JP2005181423A - Method for reproducing glass substrate for mask blanks, method for manufacturing mask blanks, and method for manufacturing transfer mask - Google Patents
Method for reproducing glass substrate for mask blanks, method for manufacturing mask blanks, and method for manufacturing transfer mask Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 121
- 239000011521 glass Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000010409 thin film Substances 0.000 claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 238000005498 polishing Methods 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 230000001172 regenerating effect Effects 0.000 claims description 12
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 7
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000000059 patterning Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 36
- 230000010363 phase shift Effects 0.000 description 25
- 230000007547 defect Effects 0.000 description 19
- 238000005530 etching Methods 0.000 description 16
- 229910021344 molybdenum silicide Inorganic materials 0.000 description 14
- -1 silicide nitride Chemical class 0.000 description 14
- 230000003746 surface roughness Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 229910021332 silicide Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000007517 polishing process Methods 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 239000004094 surface-active agent Substances 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 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000005407 aluminoborosilicate glass Substances 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- MMXSKTNPRXHINM-UHFFFAOYSA-N cerium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Ce+3].[Ce+3] MMXSKTNPRXHINM-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000004528 spin coating 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
- 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
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
本発明は、マスクブランクスや転写マスクなどのガラス基板上に形成された金属シリサイドの窒化物膜をガラス基板から剥離してマスクブランクス用ガラス基板を再生するマスクブランクス用ガラス基板の再生方法、並びに、該基板を用いたマスクブランクスの製造方法及び転写用マスクの製造方法に関する。 The present invention relates to a method for regenerating a glass substrate for mask blanks, in which a nitride film of metal silicide formed on a glass substrate such as a mask blank or a transfer mask is peeled off from the glass substrate to regenerate the glass substrate for mask blanks, and The present invention relates to a method for manufacturing a mask blank using the substrate and a method for manufacturing a transfer mask.
例えば、ＬＳＩや超ＬＳＩを製造する際に使用する転写マスクの原版であるマスクブランクスは、精密研磨されたガラス基板の表面に転写パターンとなる薄膜をスパッタリングにより形成し、さらに前記薄膜をパターニングするためのレジスト膜を同転塗布により形成してマスクブランクスが製造される。近年の半導体集積回路におけるパターンの微細化に伴って、微細パターンを転写する有効なパターン転写手法として、ハーフトーン型位相シフトマスクブランクスが使用されている。ハーフトーン型位相シフトマスクブランクスとしては、特許文献１に記載されているものなどが提案されている。 For example, mask blanks, which are masters of transfer masks used in the manufacture of LSIs and VLSIs, are used to form a transfer pattern thin film on the surface of a precisely polished glass substrate by sputtering, and to pattern the thin film. The mask blanks are manufactured by forming the resist film by the same spin coating. With the recent miniaturization of patterns in semiconductor integrated circuits, halftone phase shift mask blanks are used as an effective pattern transfer technique for transferring a fine pattern. As halftone phase shift mask blanks, those described in Patent Document 1 have been proposed.
この特許文献１で提案されているハーフトーン型位相シフトマスクブランクスは、ガラス基板上に位相シフト膜として、主として金属とシリコンと窒素とを含む金属シリサイド窒化物膜を形成したものである。この位相シフト膜は、金属シリサイドからなるスパッタターゲツトを使用し、アルゴン、キセノン等の不活性ガスと窒素を含むガスを混合した混合ガス雰囲気で、反応性スパッタリングによってガラス基板上に形成される。位相シフト膜は、スパッタターゲットの組成比や混合ガスの窒素を含むガスの流量を調整して、所望の透過率や位相差となるように制御するが、特に窒素ガスを多く含む雰囲気中でスパッタリングを行う場合、異常放電によって、位相シフト膜中にパーティクルやピンホールなどの欠陥が発生することがあった。 The halftone phase shift mask blank proposed in Patent Document 1 is obtained by forming a metal silicide nitride film mainly containing metal, silicon, and nitrogen as a phase shift film on a glass substrate. This phase shift film is formed on a glass substrate by reactive sputtering in a mixed gas atmosphere in which an inert gas such as argon or xenon and a gas containing nitrogen are mixed using a sputtering target made of metal silicide. The phase shift film is controlled by adjusting the composition ratio of the sputter target and the flow rate of the gas containing nitrogen in the mixed gas so as to obtain a desired transmittance and phase difference. In particular, sputtering is performed in an atmosphere rich in nitrogen gas. When performing the above, defects such as particles and pinholes may occur in the phase shift film due to abnormal discharge.
ハーフトーン型位相シフトマスクブランクスのようなマスクブランクスに、ハーフトーン型位相シフトマスクを製造する際に転写パターンに影響を与える欠陥が、所定の大きさ、所定の個数以上発生したマスクブランクスは、廃棄処分するのが一般的であった。それは、ガラス基板上に形成された位相シフト膜が膜残りなく完全に剥離できる保証がなく、また、例え完全に剥離できたとしてもそのガラス基板が光学特性に全く影響がないと保証できなかったからである。 Mask blanks that have a predetermined size and a greater number of defects that affect the transfer pattern when manufacturing a halftone phase shift mask on a mask blank such as a halftone phase shift mask blank are discarded. It was common to dispose of it. This is because there is no guarantee that the phase shift film formed on the glass substrate can be completely peeled off without remaining film, and even if it can be completely peeled off, it cannot be guaranteed that the glass substrate has no influence on the optical characteristics. It is.
