JPS6322299B2 - - Google Patents
Info
- Publication number
- JPS6322299B2 JPS6322299B2 JP2872281A JP2872281A JPS6322299B2 JP S6322299 B2 JPS6322299 B2 JP S6322299B2 JP 2872281 A JP2872281 A JP 2872281A JP 2872281 A JP2872281 A JP 2872281A JP S6322299 B2 JPS6322299 B2 JP S6322299B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- etching
- photomask
- light
- blank plate
- 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.)
- Expired
Links
- 239000010409 thin film Substances 0.000 claims description 62
- 239000000126 substance Substances 0.000 claims description 19
- 239000010408 film Substances 0.000 claims description 18
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 229910052715 tantalum Inorganic materials 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910020203 CeO Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000005530 etching Methods 0.000 description 36
- 239000011651 chromium Substances 0.000 description 20
- 238000010894 electron beam technology Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 230000007547 defect Effects 0.000 description 17
- 230000005611 electricity Effects 0.000 description 17
- 230000003068 static effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 12
- 238000007738 vacuum evaporation Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000001312 dry etching Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000019988 mead Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000007740 vapor 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
- G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
- G03F1/40—Electrostatic discharge [ESD] related features, e.g. antistatic coatings or a conductive metal layer around the periphery of the mask substrate
Description
【発明の詳細な説明】
本発明はフオトマスクブランク板に係り、更に
詳しくはハードマスクと一般に呼ばれる透明性基
板表面に金属薄膜、又はそれに代る遮光性物質薄
膜を蒸着又はスパツタによつて設け、フオトエツ
チングにより前記薄膜の不要部を除去して、前記
薄膜からなるIC、LSI等用のパターンを形成して
なるフオトマスクのブランク板に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photomask blank plate, and more specifically, a metal thin film or an alternative light-shielding material thin film is provided on the surface of a transparent substrate generally called a hard mask by vapor deposition or sputtering. The present invention relates to a blank plate for a photomask in which an unnecessary portion of the thin film is removed by photoetching to form a pattern for IC, LSI, etc. made of the thin film.
フオトマスクとしては従来から銀乳剤を用いた
エマルジヨンマスクの他耐久性の優れたクロムマ
スク、低反射クロムマスク、両面低反射クロムマ
スク、酸化クロムマスク、シリコンマスク、酸化
鉄マスク等いわゆるハードマスクが用いられてい
る。さらに近年ではこれらハードマスクに画像形
成後も導電性のある導電性ハードマスクも用いら
れ始めている。この導電性マスクは静電気の帯電
−放電によるパターン欠陥の発生や静電気による
ゴミの付着の減少、又遮光膜が非導電性の場合で
も電子ビームによる露光が可能であり電子ビーム
システムにより寸法測定やマスクのレジストレー
シヨンの評価等に利用出来るという利点を有して
いる。しかしこの導電性薄膜は一般に耐薬品性が
弱いものが多くフオトマスクを通常マスク洗浄に
用いられている酸アルカリ等で何回もくり返し洗
浄されると導電性部分が破壊され導電性マスクと
しての機能を失うだけでなく、導電性薄膜の破壊
とともに遮光用薄膜までも破壊されフオトマスク
としての機能までも失つてしまうという欠点を有
している。又この導電性薄膜は一般に表面硬度が
小さく、せつかく表面硬度の大きいハードマスク
を使用しているにもかかわらず、マスク全体の強
度は導電性薄膜の表面強度によつて決まる耐久性
しか得られないことになるため特に密着焼付に使
用するフオトマスクの耐久性は小さくなつてしま
う欠点がある。 Traditionally, photomasks include emulsion masks using silver emulsion, as well as so-called hard masks such as highly durable chrome masks, low-reflection chrome masks, double-sided low-reflection chrome masks, chrome oxide masks, silicon masks, and iron oxide masks. It is being Furthermore, in recent years, conductive hard masks that remain conductive even after image formation have begun to be used. This conductive mask reduces the occurrence of pattern defects due to static electricity charging and discharging and the adhesion of dust due to static electricity, and even if the light-shielding film is non-conductive, it can be exposed with an electron beam, and the electron beam system can be used to measure dimensions and mask. It has the advantage that it can be used for evaluation of registration, etc. However, this conductive thin film generally has low chemical resistance, and if a photomask is repeatedly cleaned with acid-alkali, etc., which are normally used for mask cleaning, the conductive parts will be destroyed and the function as a conductive mask will no longer function. It has the disadvantage that not only the conductive thin film is destroyed, but also the light-shielding thin film is destroyed, thereby losing its function as a photomask. In addition, this conductive thin film generally has a low surface hardness, and even though a hard mask with a high surface hardness is used, the strength of the entire mask is only as durable as the surface strength of the conductive thin film. Therefore, there is a disadvantage that the durability of the photomask especially used for contact printing is reduced.
