TW202336522A - Photomask blank, photomask, method for manufacturing a photomask, and method for manufacturing a display device - Google Patents
Photomask blank, photomask, method for manufacturing a photomask, and method for manufacturing a display device Download PDFInfo
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- TW202336522A TW202336522A TW111135343A TW111135343A TW202336522A TW 202336522 A TW202336522 A TW 202336522A TW 111135343 A TW111135343 A TW 111135343A TW 111135343 A TW111135343 A TW 111135343A TW 202336522 A TW202336522 A TW 202336522A
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- light
- photomask
- shielding film
- film
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 162
- 239000010936 titanium Substances 0.000 claims abstract description 89
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000010703 silicon Substances 0.000 claims abstract description 68
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 68
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 57
- 238000005530 etching Methods 0.000 claims description 152
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 77
- 230000003667 anti-reflective effect Effects 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 55
- 239000011651 chromium Substances 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 36
- 238000012546 transfer Methods 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- 229910021341 titanium silicide Inorganic materials 0.000 claims description 29
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052804 chromium Inorganic materials 0.000 claims description 26
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 27
- 230000015556 catabolic process Effects 0.000 abstract 2
- 239000010408 film Substances 0.000 description 460
- 239000010410 layer Substances 0.000 description 154
- 239000000203 mixture Substances 0.000 description 57
- 239000007789 gas Substances 0.000 description 53
- 238000004544 sputter deposition Methods 0.000 description 46
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 230000006378 damage Effects 0.000 description 20
- 230000003287 optical effect Effects 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 238000005477 sputtering target Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 229920002120 photoresistant polymer Polymers 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 6
- 230000008033 biological extinction Effects 0.000 description 6
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000005546 reactive sputtering Methods 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 238000001039 wet etching Methods 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000873 masking effect Effects 0.000 description 5
- 238000002310 reflectometry Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 4
- 238000004380 ashing Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000012788 optical film Substances 0.000 description 3
- 230000010363 phase shift Effects 0.000 description 3
- 238000010301 surface-oxidation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910016006 MoSi Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910006249 ZrSi Inorganic materials 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910021344 molybdenum silicide Inorganic materials 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- WEAMLHXSIBDPGN-UHFFFAOYSA-N (4-hydroxy-3-methylphenyl) thiocyanate Chemical compound CC1=CC(SC#N)=CC=C1O WEAMLHXSIBDPGN-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 229910021355 zirconium silicide Inorganic materials 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/54—Absorbers, e.g. of opaque materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/46—Antireflective coatings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/80—Etching
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
Abstract
Description
本發明例如係關於一種顯示裝置製造用之光罩基底、光罩、光罩之製造方法、及顯示裝置之製造方法。For example, the present invention relates to a photomask substrate for manufacturing a display device, a photomask, a photomask manufacturing method, and a display device manufacturing method.
近年來，以LCD(Liquid Crystal Display，液晶顯示器)為代表之FPD(Flat Panel Display，平板顯示器)等顯示裝置中，正快速推進畫面之大型化、廣視角化、以及高清化、高速顯示化。因此，對於製造FPD時曝光製程中使用之光罩，亦可使用於大尺寸透明基板上形成有微細且高精度之轉印用圖案之二元遮罩或相位偏移遮罩等。In recent years, display devices such as FPD (Flat Panel Display), represented by LCDs (Liquid Crystal Displays), are rapidly advancing toward larger screens, wider viewing angles, higher definition, and higher-speed displays. Therefore, the photomask used in the exposure process when manufacturing FPD can also be used to form a binary mask or a phase shift mask that forms a fine and high-precision transfer pattern on a large-sized transparent substrate.
光罩基底係光罩之原版。光罩例如具有透明基板、及於該透明基板上藉由濕式蝕刻將遮光膜圖案化而成之遮光膜圖案。The photomask base is the original version of the photomask. The photomask has, for example, a transparent substrate, and a light-shielding film pattern formed by patterning a light-shielding film on the transparent substrate by wet etching.
對於此種用於FPD之製造中之光罩，於曝光步驟中或搬送等操作中會帶靜電，從而引起轉印用圖案局部被靜電破壞。尤其對於將圖案微細化後之高精度之光罩，會引起微細化之圖案間之靜電破壞，因此要求光罩及光罩基底具有高度之耐靜電破壞特性。This kind of photomask used in FPD manufacturing will be charged with static electricity during the exposure step or during transportation and other operations, causing the transfer pattern to be partially destroyed by static electricity. Especially for high-precision masks after miniaturizing patterns, electrostatic damage will occur between the miniaturized patterns. Therefore, the photomask and the photomask substrate are required to have a high degree of resistance to electrostatic damage.
例如專利文獻1中，記載有代替Cr系材料而利用MoSi系材料、TaSi系材料、及ZrSi系材料等形成遮光膜。For example, Patent Document 1 describes forming a light-shielding film using MoSi-based materials, TaSi-based materials, ZrSi-based materials, etc. instead of Cr-based materials.
又，例如專利文獻2中，揭示有將遮光膜之薄片電阻值設為10 Ω/sq以下。 [先前技術文獻] [專利文獻] Furthermore, for example, Patent Document 2 discloses that the sheet resistance value of the light-shielding film is 10 Ω/sq or less. [Prior technical literature] [Patent Document]
[專利文獻1]日本專利特開2020-140106號公報 [專利文獻2]日本專利特開2019-168558號公報 [Patent Document 1] Japanese Patent Application Publication No. 2020-140106 [Patent Document 2] Japanese Patent Application Publication No. 2019-168558
[發明所欲解決之問題][Problem to be solved by the invention]
如上所述，對於用於FPD之製造之光罩，為了抑制或避免圖案間之靜電破壞，要求更高之耐靜電破壞特性。As mentioned above, in order to suppress or avoid electrostatic damage between patterns, photomasks used in FPD manufacturing are required to have higher electrostatic damage resistance properties.
又，於作為光罩製造步驟之一部分之包含遮光膜之光學膜之蝕刻中，產生蝕刻速率於圖案密度較密之區域與較稀之區域之間出現差異之搭載效應。於近年來之高清(例如1000 ppi以上)FPD製造中，為了能夠進行高解像之圖案轉印，要求形成有孔徑6 μm以下、線寬4 μm以下、具體而言直徑或寬度尺寸為1.5 μm以下之轉印用圖案之光罩。該情形時，為了精度良好地形成微細之圖案，降低搭載效應亦有用。Also, in the etching of the optical film including the light-shielding film as part of the mask manufacturing step, a piggyback effect occurs in which the etching rate differs between areas with denser pattern density and areas with thinner pattern density. In recent high-definition (for example, 1000 ppi or above) FPD manufacturing, in order to enable high-resolution pattern transfer, it is required to form an aperture with a diameter of 6 μm or less and a line width of 4 μm or less. Specifically, the diameter or width size is 1.5 μm. The following photomask for transfer printing pattern. In this case, in order to form fine patterns with high accuracy, it is also useful to reduce the mounting effect.
本發明係為了解決上述課題而完成。即，本發明之目的在於提供一種具有高度之耐靜電破壞特性，並且較先前可降低搭載效應之光罩基底、光罩、光罩之製造方法、及顯示裝置之製造方法。 [解決問題之技術手段] The present invention was completed in order to solve the above-mentioned problems. That is, the object of the present invention is to provide a photomask substrate, a photomask, a method for manufacturing the photomask, and a method for manufacturing a display device that have high resistance to electrostatic destruction and can reduce the mounting effect compared to the previous ones. [Technical means to solve problems]
為解決上述課題，本發明具有以下構成。In order to solve the above-mentioned problems, the present invention has the following configuration.
(構成1) 本發明之構成1係一種光罩基底，其特徵在於，其係具有透明基板、及設置於該透明基板上之遮光膜者，上述遮光膜含有鈦(Ti)與矽(Si)，上述遮光膜之薄片電阻值為40 Ω/sq以上。 (composition 1) Structure 1 of the present invention is a photomask substrate, which is characterized in that it has a transparent substrate and a light-shielding film provided on the transparent substrate. The light-shielding film contains titanium (Ti) and silicon (Si). The light-shielding film The sheet resistance value is above 40 Ω/sq.
(構成2) 本發明之構成2如構成1之光罩基底，其特徵在於：上述遮光膜之薄片電阻值為90 Ω/sq以下。 (composition 2) The structure 2 of the present invention is the same as the mask base of structure 1, characterized in that the sheet resistance of the light-shielding film is 90 Ω/sq or less.
(構成3) 本發明之構成3如構成1之光罩基底，其特徵在於：上述遮光膜包含遮光層，該遮光層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，上述遮光層之薄片電阻值為40 Ω/sq以上。 (composition 3) The structure 3 of the present invention is the mask base of structure 1, characterized in that the above-mentioned light-shielding film includes a light-shielding layer, and the light-shielding layer is composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and the above-mentioned light-shielding layer is The sheet resistance value is 40 Ω/sq or more.
(構成4) 本發明之構成4如構成3之光罩基底，其特徵在於：上述遮光層之薄片電阻值為90 Ω/sq以下。 (Constitution 4) The structure 4 of the present invention is the mask base of structure 3, characterized in that the sheet resistance value of the above-mentioned light shielding layer is 90 Ω/sq or less.
(構成5) 本發明之構成5如構成1至4中任一項之光罩基底，其特徵在於：上述遮光膜包含遮光層，該遮光層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，上述遮光層進而含有氮(N)或氧(O)。 (Constitution 5) The structure 5 of the present invention is the photomask base of any one of the structures 1 to 4, characterized in that the above-mentioned light-shielding film includes a light-shielding layer, and the light-shielding layer is made of a titanium silicide-based material containing titanium (Ti) and silicon (Si). It is configured that the above-mentioned light shielding layer further contains nitrogen (N) or oxygen (O).
(構成6) 本發明之構成6如構成1至5中任一項之光罩基底，其特徵在於：上述遮光膜包含遮光層，該遮光層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，於上述遮光層上具有正面抗反射層。 (composition 6) The composition 6 of the present invention is the photomask base according to any one of compositions 1 to 5, characterized in that the above-mentioned light-shielding film includes a light-shielding layer, and the light-shielding layer is made of a titanium silicide-based material containing titanium (Ti) and silicon (Si). It is composed of a front anti-reflective layer on the above-mentioned light-shielding layer.
(構成7) 本發明之構成7如構成6之光罩基底，其特徵在於：上述正面抗反射層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，且含有氮(N)或氧(O)。 (composition 7) The structure 7 of the present invention is the mask base of structure 6, wherein the front anti-reflection layer is composed of a titanium silicide material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen ( O).
(構成8) 本發明之構成8如構成1至7中任一項之光罩基底，其特徵在於：上述遮光膜包含遮光層，該遮光層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，於上述透明基板與上述遮光層之間具有背面抗反射層。 (composition 8) The composition 8 of the present invention is the photomask base according to any one of compositions 1 to 7, characterized in that the above-mentioned light-shielding film includes a light-shielding layer made of a titanium silicide-based material containing titanium (Ti) and silicon (Si). The structure includes a back anti-reflection layer between the transparent substrate and the light-shielding layer.
(構成9) 本發明之構成9如構成8之光罩基底，其特徵在於：上述背面抗反射層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，且含有氮(N)或氧(O)。 (Composition 9) The structure 9 of the present invention is the mask base of structure 8, characterized in that: the back anti-reflection layer is composed of a titanium silicate material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen ( O).
(構成10) 本發明之構成10如構成1至9中任一項之光罩基底，其特徵在於：於上述遮光膜上，具有蝕刻選擇性與該遮光膜不同之蝕刻遮罩膜。 (composition 10) The structure 10 of the present invention is the photomask base of any one of the structures 1 to 9, characterized in that: on the above-mentioned light-shielding film, there is an etching mask film with an etching selectivity different from that of the light-shielding film.
(構成11) 本發明之構成11如構成10之光罩基底，其特徵在於：上述蝕刻遮罩膜含有鉻(Cr)。 (Composition 11) The structure 11 of the present invention is the photomask base of structure 10, wherein the etching mask film contains chromium (Cr).
(構成12) 本發明之構成12如構成11之光罩基底，其特徵在於：上述蝕刻遮罩膜進而含有氮(N)或氧(O)。 (composition 12) Structure 12 of the present invention is the photomask base of structure 11, wherein the etching mask film further contains nitrogen (N) or oxygen (O).
(構成13) 本發明之構成13係一種光罩，其特徵在於，其係具有透明基板、及設置於該透明基板上之具備轉印用圖案之遮光膜者，上述遮光膜含有鈦(Ti)與矽(Si)，上述遮光膜之薄片電阻值為40 Ω/sq以上。 (Composition 13) Structure 13 of the present invention is a photomask, which is characterized in that it has a transparent substrate and a light-shielding film provided with a transfer pattern on the transparent substrate. The light-shielding film contains titanium (Ti) and silicon (Si). ), the sheet resistance value of the above-mentioned light-shielding film is 40 Ω/sq or above.
(構成14) 本發明之構成14如構成13之光罩，其特徵在於：上述遮光膜之薄片電阻值為90 Ω/sq以下。 (Composition 14) Structure 14 of the present invention is the photomask of structure 13, characterized in that the sheet resistance value of the light-shielding film is 90 Ω/sq or less.
(構成15) 本發明之構成15如構成13之光罩，其特徵在於：上述遮光膜包含遮光層，該遮光層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，上述遮光層之薄片電阻值為40 Ω/sq以上。 (composition 15) The structure 15 of the present invention is the photomask of structure 13, wherein the light-shielding film includes a light-shielding layer made of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and the light-shielding layer is a thin sheet The resistance value is 40 Ω/sq or more.
(構成16) 本發明之構成16如構成15之光罩，其特徵在於：上述遮光層之薄片電阻值為90 Ω/sq以下。 (composition 16) The structure 16 of the present invention is the photomask of structure 15, characterized in that the sheet resistance value of the light shielding layer is 90 Ω/sq or less.
(構成17) 本發明之構成17如構成13之光罩，其特徵在於：上述遮光膜包含遮光層，該遮光層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，上述遮光層進而含有氮(N)或氧(O)。 (Composition 17) The structure 17 of the present invention is the photomask of structure 13, wherein the light-shielding film includes a light-shielding layer made of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and the light-shielding layer further contains Nitrogen (N) or oxygen (O).
(構成18) 本發明之構成18如構成13之光罩，其特徵在於：上述遮光膜包含遮光層，該遮光層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，於上述遮光層上具有正面抗反射層。 (Composition 18) The structure 18 of the present invention is the photomask of structure 13, characterized in that the above-mentioned light-shielding film includes a light-shielding layer, and the light-shielding layer is composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si), on the above-mentioned light-shielding layer Has a front anti-reflective layer.
(構成19) 本發明之構成19如構成18之光罩，其特徵在於：上述正面抗反射層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，且含有氮(N)或氧(O)。 (Composition 19) The structure 19 of the present invention is the photomask of structure 18, wherein the front anti-reflection layer is made of a titanium silicide material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen (O). ).
(構成20) 本發明之構成20如構成13至19中任一項之光罩，其特徵在於：上述遮光膜包含遮光層，該遮光層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，於上述透明基板與上述遮光層之間具有背面抗反射層。 (Composition 20) The structure 20 of the present invention is the photomask according to any one of the structures 13 to 19, characterized in that the light-shielding film includes a light-shielding layer, and the light-shielding layer is composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si). , there is a back anti-reflection layer between the above-mentioned transparent substrate and the above-mentioned light-shielding layer.
