TW201425256A - Anti-sticking translucent membrane and its formation method - Google Patents
Anti-sticking translucent membrane and its formation method Download PDFInfo
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- TW201425256A TW201425256A TW101149579A TW101149579A TW201425256A TW 201425256 A TW201425256 A TW 201425256A TW 101149579 A TW101149579 A TW 101149579A TW 101149579 A TW101149579 A TW 101149579A TW 201425256 A TW201425256 A TW 201425256A
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 239000012528 membrane Substances 0.000 title abstract 7
- 239000000758 substrate Substances 0.000 claims abstract description 68
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 9
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 230000000181 anti-adherent effect Effects 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- 239000011133 lead Substances 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 150000002843 nonmetals Chemical group 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 2
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 claims description 2
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 2
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- 229960004065 perflutren Drugs 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- SKRPCQXQBBHPKO-UHFFFAOYSA-N fluorocyclobutane Chemical compound FC1CCC1 SKRPCQXQBBHPKO-UHFFFAOYSA-N 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 30
- 238000005240 physical vapour deposition Methods 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000002356 single layer Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 230000008520 organization Effects 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 22
- 230000003287 optical effect Effects 0.000 description 17
- 238000002834 transmittance Methods 0.000 description 17
- CCYWDIWYFIDBTE-UHFFFAOYSA-N [O-2].[O-2].[F].[Ti+4] Chemical compound [O-2].[O-2].[F].[Ti+4] CCYWDIWYFIDBTE-UHFFFAOYSA-N 0.000 description 8
- 230000003667 anti-reflective effect Effects 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000006870 function Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical group [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- -1 titanium ions Chemical class 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004341 Octafluorocyclobutane Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 230000016776 visual perception Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
本發明係有關於一種薄膜，特別是一種利用物理氣相沉積法製備含氟之抗沾粘之透光薄膜及其形成方法。
The present invention relates to a film, and more particularly to a fluorine-containing anti-sticking light-transmitting film which is formed by a physical vapor deposition method and a method for forming the same.
按，現今光學元件之普遍使用，例如眼鏡鏡片、望遠鏡、照相機、攝影機及顯示器等，當一光線入射於不同介質上會發生穿透、吸收、反射等現象，然，過多的光線反射會互相干擾，更進一步影響視覺上之判斷，對於需要利用視覺進行判斷差異性時，會因為過多反射光之干擾而導致判斷錯誤，例如照相機鏡頭會因為反射光過多導致顏色黯淡，導致使用照相機之民眾無法經由鏡頭擷取正確影像之顏色光澤，因此，於光學元件之鏡頭設置一抗反射膜用於降低光學元件之反射率，以增強穿透光學元件之入射光，以及讓反射光無法影響視覺之感受。
已知應用於鏡片的抗反射膜分為單層或多層膜設計。單層膜一般會以蒸鍍法制備氟化鎂(MgF2)，但氟化鎂硬度較低有耐磨性不足之缺點。而多層膜設計通常是在該鏡片上依序堆疊數層膜層，且相鄰之膜層的折射率不同，例如在鏡片表面依序堆疊SiO2、TiO2、SiO2、TiO2、…、SiO2等多層膜層，而且SiO2層之折射率小於TiO2層之折射率，藉由適當厚度與高、低折射率膜層的交錯配置，使入射光線的反射波形成破壞性干涉，進而降低反射光，達到抗反射效果。但其缺點係多層膜設計需有精確的製程控制與非常精密昂貴的設備，才能達成抗反射之光學特性。
再者，光學應用之抗反射膜通常是設於光學元件之外部，暴露於外界環境下，經常會面臨有異物沾附表面的時候，當抗反射膜表面附著有異物時，原有的光學特性即會大幅降低，導致光學元件無法正常運作。現有的抗反射膜對於抗異物沾黏之能力，使用於內視鏡時特別顯得不足；由於內視鏡是用一根細長的光學鏡頭經由人體原有的孔道伸入人體，以最少的傷害達成觀察人體內部器官的目的，操作的過程中必會碰觸人體內部之組織，首當其衝就是內視鏡的鏡頭，而習知鏡頭表面設置之抗反射膜，目前並沒有辦法達到抗沾粘的效果，使內視鏡在操作的過程中會不斷地受到干擾。
例如，台灣專利公告第I293126號「抗反射膜及其製造方法」，其係利用水解與縮合之反應使一金屬烷氧化物或金屬無機鹽類形成一膠體，以製造一層或複數層薄膜而形成一抗反射膜。其中一開始之步驟係提取一金屬烷氧化物或一金屬無機鹽類進行水解與縮合聚合反應而生成為一膠體，接續溶解膠體於一有機溶液，以便膠體與有機溶液加入反應器後可讓膠體均勻反應，然後加入一光起始劑以讓膠體於反應器進行反應，最後讓反應器生成之混合溶液以旋轉塗佈於一透明基板上，如此即可形成一抗反射膜於透明基板上。然，該前案揭露之旋轉塗佈方法對於複雜形狀，及需要高厚度精度控制之光學元件，有厚度均勻性不足問題，且溶劑揮發或促使薄膜乾燥溫度可能高達300℃以上，對於耐溫性不足之材料即無法適用，再者，其所成形之薄膜並不具有抗沾粘之特性。
又如，台灣專利公告第I302549號「經全氟聚醚改質之矽烷、含彼之表面處理劑、及抗反射濾膜」，其係一種含有無機抗反射層的抗反射濾膜，包含以二氧化矽為主的無機層形式的表面層，及在表面層上的抗結垢層，較佳為經全氟聚醚改質的矽烷。抗結垢層具有低的表面能量以及對污染物最低的黏結力，能長期維持該效果，可抵抗污染物的沈積，諸如指紋、皮膚油脂、汗與化妝品。即使當污染物沈積其上，抗結垢層使其容易拭除污染物，且擦拭時其功能受到極小的降低。然，該前案所揭露之抗反射濾膜，仍須有雙層結構，且其材料系統以二氧化矽為主，而抗結垢層採用全氟聚醚改質的矽烷及/或其部分水解縮合物，過程均需要許多溶劑參與反應如二甲苯及三氟甲苯等，對於環保非常有不利之影響。
由於現有技術尚無法完善處理此類問題，所以有加以突破、解決之必要。因此，如何提升方便性、實用性與經濟效益，此為業界應努力解決、克服之重點項目。
緣此，本發明人有鑑於習知抗反射膜及其形成方法之缺失未臻理想之事實，本案發明人即著手研發其解決方案，希望能開發出一種更具便利性、實用性與高經濟效益之抗沾黏之透光薄膜及其形成方法，以促進社會之發展，遂經多時之構思而有本發明之產生。