また導電性薄膜単体では耐薬品性の強いもので
も、この導電性薄膜と遮光用薄膜が直接接触する
ことによりその部分がある種の薬品に対して耐薬
品性を失つてしまうこともある。 Furthermore, even if the conductive thin film alone has strong chemical resistance, direct contact between the conductive thin film and the light-shielding thin film may cause that portion to lose its chemical resistance to certain chemicals.
本発明者は叙上の欠点を解消したフオトマスク
を開発すべく研究の結果、透明基板上にMo、
Ta、Nb、Ti、Cr、Ｖ、Ｗ、Zr、Au、In2O3、及
びSnO2からなる群から選択される材料よりなる
透明性を有する導電性薄膜、Al2O3、CaO、
MgO、SiO2、CeO2、及びTiO2からなる群から選
択される材料よりなる透明性を有する耐薬品性保
護膜、及びCr、Cr2O3、Si、Ta、Ta2O5、及び
Fe2O3からなる群から選択される材料よりなる遮
光性薄膜が順次積層されているブランク板を用い
れば、パターン焼付時の静電気によるシリコンウ
エーハ素子の破壊及びフオトマスクのパターン欠
陥の発生を防止するに充分な導電性を備え、又、
電子ビームシステムによる寸法測定、及びレジス
トレーシヨンの評価が可能であり、且つ使用中、
反復して強い薬品で洗浄処理することができるフ
オトマスクを製造し得るのみならず、フオトマス
クの製造をドライエツチングによつて行なうこと
が可能であることを見い出し、かかる知見にもと
づいて本発明を完成したものである。 As a result of research to develop a photomask that eliminates the above-mentioned drawbacks, the present inventor discovered that Mo,
A transparent conductive thin film made of a material selected from the group consisting of Ta, Nb, Ti, Cr, V, W, Zr, Au, In 2 O 3 and SnO 2 , Al 2 O 3 , CaO,
A transparent chemical-resistant protective film made of a material selected from the group consisting of MgO, SiO 2 , CeO 2 , and TiO 2 , and Cr, Cr 2 O 3 , Si, Ta, Ta 2 O 5 , and
By using a blank plate on which light-shielding thin films made of a material selected from the group consisting of Fe 2 O 3 are sequentially laminated, destruction of silicon wafer elements and generation of photomask pattern defects due to static electricity during pattern printing can be prevented. has sufficient conductivity, and
It is possible to measure dimensions and evaluate registration using an electron beam system, and during use,
The inventors have discovered that it is not only possible to manufacture photomasks that can be repeatedly cleaned with strong chemicals, but also that photomasks can be manufactured by dry etching, and based on this knowledge, they have completed the present invention. It is something.
即ち、本発明の要旨は透明基板上にMo、Ta、
Nb、Ti、Cr、Ｖ、Ｗ、Zr、Au、In2O3、及び
SnO2からなる群から選択される材料よりなる透
明性を有する導電性薄膜、及びAl2O3、CaO、
MgO、SiO2、CeO2及びTiO2からなる群より選択
される材料よりなる透明性を有する耐薬品性保護
膜、及びCr、Cr2O3、Si、Ta、Ta2O5、及び
Fe2O3からなる群から選択される材料よりなる遮
光性薄膜が順次積層されていることを特徴とする
フオトマスクブランク板である。 That is, the gist of the present invention is that Mo, Ta,
Nb, Ti, Cr, V, W, Zr, Au, In 2 O 3 and
A transparent conductive thin film made of a material selected from the group consisting of SnO 2 , Al 2 O 3 , CaO,
A transparent chemical-resistant protective film made of a material selected from the group consisting of MgO, SiO 2 , CeO 2 and TiO 2 , and Cr, Cr 2 O 3 , Si, Ta, Ta 2 O 5 , and
This is a photomask blank plate characterized in that light-shielding thin films made of a material selected from the group consisting of Fe 2 O 3 are sequentially laminated.
以下、本発明につき図面を参照しながら詳細に
説明する。 Hereinafter, the present invention will be explained in detail with reference to the drawings.
第１図は本発明に係るフオトマスクブランク板
５を示す。 FIG. 1 shows a photomask blank plate 5 according to the present invention.
