JPH0439660A - Substrate for photomask material, photomask material, and manufacture of them - Google Patents
Substrate for photomask material, photomask material, and manufacture of themInfo
- Publication number
- JPH0439660A JPH0439660A JP2147124A JP14712490A JPH0439660A JP H0439660 A JPH0439660 A JP H0439660A JP 2147124 A JP2147124 A JP 2147124A JP 14712490 A JP14712490 A JP 14712490A JP H0439660 A JPH0439660 A JP H0439660A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- film
- photomask material
- photomask
- transparent 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.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000002834 transmittance Methods 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical group [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 claims description 24
- 229910021344 molybdenum silicide Inorganic materials 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052804 chromium Inorganic materials 0.000 abstract description 15
- 239000011651 chromium Substances 0.000 abstract description 15
- 230000007547 defect Effects 0.000 abstract description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000423 chromium oxide Inorganic materials 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- 238000005530 etching Methods 0.000 abstract description 6
- 238000010030 laminating Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910016006 MoSi Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は半導体素子、ＩＣ，ＬＳＩ等のパターン形成用
に用いられるフォトマスクを作製するためのフォトマス
ク材用基板、フォトマスク材及びそれらの製造法に関す
る。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to substrates for photomask materials, photomask materials, and their Regarding manufacturing methods.
Ｃ従来の技術及びその問題点］
半導体素子、ＩＣ，ＬＳＩ等のパターン形成用に用いら
れるフォトマスクを作製するためのフォトマスク材とし
ては種々のものが使用されているが。C. Prior Art and Problems Thereof] Various photomask materials are used for producing photomasks used for pattern formation of semiconductor elements, ICs, LSIs, etc.
一般には石英ガラスなどの透明基板の上に遮光膜として
のクロム膜を積層したもの、さらにその上に反射防止膜
としての酸化クロム膜を積層したものが多用されている
。後者の構成を模式的に第１図に示す。同図において、
（２Ｉ）は透明基板、Ｃ２３）は遮光膜及び（２４）は
反射防止膜である。 し かし、このようなフォトマス
ク材（２６）を用いてパターン形成のためのフォトマス
クを作製すると、その作製中や、フォトマスクの使用中
に静電気に起因する種々の欠陥が発生する。すなわち、
フォトマスク作製中において現像後、純水で洗浄する際
に白系欠陥が生じたり、フォトマスクのマスターマスク
からコンタクト露光によってワーキングマスクをコピー
する際、マスターマスクが帯電するためにパターンが損
傷したり、あるいは又、マスターマスクを洗浄する際に
純水によって帯電するためにパターンが損傷したりする
のである。 このような問題は第１２図に示すように、
透明基板（２１）と遮光膜（２３）との間に透明導電膜
（２２）を設けて透明基板（２１）に蓄積される静電気
を逃がすことによって解消された。透明導電１１ｉｉ
（２２）としては−般に酸化インジウムや酸化錫が用い
られている。Generally, a structure in which a chromium film is laminated as a light shielding film on a transparent substrate such as quartz glass, and a chromium oxide film as an antireflection film is further laminated thereon is often used. The latter configuration is schematically shown in FIG. In the same figure,
(2I) is a transparent substrate, C23) is a light shielding film, and (24) is an antireflection film. However, when a photomask for pattern formation is produced using such a photomask material (26), various defects due to static electricity occur during its production or during use of the photomask. That is,
During photomask manufacturing, white defects may occur when cleaning with pure water after development, and when copying a working mask from the master mask of a photomask by contact exposure, the pattern may be damaged due to the master mask being charged. Alternatively, when cleaning the master mask, the pattern may be damaged due to charging caused by pure water. As shown in Figure 12, such a problem can be solved by
This problem was solved by providing a transparent conductive film (22) between the transparent substrate (21) and the light shielding film (23) to release static electricity accumulated on the transparent substrate (21). transparent conductive 11ii
As (22), indium oxide or tin oxide is generally used.
このような構成のフォトマスク材を＋２６’ｌで示す。A photomask material having such a configuration is indicated by +26'l.
しかしながら、従来、透明導電膜（２２）として用いら
れていた酸化インジウムや酸化錫は、フォトマスク材（
２６’）の遮光膜（２３）として用いられているクロム
膜との付着力が弱いため、フォトマスクを作製するため
にエツチングする際、透明導電膜（２２）の表面の極微
細な傷に沿ってクロム用エツチング液が透明導電膜（２
２）とクロム膜（２３）との間にしみ込み、パターンの
欠陥が発生するという問題があった。However, indium oxide and tin oxide, which have been conventionally used as the transparent conductive film (22), cannot be used as a photomask material (
26') has weak adhesion to the chromium film used as the light-shielding film (23), so when etching it to make a photomask, it is etched along the very fine scratches on the surface of the transparent conductive film (22). The etching solution for chromium is applied to the transparent conductive film (2
2) and the chromium film (23), causing pattern defects.