Press, the common use of optical components today, such as spectacle lenses, telescopes, cameras, cameras, monitors, etc., when a light is incident on different media, penetration, absorption, reflection, etc., excessive light reflection will interfere with each other. Further influence the visual judgment. When it is necessary to use the visual judgment difference, the judgment error may be caused by the interference of excessive reflected light. For example, the camera lens may be dull due to excessive reflected light, and the person using the camera cannot pass the judgment. The lens captures the color luster of the correct image. Therefore, an anti-reflection film is placed on the lens of the optical element to reduce the reflectivity of the optical element to enhance the incident light that penetrates the optical element and to prevent the reflected light from affecting the visual perception.
Antireflective films known for use in lenses are classified into single or multilayer film designs. Monolayer films are generally prepared by vapor deposition of magnesium fluoride (MgF 2 ), but magnesium fluoride has a lower hardness and has insufficient wear resistance. In the multilayer film design, a plurality of film layers are sequentially stacked on the lens, and the refractive indices of adjacent film layers are different, for example, SiO 2 , TiO 2 , SiO 2 , TiO 2 , ... are sequentially stacked on the surface of the lens. such as SiO 2 multilayer film, refractive index of SiO 2 and TiO 2 layer is less than the refractive index layers, staggered by the appropriate thickness and high and low refractive index film layer, the reflected wave destructive interference of the incident light is formed, and further Reduce the reflected light to achieve anti-reflection effect. However, the disadvantage is that the multilayer film design requires precise process control and very precise and expensive equipment to achieve anti-reflective optical properties.
Furthermore, the anti-reflection film for optical applications is usually disposed outside the optical element, and when exposed to the external environment, often faces a foreign object adhering surface, when the anti-reflective film surface is attached with foreign matter, the original optical characteristics It will be greatly reduced, resulting in the optical components not working properly. The existing anti-reflective film has the ability to resist foreign matter, and is particularly disadvantageous when used in an endoscope; since the endoscope is extended into the human body through an original hole through an elongated optical lens, the damage is achieved with minimal damage. Observing the purpose of the internal organs of the human body, the internal tissue of the human body must be touched during the operation. The first shot is the lens of the endoscope, and the anti-reflection film provided on the surface of the lens has no way to achieve the anti-adhesion effect. The endoscope is constantly disturbed during operation.
For example, Taiwan Patent Publication No. I293126 "Antireflection film and its production method" is a method in which a metal alkoxide or a metal inorganic salt is formed into a colloid by a reaction of hydrolysis and condensation to form a film or a plurality of layers of a film. An anti-reflective film. The first step is to extract a metal alkoxide or a metal inorganic salt for hydrolysis and condensation polymerization to form a colloid, and then dissolve the colloid in an organic solution, so that the colloid and the organic solution can be added to the reactor to allow the colloid. The reaction is homogeneous, and then a photoinitiator is added to allow the colloid to react in the reactor. Finally, the mixed solution formed by the reactor is spin-coated on a transparent substrate, thereby forming an anti-reflection film on the transparent substrate. However, the spin coating method disclosed in the previous case has a problem of insufficient thickness uniformity for a complicated shape and an optical component requiring high thickness precision control, and the solvent volatilizes or causes the film drying temperature to be as high as 300 ° C or more for temperature resistance. Insufficient materials are not applicable, and further, the formed film does not have anti-stick properties.