透明基板１上に透明性を有する導電性薄膜２、
透明性を有する耐薬品性保護膜３、及び遮光性薄
膜４が順次積層されている。 a transparent conductive thin film 2 on a transparent substrate 1;
A transparent chemical-resistant protective film 3 and a light-shielding thin film 4 are sequentially laminated.
而して、本発明のフオトマスクブランク板にお
いて、透明基板としては例えばソーダライムガラ
ス、石英ガラス、サフアイヤ等の光学的に透明な
任意材料からなるものを適用でき、その厚みには
本質的な制約はないが通常0.2〜６mmのものが用
いられる。 Therefore, in the photomask blank plate of the present invention, the transparent substrate can be made of any optically transparent material such as soda lime glass, quartz glass, sapphire, etc., and there are no essential restrictions on its thickness. Although there is no such thing, 0.2 to 6 mm is usually used.
次に透明性を有する導電性薄膜としてはMo、
Ta、Nb、Ti、Cr、Ｖ、Ｗ、Zr、Au、In2O3及び
SnO2からなる群から選択される材料の一種もし
くは二種以上よりなるものを適用できる。この薄
膜としては、波長200〜600nｍの光に対して60％
以上の光透過率を有し、且つ10KΩ／以下の面
積抵抗を有するものが望ましい。 Next, as a transparent conductive thin film, Mo,
Ta, Nb, Ti, Cr, V, W, Zr, Au, In 2 O 3 and
One or more materials selected from the group consisting of SnO 2 can be used. As this thin film, 60% of light with a wavelength of 200 to 600 nm
It is desirable to have a light transmittance of 10KΩ/or less and a sheet resistance of 10KΩ/or less.
又、この薄膜の厚みは10ないし1000Åであるこ
とが好ましい。 Further, the thickness of this thin film is preferably 10 to 1000 Å.
次に透明性を有する耐薬品性保護膜としては
Al2O3、CaO、MgO、SiO2、CeO2、及びTiO2か
らなる群から選択される材料よりなるものを適用
できる。この薄膜は波長200〜600nｍの光に対し
て80％以上の光透過率を有するものが望ましい。
この薄膜は耐薬品性に富み、前記導電性薄膜を保
護し、酸、アルカリ等による洗浄処理の反復によ
る導電性薄膜の破壊を防止する機能を果す。 Next, as a transparent chemical-resistant protective film,
A material selected from the group consisting of Al 2 O 3 , CaO, MgO, SiO 2 , CeO 2 and TiO 2 can be applied. This thin film preferably has a light transmittance of 80% or more for light having a wavelength of 200 to 600 nm.
This thin film has high chemical resistance and functions to protect the conductive thin film and prevent destruction of the conductive thin film due to repeated cleaning treatments with acids, alkalis, etc.
且つ、この薄膜はガラス等の透明基板から析出
するNaイオンの遮光性薄膜への悪影響を防ぐの
に充分なバリヤー機能をも果す、更にこの薄膜は
該薄膜上に設けられる遮光性薄膜をエツチングす
る場合のエツチング液もしくはエツチングガスに
対する耐薬品性をも有するものである。この薄膜
の厚みは10ないし1000Åであることが好ましい。 Moreover, this thin film also has a sufficient barrier function to prevent Na ions deposited from a transparent substrate such as glass from having an adverse effect on the light-shielding thin film, and furthermore, this thin film etches the light-shielding thin film provided on the thin film. It also has chemical resistance to etching liquids or etching gases. The thickness of this thin film is preferably 10 to 1000 Å.
次に遮光性薄膜としてはCr、Cr2O3、Si、Ta、
Ta2O5及びFe2O3からなる群から選択される１種
もしくは２種以上の材料よりなるものを適用し得
る。 Next, as light-shielding thin films, Cr, Cr 2 O 3 , Si, Ta,
One or more materials selected from the group consisting of Ta 2 O 5 and Fe 2 O 3 can be used.
又、この薄膜としては例えばクロム表面に酸化
クロム膜を積層したものの如き積層体を用いても
良い。 Further, as this thin film, a laminate such as a chromium oxide film laminated on a chromium surface may be used.
