CN219218125U - 涂覆有抗裂氟退火膜的制品 - Google Patents
涂覆有抗裂氟退火膜的制品 Download PDFInfo
- Publication number
- CN219218125U CN219218125U CN202122827231.8U CN202122827231U CN219218125U CN 219218125 U CN219218125 U CN 219218125U CN 202122827231 U CN202122827231 U CN 202122827231U CN 219218125 U CN219218125 U CN 219218125U
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- film
- fluorine
- atomic
- substrate
- yttria
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 128
- 239000011737 fluorine Substances 0.000 title claims abstract description 128
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000000137 annealing Methods 0.000 claims description 34
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000004378 air conditioning Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 29
- 229910052727 yttrium Inorganic materials 0.000 abstract description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 12
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 7
- 150000004706 metal oxides Chemical class 0.000 abstract description 7
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 48
- 238000000034 method Methods 0.000 description 36
- 239000011248 coating agent Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 19
- 238000001020 plasma etching Methods 0.000 description 15
- 238000005530 etching Methods 0.000 description 13
- 238000005240 physical vapour deposition Methods 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 238000005546 reactive sputtering Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 4
- 239000004811 fluoropolymer Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 229920006169 Perfluoroelastomer Polymers 0.000 description 3
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 229910018503 SF6 Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- 239000010702 perfluoropolyether Substances 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 2