Another example is Taiwan Patent Publication No. I302549, "Perfluoropolyether-modified decane, surface treatment agent containing the same, and anti-reflection filter", which is an anti-reflection filter film containing an inorganic anti-reflection layer, The surface layer in the form of an inorganic layer mainly composed of cerium oxide, and the anti-fouling layer on the surface layer are preferably decane modified by perfluoropolyether. The anti-fouling layer has low surface energy and minimal adhesion to contaminants. It maintains this effect for a long time and is resistant to the deposition of contaminants such as fingerprints, skin oils, sweat and cosmetics. Even when contaminants are deposited thereon, the anti-fouling layer makes it easy to wipe off contaminants and its function is minimally reduced during wiping. However, the anti-reflection filter disclosed in the previous case still needs to have a double-layer structure, and the material system thereof is mainly cerium oxide, and the anti-fouling layer is made of perfluoropolyether-modified decane and/or a part thereof. Hydrolysis of the condensate, the process requires a lot of solvents to participate in the reaction such as xylene and trifluorotoluene, which has a very adverse effect on the environment.
Since the prior art is still unable to perfect such problems, it is necessary to break through and solve them. Therefore, how to improve convenience, practicability and economic benefits is a key project that the industry should strive to solve and overcome.
Accordingly, the inventors of the present invention have developed a solution in view of the fact that the conventional anti-reflection film and its formation method are not ideal, and it is hoped that a more convenient, practical and economical economy can be developed. The invention relates to a translucent film which is resistant to stickiness and a method for forming the same, in order to promote the development of society, and to have the concept of the present invention.
本發明之目的在於提供一種抗沾黏之透光薄膜，其具有高透光、硬度佳及耐酸性等特性，對於水、油及人體模擬組織具有良好的抗沾黏性，由於薄膜摻雜比例較高的氟化物，因此只需單層結構即具有抗反射膜的功能，減少因光線反射所造成之穿透率之損失。
本發明之目的在於提供一種抗沾黏之透光薄膜形成方法，其係利用物理氣相沉積方法，於真空環境下，將氟化物摻雜加入氧化物薄膜材料中，而不需採用含有金屬或氟之前驅物，能大幅降低工業應用之成本，適合於批量式及連續式生產型態，且製程溫度低於100℃，適用於金屬、非金屬及高分子等不耐溫基材，可應用之產業極廣。
為達上述之目的，本發明係提供一種抗沾黏之透光薄膜，其包含一透光薄膜，其包括一氧化物及一氟化物。
為達上述之目的，本發明係提供一種抗沾黏之透光薄膜形成方法，其步驟包含：提供一基材於一真空環境；提供一靶材於該真空環境；通入一氟化物氣體及一氧氣於該真空環境與該靶材電漿解離之複數離子混合，且該些離子與該氧氣反應成一氧化物；及沉積一該氟化物與該氧化物於該基材。
The object of the present invention is to provide an anti-adhesive light transmissive film which has high light transmission, good hardness and acid resistance, and has good anti-sticking property for water, oil and human body simulated tissue, due to film doping ratio Higher fluoride, so only a single layer structure has the function of anti-reflection film, reducing the loss of transmittance caused by light reflection.
The object of the present invention is to provide a method for forming a light-resistant film which is resistant to sticking by using a physical vapor deposition method to dope fluoride into a film of an oxide film in a vacuum environment without using a metal or Fluoride precursor, which can greatly reduce the cost of industrial applications, is suitable for batch and continuous production, and the process temperature is lower than 100 ° C. It is suitable for non-temperature resistant substrates such as metals, non-metals and polymers. Extremely wide.
To achieve the above object, the present invention provides an anti-adhesive light transmissive film comprising a light transmissive film comprising an oxide and a fluoride.
In order to achieve the above object, the present invention provides a method for forming an anti-adhesive transparent film, the method comprising: providing a substrate in a vacuum environment; providing a target in the vacuum environment; introducing a fluoride gas and An oxygen is mixed with the plurality of ions dissociated from the target plasma in the vacuum environment, and the ions react with the oxygen to form an oxide; and depositing the fluoride and the oxide on the substrate.
