TiN_x/Ag/TiN_x低辐射膜的制备及性能研究
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摘要
建筑门窗的能耗约占到建筑物全部热损失的50%,因此减少玻璃窗的热损失对建筑节能具有非常重要的意义。由于低辐射玻璃比较高的可见光透过率,能保证室内有良好的采光,其对远红外也有很好的反射率,有很的节能效果,可以有效地减少采暖和空调费用,因此低辐射玻璃得到了越来越广泛的应用。
银系低辐射玻璃通常将TiO2、SnO2等氧化物作为介质膜,所以很难避免Ag膜被氧化,且不能对Ag起到好的保护作用。由于氮化钛薄膜具有良好的可见光透过率、化学稳定性和一定的远红外反射率。本实验将其用作低辐射膜的介质膜,研究其光学性能和耐腐蚀性能。
本课题以银靶和钛靶为靶材,N2为反应气体,Ar气为工作气体。采用射频磁控溅射法在玻璃基片上沉积TiNx/Ag/TiNx薄膜。运用X射线衍射仪(XRD)、X射线光电子能谱(XPS)、场发射描扫显微镜(SEM)、四探针电阻仪、紫外/可见/近红外分光光度计、台阶仪、傅里叶红外光谱仪等手段对制备的薄膜样品进行测试和分析。
研究表明,氮化钛薄膜呈非晶态,外层TiNx薄膜表面存在着较多的Ti-O键,对低辐射膜的可见光透过率有提高作用。低辐射膜的可见光透过率随着Ag膜的增厚先增加后降低,随着氮气流量的增加而增加,随着TiNx薄膜的溅射功率的增加先增加后降低;随着内层和外层TiNx薄膜厚度的增加,低辐射膜的透射峰发生红移但都对峰值影响不大。
随着厚度的增加,外层TiNx薄膜越来越致密。当厚度达到32nm时,对H2S气体、NaOH溶液和NaCl溶液的腐蚀可以起到较好的保护作用,但本课题研究的低辐射膜耐HCl溶液腐蚀的能力还有待进一步提高。
结构为16nmTiNx /16nmAg/32nmTiNx的低辐射膜有较高的可见光透过率,对光谱具有明显的选择性,同时具有优良的耐腐蚀性能。可见光透过率达到85%,近红外反射率可达到92%,辐射率为0.093。
The energy loss from door and window account for about 50% of total energy loss of buildings, so it’s very important to reduce the energy loss from door and windows for building energy saving. The Low-e glass have very high visible transmittance and high far-infrared (IR) reflectance, so the building have good lighting and very good energy saving effect, the Low-e glass wildly used for it can save the heating and conditioning expense.
Usually, TiO2、SnO2 films used as dielectric films of Low-e glass., but the Ag film should be oxidized. Titanium nitrides have very high visual transmittance、chemical properties and far-infrared reflectivity。Due to its character, this topic used it as the dielectric film of coatings. Study the optical and corrosion-resistance properties.
In this work, all films have been prepared by r.f. magnetron sputtering, using N2 as the reaction gas,using Ar as the working gas. The films were characterized by means of XRD, SEM, XPS, UV-VIS-NIR spectroscopy, step profiler , fourier infrared spectrometer and so on.
The results indicate that TiNx thin films are amorphous, on the surface of which exists a lot of Ti-O bonds, bears responsibility for improving the visual transmittance of multilayer film. The transmittance of films, firstly increase and then decrease with increasing of thickness of Ag thin film, is improved with the increase of nitrogen flow rate, is firstly increase and then decrease with the increase of power of TiNx thin films. The transmission peak of Low-e thin film shows red shift with the increase of thickness of insider or outsider TiNx thin films. With the increase of thickness, outsider TiNx thin films become more and more
dense. While the thickness of TiNx film comes to 32nm, the Low-e glass has good corrosion-resistance property, but the acid-resistant should be improved.
While the texture is TiNx(8nm)/Ag(16nm)/TiNx(16nm), the visible transmittance of multilayer film reach up to 85%,the far-infrared reflectance is up to 92%、the emissivity is 0.093 , the Low-e films presents very good corrosion-resistance and optical property.