ところで、近年、パターンの微細化、露光波長の短波長化がますます進み、これに伴い、ガラス基板についても、その材質自体が高品質でかつ表面平坦度等も高精度のものが要求され、高コストのものになってきている。そのような現状において、欠陥のあるマスクブランクスを全て廃棄処分にすると製造コストが高くなるとともに、資源の有効利用の観点からも好ましくない。そこで、欠陥のあるマスクブランクスのガラス基板上に形成されている薄膜を剥離液で剥離して、ガラス基板を再利用することが考えられる。この場合、上述の金属シリサイド窒化物からなる位相シフト膜を剥離する剥離液としては、これらの膜材料をエッチングする際に用いているエッチング液を利用することが考えられる。この金属シリサイド膜をエッチングするエッチング液としては、特許文献２に記載されているものが知られている。すなわち、特許文献２には、珪化モリブデン（モリブデンシリサイド）膜を、エッチングする際のエッチング液として、弗化水素アンモニウム、弗化アンモニウム、珪弗化水素酸、弗化ホウ素酸のうち何れか少なくとも一つと、過酸化水素、硝酸のうち何れか少なくとも一つとを混合した水溶液が記載されている。
しかし、特許文献１に記載されているような、金属とシリコンと窒素を含む薄膜（例えば、モリブデンシリサイド窒化物膜）を特許文献２に記載されているようなエッチング液を利用して剥離する場合、金属とシリコンと窒素とを含む薄膜のエッチングレートが遅いことから、完全に薄膜を剥離するまでにエッチング液がガラス基板と接触する時間が長く、前記薄膜が形成されていない裏面側のガラス基板の侵食が激しくなる。また、上述のエッチング液では、前記薄膜とガラス基板とのエッチング選択比があまりとれないため、前記薄膜が形成されている側のガラス基板表面も侵食される虞れもある。さらには、金属とシリコンと窒素とを含む薄膜における欠陥が存在する領域などにおいて、エッチングが均一に行われず、エッチング速度が速いところと遅いところが発生し、ガラス基板が荒れてしまうという問題も発生する。 However, when a thin film (for example, molybdenum silicide nitride film) containing metal, silicon, and nitrogen as described in Patent Document 1 is peeled off using an etching solution as described in Patent Document 2 Since the etching rate of the thin film containing metal, silicon and nitrogen is slow, it takes a long time for the etching solution to contact the glass substrate until the thin film is completely removed, and the glass substrate on the back side where the thin film is not formed. The erosion becomes intense. Further, in the above-described etching solution, the etching selectivity between the thin film and the glass substrate cannot be taken so much that the surface of the glass substrate on which the thin film is formed may be eroded. Furthermore, in a region where defects in a thin film containing metal, silicon, and nitrogen exist, etching is not performed uniformly, and there are problems that the etching rate is high and low, and the glass substrate becomes rough. .
ガラス基板の表裏面が所定以上侵食されると、仮に、均一に侵食されたとしてもガラス基板の板厚が規格から外れて再利用できないという問題が生ずる。また、表面が荒れたガラス基板は、その荒れた表面を精密研磨しなおす必要がある。しかし、この研磨は、一般的に研磨取しろを大きく取らざるを得ない場合が多く、研磨時間及びコストが嵩むとともに、基板周辺部の平坦度が悪化する虞れも高いことが判明した。しかも、研磨取しろが極端に多い場合にはガラス基板の板厚が規格から外れてしまうという問題も生じる。本発明は、上記問題点に鑑みてなされたものであり、金属とシリコンと窒素とを含む薄膜を剥離液で剥離する場合であっても、ガラス基板の荒れを抑制し、確実にマスクブランクス用ガラス基板を再生することができるマスクブランクス用ガラス基板の再生方法を提供することを第一の目的とする。また、再生されたガラス基板を使って膜下欠陥の発生しないマスクブランクス用ガラス基板、及びマスクブランクスの製造方法を提供することを第二の目的とする。また、膜下欠陥によるパターン欠陥の発生しない転写マスクの製造方法を提供することを第三の目的とする。 If the front and back surfaces of the glass substrate are eroded at a predetermined level or more, there arises a problem that even if the glass substrate is uniformly eroded, the thickness of the glass substrate deviates from the standard and cannot be reused. In addition, a glass substrate having a rough surface needs to be precisely polished again. However, it has been found that this polishing generally requires a large polishing allowance, increases the polishing time and cost, and increases the possibility that the flatness of the peripheral portion of the substrate will deteriorate. In addition, when the amount of polishing is extremely large, there is a problem that the thickness of the glass substrate deviates from the standard. The present invention has been made in view of the above problems, and even when a thin film containing metal, silicon, and nitrogen is peeled off with a peeling solution, the glass substrate is prevented from being rough and reliably used for mask blanks. It is a first object to provide a method for regenerating a glass substrate for mask blanks that can regenerate a glass substrate. It is a second object of the present invention to provide a glass substrate for mask blanks that does not cause subfilm defects and a method for manufacturing the mask blanks using the regenerated glass substrate. It is a third object of the present invention to provide a transfer mask manufacturing method in which pattern defects due to subfilm defects do not occur.