茲為使對本發明之結構特徵及所達成之功效更有進一步之瞭解與認識，謹佐以較佳之實施例圖及配合詳細之說明，說明如後：
由於光反射膜通常係暴露於外界環境，其表面容易沾粘異物，該些異物會使原有的光學特性大幅降低，導致光學元件無法正常運作，而應用於內視鏡鏡頭之抗反射膜，在鏡頭伸入人體內部後，人體之組織容易沾粘於該鏡頭，導致內視鏡操作之過程受到阻礙，鏡頭拍攝之畫面受到侷限，且習知之光反射膜尚無以單層並兼具抗沾粘及高透光之結構及形成方法，因此，本發明即提出得以改善習知缺點之技術。
首先，請參閱第一圖，其為本發明之第一較佳實施例之結構剖視圖；如圖所示，本實施例包含一透光薄膜10，該透光薄膜10之組成包括一氧化物12及一氟化物14，該氧化物12與氟化物14係沉積於一基材30表面。
該氧化物12可為金屬氧化物或非金屬氧化物，該氧化物12選自錫、銦、鋯、矽、銅、鉛、鈦、汞、鋅或鋇之氧化物擇一者。該氟化物14係為包含氟、氧及碳之化合物。
其中，該氟化物14之氟原子於該透光薄膜的含量百分比為0.2~20at.%，該氧化物12為金屬氧化物或非金屬氧化物，該氧化物12之金屬原子或非金屬原子於該透光薄膜的含量百分比為0.5~25at.%，其它氧或碳原子於該透光薄膜的含量百分比為25~55at.%。該透光薄膜10之厚度約為100~5000奈米(nm)，又以100~300奈米(nm)之厚度具最佳可見光波長範圍透光率。
該透光薄膜10係透過物理氣相沉積法形成於該基材30表面，該基材30可為一透明基材或一不透明基材，透明基材之材料選自玻璃、陶瓷或高分子材料擇一者，不透明基材之材料選自金屬或碳化鎢擇一者。本發明主要應用於透明基材，例如光學鏡片、醫療用內視鏡鏡頭、照相機鏡頭、顯示器面板、太陽能板或其他需抗沾黏及高透光之基材等。
該透光薄膜10係形成於鏡片或鏡頭表面，並具有高透光、硬度佳及耐酸性等特性，對於水、油及人體模擬組織具有良好的抗沾黏性，且只需單層結構即具有抗反射膜的功能，以減少因光線反射所造成之穿透率之損失。
請參閱第二圖，其為本發明之第二較佳實施例之結構剖視圖，其係以第一較佳實施例為基礎之技術延伸；如圖所示，本實施例與第一較佳實施例之差異，在於該透光薄膜10與基材30之間更設有一氧化物層20，其係以物理氣相沉積法形成於該基材30表面。該氧化物層20之材料選自錫、銦、鋯、矽、銅、鉛、鈦、汞、鋅或鋇之氧化物擇一者，該氧化物層之厚度為25~500奈米(nm)，最佳之厚度為100~300奈米(nm)。
由於該氧化物層20與該基材30之親和力較強，能夠穩定附著於該基材30表面，並作為該透光薄膜10與該基材30之接合媒介，以加強該透光薄膜10之附著力，使該基材30處於一活動的狀態或受到異物沾粘時，該透光薄膜10能藉由該氧化物層20穩定地附著於該基材30表面，而不易由該基材30表面剝落。
請參閱第三圖，其為本發明之第一較佳實施例之步驟流程圖；如圖所示，本實施例之抗沾黏之透光薄膜形成方法，其步驟如下：
步驟S50：提供一基材於一真空環境；
步驟S60：提供一靶材於該真空環境；
步驟S70：通入一氟化物氣體及一氧氣於該真空環境與該靶材電漿解離之複數離子混合，且該些離子與該氧氣反應成一氧化物；及
步驟S80：沉積一該氟化物與該氧化物於該基材。
該靶材之材料選自錫、銦、鋯、矽、銅、鉛、鈦、汞、鋅或鋇擇一者。該氟化物氣體選自三氟化甲烷(CHF3)、四氟甲烷(CF4)、四氟乙烷(C2H2F4)、六氟乙烷(C2F6)、六氟丙烷(C3H2F6)、七氟丙烷(C3HF7)、八氟丙烷(C3F8)或八氟環丁烷(C4F8)擇一者。
其中，該透光薄膜10之氟化物之原子含量百分比為0.2~20at.%、金屬原子含量百分比為0.5~25at.%、其它氧或碳原子含量百分比為25~55at.%。該透光薄膜10之厚度約為100~5000奈米(nm)，又以100~300奈米(nm)之厚度具最佳可見光波長範圍透光率。
該透光薄膜10係透過物理氣相沉積法形成於該基材30表面，該基材30可為一透明基材或一不透明基材，透明基材之材料選自玻璃、陶瓷或高分子材料擇一者，不透明基材之材料選自金屬或碳化鎢擇一者。本發明主要應用於透明基材，例如光學鏡片、醫療用內視鏡鏡頭、照相機鏡頭、顯示器面板、太陽能板或其他需抗沾黏及高透光之基材等。
本實施例係以物理氣相沉積法，將靶材蒸發，並於真空環境下與氟化物氣體及氧氣混合反應，最後沉積於該基材30表面，形成該透光薄膜10，藉此，不需採用含有金屬或氟之前驅物，能大幅降低工業應用之成本，適合於批量式及連續式生產型態，且製程之溫度低於100℃，適用於金屬、非金屬及高分子等不耐溫基材，應用產業極廣。
請參閱第四圖，其為本發明之第二較佳實施例之步驟流程圖，其係以第一較佳實施例之步驟為基礎之技術延伸；如圖所示，本實施例之抗沾黏之透光薄膜形成方法，於提供一基材於一真空環境後，更包括下列步驟：
步驟S52：提供一靶材於該真空環境；
步驟S54：通入一氧氣於該真空環境與該靶材電漿解離之複數離子混合，且該些離子與該氧氣反應成一氧化物；及
步驟S56：沉積一氧化物層於該基材表面。
該靶材之材料選自錫、銦、鋯、矽、銅、鉛、鈦、汞、鋅或鋇擇一者，該氧化物層20之厚度為25－500奈米(nm)，最佳之厚度為100－300奈米(nm)。
本實施例係於提供一靶材及一基材30於一真空環境後，通入一氧氣於該真空環境與該靶材電漿解離之複數離子混合，且該些離子與該氧氣反應成一氧化物，最後於該基材30表面沉積該氧化物層20。完成以上步驟後，再於該氧化物層20上進行如第一實施例之步驟，亦即將該透光薄膜10形成於該氧化物層20上，藉此，強化該透光薄膜10之附著力，使該基材30處於一活動狀態或受到異物沾粘時，該透光薄膜10能藉由該氧化物層20穩定地附著於該基材30表面，而不易由該基材30表面剝落。
以下提供一實例及實驗結果，進一步對本發明之結構及其形成方式做說明：