- 229960000909 sulfur hexafluoride Drugs 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229940105963 yttrium fluoride Drugs 0.000 description 2
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 2
- IXURVUHDDXFYDR-UHFFFAOYSA-N 1-[4-(difluoromethoxy)-3-(oxolan-3-yloxy)phenyl]-3-methylbutan-1-one Chemical compound CC(C)CC(=O)C1=CC=C(OC(F)F)C(OC2COCC2)=C1 IXURVUHDDXFYDR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003251 chemically resistant material Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007735 ion beam assisted deposition Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3471—Introduction of auxiliary energy into the plasma
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C14/083—Oxides of refractory metals or yttrium
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
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- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02192—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium
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- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02266—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by physical ablation of a target, e.g. sputtering, reactive sputtering, physical vapour deposition or pulsed laser deposition
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by physical means, e.g. sputtering, evaporation
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Abstract
本实用新型涉及涂覆有抗裂氟退火膜的制品。提供与具有优异的抗等离子体蚀刻性且可延长RIE组件的使用寿命的涂层相关的制品。制品具有真空兼容衬底及覆盖所述衬底的至少一部分的保护膜。所述膜包括含钇的氟化金属氧化物,其中使用AC电源沉积氧化钇。所述膜在所述膜的30%总厚度的深度处具有至少10的氟原子%,并且所述膜不具有当使用激光共聚焦显微镜以1000倍的放大率观察所述膜的整个深度时可见的在所述膜的表面下方的表面下裂纹。
Description
技术领域
本实用新型涉及涂覆有抗裂氟退火膜的制品。
背景技术
反应离子蚀刻(RIE)是在半导体制造工艺中使用的蚀刻技术。RIE使用化学反应等离子体,其通过电离反应气体(例如,含有氟、氯、溴、氧或其组合的气体)产生以去除沉积在晶片上的材料。然而,等离子体不仅会攻击沉积在晶片上的材料,还会攻击安装在RIE室内的组件。此外,用于将反应气体输送到RIE室中的组件也可能被反应气体腐蚀。等离子体及/或反应气体对组件造成的损坏会导致低产量、工艺不稳定及污染。
半导体制造蚀刻室使用涂覆有耐化学性材料的组件以减少下层组件的降级、提高蚀刻工艺的一致性并减少蚀刻室中的颗粒产生。尽管具有耐化学性,但涂层在清洁及定期维护期间可能会经历降级,其中蚀刻剂气体与水或其它溶液结合会产生使涂层降级的腐蚀条件,例如氢氯酸。腐蚀条件可能会缩短经涂覆组件的使用寿命,并且还可在组件重新安装在腔室中时引起蚀刻室污染。持续需要用于蚀刻室组件的改进的涂层。