第２図ないし第５図は本発明のフオトマスクブ
ランク板を用いてフオトマスクを製造する過程を
示す。第２図示の如く遮光性薄膜４上にレジスト
６をコーテイングし、次いで露光現像して第３図
示の如くレジストパターン７を形成後、第４図示
の如く露出した遮光性薄膜部分をエツチング後、
第５図示の如く、レジストを剥膜除去して所望の
フオトマスク８を得る。 2 to 5 show the process of manufacturing a photomask using the photomask blank plate of the present invention. A resist 6 is coated on the light-shielding thin film 4 as shown in the second figure, then exposed and developed to form a resist pattern 7 as shown in the third figure, and the exposed light-shielding thin film portion is etched as shown in the fourth figure.
As shown in FIG. 5, the resist is peeled off and a desired photomask 8 is obtained.
遮光性薄膜のエツチングは化学腐食、又はドラ
イエツチングのいずれの方法によつても良い。 The light-shielding thin film may be etched by either chemical etching or dry etching.
化学腐食による場合にはエツチング液として遮
光性薄膜は腐食するが耐薬品性保護膜は侵さない
例えば下記のようなエツチング液を適用し得る。 In the case of chemical corrosion, the following etching solution can be used, which corrodes the light-shielding thin film but does not attack the chemical-resistant protective film.
（遮光膜がCr又はCr2O3の場合のエツチング液の
組成）
（NH4）2Ce（NO3）6 165.0ｇ
HClO4（70％） 43.0ml
純 水 1000ml
（遮光膜がSiの場合のエツチング液の組成）
AgNO3 1.0ｇ
NH4F 0.5ｇ
HNO3 100ml
純 水 100ml
（遮光膜がFe2O3の場合のエツチング液の組成）
HCl 300ml
純 水 100ml
次にドライエツチングによる場合には平行平板
型プラズマエツチング装置を用い、且つ遮光膜が
Cr、又はCr2O3の場合はエツチングガスとして
CCl4と空気の混合ガスを用い、ガス圧0.3Torr、
印加高周波電力200W、エツチング時間５分間の
エツチング条件で、又、遮光膜がSiの場合はエツ
チングガスとしてCF4を用い、ガス圧0.02Torr、
印加高周波電力250W、エツチング時間１分間の
エツチング条件で、又、遮光膜がTa、Ta2O5の
場合はエツチングガスとしてCF4を用い、ガス圧
0.01Torr、印加高周波電力300W、エツチング時
間２分間のエツチング条件でエツチングを行な
う。(Composition of etching solution when the light shielding film is Cr or Cr 2 O 3 ) (NH 4 ) 2 Ce (NO 3 ) 6 165.0g HClO 4 (70%) 43.0ml Pure water 1000ml (When the light shielding film is Si Composition of etching solution) AgNO 3 1.0g NH 4 F 0.5g HNO 3 100ml Pure water 100ml (Composition of etching solution when the light-shielding film is Fe 2 O 3 ) HCl 300ml Pure water 100ml Next, in the case of dry etching, parallel A flat plate plasma etching device is used, and a light shielding film is used.
For Cr or Cr 2 O 3 , use as etching gas
Using a gas mixture of CCl 4 and air, the gas pressure is 0.3Torr,
The etching conditions were an applied high-frequency power of 200 W and an etching time of 5 minutes. If the light-shielding film was Si, CF 4 was used as the etching gas, and the gas pressure was 0.02 Torr.
The etching conditions were an applied high-frequency power of 250 W and an etching time of 1 minute, and when the light-shielding film was Ta or Ta 2 O 5 , CF 4 was used as the etching gas, and the gas pressure was
Etching is performed under the following conditions: 0.01 Torr, applied high frequency power of 300 W, and etching time of 2 minutes.
以上のようにして本発明のフオトマスクブラン
ク板を用いて得られたフオトマスクは導電性薄膜
を有するのでパターン焼付時の静電気によるシリ
コンウエーハ素子の破壊及びフオトマスクのパタ
ーン欠陥の発生を防止するに充分な導電性を有す
る。 The photomask obtained using the photomask blank plate of the present invention as described above has a conductive thin film, which is sufficient to prevent destruction of silicon wafer elements and generation of photomask pattern defects due to static electricity during pattern printing. Has electrical conductivity.
又、導電性薄膜は耐薬品性保護膜で表面保護さ
れているので酸、アルカリ等による洗浄処理を反
復して受けてもそれによつて損なわれることはな
い。 Further, since the surface of the conductive thin film is protected by a chemical-resistant protective film, it will not be damaged even if it is repeatedly subjected to cleaning treatment with acids, alkalis, etc.
又、電子ビームシステムによる寸法測定、及び
レジストレーシヨンの評価が可能である。 Additionally, dimension measurement and registration evaluation using an electron beam system are possible.