又、フォトマスクを作製した後に、高圧ガス洗浄やブラ
シ洗浄などのような物理的な力が加わる方法で洗浄する
と、パターンが欠落し易い。Furthermore, if the photomask is cleaned by a method that applies physical force, such as high-pressure gas cleaning or brush cleaning, after the photomask is manufactured, the pattern is likely to be lost.
さらに、酸化インジウムは耐酸性が低いのでフォトマス
クの洗浄に不可欠な強酸にたえることができず、溶解し
てしまう。これはフォトマスクとして用いる場合、重大
な欠陥となり、実用に適するものではなかった。Furthermore, since indium oxide has low acid resistance, it cannot withstand the strong acid that is essential for cleaning photomasks and dissolves. This was a serious defect when used as a photomask, and was not suitable for practical use.
本発明は以上のような問題に鑑みてなされ、帯電するこ
とのない、しかもパターン欠陥が発生しにくいフォトマ
スクを作製するためのフォトマスク材用基板、フォトマ
スク材及びそれらの製造法を提供することを目的として
いる。The present invention was made in view of the above-mentioned problems, and provides a substrate for a photomask material, a photomask material, and a manufacturing method thereof for producing a photomask that is not electrically charged and is less likely to cause pattern defects. The purpose is to
［問題点を解決するための手段］
上記目的は、透明基板の上に透明導電膜を積層したフォ
トマスク材用基板において、前記透明導電膜がモリブデ
ンシリサイド酸化窒化物であることを特徴とするフォト
マスク材用基板、及び、真空槽内に透明基板を保持し、
該透明基板に対向してモリブデンとシリコンとを主成分
とする合金をターゲットとして設け、アルゴン、酸素及
び窒素の混合ガス雰囲気中で直流マグネトロンスバッタ
リングによって前記合金をスパッタすることによって、
前記透明基板上にモリブデンシリサイド酸化窒化物の膜
を形成することを特徴とするフォトマスク材用基板の製
造法、及び、透明基板の上に透明導電膜を積層したフォ
トマスク材用基板の前記透明導電膜の上に遮光膜を積層
したフォトマスク材において、前記透明導電膜がモリブ
デンシリサイド酸化窒化物であることを特徴とするフォ
トマスク材、及び、真空槽内に透明基板を保持し、該透
明基板に対向してモリブデンとシリコンとを主成分とす
る合金をターゲットとして設け、アルゴン、酸素及び窒
素の混合ガス雰囲気中で直流マグネトロンスパッタリン
グによって前記合金をスパッタすることによって、前記
透明基板上にモリブデンシリサイド酸化窒化物の膜を形
成し、その上に遮光膜を積層することを特徴とするフォ
トマスク材の製造法、によって達成される。[Means for Solving the Problems] The above object is to provide a photomask material substrate in which a transparent conductive film is laminated on a transparent substrate, wherein the transparent conductive film is molybdenum silicide oxynitride. Holding a mask material substrate and a transparent substrate in a vacuum chamber,
An alloy mainly composed of molybdenum and silicon is provided as a target opposite to the transparent substrate, and the alloy is sputtered by direct current magnetron sputtering in a mixed gas atmosphere of argon, oxygen, and nitrogen.
A method for manufacturing a substrate for a photomask material, characterized in that a film of molybdenum silicide oxynitride is formed on the transparent substrate; A photomask material in which a light-shielding film is laminated on a conductive film, wherein the transparent conductive film is molybdenum silicide oxynitride, and a transparent substrate is held in a vacuum chamber; An alloy mainly composed of molybdenum and silicon is provided as a target opposite to the substrate, and the alloy is sputtered by direct current magnetron sputtering in a mixed gas atmosphere of argon, oxygen, and nitrogen to form molybdenum silicide on the transparent substrate. This is achieved by a method for manufacturing a photomask material, which is characterized by forming an oxynitride film and laminating a light-shielding film thereon.