实用新型内容
提供与具有优异的抗等离子体蚀刻性且可延长RIE组件的使用寿命的涂层相关的制品及方法。涂层在涂层表面上也具有最少可见的表面裂纹至没有可见的表面裂纹,或在涂层内具有最少可见的表面下裂纹至没有可见的表面下裂纹。
在本实用新型的第一方面中,制品包括衬底;及覆盖衬底的至少一部分的保护膜,其中所述膜包括含钇的氟化金属氧化物,其中所述膜在所述膜的30%总厚度的深度处具有至少10的氟原子%,并且其中所述膜不具有当使用激光共聚焦显微镜以1000倍的放大率观察膜的整个深度时可见的在膜的表面下方的表面下裂纹。
在根据第一方面的第二方面中,在氟退火之后,所述膜不具有当用激光共聚焦显微镜以400倍的放大率观察膜的表面时可见的在膜的表面上的表面裂纹。
在根据第一或第二方面的第三方面中,衬底是氧化铝。
在根据第一或第二方面的第四方面中,衬底是硅。
在根据任一前述方面的第五方面中,膜在膜的30%总厚度的深度处具有至少20的氟原子%。
在根据任一前述方面的第六方面中,膜在膜的30%总厚度的深度处具有至少30的氟原子%。
在根据任一前述方面的第七方面中,膜在膜的50%总厚度的深度处具有至少10的氟原子%。
在根据任一前述方面的第八方面中,膜在膜的50%总厚度的深度处具有至少20的氟原子%。
在根据任一前述方面的第九方面中,膜在膜的50%总厚度的深度处具有至少30的氟原子%。
在本实用新型的第十方面中,方法包括使用物理气相沉积技术使用交流(AC)电源将含钇的金属氧化物沉积到衬底上,所述金属氧化物形成覆盖衬底的膜;及使所述膜氟退火,其中在氟退火之后,所述膜在膜的30%总厚度的深度处具有至少10的氟原子%。
在根据第十方面的第十一方面中,在氟退火之后,所述膜不具有当用激光共聚焦显微镜以400倍的放大率观察膜的表面时可见的在膜的表面上的表面裂纹。
在根据第十或第十一方面的第十二方面中,在氟退火之后,所述膜不具有当使用激光共聚焦显微镜以1000倍的放大率观察膜的整个深度时可见的在膜的表面下方的表面下裂纹。
在根据第十到第十二方面中的任一个的第十三方面中,在氟退火之后,所述膜在膜的30%总厚度的深度处具有至少20的氟原子%。
在根据第十到第十二方面中的任一个的第十四方面中,在氟退火之后,所述膜在膜的30%总厚度的深度处具有至少30的氟原子%。
在根据第十到第十四方面中的任一个的第十五方面中,在氟退火之后,所述膜在膜的50%总厚度的深度处具有至少20的氟原子%。
在根据第十到第十四方面中的任一个的第十六方面中,在氟退火之后,所述膜在膜的50%总厚度的深度处具有至少30的氟原子%。
在根据第十到第十六方面中的任一个的第十七方面中,在含氟气氛中在约300℃到约650℃的温度下执行氟退火。
在根据第十到第十七方面中的任一个的第十八方面中,衬底是氧化铝。
在根据第十到第十七方面中的任一个的第十九方面中,衬底是硅。
在第二十方面中,根据第十到第十九方面中的任一个的工艺制造制品。
附图说明
以上内容将从本实用新型的实例实施例的以下更具体描述中显而易见,如附图中所说明,其中相同的参考符号在不同视图中始终指代相同部分。附图不一定按比例绘制,重点相反放在示出本实用新型的实施例上。
图1是图1中所示的数据的曲线图,其中在Y轴上展示氟原子%且在X轴上展示以微米为单位的到厚度中的深度;
图2是在通过扫描电子显微镜(SEM)进行的氟退火之后来自实例1的硅试片的截面图;
图3是基恩士激光共聚焦显微镜以1000倍的放大率拍摄的照片,并且展示在经受实例1中的条件10的氟化钇氧化物膜中的多个表面裂纹;及
图4是基恩士激光共聚焦显微镜以1000倍的放大率拍摄的照片,并且展示在经受实例2中的条件10的氟化钇氧化物膜中不存在表面裂纹。
具体实施方式
虽然本实用新型已经参考其实例实施例特定展示及描述,但所属领域的技术人员应理解,在不脱离由所附权利要求书涵盖的本实用新型的范围的情况下,可在其中进行形式及细节的各种改变。
尽管描述各种组合物及方法,但是应理解,本实用新型不限于所描述的特定分子、组合物、设计、方法或协议,因为这些分子、组合物、设计、方法或协议可能变化。还应理解,本说明书中使用的术语仅仅是出于描述特定版本或版本的目的,且并不旨在限制将仅由所附权利要求书限制的本实用新型的范围。