首先，於真空環境及適合的電場條件下，以純鈦(Ti)作為靶材形成於一基材表面，並通入氬氣(Ar)產生電漿環境，在形成鈦離子的同時，另通入反應性氣體氧氣(O2)與含氟之氣體如四氟甲烷(CF4)，最後沉積於該基材表面，形成一含氟之鈦氧化物，即為本發明之透光薄膜。
此外，在形成該含氟之鈦氧化物於該基材表面前，可先形成一金屬氧化層於該基材表面，該金屬氧化層亦可選用純鈦(Ti)作為靶材，並通入氬氣(Ar)產生電漿環境，在形成鈦離子的同時，另通入反應性氣體氧氣(O2)，最後於該基材表面沉積一鈦氧化物，即為本發明之金屬氧化層。之後，再於該鈦氧化物上形成該含氟之鈦氧化物，則能提昇該含氟之鈦氧化物之附著力。
請參閱第五A圖及第五B圖，本實例進一步調整該鈦氧化物含氟之比例，分別得到一不含氟之鈦氧化物、一低摻雜氟之鈦氧化物及一高摻雜氟之鈦氧化物，其中，低摻雜氟之鈦氧化物之氟原子含量百分比為0.2~2at.%、金屬原子含量百分比為10~25at.%、其它成分含量為氧或碳原子；高摻雜氟之鈦氧化物之氟原子含量百分比2~20at.%、金屬原子含量百分比為0.5~10at.%、其它成分含量為氧或碳原子；並將上述三種鈦氧化物與一玻璃基板同時進行疏水及疏模擬關節液特性之比較，發現水與模擬關節液於高摻雜氟之鈦氧化物表面較其它表面具有最大之接觸角，而具有較佳之抗沾粘性。
請參閱第六A圖、第六B圖及第六C圖，其依序為不含氟之鈦氧化物之透光率曲線圖、低摻雜氟之鈦氧化物之透光率曲線圖及高摻雜氟之鈦氧化物之透光率曲線圖；本實例再以不含氟之鈦氧化物、低摻雜氟之鈦氧化物及高摻雜氟之鈦氧化物進行透光率及抗反射之實驗比較；在550nm波長下，不含氟之鈦氧化物穿透率約90%，低氟摻雜之鈦氧化物穿透率92%，高氟摻雜之鈦氧化物穿透率達到100%；鈦氧化物折射係數約2.3，低氟摻雜之鈦氧化物折射係數約2.07，高氟摻雜之鈦氧化物折射係數約1.37，由此可知，高氟摻雜之鈦氧化物具備非常低折射係數膜層特性，並具有抗反射膜的功能。
內視鏡一般是以2%戊二醛滅菌液進行消毒處理，本實例將該含氟之鈦氧化物進行戊二醛滅菌前後光學透光率之比較，發現該含氟之鈦氧化物外觀及光學測試與浸泡前皆無損傷及影響，顯示含氟之鈦氧化物耐蝕能力佳。
習知的抗反射膜為氟化鎂(MgF2)，其硬度較低，約為2.89～4.41GPa，且具有溶解於酸之缺點，故應用於醫療器械會受到限制。而本實例之含氟之鈦氧化物以奈米硬度量測，其硬度高達10.86GPa，具有相當高的耐磨性，明顯優於習知的抗反射膜。
綜上所述，本案利用物理氣相沉積法於一基材表面形成一透光薄膜，該透光薄膜為含氟之氧化物，並可進一步於該基材表面與透光薄膜之間形成一氧化物層，以提昇該透光薄膜附著於該基材表面之穩定性，而本發明之抗沾黏之透光薄膜與形成方法具有以下功效：
1.抗沾黏之透光薄膜具有高透光、硬度佳及耐酸性等特性，對於水、油及人體模擬組織具有良好的抗沾黏性。
2.抗沾黏之透光薄膜為單層結構，即具有抗反射膜的功能，而能減少因光線反射所造成之穿透率之損失，並減薄抗反射膜之厚度。
3.本發明之形成方法不需採用含有金屬或氟之前驅物，能大幅降低工業應用之成本，適合於批量式及連續式生產型態。
4.本發明之製程溫度低於100℃，適用於金屬、非金屬及高分子等不耐溫基材，可應用之產業極廣。
雖然本發明已以較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。For a better understanding and understanding of the structural features and the achievable effects of the present invention, the preferred embodiments and the detailed description are as follows:
Since the light-reflecting film is usually exposed to the external environment, the surface thereof is likely to be contaminated with foreign matter, and the foreign matter may greatly reduce the original optical characteristics, resulting in the optical element not functioning properly, and the anti-reflection film applied to the endoscope lens. After the lens is inserted into the human body, the tissue of the human body is easily adhered to the lens, which causes the process of the operation of the endoscope to be hindered, and the image of the lens is limited, and the conventional light reflection film has no single layer and is resistant. The structure and formation method of sticking and high light transmission, therefore, the present invention proposes a technique for improving the conventional disadvantages.
