TWI828864B - Photomask blank, method for manufacturing photomask, and method for manufacturing display device - Google Patents
Photomask blank, method for manufacturing photomask, and method for manufacturing display device Download PDFInfo
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- TWI828864B TWI828864B TW109104966A TW109104966A TWI828864B TW I828864 B TWI828864 B TW I828864B TW 109104966 A TW109104966 A TW 109104966A TW 109104966 A TW109104966 A TW 109104966A TW I828864 B TWI828864 B TW I828864B
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- 238000004519 manufacturing process Methods 0.000 title claims description 71
- 238000000034 method Methods 0.000 title claims description 31
- 239000000758 substrate Substances 0.000 claims abstract description 239
- 238000005530 etching Methods 0.000 claims abstract description 181
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 114
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 73
- 239000001301 oxygen Substances 0.000 claims abstract description 73
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 53
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- 239000010703 silicon Substances 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 31
- 150000003624 transition metals Chemical class 0.000 claims abstract description 31
- 238000012546 transfer Methods 0.000 claims abstract description 29
- 238000001039 wet etching Methods 0.000 claims abstract description 29
- 239000010409 thin film Substances 0.000 claims abstract description 17
- 239000010408 film Substances 0.000 claims description 660
- 238000002834 transmittance Methods 0.000 claims description 39
- 239000011651 chromium Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 28
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 27
- 229910052804 chromium Inorganic materials 0.000 claims description 27
- 230000003287 optical effect Effects 0.000 claims description 16
- 238000004458 analytical method Methods 0.000 claims description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 2
- 230000007261 regionalization Effects 0.000 abstract description 15
- 230000035515 penetration Effects 0.000 abstract description 12
- 230000010363 phase shift Effects 0.000 description 480
- 239000000203 mixture Substances 0.000 description 71
- 239000007789 gas Substances 0.000 description 59
- 239000002585 base Substances 0.000 description 40
- 238000004544 sputter deposition Methods 0.000 description 35
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 22
- 239000007788 liquid Substances 0.000 description 19
- 238000004381 surface treatment Methods 0.000 description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 14
- 230000007423 decrease Effects 0.000 description 14
- 230000032683 aging Effects 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 229910021344 molybdenum silicide Inorganic materials 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 238000005477 sputtering target Methods 0.000 description 12
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 8
- 230000035882 stress Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000001307 helium Substances 0.000 description 7
- 229910052734 helium Inorganic materials 0.000 description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 7
- 238000002310 reflectometry Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910021350 transition metal silicide Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229920002120 photoresistant polymer Polymers 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 5
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000010301 surface-oxidation reaction Methods 0.000 description 5
- 229910003470 tongbaite Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000004380 ashing Methods 0.000 description 4
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052743 krypton Inorganic materials 0.000 description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- 238000005546 reactive sputtering Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- 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 2
- 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 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910021355 zirconium silicide Inorganic materials 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910016006 MoSi Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910006249 ZrSi Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical compound [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- -1 molybdenum silicide compound Chemical class 0.000 description 1
- KVMWOOXRTBUMIS-UHFFFAOYSA-N molybdenum zirconium Chemical compound [Zr].[Mo].[Mo] KVMWOOXRTBUMIS-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
- G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
Abstract
Description
本發明係關於一種光罩基底、光罩之製造方法、及顯示裝置之製造方法。The present invention relates to a photomask substrate, a photomask manufacturing method, and a display device manufacturing method.
近年來,對於以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,大畫面化、廣視角化以及高精細化、高速顯示化正快速發展。該高精細化、高速顯示化所需之要素之一係製作微細且尺寸精度較高之元件或配線等電子電路圖案。該顯示裝置用電子電路之圖案化多使用光微影法。因此,需要形成有微細且高精度之圖案之顯示裝置製造用之相移光罩。In recent years, display devices such as FPD (Flat Panel Display), represented by LCD (Liquid Crystal Display), have been rapidly developing towards larger screens, wider viewing angles, high definition, and high-speed displays. One of the elements required for this high-definition and high-speed display is the production of electronic circuit patterns such as components and wiring that are fine and have high dimensional accuracy. The patterning of electronic circuits for display devices often uses photolithography. Therefore, there is a need for a phase shift mask for manufacturing display devices in which fine and high-precision patterns are formed.
例如,於專利文獻1中,揭示有一種平板顯示器用空白遮罩及使用其之光罩,當對包含矽化鉬之薄膜進行濕式蝕刻時,利用將磷酸、過氧化氫、氟化銨於水中稀釋所得之蝕刻溶液對包含矽化鉬之薄膜進行濕式蝕刻,以使透明基板之損傷最小化。 又,於專利文獻2中,揭示有一種相位反轉空白遮罩及光罩,為了提高圖案之精密度,相位反轉膜104係以包含可利用相同之蝕刻溶液進行蝕刻之組成互不相同之膜、並且不同組成之各膜分別積層1次以上之至少2層以上之多層膜或連續膜之形態形成。 [先前技術文獻] [專利文獻]For example, Patent Document 1 discloses a blank mask for flat panel displays and a photomask using the same. When wet etching a film containing molybdenum silicide, phosphoric acid, hydrogen peroxide, and ammonium fluoride are used in water. The diluted etching solution is used to wet-etch the film containing molybdenum silicide to minimize damage to the transparent substrate. Furthermore, Patent Document 2 discloses a phase inversion blank mask and a photomask. In order to improve the precision of the pattern, the phase inversion film 104 has different compositions that can be etched with the same etching solution. The film is formed in the form of a multilayer film or a continuous film in which at least two layers of films with different compositions are laminated one or more times. [Prior technical literature] [Patent Document]
[專利文獻1]韓國專利申請公開第10-2016-0024204號公報 [專利文獻2]日本專利特開2017-167512號公報[Patent Document 1] Korean Patent Application Publication No. 10-2016-0024204 [Patent Document 2] Japanese Patent Application Publication No. 2017-167512
[發明所欲解決之問題][Problem to be solved by the invention]
近年來,作為此種顯示裝置製造用之相移光罩基底,為了可確實地轉印未達2.0 μm之微細圖案,研究使用以固定以上之比率(例如,5原子%以上、進而10原子%以上)含有氧而成之相移膜作為具有相移膜對於曝光之光之透過率為10%以上、進而20%以上之光學特性之相移膜。In recent years, in order to reliably transfer fine patterns of less than 2.0 μm as a phase shift mask base for manufacturing such display devices, studies have been conducted on using a ratio of a fixed or higher ratio (for example, 5 atomic % or more, and further 10 atomic %). The above) A phase shift film containing oxygen is a phase shift film having optical properties such that the transmittance of the phase shift film for exposure light is 10% or more, and further 20% or more.
又,用於製造顯示裝置之相移光罩基底與用於製造半導體裝置之相移光罩基底相比,尺寸大幅度增大。於此種尺寸較大之相移光罩基底之相移膜形成相移膜圖案之情形時,即便以正好使透明基板於相移膜圖案露出之時間(適量蝕刻時間)進行濕式蝕刻,亦難以避免面內分佈之CD(Critical Dimension,臨界尺寸)偏差大於100 nm。為了使相移膜圖案之CD偏差小於100 nm,要求以較適量蝕刻時間長之時間(過蝕刻時間)進行濕式蝕刻。In addition, the size of the phase shift mask substrate used for manufacturing display devices is greatly increased compared with the phase shift mask substrate used for manufacturing semiconductor devices. In the case where the phase shift film of a phase shift mask substrate with a larger size forms a phase shift film pattern, even if the wet etching is performed at the right time to expose the transparent substrate to the phase shift film pattern (appropriate etching time), It is unavoidable that the CD (Critical Dimension) deviation of the in-plane distribution is greater than 100 nm. In order to make the CD deviation of the phase shift film pattern less than 100 nm, it is required to perform wet etching with a relatively long etching time (over-etching time).
已知對此種將氧之含有率設為特定以上、例如5原子%以上、進而10原子%以上之相移膜藉由以過蝕刻時間之濕式蝕刻進行圖案化之情形時,濕式蝕刻液會滲入相移膜與透明基板之界面,使界面部分之蝕刻提前進行。所形成之相移膜圖案之邊緣部分之截面形狀會因濕式蝕刻液之滲入而成為產生所謂侵蝕之形狀。It is known that when a phase shift film having an oxygen content of more than a specific value, for example, 5 atomic % or more, and further 10 atomic % or more is patterned by wet etching for an excessive etching time, wet etching The liquid will penetrate into the interface between the phase shift film and the transparent substrate, causing the etching of the interface part to proceed in advance. The cross-sectional shape of the edge portion of the formed phase shift film pattern will become a shape that causes so-called erosion due to the penetration of the wet etching liquid.
於相移膜圖案之邊緣部分之截面形狀為產生侵蝕之形狀之情形時,相移效果減弱。因此,無法充分發揮相移效果,無法穩定地轉印未達2.0 μm之微細圖案。若將相移膜中之氧之含有率設為特定以上、例如5原子%以上、進而10原子%以上,則難以嚴格地控制相移膜圖案之邊緣部分之截面形狀,從而非常難控制線寬(CD)。 並且,於具備含有過渡金屬、矽、氧及氮之遮光膜之二元光罩基底中,藉由濕式蝕刻於遮光膜形成遮光圖案時,亦存在同樣之問題。When the cross-sectional shape of the edge portion of the phase shift film pattern is a shape that causes erosion, the phase shift effect is weakened. Therefore, the phase shift effect cannot be fully exerted, and fine patterns less than 2.0 μm cannot be stably transferred. If the oxygen content in the phase shift film is set to a certain level or more, for example, 5 atomic % or more, or 10 atomic % or more, it will be difficult to strictly control the cross-sectional shape of the edge portion of the phase shift film pattern, making it very difficult to control the line width. (CD). Furthermore, the same problem also exists when a light-shielding pattern is formed on the light-shielding film by wet etching in a binary mask substrate having a light-shielding film containing transition metal, silicon, oxygen, and nitrogen.
本發明係為了解決上述先前之問題而成者,其目的在於提供一種抑制在對圖案形成用薄膜以過蝕刻時間進行濕式蝕刻而形成於透明基板上之轉印圖案中,與透明基板之界面處產生滲入的光罩基底、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 made in order to solve the above-mentioned previous problems, and an object thereof is to provide a method for suppressing the interface between a transfer pattern formed on a transparent substrate by wet etching a pattern-forming film for an excessive etching time and the interface with the transparent substrate. A photomask substrate where infiltration occurs, a photomask manufacturing method, and a display device manufacturing method. [Technical means to solve problems]
本發明人等為了解決該等問題點,就抑制在對圖案形成用薄膜以過蝕刻時間進行濕式蝕刻而形成於透明基板上之轉印圖案中,與透明基板之界面處產生滲入的方法進行了銳意研究。本發明人等最初認為於含有過渡金屬、矽、氧及氮之圖案形成用薄膜中,與透明基板之界面處產生滲入之主要因素係圖案形成用薄膜中之氧之絕對量。然而,即便圖案形成用薄膜中之氧之絕對量為相同程度,亦存在與透明基板之界面處產生滲入者與不產生滲入者。於是本發明人等進一步進行了研究,結果發現,形成於與透明基板之界面側之圖案形成用薄膜之組成區域中之氮與氧之比率對與透明基板之界面處之滲入有較大影響。然後,本發明人等進一步進行了研究,發現若設為如下構成,即,圖案形成用薄膜中之藉由XPS(X-ray Photoelectron Spectroscopy:X射線光電子光譜)進行分析所獲得之氧之含有率為1原子%以上70原子%以下(尤其是,氧之含有率為5原子%以上70原子%以下),當定義為藉由XPS進行分析所獲得之圖案形成用薄膜中包含之過渡金屬之含有率為0原子%之位置時,於自界面往向圖案形成用薄膜之表面30 nm以內之區域中,氮相對於氧之比率具有極大值,則即便對圖案形成用薄膜以過蝕刻時間進行濕式蝕刻而形成轉印圖案,於轉印圖案中與透明基板之界面處之滲入亦得以抑制。 本發明人等推測藉由上述構成可抑制與透明基板之界面處之滲入的理由如下。當利用XPS對圖案形成用薄膜進行測定時,作為其測定之特性,於藉由XPS之測定所規定之與透明基板之界面起30 nm之區域中,出現薄膜之組成產生梯度之組成梯度區域。圖案形成用薄膜中之過渡金屬與矽係來源於靶之成分,其組成比與靶之組成比大致相同。另一方面,圖案形成用薄膜中之氧與氮均為源自氣體之成分。由於可取入至圖案形成用薄膜中之氣體之量有限,故認為若取入之氮之量增加則氧之量減少。並且,氧係使濕式蝕刻之蝕刻速率加快之元素,與此相對,氮係使濕式蝕刻之蝕刻速率減慢之元素。因此,於圖案形成用薄膜之特性方面,氮相對於氧之比率(N/O)變得重要。推測若為於藉由XPS之測定所規定之與透明基板之界面起30 nm以內之區域中氮相對於氧之比率(N/O)具有極大值的圖案形成用薄膜,則蝕刻速率會於與透明基板之界面附近適度地變慢,從而可抑制滲入,抑制侵蝕之產生。 再者,該等推測係基於現階段之見解者,並不對本發明之範圍進行任何限定。 本發明係進行如上所述之銳意研究而成者,具有以下構成。In order to solve these problems, the inventors of the present invention carried out a method of suppressing the occurrence of infiltration at the interface with the transparent substrate in the transfer pattern formed on the transparent substrate by wet etching the pattern forming film for an excessive etching time. Dedicated research. The inventors initially believed that in a pattern-forming film containing a transition metal, silicon, oxygen, and nitrogen, the main factor causing infiltration at the interface with a transparent substrate is the absolute amount of oxygen in the pattern-forming film. However, even if the absolute amount of oxygen in the pattern-forming film is the same, there are cases where penetration occurs at the interface with the transparent substrate and cases where penetration does not occur. The present inventors then conducted further research and found that the ratio of nitrogen to oxygen in the composition region of the pattern forming film formed on the interface side with the transparent substrate has a great influence on the penetration at the interface with the transparent substrate. Then, the present inventors conducted further research and found that if the following structure is adopted, that is, the oxygen content rate in the pattern forming film analyzed by XPS (X-ray Photoelectron Spectroscopy: X-ray photoelectron spectroscopy) It is 1 atomic % or more and 70 atomic % or less (especially, the oxygen content is 5 atomic % or more and 70 atomic % or less), when defined as the content of the transition metal contained in the pattern forming thin film analyzed by XPS When the ratio is 0 atomic %, the ratio of nitrogen to oxygen has a maximum value in the region within 30 nm from the interface to the surface of the pattern forming film. Even if the pattern forming film is wetted for an over-etching time, the ratio of nitrogen to oxygen has a maximum value. The transfer pattern is formed by etching, and the penetration at the interface between the transfer pattern and the transparent substrate is also suppressed. The present inventors speculate that the above-mentioned structure can suppress penetration at the interface with the transparent substrate for the following reasons. When the pattern-forming film is measured by XPS, as a characteristic of the measurement, a composition gradient region in which the composition of the film is gradient appears in a region of 30 nm from the interface with the transparent substrate specified by the XPS measurement. The transition metal and silicon in the pattern forming thin film are components derived from the target, and their composition ratio is approximately the same as that of the target. On the other hand, the oxygen and nitrogen in the pattern forming film are components derived from gases. Since the amount of gas that can be taken into the pattern forming film is limited, it is considered that if the amount of nitrogen taken in increases, the amount of oxygen will decrease. Furthermore, oxygen is an element that accelerates the etching rate of wet etching, whereas nitrogen is an element that slows down the etching rate of wet etching. Therefore, the ratio of nitrogen to oxygen (N/O) becomes important in terms of the characteristics of the pattern forming thin film. It is estimated that if it is a pattern-forming thin film with a maximum value of the ratio of nitrogen to oxygen (N/O) in the region within 30 nm from the interface with the transparent substrate specified by XPS measurement, the etching rate will be between The interface around the transparent substrate moderately slows down, thereby inhibiting penetration and the occurrence of corrosion. Furthermore, these speculations are based on current knowledge and do not limit the scope of the present invention in any way. The present invention is the result of intensive research as described above and has the following constitution.
(構成1) 一種光罩基底,其特徵在於其係於透明基板上具有圖案形成用薄膜者, 上述光罩基底係用以形成光罩之原版,上述光罩係藉由對上述圖案形成用薄膜進行濕式蝕刻而獲得,於上述透明基板上具有轉印圖案, 上述圖案形成用薄膜含有過渡金屬、矽、氧及氮,藉由XPS進行分析所獲得之上述氧之含有率為1原子%以上70原子%以下,且將上述透明基板與上述圖案形成用薄膜之界面定義為藉由上述XPS進行分析所獲得之上述圖案形成用薄膜中包含之過渡金屬之含有率為0原子%之位置時,於自上述界面往向上述圖案形成用薄膜之表面30 nm以內之區域中,氮相對於氧之比率具有極大值。(composition 1) A photomask substrate, characterized in that it has a pattern forming film on a transparent substrate, The above-mentioned photomask base is used to form the original plate of the photomask, the above-mentioned photomask is obtained by wet etching the above-mentioned pattern forming film, and has a transfer pattern on the above-mentioned transparent substrate, The pattern-forming thin film contains a transition metal, silicon, oxygen, and nitrogen, and the oxygen content obtained by XPS analysis is 1 atomic % or more and 70 atomic % or less, and the transparent substrate and the pattern-forming thin film are combined. The interface is defined as a position within 30 nm from the interface to the surface of the pattern-forming film where the content of the transition metal contained in the pattern-forming film obtained by the XPS analysis is 0 atomic %. In this region, the ratio of nitrogen to oxygen has a maximum value.
(構成2) 如構成1之光罩基底,其特徵在於上述過渡金屬係鉬。(composition 2) The photomask substrate constituting 1 is characterized in that the transition metal is molybdenum.
(構成3) 如構成1或2之光罩基底,其特徵在於上述氧之含有率為5原子%以上70原子%以下。 (構成4) 如構成1至3中任一項之光罩基底,其特徵在於上述氮之含有率為35原子%以上60原子%以下。 (構成5) 如構成1至4中任一項之光罩基底,其特徵在於上述圖案形成用薄膜具有柱狀構造。(composition 3) The photomask base constituting 1 or 2 is characterized in that the oxygen content is 5 atomic % or more and 70 atomic % or less. (Constitution 4) The photomask base constituting any one of 1 to 3 is characterized in that the nitrogen content is 35 atomic % or more and 60 atomic % or less. (Constitution 5) The photomask base constituting any one of items 1 to 4, characterized in that the pattern forming film has a columnar structure.