(構成21) 本發明之構成21如構成20之光罩，其中上述背面抗反射層由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，且含有氮(N)或氧(O)。 (Composition 21) Structure 21 of the present invention is the mask of structure 20, wherein the back anti-reflection layer is made of a titanium silicate material containing titanium (Ti) and silicon (Si), and contains nitrogen (N) or oxygen (O).
(構成22) 本發明之構成22係一種光罩之製造方法，其特徵在於包括以下步驟，即，準備如構成1至9中任一項之光罩基底；及將設置於上述遮光膜上之抗蝕膜圖案作為遮罩而對上述遮光膜進行濕式蝕刻，於上述透明基板上形成轉印用圖案。 (Composition 22) Composition 22 of the present invention is a method for manufacturing a photomask, which is characterized by including the following steps: preparing a photomask base as in any one of compositions 1 to 9; and placing a resist film pattern on the above-mentioned light-shielding film. As a mask, the light-shielding film is wet-etched to form a transfer pattern on the transparent substrate.
(構成23) 本發明之構成23係一種光罩之製造方法，其特徵在於包括以下步驟，即，準備如構成10至12中任一項之光罩基底；將設置於上述蝕刻遮罩膜上之抗蝕膜圖案作為遮罩而對上述蝕刻遮罩膜進行濕式蝕刻，於上述遮光膜上形成蝕刻遮罩膜圖案；及將上述蝕刻遮罩膜圖案作為遮罩而對上述遮光膜進行濕式蝕刻，於上述透明基板上形成轉印用圖案。 (Composition 23) The composition 23 of the present invention is a method for manufacturing a photomask, which is characterized by including the following steps: preparing a photomask base as in any one of compositions 10 to 12; applying a resist film disposed on the etching mask film The pattern is used as a mask to perform wet etching on the above-mentioned etching mask film, and an etching mask film pattern is formed on the above-mentioned light-shielding film; and the above-mentioned etching mask film pattern is used as a mask to perform wet etching on the above-mentioned light-shielding film, on A transfer pattern is formed on the transparent substrate.
(構成24) 本發明之構成24係一種顯示裝置之製造方法，其特徵在於包括以下曝光步驟，即，將藉由如構成22或23之光罩之製造方法所獲得之光罩載置於曝光裝置之光罩台，將形成於上述光罩上之上述轉印用圖案轉印至形成於顯示裝置用基板上之抗蝕劑。 (Composition 24) The structure 24 of the present invention is a method for manufacturing a display device, which is characterized by including the following exposure step, that is, placing the photomask obtained by the method of manufacturing the photomask of the structure 22 or 23 on the photomask of the exposure device. A stage is used to transfer the transfer pattern formed on the photomask to the resist formed on the display device substrate.
(構成25) 本發明之構成25係一種顯示裝置之製造方法，其特徵在於包括以下曝光步驟，即，將如構成13之光罩載置於曝光裝置之光罩台，將形成於上述光罩上之上述轉印用圖案轉印至形成於顯示裝置用基板上之抗蝕劑。 [發明之效果] (Composition 25) The structure 25 of the present invention is a manufacturing method of a display device, which is characterized by including the following exposure step, that is, placing the mask as shown in structure 13 on the mask stage of the exposure device, and converting the above-mentioned rotation formed on the mask The printing pattern is transferred to the resist formed on the display device substrate. [Effects of the invention]
根據本發明，例如於FPD製造用之光罩基底及光罩中，較先前可提高耐靜電破壞特性。根據本發明，又可降低搭載效應，故可穩定地製造高精度之光罩。According to the present invention, for example, in the photomask substrate and photomask used in FPD manufacturing, the electrostatic damage resistance can be improved compared to before. According to the present invention, the mounting effect can be reduced, so a high-precision photomask can be stably manufactured.
以下，一面參照圖式一面對本發明之實施方式具體地進行說明。再者，以下實施方式係將本發明具體化時之形態，並非係將本發明限定於其範圍內者。再者，光罩基底10例如相當於用以經過光微影步驟製造以LCD(Liquid Crystal Display)為代表之FPD(Flat Panel Display)等顯示裝置之光罩100(圖4D、圖5C)之原版。Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, the following embodiment is an embodiment of this invention and does not limit the scope of this invention. Furthermore, the mask base 10 is, for example, equivalent to a master plate for manufacturing the mask 100 (Fig. 4D, Fig. 5C) of a display device such as an FPD (Flat Panel Display) represented by an LCD (Liquid Crystal Display) through a photolithography step. .
圖1係表示本發明第1實施方式之光罩基底10之膜構成之模式性縱剖視圖。第1實施方式之光罩基底10具備透明基板20、形成於透明基板20上之作為圖案形成用薄膜之遮光膜30、及形成於遮光膜30上之蝕刻遮罩膜40。FIG. 1 is a schematic longitudinal cross-sectional view showing the film structure of the photomask base 10 according to the first embodiment of the present invention. The mask base 10 of the first embodiment includes a transparent substrate 20 , a light-shielding film 30 as a pattern forming film formed on the transparent substrate 20 , and an etching mask film 40 formed on the light-shielding film 30 .
圖2係表示本發明第2實施方式之光罩基底10之膜構成之模式圖。第2實施方式之光罩基底10具備透明基板20、及形成於透明基板20上之遮光膜30。FIG. 2 is a schematic diagram showing the film structure of the photomask base 10 according to the second embodiment of the present invention. The mask base 10 of the second embodiment includes a transparent substrate 20 and a light-shielding film 30 formed on the transparent substrate 20 .
＜透明基板20＞ 透明基板20相對於曝光之光為透明。透明基板20係於假定為無表面反射損耗時相對於曝光之光具有85%以上之透過率、較佳為90%以上之透過率者。透明基板20包含含有矽(Si)與氧(O)之材料，可由合成石英玻璃、石英玻璃、鋁矽酸鹽玻璃、鈉鈣玻璃、及低熱膨脹玻璃(SiO 2-TiO 2玻璃等)等玻璃材料構成。於顯示裝置用途下使用之透明基板20一般為矩形基板。具體而言，可使用透明基板20之主表面(形成遮光膜30之面)之短邊之長度為300 mm以上者。第1、第2實施方式之光罩基底10中，可使用主表面之短邊之長度為300 mm以上之較大尺寸之透明基板20。 <Transparent substrate 20> The transparent substrate 20 is transparent with respect to exposure light. The transparent substrate 20 has a transmittance of 85% or more, preferably 90% or more, relative to the exposure light, assuming no surface reflection loss. The transparent substrate 20 includes a material containing silicon (Si) and oxygen (O), and can be made of glass such as synthetic quartz glass, quartz glass, aluminosilicate glass, soda-lime glass, and low thermal expansion glass (SiO 2 -TiO 2 glass, etc.) Material composition. The transparent substrate 20 used in display devices is generally a rectangular substrate. Specifically, the length of the short side of the main surface of the transparent substrate 20 (the surface on which the light-shielding film 30 is formed) is 300 mm or more. In the photomask substrate 10 of the first and second embodiments, a larger-sized transparent substrate 20 having a short side length of the main surface of 300 mm or more can be used.
＜遮光膜30＞ 作為圖案形成用薄膜之遮光膜30可為僅包含遮光層31之單層構造。又，遮光膜30亦可為具備遮光層31、與正面抗反射層32及/或背面抗反射層33之多層構造。此處，圖3作為一例，其係模式性表示遮光膜30包含遮光層31、正面抗反射層32及背面抗反射層33之3層之光罩基底10的縱剖視圖。根據圖3之例，正面抗反射層32設置於遮光層31之上表面(與具有透明基板20之側為相反側之面)，背面抗反射層33設置於透明基板20與遮光層31之間。 ＜Light-shielding film 30＞ The light-shielding film 30 as the pattern forming film may have a single-layer structure including only the light-shielding layer 31 . In addition, the light-shielding film 30 may also have a multi-layer structure including a light-shielding layer 31 and a front anti-reflective layer 32 and/or a back anti-reflective layer 33 . Here, FIG. 3 is an example, which is a longitudinal cross-sectional view schematically showing the photomask base 10 in which the light-shielding film 30 includes three layers: the light-shielding layer 31 , the front anti-reflection layer 32 and the back anti-reflection layer 33 . According to the example of FIG. 3 , the front anti-reflective layer 32 is disposed on the upper surface of the light-shielding layer 31 (the side opposite to the side with the transparent substrate 20 ), and the back anti-reflective layer 33 is disposed between the transparent substrate 20 and the light-shielding layer 31 .
遮光膜30可由含有鈦(Ti)與矽(Si)之鈦矽化物系材料形成。一般而言，有用的是考慮搭載效應，即，隨著圖案變得微細，圖案密度較高之區域與稀疏區域之間蝕刻速率出現差異。根據本發明人等之研究而確認，與鉻系化合物及顯示裝置製造用之光罩基底中通用之其他金屬矽化物系材料相比，藉由將鈦矽化物系材料用於遮光膜30而降低搭載效應。所謂其他金屬矽化物系材料，例如為MoSi(鉬矽化物)系材料或ZrSi(鋯矽化物)系材料。The light-shielding film 30 may be formed of a titanium silicide-based material containing titanium (Ti) and silicon (Si). In general, it is useful to consider the piggyback effect, that is, as the pattern becomes finer, there is a difference in etch rate between areas with higher pattern density and areas with sparse pattern. According to studies by the present inventors, it was confirmed that by using a titanium silicide-based material for the light-shielding film 30, the piggyback effect. The other metal silicide-based materials are, for example, MoSi (molybdenum silicide)-based materials or ZrSi (zirconium silicide)-based materials.
又，根據第1、第2實施方式之光罩基底10，可使對遮光膜30濕式蝕刻而形成之遮光膜圖案(轉印用圖案)之邊緣剖面形狀相對於透明基板20之主表面大致垂直。尤其於第1、第2實施方式中，由均質且無梯度組成之材料可實現圖案良好之邊緣剖面形狀。因此，一方面使圖案精度或面板品質保證之精度提高，一方面遮光膜30成膜時之步驟控制變得容易。Furthermore, according to the mask base 10 of the first and second embodiments, the edge cross-sectional shape of the light-shielding film pattern (transfer pattern) formed by wet-etching the light-shielding film 30 can be approximately the same as that of the main surface of the transparent substrate 20 vertical. Especially in the first and second embodiments, a well-patterned edge cross-sectional shape can be achieved by using a material that is homogeneous and has no gradient. Therefore, on the one hand, the pattern accuracy or the accuracy of panel quality assurance is improved, and on the other hand, the step control during the formation of the light-shielding film 30 becomes easier.
遮光層31中之鈦(Ti)與矽(Si)之原子比率較佳為1:1.4至1:3.4之範圍。若鈦之比率過小，則難以確保充分之遮光性。又，自耐藥性或耐光性之觀點而言，鈦之比率之上限較佳為如上所述。The atomic ratio of titanium (Ti) and silicon (Si) in the light-shielding layer 31 is preferably in the range of 1:1.4 to 1:3.4. If the ratio of titanium is too small, it will be difficult to ensure sufficient light-shielding properties. Moreover, from the viewpoint of chemical resistance or light resistance, the upper limit of the titanium ratio is preferably as described above.
構成遮光膜30之遮光層31可進而含有氮(N)或氧(O)。藉由遮光膜30含有該等元素而可控制對濕式蝕刻劑之蝕刻速率，使圖案剖面之邊緣形狀良好。The light-shielding layer 31 constituting the light-shielding film 30 may further contain nitrogen (N) or oxygen (O). By containing these elements in the light-shielding film 30, the etching rate of the wet etchant can be controlled and the edge shape of the pattern cross-section can be improved.
具體而言，於遮光層31，氮(N)之含有率較佳為0～10原子%。又，氧(O)之含有率較佳為0～5原子%。遮光層31亦可不含有氮(N)或氧(O)。Specifically, the content rate of nitrogen (N) in the light-shielding layer 31 is preferably 0 to 10 atomic %. Moreover, the content rate of oxygen (O) is preferably 0 to 5 atomic %. The light-shielding layer 31 does not need to contain nitrogen (N) or oxygen (O).
又，正面抗反射層32及背面抗反射層33可分別由含有鈦(Ti)與矽(Si)之鈦矽化物系材料構成，且可進而含有氮(N)或氧(O)。藉由包含該等元素而可使對曝光之光或描繪光(光罩製造時對抗蝕膜進行描繪時使用之光)之反射率降低。正面抗反射層32及背面抗反射層33中，氮(N)之含有率較佳為10～55原子%。又，氧(O)之含有率較佳為0～10原子%。正面抗反射層32及背面抗反射層33亦可不含有氧(O)。In addition, the front anti-reflective layer 32 and the back anti-reflective layer 33 may each be composed of a titanium silicide-based material containing titanium (Ti) and silicon (Si), and may further contain nitrogen (N) or oxygen (O). By including these elements, the reflectivity of exposure light or drawing light (light used when drawing a resist film during mask manufacturing) can be reduced. The nitrogen (N) content in the front anti-reflective layer 32 and the back anti-reflective layer 33 is preferably 10 to 55 atomic %. Moreover, the content rate of oxygen (O) is preferably 0 to 10 atomic %. The front anti-reflective layer 32 and the back anti-reflective layer 33 may not contain oxygen (O).
又，第1、第2實施方式之光罩基底10中，為了提高耐靜電破壞特性，遮光膜30之薄片電阻值較佳為40 Ω/sq以上，更佳為42 Ω/sq以上。例如藉由增加遮光膜30中含有之氮(N)或矽(Si)之量而可提高薄片電阻值。另一方面，若氮(N)或矽(Si)之含量增加，則導致遮光性降低(換言之透過率變高)。又，於矽之含量較大之情形時，與透明基板之蝕刻選擇性變小。根據該等，較佳為將遮光膜30之薄片電阻值設定為90 Ω/sq以下。於遮光膜30為僅包含遮光層31之單層構造之情形時，為了相同目的，遮光層31之薄片電阻值較佳為40 Ω/sq以上，此外更佳為90 Ω/sq以下。In addition, in the photomask base 10 of the first and second embodiments, in order to improve the electrostatic destruction resistance, the sheet resistance value of the light-shielding film 30 is preferably 40 Ω/sq or more, and more preferably 42 Ω/sq or more. For example, the sheet resistance value can be increased by increasing the amount of nitrogen (N) or silicon (Si) contained in the light-shielding film 30 . On the other hand, if the content of nitrogen (N) or silicon (Si) increases, the light-shielding property will decrease (in other words, the transmittance will increase). In addition, when the silicon content is large, the etching selectivity with the transparent substrate becomes smaller. Based on these factors, it is preferable to set the sheet resistance value of the light-shielding film 30 to 90 Ω/sq or less. When the light-shielding film 30 has a single-layer structure including only the light-shielding layer 31, for the same purpose, the sheet resistance value of the light-shielding layer 31 is preferably 40 Ω/sq or more, and more preferably 90 Ω/sq or less.