上述の課題を解決するための手段として、第１の手段は、
マスクスブランクス用ガラス基板上に形成された薄膜を剥離してマスクブランクス用ガラス基板を再生するマスクブランクス用ガラス基板の再生方法において、
前記薄膜は主として金属とシリコンと窒素とを含むものであり、
前記薄膜の剥離は、前記薄膜が形成されたガラス基板を、弗化水素酸、珪弗化水素酸、弗化水素アンモニウムから選ばれる少なくとも一つの弗素化合物と、過酸化水素、硝酸、硫酸から選ばれる少なくとも一つの酸化剤とを含み、前記弗素化合物を０．１〜０．８ｗｔ％含む水溶液に接触させて行うものであることを特徴とするマスクブランクス用ガラス基板の再生方法である。
第２の手段は、
前記水溶液の温度を３５〜６５℃とすることを特徴とする第１の手段にかかるマスク用ブランクス用ガラス基板の再生方法である。
第３の手段は、
前記薄膜中に含まれる窒素の含有量が５〜６０原子％であることを特徴とする第１又は第２の手段にかかるマスクブランクス用ガラス基板の再生方法である。
第４の手段は、
第１〜第３の何れかの手段にかかるマスクブランクス用ガラス基板の再生方法によって再生されたマスクブランクス用ガラス基板の表面を精密研磨することを特徴とするマスクブランクス用ガラス基板の製造方法である。
第５の手段は、
第４の手段にかかるマスクブランクス用ガラス基板の製造方法によって得られたマスクブランクス用ガラス基板の主表面上に主として金属とシリコンと窒素とを含む薄膜を形成することを特徴とするマスクブランクスの製造方法である。
第６の手段は、
第５の手段にかかるマスクブランクスの製造方法によって得られたマスクブランクスにおける前記薄膜をパターニングして前記ガラス基板上に薄膜パターンを形成することを特徴とする転写用マスクの製造方法である。
As means for solving the above-mentioned problem, the first means is:
In the regeneration method of the glass substrate for mask blanks, which peels the thin film formed on the glass substrate for mask blanks and regenerates the glass substrate for mask blanks,
The thin film mainly contains metal, silicon, and nitrogen,
For the peeling of the thin film, the glass substrate on which the thin film is formed is selected from at least one fluorine compound selected from hydrofluoric acid, hydrosilicofluoric acid, and ammonium hydrogen fluoride, hydrogen peroxide, nitric acid, and sulfuric acid. And a method for regenerating a glass substrate for mask blanks, which is performed by contacting with an aqueous solution containing 0.1 to 0.8 wt% of the fluorine compound.
The second means is
The method for regenerating a glass substrate for a mask blank according to the first means, wherein the temperature of the aqueous solution is 35 to 65 ° C.
The third means is
The method for regenerating a glass substrate for mask blanks according to the first or second means, wherein the content of nitrogen contained in the thin film is 5 to 60 atomic%.
The fourth means is
A method for producing a mask blank glass substrate, comprising: precisely polishing a surface of a mask blank glass substrate regenerated by the method for regenerating a mask blank glass substrate according to any one of the first to third means. .
The fifth means is
Manufacturing of a mask blank, characterized in that a thin film mainly containing metal, silicon and nitrogen is formed on the main surface of the glass substrate for mask blank obtained by the method for manufacturing a glass substrate for mask blank according to the fourth means. Is the method.
The sixth means is
It is a manufacturing method of the transfer mask characterized by patterning the thin film in the mask blank obtained by the manufacturing method of the mask blank concerning the 5th means, and forming a thin film pattern on the glass substrate.
上述の第１の手段において、上記水溶液を用いる場合、弗化水素酸、珪弗化水素酸、弗化水素アンモニウム等の弗素化合物の濃度は、０．１〜０．８ｗｔ％とする。これら弗素化合物は、金属とシリコンと窒素とを含む薄膜及びガラス基板を優先的にエッチングする働きをする。この場合、濃度が０．１ｗｔ％未満であると、水溶液による薄膜のエッチング速度が遅くなりすぎ、剥離時間が長くなるので、好ましくない。また、濃度が０．８ｗｔ％を越えると、水溶液による薄膜のエッチング速度が早くなりすぎ、剥離後のガラス基板が著しく荒れるので好ましくない。また、過酸化水素、硝酸、硫酸等の酸化剤は、ガラス基板の侵食を抑えつつ金属とシリコンと窒素とを含む薄膜を優先的にエッチングする働きをするので、弗素化合物の濃度に応じて適宜調整する。 In the first means described above, when the aqueous solution is used, the concentration of a fluorine compound such as hydrofluoric acid, hydrosilicofluoric acid, or ammonium hydrogen fluoride is 0.1 to 0.8 wt%. These fluorine compounds function to preferentially etch a thin film and glass substrate containing metal, silicon and nitrogen. In this case, if the concentration is less than 0.1 wt%, the etching rate of the thin film with the aqueous solution becomes too slow and the peeling time becomes long, which is not preferable. On the other hand, if the concentration exceeds 0.8 wt%, the etching rate of the thin film with the aqueous solution becomes too fast, and the glass substrate after peeling becomes extremely rough, which is not preferable. In addition, an oxidizing agent such as hydrogen peroxide, nitric acid, sulfuric acid or the like acts to preferentially etch a thin film containing metal, silicon, and nitrogen while suppressing the erosion of the glass substrate, and accordingly, depending on the concentration of the fluorine compound. adjust.