First, referring to a first embodiment, which is a cross-sectional view of a first preferred embodiment of the present invention; as shown, the embodiment includes a light transmissive film 10, and the composition of the light transmissive film 10 includes an oxide 12 And a fluoride 14, the oxide 12 and the fluoride 14 are deposited on the surface of a substrate 30.
The oxide 12 can be a metal oxide or a non-metal oxide selected from the group consisting of tin, indium, zirconium, hafnium, copper, lead, titanium, mercury, zinc or antimony. The fluoride 14 is a compound containing fluorine, oxygen, and carbon.
The content of the fluorine atom of the fluoride 14 in the transparent film is 0.2-20 at.%, and the oxide 12 is a metal oxide or a non-metal oxide, and the metal atom or non-metal atom of the oxide 12 is The content of the transparent film is 0.5 to 25 at.%, and the percentage of other oxygen or carbon atoms in the transparent film is 25 to 55 at.%. The light transmissive film 10 has a thickness of about 100 to 5,000 nanometers (nm) and a light transmittance of an optimum visible wavelength range of 100 to 300 nanometers (nm).
The transparent film 10 is formed on the surface of the substrate 30 by physical vapor deposition. The substrate 30 can be a transparent substrate or an opaque substrate. The material of the transparent substrate is selected from glass, ceramic or polymer materials. Alternatively, the material of the opaque substrate is selected from the group consisting of metal or tungsten carbide. The invention is mainly applied to transparent substrates, such as optical lenses, medical endoscope lenses, camera lenses, display panels, solar panels or other substrates that are resistant to adhesion and high light transmission.
The light transmissive film 10 is formed on the surface of the lens or the lens, and has the characteristics of high light transmittance, good hardness and acid resistance, and has good anti-stick property to water, oil and human body simulated structure, and only needs a single layer structure. It has the function of anti-reflection film to reduce the loss of transmittance caused by light reflection.
Referring to the second drawing, which is a cross-sectional view of a second preferred embodiment of the present invention, which is based on the first preferred embodiment; as shown in the figure, the present embodiment and the first preferred embodiment The difference between the transparent film 10 and the substrate 30 is further provided with an oxide layer 20 formed on the surface of the substrate 30 by physical vapor deposition. The material of the oxide layer 20 is selected from the group consisting of tin, indium, zirconium, hafnium, copper, lead, titanium, mercury, zinc or antimony oxide, and the thickness of the oxide layer is 25 to 500 nanometers (nm). The optimum thickness is 100~300 nanometers (nm).
Since the affinity of the oxide layer 20 and the substrate 30 is strong, it can be stably adhered to the surface of the substrate 30, and serves as a bonding medium between the transparent film 10 and the substrate 30 to strengthen the transparent film 10. The light-transmitting film 10 can be stably attached to the surface of the substrate 30 by the oxide layer 20 when the substrate 30 is in a movable state or is adhered by foreign matter, and is not easily separated from the substrate 30. The surface is peeled off.
Please refer to the third figure, which is a flow chart of the steps of the first preferred embodiment of the present invention; as shown in the figure, the method for forming the anti-adhesive transparent film of the present embodiment has the following steps:
Step S50: providing a substrate in a vacuum environment;
Step S60: providing a target in the vacuum environment;
Step S70: mixing a fluoride gas and an oxygen gas to the plurality of ions dissociated from the target plasma in the vacuum environment, and reacting the ions with the oxygen to form an oxide; and step S80: depositing the fluoride with The oxide is on the substrate.
The material of the target is selected from the group consisting of tin, indium, zirconium, hafnium, copper, lead, titanium, mercury, zinc or alternatively. The fluoride gas is selected from the group consisting of methyl trifluoride (CHF 3 ), tetrafluoromethane (CF 4 ), tetrafluoroethane (C 2 H 2 F 4 ), hexafluoroethane (C 2 F 6 ), and hexafluoropropane. (C 3 H 2 F 6 ), heptafluoropropane (C 3 HF 7 ), octafluoropropane (C 3 F 8 ) or octafluorocyclobutane (C 4 F 8 ).
The atomic content percentage of the fluoride of the light transmissive film 10 is 0.2 to 20 at.%, the metal atom content percentage is 0.5 to 25 at.%, and the other oxygen or carbon atom content percentage is 25 to 55 at.%. The light transmissive film 10 has a thickness of about 100 to 5,000 nanometers (nm) and a light transmittance of an optimum visible wavelength range of 100 to 300 nanometers (nm).
The transparent film 10 is formed on the surface of the substrate 30 by physical vapor deposition. The substrate 30 can be a transparent substrate or an opaque substrate. The material of the transparent substrate is selected from glass, ceramic or polymer materials. Alternatively, the material of the opaque substrate is selected from the group consisting of metal or tungsten carbide. The invention is mainly applied to transparent substrates, such as optical lenses, medical endoscope lenses, camera lenses, display panels, solar panels or other substrates that are resistant to adhesion and high light transmission.