［作 用］
クロムとの密着性が良く、耐酸性も優れているモリブデ
ンシリサイド膜は比抵抗が８０〜１００μΩ・ｃｌＩで
あって導電性は良いが、遮光性の強い膜である。すなわ
ち、Ｈｇ−ｇ線（波長４３６ｎ■）においてその光学定
数はｎ−１ｋ＝４．７５−２．５９ｉであり、吸収率は
α；０．０７４６５／ｎ閣である。[Function] A molybdenum silicide film, which has good adhesion to chromium and excellent acid resistance, has a specific resistance of 80 to 100 μΩ·clI and has good conductivity, but is a film with strong light-shielding properties. That is, in the Hg-g line (wavelength: 436n), its optical constant is n-1k=4.75-2.59i, and its absorption rate is α; 0.07465/n.
ん
ところがこのモリブデンシリサイドが酸素及び窒素と反
応することによって消衰係数ｋが２．５９から１．７２
程度に下がり、遮光性が弱くなる。従って、モリブデン
シリサイド酸化窒化物を透明基板の上に積層したフォト
マスク材用基板の４３６ｎ■における透過率は７５％以
上を確保することができる。However, due to the reaction of this molybdenum silicide with oxygen and nitrogen, the extinction coefficient k changes from 2.59 to 1.72.
The light-shielding properties become weaker. Therefore, the transmittance at 436n of a photomask material substrate in which molybdenum silicide oxynitride is laminated on a transparent substrate can be ensured to be 75% or more.
一方、モリブデンシリサイド酸化窒化物の比抵抗は １
０’μΩ、ｃｍ程度に増え、導電性が落ちるが、膜厚を
５０人程度とすることにより、膜のシート抵抗は２０ｋ
Ω／□以下におさえることができる。On the other hand, the specific resistance of molybdenum silicide oxynitride is 1
The sheet resistance of the membrane increases to about 0'μΩ, cm, and the conductivity decreases, but by setting the film thickness to about 50cm, the sheet resistance of the membrane becomes 20k.
It can be kept below Ω/□.
その上、モリブデンシリサイド酸化窒化物は遮光膜とし
て用いられるクロムとの密着性も良く、また耐酸性にも
優れる。Furthermore, molybdenum silicide oxynitride has good adhesion to chromium used as a light-shielding film, and also has excellent acid resistance.
従って、本発明のように構成されるフォトマスク材用基
板、フォトマスク材及びそれらの製造法によって、帯電
することがない上にパターン欠陥が発生しにくいフォト
マスクを作製することができ、それによって、半導体製
造時に精度の高いパターンを形成することができる。Therefore, by using the substrate for photomask material, the photomask material, and the manufacturing method thereof configured as in the present invention, it is possible to produce a photomask that is not electrically charged and is less likely to cause pattern defects. , it is possible to form highly accurate patterns during semiconductor manufacturing.
［実 施 例］ 次に、実施例について図面を参照して説明する。[Example] Next, examples will be described with reference to the drawings.
第１図に本発明の各実施例に用いた直流マグネトロンス
パッタ装置の概略断面図を示す。同図において真空槽（
６）の内部にターゲット（７）とマグネット（８）とか
らなるマグネトロンカソード（９）を設け、ターゲット
（７）と対向してアノード（ｌＯ）の上に透明基板（１
１）を設けた。（１２）は排気管、（１３）はガス導入
管である。FIG. 1 shows a schematic cross-sectional view of a DC magnetron sputtering apparatus used in each embodiment of the present invention. In the figure, the vacuum chamber (
A magnetron cathode (9) consisting of a target (7) and a magnet (8) is provided inside the substrate (6), and a transparent substrate (1
1) was established. (12) is an exhaust pipe, and (13) is a gas introduction pipe.
第１実施例においては透明基板（１１）として５ｉｎ。In the first embodiment, the transparent substrate (11) is 5 inches.
平方、厚さ２．３ｍｍの石英ガラスを用い、ターゲット
（７）としてモリブデンとシリコンとの合金を用いた。A square piece of quartz glass with a thickness of 2.3 mm was used, and an alloy of molybdenum and silicon was used as the target (7).
モリブデンとシリコンの組成比はｌ：２である。透明基
板（１１）とターゲット（７）との間の距離を６０１１
Ｉ１１とし、透明基板（１１１を１００℃に保持した。The composition ratio of molybdenum and silicon is 1:2. The distance between the transparent substrate (11) and the target (7) is 6011
I11, and a transparent substrate (111) was maintained at 100°C.