実際上は、薄膜の材料、組成に合わせて水溶液中に含まれる弗素化合物、過酸化水素等の酸化剤の濃度を決定する。薄膜中に含まれる金属及び窒素の含有量が多い場合は、水溶液中に含まれる弗素化合物の濃度を上述の範囲内で高くして剥離作用を確保し、一方で、それによるガラス基板のダメージを防ぐために酸化剤の濃度を高くする。また、逆に金属、及び窒素の含有量が少ない場合は、薄膜中に含まれるシリコンが多く含まれることになるので、弗素化合物の濃度を上述の範囲内でで小さくする。なお、水溶液には、上述の弗素化合物と、酸化剤以外に、界面活性剤等含有させることもできる。界面活性剤は、面内均一に薄膜をガラス基板から剥離させる作用をするので好ましい。 In practice, the concentration of an oxidizing agent such as a fluorine compound or hydrogen peroxide contained in the aqueous solution is determined in accordance with the material and composition of the thin film. When the content of metal and nitrogen contained in the thin film is large, the concentration of the fluorine compound contained in the aqueous solution is increased within the above range to ensure the peeling action, while the glass substrate is thereby damaged. To prevent this, increase the concentration of oxidizing agent. On the contrary, when the contents of metal and nitrogen are small, a large amount of silicon is contained in the thin film, so that the concentration of the fluorine compound is reduced within the above range. The aqueous solution may contain a surfactant in addition to the above-described fluorine compound and oxidizing agent. The surfactant is preferable because it acts to peel the thin film from the glass substrate uniformly in the surface.
なお、本発明でいう薄膜付きガラス基板とは、金属とシリコンと窒素とを含む薄膜が、ガラス基板の一主表面上に形成されたマスクブランクス、及び該金属とシリコンと窒素とを含む薄膜がパターニングされ、薄膜パタ一ンが形成された転写マスクを指す。マスクブランクスの代表としては、透過型マスクブランクスが挙げられる。透過型マスクブランクスは、ガラス基板表面に露光光に対し光学的変化をもたらす薄膜（例えば、遮光機能を有する薄膜〉が形成されたフォトマスクブランクスや位相シフトマスクブランクスである。この場合の薄膜は、露光光を遮断する遮光膜や、露光光の位相差を変化させる位相シフト膜などを指す。 The glass substrate with a thin film referred to in the present invention is a mask blank in which a thin film containing metal, silicon and nitrogen is formed on one main surface of the glass substrate, and a thin film containing the metal, silicon and nitrogen. It refers to a transfer mask that has been patterned to form a thin film pattern. A representative example of the mask blank is a transmissive mask blank. The transmissive mask blank is a photomask blank or a phase shift mask blank in which a thin film (for example, a thin film having a light shielding function) that causes an optical change with respect to exposure light is formed on the surface of the glass substrate. It refers to a light shielding film that blocks exposure light, a phase shift film that changes the phase difference of exposure light, and the like.
そして、この薄膜に含まれる金属、シリコン、窒素の含有量は、上記透過型マスクブランクスの遮光膜や位相シフト膜としての機能、あるいは、反射型マスクブランクスにおける反射膜としての機能をそれぞれはたす光学特性が得られるように適宜調整される。なお、金属としては、モリブデン、タングステン、タンタル、ジルコニウム、ニッケル等が用いられる。また、窒素以外に、酸素、炭素、弗素等を含有させることもできる。尚、使用するガラス基板の材質は特に限定されず、合成石英ガラス、ソーダライムガラス、アルミノシリケートガラス、ボロシリケートガラス、アルミノボロシリケートガラスなど、露光波長に対して高い透過率を有するものであれば何でも良い。 The contents of metal, silicon, and nitrogen contained in the thin film are optical characteristics that function as a light-shielding film and a phase shift film of the transmissive mask blank or as a reflective film in the reflective mask blank, respectively. Is adjusted as appropriate so that is obtained. As the metal, molybdenum, tungsten, tantalum, zirconium, nickel, or the like is used. In addition to nitrogen, oxygen, carbon, fluorine and the like can also be contained. The material of the glass substrate to be used is not particularly limited as long as it has high transmittance with respect to the exposure wavelength, such as synthetic quartz glass, soda lime glass, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass. anything is fine.
また、第２の手段のように、水溶液の温度を３５〜６５℃とすることによって、薄膜を剥離した後のガラス基板の表面の荒れを抑制することができる。水溶液の温度を上記温度に設定することによって、薄膜を剥離した後のガラス基板の表面粗さを最大高さＲｍａｘで３０ｎｍ以下とすることができるので、精密研磨工程の負荷を低減させることができる。なお、最大高さＲｍａｘは、日本工業規格ＪＩＳＢ０６０１（１９９４）で定められたものである。具体的には、通常のガラス基板の製造工程における研削工程で得られる表面粗さの約０．０３倍以下に抑えることができるので、通常の研磨工程と比べて、薄膜剥離後の研磨工程の負荷を約１／２以下に低減することができる。より具体的には、複数段階の研磨のうち、第１段階の研磨（粗研磨）工程を省略することができる。また、研磨時間が短縮できるので、ガラス基板の周辺部の平坦度の悪化を抑えることができ、研磨後のガラス基板の平坦度が良好なものが得られるので好ましい。水溶液の温度を３５℃未満とすると、薄膜剥離後のガラス基板の表面粗さは、最大高さＲｍａｘで５０ｎｍを超え、精密研磨工程の負荷を低減させることができず、平坦度が悪化するので好ましくない。また、６５℃を超えると、水溶液の蒸発により、エッチング液（剥離液）の濃度が変化するので好ましくない。 Moreover, the roughness of the surface of the glass substrate after peeling a thin film can be suppressed by making the temperature of aqueous solution into 35-65 degreeC like a 2nd means. By setting the temperature of the aqueous solution to the above temperature, the surface roughness of the glass substrate after peeling the thin film can be reduced to 30 nm or less at the maximum height Rmax, so that the load on the precision polishing process can be reduced. . The maximum height Rmax is defined by Japanese Industrial Standard JISB0601 (1994). Specifically, since it can be suppressed to about 0.03 times or less of the surface roughness obtained in the grinding process in the normal glass substrate manufacturing process, compared with the normal polishing process, the polishing process after the thin film peeling. The load can be reduced to about ½ or less. More specifically, the first-stage polishing (rough polishing) step can be omitted among the plurality of stages of polishing. In addition, since the polishing time can be shortened, deterioration of the flatness of the peripheral portion of the glass substrate can be suppressed, and a glass substrate with good flatness after polishing can be obtained, which is preferable. If the temperature of the aqueous solution is less than 35 ° C., the surface roughness of the glass substrate after peeling the thin film exceeds 50 nm at the maximum height Rmax, and the load of the precision polishing process cannot be reduced, and the flatness deteriorates. It is not preferable. On the other hand, if it exceeds 65 ° C., the concentration of the etching solution (peeling solution) changes due to evaporation of the aqueous solution, which is not preferable.