以上、詳記した通り、本発明のフオトマスクブ
ランク板によれば、パターン焼付時の静電気によ
るシリコンウエーハ素子の破壊及びフオトマスク
のパターン欠陥の発生を防止するに充分な導電性
を有し、且つ耐薬品性に富み、又、電子ビームシ
ステムによる寸法測定、及びレジストレーシヨン
の評価が可能であるフオトマスクを得ることがで
きる。 As described in detail above, the photomask blank board of the present invention has sufficient conductivity and durability to prevent damage to silicon wafer elements and generation of photomask pattern defects due to static electricity during pattern printing. It is possible to obtain a photomask that is rich in chemical properties and allows dimension measurement and registration evaluation using an electron beam system.
又、本発明のフオトマスクブランク板によれ
ば、ウエツトエツチング方式のみならずドライエ
ツチング方式によつてもフオトマスクを製造し得
る。 Further, according to the photomask blank plate of the present invention, photomasks can be manufactured not only by the wet etching method but also by the dry etching method.
次に、実施例をあげて本発明につき具体的に説
明する。 Next, the present invention will be specifically explained with reference to Examples.
実施例 １
ガラス板上に電子ビーム加熱式真空蒸着法によ
りTaを膜厚50Åに被着し、更に、その上に電子
ビーム加熱式真空蒸着法によりSiO2を膜厚200Å
に被着し、更にその上に電子ビーム加熱式真空蒸
着法によりCr薄膜を膜厚1000Åに形成して本発
明のフオトマスクブランク板を得た。Example 1 Ta was deposited on a glass plate to a thickness of 50 Å by electron beam heating vacuum evaporation, and SiO 2 was further deposited to a thickness of 200 Å on top of it by electron beam heating vacuum evaporation.
A photomask blank plate of the present invention was obtained by depositing a Cr thin film on it to a thickness of 1000 Å using an electron beam heating vacuum evaporation method.
上記の如くして得たブランク板のCr薄膜上に
レジスト（AZ−1350、シプレー社製）をコーテ
イングし、次いで露光現像してレジストパターン
を形成後、下記組成のエツチング液を用いて、液
温20℃で40秒間エツチングして露出しているCr
薄膜部分をエツチング除去して所望のフオトマス
クを得た。 A resist (AZ-1350, manufactured by Shipley Co., Ltd.) was coated on the Cr thin film of the blank plate obtained as described above, and then exposed and developed to form a resist pattern. Cr exposed by etching at 20℃ for 40 seconds
The thin film portion was removed by etching to obtain a desired photomask.
（エツチング液の組成）
（NH4）2Ce（NO3）6 165.0ｇ
HClO4（70％） 43.0ml
純 水 1000ml
このようにして得られたフオトマスク10枚につ
いて耐久試験を行つた。(Composition of etching solution) (NH 4 ) 2 Ce(NO 3 ) 6 165.0 g HClO 4 (70%) 43.0 ml Pure water 1000 ml A durability test was conducted on 10 photomasks thus obtained.
耐薬品性の試験は濃硫酸に過酸化水素水（30％
水溶液）を20容積％混合し、110℃に加熱した溶
液中にフオトマスクを60分間浸漬することにより
行なつたが、導電性薄膜には何らの欠陥も生ぜ
ず、又、導電率も何ら変化しなかつた。 Chemical resistance tests were conducted using concentrated sulfuric acid and hydrogen peroxide (30%).
This was done by immersing the photomask in a solution of 20% by volume (aqueous solution) heated to 110°C for 60 minutes, but no defects were produced in the conductive thin film, and there was no change in conductivity. Nakatsuta.
又、静電気に対する試験を、温度22℃、湿度40
％の雰囲気中で銀乳剤被膜をもつたフオトマスク
ブランク板へのパターン転写を100回行つたが、
フオトマスクの欠陥は何ら発生しなかつた。 In addition, we conducted tests against static electricity at a temperature of 22°C and a humidity of 40°C.
The pattern was transferred 100 times to a photomask blank plate with a silver emulsion coating in an atmosphere of
No photomask defects occurred.
実施例 ２
ガラス板上に電子ビーム加熱式真空蒸着法によ
りTaを膜厚50Åに被着し、更にその上に電子ビ
ーム加熱式真空蒸着法によりSiO2を膜厚200Åに
被着し、更にその上に電子ビーム加熱式真空蒸着
法によりSi薄膜を膜厚1000Åに形成して本発明の
フオトマスクブランク板を得た。Example 2 Ta was deposited on a glass plate to a thickness of 50 Å by electron beam heating vacuum evaporation, and then SiO 2 was deposited to a thickness of 200 Å by electron beam heating vacuum evaporation. A Si thin film was formed thereon to a thickness of 1000 Å by electron beam heating vacuum evaporation to obtain a photomask blank plate of the present invention.