(構成6) 如構成1至5中任一項之光罩基底,其特徵在於上述圖案形成用薄膜係具備對於曝光之光之代表波長透過率為1%以上80%以下且相位差為160°以上200°以下之光學特性的相移膜。(composition 6) The photomask base constituting any one of 1 to 5, characterized in that the pattern forming film has a representative wavelength transmittance of 1% or more and 80% or less with respect to exposure light and a phase difference of 160° or more and 200° or less. The optical properties of the phase shift film.
(構成7) 如構成1至6中任一項之光罩基底,其特徵在於,於上述圖案形成用薄膜上具備對於該圖案形成用薄膜蝕刻選擇性不同之蝕刻遮罩膜。(composition 7) The photomask base according to any one of constitutions 1 to 6, characterized in that the pattern forming film is provided with an etching mask film having different etching selectivities with respect to the pattern forming film.
(構成8) 如構成7之光罩基底,其特徵在於上述蝕刻遮罩膜包含含有鉻且實質上不含矽之材料。(composition 8) The photomask base constituting 7 is characterized in that the etching mask film contains a material containing chromium and substantially free of silicon.
(構成9) 一種光罩之製造方法,其特徵在於包含如下步驟: 準備如構成1至6中任一項之光罩基底;及 於上述圖案形成用薄膜上形成阻劑膜,將自上述阻劑膜形成之阻劑膜圖案作為遮罩對上述圖案形成用薄膜進行濕式蝕刻,於上述透明基板上形成上述轉印圖案。(Composition 9) A method for manufacturing a photomask, which is characterized by including the following steps: Preparing a photomask substrate constituting any one of 1 to 6; and A resist film is formed on the pattern-forming film, and the pattern-forming film is wet-etched using the resist film pattern formed from the resist film as a mask to form the transfer pattern on the transparent substrate.
(構成10) 一種光罩之製造方法,其特徵在於包含如下步驟: 準備如構成7或8之光罩基底; 於上述蝕刻遮罩膜上形成阻劑膜,將自上述阻劑膜形成之阻劑膜圖案作為遮罩對上述蝕刻遮罩膜進行濕式蝕刻,於上述圖案形成用薄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對上述圖案形成用薄膜進行濕式蝕刻,於上述透明基板上形成上述轉印圖案。(composition 10) A method for manufacturing a photomask, which is characterized by including the following steps: Prepare the photomask base that constitutes 7 or 8; A resist film is formed on the etching mask film, and the etching mask film is wet-etched using the resist film pattern formed from the resist film as a mask, and the etching mask film is formed on the pattern forming film. pattern; and The pattern forming film is wet-etched using the etching mask film pattern as a mask to form the transfer pattern on the transparent substrate.
(構成11) 一種顯示裝置之製造方法,其特徵在於包含如下曝光步驟,即,將利用如構成9或10之光罩之製造方法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圖案曝光轉印至形成於顯示裝置基板上之阻劑膜。 [發明之效果](Composition 11) A method of manufacturing a display device, characterized by including an exposure step in which a photomask obtained by the method of manufacturing a photomask of constitution 9 or 10 is placed on a photomask stage of an exposure device, and the photomask formed on the photomask is The above transfer pattern is exposed and transferred to the resist film formed on the display device substrate. [Effects of the invention]
根據本發明之光罩基底,即便對圖案形成用薄膜以過蝕刻時間進行濕式蝕刻,亦可製成可將圖案形成用薄膜圖案化為與透明基板之界面處之滲入得以抑制之截面形狀良好的光罩基底。又,藉由濕式蝕刻,可製成可將圖案形成用薄膜圖案化為面內分佈之CD偏差較小之截面形狀之光罩基底。According to the photomask substrate of the present invention, even if the pattern forming film is wet-etched for an excessive etching time, the pattern forming film can be patterned into a cross-sectional shape having a good cross-sectional shape that suppresses infiltration at the interface with the transparent substrate. The photomask base. Furthermore, by wet etching, it is possible to produce a photomask substrate in which the pattern forming film can be patterned into a cross-sectional shape in which the CD deviation of the in-plane distribution is small.
又,根據本發明之光罩之製造方法,使用上述之光罩基底製造光罩。因此,可製造具有良好之轉印圖案之光罩。又,可製造具有面內分佈之CD偏差較小之轉印圖案之光罩。該光罩可應對線與間隙圖案或接觸孔之微細化。Furthermore, according to the photomask manufacturing method of the present invention, the photomask is manufactured using the above photomask base. Therefore, a photomask with a good transfer pattern can be produced. In addition, it is possible to produce a photomask having a transfer pattern with a smaller CD deviation in the in-plane distribution. This photomask can handle the miniaturization of line and space patterns or contact holes.
又,根據本發明之顯示裝置之製造方法,利用使用上述之光罩基底製造之光罩、或利用上述之光罩之製造方法獲得之光罩製造顯示裝置。因此,可製造具有微細之線與間隙圖案或接觸孔之顯示裝置。Furthermore, according to the manufacturing method of the display device of the present invention, the display device is manufactured using the mask produced using the above-mentioned mask base or the mask obtained by the above-mentioned mask manufacturing method. Therefore, a display device with fine line and gap patterns or contact holes can be manufactured.
以下,對本發明之各實施形態進行說明。於各實施形態中,對光罩基底為相移光罩基底且圖案形成用薄膜為相移膜之情形進行說明,但本發明之內容並不限定於該等。 實施形態1.2. 於實施形態1、2中,對相移光罩基底進行說明。實施形態1之相移光罩基底係用以藉由將於蝕刻遮罩膜形成有所期望之圖案之蝕刻遮罩膜圖案作為遮罩,對相移膜進行濕式蝕刻而形成於透明基板上具有相移膜圖案之相移光罩的原版。又,實施形態2之相移光罩基底係用以藉由將於阻劑膜形成有所期望之圖案之阻劑膜圖案作為遮罩,對相移膜進行濕式蝕刻而形成於透明基板上具有相移膜圖案之相移膜的原版。Each embodiment of the present invention will be described below. In each embodiment, the case where the mask base is a phase shift mask base and the pattern forming thin film is a phase shift film has been described, but the content of the present invention is not limited to this. Implementation form 1.2. In Embodiments 1 and 2, the phase shift mask base is explained. The phase shift mask substrate of Embodiment 1 is formed on a transparent substrate by wet etching the phase shift film using an etching mask film pattern that forms a desired pattern on the etching mask film as a mask. Master of phase shift mask with phase shift film pattern. In addition, the phase shift mask base of Embodiment 2 is formed on a transparent substrate by wet etching the phase shift film using a resist film pattern formed with a desired pattern on the resist film as a mask. A master plate of a phase shift film with a phase shift film pattern.
圖1係表示實施形態1之相移光罩基底10之膜構成之模式圖。 圖1所示之相移光罩基底10具備透明基板20、形成於透明基板20上之相移膜30、及形成於相移膜30上之蝕刻遮罩膜40。 圖2係表示實施形態2之相移光罩基底10之膜構成之模式圖。 圖2所示之相移光罩基底10具備透明基板20、及形成於透明基板20上之相移膜30。 以下,對構成實施形態1及實施形態2之相移光罩基底10之透明基板20、相移膜30及蝕刻遮罩膜40進行說明。FIG. 1 is a schematic diagram showing the film structure of the phase shift mask base 10 according to Embodiment 1. The phase shift mask substrate 10 shown in FIG. 1 includes a transparent substrate 20 , a phase shift film 30 formed on the transparent substrate 20 , and an etching mask film 40 formed on the phase shift film 30 . FIG. 2 is a schematic diagram showing the film structure of the phase shift mask base 10 according to the second embodiment. The phase shift mask substrate 10 shown in FIG. 2 includes a transparent substrate 20 and a phase shift film 30 formed on the transparent substrate 20 . Hereinafter, the transparent substrate 20 , the phase shift film 30 and the etching mask film 40 constituting the phase shift mask base 10 of Embodiments 1 and 2 will be described.
透明基板20對於曝光之光而言為透明。透明基板20係於設為不存在表面反射損失時,對於曝光之光而言具有85%以上之透過率、較佳為90%以上之透過率。透明基板20包含含有矽與氧之材料,可由合成石英玻璃、石英玻璃、鋁矽酸鹽玻璃、鈉鈣玻璃、低熱膨脹玻璃(SiO2 -TiO2 玻璃等)等玻璃材料構成。於透明基板20由低熱膨脹玻璃構成之情形時,可抑制由透明基板20之熱變形引起之相移膜圖案之位置變化。又,以顯示裝置用途使用之相移光罩基底用透明基板20一般使用矩形狀之基板且該透明基板之短邊之長度為300 mm以上者。本發明係可提供如下相移光罩之相移光罩基底,上述相移光罩即便透明基板之短邊之長度為300 mm以上之較大之尺寸,亦可穩定地轉印形成於透明基板上之例如未達2.0 μm之微細之相移膜圖案。The transparent substrate 20 is transparent to exposure light. When there is no surface reflection loss, the transparent substrate 20 has a transmittance of 85% or more, preferably 90% or more, for exposure light. The transparent substrate 20 includes a material containing silicon and oxygen, and may be composed of glass materials such as synthetic quartz glass, quartz glass, aluminosilicate glass, soda-lime glass, low thermal expansion glass (SiO 2 -TiO 2 glass, etc.). When the transparent substrate 20 is made of low thermal expansion glass, positional changes in the phase shift film pattern caused by thermal deformation of the transparent substrate 20 can be suppressed. In addition, the transparent substrate 20 for a phase shift mask base used for a display device generally uses a rectangular substrate and the length of the short side of the transparent substrate is 300 mm or more. The present invention can provide a phase shift mask base for a phase shift mask that can be stably transferred and formed on a transparent substrate even if the length of the short side of the transparent substrate is larger than 300 mm. The above example is a fine phase shift film pattern of less than 2.0 μm.
相移膜30包括含有過渡金屬、矽、氧及氮之過渡金屬矽化物系材料。作為過渡金屬,較佳為鉬(Mo)、鉭(Ta)、鎢(W)、鈦(Ti)、鋯(Zr)等。若含有氮,則可提高折射率,因此,就可使用以獲得相位差之膜厚較薄之方面而言較佳。又,若使相移膜30中包含之氮之含有率變多,則複折射率之吸收係數變大,無法實現較高之透過率。相移膜30中包含之氮之含有率較佳為35原子%以上60原子%以下。理想的是更佳為37原子%以上55原子%以下,進而較佳為40原子%以上50原子%以下。 作為過渡金屬矽化物系材料,例如可列舉過渡金屬矽化物之氮氧化物、過渡金屬矽化物之碳氮氧化物。又,過渡金屬矽化物系材料若為矽化鉬系材料(MoSi系材料)、鋯矽化物系材料(ZrSi系材料)、鉬鋯矽化物系材料(MoZrSi系材料),則就容易藉由濕式蝕刻獲得優異之圖案截面形狀之方面而言較佳。 又,相移膜30中除了含有上述之氧、氮以外,為了膜應力之降低或控制濕式蝕刻速率,亦可含有碳或氦等其他輕元素成分。 相移膜30具有調整對於自透明基板20側入射之光之反射率(以下,有時記載為背面反射率)之功能、及調整對於曝光之光之透過率與相位差之功能。 相移膜30可利用濺鍍法形成。The phase shift film 30 includes a transition metal silicide-based material containing transition metal, silicon, oxygen, and nitrogen. As the transition metal, molybdenum (Mo), tantalum (Ta), tungsten (W), titanium (Ti), zirconium (Zr), etc. are preferred. If nitrogen is contained, the refractive index can be increased, so it is preferable in terms of a thin film thickness that can be used to obtain a phase difference. Furthermore, if the content rate of nitrogen contained in the phase shift film 30 is increased, the absorption coefficient of the complex refractive index becomes large, and high transmittance cannot be achieved. The content rate of nitrogen contained in the phase shift film 30 is preferably 35 atomic % or more and 60 atomic % or less. Ideally, the content is more preferably 37 atomic % or more and 55 atomic % or less, and still more preferably 40 atomic % or more and 50 atomic % or less. Examples of transition metal silicide-based materials include transition metal silicide oxynitrides and transition metal silicide carbonitride oxides. In addition, if the transition metal silicide-based material is a molybdenum silicide-based material (MoSi-based material), a zirconium silicide-based material (ZrSi-based material), or a molybdenum-zirconium silicide-based material (MoZrSi-based material), it can be easily processed by a wet process It is preferable in terms of obtaining an excellent cross-sectional shape of the pattern during etching. In addition, in addition to the above-mentioned oxygen and nitrogen, the phase shift film 30 may also contain other light element components such as carbon or helium for the purpose of reducing film stress or controlling the wet etching rate. The phase shift film 30 has the function of adjusting the reflectance (hereinafter sometimes referred to as back surface reflectance) for light incident from the transparent substrate 20 side, and the function of adjusting the transmittance and phase difference of the exposed light. The phase shift film 30 can be formed by sputtering.
相移膜30對於曝光之光之透過率滿足作為相移膜30所需之值。相移膜30之透過率對於曝光之光中包含之特定波長之光(以下,稱為代表波長)較佳為1%以上80%以下,更佳為5%以上70%以下,進而較佳為10%以上60%以下。即,於曝光之光為包含313 nm以上436 nm以下之波長範圍之光之複合光之情形時,相移膜30對於其波長範圍中包含之代表波長之光具有上述之透過率。例如,於曝光之光為包含i光線、h光線及g光線之複合光之情形時,相移膜30對於i光線、h光線及g光線之任一者具有上述之透過率。 相移膜30之透過率可藉由相移膜30中包含之過渡金屬與矽之原子比率進行調節。為了將相移膜30之透過率設為上述透過率,過渡金屬與矽之原子比率構成為1:1以上1:15以下。為了提高相移膜30之抗藥性(耐清洗性),更理想的是過渡金屬與矽之原子比率較佳為1:2以上1:15以下,進而較佳為1:4以上1:10以下。 透過率可使用相移量測定裝置等測定。The transmittance of the phase shift film 30 for exposure light satisfies the value required for the phase shift film 30 . The transmittance of the phase shift film 30 is preferably not less than 1% and not more than 80%, more preferably not less than 5% and not more than 70%, and still more preferably not less than 1% and not more than 80% for the light of a specific wavelength (hereinafter referred to as the representative wavelength) included in the exposure light. More than 10% and less than 60%. That is, when the exposed light is composite light including light in the wavelength range of 313 nm to 436 nm, the phase shift film 30 has the above-mentioned transmittance for the light of the representative wavelength included in the wavelength range. For example, when the exposure light is a composite light including i rays, h rays, and g rays, the phase shift film 30 has the above-mentioned transmittance for any of the i rays, h rays, and g rays. The transmittance of the phase shift film 30 can be adjusted by the atomic ratio of the transition metal and silicon contained in the phase shift film 30 . In order to set the transmittance of the phase shift film 30 to the above-mentioned transmittance, the atomic ratio of the transition metal and silicon is 1:1 or more and 1:15 or less. In order to improve the chemical resistance (cleaning resistance) of the phase shift film 30, the atomic ratio of the transition metal and silicon is preferably 1:2 or more and 1:15 or less, and further preferably 1:4 or more and 1:10 or less. . The transmittance can be measured using a phase shift amount measuring device or the like.
相移膜30相對於曝光之光之相位差滿足作為相移膜30所需之值。相移膜30之相位差相對於曝光之光中包含之代表波長之光,較佳為160°以上200°以下,更佳為170°以上190°以下。藉由該性質,可使曝光之光中包含之代表波長之光之相位於160°以上200°以下之範圍內變化。因此,於透過相移膜30之代表波長之光與僅透過透明基板20之代表波長之光之間產生160°以上200°以下之相位差。即,於曝光之光為包含313 nm以上436 nm以下之波長範圍之光之複合光之情形時,相移膜30相對於其波長範圍中包含之代表波長之光具有上述之相位差。例如,於曝光之光為包含i光線、h光線及g光線之複合光之情形時,相移膜30相對於i光線、h光線及g光線之任一者具有上述之相位差。 相位差可使用相移量測定裝置等測定。The phase difference of the phase shift film 30 with respect to the exposure light satisfies the required value for the phase shift film 30 . The phase difference of the phase shift film 30 is preferably not less than 160° and not more than 200°, more preferably not less than 170° and not more than 190° with respect to the light representative wavelength included in the exposure light. With this property, the phase of the representative wavelength of light contained in the exposed light can be changed within the range of 160° to 200°. Therefore, a phase difference of not less than 160° and not more than 200° is generated between the light of the representative wavelength transmitted through the phase shift film 30 and the light of the representative wavelength transmitted only through the transparent substrate 20 . That is, when the exposed light is composite light including light in the wavelength range of 313 nm to 436 nm, the phase shift film 30 has the above-mentioned phase difference with respect to the light of the representative wavelength included in the wavelength range. For example, when the exposure light is a composite light including i rays, h rays, and g rays, the phase shift film 30 has the above-mentioned phase difference with respect to any one of the i rays, h rays, and g rays. The phase difference can be measured using a phase shift amount measuring device or the like.
相移膜30之背面反射率係於365 nm~436 nm之波長區域為15%以下,較佳為10%以下。又,於曝光之光中包含j光線之情形時,相移膜30之背面反射率較佳為對於313 nm至436 nm之波長區域之光為20%以下,更佳為17%以下。理想的是進而較佳為15%以下。又,相移膜30之背面反射率於365 nm~436 nm之波長區域為0.2%以上,較佳為對於313 nm至436 nm之波長區域之光為0.2%以上。 背面反射率可使用分光光度計等測定。The back surface reflectance of the phase shift film 30 is 15% or less in the wavelength range of 365 nm to 436 nm, preferably 10% or less. Furthermore, when the exposure light includes j rays, the backside reflectivity of the phase shift film 30 is preferably 20% or less, more preferably 17% or less, for light in the wavelength range of 313 nm to 436 nm. It is ideal and more preferably 15% or less. In addition, the back surface reflectance of the phase shift film 30 is 0.2% or more in the wavelength range of 365 nm to 436 nm, preferably 0.2% or more for the light in the wavelength range of 313 nm to 436 nm. The back surface reflectance can be measured using a spectrophotometer or the like.