薄膜中に含まれる窒素の含有量は、第３の手段のように、５〜６０原子％とすることが好ましい。この組成範囲であれば、ガラス基板上の薄膜を膜残りなくガラス基板から剥離することが容易にできる。また、第４の手段のように、水溶液でガラス基板から薄膜を剥離した後に精密研磨することにより、膜残りを完全に除去し、ガラス基板の表面粗さ及び光学特性（透過率）を確実に所望のものにできる。この場合、精密研磨の研磨方法は特に限定されない。ガラス基板の片面ずつ研磨する片面研磨やガラス基板の両面を一度に研磨する両面研磨のいずれでも構わない。精密研磨は、好ましくは、確実に所定の表面粗さにするために、表面粗さが次第に小さくなるように、複数段階にわけて行うことが好ましい。この場合、使用する研磨剤の平均粒径を研磨段階の進行にしたがって小さくしていき、最終的に精密研磨後のガラス基板の表面粗さが最大高さＲｍａｘが２ｎｍ以下、平坦度が１μｍ以下になるようにする。複数段階の精密研磨は、研磨パッドとして軟質ポリシャを使用し、研磨剤としては、酸化セリウム、酸化ジルコニウム、酸化アルミニウム、酸化マンガン、コロイダルシリカから選ばれるものを使用し、研磨剤の平均粒径が０．０３〜３μｍの範囲で適宜調整して行う。 The content of nitrogen contained in the thin film is preferably 5 to 60 atomic% as in the third means. If it is this composition range, the thin film on a glass substrate can be easily peeled from a glass substrate without a film residue. Also, as in the fourth means, the thin film is peeled off from the glass substrate with an aqueous solution and then precisely polished to completely remove the film residue and to ensure the surface roughness and optical characteristics (transmittance) of the glass substrate. Can be as desired. In this case, the precision polishing method is not particularly limited. Either single-side polishing for polishing one side of the glass substrate or double-side polishing for polishing both surfaces of the glass substrate at one time may be used. The precision polishing is preferably performed in a plurality of stages so that the surface roughness gradually decreases in order to ensure a predetermined surface roughness. In this case, the average particle size of the abrasive used is reduced as the polishing step proceeds, and the final surface roughness of the glass substrate after precision polishing is a maximum height Rmax of 2 nm or less and a flatness of 1 μm or less. To be. For multiple stages of precision polishing, a soft polisher is used as the polishing pad, and the polishing agent is selected from cerium oxide, zirconium oxide, aluminum oxide, manganese oxide, colloidal silica, and the average particle size of the polishing agent is It adjusts suitably in the range of 0.03-3 micrometers.
また、マスクブランクスを製造する際、マスクブランクス用ガラス基板上に、主に金属とシリコンと窒素とを含む薄膜を形成する方法は特に限定されない。スパッタリング法やＣＶＤ法、真空蒸着法などが挙げられる。金属とシリコンとを含むスパッタリングターゲットを使用し、窒素ガスを含む雰囲気中でスパッタリングして成膜する反応性スパッタ法が良い。また、マスクブランクスから転写用マスクを製造する際、マスクブランクス用ガラス基板上に薄膜パターンを形成する方法は特に限定されない。前記薄膜上にレジストパターンを形成し、このレジストパターンをマスクにしてエッチングすることにより薄膜パターンを形成する方法や、予めマスクブランクス用ガラス基板上にレジストパターンを形成し、その上から薄膜を形成して薄膜パターンを形成する所謂リフトオフ法でも構わない。微細パターンを形成するという観点から前者が好ましい。 Moreover, when manufacturing a mask blank, the method of forming the thin film mainly containing a metal, a silicon | silicone, and nitrogen on the glass substrate for mask blanks is not specifically limited. Examples include a sputtering method, a CVD method, and a vacuum deposition method. A reactive sputtering method in which a sputtering target containing metal and silicon is used and sputtering is performed in an atmosphere containing nitrogen gas is preferable. Moreover, when manufacturing the transfer mask from mask blanks, the method of forming a thin film pattern on the glass substrate for mask blanks is not specifically limited. A resist pattern is formed on the thin film, and the resist pattern is used as a mask to form a thin film pattern. Alternatively, a resist pattern is formed on a glass substrate for mask blanks in advance, and a thin film is formed thereon. Thus, a so-called lift-off method for forming a thin film pattern may be used. The former is preferable from the viewpoint of forming a fine pattern.
上述の手段によれば、金属とシリコンと窒素とを含む薄膜を剥離液で剥離する場合であっても、ガラス基板の荒れを抑制し、確実にマスクブランクス用ガラス基板を再生することができる。また、再生されたガラス基板を使って膜下欠陥の発生しないマスクブランクス用ガラス基板、並びに、膜下欠陥によるパターン欠陥の発生しない転写マスクを容易に得ることが可能になる。 According to the above-described means, even when a thin film containing metal, silicon, and nitrogen is peeled off with a stripping solution, the glass substrate for mask blanks can be reliably regenerated by suppressing the roughness of the glass substrate. In addition, it becomes possible to easily obtain a glass substrate for mask blanks in which no subsurface defects occur, and a transfer mask in which pattern defects due to subfilm defects do not occur, using the regenerated glass substrate.