上記の如くして得たブランク板のSi薄膜上に電
子線レジスト（COP、ミードケミカル社製）を
コーテイングし、次いでで電子線露光及び現像を
行なつてレジストパターンを形成後、下記組成の
エツチング液を用いて液温20℃、エツチング時間
２分間でエツチングして露出しているSi薄膜部分
をエツチング除去して所望のフオトマスクを得
た。 An electron beam resist (COP, manufactured by Mead Chemical Co., Ltd.) was coated on the Si thin film of the blank plate obtained as described above, and then exposed to electron beam and developed to form a resist pattern, and then etched with the following composition. A desired photomask was obtained by etching the exposed Si thin film portion using a solution at a temperature of 20° C. and an etching time of 2 minutes.
（エツチング液の組成）
AgNO3 1.0ｇ
NH4F 0.5ｇ
HNO3 100ml
純 水 100ml
このようにして得られたフオトマスク10枚につ
いて耐久試験を行つた。(Composition of etching solution) AgNO 3 1.0 g NH 4 F 0.5 g HNO 3 100 ml Pure water 100 ml A durability test was conducted on 10 photomasks thus obtained.
耐薬品性の試験は濃硫酸に過酸化水素（30％水
溶液）を20容積％混合し、110℃に加熱した溶液
中にフオトマスクを60分間浸漬することにより行
なつたが、導電性薄膜には何らの欠陥も生ぜず、
又、導電率も何ら変化しなかつた。 The chemical resistance test was conducted by immersing the photomask in a solution of 20% by volume of hydrogen peroxide (30% aqueous solution) heated to 110°C in concentrated sulfuric acid. Does not cause any defects,
Moreover, the electrical conductivity did not change at all.
又、静電気に対する試験を温度22℃、湿度40％
の雰囲気中で銀乳剤被膜をもつたフオトマスクブ
ランク板へのパターン転写を100回行つたが、フ
オトマスクの欠陥は何ら発生しなかつた。 In addition, static electricity tests were conducted at a temperature of 22°C and a humidity of 40%.
The pattern was transferred to a photomask blank plate with a silver emulsion coating 100 times in an atmosphere of
又、上記の如くして得たフオトマスクに対して
は電子線を用いたマスクのレジストレーシヨンの
測定を精度良く行なうことができた。 Furthermore, for the photomask obtained as described above, the registration of the mask could be measured with high accuracy using an electron beam.
実施例 ３
実施例１におけるブランク板のCr薄膜の一部
を、ドライエツチング法により、エツチングガス
としてCCl4との空気の混合ガスを用い、且つガ
ス圧0.3Torr、印加高周波電力200W、エツチン
グ時間５分間のエツチング条件でエツチング除去
して所望のフオトマスクを得た。Example 3 A part of the Cr thin film of the blank plate in Example 1 was etched by dry etching using a mixed gas of air with CCl 4 as the etching gas, gas pressure 0.3 Torr, applied high frequency power 200 W, and etching time 5. The desired photomask was obtained by etching and removing the photomask under etching conditions of 1 minute.
このようにして得られたフオトマスク10枚につ
いて実施例１の場合と同様にして耐久試験及び静
電気に対する試験を行つた。 Ten photomasks thus obtained were subjected to durability tests and static electricity tests in the same manner as in Example 1.
その結果、導電性薄膜には何らの欠陥も生ぜ
ず、又、導電率の変化もみられなかつた。又、静
電気によつて生ずる欠陥も何らみられなかつた。 As a result, no defects were produced in the conductive thin film, and no change in conductivity was observed. Further, no defects caused by static electricity were observed.
実施例 ４
ガラス板上に電子ビーム加熱式真空蒸着法によ
りCr膜厚50Åを被着し、更にその上に電子ビー
ム加熱式真空蒸着法によりSiO2を膜厚200Åに被
着し、更にその上に電子ビーム加熱式真空蒸着法
によりTa薄膜を膜厚1000Åに形成してフオトマ
スクブランク板を得た。Example 4 A 50 Å thick Cr film was deposited on a glass plate by electron beam heating vacuum evaporation, and then a 200 Å thick SiO 2 film was deposited on top of that by electron beam heating vacuum evaporation. A photomask blank plate was obtained by forming a Ta thin film to a thickness of 1000 Å using electron beam heating vacuum evaporation.
