JPS62218585A - Production of photomask - Google Patents
Production of photomaskInfo
- Publication number
- JPS62218585A JPS62218585A JP61256289A JP25628986A JPS62218585A JP S62218585 A JPS62218585 A JP S62218585A JP 61256289 A JP61256289 A JP 61256289A JP 25628986 A JP25628986 A JP 25628986A JP S62218585 A JPS62218585 A JP S62218585A
- Authority
- JP
- Japan
- Prior art keywords
- light
- shielding film
- photomask
- silicide
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000758 substrate Substances 0.000 claims abstract description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims abstract description 6
- 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 claims abstract description 5
- 238000005530 etching Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 18
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 claims description 12
- 229910021344 molybdenum silicide Inorganic materials 0.000 claims description 12
- 229910021332 silicide Inorganic materials 0.000 claims description 11
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- WEAMLHXSIBDPGN-UHFFFAOYSA-N (4-hydroxy-3-methylphenyl) thiocyanate Chemical compound CC1=CC(SC#N)=CC=C1O WEAMLHXSIBDPGN-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- VKTGMGGBYBQLGR-UHFFFAOYSA-N [Si].[V].[V].[V] Chemical compound [Si].[V].[V].[V] VKTGMGGBYBQLGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910021334 nickel silicide Inorganic materials 0.000 claims description 3
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910021355 zirconium silicide Inorganic materials 0.000 claims description 3
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021342 tungsten silicide Inorganic materials 0.000 claims description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 5
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 238000010894 electron beam technology Methods 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000001020 plasma etching Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000609 electron-beam lithography Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- -1 fluorine ions Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 239000012487 rinsing solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001039 wet etching Methods 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
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
- G03F1/80—Etching
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、石英ガラス等からなる透光性基板と、その透
光性基板の一主表面上に被着した珪化モリブデン等の物
質を含有してなる遮光性膜とからなるフォトマスク基板
の遮光性膜を、選択的にエツチングする工程を経て遮光
性膜パターンを形成して、フォトマスクを製造する方法
に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention comprises a transparent substrate made of quartz glass or the like and a substance such as molybdenum silicide deposited on one main surface of the transparent substrate. The present invention relates to a method of manufacturing a photomask by forming a light-shielding film pattern through a step of selectively etching a light-shielding film of a photomask substrate comprising a light-shielding film formed by etching.
従来、フォトマスクの製造方法には、例えば以下に記す
方法がある。Conventionally, methods for manufacturing photomasks include, for example, the methods described below.
すなわち、石英ガラスからなる透光性基板の両生表面を
研磨し、その透光性基板の−・主表面上に珪化モリブデ
ンからなる遮光性膜を被着してフォトマスク基板を製作
する。次に、その遮光性膜上に電子線レジストを塗布し
てレジスト付きフォトマスク基板を製作し、その電子線
レジストに所望のレジストパターンを潜像すべく、電子
線描画装置を用いて露光する。次に、遮光性膜上に所望
の残存レジストパターンを形成すべく、現像液により所
定時間現像し、次にリンス液でリンス処理し、その後、
乾燥する。次に、その遮光性膜に対応する弗化水素酸と
硝酸との混合水溶液からなるエツチング液（引例：雑誌
［電子材料Ｊ １９８５年１月号４Ｍ ＤＲＡＭ用サ
ブミクロン基本技術 Ｐ、７４）中に所定時間浸漬して
、遮光性膜を選択的にエツチングする。すると、フォト
マスク基板を構成する透光性基板の一主表面Ｆには、残
存レジストパターンとその下の遮光性膜パターンとが残
る。次に、レジスト剥離液中に浸漬して残存レジストパ
ターンを剥離し、透光性基板の一生表面上に所望の遮光
性膜パターンを形成してフォトマスクを製造している。That is, a photomask substrate is manufactured by polishing the amphiphobic surfaces of a transparent substrate made of quartz glass, and depositing a light-shielding film made of molybdenum silicide on the main surface of the transparent substrate. Next, an electron beam resist is coated on the light-shielding film to produce a resist-coated photomask substrate, and the electron beam resist is exposed to light using an electron beam lithography apparatus in order to form a latent image of a desired resist pattern on the electron beam resist. Next, in order to form a desired residual resist pattern on the light-shielding film, it is developed with a developer for a predetermined time, and then rinsed with a rinsing solution.
dry. Next, an etching solution consisting of a mixed aqueous solution of hydrofluoric acid and nitric acid corresponding to the light-shielding film is added (Reference: Magazine [Electronic Materials J January 1985 Issue 4M Submicron Basic Technology for DRAM P, 74). The light shielding film is selectively etched by dipping for a predetermined time. Then, the residual resist pattern and the light-shielding film pattern thereunder remain on one main surface F of the light-transmitting substrate constituting the photomask substrate. Next, the remaining resist pattern is peeled off by immersion in a resist stripping solution, and a desired light-shielding film pattern is formed on the entire surface of the light-transmitting substrate, thereby producing a photomask.