银系低辐射玻璃通常将TiO2、SnO2等氧化物作为介质膜,所以很难避免Ag膜被氧化,且不能对Ag起到好的保护作用。由于氮化钛薄膜具有良好的可见光透过率、化学稳定性和一定的远红外反射率。本实验将其用作低辐射膜的介质膜,研究其光学性能和耐腐蚀性能。
本课题以银靶和钛靶为靶材,N2为反应气体,Ar气为工作气体。采用射频磁控溅射法在玻璃基片上沉积TiNx/Ag/TiNx薄膜。运用X射线衍射仪(XRD)、X射线光电子能谱(XPS)、场发射描扫显微镜(SEM)、四探针电阻仪、紫外/可见/近红外分光光度计、台阶仪、傅里叶红外光谱仪等手段对制备的薄膜样品进行测试和分析。
研究表明,氮化钛薄膜呈非晶态,外层TiNx薄膜表面存在着较多的Ti-O键,对低辐射膜的可见光透过率有提高作用。低辐射膜的可见光透过率随着Ag膜的增厚先增加后降低,随着氮气流量的增加而增加,随着TiNx薄膜的溅射功率的增加先增加后降低;随着内层和外层TiNx薄膜厚度的增加,低辐射膜的透射峰发生红移但都对峰值影响不大。
随着厚度的增加,外层TiNx薄膜越来越致密。当厚度达到32nm时,对H2S气体、NaOH溶液和NaCl溶液的腐蚀可以起到较好的保护作用,但本课题研究的低辐射膜耐HCl溶液腐蚀的能力还有待进一步提高。
结构为16nmTiNx /16nmAg/32nmTiNx的低辐射膜有较高的可见光透过率,对光谱具有明显的选择性,同时具有优良的耐腐蚀性能。可见光透过率达到85%,近红外反射率可达到92%,辐射率为0.093。
The energy loss from door and window account for about 50% of total energy loss of buildings, so it’s very important to reduce the energy loss from door and windows for building energy saving. The Low-e glass have very high visible transmittance and high far-infrared (IR) reflectance, so the building have good lighting and very good energy saving effect, the Low-e glass wildly used for it can save the heating and conditioning expense.
Usually, TiO2、SnO2 films used as dielectric films of Low-e glass., but the Ag film should be oxidized. Titanium nitrides have very high visual transmittance、chemical properties and far-infrared reflectivity。Due to its character, this topic used it as the dielectric film of coatings. Study the optical and corrosion-resistance properties.
In this work, all films have been prepared by r.f. magnetron sputtering, using N2 as the reaction gas,using Ar as the working gas. The films were characterized by means of XRD, SEM, XPS, UV-VIS-NIR spectroscopy, step profiler , fourier infrared spectrometer and so on.
The results indicate that TiNx thin films are amorphous, on the surface of which exists a lot of Ti-O bonds, bears responsibility for improving the visual transmittance of multilayer film. The transmittance of films, firstly increase and then decrease with increasing of thickness of Ag thin film, is improved with the increase of nitrogen flow rate, is firstly increase and then decrease with the increase of power of TiNx thin films. The transmission peak of Low-e thin film shows red shift with the increase of thickness of insider or outsider TiNx thin films. With the increase of thickness, outsider TiNx thin films become more and more
dense. While the thickness of TiNx film comes to 32nm, the Low-e glass has good corrosion-resistance property, but the acid-resistant should be improved.
While the texture is TiNx(8nm)/Ag(16nm)/TiNx(16nm), the visible transmittance of multilayer film reach up to 85%,the far-infrared reflectance is up to 92%、the emissivity is 0.093 , the Low-e films presents very good corrosion-resistance and optical property.
引文
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[4]张宗权.镀膜玻璃的功能、分类与性能比较[J].西北轻工业学院学报,1999,9:77-82.
[5]顽大勇、许伟均.LOW、E镀膜玻璃应尽早进入民宅[J].中国建材.1999,2:59-60.
[6] Szczyrbowski J., Dietrich A., Hartig K. Bendable silver-based low emissivity coating onglass[J]. Sol.Energy Master. 989,19:43-53.
[7] Szczyrbowski J., G. Br?uer, M. Ruske, etc. New low emissivity coating based on TwinMag sputtered TiO2 and Si3N4 layers[J]. Thin Solid Films, 1999, 351, 254-259.
[8]姜燮昌.低辐射玻璃的最新进展[J].真空.2003,2:1-6.
[9]顾翼东,谢高阳,宋沅金,松林.无机化学丛书第八卷[M].科学出版社.
[10]黄佳木,徐成俊.氮流量对磁控溅射法制备氮化钛薄膜光学性能的影响[J].光学学报, 2005,9:1293-1296.
[11]黄佳木,徐成俊,张新元等.室温直流磁控溅射氮化钛薄膜研究[J].真空科学与技术学报, 2005,12.
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[13] S. Niyomsoan, W. Grant et al. Variation of color in titanium and zirconium nitride decorative thin films[J]. Thin Solid Films. 415 (2002) 187-194.
[14] S. Logothetidis, E.I. Meletis, G. Stergioudis, A.A. Adjaottor. Room temperature oxidation behavior of TiN thin films[J]. Thin Solid Films. 338(1999)304-313.
[15]张谷令,王久丽,扬武保等.内表面栅离子体源离子注入TiN薄膜及特性研究[J].物理学报.2003.