再者，正面抗反射層32及背面抗反射層33之膜厚相比遮光層31之膜厚非常小。因此，正面抗反射層32及背面抗反射層33之薄片電阻值小至可忽視之程度。因此，即便於遮光膜30包含正面抗反射層32及/或背面抗反射層33之情形時，亦可謂遮光膜30之薄片電阻值與遮光層31之薄片電阻值實質上相同。又，由於正面抗反射層32非常薄，故於使得用以測定薄片電阻值之探針接觸光罩基底10之遮光膜30時，探針穿透正面抗反射層32而接觸遮光層31。因此，即便於遮光層31上形成有正面抗反射層32之情形時，亦可謂遮光膜30之薄片電阻值實質上與遮光層31之薄片電阻值相同。如上所述，即便形成背面抗反射層33，其薄片電阻值亦小至可忽視之程度。Furthermore, the film thickness of the front anti-reflective layer 32 and the back anti-reflective layer 33 is very small compared to the film thickness of the light-shielding layer 31 . Therefore, the sheet resistance values of the front anti-reflective layer 32 and the back anti-reflective layer 33 are so small that they can be ignored. Therefore, even when the light-shielding film 30 includes the front anti-reflective layer 32 and/or the back anti-reflective layer 33 , it can be said that the sheet resistance value of the light-shielding film 30 and the sheet resistance value of the light-shielding layer 31 are substantially the same. In addition, since the front anti-reflective layer 32 is very thin, when the probe used to measure the sheet resistance value contacts the light-shielding film 30 of the photomask base 10 , the probe penetrates the front anti-reflective layer 32 and contacts the light-shielding layer 31 . Therefore, even when the front anti-reflective layer 32 is formed on the light-shielding layer 31 , it can be said that the sheet resistance value of the light-shielding film 30 is substantially the same as the sheet resistance value of the light-shielding layer 31 . As described above, even if the back anti-reflection layer 33 is formed, its sheet resistance is so small that it can be ignored.
根據發明人等之研究，於遮光膜之導電性較高(即薄片電阻值較小)之情形時，放電電流急遽流向已圖案化之遮光膜之一部分(於透明基板露出之區域包圍外周而成之孤立圖案等)，故認為該遮光膜之一部分會溶解，結果遮光膜圖案受損。According to the inventors' research, when the conductivity of the light-shielding film is high (that is, the sheet resistance value is small), the discharge current flows rapidly to a part of the patterned light-shielding film (which is formed by surrounding the outer periphery of the exposed area of the transparent substrate). (isolated pattern, etc.), it is believed that part of the light-shielding film will dissolve, resulting in damage to the light-shielding film pattern.
另一方面，如本發明所提出，於遮光膜之導電性較低(即薄片電阻值較大)之情形時，即便萬一產生有靜電放電，亦不易如導電性較高之遮光膜般產生放電電流急遽流向遮光膜圖案之情形，故認為遮光膜圖案不會溶解，結果可提高對於靜電破壞之耐受性。On the other hand, as proposed in the present invention, when the conductivity of the light-shielding film is low (that is, the sheet resistance value is large), even if electrostatic discharge occurs, it is less likely to occur than in a light-shielding film with higher conductivity. When the discharge current flows rapidly to the light-shielding film pattern, it is considered that the light-shielding film pattern will not dissolve, and as a result, the resistance to electrostatic damage can be improved.
藉由遮光膜30及/或遮光層31具有上述範圍之薄片電阻值，例如可有效抑制FPD製造用之大型且高清之光罩100及其原版即光罩基底10之靜電破壞。By having the light-shielding film 30 and/or the light-shielding layer 31 having a sheet resistance value in the above range, for example, the large-scale and high-definition photomask 100 used in FPD manufacturing and its original plate, that is, the photomask substrate 10, can be effectively suppressed from electrostatic damage.
第1、第2實施方式之光罩基底10之遮光膜30對於曝光之光具有遮光性。具體而言，遮光膜30之光學濃度(OD：Optical Density，光學密度)可為2以上。遮光膜30之光學濃度較佳為3以上，更佳為3.5以上，進而更佳為4以上。再者，光罩基底10於遮光膜30與透明基板20之間具備與該遮光膜30不同之其他膜之情形時，只要以使遮光膜30與該其他膜之積層狀態下之光學濃度成為上述範圍之方式設定遮光膜30之光學濃度即可。光學濃度可使用分光光度計或OD計等進行測定。The light-shielding film 30 of the mask base 10 of the first and second embodiments has light-shielding properties against exposure light. Specifically, the optical density (OD: Optical Density, optical density) of the light-shielding film 30 may be 2 or more. The optical density of the light-shielding film 30 is preferably 3 or more, more preferably 3.5 or more, and still more preferably 4 or more. Furthermore, when the mask base 10 is provided with another film different from the light-shielding film 30 between the light-shielding film 30 and the transparent substrate 20, the optical density in the laminated state of the light-shielding film 30 and the other film can be as described above. The optical density of the light-shielding film 30 can be set in a range. The optical concentration can be measured using a spectrophotometer, an OD meter, or the like.
遮光膜30之背面反射率於365 nm～436 nm之波長區域較佳為15%以下，更佳為12%以下，進而更佳為10%以下。或者，遮光膜30之背面反射率於365 nm～436 nm波長區域內之代表波長下，較佳為15%以下，更佳為12%以下，進而更佳為10%以下。又，遮光膜30之背面反射率於曝光之光包含j射線(波長313 nm)之情形時，對於313 nm至436 nm波長區域之光，較佳為15%以下，更佳為12%以下。較理想為，遮光膜30之背面反射率更佳為10%以下。或者，遮光膜30之背面反射率於313 nm～436 nm波長區域內之代表波長下，較佳為15%以下，更佳為12%以下，進而更佳為10%以下。又，遮光膜30之背面反射率於365 nm～436 nm之波長區域下為0.2%以上，對於313 nm至436 nm之波長區域之光較佳為0.2%以上。遮光膜30之正面反射率亦相同。The backside reflectance of the light-shielding film 30 is preferably 15% or less in the wavelength range of 365 nm to 436 nm, more preferably 12% or less, and further preferably 10% or less. Alternatively, the back surface reflectance of the light-shielding film 30 is preferably 15% or less, more preferably 12% or less, and even more preferably 10% or less at a representative wavelength in the wavelength range of 365 nm to 436 nm. In addition, when the exposure light includes j-rays (wavelength 313 nm), the backside reflectivity of the light-shielding film 30 is preferably 15% or less, and more preferably 12% or less for light in the wavelength range of 313 nm to 436 nm. More preferably, the back surface reflectivity of the light-shielding film 30 is 10% or less. Alternatively, the back surface reflectance of the light-shielding film 30 is preferably 15% or less, more preferably 12% or less, and even more preferably 10% or less at a representative wavelength in the wavelength range of 313 nm to 436 nm. In addition, the back surface reflectance of the light-shielding film 30 is 0.2% or more in the wavelength range of 365 nm to 436 nm, and preferably 0.2% or more for the light in the wavelength range of 313 nm to 436 nm. The front reflectivity of the light-shielding film 30 is also the same.
背面反射率及正面反射率可使用分光光度計等進行測定。The back surface reflectance and the front surface reflectance can be measured using a spectrophotometer or the like.
遮光膜30之膜厚較佳為60 nm以上，更佳為80 nm以上。另一方面，遮光膜30之膜厚較佳為200 nm以下，更佳為150 nm以下。又，遮光層31之膜厚較佳為50 nm以上，更佳為60 nm以上。另一方面，遮光層31之膜厚較佳為120 nm以下，更佳為100 nm以下。又，正面抗反射層32及背面抗反射層33之膜厚較佳為10 nm以上。另一方面，正面抗反射層32及背面抗反射層33之膜厚較佳為50 nm以下。The film thickness of the light-shielding film 30 is preferably 60 nm or more, and more preferably 80 nm or more. On the other hand, the film thickness of the light-shielding film 30 is preferably 200 nm or less, more preferably 150 nm or less. In addition, the film thickness of the light-shielding layer 31 is preferably 50 nm or more, more preferably 60 nm or more. On the other hand, the film thickness of the light-shielding layer 31 is preferably 120 nm or less, more preferably 100 nm or less. In addition, the film thickness of the front anti-reflective layer 32 and the back anti-reflective layer 33 is preferably 10 nm or more. On the other hand, the film thickness of the front anti-reflective layer 32 and the back anti-reflective layer 33 is preferably 50 nm or less.
於遮光膜30為多層構造(具有正面抗反射層32及背面抗反射層33中之至少任一者之構造)之情形時，遮光層31之厚度相對於遮光膜30整體之厚度之比率較佳為0.5以上，更佳為大於0.5，進而更佳為0.6以上。另一方面，遮光層31之厚度相對於遮光膜30整體之厚度之比率較佳為0.9以下。When the light-shielding film 30 has a multi-layer structure (a structure having at least one of the front anti-reflection layer 32 and the back anti-reflection layer 33), the ratio of the thickness of the light-shielding layer 31 to the thickness of the entire light-shielding film 30 is better. It is 0.5 or more, more preferably it is more than 0.5, and it is more preferably 0.6 or more. On the other hand, the ratio of the thickness of the light-shielding layer 31 to the thickness of the entire light-shielding film 30 is preferably 0.9 or less.
單層構造之遮光膜30於波長405 nm之光下之折射率n較佳為3.0以上。另一方面，單層構造之遮光膜30於波長405 nm之光下之折射率n較佳為4.5以下。又，單層構造之遮光膜30於波長405 nm之光下之消光係數k較佳為1.5以上，更佳為2.0以上。另一方面，單層構造之遮光膜30於波長405 nm之光下之消光係數k較佳為3.5以下，更佳為3.0以下。The refractive index n of the single-layer light-shielding film 30 under light with a wavelength of 405 nm is preferably above 3.0. On the other hand, the refractive index n of the single-layer light-shielding film 30 under light with a wavelength of 405 nm is preferably 4.5 or less. In addition, the extinction coefficient k of the single-layer light-shielding film 30 under light with a wavelength of 405 nm is preferably 1.5 or more, and more preferably 2.0 or more. On the other hand, the extinction coefficient k of the single-layer light-shielding film 30 under light with a wavelength of 405 nm is preferably 3.5 or less, more preferably 3.0 or less.
於遮光膜30為多層構造(具有正面抗反射層32及背面抗反射層33中之至少任一者之構造)之情形時，遮光層31於波長405 nm之光下之折射率n較佳為3.0以上。另一方面，遮光層31於波長405 nm之光下之折射率n較佳為4.5以下。又，遮光層31於波長405 nm之光下之消光係數k較佳為1.5以上，更佳為2.0以上。另一方面，遮光層31於波長405 nm之光下之消光係數k較佳為3.5以下，更佳為3.0以下。When the light-shielding film 30 has a multi-layer structure (a structure having at least one of the front anti-reflection layer 32 and the back anti-reflection layer 33), the refractive index n of the light-shielding layer 31 under light with a wavelength of 405 nm is preferably 3.0 or above. On the other hand, the refractive index n of the light-shielding layer 31 under light with a wavelength of 405 nm is preferably 4.5 or less. In addition, the extinction coefficient k of the light-shielding layer 31 under light with a wavelength of 405 nm is preferably 1.5 or more, and more preferably 2.0 or more. On the other hand, the extinction coefficient k of the light-shielding layer 31 under light with a wavelength of 405 nm is preferably 3.5 or less, more preferably 3.0 or less.
正面抗反射層32及背面抗反射層33於波長405 nm之光下之折射率n較佳為2.0以上。另一方面，正面抗反射層32及背面抗反射層33於波長405 nm之光下之折射率n較佳為2.8以下。又，正面抗反射層32及背面抗反射層33於波長405 nm之光下之消光係數k較佳為0.2以上。另一方面，正面抗反射層32及背面抗反射層33於波長405 nm之光下之消光係數k較佳為0.8以下。The refractive index n of the front anti-reflective layer 32 and the back anti-reflective layer 33 under light with a wavelength of 405 nm is preferably above 2.0. On the other hand, the refractive index n of the front anti-reflective layer 32 and the back anti-reflective layer 33 under light with a wavelength of 405 nm is preferably 2.8 or less. In addition, the extinction coefficient k of the front anti-reflective layer 32 and the back anti-reflective layer 33 under light with a wavelength of 405 nm is preferably 0.2 or more. On the other hand, the extinction coefficient k of the front anti-reflective layer 32 and the back anti-reflective layer 33 under light with a wavelength of 405 nm is preferably 0.8 or less.
遮光膜30可藉由濺鍍法等公知之成膜方法而形成。The light-shielding film 30 can be formed by a known film forming method such as sputtering.
＜蝕刻遮罩膜40＞ 第1實施方式之顯示裝置製造用光罩基底10於遮光膜30上，具備蝕刻選擇性與遮光膜30不同之蝕刻遮罩膜40。 <Etching mask film 40> The mask substrate 10 for manufacturing a display device according to the first embodiment is provided with an etching mask film 40 having an etching selectivity different from that of the light-shielding film 30 on the light-shielding film 30 .
蝕刻遮罩膜40配置於遮光膜30之上側(與透明基板20為相反側)，由對於蝕刻遮光膜30之蝕刻液具有蝕刻耐受性(蝕刻選擇性與遮光膜30不同)之材料構成。又，蝕刻遮罩膜40可具有遮擋曝光之光透過之功能。進而，蝕刻遮罩膜40亦可具有如下功能，即，以遮光膜30對於自遮光膜30側入射之光之膜面反射率於350 nm～436 nm之波長區域成為15%以下之方式降低膜面反射率。The etching mask film 40 is disposed on the upper side of the light-shielding film 30 (opposite to the transparent substrate 20 ), and is made of a material that has etching resistance (the etching selectivity is different from that of the light-shielding film 30 ) to the etching liquid used to etch the light-shielding film 30 . In addition, the etching mask film 40 may have the function of blocking exposure light from passing through. Furthermore, the etching mask film 40 may also have a function of reducing the film surface reflectance of the light-shielding film 30 to 15% or less in the wavelength range of 350 nm to 436 nm with respect to the light incident from the light-shielding film 30 side. Surface reflectivity.
蝕刻遮罩膜40較佳為由含有鉻(Cr)之鉻系材料構成。蝕刻遮罩膜40更佳為由含有鉻、且實質上不含有矽之材料構成。所謂實質上不含有矽，係指矽之含量未達2原子%(其中，遮光膜30與蝕刻遮罩膜40之界面之梯度組成區域除外)。作為鉻系材料，更具體而言，可列舉鉻(Cr)、或包含鉻(Cr)與氧(O)、氮(N)、碳(C)中之至少任一者之材料。又，作為鉻系材料，可列舉包含鉻(Cr)與氧(O)、氮(N)、碳(C)中之至少任一者，進而包含氟(F)之材料。例如，作為構成蝕刻遮罩膜40之材料，可列舉Cr、CrO、CrN、CrF、CrCO、CrCN、CrON、CrCON、及CrCONF。The etching mask film 40 is preferably made of a chromium-based material containing chromium (Cr). The etching mask film 40 is preferably made of a material containing chromium and substantially not containing silicon. The term “substantially does not contain silicon” means that the content of silicon does not reach 2 atomic % (excluding the gradient composition region at the interface between the light-shielding film 30 and the etching mask film 40). More specific examples of the chromium-based material include chromium (Cr) or a material containing at least one of chromium (Cr) and oxygen (O), nitrogen (N), and carbon (C). Examples of the chromium-based material include materials containing chromium (Cr), at least one of oxygen (O), nitrogen (N), and carbon (C), and further containing fluorine (F). For example, examples of materials constituting the etching mask film 40 include Cr, CrO, CrN, CrF, CrCO, CrCN, CrON, CrCON, and CrCONF.