このような状態で排気管（１２）から排気しながら、ガ
ス導入管（１３）からスパッタガスとしてのアルゴン（
Ａｒ） （６０％）と反応ガスとしての酸素（０鵞）（
１０％）及び窒素（Ｎ、） （３ｏ％）との混合ガスを
導入して、真空槽（６）内部の圧力を３．ＯＸ １０−
”Ｔｏｏｒに保持し、両極間に直流電圧をかけた。電力
は０．５ＫＷとした。透明基板（１１）である石英ガラ
スの上に透明導電膜（１４）であるモリブデンシリサイ
ド酸化窒化膜（ＭｏＳｉ、ＯＮ）が５０人の厚さに形成
されるまで続け、フォトマスク材用基板とした。In this state, while exhausting air from the exhaust pipe (12), argon (as sputtering gas) is introduced from the gas introduction pipe (13).
Ar) (60%) and oxygen (0%) (
A mixed gas of 10%) and nitrogen (N, ) (3o%) was introduced to reduce the pressure inside the vacuum chamber (6) to 3. OX 10-
A DC voltage was applied between the two electrodes.The electric power was 0.5KW.A transparent conductive film (14) of molybdenum silicide oxynitride film (MoSi , ON) was formed to a thickness of 50 mm, which was used as a substrate for a photomask material.
得られたフォトマスク材用基板（１５）の概略断面図を
第２図に示す。同図において（１）は石英ガラス、（２
）はモリブデンシリサイド酸化窒化膜である。このフォ
トマスク材用基板（１５）の透過率はＨｇ−ｇ線（波長
４３６ｎｍ）において７６％であった。この分光透過率
を測定した結果を第１０図に示す。又、モリブデンシリ
サイド酸化窒化膜（２）は５０人の厚さであり、シート
抵抗は２０にΩ／□であった。A schematic cross-sectional view of the obtained photomask material substrate (15) is shown in FIG. In the figure, (1) is quartz glass, (2
) is a molybdenum silicide oxynitride film. The transmittance of this photomask material substrate (15) was 76% in the Hg-g line (wavelength 436 nm). The results of measuring this spectral transmittance are shown in FIG. The molybdenum silicide oxynitride film (2) had a thickness of 50 Ω/□ and a sheet resistance of 20 Ω/□.
これらの値は、透明導電膜として従来の酸化インジウム
や酸化錫を用いた時と同等の効果があることを示すもの
であり、帯電防止用透明導電膜としての性能は十分であ
る。These values indicate that the transparent conductive film has the same effect as conventional indium oxide or tin oxide, and the performance as an antistatic transparent conductive film is sufficient.
次いで、上記の得られたフォトマスク材用基板（１５）
を１２０℃の硫酸中で６０分間加熱処理する熱硫酸耐酸
テストを行なったが、透過率、シート抵抗、層間の密着
等に問題となるような変化は見られなかった。Next, the obtained photomask material substrate (15)
A hot sulfuric acid acid resistance test was conducted in which the film was heat-treated in sulfuric acid at 120°C for 60 minutes, but no problematic changes were observed in transmittance, sheet resistance, interlayer adhesion, etc.
次に第２実施例について述べる。先ず、上記の第１実施
例と同じ方法、条件で、石英ガラス（１）の上にモリブ
デンシリサイド酸化窒化膜（２）を形成したフォトマス
ク材用基板（１５）を得た。第３図に示すように、その
上に遮光膜であるクロム膜（３）及び反射防止膜である
酸化クロム膜（４）をそれぞれ７５０人及び３００人の
膜厚で積層して、フォトマスク材（１６）を得た。Next, a second embodiment will be described. First, a photomask material substrate (15) in which a molybdenum silicide oxynitride film (2) was formed on a quartz glass (1) was obtained using the same method and conditions as in the first example. As shown in Fig. 3, a chromium film (3) as a light-shielding film and a chromium oxide film (4) as an anti-reflection film are laminated thereon to a thickness of 750 and 300, respectively, to form a photomask material. (16) was obtained.
このフォトマスク材（１６）の上に、第４図に示すよう
にフォトレジストを塗布してフォトレジス１−膜（５）
を形成した。次いで、露光装置によってフォトレジスト
膜（５）にパターンを作製した後、第５図に示すように
現像してフォトレジスト＠（５）の所望部分を溶解除去
した。ついで第６図に示すように酸化クロム膜（４）及
びクロム膜（３）のエツチングを行なった後、第７図に
示すようにフォトレジスト膜（５）を剥離してフォトマ
スク（１７）を作製した。On this photomask material (16), a photoresist is applied as shown in FIG. 4 to form a photoresist 1-film (5).
was formed. Next, a pattern was formed on the photoresist film (5) using an exposure device, and then developed as shown in FIG. 5 to dissolve and remove a desired portion of the photoresist (5). Next, as shown in FIG. 6, after etching the chromium oxide film (4) and the chromium film (3), as shown in FIG. 7, the photoresist film (5) is peeled off and a photomask (17) is formed. Created.