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[17]胡传胜,袁泽喜.低温下的氮化钛化学气相沉积[J].国外金属热处理.1997, (3):9-11.
[18]肖国珍,黄春良,焦文强等.离子镀氮化钛涂层的工艺研究[J].稀有金属材料与工程.1997, 26(3):40-44.
[19]阎鹏勋,扬思泽,陈熙.脉冲高能量密度等离子体沉积氮化钛薄膜的结合强度[J].金属学报, 1994, 30(11):B503-507.
[20]戴达煌,谢红希,侯惠君等.用直流等离子体化学气相沉积法在硬质合金上沉积氮化钛薄膜的研究[J].广东有色金属学报,1996, 6(2):119-124.
[21]宋贵宏,杜昊,贺春林.硬质与超硬涂层.[M].北京:化学工业出版社.2007.
[22]曹祖安,金柱京等.TiN涂层高速钢刀具的应用试验[J].新工艺新技术新设备. 1994, (3):31-33.
[23] J. Szczyrbowski, G. Braèuer, M. Ruske, H. Schilling, New low emissivity coating based on TwinMagw sputtered TiO2and Si3N4 layers[J], Thin Solid Films 351 (1999):254-259.
[24] Kiyoshi Chiba, Toshiyuki Takahashi, Takashi Kageyama, Low-emissivity coating of amorphous diamond-like carbon/Ag-alloy multilayer on glass[J], Applied Surface Science 246 (2005):48-51.
[25]李晓东,可异地加工离线LOW-E及其生产控制[J],节能.环保.创新.发展,2006:372-377.
[26] Kusano E ,Kawaguchi J ,Enjougi K. J Vaccum Sci Technol[C],1986 ,A4(6) :2907.
[27]曹楚南主编.中国材料的自然环境腐蚀(第一版)[M].化学工业出版社.北京.2005年
[28] Shuiping Huang, Zhanshan Wang, Jian Xu, Determination of optical constants of functional layer of online Low-E glass based on the Drude theory, Thin Solid Films 516 (2008):3179–3183E.
[29]刘雄飞,涂国辉.工艺参数对磁控溅射TiN膜成分影响的研究[J].真空科学与技术. 1999, 19(3):225-227.
[30] Durusoy H Z,Duyar O,Aydinli A. Influence of substrate temperature and bias voltage on the optical transmittance of TiN films[J].Vacuum,2003,70: 21～28
[31] Mendibide C, Steyer P. Formation of a semiconductive surface film on nanomultilayered TiN/CrN coatings and its correlation with corrosion protection of steel[J]. Surf Coat Tech,2005,200: 109～112
[32] Kurtz S R , Gordon R G. Chemical vapor deposition of titanium nitrideat at low temperature[J]. Thin Solid Films, 1986, 140: 277～290
[33]郑鹏飞,赵高凌,张天播等.氮化钛作为新型节能玻璃涂层的研究[J].科学通报,2007,52(9):1091～1093
[34]李晓东.可异地加工离线LOW-E及生产控制[C].2006'中国玻璃行业年会论文集:372-378
[35]彭东功,吴永刚,焦宏飞等.宽截止窄带高反射滤光膜设计[J].光学学报, 2008, 28 (5) : 1001～1006
[36]张德恒,徐照方,李伯勋.DLC/Ag/DLC复合多层薄膜光学性能[J].光学学报, 2008,28(10):2031～2035
[37]唐晋发,顾培夫,刘旭,李海峰.现代光学薄膜技术[M].杭州:浙江大学出版社,2006. 242～243,
[38] E.Budke,J.KrempelHesse,H.Maidhofetal..Decorative hard coatings with improved corrosion resistance[J].Surface and Coatings Technology,1999,112:108～113.
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[2]刘志海,李超.低辐射玻璃及其应用[M].北京:化学工业出版社.2006
[3]刘起英,汪建勋,陈华等.低辐射镀膜玻璃的现状及展望[J].玻璃. 2002, 6 (165) :9-13
[4]张宗权.镀膜玻璃的功能、分类与性能比较[J].西北轻工业学院学报,1999,9:77-82.
[5]顽大勇、许伟均.LOW、E镀膜玻璃应尽早进入民宅[J].中国建材.1999,2:59-60.
[6] Szczyrbowski J., Dietrich A., Hartig K. Bendable silver-based low emissivity coating onglass[J]. Sol.Energy Master. 989,19:43-53.
[7] Szczyrbowski J., G. Br?uer, M. Ruske, etc. New low emissivity coating based on TwinMag sputtered TiO2 and Si3N4 layers[J]. Thin Solid Films, 1999, 351, 254-259.
[8]姜燮昌.低辐射玻璃的最新进展[J].真空.2003,2:1-6.