なお、上記したエツチング液を用いて遮光性膜を選択的
にエツチングする湿式エツチング法の他に、その遮光性
膜に対応する反応ガスを用いて遮光性膜を選択的にエツ
チングＭるガスプラズマエツチング法や反応性イオンエ
ツチング法という乾式エツチング法もある。In addition to the wet etching method in which the light-shielding film is selectively etched using the above-mentioned etching solution, gas plasma etching is also available in which the light-shielding film is selectively etched using a reaction gas corresponding to the light-shielding film. There is also a dry etching method called reactive ion etching method and reactive ion etching method.
しかし、弗化水素酸と硝酸との混合水溶液からなるエツ
チング液を用いて遮光性膜を選択的にエツチングする場
合、そのエツチング液中の遊離弗素イオンの濃度のコン
トロールが難しいので、石英ガラス等からなる透光性基
板が腐蝕されて透光性基板に微小な傷（いわゆる「潜傷
」）が生じたり、研磨した透光性基板において遮光性膜
を被着していない方の主表面の粗さが増大してしまった
り、残存レジストパターンのトの遮光性膜パターンの一
部が透光性基板の一生表面上から剥ぎ取られてしまうこ
とがあった。また、エツチング回数を重ねるに従って、
を記しＩＣエツチング液では遮光性膜との反応によって
遊離弗素イオン濃度が急激に低下し、エツチング力がす
ぐに低下してしまう。このため、エツチング回数を重ね
るに従ってエツチング力の低下に対応して、エツチング
時間を漸次伸ばしていく必要があった。さらに、有害物
質である弗化水素酸を含むエツチング液の取り扱いには
、多大の危険が伴い、細心の注意を払ってエツチング作
業を行う必要があった。However, when selectively etching a light-shielding film using an etching solution consisting of a mixed aqueous solution of hydrofluoric acid and nitric acid, it is difficult to control the concentration of free fluorine ions in the etching solution. Microscopic scratches (so-called "latent scratches") may occur on the light-transmitting substrate due to corrosion, or roughness may occur on the main surface of the polished light-transmitting substrate that is not coated with a light-shielding film. In some cases, the light-shielding film pattern of the remaining resist pattern may be partially peeled off from the surface of the light-transmitting substrate. Also, as the number of etching increases,
In the IC etching solution, the concentration of free fluorine ions rapidly decreases due to the reaction with the light-shielding film, and the etching power immediately decreases. Therefore, as the number of times of etching increases, it is necessary to gradually lengthen the etching time in response to the decrease in etching power. Furthermore, handling of etching solutions containing hydrofluoric acid, which is a harmful substance, involves great danger, and etching operations must be performed with extreme caution.
また、ガスプラズマエツチング法や反応性イオンエツチ
ング法等の乾式エツチング法を採用してフォトマスクを
製造する場合には、埋像・リンス処理・乾燥工程で残存
レジストパターン付きフォトマスク基板に塵埃が付着し
やすく、塵埃が付着した部分の下の遮光性膜をエツチン
グすることができず、透光性基板の一生表面上に不要の
遮光性膜が残存していわゆる黒欠陥が発生し、所望の遮
光性膜パターンを形成することができなかった。In addition, when manufacturing photomasks using dry etching methods such as gas plasma etching or reactive ion etching, dust adheres to the photomask substrate with the remaining resist pattern during the imaging, rinsing, and drying processes. This makes it impossible to etch the light-shielding film under the part where dust has adhered, and the unnecessary light-shielding film remains on the surface of the light-transmitting substrate for the entire life of the light-transmitting substrate, resulting in so-called black defects. It was not possible to form a sexual membrane pattern.