以相移膜30成為上述之相位差及透過率之方式,又,視需要以相移膜30成為上述之背面反射率之方式,調節相移膜30中包含之氧之含有率。具體而言,相移膜30係以氧之含有率成為1原子%以上70原子%以下之方式構成。相移膜30中包含之氧之含有率較佳為5原子%以上70原子%以下,進而較佳為10原子%以上60原子%以下。該相移膜30可包括複數層,亦可由單一之層構成。由單一之層構成之相移膜30就不易於相移膜30中形成界面而容易控制截面形狀之方面而言較佳。另一方面,包括複數層之相移膜30就成膜之容易度等方面而言較佳。 又,關於相移膜30中包含之氮或氧之輕元素,可於相移膜30之膜厚方向上均勻地包含,又,亦可階段性地或連續地增加或減少。再者,上述氮之含有率及氧之含有率較佳為於相移膜30之膜厚之50%以上之區域中成為上述之特定之含有率。The content rate of oxygen contained in the phase shift film 30 is adjusted so that the phase shift film 30 achieves the above-mentioned phase difference and transmittance, and if necessary, so that the phase shift film 30 achieves the above-mentioned back surface reflectivity. Specifically, the phase shift film 30 is configured such that the oxygen content is 1 atomic % or more and 70 atomic % or less. The content rate of oxygen contained in the phase shift film 30 is preferably 5 atomic % or more and 70 atomic % or less, and more preferably 10 atomic % or more and 60 atomic % or less. The phase shift film 30 may include multiple layers or may be composed of a single layer. The phase shift film 30 composed of a single layer is preferable in that an interface is not easily formed in the phase shift film 30 and the cross-sectional shape can be easily controlled. On the other hand, the phase shift film 30 including a plurality of layers is preferable in terms of ease of film formation and the like. In addition, the light element of nitrogen or oxygen contained in the phase shift film 30 may be uniformly contained in the film thickness direction of the phase shift film 30, or may be increased or decreased stepwise or continuously. Furthermore, it is preferable that the nitrogen content and the oxygen content be the above-mentioned specific content in a region of 50% or more of the film thickness of the phase shift film 30 .
又,相移膜30係於將透明基板20與相移膜30之界面定義為藉由XPS進行分析所獲得之相移膜30中包含之過渡金屬之含有率為0原子%之位置時,於自該界面往向相移膜30之表面30 nm以內之區域中,氮相對於氧之比率具有極大值。再者,該極大值並不限定於數學意義上之極大值,亦包含如圖9所示,處於自上述界面起30 nm以內之區域中、可視為自透明基板側觀察到之N/O之變化自增加轉變為減少之點。Furthermore, when the interface between the transparent substrate 20 and the phase shift film 30 is defined as a position where the content rate of the transition metal contained in the phase shift film 30 obtained by XPS analysis is 0 atomic %, the phase shift film 30 In a region within 30 nm from this interface to the surface of the phase shift film 30, the ratio of nitrogen to oxygen has a maximum value. Furthermore, the maximum value is not limited to the maximum value in the mathematical sense, but also includes the N/O value observed from the transparent substrate side in the region within 30 nm from the above-mentioned interface as shown in Figure 9. The point at which change changes from increase to decrease.
又,相移光罩基底10之相移膜30要求抗藥性(耐清洗性)較高。為了提高該相移膜30之抗藥性(耐清洗性),有效的是提高膜密度。相移膜30之膜密度與膜應力存在關聯,考慮到抗藥性(耐清洗性),相移膜30之膜應力越高越佳。另一方面,關於相移膜30之膜應力,必須考慮形成相移膜圖案時之位置偏移或相移膜圖案之缺失。就以上之觀點而言,相移膜30之膜應力較佳為0.2 GPa以上0.8 GPa以下,進而較佳為0.4 GPa以上0.8 GPa以下。 又,相移光罩基底10之相移膜30較佳為具有柱狀構造。柱狀構造可藉由對相移膜30進行截面SEM(scanning electron microscope,掃描式電子顯微鏡)觀察而確認。即,所謂柱狀構造係指構成相移膜30之含有過渡金屬、矽、氧及氮之過渡金屬矽化物化合物之粒子具有往向相移膜30之膜厚方向(上述粒子沈積之方向)延伸之柱狀之粒子構造的狀態。藉由將相移膜30設為柱狀構造,可有效地抑制對相移膜30進行濕式蝕刻時之側面蝕刻,使圖案截面形狀更良好。再者,作為柱狀構造之較佳之形態,較佳為於膜厚方向上延伸之柱狀之粒子於膜厚方向上不規則地形成。進而較佳為相移膜30之柱狀之粒子為膜厚方向之長度不一致之狀態。並且,較佳為於相移膜30中,與柱狀之粒子相比密度相對較低之稀疏部分(以下,簡稱為「稀疏部分」)於膜厚方向上連續地形成。In addition, the phase shift film 30 of the phase shift mask base 10 is required to have high chemical resistance (cleaning resistance). In order to improve the chemical resistance (cleaning resistance) of the phase shift film 30, it is effective to increase the film density. There is a correlation between the film density of the phase shift film 30 and the film stress. Considering chemical resistance (cleaning resistance), the higher the film stress of the phase shift film 30, the better. On the other hand, regarding the film stress of the phase shift film 30, it is necessary to consider the positional shift when forming the phase shift film pattern or the lack of the phase shift film pattern. From the above viewpoint, the film stress of the phase shift film 30 is preferably not less than 0.2 GPa and not more than 0.8 GPa, and further preferably not less than 0.4 GPa and not more than 0.8 GPa. In addition, the phase shift film 30 of the phase shift mask substrate 10 preferably has a columnar structure. The columnar structure can be confirmed by cross-sectional SEM (scanning electron microscope) observation of the phase shift film 30 . That is, the so-called columnar structure means that the particles of the transition metal silicide compound containing transition metal, silicon, oxygen, and nitrogen that constitute the phase shift film 30 extend in the film thickness direction of the phase shift film 30 (the direction in which the above-mentioned particles are deposited). The state of the columnar particle structure. By forming the phase shift film 30 into a columnar structure, side etching during wet etching of the phase shift film 30 can be effectively suppressed, resulting in a better pattern cross-sectional shape. Furthermore, as a preferred form of the columnar structure, columnar particles extending in the film thickness direction are preferably formed irregularly in the film thickness direction. Furthermore, it is preferable that the lengths of the columnar particles of the phase shift film 30 in the film thickness direction are inconsistent. Furthermore, it is preferable that sparse portions (hereinafter, simply referred to as “sparse portions”) having a relatively lower density than columnar particles are formed continuously in the film thickness direction in the phase shift film 30 .
蝕刻遮罩膜40係配置於相移膜30之上側,包含對於蝕刻相移膜30之蝕刻液具有耐蝕刻性(蝕刻選擇性不同)之材料。又,蝕刻遮罩膜40可具有將曝光之光之透過遮斷之功能,進而,亦可具有降低膜面反射率,使相移膜30對於自相移膜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%以下的功能。蝕刻遮罩膜40較佳為包含含有鉻且實質上不含矽之材料(鉻系材料)。作為鉻系材料,更具體而言,可列舉鉻(Cr)、或含有鉻(Cr)與氧(O)、氮(N)、碳(C)中之至少任一個之材料。或者,可列舉包含鉻(Cr)與氧(O)、氮(N)、碳(C)中之至少任一個且進而包含氟(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、CrCONF。 蝕刻遮罩膜40可利用濺鍍法形成。The etching mask film 40 is disposed on the upper side of the phase shift film 30 and includes a material with etching resistance (different etching selectivity) to the etching liquid used to etch the phase shift film 30 . In addition, the etching mask film 40 can have the function of blocking the transmission of exposure light, and further, can also have the function of reducing the film surface reflectivity, so that the phase shift film 30 can reflect the film surface of the light incident from the phase shift film 30 side. The rate becomes less than 15% in the wavelength range of 350 nm to 436 nm. The etching mask film 40 preferably contains a material containing chromium and substantially not containing silicon (chromium-based material). More specifically, the chromium-based material may include chromium (Cr) or a material containing at least one of chromium (Cr) and oxygen (O), nitrogen (N), or carbon (C). Alternatively, a material containing at least one of chromium (Cr) and oxygen (O), nitrogen (N), and carbon (C) and further containing fluorine (F) can be cited. For example, materials constituting the etching mask film 40 include Cr, CrO, CrN, CrF, CrCO, CrCN, CrON, CrCON, and CrCONF. The etching mask film 40 can be formed by sputtering.
於蝕刻遮罩膜40具有將曝光之光之透過遮斷之功能之情形時,於相移膜30與蝕刻遮罩膜40積層之部分,相對於曝光之光之光學密度較佳為3.0以上,更佳為3.5以上,進而較佳為4.0以上。 光學密度可使用分光光度計或OD(Optical Density,光學密度)測定計等測定。When the etching mask film 40 has a function of blocking the transmission of exposure light, the optical density of the portion where the phase shift film 30 and the etching mask film 40 are laminated relative to the exposure light is preferably 3.0 or more. More preferably, it is 3.5 or more, and still more preferably, it is 4.0 or more. The optical density can be measured using a spectrophotometer or an OD (Optical Density) meter.
蝕刻遮罩膜40根據功能可為由組成均勻之單一之膜構成之情形,亦可為包括組成不同之複數個膜之情形,還可為由在厚度方向上組成連續地變化之單一之膜構成之情形。The etching mask film 40 may be composed of a single film with a uniform composition depending on the function, may be composed of a plurality of films with different compositions, or may be composed of a single film whose composition continuously changes in the thickness direction. situation.
再者,圖1所示之相移光罩基底10於相移膜30上具備蝕刻遮罩膜40,但亦可對在相移膜30上具備蝕刻遮罩膜40且於蝕刻遮罩膜40上具備阻劑膜之相移光罩基底應用本發明。Furthermore, the phase shift mask substrate 10 shown in FIG. 1 is provided with the etching mask film 40 on the phase shift film 30 , but it may also be provided with the etching mask film 40 on the phase shift film 30 and the etching mask film 40 The present invention is applied to a phase shift mask substrate with a resist film on it.
又,相移光罩基底10較佳為構成為於相移膜30與蝕刻遮罩膜40之界面形成組成梯度區域,於該組成梯度區域包含氧之比率往向深度方向階段性地及/或連續地增加之區域。更具體而言,較佳為於上述組成梯度區域中,至少具有於自相移膜30與蝕刻遮罩膜40之界面往向透明基板20側之深度方向上氧之比率階段性地及/或連續地增加的區域。 並且,相移光罩基底10較佳為構成為遍及自相移膜30與蝕刻遮罩膜40之界面起10 nm之深度之區域,氧相對於矽之含有比率為3.0以下。當對相移光罩基底10藉由X射線光電子光譜法進行組成分析時,過渡金屬之比率自相移膜30往向蝕刻遮罩膜40減少,將過渡金屬之含有率初次成為0原子%之位置設為該界面。又,此處言及之上述組成梯度區域係指相移膜30與蝕刻遮罩膜40之界面(過渡金屬之比率自相移膜30往向蝕刻遮罩膜40減少、過渡金屬之含有率初次成為0原子%的位置)與鉻之比率自蝕刻遮罩膜40往向相移膜30減少、鉻之含有率初次成為0原子%之位置為止的區域。 遍及自相移膜30與蝕刻遮罩膜40之界面起10 nm之深度之區域的氧相對於矽之含有比率較佳為3.0以下,更佳為2.8以下,進而較佳為2.5以下,更進一步較佳為2.0以下。再者,就相移膜30與組成梯度區域之膜質連續性之觀點而言,上述氧相對於矽之含有比率較佳為0.3以上,進而較佳為0.5以上。Furthermore, the phase shift mask substrate 10 is preferably configured such that a composition gradient region is formed at the interface between the phase shift film 30 and the etching mask film 40, and the ratio of oxygen contained in the composition gradient region gradually and/or gradually increases in the depth direction. A continuously increasing area. More specifically, it is preferable that the ratio of oxygen in the depth direction from the interface between the phase shift film 30 and the etching mask film 40 toward the transparent substrate 20 side is gradually and/or Continuously increasing area. Furthermore, the phase shift mask base 10 is preferably configured to have an oxygen to silicon content ratio of 3.0 or less throughout a region extending to a depth of 10 nm from the interface between the phase shift film 30 and the etching mask film 40 . When the composition of the phase shift mask substrate 10 is analyzed by X-ray photoelectron spectroscopy, the ratio of the transition metal decreases from the phase shift film 30 toward the etching mask film 40, bringing the content of the transition metal to 0 atomic % for the first time. The location is set to this interface. In addition, the composition gradient region mentioned here refers to the interface between the phase shift film 30 and the etching mask film 40 (the ratio of the transition metal decreases from the phase shift film 30 toward the etching mask film 40, and the content of the transition metal becomes The ratio of 0 atomic %) to chromium decreases from the etching mask film 40 toward the phase shift film 30 until the chromium content becomes 0 atomic % for the first time. The content ratio of oxygen to silicon in the region at a depth of 10 nm from the interface between the phase shift film 30 and the etching mask film 40 is preferably 3.0 or less, more preferably 2.8 or less, still more preferably 2.5 or less, and still more preferably Preferably it is 2.0 or less. Furthermore, from the viewpoint of film quality continuity between the phase shift film 30 and the composition gradient region, the content ratio of oxygen to silicon is preferably 0.3 or more, and more preferably 0.5 or more.
接下來,對該實施形態1及2之相移光罩基底10之製造方法進行說明。圖1所示之相移光罩基底10係藉由進行以下之老化步驟、相移膜形成步驟及蝕刻遮罩膜形成步驟製造。圖2所示之相移光罩基底10係藉由老化步驟與相移膜形成步驟製造。 以下,對各步驟詳細地進行說明。Next, the manufacturing method of the phase shift mask base 10 of Embodiment 1 and 2 is demonstrated. The phase shift mask substrate 10 shown in FIG. 1 is manufactured by performing the following aging steps, phase shift film forming steps and etching mask film forming steps. The phase shift mask substrate 10 shown in FIG. 2 is manufactured through an aging step and a phase shift film forming step. Each step is explained in detail below.
1.老化步驟 首先,於將透明基板20導入成膜室內之前進行老化步驟,即,利用濺鍍法使粒子自靶飛出,使靶之表面狀態接近薄膜形成步驟時之表面狀態。於該實施形態1及2之老化步驟中,除了濺鍍效率較高之稀有氣體(氬氣等)以外,還將氮氣導入至成膜室內,使該稀有氣體與氮氣之電漿碰撞靶之表面而使構成靶之表面之各原子彈飛,藉此清潔靶之表面。並且,使稀有氣體與氮氣殘留於成膜室內。1. Aging steps First, an aging step is performed before the transparent substrate 20 is introduced into the film forming chamber. That is, the sputtering method is used to fly particles from the target so that the surface state of the target is close to the surface state during the thin film forming step. In the aging steps of Embodiments 1 and 2, in addition to rare gases (argon gas, etc.) with high sputtering efficiency, nitrogen gas is also introduced into the film-forming chamber, so that the plasma of the rare gas and nitrogen collides with the surface of the target. The atoms constituting the surface of the target are blown away, thereby cleaning the surface of the target. Furthermore, rare gas and nitrogen gas are allowed to remain in the film forming chamber.
2.相移膜形成步驟 繼而,準備透明基板20。透明基板20只要對於曝光之光為透明,則可為由合成石英玻璃、石英玻璃、鋁矽酸鹽玻璃、鈉鈣玻璃、低熱膨脹玻璃(SiO2 -TiO2 玻璃等)等任一種玻璃材料構成者。2. Phase Shift Film Formation Step Next, the transparent substrate 20 is prepared. The transparent substrate 20 may be made of any glass material such as synthetic quartz glass, quartz glass, aluminosilicate glass, soda-lime glass, low thermal expansion glass (SiO 2 -TiO 2 glass, etc.) as long as it is transparent to exposure light. By.
繼而,於透明基板20上利用濺鍍法形成相移膜30。 相移膜30之成膜係使用包含作為構成相移膜30之材料之主成分之過渡金屬與矽之濺鍍靶、或包含過渡金屬、矽以及氧及/或氮之濺鍍靶,例如在由濺鍍氣體氛圍與活性氣體之混合氣體構成的濺鍍氣體氛圍下進行,濺鍍氣體氛圍由包含選自由氦氣、氖氣、氬氣、氪氣及氙氣所組成之群之至少一種之惰性氣體構成,活性氣體係選自由氧氣、氮氣、二氧化碳氣體、一氧化氮氣體、二氧化氮氣體所組成之群之至少包含氧與氮的氣體。Then, the phase shift film 30 is formed on the transparent substrate 20 by sputtering. The phase shift film 30 is formed using a sputtering target containing a transition metal and silicon as the main components of the material constituting the phase shift film 30, or a sputtering target containing a transition metal, silicon, and oxygen and/or nitrogen. For example, It is carried out in a sputtering gas atmosphere composed of a mixture of a sputtering gas atmosphere and an active gas. The sputtering gas atmosphere consists of at least one inert gas selected from the group consisting of helium, neon, argon, krypton and xenon. Composed of gas, the active gas system is selected from the group consisting of oxygen, nitrogen, carbon dioxide gas, nitric oxide gas, and nitrogen dioxide gas, and contains at least oxygen and nitrogen.
