klemm, H. S. Patterson, et al. Protective Optical Coatings for Diamond Infrared Windows. Proc. SPIE 1994, 2286: 347～353
23.杨生荣,王金清,刘晓红.Y_2O_3薄膜的制备以及抗划伤性能和摩擦学性能研究.[A].材料保护,2004年7月第37卷第7期
24. M. H. Cho, D. H. Ko, et al. Structural transition of crystalline Y_2O_3 film on Si(111) with substrate temperature, [J] Thin Solid Films, 1999, 349: 266～269.
25. L. Manchanda et al. Yttrium Oxide/Silicon Dioxide: A New Dielectric Structure for VLSI/ULSI Circuits. [J]. IEEE ELECTRON DEVICE LETTERS, Vol.9, No.4, april 1988.
26. Wang Y, Lu Z H. Preparation of Y_2O_3 thin films deposited by pulse ultrasonic spray pyrolysis [J]. Materials Chemistry and Physics, 2002, 78: 542-545.
27. Paumier F, Gaboriaud R J, Kaul A R, Yttrium oxide thin films: chemistry stoichiometry-strain and microstructure[J]. Crystal Engineering, 2002, 5: 169-175.
28. Agarwal M, DeGuire M R, Heuer A H. synthesis of yttrium Oxide thin films with and without the use of organic self-assembled monolayers [J]. Appl Phys Lett, 1997, 71: 891-893.
29. R. E. Sah, C. J. Kelly, et al. Amorphous Hydrogenated Carbon-germanium Films for Hard Multilayers IR Optical Coatings. Proc. SPIE 1990, 1275: 59
30.林永昌,卢维强.光学薄膜原理.国防工业出版社,1990
31.尹树百.薄膜光学—理论与实践.科学出版社,1987
32.唐晋发,顾培夫.薄膜光学与技术.机械工业出版社,1989
33.周健,林永昌.一种新的膜系设计方法—Neddle法.光学学报.1997,17(10):1445～1449
34.林永昌,顾永琳,张诚等.针法与初始膜系设计.光学学报.1997,(10):27～31
35. Paul Klocek, Thomas McKenna, John Trombetta. Thermo-optic, thermo-mechanical, and electromagnetic effects in IR windows and domes, and the rationale for GaAs, GaP, and diamond. Proc. SPIE 1994, 2286: 71～90
36. P. J. Kelly, R. D. Amell. Magnetron Sputtering: A Review of Developments and Application. Vaccum. 2000, (56): 159～172
37.王力衡,黄运添,郑海涛.薄膜技术.清华大学出版社.1991
38.严一心,林鸿海.薄膜技术.国防工业出版社,1994
39.陈国平.薄膜科学与技术.东南大学出版社,1993
40.田民波,刘德令.薄膜科学与技术手册(上册).机械工业出版社,1991
41. J. L. Vossoen, W. Kerfned. Thin Film Processing. Academic Press. 1978
42.许小红、武海顺.压电薄膜的制备、结构与应用.科学出版社.
43.宋健全.ZnS头罩增透保护膜系的设计、制备及计算机模拟.西北工业大学博士论文.2001
44. R. D. Gould, S. A. Awan, Deposition and DC electrical characterisation of rf magnetron sputtered silicon nitride thin films, Thin Solid Films, 2006, In press.
45.刘正堂,朱景芝,宋健全等.反应溅射Ge_xC(1-x)薄膜的沉积速率.材料工程, 1998(2)
46.李学丹等.真空沉积技术.浙江大学出版社,1994
2.张贵峰.新型红外增透膜与保护膜.红外技术,1995.17(5):23
3. Daniel C. Harris. Materials for Infrared Windows and Domes. SPIE Optical Engineering Press. 1999.
4.彭鸿雁,赵立新.类金刚石膜的制备、性能与应用.北京:科学出版社,2004
5. Jane Yuan Howe. The Oxidation of Diamond. Thesis for Doctor Degree. Alfred University, New York(February, 2001)
6. Chang Q Sun. model of bonding and band-forming for oxides and nitrides. Appl. Phys. Lett, 1998, 72: 1706
7. Chang Q Sun et al. Preferential Oxidation of Diamond {111}. J. Phys. D: Appl. Phys, 2000, 33: 2196
8. P. John et al. The Oxidation of (100) Textured Diamond. Diamond and Related Materials, 2002, 11: 862
9. K. P. Loh et al. Surface oxygenation studies on (100)-oriented diamond using an atom beam source and local anodic oxidation. Surface Science, 2002, 11: 862
10. Chen J et al. Graphitization of nano diamond powder annealed in argon ambient. Appl. Phys. Lett, 1999, 74: 3651
11.巨志高.金刚石衬底上红外增透及抗氧化膜系的制备与性能研究.西北工业大学硕士学位论文,2005年
12. Grannen K J, Tsu D V, Meliunas R Jet al. Oxidation studies of fluorine containing diamond films [J]. Applied Physics Letters, 1991, 59(6): 745-747
13. Miyata K, Kobashi K. Air oxidation of undoped and B-doped polycrystalline diamond films at high temperature [J]. Journal of Material Research, 1996, 11: 296-305
14. Yoshihito Hara. ALN formation and enhancement of high-temperature oxidation resistance by plasma-based ion implantation. Surface and Coatings Technology, 169-170(2003) 359
15. V. N. Inkin. Properties of aluminum nitride coating obtained by vacuum arc discharge method with plasma flow separation. Diamond and Related Materials, 2001, 10: 1314
16. S. P. McGeoch EM. Waddell, et al. Aluminum Nitride Coatings for Protection of Diamond at High Temperature in Air. Proc. SPIE1999, 3705: 163～169
17.乔保卫.磁控反应溅射AlN薄膜的制备工艺与性能研究.西北工业大学硕士学位论文,2003年
18.刘金声.离子束沉积薄膜技术及应用.北京:国防工业出版社,2003.