本発明は、以上のような事情を鑑みてなされたものであ
り、エツチング時に透光性基板が腐蝕されて潜傷が生じ
ることと、透光性基板において遮光性膜を被着していな
い方の主表面の粗さが増大することとをそれぞれ抑制で
き、また、残存レジストパターンの下の遮光性膜パター
ンの一部が透光性基板の一生表面上から剥ぎ取られるこ
と、及び黒欠陥が発生することを防止して所望の遮光性
膜パターンを形成することができ、さらに、多数回のエ
ツチング処理を行っても略同−の所定のエツチング時間
を経て所望の遮光性膜パターンを形成することができる
フォトマスクの製造方法を捉供することを目的とする。The present invention has been made in view of the above-mentioned circumstances, and it solves the problem that the transparent substrate is corroded during etching and latent scratches occur, and that the transparent substrate is not coated with a light-shielding film. In addition, it is possible to suppress the increase in the roughness of the main surface of the transparent substrate, and also to prevent part of the light-shielding film pattern under the remaining resist pattern from being peeled off from the surface of the light-transmitting substrate during the lifetime, and to prevent black defects from increasing. A desired light-shielding film pattern can be formed by preventing this from occurring, and furthermore, even if etching is performed multiple times, the desired light-shielding film pattern can be formed after approximately the same predetermined etching time. The purpose of the present invention is to provide a method for manufacturing a photomask that can be used.
本発明は、上記の目的を達成するためになされたもので
あり、透光性基板の一生表面上に遮光性膜を被着してな
るフォトマスク基板の前記遮光性膜上にレジストを塗布
し、前記レジストを露光・現像して前記遮光性膜上に残
存レジストパターンを形成し、次に、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を用いて前
記遮光性膜を選択的にエツチングし、次に前記残存レジ
ストパターンを剥離することを特徴とするフォトマスク
の製造方法である。さらに、本発明の第１の実施態様は
、前記遮光性膜がモリブデン、タングステン、タンタル
、バナジウム。The present invention has been made to achieve the above-mentioned object, and includes coating a resist on the light-shielding film of a photomask substrate, which is formed by coating a light-shielding film on the entire surface of a light-transmitting substrate. , the resist is exposed and developed to form a residual resist pattern on the light-shielding film, and then at least one of ammonium hydrogen fluoride, ammonium fluoride, hydrosilicofluoric acid, and fluoroboric acid and selectively etching the light-shielding film using an aqueous solution containing at least one of hydrogen peroxide and nitric acid, and then peeling off the remaining resist pattern. It's a method. Furthermore, in the first embodiment of the present invention, the light-shielding film is made of molybdenum, tungsten, tantalum, or vanadium.
二Ａブ、コバルト、ジルコニウム、ニッケルのうち何れ
か少なくとも一つを含有してなることを特徴どするフォ
トマスクの製造方法であり、第２の実施態様は、前記遮
光性膜が珪化モリブデン、珪化タングステン、珪化タン
タル、珪化バナジウム。A second embodiment is a method for producing a photomask, characterized in that the photomask contains at least one of nickel, cobalt, zirconium, and nickel; Tungsten, tantalum silicide, vanadium silicide.
珪化ニオブ、珪化」バルト、珪化ジルコニウム。Niobium silicide, Balt silicide, zirconium silicide.
珪化ニッケルのうら何れか少なくとも−・つを含有して
なることを特徴とするフォトマスクの製造方法である。A method for producing a photomask characterized in that the photomask contains at least one of the following: nickel silicide.
弗化水素アンモニウム、弗化アン上ニウム、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どを混合した
水溶液では、遊離弗素イオン濃度が低下しにくいので、
エツチング液が低下しにくい。In an aqueous solution containing at least one of ammonium hydrogen fluoride, ammonium fluoride, hydrosilicofluoric acid, and fluoroboric acid, and at least one of hydrogen peroxide and nitric acid, free fluorine ions Since the concentration is less likely to decrease,
Etching solution does not easily deteriorate.
以下、本発明の実施例によるフォトマスクの製造方法に
ついて詳細に説明でる。Hereinafter, a method for manufacturing a photomask according to an embodiment of the present invention will be described in detail.