上記の如くして得たブランク板のTa薄膜の一
部を、ドライエツチング法により、エツチングガ
スとしてCF4を用い、且つガス圧0.01Torr、印加
高周波電力300W、エツチング時間２分間のエツ
チング条件で除去して所望のフオトマスクを得
た。 A part of the Ta thin film on the blank plate obtained as above was removed by dry etching using CF 4 as an etching gas under the conditions of gas pressure 0.01 Torr, applied high frequency power 300 W, and etching time 2 minutes. The desired photomask was obtained.
このようにして得られたフオトマスク10枚につ
いて実施例１の場合と同様にして耐久試験及び静
電気に対する試験を行つた。 Ten photomasks thus obtained were subjected to durability tests and static electricity tests in the same manner as in Example 1.
その結果、導電性薄膜には何らの欠陥も生ぜ
ず、又、導電率の変化もみられなかつた。又、静
電気によつて生ずる欠陥も何らみられなかつた。 As a result, no defects were produced in the conductive thin film, and no change in conductivity was observed. Further, no defects caused by static electricity were observed.
実施例 ５
実施例２におけるブランク板のSi薄膜の一部
を、ドライエツチング法により、エツチングガス
としてCCl4ガスを用い、且つ、ガス圧0.02Torr、
印加高周波電力250W、エツチング時間１分間の
エツチング条件でエツチング除去して所望のフオ
トマスクを得た。Example 5 A part of the Si thin film of the blank plate in Example 2 was dry etched using CCl 4 gas as the etching gas and at a gas pressure of 0.02 Torr.
The desired photomask was obtained by etching and removing under the etching conditions of an applied high frequency power of 250 W and an etching time of 1 minute.
このようにして得られたフオトマスク10枚につ
いて実施例１の場合と同様にして耐久試験及び静
電気に対する試験を行つた。 Ten photomasks thus obtained were subjected to durability tests and static electricity tests in the same manner as in Example 1.
その結果、導電性薄膜には何らの欠陥も生ぜ
ず、又、導電率の変化もみられなかつた。又、静
電気によつて生ずる欠陥も何らみられなかつた。 As a result, no defects were produced in the conductive thin film, and no change in conductivity was observed. Further, no defects caused by static electricity were observed.
実施例 ６
ガラス板上に電子ビーム加熱式真空蒸着法によ
りCrを膜厚50Åに被着し、更に、その上に電子
ビーム加熱式真空蒸着法によりSiO2を膜厚200Å
に被着し、更にその上に電子ビーム加熱式真空蒸
着法によりSi薄膜を膜厚1000Åに形成してフオト
マスクブランク板を得た。Example 6 Cr was deposited on a glass plate to a thickness of 50 Å by electron beam heating vacuum evaporation, and then SiO 2 was deposited to a thickness of 200 Å on top of it by electron beam heating vacuum evaporation.
A photomask blank plate was obtained by depositing a Si thin film on it to a thickness of 1000 Å using an electron beam heating vacuum evaporation method.
上記の如くして得たブランク板のSi薄膜の一部
を実施例２の場合と同様にしてエツチング除去し
て所望のフオトマスクを得た。 A portion of the Si thin film of the blank plate obtained as described above was removed by etching in the same manner as in Example 2 to obtain a desired photomask.
このようにして得られたフオトマスク10枚につ
いて実施例１の場合の同様にして耐久試験及び静
電気に対する試験を行つた。 Ten photomasks thus obtained were subjected to durability tests and static electricity tests in the same manner as in Example 1.
その結果、導電性薄膜には何らの欠陥も生ぜ
ず、又、導電率の変化もみられなかつた。又、静
電気によつて生ずる欠陥も何らみられなかつた。 As a result, no defects were produced in the conductive thin film, and no change in conductivity was observed. Further, no defects caused by static electricity were observed.
実施例 ７
実施例６におけるブランク板のSi薄膜の一部
を、ドライエツチング法により、エツチングガス
としてCCl4ガスを用い、且つ、ガス圧0.02Torr、
印加高周波電力250W、エツチング時間１分間の
エツチング条件でエツチング除去して所望のフオ
トマスクを得た。Example 7 A part of the Si thin film of the blank plate in Example 6 was dry etched using CCl 4 gas as the etching gas and at a gas pressure of 0.02 Torr.
The desired photomask was obtained by etching and removing under the etching conditions of an applied high frequency power of 250 W and an etching time of 1 minute.