In this embodiment, the target material is evaporated by a physical vapor deposition method, mixed with a fluoride gas and oxygen under a vacuum environment, and finally deposited on the surface of the substrate 30 to form the transparent film 10, thereby not It needs to use metal or fluorine precursors, which can greatly reduce the cost of industrial applications. It is suitable for batch and continuous production, and the process temperature is lower than 100 °C. It is suitable for metal, non-metal and polymer. Warm substrate, the application industry is extremely wide.
Please refer to the fourth embodiment, which is a flow chart of the steps of the second preferred embodiment of the present invention, which is based on the steps of the first preferred embodiment; as shown in the figure, the anti-sticking of the embodiment The method for forming a viscous light-transmissive film further comprises the following steps after providing a substrate in a vacuum environment:
Step S52: providing a target in the vacuum environment;
Step S54: mixing a plurality of ions in which the oxygen is dissociated from the target plasma in the vacuum environment, and reacting the ions with the oxygen to form an oxide; and step S56: depositing an oxide layer on the surface of the substrate.
The material of the target is selected from the group consisting of tin, indium, zirconium, hafnium, copper, lead, titanium, mercury, zinc or alternatively. The thickness of the oxide layer 20 is 25-500 nanometers (nm), preferably The thickness is 100-300 nanometers (nm).
In this embodiment, after a target material and a substrate 30 are provided in a vacuum environment, a plurality of ions are mixed with oxygen in the vacuum environment to dissociate from the target plasma, and the ions react with the oxygen to form an oxidation. Finally, the oxide layer 20 is deposited on the surface of the substrate 30. After the above steps are completed, the step of the first embodiment is performed on the oxide layer 20, that is, the transparent film 10 is formed on the oxide layer 20, thereby reinforcing the adhesion of the transparent film 10. When the substrate 30 is in an active state or is adhered by foreign matter, the transparent film 10 can be stably attached to the surface of the substrate 30 by the oxide layer 20, and is not easily peeled off from the surface of the substrate 30.
An example and experimental results are provided below to further illustrate the structure of the present invention and its formation:
First, in a vacuum environment and a suitable electric field, pure titanium (Ti) is used as a target to form a surface of a substrate, and argon gas (Ar) is introduced to generate a plasma environment, and titanium ions are formed simultaneously. The reactive gas oxygen (O 2 ) and a fluorine-containing gas such as tetrafluoromethane (CF 4 ) are finally deposited on the surface of the substrate to form a fluorine-containing titanium oxide, which is the light-transmissive film of the present invention.
In addition, before forming the fluorine-containing titanium oxide on the surface of the substrate, a metal oxide layer may be formed on the surface of the substrate, and the metal oxide layer may also be made of pure titanium (Ti) as a target. Argon gas (Ar) generates a plasma environment, and while forming titanium ions, a reactive gas oxygen (O 2 ) is introduced, and finally a titanium oxide is deposited on the surface of the substrate, which is the metal oxide layer of the present invention. Thereafter, by forming the fluorine-containing titanium oxide on the titanium oxide, the adhesion of the fluorine-containing titanium oxide can be enhanced.
Referring to FIG. 5A and FIG. 5B, the present example further adjusts the proportion of the fluorine oxide of the titanium oxide to obtain a fluorine-free titanium oxide, a low-doped fluorine titanium oxide, and a high doping. Fluorine titanium oxide, wherein the fluorine content of the low-doped fluorine titanium oxide is 0.2 to 2 at.%, the metal atom content percentage is 10 to 25 at.%, and the other components are oxygen or carbon atoms; The fluorine atom content of the fluorine-containing titanium oxide is 2 to 20 at.%, the metal atom content percentage is 0.5 to 10 at.%, and the other component content is oxygen or carbon atoms; and the above three titanium oxides are simultaneously performed with a glass substrate. Comparing the characteristics of hydrophobic and sparse simulated joint fluids, it was found that water and simulated joint fluid have the largest contact angle on the surface of highly doped fluorine titanium oxide than other surfaces, and have better anti-adhesion.
Please refer to the sixth A diagram, the sixth B diagram and the sixth C diagram, which are sequentially the transmittance curve of the fluorine-free titanium oxide, the transmittance curve of the low-doped fluorine titanium oxide and Transmittance curve of highly doped fluorine titanium oxide; in this example, light transmittance and resistance are performed by titanium oxide without fluorine, titanium oxide with low doping of fluorine, and titanium oxide with high doping of fluorine. Experimental comparison of reflection; at a wavelength of 550 nm, the fluorine-free titanium oxide has a transmittance of about 90%, the low-fluorium-doped titanium oxide has a transmittance of 92%, and the high-fluorine-doped titanium oxide has a transmittance of 100%; titanium oxide refractive index of about 2.3, low fluorine doped titanium oxide refractive index of about 2.07, high fluorine doped titanium oxide refractive index of about 1.37, it is known that high fluorine doped titanium oxide has Very low refractive index film properties and has the function of an anti-reflective film.
The endoscope is generally sterilized by a 2% glutaraldehyde sterilization solution. In this example, the fluorine-containing titanium oxide is compared with the optical transmittance before and after glutaraldehyde sterilization, and the appearance of the fluorine-containing titanium oxide is found. There is no damage and influence before optical testing and immersion, indicating that the fluorine-containing titanium oxide has good corrosion resistance.