还必须注意,如本文中及所附权利要求书中所使用,除非上下文另外明确指示,否则单数形式“一(a/an)”及“所述”包含多个参考物。因此,举例来说,对“膜”的提及是对所属领域的技术人员已知的一或多个膜及其等效物的提及等等。除非另外定义,否则本文中所使用的所有技术及科学术语具有如所属领域的一般技术人员通常理解的相同含义。与本文所描述的方法及材料类似或等效的方法及材料也可用于实践或测试本实用新型的版本。本文中所提及的所有出版物都以全文引用的方式并入本文中。本文中的任何内容均不应被理解为承认本实用新型因先前公开内容而无权先于此公开内容。“任选的”或“任选地”意指随后描述的事件或情况可能会或可能不会发生,并且所述描述包含所述事件发生的实例及所述事件未发生的实例。不管是否明确指示,本文中所有数值都可由术语“约”修饰。术语“约”通常是指本领域的技术人员认为等同于所阐述值(即,具有相同的功能或结果)的数字范围。在一些版本中,术语“约”是指所陈述值的±10%,在其它版本中,术语“约”是指所陈述值的±2%。虽然组合物及方法以“包括”各种组分或步骤(解释为意指“包含但不限于”)的方面描述,但组合物及方法也可“基本上由”或“由”各种组分及步骤“组成”,这类术语应该被解释为定义基本上封闭的成员组。
以下描述本实用新型的实例实施例。
包含氧化钇(氧化钇)的涂层用于RIE组件上以提供抗等离子体蚀刻性。此类涂层可通过各种方法应用于RIE组件,包含热喷涂、气溶胶、物理气相沉积(PVD)、化学气相沉积(CVD)及电子束蒸镀。然而,在RIE室及组件的维护期间,氧化钇涂层可能会被氯化氢(HCl)腐蚀。
在氯等离子体RIE工艺之后,残余氯残留在RIE组件上。当在维护期间用去离子(DI)水清洁组件时,残余氯及DI变成HCl,这会腐蚀氧化钇涂层,从而阻止氧化钇涂层在下一RIE工艺期间保护底层衬底。另外,RIE室中的氧化钇涂层可能会在等离子体蚀刻工艺期间形成微粒。颗粒会落在硅晶片上,从而导致制造的半导体装置出现缺陷并导致晶片产量损失。
本实用新型的版本提供用于通过对含钇的金属氧化物膜(例如,在膜的表面上具有最少表面裂纹至没有表面裂纹并且在膜中具有最少表面下裂纹至没有表面下裂纹的氧化钇及氧化钇铝)进行氟退火来保护RIE组件的改进的制品及方法。当氧化钇沉积工艺依赖于脉冲式直流(DC)电源时,形成具有表面裂纹及表面下裂纹的先前膜。如本文所公开,在氧化钇沉积工艺期间使用交流(AC)电源可出乎意料地最小化或防止在氟退火工艺期间表面裂纹及表面下裂纹的形成。如本文所使用,“表面裂纹”是当用激光共聚焦显微镜以400倍的放大率观察膜的表面时可见的在膜的表面上的裂纹。如本文所使用,“表面下裂纹”是当使用激光共聚焦显微镜以1000倍的放大率观察膜的整个深度时可见的在膜的表面下方的裂纹。
氟退火工艺包含通过在含氟气氛中在300℃至650℃下对膜进行退火而将氟引入到含钇的金属氧化钇物膜中。氟退火工艺的加热升温速率可在每小时50℃到每小时200℃之间。
氟退火的氧化钇膜提供几个优点并且具有几个合乎需要的特性,包含高的抗氟等离子体蚀刻性(例如,约0.1到约0.2微米/小时)、高的抗湿式化学蚀刻性(例如,约5到约120分钟,在5%HCl中)、对腔室组件的良好粘附性(例如,约5N到约15N的第二临界负荷(LC2)粘附性),及保形涂覆能力。另外,氟退火的氧化钇膜在材料、机械特性及微观结构方面是可调谐的。可制造包括氧化钇、氟退火的氧化钇或氧化钇及氟退火的氧化钇两者的混合物的膜,以满足特定的涂覆或蚀刻环境的需要。举例来说,可将膜的氟含量控制为约4原子百分比至约60原子百分比,如通过扫描电子显微镜(SEM)结合能量色散谱(EDS)探针所测量,并且可将氟深度控制为约0.5微米至约20微米。氟化氧化钇的抗蚀刻性随着膜中的氟含量增大。本文所公开的使用AC电源沉积的氟退火的氧化钇膜还提供以下额外优点:优异抗裂性(关于表面裂纹及表面下裂纹两者),及在高温下的改进的完整性对比使用DC或脉冲式DC电源沉积的氟退火的氧化钇膜。
在一些实施例中,使用交流(AC)电源将氧化钇沉积在衬底上,随后进行氟退火工艺以将氧化钇转换成氧氟化钇或氧化钇及氧氟化钇的混合物。氧化钇及/或氟氧化钇形成覆盖及保护衬底的膜。所述膜提供与真空室中的蚀刻环境接触的最外层。
首先将含钇的金属氧化物(例如,氧化钇及氧化钇铝)的膜沉积到衬底上。金属氧化物膜的沉积可通过使用AC电源的各种物理气相沉积(PVD)方法进行,包含溅射及离子束辅助沉积。AC电源可在约30kHz到约100kHz的范围内的频率下操作。在沉积之后,所述膜在含氟环境中在约300℃至约650℃下进行氟退火。如第2016/0273095号美国公开案中所描述,可执行氟化过程,所述美国公开案特此以全文引用的方式并入。氟化过程可使用几种方法进行,包含例如氟离子植入随后退火、在300℃或更高温度下的氟等离子体处理、氟聚合物燃烧方法、高温下的氟气体反应,及用氟气体进行UV处理或前述的任何组合。