藉由上述之老化步驟,以氮殘留於成膜室內之狀態進行相移膜30之成膜。因此,於相移膜30中自成膜最初便取入氮。另一方面,殘留於成膜室內之氮之量係固定量,相移膜形成步驟時供給之混合氣體移動至成膜室內之濺鍍靶周圍需要一定時間。因此,於自相移膜30之成膜開始相對較早之階段,殘留於成膜室內之氮之大部分被取入至相移膜30中或被排出,因此缺乏,之後取入之相移膜中之氮之量暫且減少。另一方面,認為如上所述,若取入至相移膜30中之氮之量減少,則氧之量增加,氮相對於氧之比率(N/O)暫且減少。其後,供給至成膜室內之混合氣體遍佈成膜室內,相移膜中之氮之量、以及氮相對於氧之比率(N/O)再次上升。如此,相移膜30成為於自透明基板20側起之附近區域(自藉由XPS進行分析所獲得之界面起30 nm以內之區域),氮相對於氧之比率具有極大值。 相移膜30之組成及厚度係以使相移膜30成為上述之相位差及透過率之方式調整。相移膜30之組成可藉由構成濺鍍靶之元素之含有比率(例如,過渡金屬之含有率與矽之含有率之比)、濺鍍氣體之組成及流量等進行控制。相移膜30之厚度可藉由濺鍍功率、濺鍍時間等進行控制。又,於濺鍍裝置為連續式濺鍍裝置之情形時,藉由基板之搬送速度,亦可控制相移膜30之厚度。如此,以相移膜30之氧之含有率成為1原子%以上70原子%以下之方式進行控制。Through the above aging step, the phase shift film 30 is formed with nitrogen remaining in the film forming chamber. Therefore, nitrogen is introduced into the phase shift film 30 from the beginning of film formation. On the other hand, the amount of nitrogen remaining in the film formation chamber is a fixed amount, and it takes a certain amount of time for the mixed gas supplied during the phase shift film formation step to move around the sputtering target in the film formation chamber. Therefore, at a relatively early stage from the start of the film formation of the phase shift film 30, most of the nitrogen remaining in the film formation chamber is taken into the phase shift film 30 or discharged, and therefore is insufficient for the phase shift taken in later. The amount of nitrogen in the membrane is temporarily reduced. On the other hand, it is considered that when the amount of nitrogen introduced into the phase shift film 30 decreases as described above, the amount of oxygen increases, and the ratio of nitrogen to oxygen (N/O) temporarily decreases. Thereafter, the mixed gas supplied to the film forming chamber spreads throughout the film forming chamber, and the amount of nitrogen in the phase shift film and the ratio of nitrogen to oxygen (N/O) increase again. In this manner, the phase shift film 30 has a maximum value in the ratio of nitrogen to oxygen in the vicinity of the transparent substrate 20 side (the region within 30 nm from the interface obtained by XPS analysis). The composition and thickness of the phase shift film 30 are adjusted so that the phase shift film 30 achieves the above-mentioned phase difference and transmittance. The composition of the phase shift film 30 can be controlled by the content ratio of elements constituting the sputtering target (for example, the ratio of the content ratio of transition metal to the content ratio of silicon), the composition and flow rate of the sputtering gas, and the like. The thickness of the phase shift film 30 can be controlled by sputtering power, sputtering time, etc. In addition, when the sputtering device is a continuous sputtering device, the thickness of the phase shift film 30 can also be controlled by the conveyance speed of the substrate. In this way, the oxygen content of the phase shift film 30 is controlled so that it becomes 1 atomic % or more and 70 atomic % or less.
於相移膜30分別由組成均勻之單一之膜構成之情形時,不改變濺鍍氣體之組成及流量地僅進行上述之成膜製程1次。於相移膜30包括組成不同之複數個膜之情形時,對每一次成膜製程改變濺鍍氣體之組成及流量,進行複數次上述之成膜製程。亦可使用構成濺鍍靶之元素之含有比率不同之靶成膜相移膜30。於相移膜30由在厚度方向上組成連續地變化之單一之膜構成之情形時,使濺鍍氣體之組成及流量隨著成膜製程之時間經過而變化並且僅進行上述之成膜製程1次。於進行複數次成膜製程之情形時,可減小對濺鍍靶施加之濺鍍功率。When the phase shift films 30 are each composed of a single film with a uniform composition, the above-mentioned film forming process is only performed once without changing the composition and flow rate of the sputtering gas. When the phase shift film 30 includes a plurality of films with different compositions, the composition and flow rate of the sputtering gas are changed for each film formation process, and the above film formation process is performed a plurality of times. The phase shift film 30 may be formed using targets having different content ratios of elements constituting the sputtering target. When the phase shift film 30 is composed of a single film whose composition continuously changes in the thickness direction, the composition and flow rate of the sputtering gas are changed with the passage of time in the film formation process and only the above-mentioned film formation process 1 is performed. Second-rate. When performing a plurality of film forming processes, the sputtering power applied to the sputtering target can be reduced.
3.表面處理步驟 形成包括含有過渡金屬、矽及氧之過渡金屬矽化物材料之相移膜30後,相移膜30之表面容易被氧化,容易生成過渡金屬之氧化物。為了抑制因存在過渡金屬之氧化物而導致蝕刻液滲入,進行調整相移膜30之表面氧化之狀態之表面處理步驟。 作為調整相移膜30之表面氧化之狀態之表面處理步驟,可列舉利用酸性之水溶液進行表面處理之方法、利用鹼性之水溶液進行表面處理之方法、利用灰化等乾式處理進行表面處理之方法等。 於下述蝕刻遮罩膜形成步驟之後,可進行任意之表面處理步驟,只要於相移膜30與蝕刻遮罩膜40之界面形成組成梯度區域,於該組成梯度區域中,包含氧之比率往向深度方向階段性地及/或連續地增加之區域,進而,遍及自相移膜30與蝕刻遮罩膜40之界面起10 nm之深度之區域的氧相對於矽之含有比率成為3.0以下即可。 例如,於利用酸性之水溶液進行表面處理之方法、利用鹼性之水溶液進行表面處理之方法中,藉由適當調整酸性或鹼性之水溶液之濃度、溫度、時間,可調整相移膜30之表面氧化之狀態。作為利用酸性之水溶液進行表面處理之方法、利用鹼性之水溶液進行表面處理之方法,可列舉將於透明基板20上形成有相移膜30之帶相移膜之基板浸漬於上述水溶液之方法、或使上述水溶液接觸於相移膜30上之方法等。就使與蝕刻遮罩膜40之界面處之截面形狀良好之觀點而言,較佳為進行該表面處理步驟,但並非必需之步驟。 如此,可獲得實施形態2之相移光罩基底10。實施形態1之相移光罩基底10之製造進而進行以下之蝕刻遮罩膜形成步驟。3. Surface treatment steps After the phase shift film 30 including the transition metal silicide material containing transition metal, silicon and oxygen is formed, the surface of the phase shift film 30 is easily oxidized, and transition metal oxides are easily generated. In order to prevent the etching liquid from penetrating due to the presence of transition metal oxides, a surface treatment step is performed to adjust the surface oxidation state of the phase shift film 30 . Examples of surface treatment steps for adjusting the surface oxidation state of the phase shift film 30 include surface treatment with an acidic aqueous solution, surface treatment with an alkaline aqueous solution, and surface treatment with dry treatment such as ashing. wait. After the etching mask film formation step described below, any surface treatment step can be performed as long as a composition gradient region is formed at the interface between the phase shift film 30 and the etching mask film 40. In the composition gradient region, the ratio of oxygen is In a region that increases stepwise and/or continuously in the depth direction, and further in a region with a depth of 10 nm from the interface between the phase shift film 30 and the etching mask film 40, the oxygen to silicon content ratio becomes 3.0 or less, that is, Can. For example, in the surface treatment method using an acidic aqueous solution or the surface treatment method using an alkaline aqueous solution, the surface of the phase shift film 30 can be adjusted by appropriately adjusting the concentration, temperature, and time of the acidic or alkaline aqueous solution. The state of oxidation. Examples of the surface treatment method using an acidic aqueous solution and the surface treatment method using an alkaline aqueous solution include a method of immersing a substrate with a phase shift film on which the phase shift film 30 is formed on the transparent substrate 20 in the above aqueous solution. Or a method of bringing the above-mentioned aqueous solution into contact with the phase shift film 30, etc. From the viewpoint of improving the cross-sectional shape at the interface with the etching mask film 40, it is preferable to perform this surface treatment step, but it is not a necessary step. In this way, the phase shift mask base 10 of Embodiment 2 can be obtained. The phase shift mask substrate 10 of Embodiment 1 is manufactured by further performing the following steps of forming an etching mask film.
4.蝕刻遮罩膜形成步驟 進行調整相移膜30之表面之表面氧化之狀態之表面處理之後,藉由濺鍍法,於相移膜30上形成蝕刻遮罩膜40。 如此,獲得相移光罩基底10。 蝕刻遮罩膜40之成膜係使用包含鉻或鉻化合物(氧化鉻、氮化鉻、碳化鉻、氮氧化鉻、碳氮氧化鉻等)之濺鍍靶,例如,於由包含選自由氦氣、氖氣、氬氣、氪氣及氙氣所組成之群之至少一種之惰性氣體構成的濺鍍氣體氛圍、或由包含選自由氦氣、氖氣、氬氣、氪氣及氙氣所組成之群之至少一種之惰性氣體與包含選自由氧氣、氮氣、一氧化氮氣體、二氧化氮氣體、二氧化碳氣體、烴系氣體、氟系氣體所組成之群之至少一種之活性氣體之混合氣體構成的濺鍍氣體氛圍下進行。作為烴系氣體,例如可列舉甲烷氣體、丁烷氣體、丙烷氣體、苯乙烯氣體等。4. Etching mask film formation steps After performing surface treatment to adjust the surface oxidation state of the surface of the phase shift film 30, an etching mask film 40 is formed on the phase shift film 30 by a sputtering method. In this way, the phase shift mask substrate 10 is obtained. The etching mask film 40 is formed by using a sputtering target containing chromium or a chromium compound (chromium oxide, chromium nitride, chromium carbide, chromium oxynitride, chromium oxycarbonitride, etc.), for example, in a gas containing helium gas. , a sputtering gas atmosphere composed of at least one inert gas selected from the group consisting of neon, argon, krypton and xenon, or a sputtering gas atmosphere containing a group selected from the group consisting of helium, neon, argon, krypton and xenon A sputter consisting of at least one inert gas and a mixed gas containing at least one active gas selected from the group consisting of oxygen, nitrogen, nitric oxide gas, nitrogen dioxide gas, carbon dioxide gas, hydrocarbon gas, and fluorine gas. Conducted under plating gas atmosphere. 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由組成均勻之單一之膜構成之情形時,不改變濺鍍氣體之組成及流量地僅進行上述之成膜製程1次。於蝕刻遮罩膜40包括組成不同之複數種膜之情形時,對每一次成膜製程改變濺鍍氣體之組成及流量,進行複數次上述之成膜製程。於蝕刻遮罩膜40由在厚度方向上組成連續地變化之單一之膜構成之情形時,使濺鍍氣體之組成及流量隨著成膜製程之時間經過而變化,並且僅進行上述之成膜製程1次。 如此,可獲得實施形態1之相移光罩基底10。When the etching mask film 40 is composed of a single film with a uniform composition, the above-mentioned film forming process is only performed once without changing the composition and flow rate of the sputtering gas. When the etching mask film 40 includes a plurality of films with different compositions, the composition and flow rate of the sputtering gas are changed for each film-forming process, and the above-mentioned film-forming process is performed a plurality of times. When the etching mask film 40 is composed of a single film whose composition continuously changes in the thickness direction, the composition and flow rate of the sputtering gas are changed with the passage of time in the film formation process, and only the above-mentioned film formation is performed. Process 1 time. In this way, the phase shift mask base 10 of Embodiment 1 can be obtained.
藉由如此進行相移膜30與蝕刻遮罩膜40之成膜製程、及調整相移膜30之表面之表面氧化之狀態之表面處理,可將相移膜30與蝕刻遮罩膜40成膜為於相移膜30與蝕刻遮罩膜40之界面形成組成梯度區域,於該組成梯度區域中,包含氧之比率往向深度方向階段性地及/或連續地增加之區域,遍及自相移膜與上述蝕刻遮罩膜之界面起10 nm之深度之區域的氧相對於矽之含有比率為3.0以下。By performing the film formation process of the phase shift film 30 and the etching mask film 40 in this way, and adjusting the surface oxidation state of the surface of the phase shift film 30, the phase shift film 30 and the etching mask film 40 can be formed. In order to form a composition gradient region at the interface between the phase shift film 30 and the etching mask film 40, the composition gradient region includes a region in which the ratio of oxygen increases stepwise and/or continuously in the depth direction, throughout the self-phase shift The content ratio of oxygen to silicon in a region with a depth of 10 nm from the interface between the film and the etching mask film is 3.0 or less.
再者,對調整相移膜30之表面之表面氧化之狀態之表面處理進行了說明,但亦可於相移膜30之成膜製程中,於成膜製程之後半部分,變更為使相移膜30之表面不易被表面氧化之氣體種類或者添加上述氣體種類等,藉此,使得包含上述組成梯度區域中之氧之比率往向深度方向階段性地及/或連續地增加之區域,將遍及自相移膜與上述蝕刻遮罩膜之界面起10 nm之深度之區域的氧相對於矽之含有比率設為3.0以下。Furthermore, the surface treatment for adjusting the surface oxidation state of the surface of the phase shift film 30 has been described. However, in the film formation process of the phase shift film 30, the phase shift may be changed in the second half of the film formation process. The surface of the film 30 is not easily oxidized by gas species or by adding the above-mentioned gas species, so that the ratio of oxygen in the composition gradient region including the above-mentioned composition gradient region increases stepwise and/or continuously in the depth direction. The content ratio of oxygen to silicon in a region at a depth of 10 nm from the interface between the phase shift film and the etching mask film is set to 3.0 or less.
再者,圖1所示之相移光罩基底10於相移膜30上具備蝕刻遮罩膜40,因此,當製造相移光罩基底10時,進行蝕刻遮罩膜形成步驟。又,當製造於相移膜30上具備蝕刻遮罩膜40且於蝕刻遮罩膜40上具備阻劑膜之相移光罩基底時,於蝕刻遮罩膜形成步驟後,於蝕刻遮罩膜40上形成阻劑膜。又,當製造於圖2所示之相移光罩基底10中於相移膜30上具備阻劑膜之相移光罩基底時,於相移膜形成步驟後形成阻劑膜。Furthermore, the phase shift mask substrate 10 shown in FIG. 1 is provided with an etching mask film 40 on the phase shift film 30. Therefore, when manufacturing the phase shift mask substrate 10, an etching mask film forming step is performed. In addition, when the phase shift mask substrate is manufactured with the etching mask film 40 on the phase shift film 30 and the resist film on the etching mask film 40, after the etching mask film forming step, the etching mask film is A resist film is formed on 40. Furthermore, when a phase shift mask substrate having a resist film on the phase shift film 30 is manufactured in the phase shift mask substrate 10 shown in FIG. 2 , the resist film is formed after the phase shift film forming step.
該實施形態1及2之相移光罩基底10係以如下方式構成相移膜30,即,含有過渡金屬、矽、氧及氮,藉由XPS進行分析所獲得之氧之含有率為1原子%以上70原子%以下(較佳為氧之含有率為5原子%以上70原子%以下),且將透明基板20與相移膜30之界面定義為藉由XPS進行分析所獲得之相移膜30中包含之過渡金屬之含有率為0原子%之位置時,於自該界面往向相移膜30之表面30 nm以內之區域中,氮相對於氧之比率具有極大值。藉此,於對相移膜30以過蝕刻時間進行濕式蝕刻而形成於透明基板20上之相移膜圖案30a中,與透明基板20之界面處之滲入得以抑制。又,該實施形態1之相移光罩基底10可藉由濕式蝕刻形成截面形狀良好、面內分佈之CD偏差較小且透過率較高的相移膜圖案30a。因此,可獲得可製造可高精度地轉印高精細之相移膜圖案30a之相移光罩100的相移光罩基底。The phase shift mask base 10 of Embodiments 1 and 2 is configured such that the phase shift film 30 contains a transition metal, silicon, oxygen, and nitrogen, and the oxygen content obtained by XPS analysis is 1 atom. % or more and 70 atomic % or less (preferably, the oxygen content is 5 atomic % or more and 70 atomic % or less), and the interface between the transparent substrate 20 and the phase shift film 30 is defined as the phase shift film analyzed by XPS When the content rate of the transition metal contained in 30 is 0 atomic %, the ratio of nitrogen to oxygen has a maximum value in a region within 30 nm from the interface to the surface of the phase shift film 30 . Thereby, in the phase shift film pattern 30a formed on the transparent substrate 20 by wet-etching the phase shift film 30 with an over-etching time, penetration at the interface with the transparent substrate 20 is suppressed. In addition, the phase shift mask substrate 10 of Embodiment 1 can form a phase shift film pattern 30 a with good cross-sectional shape, small CD deviation in in-plane distribution, and high transmittance by wet etching. Therefore, a phase shift mask substrate capable of manufacturing the phase shift mask 100 capable of transferring the high-definition phase shift film pattern 30a with high accuracy can be obtained.
實施形態3.4. 於實施形態3、4中,對相移光罩100之製造方法進行說明。Implementation form 3.4. In Embodiments 3 and 4, a method of manufacturing the phase shift mask 100 will be described.
圖3係表示實施形態3之相移光罩之製造方法之模式圖。圖4係表示實施形態4之相移光罩之製造方法之模式圖。 圖3所示之相移光罩之製造方法係使用圖1所示之相移光罩基底10製造相移光罩之方法,包含以下的於相移光罩基底10之蝕刻遮罩膜40上形成阻劑膜之步驟、藉由在阻劑膜上描繪所期望之圖案並進行顯影而形成第1阻劑膜圖案50(第1阻劑膜圖案形成步驟)、將第1阻劑膜圖案50作為遮罩對蝕刻遮罩膜40進行濕式蝕刻而於相移膜30上形成第1蝕刻遮罩膜圖案40a的步驟(第1蝕刻遮罩膜圖案形成步驟)、及將第1蝕刻遮罩膜圖案40a作為遮罩對相移膜30進行濕式蝕刻而於透明基板20上形成相移膜圖案30a的步驟(相移膜圖案形成步驟)。並且,進而包含第2阻劑膜圖案形成步驟與第2蝕刻遮罩膜圖案形成步驟。FIG. 3 is a schematic diagram showing a manufacturing method of the phase shift mask according to Embodiment 3. FIG. 4 is a schematic diagram showing a manufacturing method of the phase shift mask according to Embodiment 4. The manufacturing method of the phase shift mask shown in Figure 3 is a method of manufacturing the phase shift mask using the phase shift mask substrate 10 shown in Figure 1, including the following on the etching mask film 40 of the phase shift mask substrate 10 The step of forming the resist film is to form a first resist film pattern 50 by drawing a desired pattern on the resist film and developing it (first resist film pattern forming step). The first resist film pattern 50 is The step of wet etching the etching mask film 40 as a mask to form the first etching mask film pattern 40 a on the phase shift film 30 (the first etching mask film pattern forming step), and applying the first etching mask film 40 to the phase shift film 30 . The phase shift film 30 is wet-etched using the film pattern 40a as a mask to form the phase shift film pattern 30a on the transparent substrate 20 (phase shift film pattern forming step). Furthermore, it further includes a second resist film pattern forming step and a second etching mask film pattern forming step.