蝕刻遮罩膜40可藉由濺鍍法等公知之成膜方法而形成。The etching mask film 40 can be formed by a known film forming method such as sputtering.
蝕刻遮罩膜40根據功能而可包含組成均勻之單一之膜。又，蝕刻遮罩膜40亦可包含組成不同之複數之膜。又，蝕刻遮罩膜40可包含其組成於厚度方向上連續變化之單一之膜。The etch mask film 40 may comprise a single film of uniform composition depending on the function. In addition, the etching mask film 40 may also include a plurality of films with different compositions. In addition, the etching mask film 40 may include a single film whose composition continuously changes in the thickness direction.
再者，圖1所示之第1實施方式之光罩基底10於遮光膜30上具備蝕刻遮罩膜40。第1實施方式之光罩基底10包含如下構造之光罩基底10，即，於遮光膜30上具備蝕刻遮罩膜40，且於蝕刻遮罩膜40上具備抗蝕膜。Furthermore, the photomask base 10 of the first embodiment shown in FIG. 1 is provided with an etching mask film 40 on the light-shielding film 30 . The photomask substrate 10 of the first embodiment includes a photomask substrate 10 having a structure including an etching mask film 40 on the light-shielding film 30 and a resist film on the etching mask film 40 .
＜光罩基底10之製造方法＞ 其次，對光罩基底10之製造方法進行說明。圖1所示之第1實施方式之光罩基底10藉由遮光膜30之形成步驟、與蝕刻遮罩膜40之形成步驟而製造。圖2所示之第2實施方式之光罩基底10藉由遮光膜30之形成步驟而製造。 <Manufacturing method of photomask substrate 10> Next, a method of manufacturing the photomask base 10 will be described. The photomask substrate 10 of the first embodiment shown in FIG. 1 is manufactured through the steps of forming the light-shielding film 30 and the step of forming the etching masking film 40 . The photomask base 10 of the second embodiment shown in FIG. 2 is manufactured through the step of forming the light-shielding film 30 .
以下，對各步驟詳細地進行說明。Each step is explained in detail below.
≪遮光膜形成步驟≫ 首先，準備透明基板20。透明基板20只要相對於曝光之光為透明，則可由選自合成石英玻璃、石英玻璃、鋁矽酸鹽玻璃、鈉鈣玻璃、及低熱膨脹玻璃(SiO 2-TiO 2玻璃等)等之玻璃材料構成。 ≪Light-shielding film formation step≫ First, the transparent substrate 20 is prepared. As long as the transparent substrate 20 is transparent to the exposure light, it can be made of glass materials selected from synthetic quartz glass, quartz glass, aluminosilicate glass, soda-lime glass, and low thermal expansion glass (SiO 2 -TiO 2 glass, etc.) composition.
其次，於透明基板20上藉由濺鍍法而形成遮光膜30。Next, the light-shielding film 30 is formed on the transparent substrate 20 by sputtering.
遮光膜30之成膜可使用特定之濺鍍靶且於特定之濺鍍氣體環境中進行。所謂特定之濺鍍靶，例如係包含成為構成遮光膜30之材料之主成分之鈦與矽之鈦矽化物靶、或包含鈦、矽及氮之鈦矽化物靶。所謂特定之濺鍍氣體環境，例如係包含含有選自由氦氣、氖氣、氬氣、氪氣及氙氣所組成之群中之至少一種之惰性氣體的濺鍍氣體環境、或包含含有上述惰性氣體、氮氣、及視情形選自由氧氣、二氧化碳氣體、一氧化氮氣體及二氧化氮氣體所組成之群之氣體之混合氣體的濺鍍氣體環境。遮光膜30之形成可於進行濺鍍時成膜室內之氣體壓力為0.3 Pa以上3.0 Pa以下、較佳為0.43 Pa以上2.0 Pa以下之狀態下進行。The light-shielding film 30 can be formed using a specific sputtering target and in a specific sputtering gas environment. The specific sputtering target is, for example, a titanium silicide target containing titanium and silicon, which are the main components of the material constituting the light-shielding film 30, or a titanium silicide target containing titanium, silicon, and nitrogen. The specific sputtering gas environment includes, for example, a sputtering gas environment containing at least one inert gas selected from the group consisting of helium, neon, argon, krypton, and xenon, or a sputtering gas environment containing the above inert gas. , nitrogen, and a sputtering gas environment of a mixed gas selected from the group consisting of oxygen, carbon dioxide gas, nitric oxide gas, and nitrogen dioxide gas as appropriate. The light-shielding film 30 can be formed in a state where the gas pressure in the film-forming chamber during sputtering is 0.3 Pa or more and 3.0 Pa or less, preferably 0.43 Pa or more and 2.0 Pa or less.
調整遮光膜30之組成及厚度，使得遮光膜30成為上述光學濃度。遮光膜30之組成可根據構成濺鍍靶之元素之含有比率(例如，鈦之含有率與矽之含有率之比)、濺鍍氣體之組成及流量等而控制。遮光膜30之厚度可根據濺鍍功率、及濺鍍時間等而控制。又，遮光膜30較佳為使用連續式濺鍍裝置形成。於濺鍍裝置為連續式濺鍍裝置之情形時，根據透明基板之搬送速度亦可控制遮光膜30之厚度。The composition and thickness of the light-shielding film 30 are adjusted so that the light-shielding film 30 has the above-mentioned optical density. The composition of the light-shielding film 30 can be controlled based on the content ratio of elements constituting the sputtering target (for example, the ratio of the content ratio of titanium to the content ratio of silicon), the composition and flow rate of the sputtering gas, and the like. The thickness of the light-shielding film 30 can be controlled according to the sputtering power, sputtering time, etc. In addition, the light-shielding film 30 is preferably formed using a continuous sputtering device. When the sputtering device is a continuous sputtering device, the thickness of the light-shielding film 30 can also be controlled according to the conveying speed of the transparent substrate.
於遮光膜30包含單一之膜(遮光層31)之情形時，適當調整濺鍍氣體之組成及流量而僅進行1次上述成膜製程。於遮光膜30包含組成不同之複數個膜之情形時，例如遮光膜30除包含遮光層31外還包含正面抗反射層32及/或背面抗反射層33之情形時，適當調整濺鍍氣體之組成及流量而進行複數次上述成膜製程。亦可使用構成濺鍍靶之元素之含有比率不同之靶來成膜遮光膜30。於進行複數次成膜製程之情形時，亦可於每一次成膜製程中變更施加至濺鍍靶之濺鍍功率。When the light-shielding film 30 includes a single film (light-shielding layer 31 ), the composition and flow rate of the sputtering gas are appropriately adjusted and the above-mentioned film forming process is performed only once. When the light-shielding film 30 includes a plurality of films with different compositions, for example, when the light-shielding film 30 includes a front anti-reflective layer 32 and/or a back anti-reflective layer 33 in addition to the light-shielding layer 31 , the sputtering gas should be appropriately adjusted. The above-mentioned film-forming process is performed multiple times according to the composition and flow rate. The light-shielding film 30 may be formed using targets having different content ratios of elements constituting the sputtering target. When a plurality of film forming processes are performed, the sputtering power applied to the sputtering target can also be changed in each film forming process.
≪表面處理步驟≫ 遮光膜30可包含除含有鈦、矽及氮以外還含有氧之鈦矽化物材料(氮氧化鈦矽化物)。此處，氧之含量超過0原子%且為5原子%以下。如此於遮光膜30包含氧之情形時，為了抑制因存在鈦之氧化物而導致蝕刻液滲入遮光膜30表面，亦可進行調整遮光膜30之表面氧化狀態之表面處理步驟。再者，於遮光膜30包含含有鈦、矽、及氮之鈦矽化物之氮化物之情形時，與上述含有氧之鈦矽化物材料相比，鈦之氧化物之含有率較小。因此，於遮光膜30之材料為鈦矽化物之氮化物之情形時，可進行上述表面處理步驟，亦可不進行。 ≪Surface treatment steps≫ The light-shielding film 30 may include a titanium silicide material (titanium oxynitride silicide) containing oxygen in addition to titanium, silicon, and nitrogen. Here, the oxygen content exceeds 0 atomic % and is 5 atomic % or less. When the light-shielding film 30 contains oxygen, in order to prevent the etching liquid from penetrating into the surface of the light-shielding film 30 due to the presence of titanium oxide, a surface treatment step for adjusting the surface oxidation state of the light-shielding film 30 may also be performed. Furthermore, when the light-shielding film 30 includes a nitride of titanium silicide containing titanium, silicon, and nitrogen, the content rate of titanium oxide is smaller than that of the titanium silicide material containing oxygen. Therefore, when the material of the light-shielding film 30 is titanium silicide nitride, the above surface treatment step may or may not be performed.
作為調整遮光膜30(遮光層31或正面抗反射層32)之表面氧化狀態之表面處理步驟，可列舉以酸性水溶液進行表面處理之方法、以鹼性水溶液進行表面處理之方法、及以灰化等乾式處理進行表面處理之方法等。As a surface treatment step for adjusting the surface oxidation state of the light-shielding film 30 (light-shielding layer 31 or front anti-reflective layer 32), surface treatment with an acidic aqueous solution, surface treatment with an alkaline aqueous solution, and ashing Surface treatment methods such as dry treatment, etc.
以此方式，可獲得第2實施方式之光罩基底10。In this way, the photomask base 10 of the second embodiment can be obtained.
≪蝕刻遮罩膜形成步驟≫ 第1實施方式之光罩基底10進而具有蝕刻遮罩膜40。該情形時，進而進行以下蝕刻遮罩膜形成步驟。再者，蝕刻遮罩膜40較佳為由含有鉻、且實質上不含有矽之材料構成。 ≪Etching mask film formation steps≫ The photomask base 10 of the first embodiment further has an etching mask film 40 . In this case, the following etching mask film forming step is further performed. Furthermore, the etching mask film 40 is preferably made of a material containing chromium and substantially not containing silicon.
遮光膜形成步驟之後，視需要進行調整遮光膜30(遮光層31或正面抗反射層32)表面之表面氧化狀態之表面處理，其後，藉由濺鍍法而於遮光膜30上形成蝕刻遮罩膜40。蝕刻遮罩膜40較佳為使用連續式濺鍍裝置形成。於濺鍍裝置為連續式濺鍍裝置之情形時，藉由透明基板20之搬送速度亦可控制蝕刻遮罩膜40之厚度。After the light-shielding film forming step, if necessary, a surface treatment is performed to adjust the surface oxidation state of the light-shielding film 30 (light-shielding layer 31 or front anti-reflective layer 32). Thereafter, an etching mask is formed on the light-shielding film 30 by a sputtering method. Cover film 40. The etching mask film 40 is preferably formed using a continuous sputtering device. When the sputtering device is a continuous sputtering device, the thickness of the etching mask film 40 can also be controlled by the conveying speed of the transparent substrate 20 .
蝕刻遮罩膜40之成膜可使用包含鉻或鉻化合物(氧化鉻、氮化鉻、碳化鉻、氮氧化鉻、氮化碳化鉻、及氮氧化碳化鉻等)之濺鍍靶，於包含惰性氣體之濺鍍氣體環境、或包含惰性氣體與活性氣體之混合氣體之濺鍍氣體環境下進行。惰性氣體例如可包含選自由氦氣、氖氣、氬氣、氪氣及氙氣所組成之群中之至少一種。活性氣體可包含選自由氧氣、氮氣、一氧化氮氣體、二氧化氮氣體、二氧化碳氣體、烴系氣體及氟系氣體所組成之群中之至少一種。作為烴系氣體，例如可列舉甲烷氣體、丁烷氣體、丙烷氣體及苯乙烯氣體等。The etching mask film 40 can be formed by using a sputtering target containing chromium or a chromium compound (chromium oxide, chromium nitride, chromium carbide, chromium oxynitride, chromium oxycarbide, chromium oxycarbide, etc.), containing an inert It is carried out in a sputtering gas environment of gas, or a sputtering gas environment of a mixed gas containing an inert gas and an active gas. The inert gas may include, for example, at least one selected from the group consisting of helium, neon, argon, krypton, and xenon. The active gas may include at least one selected from the group consisting of oxygen, nitrogen, nitric oxide gas, nitrogen dioxide gas, carbon dioxide gas, hydrocarbon-based gas, and fluorine-based gas. Examples of the hydrocarbon-based gas include methane gas, butane gas, propane gas, styrene gas, and the like.
於蝕刻遮罩膜40包含組成均勻之單一之膜之情形時，不改變濺鍍氣體之組成及流量而僅進行1次上述成膜製程。於蝕刻遮罩膜40包含組成不同之複數個膜之情形時，進行複數次上述成膜製程，且在每一次成膜製程中改變濺鍍氣體之組成及流量。於蝕刻遮罩膜40包含組成在厚度方向上連續變化之單一之膜之情形時，僅進行1次上述成膜製程，並且使濺鍍氣體之組成及流量隨成膜製程之經過時間而變化。When the etching mask film 40 includes a single film with a uniform composition, the composition and flow rate of the sputtering gas are not changed and the above-mentioned film forming process is only performed once. When the etching mask film 40 includes a plurality of films with different compositions, the above-mentioned film forming process is performed a plurality of times, and the composition and flow rate of the sputtering gas are changed in each film forming process. When the etching mask film 40 includes a single film whose composition continuously changes in the thickness direction, the above-mentioned film forming process is performed only once, and the composition and flow rate of the sputtering gas are changed with the elapsed time of the film forming process.
以此方式，可獲得具有蝕刻遮罩膜40之第1實施方式之光罩基底10。In this way, the photomask base 10 of the first embodiment having the etching mask film 40 can be obtained.
再者，圖1所示之第1實施方式之光罩基底10於遮光膜30上具備蝕刻遮罩膜40，故於製造光罩基底10時，進行蝕刻遮罩膜形成步驟。又，當製造於遮光膜30上具備蝕刻遮罩膜40、且於蝕刻遮罩膜40上具備抗蝕膜之光罩基底10時，於蝕刻遮罩膜形成步驟後，於蝕刻遮罩膜40上形成抗蝕膜。又，對於圖2所示之第2實施方式之光罩基底10，製造於遮光膜30上具備抗蝕膜之光罩基底10時，於遮光膜形成步驟後形成抗蝕膜。Furthermore, the photomask base 10 of the first embodiment shown in FIG. 1 is provided with the etching mask film 40 on the light shielding film 30. Therefore, when manufacturing the photomask base 10, an etching mask film forming step is performed. Furthermore, when the photomask base 10 having the etching mask film 40 on the light shielding film 30 and the resist film on the etching mask film 40 is manufactured, after the etching mask film forming step, the etching mask film 40 is A resist film is formed on it. Furthermore, when manufacturing the photomask base 10 having the resist film on the light-shielding film 30 of the second embodiment shown in FIG. 2 , the resist film is formed after the light-shielding film forming step.
＜光罩100之製造方法＞ 其次，對光罩100之製造方法進行說明。 <Manufacturing method of photomask 100> Next, a method of manufacturing the photomask 100 will be described.