先ず、透光性基板（材料：石英ガラス、５×５Ｘ Ｏ，
０９インチ）の両生表面を研磨し、その透光性基板の一
主表面上に、スパッタリング法により遮光性膜として珪
化モリブデン膜（光学濃度：３．０．膜厚： １０００
人）を被着してフォトマスク基板を製作する。次に、こ
の珪化モリブデン膜上にポジ型電子線レジスト（例：ヂ
ッソ■製のＰＢＳ。First, a transparent substrate (material: quartz glass, 5×5×O,
A molybdenum silicide film (optical density: 3.0, film thickness: 1000
A photomask substrate is manufactured by depositing a photomask (person) on the photomask substrate. Next, a positive electron beam resist (for example, PBS manufactured by Jisso ■) was applied on this molybdenum silicide film.
Ｓ厚： ４０００人）をスピンコード法によって塗布し
てレジスト付きフォトマスク基板を製作する。A resist-coated photomask substrate is manufactured by applying a film (thickness: 4,000) by a spin code method.
次に、このレジスト付きフォトマスク基板のレジストに
所望のレジストパターンを潜像づべく、電子線描画装置
（例：バーキン・エルマー社製ＨＥＢＥＳ −Ｉ［［）
を用いて露光し、さらに、露光部分を除去して珪化モリ
ブデン膜上に所望の残存レジストパターンを形成すべく
、現像液（例： ＰＢＳ専用デベロッパ）を用いて現像
する。次に、リンス液（例：イソブロビルアル−コール
液（以下、単にｒＩＰＡ液」という。））中に浸漬して
リンス処理した後、遠心力によりリンス液を振り飛ばし
て乾燥するスピン乾燥法によって乾燥する。Next, in order to form a latent image of a desired resist pattern on the resist of this resist-coated photomask substrate, an electron beam lithography device (for example, HEBES-I manufactured by Birkin-Elmer Co., Ltd.
Further, in order to remove the exposed portion and form a desired residual resist pattern on the molybdenum silicide film, development is performed using a developer (for example, a developer exclusively for PBS). Next, after rinsing by immersing in a rinsing solution (e.g. isobrobyl alcohol solution (hereinafter simply referred to as rIPA solution)), a spin drying method is used in which the rinsing solution is shaken off using centrifugal force and dried. dry.
次に、弗化水素アンモニウム（ｌ ｗｔ％）と過酸化水
素（４，４ｗｔ％）と純水（９４，６ｗｔ％）との置台
水溶液からなるエツチング液中に、残存レジストパター
ン付きフォトマスク基板を所定時間（例；２００秒）浸
漬して、珪化モリブデン膜を選択的にエツチングする。Next, the photomask substrate with the remaining resist pattern was placed in an etching solution consisting of an aqueous solution of ammonium hydrogen fluoride (1 wt%), hydrogen peroxide (4.4 wt%), and pure water (94.6 wt%). The molybdenum silicide film is selectively etched by dipping for a predetermined time (eg, 200 seconds).
すると、透光性基板の一主表面上には、残存レジストパ
ターンとその下の珪化モリブデン膜パターンとが残る。Then, the remaining resist pattern and the underlying molybdenum silicide film pattern remain on one main surface of the light-transmitting substrate.
次に、レジスト剥離液（例：１１硫酸と過酸化水素とを
混合した溶液）中に浸漬して残存レジストパターンを剥
離し、透光性基板の一主表面上に所望の遮光性膜パター
ンとしての珪化モリブデン膜パターンを形成してフォト
マスクを製造した。Next, the remaining resist pattern is peeled off by immersion in a resist stripping solution (e.g., a solution containing 11 sulfuric acid and hydrogen peroxide), and a desired light-shielding film pattern is formed on one main surface of the light-transmitting substrate. A photomask was manufactured by forming a molybdenum silicide film pattern.