以上のようにして得られたフォトマスク（１７）を用い
て９０℃の熱硫酸中で５分間加熱処理した後、ナイロン
スポンジで５０回摩擦するスクラブ洗浄を３回繰返した
後に、光学顕微鏡及びパターンチエッカ−で検査したと
ころ、このフォトマスク（１７）にはエツチング液の染
み込みによるパターン不良やスクラブ洗浄によるパター
ン欠落等の欠陥は見られなかった。The photomask (17) obtained as described above was heat-treated in hot sulfuric acid at 90°C for 5 minutes, and then scrubbed with a nylon sponge 50 times and washed 3 times. When inspected with a checker, this photomask (17) was found to have no defects such as poor patterns due to penetration of etching solution or missing patterns due to scrub cleaning.
以上、本発明の各実施例について説明したが、勿論、本
発明はこれらに限定されることなく、本発明の技術的思
想に基き種々の変形が可能である。Although each embodiment of the present invention has been described above, the present invention is of course not limited to these, and various modifications can be made based on the technical idea of the present invention.
例えば、各実施例ではモリブデンシリサイド酸化窒化膜
（２）を形成する際に、混合ガスとしてＡｒ（６０％）
＋０２（１０％） ＋ Ｎ、 （３０％）の比率のもの
を用いたが、Ａｒ （６０％）十〇□（０〜４０％）
＋ Ｎｚ （４０〜０％）の範囲でも透明導電膜として
の性能を持つ膜が得られる。For example, in each example, when forming the molybdenum silicide oxynitride film (2), Ar (60%) was used as the mixed gas.
+02 (10%) + N, (30%) ratio was used, but Ar (60%) 〇□ (0 to 40%)
+Nz (40% to 0%), a film having performance as a transparent conductive film can be obtained.
又、上記モリブデンシリサイド酸化窒化膜（２）を形成
するために、各実施例では直流マグネトロンスパッタリ
ング法を用いたが、他の真空蒸着法、イオンブレーティ
ング法又は高周波スパッタリング法によっても良い。In addition, in order to form the molybdenum silicide oxynitride film (2), in each embodiment, a DC magnetron sputtering method was used, but other vacuum evaporation methods, ion blasting methods, or high frequency sputtering methods may be used.
又、第２実施例ではフォトマスク材用基板（１５）のモ
リブデンシリサイド酸化窒化膜（２）の上にクロム膜（
３）及び酸化クロム膜（４）を積層したフォトマスク材
（１６）を作製したが、第８図に示すような単層のクロ
ム膜（３）だけを積層したフォトマスク（１６’）でも
良く、あるいは第９図に示すように酸化クロム膜（４）
、クロム膜（３）、さらに酸化クロム膜（４）の三層を
積層したフォトマスク材（１６”）でも良い。この三層
積層の場合、クロム膜（３）を６００人、酸化クロム膜
（４）をそれぞれ３００人の厚さにして良好な結果を得
た。モリブデンシリサイド酸化窒化膜（２）は酸化クロ
ム膜（４）との密着性も十分に大きい。In addition, in the second embodiment, a chromium film (
Although a photomask material (16) was prepared in which 3) and a chromium oxide film (4) were laminated, a photomask material (16') in which only a single layer of chromium film (3) was laminated as shown in Fig. 8 may also be used. , or a chromium oxide film (4) as shown in Figure 9.
It is also possible to use a photomask material (16") in which three layers are stacked: , chromium film (3), and chromium oxide film (4). In the case of this three-layer stack, 600 layers of chromium film (3) and chromium oxide film (4) may be used. Good results were obtained by using 4) to a thickness of 300 mm each.The molybdenum silicide oxynitride film (2) also has sufficient adhesion to the chromium oxide film (4).
又、各実施例では透明基板（１１として石英ガラスを使
用したが、代わりに青板ガラスや市販の低膨張ガラスを
使用しても良い。Further, in each embodiment, quartz glass was used as the transparent substrate (11), but blue plate glass or commercially available low expansion glass may be used instead.
又、本発明にかかるフォトマスク材用基板（１５）は、
フォトマスク材用としてだけでなく、液晶表示装置のた
めの透明導電性基板としても使用し得る。Further, the photomask material substrate (15) according to the present invention includes:
It can be used not only as a photomask material but also as a transparent conductive substrate for liquid crystal display devices.