＜第1實施方式之光罩100之製造方法＞ 圖4A至圖4D係用以說明使用圖1所示之第1實施方式之光罩基底10製造光罩100之方法之模式圖。第1實施方式之光罩100之製造方法包括以下步驟，即，準備光罩基底10；於蝕刻遮罩膜40上形成抗蝕膜，將由抗蝕膜形成之抗蝕膜圖案作為遮罩對蝕刻遮罩膜40進行濕式蝕刻，於遮光膜30上形成蝕刻遮罩膜圖案40a；及將蝕刻遮罩膜圖案40a作為遮罩對遮光膜30進行濕式蝕刻，於透明基板20上形成轉印用圖案30a。 <Method for manufacturing the photomask 100 of the first embodiment> 4A to 4D are schematic diagrams for explaining a method of manufacturing the photomask 100 using the photomask substrate 10 of the first embodiment shown in FIG. 1 . The manufacturing method of the photomask 100 of the first embodiment includes the following steps: preparing the photomask substrate 10; forming a resist film on the etching mask film 40; and using the resist film pattern formed by the resist film as a mask for etching. The mask film 40 is wet-etched to form an etching mask film pattern 40a on the light-shielding film 30; and the light-shielding film 30 is wet-etched using the etching mask film pattern 40a as a mask to form a transfer pattern on the transparent substrate 20. Use pattern 30a.
再者，本說明書中之轉印用圖案係藉由將形成於透明基板20上之至少1個光學膜圖案化而獲得者。上述光學膜可設為遮光膜30、或遮光膜30及蝕刻遮罩膜40，亦可進而包含其他膜(相位偏移膜、半透光膜、導電性膜等)。即，轉印用圖案可包含經圖案化之遮光膜、或經圖案化之遮光膜及蝕刻遮罩膜，亦可進而包含經圖案化之其他膜。In addition, the transfer pattern in this specification is obtained by patterning at least one optical film formed on the transparent substrate 20 . The above-mentioned optical film may be the light-shielding film 30, or the light-shielding film 30 and the etching mask film 40, and may further include other films (phase shift film, semi-transmissive film, conductive film, etc.). That is, the transfer pattern may include a patterned light-shielding film, or a patterned light-shielding film and an etching mask film, or may further include other patterned films.
以下，參照圖4A至圖4D，對第1實施方式之光罩100之製造方法具體地進行說明。Hereinafter, the manufacturing method of the photomask 100 of the first embodiment will be specifically described with reference to FIGS. 4A to 4D .
首先，於圖1所示之光罩基底10之蝕刻遮罩膜40上形成抗蝕膜。其次，藉由於抗蝕膜上進行所需圖案之描繪、顯影而形成抗蝕膜圖案50(參照圖4A，抗蝕膜圖案50之形成步驟)。其次，將該抗蝕膜圖案50作為遮罩對蝕刻遮罩膜40進行濕式蝕刻，於遮光膜30上形成蝕刻遮罩膜圖案40a(參照圖4B，蝕刻遮罩膜圖案40a之形成步驟)。其次，將上述蝕刻遮罩膜圖案40a作為遮罩，對遮光膜30進行濕式蝕刻而於透明基板20上形成遮光膜圖案30a(參照圖4C，遮光膜圖案30a之形成步驟)。其後，可進而包含將蝕刻遮罩膜圖案40a剝離之步驟(參照圖4D)。First, a resist film is formed on the etching mask film 40 of the photomask substrate 10 shown in FIG. 1 . Next, the resist film pattern 50 is formed by drawing and developing a desired pattern on the resist film (refer to FIG. 4A , the step of forming the resist film pattern 50). Next, the etching mask film 40 is wet-etched using the resist film pattern 50 as a mask to form the etching mask film pattern 40a on the light-shielding film 30 (refer to FIG. 4B , steps for forming the etching mask film pattern 40a). . Next, using the above-mentioned etching mask film pattern 40a as a mask, the light-shielding film 30 is wet-etched to form the light-shielding film pattern 30a on the transparent substrate 20 (refer to FIG. 4C, the step of forming the light-shielding film pattern 30a). Thereafter, the step of peeling off the etching mask film pattern 40a may be further included (see FIG. 4D).
更具體而言，於抗蝕膜圖案50之形成步驟中，首先，於光罩基底10之蝕刻遮罩膜40上形成抗蝕膜。使用之抗蝕膜材料並未特別限制。抗蝕膜例如只要係對具有選自350 nm～436 nm波長區域之任一波長之雷射光感光者即可。又，抗蝕膜亦可為正型、負型之任一者。More specifically, in the step of forming the resist film pattern 50, first, a resist film is formed on the etching mask film 40 of the photomask substrate 10. The resist film material used is not particularly limited. For example, the resist film may be one that is sensitive to laser light having any wavelength selected from the wavelength range of 350 nm to 436 nm. In addition, the resist film may be either a positive type or a negative type.
其後，使用具有選自350 nm～436 nm波長區域之任一波長之雷射光，於抗蝕膜描繪所需之圖案。描繪於抗蝕膜之圖案係形成於遮光膜30之圖案。作為描繪於抗蝕膜之圖案，可列舉線與間隙圖案及孔圖案。Thereafter, laser light with any wavelength selected from the wavelength range of 350 nm to 436 nm is used to draw the desired pattern on the resist film. The pattern drawn on the resist film is a pattern formed on the light-shielding film 30 . Examples of patterns drawn on the resist film include line and space patterns and hole patterns.
其後，利用特定之顯影液對抗蝕膜進行顯影，如圖4A所示，於蝕刻遮罩膜40上形成抗蝕膜圖案50。Thereafter, the resist film is developed using a specific developer, and as shown in FIG. 4A , a resist film pattern 50 is formed on the etching mask film 40 .
≪蝕刻遮罩膜圖案40a之形成步驟≫ 於蝕刻遮罩膜圖案40a之形成步驟中，首先，將抗蝕膜圖案50作為遮罩對蝕刻遮罩膜40進行蝕刻，形成蝕刻遮罩膜圖案40a。蝕刻遮罩膜40可由包含鉻(Cr)之鉻系材料形成。對蝕刻遮罩膜40進行蝕刻之蝕刻液只要係可選擇性地對蝕刻遮罩膜40進行蝕刻者，則並不特別限制。具體而言，可列舉包含硝酸鈰銨與過氯酸之蝕刻液。 ≪Steps for forming etching mask film pattern 40a≫ In the step of forming the etching mask film pattern 40a, first, the etching mask film 40 is etched using the resist film pattern 50 as a mask to form the etching mask film pattern 40a. The etching mask film 40 may be formed of a chromium-based material including chromium (Cr). The etching liquid used to etch the etching mask film 40 is not particularly limited as long as it can selectively etch the etching mask film 40 . Specific examples include an etching solution containing ceric ammonium nitrate and perchloric acid.
其後，使用抗蝕劑剝離液或藉由灰化而如圖4B所示般將抗蝕膜圖案50剝離。視情形，亦可不剝離抗蝕膜圖案50而進行接下來的遮光膜圖案30a之形成步驟。Thereafter, the resist film pattern 50 is peeled off as shown in FIG. 4B using a resist stripping liquid or ashing. Depending on the situation, the next step of forming the light-shielding film pattern 30a may be performed without peeling off the resist film pattern 50.
≪遮光膜圖案30a之形成步驟≫ 於遮光膜圖案30a之形成步驟中，將蝕刻遮罩膜圖案40a作為遮罩對遮光膜30進行濕式蝕刻，如圖4C所示形成遮光膜圖案30a。作為遮光膜圖案30a，可列舉線與間隙圖案及孔圖案。對遮光膜30進行蝕刻之蝕刻液只要係可選擇性地蝕刻遮光膜30者，則並不特別限制。例如可列舉蝕刻液A(包含氟化氫銨與過氧化氫之蝕刻液等)或蝕刻液B(包含氟化銨、磷酸、及過氧化氫之蝕刻液等)。 ≪Steps for forming light-shielding film pattern 30a≫ In the step of forming the light-shielding film pattern 30a, the light-shielding film pattern 30 is wet-etched using the etching masking film pattern 40a as a mask to form the light-shielding film pattern 30a as shown in FIG. 4C. Examples of the light-shielding film pattern 30a include a line and space pattern and a hole pattern. The etching liquid for etching the light-shielding film 30 is not particularly limited as long as it can selectively etch the light-shielding film 30 . Examples include etching liquid A (an etching liquid containing ammonium bifluoride and hydrogen peroxide, etc.) or etching liquid B (an etching liquid containing ammonium fluoride, phosphoric acid, and hydrogen peroxide, etc.).
為了使遮光膜圖案30a之剖面形狀良好，較佳為以較遮光膜圖案30a中透明基板20露出之前之時間(適量蝕刻時間)長的時間(過蝕刻時間)進行濕式蝕刻。作為過蝕刻時間，若考慮對透明基板20之影響等，則較佳為設為對適量蝕刻時間加上該適量蝕刻時間之20%之時間所得的時間內，更佳為設為加上該適量蝕刻時間之10%之時間所得的時間內。In order to make the cross-sectional shape of the light-shielding film pattern 30a good, it is preferable to perform wet etching for a longer time (over-etching time) than the time before the transparent substrate 20 is exposed in the light-shielding film pattern 30a (an appropriate etching time). As the over-etching time, considering the impact on the transparent substrate 20 and the like, the over-etching time is preferably set to the time obtained by adding 20% of the appropriate etching time to the appropriate etching time, and more preferably, the over-etching time is set to be the time plus the appropriate amount. The time obtained is 10% of the etching time.
其後，視需要將蝕刻遮罩膜圖案40a剝離，獲得光罩100(圖4D)。再者，於不剝離抗蝕膜圖案50而進行遮光膜圖案30a之形成步驟之情形時，於剝離蝕刻遮罩膜圖案40a之前，使用抗蝕劑剝離液或藉由灰化將抗蝕膜圖案50剝離。Thereafter, if necessary, the etching mask film pattern 40a is peeled off to obtain the photomask 100 (FIG. 4D). Furthermore, when the step of forming the light-shielding film pattern 30a is performed without peeling off the resist film pattern 50, the resist film pattern is removed using a resist stripping liquid or ashing before peeling off the etching mask film pattern 40a. 50 peel.
以此方式，可獲得光罩100。即，第1實施方式之光罩100具有之轉印用圖案可包含遮光膜圖案30a，進而亦可包含蝕刻遮罩膜圖案40a。再者，於蝕刻遮罩膜40包含含有鉻(Cr)之鉻系材料之情形時，自提高耐靜電破壞特性之觀點而言，較佳為將蝕刻遮罩膜40剝離。In this way, the photomask 100 can be obtained. That is, the transfer pattern of the photomask 100 of the first embodiment may include the light-shielding film pattern 30a, and further may include the etching masking film pattern 40a. Furthermore, when the etching mask film 40 contains a chromium-based material containing chromium (Cr), from the viewpoint of improving the electrostatic destruction resistance, it is preferable to peel off the etching mask film 40 .
根據第1實施方式之光罩100之製造方法，由於使用圖1所示之光罩基底10，故可形成邊緣剖面形狀良好之遮光膜圖案30a。According to the manufacturing method of the photomask 100 of the first embodiment, since the photomask base 10 shown in FIG. 1 is used, the light-shielding film pattern 30a with a good edge cross-sectional shape can be formed.
又，可降低遮光膜圖案30a之形成步驟中之搭載效應。因此，可製造能夠精度良好地轉印包含高清之遮光膜圖案30a之轉印用圖案之光罩100。如此製造之光罩100可應對線與間隙圖案及/或接觸孔之微細化。In addition, the piggyback effect in the formation step of the light-shielding film pattern 30a can be reduced. Therefore, it is possible to manufacture the photomask 100 that can accurately transfer the transfer pattern including the high-definition light-shielding film pattern 30a. The photomask 100 thus manufactured can cope with the miniaturization of line and space patterns and/or contact holes.
進而，如下所述，藉由將遮光膜圖案30a之薄片電阻值設為40 Ω/sq以上而可提高耐靜電破壞特性。Furthermore, as described below, by setting the sheet resistance value of the light-shielding film pattern 30a to 40 Ω/sq or more, the electrostatic destruction resistance can be improved.
≪第2實施方式之光罩100之製造方法≫ 圖5A至圖5C係用以說明使用圖2所示之光罩基底10製造光罩100之方法之模式圖。第2實施方式之光罩100之製造方法包括以下步驟，即，準備光罩基底10；於遮光膜30上形成抗蝕膜，將由抗蝕膜形成之抗蝕膜圖案作為遮罩對遮光膜30進行濕式蝕刻，於透明基板20上形成轉印用圖案。 ≪Method for manufacturing photomask 100 of second embodiment≫ 5A to 5C are schematic diagrams illustrating a method of manufacturing the photomask 100 using the photomask substrate 10 shown in FIG. 2 . The manufacturing method of the photomask 100 of the second embodiment includes the following steps: preparing the photomask substrate 10; forming a resist film on the light-shielding film 30; and using the resist film pattern formed by the resist film as a mask for the light-shielding film 30 Wet etching is performed to form a transfer pattern on the transparent substrate 20 .
以下，參照圖5A至圖5C，對第2實施方式之光罩100之製造方法具體地進行說明。Hereinafter, the manufacturing method of the photomask 100 of the second embodiment will be specifically described with reference to FIGS. 5A to 5C .
首先，於圖2所示之光罩基底10上形成抗蝕膜。其次，藉由於抗蝕膜上進行所需圖案之描繪、顯影而形成抗蝕膜圖案50(圖5A，抗蝕膜圖案50之形成步驟)。其次，將該抗蝕膜圖案50作為遮罩對遮光膜30進行濕式蝕刻，於透明基板20上形成遮光膜圖案30a(圖5B及圖5C，遮光膜圖案30a之形成步驟)。First, a resist film is formed on the photomask substrate 10 shown in FIG. 2 . Next, the resist film pattern 50 is formed by drawing and developing a desired pattern on the resist film (FIG. 5A, step of forming the resist film pattern 50). Next, the resist film pattern 50 is used as a mask to wet-etch the light-shielding film 30 to form the light-shielding film pattern 30a on the transparent substrate 20 (FIG. 5B and FIG. 5C, steps of forming the light-shielding film pattern 30a).
更具體而言，於抗蝕膜圖案之形成步驟中，首先，於圖2所示之第2實施方式之光罩基底10之遮光膜30上形成抗蝕膜。使用之抗蝕膜材料與以上說明之材料相同。再者，視需要，於形成抗蝕膜之前，為了使遮光膜30(遮光層31或正面抗反射層32)與抗蝕膜之密接性良好，可對遮光膜30進行表面改質處理。與上述同樣地，於形成抗蝕膜之後，例如使用具有選自350 nm～436 nm波長區域之任一波長之雷射光，將所需之圖案描繪於抗蝕膜。其後，利用特定之顯影液對抗蝕膜進行顯影，如圖5A所示，於遮光膜30上形成抗蝕膜圖案50。More specifically, in the step of forming the resist film pattern, first, a resist film is formed on the light-shielding film 30 of the photomask substrate 10 of the second embodiment shown in FIG. 2 . The resist film material used is the same as that described above. Furthermore, if necessary, before forming the resist film, in order to ensure good adhesion between the light-shielding film 30 (light-shielding layer 31 or front anti-reflective layer 32) and the resist film, the light-shielding film 30 may be surface modified. In the same manner as above, after the resist film is formed, a desired pattern is drawn on the resist film using, for example, laser light having any wavelength selected from the wavelength range of 350 nm to 436 nm. Thereafter, the resist film is developed using a specific developer, and as shown in FIG. 5A , a resist film pattern 50 is formed on the light-shielding film 30 .