圖4所示之相移光罩之製造方法係使用圖2所示之相移光罩基底10製造相移光罩之方法,包含以下的於相移光罩基底10上形成阻劑膜之步驟、藉由在阻劑膜上描繪所期望之圖案並進行顯影而形成第1阻劑膜圖案50(第1阻劑膜圖案形成步驟)、及將第1阻劑膜圖案50作為遮罩對相移膜30進行濕式蝕刻而於透明基板20上形成相移膜圖案30a的步驟(相移膜圖案形成步驟)。 以下,對實施形態3及4之相移光罩之製造步驟之各步驟詳細地進行說明。The manufacturing method of the phase shift mask shown in FIG. 4 is a method of manufacturing the phase shift mask using the phase shift mask substrate 10 shown in FIG. 2, and includes the following steps of forming a resist film on the phase shift mask substrate 10. , forming the first resist film pattern 50 by drawing a desired pattern on the resist film and developing it (first resist film pattern forming step), and using the first resist film pattern 50 as a mask to the opposite surface The transfer film 30 is subjected to wet etching to form a phase shift film pattern 30 a on the transparent substrate 20 (phase shift film pattern forming step). Hereinafter, each step of the manufacturing process of the phase shift mask according to Embodiments 3 and 4 will be described in detail.
實施形態3之相移光罩之製造步驟 1.第1阻劑膜圖案形成步驟 於第1阻劑膜圖案形成步驟中,首先,於實施形態1之相移光罩基底10之蝕刻遮罩膜40上形成阻劑膜。使用之阻劑膜材料並無特別限制。例如,只要為對於具有自下述之350 nm~436 nm之波長區域選擇之任意波長之雷射光感光者即可。又,阻劑膜可為正型、負型之任一種。 其後,使用具有自350 nm~436 nm之波長區域選擇之任意波長之雷射光,於阻劑膜上描繪所期望之圖案。描繪於阻劑膜之圖案係形成於相移膜30之圖案。作為描繪於阻劑膜之圖案,可列舉線與間隙圖案或孔圖案。 其後,利用特定之顯影液對阻劑膜進行顯影,如圖3(a)所示,於蝕刻遮罩膜40上形成第1阻劑膜圖案50。Manufacturing steps of phase shift mask according to Embodiment 3 1. First resist film pattern forming step In the first resist film pattern forming step, first, a resist film is formed on the etching mask film 40 of the phase shift mask substrate 10 of the first embodiment. The resist film material used is not particularly limited. For example, it suffices as long as it is sensitive to laser light having any wavelength selected from the following wavelength range of 350 nm to 436 nm. In addition, the resist film may be either a positive type or a negative type. Thereafter, the desired pattern is drawn on the resist film using laser light with any wavelength selected from the wavelength range of 350 nm to 436 nm. The pattern drawn on the resist film is a pattern formed on the phase shift film 30 . Examples of patterns drawn on the resist film include line and space patterns and hole patterns. Thereafter, the resist film is developed using a specific developer, and as shown in FIG. 3(a) , a first resist film pattern 50 is formed on the etching mask film 40 .
2.第1蝕刻遮罩膜圖案形成步驟 於第1蝕刻遮罩膜圖案形成步驟中,首先,將第1阻劑膜圖案50作為遮罩對蝕刻遮罩膜40進行蝕刻,形成第1蝕刻遮罩膜圖案40a。蝕刻遮罩膜40由含有鉻(Cr)且實質上不含矽之鉻系材料形成。對蝕刻遮罩膜40進行蝕刻之蝕刻液只要可對蝕刻遮罩膜40選擇性地進行蝕刻,則並無特別限制。具體而言,可列舉包含硝酸鈰銨與過氯酸之蝕刻液。 其後,使用阻劑剝離液,或者,藉由灰化,如圖3(b)所示,將第1阻劑膜圖案50剝離。視情形,亦可不將第1阻劑膜圖案50剝離而進行接下來之相移膜圖案形成步驟。2. The first etching mask film pattern formation step In the first etching mask film pattern forming step, first, the etching mask film 40 is etched using the first resist film pattern 50 as a mask to form the first etching mask film pattern 40a. The etching mask film 40 is formed of a chromium-based material containing chromium (Cr) and substantially free of silicon. 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. Thereafter, the first resist film pattern 50 is peeled off using a resist stripping liquid or by ashing as shown in FIG. 3(b) . Depending on the situation, the next step of forming the phase shift film pattern may be performed without peeling off the first resist film pattern 50 .
3.相移膜圖案形成步驟 於第1相移膜圖案形成步驟中,將第1蝕刻遮罩膜圖案40a作為遮罩對相移膜30進行蝕刻,如圖3(c)所示,形成相移膜圖案30a。作為相移膜圖案30a,可列舉線與間隙圖案或孔圖案。對相移膜30進行蝕刻之蝕刻液只要可對相移膜30選擇性地進行蝕刻,則並無特別限制。例如,可列舉包含氟化銨、磷酸及過氧化氫之蝕刻液、包含氟化氫銨與氯化氫之蝕刻液。 為了使相移膜圖案30a之截面形狀良好,進行濕式蝕刻之時間較佳為較正好使透明基板20於相移膜圖案30a露出之時間(適量蝕刻時間)更長(過蝕刻時間)。作為過蝕刻時間,考慮到對透明基板20之影響等,較佳為設為適量蝕刻時間加上該適量蝕刻時間之10%之時間所得之時間內。3. Phase shift film pattern formation steps In the first phase shift film pattern forming step, the phase shift film 30 is etched using the first etching mask film pattern 40a as a mask. As shown in FIG. 3(c), the phase shift film pattern 30a is formed. Examples of the phase shift film pattern 30a include a line and space pattern or a hole pattern. The etching liquid used to etch the phase shift film 30 is not particularly limited as long as it can selectively etch the phase shift film 30 . For example, an etching liquid containing ammonium fluoride, phosphoric acid, and hydrogen peroxide, and an etching liquid containing ammonium bifluoride and hydrogen chloride can be cited. In order to make the cross-sectional shape of the phase shift film pattern 30a good, the wet etching time is preferably longer (an over-etching time) than just enough to expose the transparent substrate 20 to the phase shift film pattern 30a (an appropriate etching time). The over-etching time is preferably a time obtained by adding an appropriate amount of etching time and 10% of the appropriate amount of etching time, taking into consideration the impact on the transparent substrate 20 and the like.
4.第2阻劑膜圖案形成步驟 於第2阻劑膜圖案形成步驟中,首先,形成覆蓋第1蝕刻遮罩膜圖案40a之阻劑膜。使用之阻劑膜材料並無特別限制。例如,只要為對於具有自下述之350 nm~436 nm之波長區域選擇之任意波長之雷射光感光者即可。又,阻劑膜可為正型、負型之任一種。 其後,使用具有自350 nm~436 nm之波長區域選擇之任意波長之雷射光,於阻劑膜上描繪所期望之圖案。描繪於阻劑膜之圖案係將相移膜30中形成有圖案之區域之外周區域遮光之遮光帶圖案、及將相移膜圖案之中央部遮光之遮光帶圖案。再者,描繪於阻劑膜之圖案根據相移膜30對於曝光之光之透過率,亦有不存在將相移膜圖案30a之中央部遮光之遮光帶圖案之圖案之情形。 其後,利用特定之顯影液對阻劑膜進行顯影,如圖3(d)所示,於第1蝕刻遮罩膜圖案40a上形成第2阻劑膜圖案60。4. Second resist film pattern forming step In the second resist film pattern forming step, first, a resist film covering the first etching mask film pattern 40a is formed. The resist film material used is not particularly limited. For example, it suffices as long as it is sensitive to laser light having any wavelength selected from the following wavelength range of 350 nm to 436 nm. In addition, the resist film may be either a positive type or a negative type. Thereafter, the desired pattern is drawn on the resist film using laser light with any wavelength selected from the wavelength range of 350 nm to 436 nm. The pattern drawn on the resist film is a light-shielding band pattern that blocks light from the outer peripheral area of the area where the pattern is formed in the phase shift film 30, and a light-shielding band pattern that blocks light from the central portion of the phase shift film pattern. Furthermore, depending on the transmittance of the phase shift film 30 to the exposure light, the pattern drawn on the resist film may have a pattern that does not have a light-shielding strip pattern that shields the central portion of the phase shift film pattern 30a from light. Thereafter, the resist film is developed using a specific developer, and as shown in FIG. 3(d) , a second resist film pattern 60 is formed on the first etching mask film pattern 40a.
5.第2蝕刻遮罩膜圖案形成步驟 於第2蝕刻遮罩膜圖案形成步驟中,將第2阻劑膜圖案60作為遮罩對第1蝕刻遮罩膜圖案40a進行蝕刻,如圖3(e)所示,形成第2蝕刻遮罩膜圖案40b。第1蝕刻遮罩膜圖案40a由含有鉻(Cr)且實質上不含矽之鉻系材料形成。對第1蝕刻遮罩膜圖案40a進行蝕刻之蝕刻液只要可對第1蝕刻遮罩膜圖案40a選擇性地進行蝕刻,則並無特別限制。例如,可列舉包含硝酸鈰銨與過氯酸之蝕刻液。 其後,使用阻劑剝離液,或者,藉由灰化,將第2阻劑膜圖案60剝離。 如此,可獲得相移光罩100。 再者,於上述說明中,對蝕刻遮罩膜40具有將曝光之光之透過遮斷之功能之情形進行了說明,但於蝕刻遮罩膜40僅具有對相移膜30進行蝕刻時之硬質遮罩之功能之情形時,於上述說明中,不進行第2阻劑膜圖案形成步驟與第2蝕刻遮罩膜圖案形成步驟,而於相移膜圖案形成步驟之後,將第1蝕刻遮罩膜圖案剝離,製作相移光罩100。5. Second etching mask film pattern formation step In the second etching mask film pattern forming step, the first etching mask film pattern 40a is etched using the second resist film pattern 60 as a mask, as shown in FIG. 3(e), to form a second etching mask. Film pattern 40b. The first etching mask film pattern 40a is formed of a chromium-based material containing chromium (Cr) and substantially free of silicon. The etching liquid used to etch the first etching mask film pattern 40a is not particularly limited as long as it can selectively etch the first etching mask film pattern 40a. For example, an etching solution containing ceric ammonium nitrate and perchloric acid can be used. Thereafter, the second resist film pattern 60 is peeled off using a resist stripping liquid or ashing. In this way, the phase shift mask 100 can be obtained. Furthermore, in the above description, the case where the etching mask film 40 has the function of blocking the transmission of exposure light has been described. However, in the case where the etching mask film 40 only has the hardness to etch the phase shift film 30 In the case of the function of the mask, in the above description, the second resist film pattern forming step and the second etching mask film pattern forming step are not performed, but after the phase shift film pattern forming step, the first etching mask is The film pattern is peeled off, and the phase shift mask 100 is produced.
根據該實施形態2之相移光罩之製造方法,使用實施形態1之相移光罩基底,因此,可形成截面形狀良好且面內分佈之CD偏差較小之相移膜圖案。因此,可製造可高精度地轉印高精細之相移膜圖案之相移光罩。如此製造之相移光罩可應對線與間隙圖案或接觸孔之微細化。According to the manufacturing method of the phase shift mask of Embodiment 2, the phase shift mask base of Embodiment 1 is used. Therefore, a phase shift film pattern with good cross-sectional shape and small CD deviation in in-plane distribution can be formed. Therefore, a phase shift mask capable of transferring a high-definition phase shift film pattern with high precision can be manufactured. The phase shift mask thus fabricated can cope with the miniaturization of line and space patterns or contact holes.
實施形態4之相移光罩之製造步驟 1.阻劑膜圖案形成步驟 於阻劑膜圖案形成步驟中,首先,於實施形態2之相移光罩基底10之相移膜30上形成阻劑膜。使用之阻劑膜材料與實施形態3中所說明之材料相同。再者,亦可視需要於形成阻劑膜之前對相移膜30進行表面改質處理,以使與相移膜30之密接性良好。與上述同樣地,形成阻劑膜之後,使用具有自350 nm~436 nm之波長區域選擇之任意波長之雷射光,於阻劑膜描繪所期望之圖案。其後,利用特定之顯影液對阻劑膜進行顯影,如圖4(a)所示,於相移膜30上形成第1阻劑膜圖案50。 2.相移膜圖案形成步驟 於相移膜圖案形成步驟中,將第1阻劑膜圖案50作為遮罩對相移膜30進行蝕刻,如圖4(b)所示,形成相移膜圖案30a。對相移膜圖案30a或相移膜30進行蝕刻之蝕刻液或過蝕刻時間與實施形態3中所說明者相同。 其後,使用阻劑剝離液,或者,藉由灰化,將第1阻劑膜圖案50剝離(圖4(c))。 如此,可獲得相移光罩100。 根據該實施形態4之相移光罩之製造方法,使用實施形態2之相移光罩基底,因此,不會因濕式蝕刻液對基板造成之損傷而導致透明基板之透過率降低,可縮短蝕刻時間,且可形成截面形狀良好之相移膜圖案。因此,可製造可高精度地轉印高精細之相移膜圖案之相移光罩。如此製造之相移光罩可應對線與間隙圖案或接觸孔之微細化。Manufacturing steps of phase shift mask according to Embodiment 4 1. Resistor film pattern formation step In the resist film pattern forming step, first, a resist film is formed on the phase shift film 30 of the phase shift mask substrate 10 of Embodiment 2. The resist film material used is the same as that described in Embodiment 3. Furthermore, if necessary, the phase shift film 30 may also be surface modified before forming the resist film to ensure good adhesion with the phase shift film 30 . In the same manner as above, after the resist film is formed, a desired pattern is drawn on the resist film using laser light having an arbitrary 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. 4(a) , a first resist film pattern 50 is formed on the phase shift film 30 . 2. Phase shift film pattern formation steps In the phase shift film pattern forming step, the phase shift film 30 is etched using the first resist film pattern 50 as a mask. As shown in FIG. 4(b) , a phase shift film pattern 30a is formed. The etching liquid or over-etching time for etching the phase shift film pattern 30a or the phase shift film 30 is the same as that described in Embodiment 3. Thereafter, the first resist film pattern 50 is peeled off using a resist stripping liquid or ashing (Fig. 4(c)). In this way, the phase shift mask 100 can be obtained. According to the manufacturing method of the phase shift mask of the fourth embodiment, the phase shift mask substrate of the second embodiment is used. Therefore, the transmittance of the transparent substrate will not be reduced due to the damage caused by the wet etching liquid to the substrate, and the shortening time can be shortened. The etching time can be reduced, and a phase shift film pattern with good cross-sectional shape can be formed. Therefore, a phase shift mask capable of transferring a high-definition phase shift film pattern with high precision can be manufactured. The phase shift mask thus fabricated can cope with the miniaturization of line and space patterns or contact holes.
實施形態5. 於實施形態5中,對顯示裝置之製造方法進行說明。顯示裝置係藉由進行使用利用上述之相移光罩基底10製造之相移光罩100、或使用利用上述之相移光罩100之製造方法製造之相移光罩100的步驟(光罩載置步驟)、及將轉印圖案曝光轉印至顯示裝置上之阻劑膜之步驟(圖案轉印步驟)而製造。 以下,對各步驟詳細地進行說明。Implementation form 5. In Embodiment 5, a method of manufacturing a display device will be described. The display device is manufactured by using the phase shift mask 100 manufactured using the above-mentioned phase shift mask substrate 10 or using the above-mentioned manufacturing method of the phase shift mask 100 (mask carrier). (setting step), and a step of exposing and transferring the transfer pattern to the resist film on the display device (pattern transfer step). Each step is explained in detail below.
1.載置步驟 於載置步驟中,將實施形態3中製造之相移光罩載置於曝光裝置之光罩台。此處,相移光罩係以介隔曝光裝置之投影光學系統與形成於顯示裝置基板上之阻劑膜對向之方式配置。1. Installation steps In the placement step, the phase shift mask produced in Embodiment 3 is placed on the mask stage of the exposure device. Here, the phase shift mask is arranged in such a manner that the projection optical system of the exposure device is opposed to the resist film formed on the display device substrate.
2.圖案轉印步驟 於圖案轉印步驟中,對相移光罩100照射曝光之光,將相移膜圖案轉印至形成於顯示裝置基板上之阻劑膜。曝光之光係包含自365 nm~436 nm之波長區域選擇之複數個波長之光之複合光或自365 nm~436 nm之波長區域將某波長區域利用濾波器等截止而選擇之單色光。例如,曝光之光係包含i光線、h光線及g光線之複合光或i光線之單色光。若使用複合光作為曝光之光,則可提高曝光之光強度而提高產出量,因此,可降低顯示裝置之製造成本。2. Pattern transfer steps In the pattern transfer step, the phase shift mask 100 is irradiated with exposure light to transfer the phase shift film pattern to the resist film formed on the display device substrate. The exposure light contains composite light of multiple wavelengths selected from the wavelength range of 365 nm to 436 nm or monochromatic light selected by cutting off a certain wavelength range with a filter or the like from the wavelength range of 365 nm to 436 nm. For example, the exposure light includes a composite light of i ray, h ray and g ray or a monochromatic light of i ray. If composite light is used as the exposure light, the exposure light intensity can be increased and the output can be increased. Therefore, the manufacturing cost of the display device can be reduced.
根據該實施形態5之顯示裝置之製造方法,可製造可抑制CD誤差、高解像度且具有微細之線與間隙圖案或接觸孔的高精細之顯示裝置。 [實施例]According to the method of manufacturing a display device according to the fifth embodiment, it is possible to manufacture a high-definition display device that can suppress CD errors, has high resolution, and has a fine line and space pattern or contact holes. [Example]
實施例1. A.相移光罩基底及其製造方法 為了製造實施例1之相移光罩基底,首先,於連續式濺鍍裝置之腔室內,於搬入透明基板20之前,一面將氮氣(N2 )與氬氣(Ar)之混合氣體導入,一面對包含鉬與矽之第1濺鍍靶(鉬:矽=1:9)施加6.0 kW之濺鍍功率,進行老化步驟60分鐘。Example 1. A. Phase-shift mask substrate and manufacturing method thereof. In order to manufacture the phase-shift mask substrate of Example 1, first, before loading the transparent substrate 20 into the chamber of the continuous sputtering device, nitrogen gas ( A mixed gas of N 2 ) and argon (Ar) was introduced, and a sputtering power of 6.0 kW was applied to the first sputtering target containing molybdenum and silicon (molybdenum: silicon = 1:9), and the aging step was performed for 60 minutes.