以下、ハーフトーン型位相シフトマスクブランクスのガラス基板を再生する例を掲げて本件発明の実施例１にかかるマスクブランクス用ガラス基板の再生方法、マスクブランクスの製造方法及び転写用マスクの製造方法を説明する。
（１）ハーフトーン型位相シフトマスクブランクスの製造
ガラス基板の表面粗さが原子間力顕微鏡による粗さ測定で、最大高さ（Ｒｍａｘ）で２ｎｍ以下に鏡面研磨された合成石英ガラス基板上に、ＤＣマグネトロンスパッタリング法により、モリブデンとシリコンとの混合ターゲツトを用いて、アルゴンガスと窒素ガスの混合ガス雰囲気中でスパッタ成膜し、ガラス基板上にモリブデンシリサイド窒化膜を形成したハーフトーン型位相シフトマスクブランクスを得た。なお、ガラス基板上に形成されたモリブデンシリサイド窒化膜の膜厚は約８５０オングストロームで、膜組成（全体の平均値）は、Ｍｏ：１２．５ａｔ％、Ｓｉ：４０．２ａｔ％、Ｎ：４７．３ａｔ％であった（ＥＳＣＡ分析）。
Hereinafter, a method for regenerating a glass substrate for a mask blank according to Example 1 of the present invention, a method for manufacturing a mask blank, and a method for manufacturing a transfer mask will be described with an example of regenerating a glass substrate of a halftone phase shift mask blank. To do.
(1) Production of halftone phase shift mask blanks On a synthetic quartz glass substrate whose surface roughness is mirror-polished to a maximum height (Rmax) of 2 nm or less by measuring the roughness with an atomic force microscope, A halftone phase shift mask in which a molybdenum silicide nitride film is formed on a glass substrate by sputtering in a mixed gas atmosphere of argon gas and nitrogen gas using a mixed target of molybdenum and silicon by a DC magnetron sputtering method. Blanks were obtained. The film thickness of the molybdenum silicide nitride film formed on the glass substrate is about 850 angstroms, and the film composition (total average value) is Mo: 12.5 at%, Si: 40.2 at%, N: 47. 3 at% (ESCA analysis).
（２）表面欠陥検査
この得られたハーフト一ン型位相シフトマスクブランクスを、表面欠陥検査装置にて検査したところ、ガラス基板とモリブデンシリサイド窒化膜との間に異物が介在したと思われる凸状の膜下欠陥を発見した。このような膜下欠陥はその後の工程で修正することができない。よって、以下の方法によりモリブデンシリサイド窒化膜を剥離し、ガラス基板を再生した。
(2) Surface defect inspection When the obtained half-tone type phase shift mask blanks are inspected with a surface defect inspection apparatus, a convex shape that is considered to have foreign matters interposed between the glass substrate and the molybdenum silicide nitride film. I found a subfilm defect. Such subfilm defects cannot be corrected in subsequent processes. Therefore, the molybdenum silicide nitride film was peeled off by the following method to regenerate the glass substrate.
（３）ガラス基板の再生
水溶液として、弗化水素アンモニウム（０．５ｗｔ％）＋過酸化水素（２．０ｗｔ％）＋純水（９７．５ｗｔ％）の混合水溶液を用い、浸漬法によりモリブデンシリサイド窒化膜をガラス基板から剥離した。なお、このときの剥離液の温度を４０℃、処理時間を３０分とし、処理中、ガラス基板を揺動させて行った。モリブデンシリサイド窒化膜を剥離したガラス基板の表面をＡＥＳ（Ａｕｇｅｒ Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ）で組成分析して確認したところ、モリブデンシリサイド窒化膜の残渣は確認されなかった。また、剥離したガラス基板の表面粗さは最大高さ（Ｒｍａｘ）で１８ｎｍであった。このガラス基板表面を精密研磨することによって、ガラス基板の表面粗さを最大高さＲｍａｘで２ｎｍ以下にしてマスクブランクス用ガラス基板を得た。精密研磨は、両面研磨装置で、スウェードタイプの研磨パッドとガラス基板の間に平均粒径が１μｍの硫化セリウム研磨剤を供給して研磨をした後、スウェードタイプの研磨パッドとガラス基板との間に平均粒径が１００μｍのコロイダルシリカ研磨剤と供給して研磨を２段階の精密研磨を実施した。なお、精密研磨の加工荷重、研磨時間は、所望の表面粗さになるように適宜調整して行った。
(3) Regeneration of glass substrate As an aqueous solution, a mixed aqueous solution of ammonium hydrogen fluoride (0.5 wt%) + hydrogen peroxide (2.0 wt%) + pure water (97.5 wt%) is used, and molybdenum silicide is obtained by an immersion method. The nitride film was peeled from the glass substrate. Note that the temperature of the stripping solution at this time was 40 ° C., the treatment time was 30 minutes, and the glass substrate was rocked during the treatment. When the surface of the glass substrate from which the molybdenum silicide nitride film was peeled was confirmed by composition analysis using AES (Auger Electron Spectroscopy), no residue of the molybdenum silicide nitride film was confirmed. The surface roughness of the peeled glass substrate was 18 nm at the maximum height (Rmax). By precisely polishing the glass substrate surface, the glass substrate for mask blanks was obtained by setting the surface roughness of the glass substrate to 2 nm or less at the maximum height Rmax. Precision polishing is a double-side polishing machine that supplies a cerium sulfide abrasive with an average particle size of 1 μm between a suede type polishing pad and a glass substrate, and then polishes between the suede type polishing pad and the glass substrate. A colloidal silica abrasive having an average particle size of 100 μm was supplied to the substrate to carry out polishing in two stages. The processing load and polishing time for precision polishing were appropriately adjusted so as to obtain a desired surface roughness.