［発明の効果］
本発明は以上のような構成であるので、以下のような効
果を有する。[Effects of the Invention] Since the present invention has the above configuration, it has the following effects.
すなわち、モリブデンシリサイド酸化窒化物の膜はシー
ト抵抗、光（４３６ｎｍ）の透過率等の特性が透明導電
膜の性能として十分なだけでなく、遮光膜として用いら
れるクロム膜や反射防止膜としての酸化クロム膜との密
着性が大きいのでエツチンダ液のしみ込みがなく、パタ
ーンの欠陥が発生しにくい。又、耐酸性に優れるので、
強酸による洗浄にも十分耐えることができる。In other words, the molybdenum silicide oxynitride film not only has properties such as sheet resistance and light (436 nm) transmittance that are sufficient as a transparent conductive film, but also has sufficient properties as a chromium film used as a light-shielding film and an oxidized film used as an antireflection film. Because it has great adhesion to the chromium film, there is no seepage of the etching agent, and pattern defects are less likely to occur. In addition, it has excellent acid resistance, so
It can also withstand cleaning with strong acids.
従って、本発明のように構成されているフォトマスク材
用基板及びフォトマスク材によって、帯電することがな
い上にパターン欠陥が発生しにくいフォトマスクを作製
することができ、それによって半導体製造時に精度の高
いパターンを形成することができる。Therefore, by using the substrate for photomask material and the photomask material configured as in the present invention, it is possible to produce a photomask that is not electrically charged and is less likely to cause pattern defects, thereby improving precision during semiconductor manufacturing. It is possible to form a high pattern.
又、本発明にかかるフォトマスク材用基板及びフォトマ
スク材の製造法によって、それらの量産が容易になる。Furthermore, the method for manufacturing a photomask material substrate and photomask material according to the present invention facilitates their mass production.
第１図は本発明にかかる各実施例のフォトマスク材用基
板及びフォトマスク材を製造するのに用いられた直流マ
グネトロンスパッタ装置の概略断面図、第２図は第１実
施例で得られた本発明にかかるフォトマスク材用基板の
概略断面図、第３図は第２実施例で得られた本発明にか
かるフォトマスク材の概略断面図、第４図は前記フォト
マスク材の上にフォトレジスト膜を形成した状態を示す
概略断面図、第５図は露光後に前記フォトレジスト膜を
現像した状態を示す概略断面図、第６図は更にエツチン
グした状態を示す概略断面図、第７図はフォトレジスト
膜を除去して得られたフォトマスクの概略断面図、第８
図は本発明にかかるフォトマスク材の変形例の概略断面
図、第９図は本発明にかかるフォトマスク材の他の変形
例の概略断面図、第１０図は第１実施例で得られたフォ
トマスク材用基板の分光透過率を測定した結果を示すグ
ラフ、第１１図は従来例のフォトマスク材の概略断面図
及び第１２図は他の従来例のフォトマスク材の概略断面
図である。
なお、図において
（１）・・・・・・・・・・・・・・石英ガラス（２）
・・・・・・・・・・・・・・ モリブデンシリサイド
酸化窒化膜
（３） ・・・・・・・・・・・・・・ り
ロ ム 膜（４）・・・・−・・・・・・・・
・ 酸化クロム膜（７） ・・・・−・・・・・・・・
・ タ − ゲ ッ ト８） ・・・・・
・・・・・・・・・
１１）・・・・・・・・・・・・・・
１４）・・・・・・・・・・・・・・
１５）・・・・・・・・・・・・・・
１６１ （１６°）（１６”）・・・・マグネット
透 明 基 板
透明導電膜
フォトマスク材用基板
フォトマスク材
第１図
代
飯
理
阪
人
泰
雄
７・・・・・・・・・ターゲット
１４・・・・・・・・・透明導電膜
１５・・・・・・・・・フォトマスク材用基板第６図
第７
図
第８
図
第９図
第１０図
波
長
（ｎｍ）FIG. 1 is a schematic cross-sectional view of the photomask material substrate of each embodiment of the present invention and a DC magnetron sputtering apparatus used to manufacture the photomask material, and FIG. FIG. 3 is a schematic cross-sectional view of a substrate for photomask material according to the present invention, FIG. 3 is a schematic cross-sectional view of the photomask material according to the present invention obtained in the second example, and FIG. FIG. 5 is a schematic cross-sectional view showing the state in which the photoresist film is developed after exposure, FIG. 6 is a schematic cross-sectional view showing the state in which the photoresist film is further etched, and FIG. Schematic cross-sectional view of the photomask obtained by removing the photoresist film, No. 8