取决于所采用的氟退火方法,可使用各种氟源。对于氟聚合物燃烧方法,需要氟聚合物材料并且氟聚合物材料可为例如,PVF(聚氟乙烯)、PVDF(聚偏二氟乙烯)、PTFE(聚四氟乙烯)、PCTFE(聚氯三氟乙烯)、PFA、MFA(全氟烷氧基聚合物)、FEP(氟化乙烯-丙烯)、ETFE(聚乙烯四氟乙烯)、ECTFE(聚乙烯氯三氟乙烯)、FFPM/FFKM(全氟化弹性体[全氟弹性体])、FPM/FKM(碳氟化合物[氯三氟乙烯偏二氟乙烯])、PFPE(全氟聚醚)、PFSA(全氟磺酸),及全氟聚氧杂环丁烷。
对于其它氟退火方法,包含氟离子植入随后退火、在300℃或更高温度下的氟等离子体处理、高温下的氟气体反应及用氟气体进行UV处理,反应需要氟化气体及氧气。氟化气体可为例如氢氟碳(HFC)、全氟化碳(PFC)、六氟化硫(SF6)、HF蒸气、NF3及来自氟聚合物燃烧的气体。
氧化钇或氧化钇铝膜的结构优选地为柱状,以使得所述结构允许氟在氟退火工艺期间穿过晶界穿透膜。非晶氧化钇结构(即,非柱状或较小柱状)不允许氟在氟退火工艺期间容易地穿透。
本实用新型的氟退火膜可应用于真空兼容衬底,例如半导体制造系统中的组件。蚀刻室组件可包含喷淋头、护罩、喷嘴及窗口。蚀刻室组件还可包含用于衬底、晶片处理夹具及腔室内衬的载台。腔室组件可由陶瓷材料制成。陶瓷材料的实例包含氧化铝、碳化硅及氮化铝。尽管本说明书涉及蚀刻室组件,但本文公开的实施例不限于蚀刻室组件,并且也可如本文所描述涂覆将受益于改进的耐腐蚀性的其它陶瓷制品及衬底。实例包含陶瓷晶片载体及晶片支架、基座、心轴、卡盘、环、挡板及紧固件。真空兼容衬底也可为硅、石英、钢、金属或金属合金。真空兼容衬底也可为或包含例如在半导体工业中使用的塑料,例如聚醚醚酮(PEEK)及聚酰亚胺,例如在干式蚀刻中。
氟退火的膜为可调谐的,其中氟退火工艺允许膜的氟化的深度及密度变化。在一些实施例中,氟退火的膜完全氟化(完全饱和),其中氟遍及膜的深度定位。在其它实施例中,氟退火的膜部分氟化,其中氟沿着膜的外部部分而非遍及膜的整个深度定位。另外,膜可为梯度膜,其中氟含量在膜的深度上变化。举例来说,膜的顶部(最外)部分可包含最高氟含量,其中氟含量在膜朝向膜的最接近衬底并且与衬底交接的底部(最内)部分的深度上逐渐减小。膜的最外部分为面向蚀刻环境的部分。在一些实施例中,膜可包含约60原子%或更小、约55原子%或更小、约50原子%或更小、约45原子%或更小、约40原子%或更小、约35原子%或更小、约30原子%或更小、约25原子%或更小、约20原子%或更小、约15原子%或更小的表面氟量。使用扫描电子显微镜(SEM)结合能量色散谱(EDS)探针测量本文所公开的氟值的所有原子%。在一些实施例中,膜的厚度可在约1微米到约20微米的范围内。在一些实施例中,在10%膜厚度的深度处(如从距衬底最远的表面测量)的氟量至少为约10原子%、约15原子%、约20原子%、约25原子%、约30原子%或约35原子%。在一些实施例中,在30%膜厚度的深度处(如从距衬底最远的表面测量)的氟量至少为约10原子%、约15原子%、约20原子%、约25原子%、约30原子%,或约35原子%。在一些实施例中,在50%膜厚度的深度处(如从距衬底最远的表面测量)的氟量至少为约10原子%、约15原子%、约20原子%、约25原子%、约30原子%或约35原子%。
可在氟退火期间通过改变工艺参数(例如氟退火时间及温度)来控制膜的氟化深度。如图1中所示(并且下文在实例1中更详细地描述),在更高的氟退火时间及温度下氟更深地扩散到膜中。
所述膜提供覆盖衬底的保护层,所述保护层是与真空室内部的环境接触的经涂覆制品的最外层。
在膜未完全氟化的一些实施例中,膜的顶部或最外部部分是氟氧化钇,且膜的其余深度是氧化钇。在膜未完全氟化的其它实施例中,膜的顶部或最外部部分是氟氧化钇铝,且膜的其余深度是氧化钇铝。
在一些实施例中,使用AC电源在含氧气氛中已经通过物理气相沉积用钇涂覆衬底。在一些实施例中,衬底已经在反应气体气氛中通过反应溅射用钇涂覆。反应气体可为作为氧气源的气体并且可包含空气。因此,膜可为包含钇及氧的陶瓷材料,并且可使用例如反应溅射的物理气相沉积(PVD)技术制造。在沉积期间的含氧气氛还可包含惰性气体,例如氩气。
在一些实施例中,本文公开已经涂覆有使用AC电源通过反应溅射沉积的氧化钇膜的陶瓷衬底,其中涂层及衬底在含有氟气氛的烘箱中在300℃至650℃下退火。氟退火涂层是包含钇、氧及氟的陶瓷材料。衬底及氟退火膜可在高真空(5E至6托)下在150摄氏度下烘烤,而不会从涂层中损失氟。