（４）ハーフト一ン型位相シフトマスクブランクスの再製造
この再生されたガラス基板を使用して、再度ＤＣマグネトロンスパッタリング法により、ガラス基板上にモリブデンシリサイド窒化膜を形成し、ハーフトーン型位相シフトマスクブランクスを得た。この得られたハーフト−ン型位相シフトマスクブランクスを、表面欠陥検査装置にて検査したところ、上述の凸状の膜下欠陥は確認されなかった。この膜下欠陥のないハーフトーン型位相シフトマスクブランクス上にレジストをコートし、描画によりレジストパターンを形成した。このレジストパターンをマスクにしてモリブデンシリサイド窒化膜を、弗素ガスを用いたドライエッチングにより、モリブデンシリサイド窒化膜からなるハーフトーン膜パターンをガラス基板上に形成してハーフトーン型位相シフトマスクを得た。得られたハーフトーン型位相シフトマスクについてパターン欠陥、位相欠陥を確認したところ両欠陥とも確認されなかった。
(4) Remanufacture of halftone phase shift mask blanks Using this regenerated glass substrate, a molybdenum silicide nitride film is again formed on the glass substrate by DC magnetron sputtering, and a halftone phase shift mask is obtained. Blanks were obtained. When the obtained half-toned phase shift mask blanks were inspected with a surface defect inspection apparatus, the above-mentioned convex subfilm defects were not confirmed. A resist was coated on the halftone phase shift mask blank having no subfilm defects, and a resist pattern was formed by drawing. Using this resist pattern as a mask, a half-tone phase shift mask was obtained by forming a molybdenum silicide nitride film on a glass substrate by dry etching using a fluorine gas and forming a half-tone film pattern made of a molybdenum silicide nitride film on a glass substrate. When the pattern defect and the phase defect were confirmed about the obtained halftone type phase shift mask, neither defect was confirmed.
次に、上述の実施例１において、処理中の水溶液の温度（処理時間）を、３０（６０分）℃、５０℃（３０分）、６５℃（２５分）、７０℃（２０分）と変化させた以外は実施例１と同様にしてガラス基板上からモリブデンシリサイド窒化膜を剥離した。その結果、水溶液の温度が３０℃の場合、剥離した後のガラス基板の表面粗さは、最大高さＲｍａｘで９０ｎｍとなり、表面粗さが悪化した。水溶液の温度を３５℃以上にすると最大高さＲｍａｘが３０ｎｍ以下になったが、７０℃を超えると、水溶液の蒸発により濃度が無視できないほど変化するのでこのましくないことがわかった。 Next, in Example 1 described above, the temperature (treatment time) of the aqueous solution during treatment was 30 (60 minutes) ° C., 50 ° C. (30 minutes), 65 ° C. (25 minutes), and 70 ° C. (20 minutes). Except for the change, the molybdenum silicide nitride film was peeled off from the glass substrate in the same manner as in Example 1. As a result, when the temperature of the aqueous solution was 30 ° C., the surface roughness of the glass substrate after peeling was 90 nm at the maximum height Rmax, and the surface roughness was deteriorated. When the temperature of the aqueous solution was 35 ° C. or higher, the maximum height Rmax became 30 nm or less. However, when the temperature exceeded 70 ° C., the concentration changed to a degree that could not be ignored due to evaporation of the aqueous solution.
次に、上述の実施例１において、弗化水素アンモニウムと過酸化水素とのそれぞれの濃度を変えた以外は実施例１と同様にしてガラス基板の再生を行った結果を実施例２〜６、比較例１〜４として表１にして示す。また、弗化水素アンモニウムのかわりに、弗化水素酸、珪弗化水素酸を用い、同様にそれぞれの濃度を変えたものを実施例７〜１４として表２にして示す。表１及び表２から以下のことが分かる。弗素化合物が０．１〜０．８ｗｔ％含む水溶液を用いることにより、ハーフトーン型位相シフトマスクブランクスのガラス基板を良好に再生することができる。一方、弗素化合物の濃度が０．１ｗｔ％未満であると、水溶液による薄膜のエッチング速度が遅くなりすぎ、剥離時間が長くなるので、好ましくない。また、濃度が０．８ｗｔ％を越えると、水溶液による薄膜のエッチング速度が早くなりすぎ、剥離後のガラス基板が著しく荒れるので好ましくない。
本発明は、マスクブランクスや転写マスクなどのガラス基板上に形成された金属シリサイドの窒化物膜をガラス基板から剥離してマスクブランクス用ガラス基板を再生して該基板を用いたマスクブランクスや転写用マスクを製造する場合に利用できる。 In the present invention, a nitride film of metal silicide formed on a glass substrate such as a mask blank or a transfer mask is peeled off from the glass substrate to regenerate the mask blank glass substrate, and the mask blank or transfer material using the substrate is regenerated. It can be used when manufacturing a mask.