The conventional antireflection film is magnesium fluoride (MgF 2 ), which has a low hardness of about 2.89 to 4.41 GPa and has the disadvantage of being dissolved in an acid, so that it is limited in medical devices. The fluorine-containing titanium oxide of the present example has a hardness of up to 10.86 GPa as measured by nano hardness, and has a relatively high abrasion resistance, and is superior to the conventional anti-reflection film.
In summary, the present invention forms a light transmissive film on the surface of a substrate by physical vapor deposition, the light transmissive film is a fluorine-containing oxide, and further forms a gap between the surface of the substrate and the light transmissive film. The oxide layer is used to enhance the stability of the light-transmissive film attached to the surface of the substrate, and the anti-adhesive light-transmissive film of the present invention has the following effects:
1. Anti-adhesive transparent film has high light transmission, good hardness and acid resistance, and has good anti-sticking property for water, oil and human body simulated tissue.
2. The anti-adhesive transparent film has a single-layer structure, that is, has the function of an anti-reflection film, and can reduce the loss of transmittance caused by light reflection, and reduce the thickness of the anti-reflection film.
3. The formation method of the present invention does not require the use of a metal or fluorine precursor, which can greatly reduce the cost of industrial applications, and is suitable for batch type and continuous production type.
4. The process temperature of the invention is lower than 100 ° C, and is suitable for non-temperature resistant substrates such as metals, non-metals and polymers, and the applicable industries are extremely wide.
While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.
10．．．透光薄膜10. . . Light transmissive film
12．．．氧化物12. . . Oxide
14．．．氟化物14. . . Fluoride
20．．．氧化物層20. . . Oxide layer
30．．．基材30. . . Substrate
第一圖為本發明之第一較佳實施例之結構剖視圖；
第二圖為本發明之第二較佳實施例之結構剖視圖；
第三圖為本發明之第一較佳實施例之步驟流程圖；
第四圖為本發明之第二較佳實施例之步驟流程圖；
第五A圖為本發明之疏水及疏模擬關節液之實驗比較圖(一)
第五B圖為本發明之疏水及疏模擬關節液之實驗比較圖(二)
第六A圖為本發明之不含氟之鈦氧化物之透光率曲線圖；
第六B圖為本發明之低摻雜氟之鈦氧化物之透光率曲線圖；及
第六C圖為本發明之高摻雜氟之鈦氧化物之透光率曲線圖。
1 is a cross-sectional view showing the structure of a first preferred embodiment of the present invention;
Figure 2 is a cross-sectional view showing the structure of a second preferred embodiment of the present invention;
Figure 3 is a flow chart showing the steps of the first preferred embodiment of the present invention;
Figure 4 is a flow chart showing the steps of a second preferred embodiment of the present invention;
The fifth A picture is the experimental comparison chart of the hydrophobic and sparse simulated joint fluid of the present invention (1)
The fifth B is an experimental comparison diagram of the hydrophobic and sparse simulated joint fluid of the present invention (2)
6A is a graph showing the transmittance of the fluorine-free titanium oxide of the present invention;
6B is a graph showing the transmittance of the low-doped fluorine-titanium oxide of the present invention; and FIG. 6C is a graph showing the transmittance of the highly-doped fluorine-titanium oxide of the present invention.
10．．．透光薄膜10. . . Light transmissive film
12．．．氧化物12. . . Oxide
14．．．氟化物14. . . Fluoride
30．．．基材30. . . Substrate
Claims (14)
一透光薄膜，其包括一氧化物及一氟化物。An anti-stick translucent film comprising:
A light transmissive film comprising an oxide and a fluoride.
提供一基材於一真空環境；
提供一靶材於該真空環境；
通入一氟化物氣體及一氧氣於該真空環境與該靶材電漿解離之複數離子混合，且該些離子與該氧氣反應成一氧化物；及
沉積一該氟化物與該氧化物於該基材。A method for forming an anti-adhesive transparent film, the steps comprising:
Providing a substrate in a vacuum environment;
Providing a target in the vacuum environment;
Passing a fluoride gas and an oxygen gas mixed with the plurality of ions dissociated from the target plasma in the vacuum environment, and reacting the ions with the oxygen to form an oxide; and depositing the fluoride and the oxide on the base material.
提供一靶材於該真空環境；
通入一氧氣於該真空環境與該靶材電漿解離之複數離子混合，且該些離子與該氧氣反應成一氧化物；及
沉積一氧化物層於該基材表面。The method for forming an anti-adhesive transparent film according to claim 8 , wherein after the substrate is provided in a vacuum environment, the method further comprises the following steps:
Providing a target in the vacuum environment;
An oxygen is introduced into the vacuum environment to mix with the plurality of ions dissociated from the target plasma, and the ions react with the oxygen to form an oxide; and an oxide layer is deposited on the surface of the substrate.
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| TW101149579A TW201425256A (en) | 2012-12-24 | 2012-12-24 | Anti-sticking translucent membrane and its formation method |
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| TWI360470B (en) * | 2009-12-29 | 2012-03-21 | Metal Ind Res & Dev Ct | Antisticking mold and manufacturing method thereof |
| JP5824365B2 (en) * | 2012-01-16 | 2015-11-25 | 三星ダイヤモンド工業株式会社 | Breaking method for brittle material substrate |
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