The figure is a schematic cross-sectional view of a modified example of the photomask material according to the present invention, FIG. 9 is a schematic cross-sectional view of another modified example of the photomask material according to the present invention, and FIG. 10 is a schematic cross-sectional view of a modified example of the photomask material according to the present invention. A graph showing the results of measuring the spectral transmittance of a substrate for photomask material, FIG. 11 is a schematic cross-sectional view of a conventional photomask material, and FIG. 12 is a schematic cross-sectional view of another conventional photomask material. . In addition, in the figure (1)...................................................................quartz glass (2)
・・・・・・・・・・・・・・・ Molybdenum silicide oxynitride film (3) ・・・・・・・・・・・・・・・
Rom film (4)・・・・・・・・・・・・・・・
・Chromium oxide film (7) ・・・・・・・・・・・・・・・・・
・Target 8)
・・・・・・・・・ 11)・・・・・・・・・・・・・・・ 14)・・・・・・・・・・・・ 15)・・・・・・・・・...... 161 (16°) (16")... Magnet transparent substrate Transparent conductive film Substrate for photomask material Photomask material Figure 1 Yasuo Iiri Hanto 7... ...Target 14...Transparent conductive film 15...Substrate for photomask material Fig. 6 Fig. 7 Fig. 8 Fig. 9 Fig. 10 Wavelength (nm)
Claims (12)
スク材用基板において、前記透明導電膜がモリブデンシ
リサイド酸化窒化物であることを特徴とするフォトマス
ク材用基板。(1) A photomask material substrate comprising a transparent conductive film laminated on a transparent substrate, wherein the transparent conductive film is molybdenum silicide oxynitride.
に記載のフォトマスク材用基板。(2) Claim (1) wherein the transparent substrate is made of quartz glass.
A substrate for photomask material as described in .
長の光の透過率が７５％以上である請求項（１）又は（
２）に記載のフォトマスク材用基板。(3) Claim (1) or (3) wherein the photomask material substrate has a transmittance of 75% or more for light with a wavelength of 436 nm.
2) The substrate for photomask material according to item 2).
抵抗が２０ｋΩ／□以下である請求項（１）、（２）及
び（３）のいずれかに記載のフォトマスク材用基板。(4) The substrate for a photomask material according to any one of claims (1), (2), and (3), wherein the molybdenum silicide oxynitride has a sheet resistance of 20 kΩ/□ or less.
向してモリブデンとシリコンとを主成分とする合金をタ
ーゲットとして設け、アルゴン、酸素及び窒素の混合ガ
ス雰囲気中で直流マグネトロンスパッタリングによって
前記合金をスパッタすることによって、前記透明基板上
にモリブデンシリサイド酸化窒化物の膜を形成すること
を特徴とするフォトマスク材用基板の製造法。(5) A transparent substrate is held in a vacuum chamber, an alloy mainly composed of molybdenum and silicon is provided as a target opposite to the transparent substrate, and sputtering is performed by direct current magnetron sputtering in a mixed gas atmosphere of argon, oxygen, and nitrogen. A method for manufacturing a substrate for a photomask material, characterized in that a film of molybdenum silicide oxynitride is formed on the transparent substrate by sputtering the alloy.
：０〜４０％、窒素：４０〜０％である請求項（５）に
記載のフォトマスク材用基板の製造法。(6) The method for manufacturing a substrate for a photomask material according to (5), wherein the proportions of the mixed gas are argon: 60%, oxygen: 0 to 40%, and nitrogen: 40 to 0%.
スク材用基板の前記透明導電膜の上に遮光膜を積層した
フォトマスク材において、前記透明導電膜がモリブデン
シリサイド酸化窒化物であることを特徴とするフォトマ
スク材。(7) In a photomask material in which a light-shielding film is laminated on the transparent conductive film of a photomask material substrate in which a transparent conductive film is laminated on a transparent substrate, the transparent conductive film is molybdenum silicide oxynitride. A photomask material featuring:
に記載のフォトマスク材。(8) Claim (7) wherein the transparent substrate is made of quartz glass.
Photomask material described in .
長の透過率が７５％以上である請求項（７）又は（８）
に記載のフォトマスク材。(9) Claim (7) or (8), wherein the photomask material substrate has a transmittance of 75% or more at a wavelength of 436 nm.
Photomask material described in .