繼而,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。 其後,將合成石英玻璃基板使主表面朝向下側地搭載於托盤(未圖示),搬入至連續式濺鍍裝置之腔室內。 為了於透明基板20之主表面上形成相移膜30,於使第1腔室內之濺鍍氣體壓力為1.7 Pa之狀態下,將包括氬氣(Ar)、氮氣(N2 )及氦氣(He)之惰性氣體與作為反應性氣體之一氧化氮氣體(NO)之混合氣體(Ar:18 sccm、N2 :15 sccm、He:50 sccm、NO:4 sccm)導入。藉由該成膜條件,於透明基板20上形成包含矽化鉬之氮氧化物之相移膜30(膜厚:135 nm)。Next, a 1214-size (1220 mm×1400 mm) synthetic quartz glass substrate is prepared as the transparent substrate 20 . Thereafter, the synthetic quartz glass substrate is placed on a tray (not shown) with the main surface facing downward, and is carried into the chamber of the continuous sputtering apparatus. In order to form the phase shift film 30 on the main surface of the transparent substrate 20, the sputtering gas pressure in the first chamber is 1.7 Pa, including argon (Ar), nitrogen (N 2 ) and helium ( A mixed gas (Ar: 18 sccm, N 2 : 15 sccm, He: 50 sccm, NO: 4 sccm) of an inert gas of He and nitrogen oxide gas (NO) which is one of the reactive gases is introduced. Under these film formation conditions, the phase shift film 30 (film thickness: 135 nm) containing molybdenum silicide oxynitride is formed on the transparent substrate 20 .
繼而,將表面處理後之帶相移膜30之透明基板20搬入至第2腔室內,於將第2腔室內設為特定之真空度之狀態下,將氬氣(Ar)與氮氣(N2 )之混合氣體(Ar:65 sccm、N2 :15 sccm)導入。然後,對包含鉻之第2濺鍍靶施加1.5 kW之濺鍍功率,藉由反應性濺鍍,於相移膜30上形成含有鉻與氮之鉻氮化物(CrN)(膜厚15 nm)。繼而,於將第3腔室內設為特定之真空度之狀態下,將氬氣(Ar)與甲烷(CH4 :4.9%)氣體之混合氣體(30 sccm)導入,並對包含鉻之第3濺鍍靶施加8.5 kW之濺鍍功率,藉由反應性濺鍍於CrN上形成含有鉻與碳之鉻碳化物(CrC)(膜厚60 nm)。最後,於將第4腔室內設為特定之真空度之狀態下,將氬氣(Ar)與甲烷(CH4 :5.5%)氣體之混合氣體及氮氣(N2 )與氧氣(O2 )之混合氣體(Ar+CH4 :30 sccm、N2 :8 sccm、O2 :3 sccm)導入,並對包含鉻之第4濺鍍靶施加2.0 kW之濺鍍功率,藉由反應性濺鍍於CrC上形成含有鉻、碳、氧及氮之鉻碳氮氧化物(CrCON)(膜厚30 nm)。如上,於相移膜30上形成CrN層、CrC層及CrCON層之積層構造之蝕刻遮罩膜40。 如此,獲得於透明基板20上形成有相移膜30與蝕刻遮罩膜40之相移光罩基底10。Then, the surface-treated transparent substrate 20 with the phase shift film 30 is moved into the second chamber, and with the second chamber set to a specific vacuum degree, argon (Ar) and nitrogen (N 2 ) are added. ) mixed gas (Ar: 65 sccm, N 2 : 15 sccm) is introduced. Then, a sputtering power of 1.5 kW is applied to the second sputtering target containing chromium, and chromium nitride (CrN) containing chromium and nitrogen is formed on the phase shift film 30 by reactive sputtering (film thickness 15 nm) . Next, with a specific degree of vacuum in the third chamber, a mixed gas (30 sccm) of argon (Ar) and methane (CH 4 : 4.9%) gas was introduced, and the third chamber containing chromium was introduced. The sputtering target applies a sputtering power of 8.5 kW to form chromium carbide (CrC) containing chromium and carbon (film thickness 60 nm) on CrN through reactive sputtering. Finally, with the fourth chamber set to a specific degree of vacuum, a mixture of argon (Ar) and methane (CH 4 : 5.5%) and a mixture of nitrogen (N 2 ) and oxygen (O 2 ) were added. Mixed gas (Ar+CH 4 : 30 sccm, N 2 : 8 sccm, O 2 : 3 sccm) was introduced, and a sputtering power of 2.0 kW was applied to the fourth sputtering target containing chromium, and reactive sputtering was performed on the Chromium carbonitride oxide (CrCON) containing chromium, carbon, oxygen and nitrogen is formed on CrC (film thickness 30 nm). As above, the etching mask film 40 having a stacked structure of the CrN layer, the CrC layer, and the CrCON layer is formed on the phase shift film 30 . In this way, the phase shift mask substrate 10 with the phase shift film 30 and the etching mask film 40 formed on the transparent substrate 20 is obtained.
對所獲得之相移光罩基底10之相移膜30(對相移膜30之表面利用鹼系水溶液進行表面處理所得之相移膜30),藉由Lasertec公司製造之MPM-100測定透過率及相位差。相移膜30之透過率及相位差之測定係使用設置於同一個托盤製作的於合成石英玻璃基板之主表面上成膜有相移膜30之帶相移膜之基板(虛設基板)。相移膜30之透過率、相位差係於形成蝕刻遮罩膜40之前將帶相移膜之基板(虛設基板)自腔室取出進行測定。其結果,透過率為34%(波長:365 nm),相位差為160度(波長:365 nm),背面反射率為11.1%(波長:365 nm)。 又,對相移膜30使用UltraFLAT 200M(Corning TROPEL公司製造)測定平坦度變化,計算膜應力,結果為0.24 GPa。該相移膜30對於相移光罩之清洗時使用之藥液(硫酸過氧化氫混合物、氨水過氧化氫混合物、臭氧水)的透過率變化量及相位差變化量均較小,具有較高之抗藥性、耐清洗性。The transmittance of the phase shift film 30 of the obtained phase shift mask base 10 (the phase shift film 30 obtained by surface-treating the surface of the phase shift film 30 with an alkali aqueous solution) was measured using MPM-100 manufactured by Lasertec Corporation. and phase difference. The transmittance and phase difference of the phase shift film 30 were measured using a phase shift film-attached substrate (dummy substrate) in which the phase shift film 30 was formed on the main surface of a synthetic quartz glass substrate and was placed on the same tray. The transmittance and phase difference of the phase shift film 30 are measured by taking the substrate (dummy substrate) with the phase shift film out of the chamber before forming the etching mask film 40. As a result, the transmittance was 34% (wavelength: 365 nm), the phase difference was 160 degrees (wavelength: 365 nm), and the back reflectance was 11.1% (wavelength: 365 nm). Furthermore, the change in flatness of the phase shift film 30 was measured using UltraFLAT 200M (manufactured by Corning TROPEL Co., Ltd.) and the film stress was calculated. The result was 0.24 GPa. The phase shift film 30 has a small change in transmittance and a change in phase difference with respect to the chemicals (sulfuric acid hydrogen peroxide mixture, ammonia water hydrogen peroxide mixture, ozone water) used in cleaning the phase shift mask, and has a high Antibacterial and cleaning resistance.
又,對所獲得之相移光罩基底10藉由島津製作所公司製造之分光光度計SolidSpec-3700測定膜面反射率及光學密度。相移光罩基底(蝕刻遮罩膜40)之膜面反射率為8.3%(波長:436 nm),光學密度OD為4.0(波長:436 nm)。得知該蝕刻遮罩膜40作為膜表面之反射率較低之遮光膜發揮功能。Furthermore, the film surface reflectance and optical density of the obtained phase shift mask substrate 10 were measured using a spectrophotometer SolidSpec-3700 manufactured by Shimadzu Corporation. The film surface reflectance of the phase shift mask substrate (etched mask film 40) is 8.3% (wavelength: 436 nm), and the optical density OD is 4.0 (wavelength: 436 nm). It is found that the etching mask film 40 functions as a light-shielding film with a low reflectivity on the film surface.
又,藉由X射線光電子光譜法(XPS)對所獲得之相移光罩基底10進行了深度方向之組成分析。圖5表示藉由XPS對實施例1之相移光罩基底進行之深度方向之組成分析結果。圖5表示相移光罩基底中之相移膜30側之蝕刻遮罩膜40與相移膜30之組成分析結果。圖5之橫軸表示以蝕刻遮罩膜40之最表面為基準之相移光罩基底10之以SiO2 換算之深度(nm),縱軸表示含有率(原子%)。於圖5中,各曲線分別表示矽(Si)、氮(N)、氧(O)、碳(C)、鉻(Cr)、鉬(Mo)之含有率變化。 又,圖11係表示針對實施例1、2、比較例1之相移光罩基底的自利用XPS所得之基板界面起之距離與N/O之比率的圖。Furthermore, the composition of the obtained phase shift mask substrate 10 was analyzed in the depth direction by X-ray photoelectron spectroscopy (XPS). FIG. 5 shows the composition analysis results in the depth direction of the phase shift mask substrate of Example 1 by XPS. FIG. 5 shows the composition analysis results of the etching mask film 40 and the phase shift film 30 on the phase shift film 30 side of the phase shift mask substrate. The horizontal axis of FIG. 5 represents the depth (nm) in terms of SiO 2 of the phase shift mask substrate 10 based on the outermost surface of the etching mask film 40, and the vertical axis represents the content rate (atomic %). In Figure 5, each curve represents the changes in the content rates of silicon (Si), nitrogen (N), oxygen (O), carbon (C), chromium (Cr), and molybdenum (Mo) respectively. 11 is a graph showing the distance from the substrate interface obtained by XPS and the N/O ratio for the phase shift mask substrates of Examples 1 and 2 and Comparative Example 1.
如圖5所示,在藉由XPS對相移光罩基底10進行之深度方向之組成分析結果中,於自相移膜30與透明基板20之界面(相移膜30中包含之鉬之含有率成為0原子%之位置)往向相移膜30之表面30 nm以內之區域(組成梯度區域)中,氧之含有率自與透明基板20之界面急遽減少,然後成為大致固定。另一方面,氮之含有率自與透明基板20之界面急遽增加,然後略微減少。即,如圖11所示,已知於實施例1中,N/O之比率於自與透明基板20之界面起28.4 nm之距離、即30 nm以內之區域中具有極大值。As shown in FIG. 5 , in the composition analysis results of the phase shift mask substrate 10 in the depth direction by XPS, the content of molybdenum contained in the phase shift film 30 at the interface between the phase shift film 30 and the transparent substrate 20 In the region (composition gradient region) within 30 nm of the surface of the phase shift film 30 (the position where the oxygen content becomes 0 atomic %), the oxygen content rate rapidly decreases from the interface with the transparent substrate 20 and then becomes approximately constant. On the other hand, the nitrogen content rapidly increases from the interface with the transparent substrate 20 and then decreases slightly. That is, as shown in FIG. 11 , it is known that in Example 1, the N/O ratio has a maximum value in a region within a distance of 28.4 nm from the interface with the transparent substrate 20 , that is, within 30 nm.
B.相移光罩及其製造方法 為了使用以如上方式製造之相移光罩基底10製造相移光罩100,首先,使用阻劑塗佈裝置於相移光罩基底10之蝕刻遮罩膜40上塗佈光阻劑膜。 其後,經過加熱、冷卻步驟,形成膜厚520 nm之光阻劑膜。 其後,使用雷射描繪裝置對光阻劑膜進行描繪,並經由顯影、沖洗步驟,於蝕刻遮罩膜上形成孔徑為1.5 μm之孔圖案之阻劑膜圖案。B. Phase shift mask and manufacturing method thereof In order to manufacture the phase shift mask 100 using the phase shift mask substrate 10 manufactured in the above manner, first, a photoresist film is coated on the etching mask film 40 of the phase shift mask substrate 10 using a resist coating device. Thereafter, after heating and cooling steps, a photoresist film with a film thickness of 520 nm is formed. Thereafter, a laser drawing device is used to draw the photoresist film, and through development and rinsing steps, a resist film pattern with a hole pattern of 1.5 μm in diameter is formed on the etching mask film.
其後,將阻劑膜圖案作為遮罩,藉由包含硝酸鈰銨與過氯酸之鉻蝕刻液對蝕刻遮罩膜40進行濕式蝕刻,形成第1蝕刻遮罩膜圖案40a。Thereafter, using the resist film pattern as a mask, the etching mask film 40 is wet-etched with a chromium etching solution containing ammonium cerium nitrate and perchloric acid to form the first etching mask film pattern 40a.
其後,將第1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所得之矽化鉬蝕刻液對相移膜30進行濕式蝕刻,形成相移膜圖案30a。為了使截面形狀垂直化且形成所要求之微細之圖案,該濕式蝕刻以110%之過蝕刻時間進行。 其後,將阻劑膜圖案剝離。Thereafter, using the first etching mask film pattern 40a as a mask, the phase shift film 30 is wet-etched using a molybdenum silicide etching liquid obtained by diluting a mixed solution of ammonium bifluoride and hydrogen peroxide with pure water to form a phase shift film. Transfer film pattern 30a. In order to verticalize the cross-sectional shape and form the required fine pattern, the wet etching was performed with an over-etching time of 110%. Thereafter, the resist film pattern is peeled off.
其後,使用阻劑塗佈裝置,以覆蓋第1蝕刻遮罩膜圖案40a之方式塗佈光阻劑膜。 其後,經過加熱、冷卻步驟,形成膜厚520 nm之光阻劑膜。 其後,使用雷射描繪裝置對光阻劑膜進行描繪,並經過顯影、沖洗步驟,於第1蝕刻遮罩膜圖案40a上形成用以形成遮光帶之第2阻劑膜圖案60。Thereafter, a resist coating device is used to apply a photoresist film so as to cover the first etching mask film pattern 40a. Thereafter, after heating and cooling steps, a photoresist film with a film thickness of 520 nm is formed. Thereafter, a laser drawing device is used to draw the photoresist film, and through development and rinsing steps, a second resist film pattern 60 for forming a light shielding strip is formed on the first etching mask film pattern 40a.
其後,將第2阻劑膜圖案60作為遮罩,藉由包含硝酸鈰銨與過氯酸之鉻蝕刻液,對形成於轉印圖案形成區域之第1蝕刻遮罩膜圖案40a進行濕式蝕刻。 其後,將第2阻劑膜圖案60剝離。Thereafter, using the second resist film pattern 60 as a mask, the first etching mask film pattern 40a formed in the transfer pattern formation area is wet-etched using a chromium etching solution containing cerium ammonium nitrate and perchloric acid. etching. Thereafter, the second resist film pattern 60 is peeled off.
如此,獲得相移光罩100,其於透明基板20上,於轉印圖案形成區域形成有相移膜圖案30a、及由相移膜圖案30a與第2蝕刻遮罩膜圖案40b之積層構造構成之遮光帶。In this way, the phase shift mask 100 is obtained, which has the phase shift film pattern 30a formed in the transfer pattern formation area on the transparent substrate 20, and is composed of a laminated structure of the phase shift film pattern 30a and the second etching mask film pattern 40b. The shading tape.
對所獲得之相移光罩之截面藉由掃描式電子顯微鏡進行觀察。於以下之實施例1、實施例2及比較例1中,觀察相移光罩之截面時使用掃描式電子顯微鏡。圖6之截面照片係於實施例1之相移光罩之製造步驟中,將第1蝕刻遮罩膜圖案40a作為遮罩,藉由矽化鉬蝕刻液對相移膜30進行濕式蝕刻(110%之過蝕刻),形成相移膜圖案30a,並將阻劑膜圖案剝離後的截面照片。The cross-section of the obtained phase shift mask was observed with a scanning electron microscope. In the following Example 1, Example 2 and Comparative Example 1, a scanning electron microscope was used to observe the cross section of the phase shift mask. The cross-sectional photograph of FIG. 6 is taken during the manufacturing step of the phase shift mask in Embodiment 1. The first etching mask film pattern 40a is used as a mask, and the phase shift film 30 is wet-etched with molybdenum silicide etching liquid (110 % over-etching) to form a phase shift film pattern 30a, and a cross-sectional photograph after peeling off the resist film pattern.
如圖6所示,實施例1之相移光罩100中形成之相移膜圖案30a具有可充分發揮相移效果之接近垂直之截面形狀。又,於相移膜圖案30a,於與蝕刻遮罩膜圖案之界面、及與基板之界面之任一者均未出現滲入。又,具有下端寬度較小、面內之CD偏差小至70 nm之相移膜圖案30a。詳細而言,相移膜圖案30a之截面由相移膜圖案30a之上表面、下表面及側面構成。於該相移膜圖案30a之截面中,上表面與側面相接之部位(上邊)同側面與下表面相接之部位(下邊)所成之角度為74度。因此,可獲得如下相移光罩100,其於包含300 nm以上500 nm以下之波長範圍之光之曝光之光、更具體而言、包含i光線、h光線及g光線之複合光之曝光之光下具有優異之相移效果。 因此,認為將實施例1之相移光罩100設置於曝光裝置之光罩台,並曝光轉印至顯示裝置上之阻劑膜之情形時,可高精度地轉印未達2.0 μm之微細圖案。As shown in FIG. 6 , the phase shift film pattern 30 a formed in the phase shift mask 100 of Embodiment 1 has a nearly vertical cross-sectional shape that can fully exert the phase shift effect. In addition, in the phase shift film pattern 30a, penetration did not occur in any of the interface with the etching mask film pattern and the interface with the substrate. Furthermore, it has a phase shift film pattern 30a with a small bottom width and an in-plane CD deviation as small as 70 nm. Specifically, the cross section of the phase shift film pattern 30a is composed of the upper surface, the lower surface, and the side surfaces of the phase shift film pattern 30a. In the cross-section of the phase shift film pattern 30a, the angle between the portion where the upper surface and the side surface meet (the upper edge) and the portion where the side surface and the lower surface meet (the lower edge) is 74 degrees. Therefore, a phase shift mask 100 can be obtained that exposes light including light in the wavelength range of 300 nm to 500 nm, more specifically, composite light including i rays, h rays, and g rays. It has excellent phase shifting effect under light. Therefore, it is considered that when the phase shift mask 100 of Example 1 is placed on the mask stage of the exposure device and exposed to the resist film transferred to the display device, fine particles less than 2.0 μm can be transferred with high precision. pattern.