在高温下对氧化钇膜进行退火的持续时间可为约0.5小时至约6.5小时或更长。
氧化钇在陶瓷衬底(例如,氧化铝)上的氟退火显著地提高氧化钇膜的湿式化学(5%HCl)耐蚀刻性。
本文所公开的氟退火的氧化钇膜可表征为粘附到底层陶瓷衬底的那些氧化钇膜,在室温下与5%盐酸水溶液接触5分钟或更多之后,膜粘附到陶瓷衬底。在一些版本中,氟退火的氧化钇膜粘附到底层陶瓷衬底达15分钟到30分钟之间,在一些情况下为30分钟到45分钟,而在其它情况下,当在室温下接触5%HCl水溶液或浸没在5%HCl水溶液中时,膜在100到120分钟后粘附到底层衬底。本文所公开的氧化钇膜可用作在含卤素气体的等离子体蚀刻器中使用的组件的保护涂层。举例来说,含卤素气体可包含NF3、F2、Cl2等。
氟退火氧化钇膜在氟基蚀刻系统中特别有利,因为膜中氟的存在允许腔室更快速地稳定或老化。这有助于消除在老化及使用期间的过程漂移,并减少对于通过含氟或含氯气体的老化的蚀刻器停机时间。
如上文所论述,本文所公开的氟退火的氧化钇膜具有最少表面裂纹及/或表面下裂纹至没有表面裂纹及/或表面下裂纹。据信所述膜的优异抗裂性归因于使用AC电源沉积氧化钇膜。使用AC电源而不是DC或脉冲式DC电源沉积的氧化钇膜具有极少(例如,5个裂纹或更少、4个裂纹或更少、3个裂纹或更少,或2个裂纹或更少)至没有表面裂纹及/或表面下裂纹,包含对于与氧化钇在热膨胀系数方面具有显着差异的衬底,例如石英衬底。在氟化氧化钇膜之后,包含当在高温下及/或持续时间下进行氟退火时,还存在极少(例如,5个裂纹或更少、4个裂纹或更少、3个裂纹或更少,或2个裂纹或更少)至没有表面裂纹及/或表面下裂纹的构造,由此导致整个膜深度的氟原子%更高。举例来说,对于在膜的30%总厚度的深度处具有至少10的氟原子%、在膜的30%总厚度的深度处具有至少20的氟原子%、在膜的30%总厚度的深度处具有至少30的氟原子%、在膜的50%总厚度的深度处具有至少10的氟原子%、在膜的50%总厚度的深度处具有至少20的氟原子%、在膜的50%总厚度的深度处具有至少30的氟原子%的膜,当用激光共聚焦显微镜以400倍的放大率观察膜的表面时,在膜的表面上可见最少表面裂纹至没有表面裂纹,及/或当使用激光共聚焦显微镜以1000倍的放大率观察膜的整个深度时,在膜的表面下方可见最少表面下裂纹至没有表面下裂纹。这些结果是出乎意料的,因为使用DC或脉冲式DC电源沉积氧化钇薄膜的具有类似氟原子%深度分布的膜会导致表面裂纹及/或表面下裂纹。
实例1
使用交流(AC)电源在含氧气氛中通过钇物理气相沉积(即,反应溅射)将具有约5微米厚度的氧化钇膜沉积到硅的试片大小的衬底(大致0.75英寸×0.75英寸)上。接下来,试片经受氟退火,在此期间试片根据在下表1中列出的以下条件中的一个在含氟气氛中在烘箱中加热。条件9及10的氟前体量是条件1到8的两倍,以确保在氟退火处理结束之前所有的氟都不会用完。使用扫描电子显微镜结合电子色散谱(EDS)探针,对于经受表1中列出的10个条件中的每一个的试片在整个5微米厚度的膜上测量氟的原子%。图1中展示数据的曲线图,其中在Y轴上展示氟原子%且在X轴上展示以微米为单位的到厚度中的深度。对于500C/5hr 2X及550C/5hr 2X,图1的图例中的“2X”是指在这些条件下氟前体量是两倍。在激光共聚焦显微镜下以400倍的放大率观察每个试片的涂层表面,以检查涂层的表面上的可见表面裂纹。还用激光共聚焦显微镜观察每个试片的涂层,以在1000倍的放大率下观察膜的整个深度来检查涂层表面下方的表面下裂纹。表1还报告在十个条件中的每一个下是否可见表面裂纹及表面下裂纹。
表1:硅衬底上的氟化氧化钇膜
*条件9及10的氟前体量是条件1到8的两倍。
如图1中可看到,从条件1到条件10的总体趋势是涂层表面的氟原子%随着氟退火温度及持续时间增加而增加。在图1中还可看到,对于条件6、7、8及9实现贯穿涂层厚度的氟化。图2是通过扫描电子显微镜(SEM)获得的经受以上氟退火条件中的一个的试片的截面图。如表1中所示,直到550摄氏度下的条件10才出现表面裂纹及表面下裂纹。图3是用基恩士激光共聚焦显微镜以1000倍的放大率拍摄的照片并且展示多个表面裂纹。据信,条件1到9的涂层中没有可见的表面裂纹及表面下裂纹是由于使用在氧化钇沉积期间使用交流(AC)电源。
实例2