本実施例によって製造したフォトマスクの透光性基板を
、電子顕微鏡を用いて観察してみたが、潜傷はほとんど
発生していなかった。さらに、光学式顕微鏡を用いて珪
化モリブデン膜パターンを観察してみたが、珪化モリブ
デン膜パターンの一 ９一
部が剥ぎ取られることに起因する白欠陥（例：かけ、ピ
ンホール、断線）の発生もなかった。また、本実施例中
で記したと同一寸法のレジスト付きフォトマスク基板を
用い、反応性イオンエツチング法を採用してフォトマス
クを製造した場合と、本実施例中に記した方法でフォト
マスクを製造した場合とにおいて、何れも試料数２０枚
で、１μ論以上の寸法を有する黒欠陥の発生数を比較す
ると、上記前者の場合ではその発生数が３０〜５０個あ
ったものが、上記後者の場合では、０〜５個であった。When the light-transmitting substrate of the photomask manufactured according to this example was observed using an electron microscope, almost no latent scratches were observed. Furthermore, when we observed the molybdenum silicide film pattern using an optical microscope, we found that white defects (e.g. chips, pinholes, wire breaks) occurred due to part of the molybdenum silicide film pattern being peeled off. There wasn't. In addition, there are two cases in which a photomask is manufactured using a photomask substrate with a resist having the same dimensions as described in this example and by adopting the reactive ion etching method. Comparing the number of black defects with a size of 1 μm or more in both cases using 20 samples, the former case had 30 to 50 defects, while the latter case had 30 to 50 black defects. In this case, the number was 0 to 5.
さらに、有害物質である弗化水素酸を用いないため、エ
ツチング液の取り扱い」−の危険性も減少した。また、
緩衝作用のため１ツチングカが低下しにくいので、残存
レジストパターン付きフォトマスク基板を略一定のエツ
チング時間で多数回エツチング処理することができた。Furthermore, since hydrofluoric acid, which is a hazardous substance, is not used, the risk of handling the etching solution is reduced. Also,
Because the buffering effect makes it difficult for the etching force to decrease, the photomask substrate with the remaining resist pattern could be etched many times in a substantially constant etching time.
本発明は、上記した実施例に限定されるものではない。The present invention is not limited to the embodiments described above.
エツチング液としては、弗化水素アンモニウム。Ammonium hydrogen fluoride is used as an etching solution.
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ｎ１合した水溶液を用いてもよい
。また、それらの混合比は必要に応じて適宜決定されう
る。さらに、上記エツチング液は、遮光性膜を選択的に
エツチングする工程に用いられるのみならず、透光性基
板の主表面上に被着した遮光性膜を剥離するために用い
てもよい。An aqueous solution in which at least one of ammonium fluoride, hydrosilicofluoric acid, and fluoroboric acid is combined with at least one of hydrogen peroxide and nitric acid may be used. Further, the mixing ratio thereof can be appropriately determined as necessary. Further, the etching solution described above is not only used in the step of selectively etching the light-shielding film, but also may be used to peel off the light-shielding film deposited on the main surface of the light-transmitting substrate.
透光性基板は石英ガラスの他に、アルミノシリケート、
ボロシリケート及びソーダライム等の多成分系ガラスや
サファイヤからなってもよいし、その大きさも適宜決定
されうる。In addition to quartz glass, the transparent substrate is made of aluminosilicate,
It may be made of multi-component glass such as borosilicate and soda lime, or sapphire, and its size may be determined as appropriate.
遮光性膜としては珪化モリブデン膜の他に、珪化タング
ステン、珪化タンタル、珪化バナジウム。In addition to molybdenum silicide, tungsten silicide, tantalum silicide, and vanadium silicide are used as light-shielding films.
珪化ニオブ、珪化コバルト、珪化ジルコニウム。Niobium silicide, cobalt silicide, zirconium silicide.
珪化ニッケル等のエツチング可能な金属珪化物のうち何
れか少なくとも一つを含有してなるものであってもよく
、また、これ等金属珪化物の窒化物。It may contain at least one of etched metal silicides such as nickel silicide, or nitrides of these metal silicides.
炭化物、酸化物等の膜や、これ等二双上の多層膜でもよ
い。さらに、遮光性膜としては、モリブデン、タングス
テン、タンタル、バナジウム、ニオブ、コバルト、ジル
コニウム、ニッケルのうち何れか少なくとも一つを含有
してなるものであってもよい。さらに、遮光性膜中には
、少量のリンや鉄等の不純物が含有されていてもよい。A film of carbide, oxide, etc., or a multilayer film of two layers of these may be used. Furthermore, the light-shielding film may contain at least one of molybdenum, tungsten, tantalum, vanadium, niobium, cobalt, zirconium, and nickel. Furthermore, the light-shielding film may contain a small amount of impurities such as phosphorus and iron.
また、遮光性膜の膜厚は１０００人に限定されず、所定
の光学濃度に従って適宜決定されうる。Further, the thickness of the light-shielding film is not limited to 1000, and can be determined as appropriate according to a predetermined optical density.