[9]顾翼东,谢高阳,宋沅金,松林.无机化学丛书第八卷[M].科学出版社.
[10]黄佳木,徐成俊.氮流量对磁控溅射法制备氮化钛薄膜光学性能的影响[J].光学学报, 2005,9:1293-1296.
[11]黄佳木,徐成俊,张新元等.室温直流磁控溅射氮化钛薄膜研究[J].真空科学与技术学报, 2005,12.
[12] R Gordon. Chemical vapour deposition of coatings on glass[J]. Journal of Non-Crystalline Solids.1997,218:81-91.
[13] S. Niyomsoan, W. Grant et al. Variation of color in titanium and zirconium nitride decorative thin films[J]. Thin Solid Films. 415 (2002) 187-194.
[14] S. Logothetidis, E.I. Meletis, G. Stergioudis, A.A. Adjaottor. Room temperature oxidation behavior of TiN thin films[J]. Thin Solid Films. 338(1999)304-313.
[15]张谷令,王久丽,扬武保等.内表面栅离子体源离子注入TiN薄膜及特性研究[J].物理学报.2003.
[16]杨邦朝编著.薄膜物理与技术.(第一版)[M].成都:电子科技大学出版社.1993.
[17]胡传胜,袁泽喜.低温下的氮化钛化学气相沉积[J].国外金属热处理.1997, (3):9-11.
[18]肖国珍,黄春良,焦文强等.离子镀氮化钛涂层的工艺研究[J].稀有金属材料与工程.1997, 26(3):40-44.
[19]阎鹏勋,扬思泽,陈熙.脉冲高能量密度等离子体沉积氮化钛薄膜的结合强度[J].金属学报, 1994, 30(11):B503-507.
[20]戴达煌,谢红希,侯惠君等.用直流等离子体化学气相沉积法在硬质合金上沉积氮化钛薄膜的研究[J].广东有色金属学报,1996, 6(2):119-124.
[21]宋贵宏,杜昊,贺春林.硬质与超硬涂层.[M].北京:化学工业出版社.2007.
[22]曹祖安,金柱京等.TiN涂层高速钢刀具的应用试验[J].新工艺新技术新设备. 1994, (3):31-33.
[23] J. Szczyrbowski, G. Braèuer, M. Ruske, H. Schilling, New low emissivity coating based on TwinMagw sputtered TiO2and Si3N4 layers[J], Thin Solid Films 351 (1999):254-259.
[24] Kiyoshi Chiba, Toshiyuki Takahashi, Takashi Kageyama, Low-emissivity coating of amorphous diamond-like carbon/Ag-alloy multilayer on glass[J], Applied Surface Science 246 (2005):48-51.
[25]李晓东,可异地加工离线LOW-E及其生产控制[J],节能.环保.创新.发展,2006:372-377.
[26] Kusano E ,Kawaguchi J ,Enjougi K. J Vaccum Sci Technol[C],1986 ,A4(6) :2907.
[27]曹楚南主编.中国材料的自然环境腐蚀(第一版)[M].化学工业出版社.北京.2005年
[28] Shuiping Huang, Zhanshan Wang, Jian Xu, Determination of optical constants of functional layer of online Low-E glass based on the Drude theory, Thin Solid Films 516 (2008):3179–3183E.
[29]刘雄飞,涂国辉.工艺参数对磁控溅射TiN膜成分影响的研究[J].真空科学与技术. 1999, 19(3):225-227.
[30] Durusoy H Z,Duyar O,Aydinli A. Influence of substrate temperature and bias voltage on the optical transmittance of TiN films[J].Vacuum,2003,70: 21～28
[31] Mendibide C, Steyer P. Formation of a semiconductive surface film on nanomultilayered TiN/CrN coatings and its correlation with corrosion protection of steel[J]. Surf Coat Tech,2005,200: 109～112
[32] Kurtz S R , Gordon R G. Chemical vapor deposition of titanium nitrideat at low temperature[J]. Thin Solid Films, 1986, 140: 277～290
[33]郑鹏飞,赵高凌,张天播等.氮化钛作为新型节能玻璃涂层的研究[J].科学通报,2007,52(9):1091～1093
[34]李晓东.可异地加工离线LOW-E及生产控制[C].2006'中国玻璃行业年会论文集:372-378
[35]彭东功,吴永刚,焦宏飞等.宽截止窄带高反射滤光膜设计[J].光学学报, 2008, 28 (5) : 1001～1006
[36]张德恒,徐照方,李伯勋.DLC/Ag/DLC复合多层薄膜光学性能[J].光学学报, 2008,28(10):2031～2035
[37]唐晋发,顾培夫,刘旭,李海峰.现代光学薄膜技术[M].杭州:浙江大学出版社,2006. 242～243,
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