實施例2. A.相移光罩基底及其製造方法 為了製造實施例2之相移光罩基底10,首先,於連續式濺鍍裝置之腔室內,於搬入透明基板20之前,以與實施例1相同之條件進行老化步驟。然後,為了於透明基板20之主表面上形成相移膜30,於將第1腔室內之濺鍍氣體壓力設為1.9 Pa之狀態下,將包括氬氣(Ar)、氮氣(N2 )及氦氣(He)之惰性氣體(Ar:18 sccm、N2 :13 sccm、He:50 sccm)導入。藉由該成膜條件,於透明基板20上形成包含矽化鉬之氮氧化物之相移膜30(膜厚:141 nm)。Example 2. A. Phase-shift mask substrate and manufacturing method thereof. In order to manufacture the phase-shift mask substrate 10 of Example 2, first, in the chamber of the continuous sputtering device, before loading the transparent substrate 20, and The aging step was performed under the same conditions as Example 1. Then, in order to form the phase shift film 30 on the main surface of the transparent substrate 20, the sputtering gas pressure in the first chamber is set to 1.9 Pa, including argon (Ar), nitrogen (N 2 ) and Helium (He) inert gas (Ar: 18 sccm, N 2 : 13 sccm, He: 50 sccm) was introduced. Under these film formation conditions, the phase shift film 30 (film thickness: 141 nm) containing molybdenum silicide oxynitride is formed on the transparent substrate 20 .
繼而,於透明基板20形成相移膜30之後,不進行相移膜30之表面處理,與實施例1同樣地,於相移膜30上形成CrN層、CrC層及CrCON層之積層構造之蝕刻遮罩膜40。 如此,獲得於透明基板20上形成有相移膜30與蝕刻遮罩膜40之相移光罩基底10。Next, after the phase shift film 30 is formed on the transparent substrate 20 , the surface treatment of the phase shift film 30 is not performed. In the same manner as in Example 1, etching is performed to form a stacked structure of the CrN layer, the CrC layer, and the CrCON layer on the phase shift film 30 . Masking film 40. In this way, the phase shift mask substrate 10 with the phase shift film 30 and the etching mask film 40 formed on the transparent substrate 20 is obtained.
對所獲得之相移光罩基底10之相移膜30藉由Lasertec公司製造之MPM-100測定透過率及相位差。相移膜之透過率及相位差之測定係使用設置於同一個托盤製作的於合成石英玻璃基板之主表面上成膜有相移膜30之帶相移膜之基板(虛設基板)。相移膜30之透過率、相位差係於形成蝕刻遮罩膜40之前將帶相移膜之基板(虛設基板)自腔室取出測定。其結果,透過率為33%(波長:365 nm),相位差為171度(波長:365 nm),背面反射率為7.8%(波長:365 nm)。 又,對相移膜30使用UltraFLAT 200M(Corning TROPEL公司製造)測定平坦度變化,計算膜應力,結果為0.22 GPa。該相移膜30係對於相移光罩之清洗時使用之藥液(硫酸過氧化氫混合物、氨水過氧化氫混合物、臭氧水)的透過率變化量及相位差變化量均較小,具有較高之抗藥性與耐清洗性。The transmittance and phase difference of the phase shift film 30 of the obtained phase shift mask base 10 were measured using MPM-100 manufactured by Lasertec Corporation. The transmittance and phase difference of the phase shift film were measured using a phase shift film-attached substrate (dummy substrate) in which a phase shift film 30 was formed on the main surface of a synthetic quartz glass substrate and was placed on the same tray. The transmittance and phase difference of the phase shift film 30 are measured by taking the substrate (dummy substrate) with the phase shift film out of the chamber before forming the etching mask film 40 . As a result, the transmittance was 33% (wavelength: 365 nm), the phase difference was 171 degrees (wavelength: 365 nm), and the back reflectance was 7.8% (wavelength: 365 nm). Furthermore, the change in flatness of the phase shift film 30 was measured using UltraFLAT 200M (manufactured by Corning TROPEL Co., Ltd.) and the film stress was calculated. The result was 0.22 GPa. The phase shift film 30 has a relatively small change in transmittance and a change in phase difference with respect to the chemicals used in cleaning the phase shift mask (sulfuric acid hydrogen peroxide mixture, ammonia water hydrogen peroxide mixture, ozone water). High chemical resistance and cleaning resistance.
又,對所獲得之相移光罩基底10藉由島津製作所公司製造之分光光度計SolidSpec-3700,測定膜面反射率及光學密度。相移光罩基底10(蝕刻遮罩膜40)之膜面反射率為8.3%(波長:436 nm),光學密度OD為4.0(波長:436 nm)。得知該蝕刻遮罩膜40作為膜表面之反射率較低之遮光膜發揮功能。Furthermore, the film surface reflectance and optical density of the obtained phase shift mask substrate 10 were measured using a spectrophotometer SolidSpec-3700 manufactured by Shimadzu Corporation. The film surface reflectance of the phase shift mask substrate 10 (etching mask film 40) is 8.3% (wavelength: 436 nm), and the optical density OD is 4.0 (wavelength: 436 nm). It is found that the etching mask film 40 functions as a light-shielding film with a low reflectivity on the film surface.
又,對所獲得之相移光罩基底10,藉由X射線光電子光譜法(XPS)進行深度方向之組成分析。Furthermore, the composition of the obtained phase shift mask substrate 10 in the depth direction was analyzed by X-ray photoelectron spectroscopy (XPS).
其結果,體現與實施例1同樣之傾向,藉由XPS對相移光罩基底10進行之深度方向之組成分析結果中,於自相移膜30與透明基板20之界面(相移膜30中包含之鉬之含有率成為0原子%之位置)往向相移膜30之表面30 nm以內之區域(組成梯度區域)中,氧之含有率自與透明基板20之界面起急遽減少,然後成為大致固定。另一方面,氮之含有率自與透明基板20之界面起急遽增加,然後,略微減少。即,如圖11所示,已知於實施例2中,N/O之比率於自與透明基板20之界面起27.6 nm之距離、即30 nm以內之區域具有極大值。As a result, the same tendency as in Example 1 was shown. In the composition analysis results of the phase shift mask substrate 10 in the depth direction by XPS, at the interface between the phase shift film 30 and the transparent substrate 20 (in the phase shift film 30 In the region (composition gradient region) within 30 nm of the surface of the phase shift film 30 (the position where the molybdenum content rate becomes 0 atomic %), the oxygen content rate decreases rapidly from the interface with the transparent substrate 20, and then becomes Roughly fixed. On the other hand, the nitrogen content rapidly increases from the interface with the transparent substrate 20 and then slightly decreases. That is, as shown in FIG. 11 , it is known that in Example 2, the N/O ratio has a maximum value in a region within 27.6 nm from the interface with the transparent substrate 20 , that is, within 30 nm.
B.相移光罩及其製造方法 使用以如上方式製造之相移光罩基底10,藉由與實施例1相同之方法,製造相移光罩100。再者,為了使截面形狀垂直化且形成所要求之微細圖案,濕式蝕刻以110%之過蝕刻時間進行。 對所獲得之相移光罩100之截面藉由掃描式電子顯微鏡進行觀察。圖7之截面照片係於實施例2之相移光罩之製造步驟中,將第1蝕刻遮罩膜圖案40a作為遮罩,藉由矽化鉬蝕刻液對相移膜30進行濕式蝕刻(110%之過蝕刻),形成相移膜圖案30a後的截面照片。B. Phase shift mask and manufacturing method thereof Using the phase shift mask substrate 10 manufactured in the above manner, the phase shift mask 100 is manufactured by the same method as in Embodiment 1. Furthermore, in order to verticalize the cross-sectional shape and form the required fine pattern, wet etching is performed with an over-etching time of 110%. The cross-section of the obtained phase shift mask 100 was observed with a scanning electron microscope. The cross-sectional photograph in FIG. 7 is taken during the manufacturing step of the phase shift mask in Embodiment 2. The first etching mask film pattern 40a is used as a mask, and the phase shift film 30 is wet-etched with molybdenum silicide etching liquid (110 % over-etching), a cross-sectional photo after forming the phase shift film pattern 30a.
如圖7所示,實施例2之相移光罩100中形成之相移膜圖案30a具有可充分發揮相移效果之接近垂直之截面形狀。又,於相移膜圖案30a,於與蝕刻遮罩膜圖案40b之界面及與透明基板20之界面之任一者均未出現滲入。又,具有下端寬度較小且面內之CD偏差小至70 nm之相移膜圖案30a。詳細而言,相移膜圖案30a之截面由相移膜圖案30a之上表面、下表面及側面構成。於該相移膜圖案30a之截面中,上表面與側面相接之部位(上邊)同側面與下表面相接之部位(下邊)所成之角度為71度。因此,獲得如下相移光罩100,其於包含300 nm以上500 nm以下之波長範圍之光之曝光之光、更具體而言、包含i光線、h光線及g光線之複合光之曝光之光下具有優異之相移效果。 因此,認為將實施例2之相移光罩100設置於曝光裝置之光罩台,並曝光轉印至顯示裝置上之阻劑膜之情形時,可高精度地轉印未達2.0 m之微細圖案。As shown in FIG. 7 , the phase shift film pattern 30 a formed in the phase shift mask 100 of Embodiment 2 has a nearly vertical cross-sectional shape that can fully exert the phase shift effect. In addition, penetration did not occur in any of the phase shift film pattern 30a, the interface with the etching mask film pattern 40b, and the interface with the transparent substrate 20. Furthermore, it has a phase shift film pattern 30a with a small bottom width and an in-plane CD deviation as small as 70 nm. Specifically, the cross section of the phase shift film pattern 30a is composed of the upper surface, the lower surface, and the side surfaces of the phase shift film pattern 30a. In the cross-section of the phase shift film pattern 30a, the angle between the part where the upper surface and the side surface are connected (the upper edge) and the part where the side surface and the lower surface are connected (the lower edge) is 71 degrees. Therefore, a phase shift mask 100 is obtained that exposes light including light in the wavelength range of 300 nm to 500 nm, more specifically, exposure light including composite light of i rays, h rays, and g rays. It has excellent phase shifting effect. Therefore, it is considered that when the phase shift mask 100 of Example 2 is placed on the mask stage of the exposure device and exposed to the resist film to be transferred to the display device, it is considered that fine particles less than 2.0 m can be transferred with high precision. pattern.
比較例1. A.相移光罩基底及其製造方法 為了製造比較例1之相移光罩基底,首先,於連續式濺鍍裝置之腔室內,於搬入透明基板之前,進行老化步驟。但,將老化步驟中導入之氣體僅設為氬氣(Ar),將時間設為30分鐘。老化步驟中之其他條件設為與實施例1、2相同之設定。並且,以與實施例1相同之條件,於透明基板上成膜相移膜與蝕刻遮罩膜。 如此,獲得於透明基板上形成有相移膜與蝕刻遮罩膜之相移光罩基底。再者,相移膜之膜厚為135 nm。Comparative example 1. A. Phase shift mask substrate and manufacturing method thereof In order to manufacture the phase shift mask substrate of Comparative Example 1, first, an aging step was performed in the chamber of a continuous sputtering device before the transparent substrate was loaded into the chamber. However, the gas introduced in the aging step was only argon gas (Ar), and the time was set to 30 minutes. Other conditions in the aging step were the same as those in Examples 1 and 2. Furthermore, under the same conditions as in Example 1, a phase shift film and an etching mask film were formed on the transparent substrate. In this way, a phase shift mask substrate with a phase shift film and an etching mask film formed on the transparent substrate is obtained. Furthermore, the film thickness of the phase shift film is 135 nm.
對所獲得之相移光罩基底之相移膜(將相移膜之表面利用純水清洗後之相移膜)藉由Lasertec公司製造之MPM-100測定透過率及相位差。相移膜之透過率及相位差之測定係使用設置於同一個托盤製作的於合成石英玻璃基板之主表面上成膜有相移膜之帶相移膜之基板(虛設基板)。相移膜之透過率及相位差係於形成蝕刻遮罩膜之前將帶相移膜之基板(虛設基板)自腔室取出測定。其結果,與實施例1之相移膜之光學特性相比基本相同,透過率為34%(波長:365 nm),相位差為160度(波長:365 nm),背面反射率為11.0%(波長:365 nm)。 又,對相移膜使用UltraFLAT 200M(Corning TROPEL公司製造)測定平坦度變化,計算膜應力,結果為0.24 GPa。該相移膜30係對於相移光罩之清洗時使用之藥液(硫酸過氧化氫混合物、氨水過氧化氫混合物、臭氧水)的透過率變化量及相位差變化量均較小,且具有較高之抗藥性與耐清洗性。The transmittance and phase difference of the phase shift film of the obtained phase shift mask base (the phase shift film obtained by cleaning the surface of the phase shift film with pure water) were measured using MPM-100 manufactured by Lasertec Corporation. The transmittance and phase difference of the phase shift film were measured using a substrate with a phase shift film (dummy substrate) in which a phase shift film was formed on the main surface of a synthetic quartz glass substrate and placed on the same tray. The transmittance and phase difference of the phase shift film are measured by taking the substrate with the phase shift film (dummy substrate) out of the chamber before forming the etching mask film. The results are basically the same as the optical properties of the phase shift film of Example 1, with a transmittance of 34% (wavelength: 365 nm), a phase difference of 160 degrees (wavelength: 365 nm), and a back reflectance of 11.0% ( Wavelength: 365 nm). Furthermore, the change in flatness of the phase shift film was measured using UltraFLAT 200M (manufactured by Corning TROPEL Co., Ltd.) and the film stress was calculated. The result was 0.24 GPa. The phase shift film 30 has a small change in transmittance and a change in phase difference with respect to the chemical solution (sulfuric acid hydrogen peroxide mixture, ammonia water hydrogen peroxide mixture, ozone water) used in cleaning the phase shift mask, and has High chemical resistance and cleaning resistance.
又,對所獲得之相移光罩基底藉由島津製作所公司製造之分光光度計SolidSpec-3700測定膜面反射率及光學密度。相移光罩基底(蝕刻遮罩膜)之膜面反射率為8.3%(波長:436 nm),光學密度OD為4.0(波長:436 nm)。得知該蝕刻遮罩膜作為膜表面之反射率較低之遮光膜發揮功能。Furthermore, the film surface reflectance and optical density of the obtained phase shift mask base were measured using a spectrophotometer SolidSpec-3700 manufactured by Shimadzu Corporation. The film surface reflectance of the phase shift mask substrate (etched mask film) is 8.3% (wavelength: 436 nm), and the optical density OD is 4.0 (wavelength: 436 nm). It was found that this etching mask film functions as a light-shielding film with a low reflectivity on the film surface.
又,藉由X射線光電子光譜法(XPS)對所獲得之相移光罩基底進行深度方向之組成分析。Furthermore, the composition of the obtained phase shift mask substrate in the depth direction was analyzed by X-ray photoelectron spectroscopy (XPS).
其結果,藉由XPS對相移光罩基底進行之深度方向之組成分析結果中,於自相移膜與透明基板之界面(相移膜中包含之鉬之含有率成為0原子%之位置)往向相移膜之表面30 nm以內之區域(組成梯度區域)中,氧之含有率自與透明基板之界面起急遽減少,然後成為大致固定。另一方面,氮之含有率自與透明基板之界面急遽起增加,然後,不轉變為減少而緩慢地增加。即,如圖11所示,得知於比較例1中,N/O之比率於自與透明基板之界面起30 nm以內之區域中不具有極大值。As a result, the composition analysis of the phase shift mask substrate in the depth direction by XPS showed that the interface between the phase shift film and the transparent substrate (the position where the content of molybdenum contained in the phase shift film becomes 0 atomic %) In the region within 30 nm of the surface of the phase shift film (composition gradient region), the oxygen content decreases sharply from the interface with the transparent substrate, and then becomes approximately constant. On the other hand, the nitrogen content rate suddenly increases from the interface with the transparent substrate, and then slowly increases without converting into a decrease. That is, as shown in FIG. 11 , it was found that in Comparative Example 1, the N/O ratio did not have a maximum value in the region within 30 nm from the interface with the transparent substrate.
B.相移光罩及其製造方法 使用以如上方式製造之相移光罩基底,藉由與實施例1相同之方法製造相移光罩。 對所獲得之相移光罩之截面藉由掃描式電子顯微鏡進行觀察。圖10之截面照片係於比較例1之相移光罩之製造步驟中,將第1蝕刻遮罩膜圖案作為遮罩,藉由矽化鉬蝕刻液對相移膜進行濕式蝕刻(110%之過蝕刻),形成相移膜圖案,並將阻劑膜圖案剝離後的截面照片。B. Phase shift mask and manufacturing method thereof Using the phase shift mask substrate manufactured in the above manner, a phase shift mask was manufactured by the same method as in Example 1. The cross-section of the obtained phase shift mask was observed with a scanning electron microscope. The cross-sectional photograph in Figure 10 was taken during the manufacturing step of the phase shift mask of Comparative Example 1. The first etching mask film pattern was used as a mask, and the phase shift film was wet-etched (110%) with molybdenum silicide etching liquid. Over-etching), forming a phase shift film pattern, and a cross-sectional photo after peeling off the resist film pattern.
如圖10所示,比較例1之相移光罩中形成之相移膜圖案於與透明基板之界面附近產生滲入,為產生侵蝕之形狀。因此,預測比較例1之相移光罩無法高精度地製作未達2.0 μm之微細圖案。As shown in FIG. 10 , the phase shift film pattern formed in the phase shift mask of Comparative Example 1 penetrates near the interface with the transparent substrate and has a shape that causes erosion. Therefore, it is predicted that the phase shift mask of Comparative Example 1 cannot produce fine patterns of less than 2.0 μm with high accuracy.