遮光性膜の成膜手段としては、スパッタリング法の他に
真空蒸着法やイオンブレーティング法やＣＶＤ法等を採
用してもよい。As a method for forming the light-shielding film, in addition to the sputtering method, a vacuum evaporation method, an ion-blating method, a CVD method, or the like may be employed.
レジストは、ポジ型電子線レジストの他に、例えば東洋
曹達工業−社製のＣＭＳ−ＥＸ（ｓｓ）等のネガ型電子
線レジストや、ポジ型及びネガ型フォトレジスト等であ
ってもよい。また、レジストの膜厚は４０００人に限定
されず、適宜決定されうる。In addition to a positive electron beam resist, the resist may be a negative electron beam resist such as CMS-EX (ss) manufactured by Toyo Soda Kogyo Co., Ltd., or a positive or negative photoresist. Further, the film thickness of the resist is not limited to 4000, and can be determined as appropriate.
露光工程では、電子線レジストに対しては、電子線描画
装置を用い電子線で露光したが、フォトレジストに対し
ては遠紫外光や紫外光等の光で露光する。In the exposure step, the electron beam resist is exposed to an electron beam using an electron beam lithography device, while the photoresist is exposed to light such as far ultraviolet light or ultraviolet light.
上記実施例中ではリンス処理時のリンス液としてＩＰＡ
液を用いたが、電子線レジストに対しては、純水あるい
はＩＰＡ液以外の有機溶媒をリンス液として用いてもよ
いし、フォトレジストに対しては、純水をリンス液とし
て用いる。In the above examples, IPA was used as the rinsing liquid during the rinsing process.
Although a liquid was used as the rinsing liquid, pure water or an organic solvent other than the IPA liquid may be used as the rinsing liquid for electron beam resist, and pure water may be used as the rinsing liquid for photoresist.
乾燥法としてはスピン乾燥法を採用したが、残存レジス
トパターン付きフォトマスク基板を乾燥できる他の乾燥
法を採用してもよい。Although a spin drying method was used as the drying method, other drying methods that can dry the photomask substrate with a residual resist pattern may be used.
本発明のフォトマスクの製造方法によれば、エツチング
液に透光性基板が腐蝕されて潜傷が生じることと、透光
性基板において遮光性膜を被着していない方の主表面の
粗さが増大することとをそれぞれ抑制でき、また、残存
レジストパターンの下の遮光性膜パターンの一部が透光
性基板の−・主表面上から剥ぎ取られること、及び黒欠
陥が発生することを防止して所望の遮光性膜パターンを
形成することができ、さらに、多数回エツチング処理を
行っても所定のエツチング時間を経て所望の遮光性膜パ
ターンを形成づることができる。According to the photomask manufacturing method of the present invention, the etching solution corrodes the light-transmitting substrate and causes latent scratches, and the main surface of the light-transmitting substrate on which the light-shielding film is not coated is rough. In addition, it is possible to prevent a part of the light-shielding film pattern under the remaining resist pattern from being peeled off from the main surface of the light-transmitting substrate, and to prevent black defects from occurring. It is possible to form a desired light-shielding film pattern while preventing the above-mentioned problems.Furthermore, even if etching is performed many times, the desired light-shielding film pattern can be formed after a predetermined etching time.
Claims (3)
るフォトマスク基板の前記遮光性膜上にレジストを塗布
し、前記レジストを露光・現像して前記遮光性膜上に残
存レジストパターンを形成し、次に、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を用いて前
記遮光性膜を選択的にエッチングし、次に前記残存レジ
ストパターンを剥離することを特徴とするフォトマスク
の製造方法。(1) A resist is coated on the light-shielding film of a photomask substrate formed by coating a light-shielding film on one main surface of a light-transmitting substrate, and the resist is exposed and developed to coat the light-shielding film. A residual resist pattern is formed, and then, at least one of ammonium hydrogen fluoride, ammonium fluoride, hydrosilicic acid, and fluoroboric acid, and at least one of hydrogen peroxide and nitric acid are added. A method for manufacturing a photomask, comprising selectively etching the light-shielding film using an aqueous solution containing a mixture of the following: and then peeling off the remaining resist pattern.
ル、バナジウム、ニオブ、コバルト、ジルコニウム、ニ
ッケルのうち何れか少なくとも一つを含有してなること
を特徴とする特許請求の範囲第（１）項記載のフォトマ
スクの製造方法。(2) Claim (1) characterized in that the light-shielding film contains at least one of molybdenum, tungsten, tantalum, vanadium, niobium, cobalt, zirconium, and nickel. A method for manufacturing a photomask.