≪遮光膜圖案30a之形成步驟≫ 於遮光膜圖案30a之形成步驟中，將抗蝕膜圖案50作為遮罩對遮光膜30進行蝕刻，如圖5B所示，形成遮光膜圖案30a。對遮光膜30進行蝕刻之蝕刻液及過蝕刻時間與上述圖4C所示之實施方式中之說明相同。 ≪Steps for forming light-shielding film pattern 30a≫ In the step of forming the light-shielding film pattern 30a, the light-shielding film 30 is etched using the resist film pattern 50 as a mask. As shown in FIG. 5B, the light-shielding film pattern 30a is formed. The etching liquid and over-etching time for etching the light-shielding film 30 are the same as those described in the embodiment shown in FIG. 4C .
其後，使用抗蝕劑剝離液或藉由灰化將抗蝕膜圖案50剝離(圖5C)。Thereafter, the resist film pattern 50 is peeled off using a resist stripping liquid or ashing (Fig. 5C).
以此方式，可獲得光罩100。再者，第2實施方式之光罩100所具有之轉印用圖案僅由遮光膜圖案30a構成，但亦可進而包含其他膜圖案。作為其他膜，例如可列舉相位偏移膜、半透光膜、導電性膜等。In this way, the photomask 100 can be obtained. In addition, the transfer pattern of the photomask 100 of the second embodiment is composed only of the light-shielding film pattern 30a, but may further include other film patterns. Examples of other films include phase shift films, semi-transmissive films, conductive films, and the like.
根據第2實施方式之光罩100之製造方法，由於使用圖2所示之光罩基底10，故可形成邊緣剖面形狀良好之遮光膜圖案30a。According to the manufacturing method of the photomask 100 of the second embodiment, since the photomask base 10 shown in FIG. 2 is used, the light-shielding film pattern 30a with a good edge cross-sectional shape can be formed.
又，可降低遮光膜圖案30a之形成步驟中之搭載效應。因此，可製造能夠精度良好地轉印包含高清之遮光膜圖案30a之轉印用圖案之光罩100。如此製造之光罩100可應對線與間隙圖案及/或接觸孔之微細化。In addition, the piggyback effect in the formation step of the light-shielding film pattern 30a can be reduced. Therefore, it is possible to manufacture the photomask 100 that can accurately transfer the transfer pattern including the high-definition light-shielding film pattern 30a. The photomask 100 thus manufactured can cope with the miniaturization of line and space patterns and/or contact holes.
進而，如下所述，藉由將遮光膜圖案30a之薄片電阻值設為40 Ω/sq以上而可提高耐靜電破壞特性。Furthermore, as described below, by setting the sheet resistance value of the light-shielding film pattern 30a to 40 Ω/sq or more, the electrostatic destruction resistance can be improved.
＜顯示裝置之製造方法＞ 對第1、第2實施方式之顯示裝置之製造方法進行說明。第1、第2實施方式之顯示裝置之製造方法包括曝光步驟，該曝光步驟係將上述實施方式之光罩100載置於曝光裝置之光罩台，將形成於光罩100上之轉印用圖案曝光轉印至形成於顯示裝置用基板上之抗蝕膜。 ＜Manufacturing method of display device＞ The manufacturing method of the display device according to the first and second embodiments will be described. The manufacturing method of the display device according to the first and second embodiments includes an exposure step in which the photomask 100 of the above embodiment is placed on the photomask stage of the exposure device, and the transfer pattern formed on the photomask 100 is The pattern is exposed and transferred to the resist film formed on the display device substrate.
具體而言，第1、第2實施方式之顯示裝置之製造方法包括以下步驟，即，將使用上述光罩基底10製造之光罩100載置於曝光裝置之光罩台(遮罩載置步驟)、及將轉印用圖案曝光轉印至顯示裝置用基板上之抗蝕膜(曝光步驟)。以下，詳細說明各步驟。Specifically, the manufacturing method of the display device according to the first and second embodiments includes the following steps: placing the mask 100 produced using the mask base 10 on the mask stage of the exposure device (mask placing step) ), and exposing and transferring the transfer pattern to the resist film on the display device substrate (exposure step). Each step is explained in detail below.
≪遮罩載置步驟≫ 於遮罩載置步驟中，將第1、第2實施方式之光罩100載置於曝光裝置之光罩台。此處，光罩100配置成隔著曝光裝置之投影光學系統而與形成於顯示裝置用基板上之抗蝕膜對向。 ≪Mask placement steps≫ In the mask placing step, the mask 100 of the first and second embodiments is placed on the mask stage of the exposure device. Here, the mask 100 is disposed so as to face the resist film formed on the display device substrate via the projection optical system of the exposure device.
≪圖案轉印步驟≫ 圖案轉印步驟中，對光罩100照射曝光之光，將包含遮光膜圖案30a之轉印用圖案轉印至形成於顯示裝置用基板上之抗蝕膜。曝光之光係包含選自313 nm～436 nm波長區域之複數種波長之光之複合光、或自313 nm～436 nm波長區域將某波長區域利用濾波器等截止並選擇之單色光、或自具有313 nm～436 nm波長區域之光源發出之單色光。例如，曝光之光係包含i射線、h射線及g射線中之至少1者之複合光、或i射線之單色光。藉由使用複合光作為曝光之光而可提高曝光之光強度，使產量提高。因此，可降低顯示裝置之製造成本。 ≪Pattern transfer steps≫ In the pattern transfer step, the photomask 100 is irradiated with exposure light to transfer the transfer pattern including the light-shielding film pattern 30a to the resist film formed on the display device substrate. The exposure light is a composite light containing a plurality of wavelengths of light selected from the wavelength range of 313 nm to 436 nm, or a monochromatic light that cuts off and selects a certain wavelength range with a filter from the wavelength range of 313 nm to 436 nm, or Monochromatic light emitted from a light source with a wavelength range of 313 nm to 436 nm. For example, the light for exposure includes composite light of at least one of i-rays, h-rays, and g-rays, or monochromatic light of i-rays. By using composite light as the exposure light, the intensity of the exposure light can be increased and the output can be increased. Therefore, the manufacturing cost of the display device can be reduced.
根據第1、第2實施方式之顯示裝置之製造方法，可製造具有高解像度、微細之線與間隙圖案及/或接觸孔之高清顯示裝置。 [實施例] According to the display device manufacturing method of the first and second embodiments, a high-definition display device having high resolution, fine line and space patterns, and/or contact holes can be manufactured. [Example]
以下，藉由實施例具體地說明本發明，但本發明並非限定於該等實施例。Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
實施例1. A.光罩基底及其製造方法 為了製造實施例1之光罩基底，首先，準備1214尺寸(1220 mm×1400 mm)之合成石英玻璃基板作為透明基板20。 Example 1. A. Photomask substrate and manufacturing method thereof In order to manufacture the photomask substrate of Example 1, first, a 1214-size (1220 mm×1400 mm) synthetic quartz glass substrate is prepared as the transparent substrate 20 .
其後，將合成石英玻璃基板以其主表面朝下側之方式搭載於托盤(未圖示)，搬入至連續式濺鍍裝置之腔室內。Thereafter, the synthetic quartz glass substrate is placed on a tray (not shown) with its main surface facing downward, and is moved into the chamber of the continuous sputtering apparatus.
為了於透明基板20之主表面上形成作為遮光膜30之遮光層31，首先，將氬氣(Ar)導入至第1腔室內。繼而，對包含鈦與矽之第1濺鍍靶(鈦:矽＝1:3)施加特定之濺鍍功率進行濺鍍，藉此於透明基板20之主表面上成膜包含鈦與矽之鈦矽化物之遮光膜30(遮光層31)。In order to form the light-shielding layer 31 as the light-shielding film 30 on the main surface of the transparent substrate 20, first, argon gas (Ar) is introduced into the first chamber. Then, a specific sputtering power is applied to the first sputtering target containing titanium and silicon (titanium: silicon = 1:3) to perform sputtering, whereby a titanium film containing titanium and silicon is formed on the main surface of the transparent substrate 20 Silicone light-shielding film 30 (light-shielding layer 31).
繼而，將成膜有遮光層31之透明基板20搬入至第2腔室內，將由氬氣(Ar)與氮氣(N 2)構成之混合氣體導入至第2腔室內。繼而，對包含鉻之第2濺鍍靶施加特定之濺鍍功率進行反應性濺鍍，藉此於遮光層31上成膜含有鉻與氮之鉻氮化物之蝕刻遮罩膜40。 Then, the transparent substrate 20 on which the light-shielding layer 31 is formed is moved into the second chamber, and a mixed gas composed of argon (Ar) and nitrogen (N 2 ) is introduced into the second chamber. Then, a specific sputtering power is applied to the second sputtering target containing chromium to perform reactive sputtering, thereby forming an etching mask film 40 of chromium nitride containing chromium and nitrogen on the light shielding layer 31 .
以此方式，獲得於透明基板20上形成有僅包含遮光層31之遮光膜30與蝕刻遮罩膜40之光罩基底10。In this way, the photomask substrate 10 in which the light-shielding film 30 including only the light-shielding layer 31 and the etching masking film 40 are formed on the transparent substrate 20 is obtained.
以如下方式對所獲得之光罩基底10之遮光膜30之各特性進行測定。 [光學濃度(OD)] 使用分光光度計測定僅包含遮光層31之遮光膜30之光學濃度(OD)，結果為3.6(波長405 nm)。於遮光膜30之光學濃度之測定中，使用置於同一托盤而製成的、在合成石英玻璃基板之主表面上成膜有僅包含遮光層31之遮光膜30的附遮光膜之基板(虛設基板)。遮光膜30之光學濃度係於形成蝕刻遮罩膜40之前將附遮光膜之基板(虛設基板)自腔室取出後進行測定。 Each characteristic of the light-shielding film 30 of the obtained photomask base 10 was measured in the following manner. [Optical Density (OD)] The optical density (OD) of the light-shielding film 30 including only the light-shielding layer 31 was measured using a spectrophotometer, and the result was 3.6 (wavelength 405 nm). In the measurement of the optical density of the light-shielding film 30, a light-shielding film-attached substrate (dummy) in which the light-shielding film 30 including only the light-shielding layer 31 was formed on the main surface of a synthetic quartz glass substrate was used and was placed on the same tray. substrate). The optical density of the light-shielding film 30 is measured after taking the substrate with the light-shielding film (dummy substrate) out of the chamber before forming the etching mask film 40 .
[薄片電阻] 又，使用上述虛設基板，藉由四端子法測定實施例1之遮光膜30之薄片電阻，結果為62.9 Ω/sq。 [Sheet resistor] Furthermore, the sheet resistance of the light-shielding film 30 of Example 1 was measured by the four-terminal method using the above-mentioned dummy substrate, and the result was 62.9 Ω/sq.
進而，對遮光膜30藉由X射線光電子分光法(XPS，X-ray photoelectron spectroscopy)進行深度方向之組成分析。於實際測定中使用虛設基板。其結果，遮光膜30中，除透明基板20與遮光膜30之界面之梯度組成區域外，各構成元素之含有率朝深度方向為大致固定。具體之膜組成(原子%)為：鈦38%，矽55%，氮5原子%，氧2%。Furthermore, the composition of the light-shielding film 30 in the depth direction is analyzed by X-ray photoelectron spectroscopy (XPS, XPS). Use a dummy substrate in actual measurements. As a result, in the light-shielding film 30 , except for the gradient composition region at the interface between the transparent substrate 20 and the light-shielding film 30 , the content ratio of each constituent element is substantially constant in the depth direction. The specific film composition (atomic %) is: titanium 38%, silicon 55%, nitrogen 5 atomic%, and oxygen 2%.
B.光罩及其製造方法 為了使用以上述方式製造之光罩基底10來製造光罩100，首先，使用抗蝕劑塗佈裝置將光阻劑塗佈於光罩基底10之蝕刻遮罩膜40上。 其後，經加熱、冷卻步驟而形成光阻膜。 其後，使用雷射描繪裝置描繪光阻膜，經顯影、洗滌步驟而於蝕刻遮罩膜40上形成包含線與間隙圖案之抗蝕膜圖案50。 B. Photomask and manufacturing method thereof In order to manufacture the photomask 100 using the photomask substrate 10 manufactured in the above manner, first, a resist coating device is used to coat the photoresist on the etching mask film 40 of the photomask substrate 10 . Thereafter, a photoresist film is formed through heating and cooling steps. Thereafter, a laser drawing device is used to draw the photoresist film, and a resist film pattern 50 including a line and space pattern is formed on the etching mask film 40 through development and cleaning steps.
其後，將抗蝕膜圖案50作為遮罩，藉由包含硝酸鈰銨與過氯酸之Cr蝕刻液對蝕刻遮罩膜40進行濕式蝕刻，形成蝕刻遮罩膜圖案40a。繼而，將抗蝕膜圖案50剝離。其次，將蝕刻遮罩膜圖案40a作為遮罩，藉由將氟化氫銨與過氧化氫之混合溶液利用純水稀釋後之鈦矽化物蝕刻液而對遮光膜30進行濕式蝕刻，形成遮光膜圖案30a。進而，利用上述Cr蝕刻液將蝕刻遮罩膜40剝離。Thereafter, using the resist film pattern 50 as a mask, the etching mask film 40 is wet-etched with a Cr etching solution containing cerium ammonium nitrate and perchloric acid to form the etching mask film pattern 40a. Next, the resist film pattern 50 is peeled off. Next, using the etching mask film pattern 40a as a mask, the light-shielding film 30 is wet-etched by diluting a mixed solution of ammonium bifluoride and hydrogen peroxide with a titanium silicide etching solution diluted with pure water to form a light-shielding film pattern. 30a. Furthermore, the etching mask film 40 is peeled off using the Cr etching liquid.
對所獲得之光罩100製造時之搭載效應進行試驗。首先，根據上述方法而準備光罩100，該光罩100包含圖案間距為4 μm之複數個線與間隙(L&S)圖案、包圍該複數個線與間隙圖案之外周之透光區域(露出有透明基板之區域)及包圍該透光區域之外周之遮光區域(參照圖6)。圖6中，白色區域表示遮光膜圖案(線圖案及遮光區域)，灰色區域表示間隙圖案及透光區域。再者，於關於搭載效應之試驗中，設為於遮光膜圖案30a(線圖案及遮光區域)上存在蝕刻遮罩膜之狀態。其他實施例及比較例亦相同。再者，於對遮光膜30進行蝕刻時，為了明確搭載效應之有無及程度之差異，以相對於適量蝕刻時間為200%之過蝕刻時間進行。The mounting effect during manufacturing of the obtained photomask 100 was tested. First, a photomask 100 is prepared according to the above method. The photomask 100 includes a plurality of line and space (L&S) patterns with a pattern pitch of 4 μm, and a light-transmitting area (exposed transparent area) surrounding the outer periphery of the plurality of line and space patterns. area of the substrate) and a light-shielding area surrounding the outer periphery of the light-transmitting area (see Figure 6). In Figure 6, the white area represents the light-shielding film pattern (line pattern and light-shielding area), and the gray area represents the gap pattern and light-transmitting area. In addition, in the test regarding the mounting effect, it was assumed that the etching mask film was present on the light-shielding film pattern 30a (line pattern and light-shielding area). The same applies to other Examples and Comparative Examples. Furthermore, when etching the light-shielding film 30 , in order to clarify the difference in the presence and degree of the mounting effect, an over-etching time of 200% is used relative to the appropriate etching time.