使用交流(AC)电源在含氧气氛中通过钇物理气相沉积(即,反应溅射)将具有约5微米厚度的氧化钇膜沉积到氧化铝的试片大小的衬底(大致0.75英寸直径圆盘)上。接下来,试片经受氟退火,在此期间试片根据在下表2中列出的以下条件中的一个在含氟气氛中在烘箱中加热。条件9及10的氟前体量是条件1到8的两倍,以确保在氟退火处理结束之前所有的氟都不会用完。据信,对于经受条件1至10的每个试片,Y轴上展示的氟原子%及X轴上展示的以微米为单位的到厚度中的深度的曲线图将类似于图1中所示的曲线图。在激光共聚焦显微镜下以400倍的放大率观察每个试片的涂层表面,以检查涂层的表面上的可见表面裂纹。还用激光共聚焦显微镜观察每个试片的涂层,以在1000倍的放大率下观察膜的整个深度来检查涂层表面下方的表面下裂纹。表2还报告在十个条件中的每一个下是否可见表面裂纹及表面下裂纹。
表2:氧化铝衬底上的氟化氧化钇膜
条件 | 温度(C) | 时间(小时) | 表面裂纹 | 表面下裂纹 |
1 | 350 | 1 | 否 | 否 |
2 | 350 | 2 | 否 | 否 |
3 | 400 | 1 | 否 | 否 |
4 | 400 | 2 | 否 | 否 |
5 | 450 | 1 | 否 | 否 |
6 | 450 | 2 | 否 | 否 |
7 | 500 | 1 | 否 | 否 |
8 | 500 | 5 | 否 | 否 |
9 | 500 | 5 | 否 | 否 |
10 | 550 | 5 | 否 | 否 |
*条件9及10的氟前体量是条件1到8的两倍。
据信,条件1到10的涂层中没有可见的表面裂纹及表面下裂纹是由于使用在氧化钇沉积期间使用交流(AC)电源。图4是用基恩士激光共聚焦显微镜以1000倍的放大率拍摄的照片并且展示不存在表面裂纹。
实例3
使用交流(AC)电源在含氧气氛中通过钇物理气相沉积(即,反应溅射)将具有约5微米厚度的氧化钇膜沉积到石英及蓝宝石的试片大小的衬底(直径为大致0.75英寸)上。接下来,试片经受氟退火,在此期间试片根据在实例1及2中使用的条件1到10在含氟气氛中在烘箱中加热。涂覆的氧化钇膜中不存在表面裂纹或表面下裂纹,然而根据条件1到10中的每一个执行氟退火之后确实形成裂纹及表面下裂纹。
本文中所引用的所有专利、公开申请案以及参考的教示均以全文引用的方式并入。
尽管已相对于一或多个实施方案展示及描述本实用新型,但本领域的技术人员在阅读及理解本说明书及附图后将想到等效更改及修改。
本实用新型包含所有此类修改及更改,并且只受到所附权利要求书的范围的限制。另外,尽管可能已相对于几种实施方案中的仅一个公开本实用新型的特定特征或方面,但此类特征或方面可与其它实施方案中的一或多个特征或方面相结合,只要对于任何给定或特定的应用是有需要或有利的。此外,就具体实施方式或权利要求书中使用术语“包含(includes)”、“具有(having/has)”、“带有(with)”或其变体而言,此类术语意在以类似于术语“包括(comprising)”的方式是包含性的。而且,术语“示例性”仅意图意味着一个实例而并非最佳者。应理解,本文中所描绘的特征及/或元件是出于简单及易于理解的目的相对于彼此以特定尺寸及/或定向说明的,并且实际尺寸及/或定向可能基本上不同于所说明的。
虽然本实用新型已经参考其实例实施例具体地展示及描述,但所属领域的技术人员应理解,在不脱离由所附权利要求书涵盖的本实用新型的范围的情况下,可在其中进行形式及细节的各种改变。
Claims (4)
1.一种涂覆有抗裂氟退火膜的制品,其特征在于所述制品包括:
衬底;及
保护膜,其覆盖所述衬底的至少一部分,
其中所述膜不具有当使用激光共聚焦显微镜以1000倍的放大率观察所述膜的整个深度时可见的在所述膜的表面下方的表面下裂纹。
2.根据权利要求1所述的涂覆有抗裂氟退火膜的制品,其特征在于在氟退火之后,所述膜不具有当使用激光共聚焦显微镜以400倍的放大率观察所述膜的所述表面时可见的在所述膜的所述表面上的表面裂纹。
3.根据权利要求1所述的涂覆有抗裂氟退火膜的制品,其特征在于所述衬底是氧化铝。
4.根据权利要求1所述的涂覆有抗裂氟退火膜的制品,其特征在于所述衬底是硅。
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WO2022108888A1 (en) | 2022-05-27 |
EP4248481A1 (en) | 2023-09-27 |
US20220154325A1 (en) | 2022-05-19 |
JP2023552291A (ja) | 2023-12-15 |
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