ト抵抗が２０Ω／□以下である請求項（７）、（８）、
及び（９）のいずれかに記載のフォトマスク材。(10) Claims (7), (8), wherein the sheet resistance of the molybdenum silicide oxynitride is 20Ω/□ or less,
and the photomask material according to any one of (9).
対向してモリブデンとシリコンとを主成分とする合金を
ターゲットとして設け、アルゴン、酸素及び窒素の混合
ガス雰囲気中で直流マグネトロンスパッタリングによっ
て前記合金をスパッタすることによって、前記透明基板
上にモリブデンシリサイド酸化窒化物の膜を形成し、そ
の上に遮光膜を積層することを特徴とするフォトマスク
材の製造法。(11) A transparent substrate is held in a vacuum chamber, an alloy mainly composed of molybdenum and silicon is provided as a target opposite to the transparent substrate, and sputtering is performed by direct current magnetron sputtering in a mixed gas atmosphere of argon, oxygen, and nitrogen. A method for producing a photomask material, characterized in that a film of molybdenum silicide oxynitride is formed on the transparent substrate by sputtering the alloy, and a light shielding film is laminated thereon.
素：０〜４０％、窒素：４０〜０％である請求項（１１
）に記載のフォトマスク材の製造法。(12) Claim (11) wherein the ratio of the mixed gas is argon: 60%, oxygen: 0-40%, nitrogen: 40-0%.
) The method for producing a photomask material described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14712490A JP2984030B2 (en) | 1990-06-05 | 1990-06-05 | Substrate for photomask material, photomask material, and method for producing them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14712490A JP2984030B2 (en) | 1990-06-05 | 1990-06-05 | Substrate for photomask material, photomask material, and method for producing them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0439660A true JPH0439660A (en) | 1992-02-10 |
| JP2984030B2 JP2984030B2 (en) | 1999-11-29 |
Family
ID=15423088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14712490A Expired - Lifetime JP2984030B2 (en) | 1990-06-05 | 1990-06-05 | Substrate for photomask material, photomask material, and method for producing them |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2984030B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180291B1 (en) * | 1999-01-22 | 2001-01-30 | International Business Machines Corporation | Static resistant reticle |
| JP2006267595A (en) * | 2005-03-24 | 2006-10-05 | Toshiba Corp | Mask blank and its manufacturing method and using method, and mask and its manufacturing method and using method |
| WO2009136564A1 (en) * | 2008-05-09 | 2009-11-12 | Hoya株式会社 | Reflective mask, reflective mask blank and method for manufacturing reflective mask |
| JP2010186159A (en) * | 2009-01-14 | 2010-08-26 | Seiko Epson Corp | Optical article and manufacturing method of the same |
| JP2015114356A (en) * | 2013-12-09 | 2015-06-22 | Hoya株式会社 | Manufacturing method of substrate having functional film, manufacturing method of substrate having multilayer film, manufacturing method of mask blank, and manufacturing method of mask for transfer |
-
1990
- 1990-06-05 JP JP14712490A patent/JP2984030B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180291B1 (en) * | 1999-01-22 | 2001-01-30 | International Business Machines Corporation | Static resistant reticle |
| JP2006267595A (en) * | 2005-03-24 | 2006-10-05 | Toshiba Corp | Mask blank and its manufacturing method and using method, and mask and its manufacturing method and using method |
| WO2009136564A1 (en) * | 2008-05-09 | 2009-11-12 | Hoya株式会社 | Reflective mask, reflective mask blank and method for manufacturing reflective mask |
| JPWO2009136564A1 (en) * | 2008-05-09 | 2011-09-08 | Hoya株式会社 | Reflective mask, reflective mask blank and manufacturing method thereof |
| US8372564B2 (en) | 2008-05-09 | 2013-02-12 | Hoya Corporation | Reflective mask, reflective mask blank and method of manufacturing reflective mask |
| JP5711533B2 (en) * | 2008-05-09 | 2015-05-07 | Hoya株式会社 | Reflective mask, reflective mask blank and manufacturing method thereof |
| JP2015128183A (en) * | 2008-05-09 | 2015-07-09 | Hoya株式会社 | Reflective mask, reflective mask blank, and method for manufacturing the same |
| JP2010186159A (en) * | 2009-01-14 | 2010-08-26 | Seiko Epson Corp | Optical article and manufacturing method of the same |
| JP2015114356A (en) * | 2013-12-09 | 2015-06-22 | Hoya株式会社 | Manufacturing method of substrate having functional film, manufacturing method of substrate having multilayer film, manufacturing method of mask blank, and manufacturing method of mask for transfer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2984030B2 (en) | 1999-11-29 |
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