このようにして得られたフオトマスク10枚につ
いて実施例１の場合と同様にして耐久試験及び静
電気に対する試験を行つた。 Ten photomasks thus obtained were subjected to durability tests and static electricity tests in the same manner as in Example 1.
その結果、導電性薄膜には何らの欠陥も生ぜ
ず、又、導電率の変化もみられなかつた。又、静
電気によつて生ずる欠陥も何らみられなかつた。 As a result, no defects were produced in the conductive thin film, and no change in conductivity was observed. Further, no defects caused by static electricity were observed.
第１図は本発明のフオトマスクブランク板の断
面図、第２図ないし第５図は前記ブランク板を用
いたフオトマスクの製造過程を示す断面図であ
る。
１……透明基板、２……透明性を有する導電性
薄膜、３……透明性を有する耐薬品性保護膜、４
……遮光性薄膜。
FIG. 1 is a sectional view of a photomask blank plate of the present invention, and FIGS. 2 to 5 are sectional views showing the process of manufacturing a photomask using the blank plate. 1... Transparent substrate, 2... Transparent conductive thin film, 3... Transparent chemical-resistant protective film, 4
...Light-shielding thin film.
Claims (1)
Au、In2O3、及びSnO2からなる群から選択され
る材料よりなる透明性を有する導電性薄膜、及び
Al2O3、CaO、MgO、SiO2、CeO2及びTiO2から
なる群より選択される材料よりなる透明性を有す
る耐薬品性保護膜、及びCr、Cr2O3、Si、Ta、
Ta2O5、及びFe2O3からなる群から選択される材
料よりなる遮光性薄膜が順次積層されていること
を特徴とするフオトマスクブランク板。1 Mo, Nb, Ti, V, W, Zr, on a transparent substrate
a transparent conductive thin film made of a material selected from the group consisting of Au, In 2 O 3 and SnO 2 ;
A transparent chemical-resistant protective film made of a material selected from the group consisting of Al 2 O 3 , CaO, MgO, SiO 2 , CeO 2 and TiO 2 , and Cr, Cr 2 O 3 , Si, Ta,
1. A photomask blank plate characterized in that light-shielding thin films made of a material selected from the group consisting of Ta 2 O 5 and Fe 2 O 3 are sequentially laminated.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2872281A JPS57144550A (en) | 1981-02-28 | 1981-02-28 | Blank plate for photomask |
| EP81107702A EP0049799B1 (en) | 1980-10-09 | 1981-09-28 | Photomask blank and photomask |
| DE8181107702T DE3173769D1 (en) | 1980-10-09 | 1981-09-28 | Photomask blank and photomask |
| US06/318,201 US4440841A (en) | 1981-02-28 | 1981-11-04 | Photomask and photomask blank |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2872281A JPS57144550A (en) | 1981-02-28 | 1981-02-28 | Blank plate for photomask |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57144550A JPS57144550A (en) | 1982-09-07 |
| JPS6322299B2 true JPS6322299B2 (en) | 1988-05-11 |
Family
ID=12256324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2872281A Granted JPS57144550A (en) | 1980-10-09 | 1981-02-28 | Blank plate for photomask |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57144550A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57182741A (en) * | 1981-05-07 | 1982-11-10 | Dainippon Printing Co Ltd | Photomask blank plate |
| JP2788649B2 (en) * | 1989-05-30 | 1998-08-20 | ホーヤ株式会社 | Photomask blank and photomask |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4953039A (en) * | 1972-06-20 | 1974-05-23 | ||
| JPS5352073A (en) * | 1976-10-22 | 1978-05-12 | Hoya Denshi Kk | Photomask for ic |
| JPS5446479A (en) * | 1977-09-20 | 1979-04-12 | Mitsubishi Electric Corp | Negative plate for photo mask |
| JPS5451831A (en) * | 1977-09-30 | 1979-04-24 | Konishiroku Photo Ind Co Ltd | Photomask material |
-
1981
- 1981-02-28 JP JP2872281A patent/JPS57144550A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4953039A (en) * | 1972-06-20 | 1974-05-23 | ||
| JPS5352073A (en) * | 1976-10-22 | 1978-05-12 | Hoya Denshi Kk | Photomask for ic |
| JPS5446479A (en) * | 1977-09-20 | 1979-04-12 | Mitsubishi Electric Corp | Negative plate for photo mask |
| JPS5451831A (en) * | 1977-09-30 | 1979-04-24 | Konishiroku Photo Ind Co Ltd | Photomask material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57144550A (en) | 1982-09-07 |
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