實施例1中，如圖6所示，藉由算出圖案較密之點1處的遮光膜30之側蝕量P1(包含遮光膜30之線圖案之邊緣之後退量)、與圖案較疏之點3處的遮光膜30之側蝕量P3(包含遮光膜30之遮光帶之外框側之邊緣之後退量)之比P1/P3，而確認搭載效應之程度。所謂側蝕量(邊緣之後退量)，係指遮光膜30自蝕刻遮罩膜圖案40a之邊緣位置起能被側蝕多少。具體而言，於光罩100之剖視圖中，藉由算出蝕刻遮罩膜圖案40a之邊緣至遮光膜30之邊緣之距離(尺寸)而求出側蝕量。In Embodiment 1, as shown in FIG. 6 , by calculating the undercut amount P1 of the light-shielding film 30 at point 1 of the denser pattern (including the edge retreat amount of the line pattern of the light-shielding film 30 ), and the amount of undercutting The degree of the mounting effect is confirmed by the ratio P1/P3 of the amount of side etching P3 of the light-shielding film 30 at point 3 (including the amount of backlash of the edge of the light-shielding tape on the outer frame side of the light-shielding film 30). The so-called side etching amount (the edge retreat amount) refers to how much the light shielding film 30 can be side etched from the edge position of the etched mask film pattern 40a. Specifically, in the cross-sectional view of the photomask 100 , the amount of undercut is obtained by calculating the distance (size) from the edge of the etching mask film pattern 40 a to the edge of the light shielding film 30 .
P1/P3係指點1處之蝕刻速率相對於點3處之蝕刻速率之比。P1/P3越接近1，則表示點1與點3之間蝕刻速率之差越小，可謂能夠降低搭載效應。較理想為，點1處之側蝕量為點3處之側蝕量之±20%以內。由此，只要蝕刻速率之比P1/P3為0.8以上1.2以下之範圍內，則可良好地降低搭載效應，若P1/P3未達0.8或大於1.2，則判斷為未能良好地降低搭載效應。P1/P3 refers to the ratio of the etching rate at point 1 to the etching rate at point 3. The closer P1/P3 is to 1, the smaller the difference in etching rate between point 1 and point 3 is, which can reduce the piggyback effect. Ideally, the amount of side erosion at point 1 is within ±20% of the amount of side erosion at point 3. Therefore, as long as the etching rate ratio P1/P3 is in the range of 0.8 to 1.2, the mounting effect can be reduced satisfactorily. If P1/P3 is less than 0.8 or greater than 1.2, it is judged that the mounting effect cannot be reduced satisfactorily.
於使用有實施例1之光罩基底10之光罩100中，P1/P3為0.93。即，顯然實施例1之光罩基底10可良好地降低搭載效應。又，對所獲得之光罩進行靜電破壞試驗，取得良好結果。In the photomask 100 using the photomask base 10 of Example 1, P1/P3 is 0.93. That is, it is obvious that the photomask base 10 of Embodiment 1 can effectively reduce the mounting effect. Furthermore, the obtained photomask was subjected to an electrostatic destruction test and good results were obtained.
實施例2. A.光罩基底及其製造方法 為了製造實施例2之光罩基底，與實施例1同樣地，準備1214尺寸(1220 mm×1400 mm)之合成石英玻璃基板作為透明基板。 藉由與實施例1相同之方法將合成石英玻璃基板搬入至連續式濺鍍裝置之腔室。繼而，將由氬氣(Ar)及氮氣(N 2)構成之混合氣體導入至第1腔室內。繼而，對包含鈦與矽之第1濺鍍靶(鈦:矽＝1:3)施加特定之濺鍍功率而進行反應性濺鍍，藉此於透明基板20之主表面上成膜含有鈦、矽及氮之鈦矽化物之氮化物之背面抗反射層33(圖3)。 Example 2. A. Photomask substrate and manufacturing method thereof In order to manufacture the photomask substrate of Example 2, a 1214-size (1220 mm×1400 mm) synthetic quartz glass substrate was prepared as a transparent substrate in the same manner as in Example 1. The synthetic quartz glass substrate was moved into the chamber of the continuous sputtering device in the same manner as in Example 1. Then, a mixed gas composed of argon gas (Ar) and nitrogen gas (N 2 ) is introduced into the first chamber. Then, a specific sputtering power is applied to the first sputtering target containing titanium and silicon (titanium: silicon = 1:3) to perform reactive sputtering, whereby a film containing titanium and silicon is formed on the main surface of the transparent substrate 20. Backside anti-reflective layer 33 of silicon and nitrogen titanium silicide nitride (Fig. 3).
其次，將成膜有背面抗反射層33之透明基板20搬入至第2腔室內。將氬氣(Ar)導入至第2腔室內。繼而，對包含鈦與矽之第2濺鍍靶(鈦:矽＝1:3)施加特定之濺鍍功率進行濺鍍，藉此於背面抗反射膜33上成膜包含鈦與矽之鈦矽化物之遮光層31。Next, the transparent substrate 20 on which the back anti-reflection layer 33 is formed is moved into the second chamber. Argon gas (Ar) is introduced into the second chamber. Then, a specific sputtering power is applied to the second sputtering target containing titanium and silicon (titanium: silicon = 1:3) to perform sputtering, whereby a titanium silicon film containing titanium and silicon is formed on the back antireflection film 33 The light-shielding layer 31 of the object.
繼而，將成膜有背面抗反射層33與遮光層31之透明基板20搬入至第3腔室內。將由氬氣(Ar)及氮氣(N 2)構成之混合氣體導入至第3腔室內。繼而，對包含鈦與矽之第3濺鍍靶(鈦:矽＝1:3)施加特定濺鍍功率進行反應性濺鍍，藉此於遮光層31上成膜含有鉬、矽及氮之鈦矽化物之氮化物之正面抗反射層32。 Then, the transparent substrate 20 on which the back antireflection layer 33 and the light-shielding layer 31 are formed is moved into the third chamber. A mixed gas consisting of argon (Ar) and nitrogen (N 2 ) is introduced into the third chamber. Then, a specific sputtering power is applied to the third sputtering target containing titanium and silicon (titanium: silicon = 1:3) to perform reactive sputtering, thereby forming a titanium film containing molybdenum, silicon and nitrogen on the light-shielding layer 31 Front anti-reflective layer 32 of silicon nitride.
繼而，將成膜有正面抗反射層32之透明基板20搬入至第4腔室內，將由氬氣(Ar)與氮氣(N 2)構成之混合氣體導入至第4腔室內。繼而，對包含鉻之第4濺鍍靶施加特定之濺鍍功率進行反應性濺鍍，藉此於正面抗反射層32上成膜含有鉻與氮之鉻氮化物之蝕刻遮罩膜40。 Then, the transparent substrate 20 on which the front anti-reflective layer 32 is formed is moved into the fourth chamber, and a mixed gas composed of argon (Ar) and nitrogen (N 2 ) is introduced into the fourth chamber. Then, a specific sputtering power is applied to the fourth sputtering target containing chromium to perform reactive sputtering, thereby forming an etching mask film 40 of chromium nitride containing chromium and nitrogen on the front anti-reflective layer 32 .
以此方式，獲得於透明基板20上形成有具有背面抗反射層33、遮光層31、及正面抗反射層32之積層構造之遮光膜30及蝕刻遮罩膜40的光罩基底10。In this way, the photomask base 10 in which the light-shielding film 30 and the etching mask film 40 having a multilayer structure of the back anti-reflection layer 33, the light-shielding layer 31, and the front anti-reflection layer 32 are formed on the transparent substrate 20 is obtained.
利用分光光度計測定所獲得之光罩基底10中之包含背面抗反射層33、遮光層31、及正面抗反射層32之積層構造之遮光膜30之光學濃度，其結果為4.9(波長405 nm)。又，以與實施例1相同之方法測定實施例2之遮光膜30之薄片電阻，結果為42.8 Ω/sq。再者，與實施例1同樣地，於遮光膜30之光學濃度及薄片電阻之測定中，使用置於同一托盤而製成的、在合成石英玻璃基板之主表面上成膜有遮光膜30之附遮光膜之基板(虛設基板)。A spectrophotometer was used to measure the optical concentration of the light-shielding film 30 in the laminated structure including the back anti-reflection layer 33, the light-shielding layer 31, and the front anti-reflection layer 32 in the obtained mask substrate 10. The result was 4.9 (wavelength 405 nm). ). Furthermore, the sheet resistance of the light-shielding film 30 of Example 2 was measured in the same manner as Example 1, and the result was 42.8 Ω/sq. In addition, in the same manner as in Example 1, the optical density and sheet resistance of the light-shielding film 30 were measured using a synthetic quartz glass substrate in which the light-shielding film 30 was formed on the main surface of the same tray. A substrate with a light-shielding film (dummy substrate).
進而，對遮光膜30藉由X射線光電子分光法(XPS)進行深度方向之組成分析。於實際之測定中使用虛設基板。其結果，遮光膜30中，除透明基板20與背面抗反射層33之界面之梯度組成區域、背面抗反射層33與遮光層31之界面之梯度組成區域、及遮光層31與正面抗反射層32之界面之梯度組成區域外，各層之各構成元素之含有率朝深度方向為大致固定。關於具體之膜組成，於遮光層31中，鈦為37原子%，矽為60原子%，氮為3原子%。於正面抗反射層32中，鈦為10原子%，矽為37原子%，氮為53原子%。於背面抗反射層33中，鈦為10原子%，矽為37原子%，氮為53原子%。Furthermore, composition analysis in the depth direction of the light-shielding film 30 was performed by X-ray photoelectron spectroscopy (XPS). Use dummy substrates in actual measurements. As a result, in the light-shielding film 30 , except for the gradient composition area of the interface between the transparent substrate 20 and the back anti-reflection layer 33 , the gradient composition area of the interface between the back anti-reflection layer 33 and the light-shielding layer 31 , and the light-shielding layer 31 and the front anti-reflection layer Outside the gradient composition area of the 32-layer interface, the content rates of each constituent element in each layer are approximately constant in the depth direction. Regarding the specific film composition, in the light-shielding layer 31, titanium is 37 atomic %, silicon is 60 atomic %, and nitrogen is 3 atomic %. In the front anti-reflective layer 32, the titanium content is 10 atomic %, the silicon content is 37 atomic %, and the nitrogen content is 53 atomic %. In the back anti-reflection layer 33, the titanium content is 10 atomic %, the silicon content is 37 atomic %, and the nitrogen content is 53 atomic %.
進而，遮光膜30之正面反射率為3.3%(波長405 nm)，背面反射率為4%(波長405 nm)。即，實施例2之光罩基底10係可提高圖案描繪時或圖案轉印時之精度者。Furthermore, the light-shielding film 30 has a front reflectance of 3.3% (wavelength 405 nm) and a back reflectance of 4% (wavelength 405 nm). That is, the mask base 10 of Example 2 can improve the accuracy during pattern drawing or pattern transfer.
B.光罩及其製造方法 為了使用以上述方式製造之光罩基底10來製造光罩100，首先，使用抗蝕劑塗佈裝置將光阻劑塗佈於光罩基底10之蝕刻遮罩膜40上。 其後，經加熱、冷卻步驟而形成光阻膜。 其後，使用雷射描繪裝置描繪光阻膜，經顯影、洗滌步驟而於蝕刻遮罩膜上形成包含線與間隙圖案之抗蝕膜圖案50。 B. Photomask and manufacturing method thereof In order to manufacture the photomask 100 using the photomask substrate 10 manufactured in the above manner, first, a resist coating device is used to coat the photoresist on the etching mask film 40 of the photomask substrate 10 . Thereafter, a photoresist film is formed through heating and cooling steps. Thereafter, a laser drawing device is used to draw the photoresist film, and through development and cleaning steps, a resist film pattern 50 including a line and space pattern is formed on the etching mask film.
其後，將抗蝕膜圖案50作為遮罩，藉由包含硝酸鈰銨與過氯酸之Cr蝕刻液對蝕刻遮罩膜40進行濕式蝕刻，形成蝕刻遮罩膜圖案40a。繼而，將抗蝕膜圖案50剝離。其次，將蝕刻遮罩膜圖案40a作為遮罩，藉由將氟化氫銨與過氧化氫之混合溶液利用純水稀釋後之鈦矽化物蝕刻液對遮光膜30進行濕式蝕刻，形成遮光膜圖案30a。進而，利用上述Cr蝕刻液將蝕刻遮罩膜圖案40a剝離。Thereafter, using the resist film pattern 50 as a mask, the etching mask film 40 is wet-etched with a Cr etching solution containing cerium ammonium nitrate and perchloric acid to form the etching mask film pattern 40a. Next, the resist film pattern 50 is peeled off. Next, using the etching mask film pattern 40a as a mask, the light-shielding film 30 is wet-etched by using a mixed solution of ammonium bifluoride and hydrogen peroxide diluted with pure water to form the light-shielding film pattern 30a. . Furthermore, the etching mask film pattern 40a is peeled off using the Cr etching liquid.
對所獲得之光罩100製造時之搭載效應進行與實施例1相同之試驗，結果在使用有實施例2之光罩基底10之光罩100中，亦獲得與實施例1之光罩基底10相同之結果。又，關於對所獲得之光罩之靜電破壞之耐受性，亦獲得與實施例1同等良好之結果。因此，可謂實施例2之光罩100亦可良好地降低搭載效應，並且對於靜電破壞具有較高之耐受性。The same test as in Example 1 was performed on the mounting effect when manufacturing the obtained photomask 100. As a result, in the photomask 100 using the photomask base 10 of Example 2, the photomask base 10 of Example 1 was also obtained. Same result. In addition, regarding the resistance to electrostatic destruction of the obtained photomask, the same good results as those in Example 1 were obtained. Therefore, it can be said that the photomask 100 of Embodiment 2 can also effectively reduce the mounting effect and has high tolerance to electrostatic damage.
比較例1. A.光罩基底及其製造方法 為了製造比較例1之光罩基底，與實施例1同樣地，準備1214尺寸(1220 mm×1400 mm)之合成石英玻璃基板作為透明基板，將該合成石英玻璃基板搬入至連續式濺鍍裝置之腔室。 Comparative example 1. A. Photomask substrate and manufacturing method thereof In order to manufacture the mask substrate of Comparative Example 1, in the same manner as in Example 1, a 1214-size (1220 mm × 1400 mm) synthetic quartz glass substrate was prepared as a transparent substrate, and the synthetic quartz glass substrate was moved into a continuous sputtering device Chamber.