19. T P Mollart, K L lewis, CJK Wort and CSJ Pickles. Coating Technology for CVD diamond Optics. Window and Dome Technologies and Materials Ⅶ.SPIE, Vol.4375(2001).
20. Ken-ichi Onisawa, Moriaki Fuyama, et al. Dielectric properties of rf-sputtered Y_2O_3 thin films. J. Appl. Phys. 68(2), 15 July 1990
21.周玉.陶瓷材料学.哈尔滨工业大学出版社.1995
22. K. A. Klemm, H. S. Patterson, et al. Protective Optical Coatings for Diamond Infrared Windows. Proc. SPIE 1994, 2286: 347～353
23.杨生荣,王金清,刘晓红.Y_2O_3薄膜的制备以及抗划伤性能和摩擦学性能研究.[A].材料保护,2004年7月第37卷第7期
24. M. H. Cho, D. H. Ko, et al. Structural transition of crystalline Y_2O_3 film on Si(111) with substrate temperature, [J] Thin Solid Films, 1999, 349: 266～269.
25. L. Manchanda et al. Yttrium Oxide/Silicon Dioxide: A New Dielectric Structure for VLSI/ULSI Circuits. [J]. IEEE ELECTRON DEVICE LETTERS, Vol.9, No.4, april 1988.
26. Wang Y, Lu Z H. Preparation of Y_2O_3 thin films deposited by pulse ultrasonic spray pyrolysis [J]. Materials Chemistry and Physics, 2002, 78: 542-545.
27. Paumier F, Gaboriaud R J, Kaul A R, Yttrium oxide thin films: chemistry stoichiometry-strain and microstructure[J]. Crystal Engineering, 2002, 5: 169-175.
28. Agarwal M, DeGuire M R, Heuer A H. synthesis of yttrium Oxide thin films with and without the use of organic self-assembled monolayers [J]. Appl Phys Lett, 1997, 71: 891-893.
29. R. E. Sah, C. J. Kelly, et al. Amorphous Hydrogenated Carbon-germanium Films for Hard Multilayers IR Optical Coatings. Proc. SPIE 1990, 1275: 59
30.林永昌,卢维强.光学薄膜原理.国防工业出版社,1990
31.尹树百.薄膜光学—理论与实践.科学出版社,1987
32.唐晋发,顾培夫.薄膜光学与技术.机械工业出版社,1989
33.周健,林永昌.一种新的膜系设计方法—Neddle法.光学学报.1997,17(10):1445～1449
34.林永昌,顾永琳,张诚等.针法与初始膜系设计.光学学报.1997,(10):27～31
35. Paul Klocek, Thomas McKenna, John Trombetta. Thermo-optic, thermo-mechanical, and electromagnetic effects in IR windows and domes, and the rationale for GaAs, GaP, and diamond. Proc. SPIE 1994, 2286: 71～90
36. P. J. Kelly, R. D. Amell. Magnetron Sputtering: A Review of Developments and Application. Vaccum. 2000, (56): 159～172
37.王力衡,黄运添,郑海涛.薄膜技术.清华大学出版社.1991
38.严一心,林鸿海.薄膜技术.国防工业出版社,1994
39.陈国平.薄膜科学与技术.东南大学出版社,1993
40.田民波,刘德令.薄膜科学与技术手册(上册).机械工业出版社,1991
41. J. L. Vossoen, W. Kerfned. Thin Film Processing. Academic Press. 1978
42.许小红、武海顺.压电薄膜的制备、结构与应用.科学出版社.
43.宋健全.ZnS头罩增透保护膜系的设计、制备及计算机模拟.西北工业大学博士论文.2001
44. R. D. Gould, S. A. Awan, Deposition and DC electrical characterisation of rf magnetron sputtered silicon nitride thin films, Thin Solid Films, 2006, In press.
45.刘正堂,朱景芝,宋健全等.反应溅射Ge_xC(1-x)薄膜的沉积速率.材料工程, 1998(2)
46.李学丹等.真空沉积技术.浙江大学出版社,1994