實施例3. A.相移光罩基底及其製造方法 為了製造實施例3之相移光罩基底10,首先,於連續式濺鍍裝置之腔室內,於搬入透明基板20之前,以與實施例1相同之條件進行老化步驟。於實施例3中,作為包含鉬與矽之第1濺鍍靶使用鉬:矽=8:92者。然後,為了於透明基板20之主表面上形成相移膜30,於將第1腔室內之濺鍍氣體壓力設為1.7 Pa之狀態下,將包括氬氣(Ar)、氮氣(N2 )及氦氣(He)之惰性氣體與作為反應性氣體之一氧化氮氣體(NO)之混合氣體(Ar:18 sccm、N2 :15 sccm、He:50 sccm、NO:4 sccm)導入。藉由該成膜條件,於透明基板20上形成包含矽化鉬之氮氧化物之相移膜30(膜厚:153 nm)。 繼而,於透明基板20形成相移膜30之後,不進行相移膜30之表面處理,而與實施例1同樣地,於相移膜30上形成CrN層、CrC層及CrCON層之積層構造之蝕刻遮罩膜40。 如此,獲得於透明基板20上形成有相移膜30與蝕刻遮罩膜40之相移光罩基底10。Embodiment 3. A. Phase-shift mask substrate and manufacturing method thereof. In order to manufacture the phase-shift mask substrate 10 of Embodiment 3, first, before moving the transparent substrate 20 into the chamber of the continuous sputtering device, and The aging step was performed under the same conditions as Example 1. In Example 3, molybdenum:silicon=8:92 was used as the first sputtering target containing molybdenum and silicon. Then, in order to form the phase shift film 30 on the main surface of the transparent substrate 20, the sputtering gas pressure in the first chamber is set to 1.7 Pa, including argon (Ar), nitrogen (N 2 ) and A mixed gas of helium (He) as an inert gas and nitrogen oxide gas (NO) as one of the reactive gases (Ar: 18 sccm, N 2 : 15 sccm, He: 50 sccm, NO: 4 sccm) is introduced. Under these film formation conditions, the phase shift film 30 (film thickness: 153 nm) containing molybdenum silicide oxynitride is formed on the transparent substrate 20 . Next, after the phase shift film 30 is formed on the transparent substrate 20, the surface treatment of the phase shift film 30 is not performed, and a laminated structure of the CrN layer, the CrC layer, and the CrCON layer is formed on the phase shift film 30 in the same manner as in Example 1. The mask film 40 is etched. In this way, the phase shift mask substrate 10 with the phase shift film 30 and the etching mask film 40 formed on the transparent substrate 20 is obtained.
對所獲得之相移光罩基底10之相移膜30藉由Lasertec公司製造之MPM-100測定透過率及相位差。相移膜之透過率及相位差之測定係使用設置於同一個托盤製作的於合成石英玻璃基板之主表面上成膜有相移膜30之帶相移膜之基板(虛設基板)。相移膜30之透過率及相位差係於形成蝕刻遮罩膜40之前將帶相移膜之基板(虛設基板)自腔室取出測定。其結果,透過率為37%(波長:365 nm),相位差為187度(波長:365 nm),背面反射率為2.5%(波長:365 nm)。 又,該相移膜30係對於相移光罩之清洗時使用之藥液(硫酸過氧化氫混合物、氨水過氧化氫混合物、臭氧水)的透過率變化量及相位差變化量均較小,且具有較高之抗藥性與耐清洗性。 又,對所獲得之相移光罩基底10藉由島津製作所公司製造之分光光度計SolidSpec-3700測定膜面反射率及光學密度。相移光罩基底10(蝕刻遮罩膜40)之膜面反射率為8.3%(波長:436 nm),光學密度OD為4.0(波長:436 nm)。已知該蝕刻遮罩膜40作為膜表面之反射率較低之遮光膜發揮功能。 又,藉由X射線光電子光譜法(XPS)對所獲得之相移光罩基底10進行深度方向之組成分析。 其結果,如圖8所示,體現與實施例1同樣之傾向,於藉由XPS對相移光罩基底10進行之深度方向之組成分析結果中,於自相移膜30與透明基板20之界面(相移膜30中包含之鉬之含有率成為0原子%之位置)往向相移膜30之表面30 nm以內之區域(組成梯度區域)中,氧之含有率自與透明基板20之界面急遽減少,然後,成為大致固定。另一方面,氮之含有率自與透明基板20之界面起急遽增加,然後,略微減少。即,如圖12所示,得知於實施例3中,N/O之比率於自與透明基板20之界面起22.7 nm之距離、即30 nm以內之區域中具有極大值。 又,於所獲得之相移光罩基底10之轉印圖案形成區域之中央之位置,以80000倍之倍率進行截面SEM(掃描電子顯微鏡)觀察,結果可確認到相移膜30具有柱狀構造。即,可確認到構成相移膜30之矽化鉬化合物之粒子具有往向相移膜30之膜厚方向延伸之柱狀之粒子構造。並且,可確認到相移膜30之柱狀之粒子構造係如下狀態,即,膜厚方向之柱狀之粒子不規則地形成,且柱狀之粒子之膜厚方向之長度亦不一致。又,亦可確認到相移膜30之稀疏之部分係於膜厚方向上連續地形成。The transmittance and phase difference of the phase shift film 30 of the obtained phase shift mask base 10 were measured using MPM-100 manufactured by Lasertec Corporation. The transmittance and phase difference of the phase shift film were measured using a phase shift film-attached substrate (dummy substrate) in which a phase shift film 30 was formed on the main surface of a synthetic quartz glass substrate and was placed on the same tray. The transmittance and phase difference of the phase shift film 30 are measured by taking the substrate with the phase shift film (dummy substrate) out of the chamber before forming the etching mask film 40 . As a result, the transmittance was 37% (wavelength: 365 nm), the phase difference was 187 degrees (wavelength: 365 nm), and the back reflectance was 2.5% (wavelength: 365 nm). In addition, the phase shift film 30 has a small change in transmittance and a change in phase difference with respect to the chemicals (sulfuric acid hydrogen peroxide mixture, ammonia water hydrogen peroxide mixture, ozone water) used in cleaning the phase shift mask. And it has high chemical resistance and cleaning resistance. Furthermore, the film surface reflectance and optical density of the obtained phase shift mask substrate 10 were measured using a spectrophotometer SolidSpec-3700 manufactured by Shimadzu Corporation. The film surface reflectance of the phase shift mask substrate 10 (etching mask film 40) is 8.3% (wavelength: 436 nm), and the optical density OD is 4.0 (wavelength: 436 nm). It is known that the etching mask film 40 functions as a light-shielding film with a low reflectivity on the film surface. Furthermore, the composition of the obtained phase shift mask substrate 10 was analyzed in the depth direction by X-ray photoelectron spectroscopy (XPS). As a result, as shown in FIG. 8 , the same trend as that of Example 1 was reflected. In the composition analysis results of the phase shift mask substrate 10 in the depth direction by XPS, the difference between the self-phase shift film 30 and the transparent substrate 20 was In the interface (the position where the content of molybdenum contained in the phase shift film 30 becomes 0 atomic %) and the region within 30 nm of the surface of the phase shift film 30 (the composition gradient region), the oxygen content is from that of the transparent substrate 20 The interface suddenly decreased, and then became roughly fixed. On the other hand, the nitrogen content rapidly increases from the interface with the transparent substrate 20 and then slightly decreases. That is, as shown in FIG. 12 , it is found that in Example 3, the N/O ratio has a maximum value in a region within 22.7 nm from the interface with the transparent substrate 20 , that is, within 30 nm. Furthermore, a cross-sectional SEM (scanning electron microscope) observation was conducted at a magnification of 80,000 times at the center of the transfer pattern formation area of the obtained phase shift mask substrate 10. As a result, it was confirmed that the phase shift film 30 has a columnar structure. . That is, it was confirmed that the particles of the molybdenum silicide compound constituting the phase shift film 30 have a columnar particle structure extending in the film thickness direction of the phase shift film 30 . Furthermore, it was confirmed that the columnar particle structure of the phase shift film 30 was in such a state that the columnar particles in the film thickness direction were formed irregularly, and the lengths of the columnar particles in the film thickness direction were also inconsistent. In addition, it was also confirmed that the sparse portions of the phase shift film 30 were formed continuously in the film thickness direction.
B.相移光罩及其製造方法 使用以如上方式製造之相移光罩基底10,藉由與實施例1相同之方法,製造相移光罩100。再者,為了使截面形狀垂直化且形成所要求之微細圖案,濕式蝕刻以110%之過蝕刻時間進行。 對所獲得之相移光罩100之截面藉由掃描式電子顯微鏡進行觀察。圖9之截面照片係於實施例3之相移光罩之製造步驟中,將第1蝕刻遮罩膜圖案40a作為遮罩,藉由矽化鉬蝕刻液對相移膜30進行濕式蝕刻(110%之過蝕刻),形成相移膜圖案30a後的截面照片。 如圖9所示,實施例3之相移光罩100中形成之相移膜圖案30a具有可充分發揮相移效果之接近垂直之截面形狀。又,於相移膜圖案30a,於與蝕刻遮罩膜圖案40b之界面及與透明基板20之界面之任一者均未出現滲入。又,具有下端寬度較小且面內之CD偏差小至65 nm之相移膜圖案30a。詳細而言,相移膜圖案30a之截面由相移膜圖案30a之上表面、下表面及側面構成。於該相移膜圖案30a之截面中,上表面與側面相接之部位(上邊)同側面與下表面相接之部位(下邊)所成之角度為81度。因此,獲得如下相移光罩100,其於包含300 nm以上500 nm以下之波長範圍之光之曝光之光、更具體而言、包含i光線、h光線及g光線之複合光之曝光之光下具有優異之相移效果。 因此,將實施例3之相移光罩100設置於曝光裝置之光罩台,並曝光轉印至顯示裝置上之阻劑膜之情形時,認為可高精度地轉印未達2.0 μm之微細圖案。B. Phase shift mask and manufacturing method thereof Using the phase shift mask substrate 10 manufactured in the above manner, the phase shift mask 100 is manufactured by the same method as in Embodiment 1. Furthermore, in order to verticalize the cross-sectional shape and form the required fine pattern, wet etching is performed with an over-etching time of 110%. The cross-section of the obtained phase shift mask 100 was observed with a scanning electron microscope. The cross-sectional photograph in Figure 9 is taken during the manufacturing step of the phase shift mask in Embodiment 3. The first etching mask film pattern 40a is used as a mask, and the phase shift film 30 is wet-etched with molybdenum silicide etching liquid (110 % over-etching), a cross-sectional photo after forming the phase shift film pattern 30a. As shown in FIG. 9 , the phase shift film pattern 30 a formed in the phase shift mask 100 of Embodiment 3 has a nearly vertical cross-sectional shape that can fully exert the phase shift effect. In addition, penetration did not occur in any of the phase shift film pattern 30a, the interface with the etching mask film pattern 40b, and the interface with the transparent substrate 20. Furthermore, it has a phase shift film pattern 30a with a small bottom width and an in-plane CD deviation as small as 65 nm. Specifically, the cross section of the phase shift film pattern 30a is composed of the upper surface, the lower surface, and the side surfaces of the phase shift film pattern 30a. In the cross-section of the phase shift film pattern 30a, the angle between the part where the upper surface and the side surface are connected (the upper side) and the part where the side surface and the lower surface are connected (the lower side) is 81 degrees. Therefore, a phase shift mask 100 is obtained that exposes light including light in the wavelength range of 300 nm to 500 nm, more specifically, exposure light including composite light of i rays, h rays, and g rays. It has excellent phase shifting effect. Therefore, when the phase shift mask 100 of Example 3 is placed on the mask stage of the exposure device and exposed to the resist film transferred to the display device, it is considered that fine particles less than 2.0 μm can be transferred with high precision. pattern.
再者,於上述實施例中,對使用鉬作為過渡金屬之情形進行了說明,但於其他過渡金屬之情形時,亦可獲得與上述同等之效果。 又,於上述實施例中,對顯示裝置製造用之相移光罩基底或顯示裝置製造用之相移光罩之例進行了說明,但並不限於此。本發明之相移光罩基底或相移光罩亦可應用於半導體裝置製造用、MEMS(Micro-Electro-Mechanical System,微機電系統)製造用、印刷基板用等。 又,於上述實施例中,對透明基板之尺寸為8092尺寸(800 mm×920 mm×10 mm)之例進行了說明,但並不限於此。於顯示裝置製造用之相移光罩基底之情形時,使用大型(Large Size)之透明基板,該透明基板之尺寸係一邊之長度為300 mm以上。顯示裝置製造用之相移光罩基底使用之透明基板之尺寸例如為330 mm×450 mm以上2280 mm×3130 mm以下。 又,於半導體裝置製造用、MEMS製造用、印刷基板用之相移光罩基底之情形時,使用小型(Small Size)之透明基板,該透明基板之尺寸係一邊之長度為9英吋以下。上述用途之相移光罩基底使用之透明基板之尺寸例如為63.1 mm×63.1 mm以上228.6 mm×228.6 mm以下。通常,半導體製造用、MEMS製造用係使用6025尺寸(152 mm×152 mm)或5009尺寸(126.6 mm×126.6 mm),印刷基板用係使用7012尺寸(177.4 mm×177.4 mm)或9012尺寸(228.6 mm×228.6 mm)。Furthermore, in the above-mentioned embodiments, the case where molybdenum is used as the transition metal has been described, but the same effect as above can be obtained in the case of other transition metals. Furthermore, in the above-mentioned embodiments, examples of the phase shift mask base for display device manufacturing or the phase shift mask for display device manufacturing have been described, but the invention is not limited thereto. The phase shift mask substrate or phase shift mask of the present invention can also be used in semiconductor device manufacturing, MEMS (Micro-Electro-Mechanical System) manufacturing, printed circuit boards, etc. Furthermore, in the above-mentioned embodiment, the example in which the size of the transparent substrate is 8092 size (800 mm×920 mm×10 mm) has been described, but the invention is not limited to this. In the case of a phase shift mask substrate for display device manufacturing, a large size transparent substrate is used, and the size of the transparent substrate is that the length of one side is 300 mm or more. The size of the transparent substrate used in the phase shift mask base for display device manufacturing is, for example, 330 mm × 450 mm or more and 2280 mm × 3130 mm or less. In addition, in the case of phase shift mask substrates for semiconductor device manufacturing, MEMS manufacturing, and printed circuit boards, small size transparent substrates are used, and the size of the transparent substrate is that the length of one side is 9 inches or less. The size of the transparent substrate used for the phase shift mask base for the above-mentioned purposes is, for example, 63.1 mm × 63.1 mm or more and 228.6 mm × 228.6 mm or less. Generally, systems for semiconductor manufacturing and MEMS manufacturing use 6025 size (152 mm × 152 mm) or 5009 size (126.6 mm × 126.6 mm), and systems for printed circuit boards use 7012 size (177.4 mm × 177.4 mm) or 9012 size (228.6 mm×228.6 mm).
10:相移光罩基底(光罩基底) 20:透明基板 30:相移膜(圖案形成用薄膜) 30a:相移膜圖案(轉印圖案) 40:蝕刻遮罩膜 40a:第1蝕刻遮罩膜圖案 40b:第2蝕刻遮罩膜圖案 50:第1阻劑膜圖案 60:第2阻劑膜圖案 100:相移光罩(光罩)10: Phase shift mask base (mask base) 20:Transparent substrate 30: Phase shift film (film for pattern formation) 30a: Phase shift film pattern (transfer pattern) 40: Etching mask film 40a: 1st etching mask film pattern 40b: 2nd etching mask film pattern 50: 1st resist film pattern 60: 2nd resist film pattern 100: Phase shift mask (mask)
圖1係表示實施形態1之相移光罩基底之膜構成之模式圖。 圖2係表示實施形態2之相移光罩基底之膜構成之模式圖。 圖3(a)~(e)係表示實施形態3之相移光罩之製造步驟之模式圖。 圖4(a)~(c)係表示實施形態4之相移光罩之製造步驟之模式圖。 圖5係表示對於實施例1之相移光罩基底之深度方向之組成分析結果之圖。 圖6係實施例1之相移光罩之截面照片。 圖7係實施例2之相移光罩之截面照片。 圖8係表示對於實施例3之相移光罩基底之深度方向之組成分析結果之圖。 圖9係實施例3之相移光罩之截面照片。 圖10係比較例1之相移光罩之截面照片。 圖11係表示針對實施例1、2、比較例1之相移光罩基底的自利用XPS所得之基板界面起之距離與N/O之比率的圖。 圖12係表示針對實施例3之相移光罩基底的自利用XPS所得之基板界面起之距離與N/O之比率的圖。FIG. 1 is a schematic diagram showing the film structure of a phase shift mask base according to Embodiment 1. FIG. 2 is a schematic diagram showing the film structure of a phase shift mask base according to Embodiment 2. 3 (a) to (e) are schematic diagrams showing the manufacturing steps of the phase shift mask according to Embodiment 3. 4 (a) to (c) are schematic diagrams showing the manufacturing steps of the phase shift mask according to Embodiment 4. FIG. 5 is a graph showing the results of composition analysis in the depth direction of the phase shift mask substrate of Example 1. Figure 6 is a cross-sectional photograph of the phase shift mask of Example 1. Figure 7 is a cross-sectional photograph of the phase shift mask of Example 2. FIG. 8 is a graph showing the results of composition analysis in the depth direction of the phase shift mask substrate of Example 3. Figure 9 is a cross-sectional photograph of the phase shift mask of Example 3. Figure 10 is a cross-sectional photograph of the phase shift mask of Comparative Example 1. 11 is a graph showing the distance from the substrate interface obtained by XPS and the N/O ratio for the phase shift mask substrates of Examples 1 and 2 and Comparative Example 1. FIG. 12 is a graph showing the distance from the substrate interface obtained by XPS and the ratio of N/O for the phase shift mask substrate of Example 3.
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TW201437739A (en) * | 2012-11-20 | 2014-10-01 | Hoya Corp | Mask blank, transfer mask, method for producing mask blank, method for producing transfer mask, and method for manufacturing semiconductor device |
TW201525608A (en) * | 2013-12-27 | 2015-07-01 | Hoya Corp | Phase shift mask substrate and manufacturing method thereof, and phase shift mask manufacturing method |
TW201608329A (en) * | 2014-05-29 | 2016-03-01 | Hoya Corp | Phase shift mask substrate and manufacturing method thereof and method for manufacturing phase shift mask |
TW201821898A (en) * | 2016-09-21 | 2018-06-16 | 日商Hoya股份有限公司 | Photomask blank, method of manufacturing photomask blank, method of manufacturing photomask using them, and method of manufacturing display device |
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JP7297692B2 (en) | 2023-06-26 |
TW202105043A (en) | 2021-02-01 |
JP2020144358A (en) | 2020-09-10 |
KR20200105417A (en) | 2020-09-07 |
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