使用Cr(鉻)靶作為濺鍍靶。繼而，將Ar氣體與N 2氣體之混合氣體作為濺鍍氣體導入至腔室內，成膜CrN(氮化鉻)層，其次，將Ar氣體與CH 4氣體作為濺鍍氣體而成膜CrC層，其次，將Ar氣體與NO氣體作為濺鍍氣體而連續成膜25 nm之CrON層。以此方式，獲得於透明基板20上形成有遮光膜30之光罩基底10。 A Cr (chromium) target is used as a sputtering target. Then, a mixed gas of Ar gas and N 2 gas is introduced into the chamber as a sputtering gas to form a CrN (chromium nitride) layer. Next, Ar gas and CH 4 gas are used as a sputtering gas to form a CrC layer. Next, Ar gas and NO gas were used as sputtering gases to continuously form a 25 nm CrON layer. In this way, the mask base 10 in which the light-shielding film 30 is formed on the transparent substrate 20 is obtained.
利用分光光度計測定所獲得之光罩基底10之遮光膜30之光學濃度，結果為3.0(波長405 nm)。又，以與實施例1相同之方法測定實施例2之遮光膜30之薄片電阻，結果為23 Ω/sq。再者，與實施例1同樣地，於遮光膜30之光學濃度及薄片電阻之測定中，使用置於同一托盤而製成的、在合成石英玻璃基板之主表面上成膜有遮光膜30之附遮光膜之基板(虛設基板)。The optical concentration of the light-shielding film 30 of the obtained photomask base 10 was measured using a spectrophotometer, and the result was 3.0 (wavelength 405 nm). Furthermore, the sheet resistance of the light-shielding film 30 of Example 2 was measured in the same manner as Example 1, and the result was 23 Ω/sq. In addition, in the same manner as in Example 1, the optical density and sheet resistance of the light-shielding film 30 were measured using a synthetic quartz glass substrate in which the light-shielding film 30 was formed on the main surface of the same tray. A substrate with a light-shielding film (dummy substrate).
B.光罩及其製造方法 為了使用以上述方式製造之光罩基底10來製造光罩100，首先，使用抗蝕劑塗佈裝置將光阻劑塗佈於光罩基底10之遮光膜30上。 其後，經加熱、冷卻步驟而形成光阻膜。 其後，使用雷射描繪裝置描繪光阻膜，經顯影、洗滌步驟而於遮光膜上形成包含線與間隙圖案之抗蝕膜圖案50。 B. Photomask and manufacturing method thereof In order to manufacture the photomask 100 using the photomask substrate 10 manufactured in the above manner, first, a resist coating device is used to coat the photoresist on the light-shielding film 30 of the photomask substrate 10 . Thereafter, a photoresist film is formed through heating and cooling steps. Thereafter, a laser drawing device is used to draw the photoresist film, and a resist film pattern 50 including a line and space pattern is formed on the light-shielding film through development and cleaning steps.
其後，將抗蝕膜圖案50作為遮罩，藉由包含硝酸鈰銨與過氯酸之Cr蝕刻液對遮光膜30進行濕式蝕刻，形成遮光膜圖案30a。進而，將抗蝕膜圖案50剝離。Thereafter, using the resist film pattern 50 as a mask, the light-shielding film 30 is wet-etched with a Cr etching solution containing cerium ammonium nitrate and perchloric acid to form the light-shielding film pattern 30a. Furthermore, the resist film pattern 50 is peeled off.
對所獲得之光罩100製造時之搭載效應進行與實施例1相同之試驗。其結果，上述之比P1/P3為1.3。即，使用有比較例1之光罩基底10之光罩100中，未能降低搭載效應。因此，可謂比較例1之光罩基底10並不足以精度良好地形成微細圖案。The same test as in Example 1 was performed on the mounting effect during manufacturing of the obtained photomask 100 . As a result, the above ratio P1/P3 is 1.3. That is, in the photomask 100 using the photomask base 10 of Comparative Example 1, the mounting effect cannot be reduced. Therefore, it can be said that the mask substrate 10 of Comparative Example 1 is not sufficient to form fine patterns with high accuracy.
又，關於對所獲得之光罩之靜電破壞之耐受性亦進行了調研，發現遮光膜圖案受到破壞。即，不可謂比較例1之光罩基底10及光罩100具有對於靜電破壞之充分之耐受性。Furthermore, the resistance of the obtained photomask to electrostatic damage was also investigated, and it was found that the light-shielding film pattern was damaged. That is, it cannot be said that the photomask base 10 and the photomask 100 of Comparative Example 1 have sufficient resistance to electrostatic destruction.
比較例2. A.光罩基底及其製造方法 為了製造比較例2之光罩基底，與實施例1同樣地，準備1214尺寸(1220 mm×1400 mm)之合成石英玻璃基板作為透明基板。繼而，將該合成石英玻璃基板(透明基板20)搬入至連續式濺鍍裝置之腔室。為了於該合成石英玻璃基板之主表面上形成遮光膜30，首先，將由氬氣(Ar)與氦氣(He)構成之混合氣體導入至第1腔室內。繼而，對包含鉬與矽之第1濺鍍靶(鉬:矽＝1:4)施加特定之濺鍍功率進行濺鍍，藉此於透明基板20之主表面上成膜包含鉬與矽之鉬矽化物之遮光層31。 Comparative example 2. A. Photomask substrate and manufacturing method thereof In order to manufacture the photomask substrate of Comparative Example 2, a 1214-size (1220 mm×1400 mm) synthetic quartz glass substrate was prepared as a transparent substrate in the same manner as in Example 1. Then, the synthetic quartz glass substrate (transparent substrate 20) is moved into the chamber of the continuous sputtering apparatus. In order to form the light-shielding film 30 on the main surface of the synthetic quartz glass substrate, first, a mixed gas composed of argon (Ar) and helium (He) is introduced into the first chamber. Then, a specific sputtering power is applied to the first sputtering target containing molybdenum and silicon (molybdenum: silicon = 1:4) to perform sputtering, thereby forming a molybdenum film containing molybdenum and silicon on the main surface of the transparent substrate 20 Silicone light-shielding layer 31.
其次，將成膜有遮光層31之透明基板20搬入至第2腔室內，將由氬氣(Ar)與一氧化氮氣體(NO)及氦氣(He)構成之混合氣體導入至第2腔室內。繼而，對包含鉬與矽之第2濺鍍靶(鉬:矽＝1:4)施加特定之濺鍍功率進行反應性濺鍍，藉此於遮光層31上成膜含有鉬、矽、氧及氮之鉬矽化物之氮氧化物之正面抗反射層32。Next, the transparent substrate 20 on which the light-shielding layer 31 is formed is moved into the second chamber, and a mixed gas composed of argon (Ar), nitric oxide gas (NO), and helium (He) is introduced into the second chamber. . Then, a specific sputtering power is applied to the second sputtering target containing molybdenum and silicon (molybdenum: silicon = 1:4) to perform reactive sputtering, thereby forming a film containing molybdenum, silicon, oxygen and Front anti-reflective layer 32 of nitrogen-molybdenum silicide-oxynitride.
繼而，將成膜有遮光層31、正面抗反射層32之透明基板20搬入至第3腔室內，將由氬氣(Ar)與氮氣(N 2)構成之混合氣體導入至第3腔室內。繼而，對包含鉻之第3濺鍍靶施加特定之濺鍍功率進行反應性濺鍍，藉此於正面抗反射層32上成膜含有鉻與氮之鉻氮化物之蝕刻遮罩膜40。 Then, the transparent substrate 20 on which the light-shielding layer 31 and the front anti-reflective layer 32 are formed is moved into the third chamber, and a mixed gas composed of argon (Ar) and nitrogen (N 2 ) is introduced into the third chamber. Then, a specific sputtering power is applied to the third sputtering target containing chromium to perform reactive sputtering, thereby forming an etching mask film 40 of chromium nitride containing chromium and nitrogen on the front anti-reflective layer 32 .
以此方式，獲得於透明基板20上形成有遮光膜30及蝕刻遮罩膜40之光罩基底。In this way, a photomask substrate in which the light-shielding film 30 and the etching masking film 40 are formed on the transparent substrate 20 is obtained.
與實施例1同樣地，使用虛設基板，利用分光光度計測定所獲得之光罩基底中之遮光膜之光學濃度，其結果為4.0(波長405 nm)。又，使用上述虛設基板測定比較例2之遮光膜30之薄片電阻，結果為80 Ω/sq。In the same manner as in Example 1, the optical density of the light-shielding film in the obtained mask base was measured using a spectrophotometer using a dummy substrate. The result was 4.0 (wavelength: 405 nm). Furthermore, the sheet resistance of the light-shielding film 30 of Comparative Example 2 was measured using the above-mentioned dummy substrate, and the result was 80 Ω/sq.
B.光罩及其製造方法 為了使用以上述方式製造之光罩基底來製造光罩，首先，使用抗蝕劑塗佈裝置將光阻劑塗佈於遮光膜之表面(正面抗反射層之表面)。其後，經加熱、冷卻步驟而形成光阻膜。其後，使用雷射描繪裝置描繪光阻膜，經顯影、洗滌步驟而於蝕刻遮罩40膜上形成包含線與間隙圖案之抗蝕膜圖案50。 B. Photomask and manufacturing method thereof In order to manufacture a photomask using the photomask substrate manufactured in the above manner, first, a photoresist is coated on the surface of the light-shielding film (the surface of the front anti-reflective layer) using a resist coating device. Thereafter, a photoresist film is formed through heating and cooling steps. Thereafter, a laser drawing device is used to draw the photoresist film, and through development and cleaning steps, a resist film pattern 50 including a line and space pattern is formed on the etching mask 40 film.
其後，將抗蝕膜圖案50作為遮罩，藉由包含硝酸鈰銨與過氯酸之Cr蝕刻液對蝕刻遮罩膜40進行濕式蝕刻，形成蝕刻遮罩膜圖案40a。繼而，將抗蝕膜圖案50剝離。其次，將蝕刻遮罩膜圖案40a作為遮罩，藉由將氟化氫銨與過氧化氫之混合溶液利用純水稀釋後之鉬矽化物蝕刻液而對遮光膜30進行濕式蝕刻，形成遮光膜圖案30a。進而，利用上述Cr蝕刻液將蝕刻遮罩膜圖案40a剝離。Thereafter, using the resist film pattern 50 as a mask, the etching mask film 40 is wet-etched with a Cr etching solution containing cerium ammonium nitrate and perchloric acid to form the etching mask film pattern 40a. Next, the resist film pattern 50 is peeled off. Next, using the etching mask film pattern 40a as a mask, the light-shielding film 30 is wet-etched by using a mixed solution of ammonium bifluoride and hydrogen peroxide diluted with pure water using a molybdenum silicide etching solution to form a light-shielding film pattern. 30a. Furthermore, the etching mask film pattern 40a is peeled off using the Cr etching liquid.
對所獲得之光罩100製造時之搭載效應進行與實施例1相同之試驗。其結果，對於使用有比較例2之光罩基底10之光罩100，比P1/P3成為較大地背離1.0之值0.25，而未能降低搭載效應。The same test as in Example 1 was performed on the mounting effect during manufacturing of the obtained photomask 100 . As a result, for the mask 100 using the mask base 10 of Comparative Example 2, the ratio P1/P3 became a value of 0.25 that greatly deviated from 1.0, and the mounting effect could not be reduced.
又，關於對所獲得之光罩之靜電破壞之耐受性亦進行了調研，結果為，在比較例2中，由於薄片電阻為40 Ω/sq以上，故與實施例1同等地具有對於靜電破壞之充分之耐受性。然而，如上所述，比較例2中，比P1/P3為遠小於1.0之值，未能降低搭載效應。即，可謂比較例2之光罩基底10並不足以精度良好地形成微細圖案。Furthermore, the obtained photomask was also investigated for its resistance to static electricity destruction. As a result, in Comparative Example 2, the sheet resistance was 40 Ω/sq or more, and therefore it had the same resistance to static electricity as Example 1. Sufficient tolerance for damage. However, as mentioned above, in Comparative Example 2, the ratio P1/P3 is a value far less than 1.0, and the piggyback effect cannot be reduced. That is, it can be said that the mask base 10 of Comparative Example 2 is not sufficient to form a fine pattern with high accuracy.
10:光罩基底 20:透明基板 30:遮光膜(圖案形成用薄膜) 30a:遮光膜圖案 31:遮光層 32:正面抗反射層 33:背面抗反射層 40:蝕刻遮罩膜 40a:蝕刻遮罩膜圖案 50:抗蝕膜圖案 100:光罩 10: Photomask base 20:Transparent substrate 30: Light-shielding film (film for pattern formation) 30a:Light-shielding film pattern 31:Light shielding layer 32: Front anti-reflective layer 33: Back anti-reflective layer 40: Etching mask film 40a: Etch mask film pattern 50: Resist film pattern 100: Photomask
圖1係表示本發明第1實施方式之光罩基底之膜構成之模式性剖視圖。 圖2係表示本發明第2實施方式之光罩基底之膜構成之模式性剖視圖。 圖3係本發明第1實施方式之光罩基底之模式性剖視圖，尤其係詳細表示遮光膜之層構成之剖視圖。 圖4A係表示由本發明第1實施方式之光罩基底製造光罩之步驟之模式性剖視圖。 圖4B係進而表示由第1實施方式之光罩基底製造光罩之步驟之模式性剖視圖。 圖4C係進而表示由第1實施方式之光罩基底製造光罩之步驟之模式性剖視圖。 圖4D係進而表示由第1實施方式之光罩基底製造光罩之步驟之模式性剖視圖。 圖5A係表示由本發明第2實施方式之光罩基底製造光罩之步驟之模式性剖視圖。 圖5B係進而表示由第2實施方式之光罩基底製造光罩之步驟之模式性剖視圖。 圖5C係進而表示由第2實施方式之光罩基底製造光罩之步驟之模式性剖視圖。 圖6表示本發明之實施例中用於測定搭載效應之程度之遮光膜圖案之模式性俯視圖。 FIG. 1 is a schematic cross-sectional view showing the film structure of the photomask base according to the first embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing the film structure of the photomask base according to the second embodiment of the present invention. 3 is a schematic cross-sectional view of the photomask base according to the first embodiment of the present invention, particularly a cross-sectional view showing the layer structure of the light-shielding film in detail. 4A is a schematic cross-sectional view showing the steps of manufacturing a photomask from the photomask base according to the first embodiment of the present invention. 4B is a schematic cross-sectional view further showing the steps of manufacturing a photomask from the photomask base of the first embodiment. 4C is a schematic cross-sectional view further showing the steps of manufacturing a photomask from the photomask base of the first embodiment. 4D is a schematic cross-sectional view further showing the steps of manufacturing a photomask from the photomask base of the first embodiment. 5A is a schematic cross-sectional view showing the steps of manufacturing a photomask from the photomask base according to the second embodiment of the present invention. 5B is a schematic cross-sectional view further showing the steps of manufacturing a photomask from the photomask base of the second embodiment. 5C is a schematic cross-sectional view further showing the steps of manufacturing a photomask from the photomask base of the second embodiment. 6 is a schematic plan view of a light-shielding film pattern used for measuring the degree of mounting effect in an embodiment of the present invention.
10:光罩基底 10: Photomask base
20:透明基板 20:Transparent substrate
30:遮光膜(圖案形成用薄膜) 30: Light-shielding film (film for pattern formation)
40:蝕刻遮罩膜 40: Etching mask film
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