Claims (6)
前記薄膜は主として金属とシリコンと窒素とを含むものであり、
前記薄膜の剥離は、前記薄膜が形成されたガラス基板を、弗化水素酸、珪弗化水素酸、弗化水素アンモニウムから選ばれる少なくとも一つの弗素化合物と、過酸化水素、硝酸、硫酸から選ばれる少なくとも一つの酸化剤とを含み、前記弗素化合物を０．１〜０．８ｗｔ％含む水溶液に接触させて行うものであることを特徴とするマスクブランクス用ガラス基板の再生方法。 In the regeneration method of the glass substrate for mask blanks, which peels the thin film formed on the glass substrate for mask blanks and regenerates the glass substrate for mask blanks,
The thin film mainly contains metal, silicon, and nitrogen,
For the peeling of the thin film, the glass substrate on which the thin film is formed is selected from at least one fluorine compound selected from hydrofluoric acid, hydrosilicofluoric acid, and ammonium hydrogen fluoride, hydrogen peroxide, nitric acid, and sulfuric acid. A method for regenerating a glass substrate for mask blanks, comprising: contacting with an aqueous solution containing 0.1 to 0.8 wt% of the fluorine compound.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012053120A (en) * | 2010-08-31 | 2012-03-15 | Hoya Corp | Method for manufacturing mask blank substrate and mask blank |
| JP2016031451A (en) * | 2014-07-29 | 2016-03-07 | 株式会社Adeka | Composition and method for mask blank removal |
| JP2017120437A (en) * | 2012-03-30 | 2017-07-06 | Hoya株式会社 | Method for manufacturing substrate with multilayer reflection film, method for manufacturing reflective mask blank, method for manufacturing reflective mask, method for manufacturing transmissive mask blank, method for manufacturing transmissive mask, and method for manufacturing semiconductor device |
| JP2017181733A (en) * | 2016-03-30 | 2017-10-05 | Hoya株式会社 | Method for regenerating substrate with multilayer film, method for manufacturing substrate with multilayer reflection film and method for manufacturing reflection type mask blank |
| JP2018045253A (en) * | 2012-09-26 | 2018-03-22 | 大日本印刷株式会社 | Glass regeneration production method, regenerated glass substrate and photomask blanks and photomask using the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62218585A (en) * | 1985-10-31 | 1987-09-25 | Hoya Corp | Production of photomask |
| JPH03100550A (en) * | 1989-09-13 | 1991-04-25 | Fujitsu Ltd | Method for regenerating reticule mask |
| JP2966369B2 (en) * | 1996-03-30 | 1999-10-25 | ホーヤ株式会社 | Phase shift mask and phase shift mask blank |
| JP2002062634A (en) * | 2000-08-15 | 2002-02-28 | Hitachi Ltd | Method for producing photomask, method for producing photomask blank and method for regenerating photomask |
| JP2003145426A (en) * | 2001-11-19 | 2003-05-20 | Mtc:Kk | Pattern eliminating method for recycle of masked substrate, and pattern eliminating device, and masking- pattern-eliminated substrate |
-
2003
- 2003-12-16 JP JP2003418335A patent/JP4497909B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62218585A (en) * | 1985-10-31 | 1987-09-25 | Hoya Corp | Production of photomask |
| JPH03100550A (en) * | 1989-09-13 | 1991-04-25 | Fujitsu Ltd | Method for regenerating reticule mask |
| JP2966369B2 (en) * | 1996-03-30 | 1999-10-25 | ホーヤ株式会社 | Phase shift mask and phase shift mask blank |
| JP2002062634A (en) * | 2000-08-15 | 2002-02-28 | Hitachi Ltd | Method for producing photomask, method for producing photomask blank and method for regenerating photomask |
| JP2003145426A (en) * | 2001-11-19 | 2003-05-20 | Mtc:Kk | Pattern eliminating method for recycle of masked substrate, and pattern eliminating device, and masking- pattern-eliminated substrate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012053120A (en) * | 2010-08-31 | 2012-03-15 | Hoya Corp | Method for manufacturing mask blank substrate and mask blank |
| JP2017120437A (en) * | 2012-03-30 | 2017-07-06 | Hoya株式会社 | Method for manufacturing substrate with multilayer reflection film, method for manufacturing reflective mask blank, method for manufacturing reflective mask, method for manufacturing transmissive mask blank, method for manufacturing transmissive mask, and method for manufacturing semiconductor device |
| US9897909B2 (en) | 2012-03-30 | 2018-02-20 | Hoya Corporation | Mask blank substrate, substrate with multilayer reflection film, transmissive mask blank, reflective mask blank, transmissive mask, reflective mask, and semiconductor device fabrication method |
| US10429728B2 (en) | 2012-03-30 | 2019-10-01 | Hoya Corporation | Mask blank substrate, substrate with multilayer reflection film, transmissive mask blank, reflective mask blank, transmissive mask, reflective mask, and semiconductor device fabrication method |
| US10620527B2 (en) | 2012-03-30 | 2020-04-14 | Hoya Corporation | Mask blank substrate, substrate with multilayer reflection film, transmissive mask blank, reflective mask blank, transmissive mask, reflective mask, and semiconductor device fabrication method |
| JP2018045253A (en) * | 2012-09-26 | 2018-03-22 | 大日本印刷株式会社 | Glass regeneration production method, regenerated glass substrate and photomask blanks and photomask using the same |
| JP2016031451A (en) * | 2014-07-29 | 2016-03-07 | 株式会社Adeka | Composition and method for mask blank removal |
| JP2017181733A (en) * | 2016-03-30 | 2017-10-05 | Hoya株式会社 | Method for regenerating substrate with multilayer film, method for manufacturing substrate with multilayer reflection film and method for manufacturing reflection type mask blank |
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