、珪化タンタル、珪化バナジウム、珪化ニオブ、珪化コ
バルト、珪化ジルコニウム、珪化ニッケルのうち何れか
少なくとも一つを含有してなることを特徴とする特許請
求の範囲第（１）項記載のフォトマスクの製造方法。(3) A patent claim characterized in that the light-shielding film contains at least one of molybdenum silicide, tungsten silicide, tantalum silicide, vanadium silicide, niobium silicide, cobalt silicide, zirconium silicide, and nickel silicide. A method for manufacturing a photomask according to scope (1).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-244719 | 1985-10-31 | ||
| JP24471985 | 1985-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62218585A true JPS62218585A (en) | 1987-09-25 |
Family
ID=17122885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61256289A Pending JPS62218585A (en) | 1985-10-31 | 1986-10-28 | Production of photomask |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62218585A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1383161A1 (en) * | 2002-07-15 | 2004-01-21 | Texas Instruments Incorporated | Method of etching a silicate gate dielectric using a HF-containing solution |
| JP2005181423A (en) * | 2003-12-16 | 2005-07-07 | Hoya Corp | Method for reproducing glass substrate for mask blanks, method for manufacturing mask blanks, and method for manufacturing transfer mask |
| JP2007256922A (en) * | 2006-02-22 | 2007-10-04 | Hoya Corp | Pattern forming method, method of manufacturing gray tone mask, and pattern transfer method |
| JP2007271720A (en) * | 2006-03-30 | 2007-10-18 | Hoya Corp | Mask blank and photomask |
| JP2007271775A (en) * | 2006-03-30 | 2007-10-18 | Hoya Corp | Mask blank and photomask |
| JP2007271774A (en) * | 2006-03-30 | 2007-10-18 | Hoya Corp | Mask blank and photomask |
| JP2008116933A (en) * | 2006-10-12 | 2008-05-22 | Hoya Corp | Method for manufacturing photomask |
| KR101382952B1 (en) * | 2006-10-12 | 2014-04-08 | 호야 가부시키가이샤 | Method for manufacturing photomask |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56158875A (en) * | 1980-04-17 | 1981-12-07 | Rexall Drug Chemical | Aqueous peeling solution |
| JPS59123774A (en) * | 1982-12-27 | 1984-07-17 | Toppan Printing Co Ltd | Treatment of image forming material and treatment of metallic image |
-
1986
- 1986-10-28 JP JP61256289A patent/JPS62218585A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56158875A (en) * | 1980-04-17 | 1981-12-07 | Rexall Drug Chemical | Aqueous peeling solution |
| JPS59123774A (en) * | 1982-12-27 | 1984-07-17 | Toppan Printing Co Ltd | Treatment of image forming material and treatment of metallic image |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1383161A1 (en) * | 2002-07-15 | 2004-01-21 | Texas Instruments Incorporated | Method of etching a silicate gate dielectric using a HF-containing solution |
| JP2005181423A (en) * | 2003-12-16 | 2005-07-07 | Hoya Corp | Method for reproducing glass substrate for mask blanks, method for manufacturing mask blanks, and method for manufacturing transfer mask |
| JP4497909B2 (en) * | 2003-12-16 | 2010-07-07 | Ｈｏｙａ株式会社 | Method for regenerating glass substrate for mask blank, method for manufacturing mask blank, and method for manufacturing transfer mask |
| JP2007256922A (en) * | 2006-02-22 | 2007-10-04 | Hoya Corp | Pattern forming method, method of manufacturing gray tone mask, and pattern transfer method |
| JP2007271720A (en) * | 2006-03-30 | 2007-10-18 | Hoya Corp | Mask blank and photomask |
| JP2007271775A (en) * | 2006-03-30 | 2007-10-18 | Hoya Corp | Mask blank and photomask |
| JP2007271774A (en) * | 2006-03-30 | 2007-10-18 | Hoya Corp | Mask blank and photomask |
| JP2008116933A (en) * | 2006-10-12 | 2008-05-22 | Hoya Corp | Method for manufacturing photomask |
| KR101382952B1 (en) * | 2006-10-12 | 2014-04-08 | 호야 가부시키가이샤 | Method for manufacturing photomask |
| 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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