JPS6237384B2 - - Google Patents
Info
- Publication number
- JPS6237384B2 JPS6237384B2 JP19985583A JP19985583A JPS6237384B2 JP S6237384 B2 JPS6237384 B2 JP S6237384B2 JP 19985583 A JP19985583 A JP 19985583A JP 19985583 A JP19985583 A JP 19985583A JP S6237384 B2 JPS6237384 B2 JP S6237384B2
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- transparent substrate
- film
- mask blank
- gas
- 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 42
- 239000011651 chromium Substances 0.000 claims description 34
- 229910052804 chromium Inorganic materials 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 23
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 19
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 238000007733 ion plating Methods 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000005361 soda-lime glass Substances 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- -1 Next Chemical class 0.000 description 1
- 239000005407 aluminoborosilicate glass Substances 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229960001730 nitrous oxide Drugs 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation 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
- G03F1/88—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 prepared by photographic processes for production of originals simulating relief
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Physical Vapour Deposition (AREA)
Description
【発明の詳細な説明】
本発明は、半導体素子、IC、LSI等の半導体製
造に使用されるクロムマスクブランクとその製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chrome mask blank used for manufacturing semiconductors such as semiconductor devices, ICs, and LSIs, and a method for manufacturing the same.
このクロムマスクブランクとしては、第１図ａ
に示すように透明基板１上にクロム膜２（700〜
1000Å）を被覆した、比較的表面反射率の高いも
のと、同図ｂに示すように前記クロム膜２上に更
に酸化クロム膜３（150〜300Å）を被覆させて反
射防止膜付きのもの（低反射クロムマスクブラン
ク）と、同図Ｃに示すように透明基板１上に酸化
インジウム、酸化スズ等の帯電防止用の透明導電
膜1′（200〜300Å）を被覆して、導電性をもつた
透明基板１″を使用し、この透明基板１″上に前記
したクロム膜２、又は更にこのクロム膜２上に酸
化クロム膜３を被覆した透明導電膜付きクロムマ
スクブランクがある。それ故、本発明において
は、単に透明基板というときは、後述するような
ソーダライムガラス等の透明基板単板の他に、透
明導電膜付きのものが含まれる。 This chrome mask blank is shown in Figure 1a.
As shown in the figure, a chromium film 2 (700~
1000 Å) with a relatively high surface reflectance, and as shown in Figure b, the chromium film 2 is further coated with a chromium oxide film 3 (150 to 300 Å) with an anti-reflection coating ( As shown in Figure C, a transparent conductive film 1' (200 to 300 Å) made of indium oxide, tin oxide, etc. for antistatic purposes is coated on the transparent substrate 1 to make it conductive. There is a chromium mask blank with a transparent conductive film, which uses a transparent substrate 1'' and has the above-mentioned chromium film 2 on the transparent substrate 1'', or further coats the chromium oxide film 3 on the chromium film 2. Therefore, in the present invention, when simply referring to a transparent substrate, it includes not only a single transparent substrate made of soda lime glass or the like as described later, but also one with a transparent conductive film.
このようなクロムマスクヤブランクに対して、
(1)透明基板上のクロムの内部応力、すなわちこれ
に起因する透明基板における平坦度変化量の小さ
いこと、(2)ピンホールの少ないことが要求されて
いる。そして、(1)項を満足させたクロムマスクブ
ランクとして、「クロム膜」の代わりに「クロム
窒化膜」を使用する手段が提案されている。 For such chrome mask Yablank,
(1) It is required that the internal stress of chromium on the transparent substrate, that is, the amount of flatness change in the transparent substrate caused by this is small, and (2) that there are few pinholes. As a chromium mask blank that satisfies item (1), it has been proposed to use a "chromium nitride film" instead of a "chromium film."
この手段によるクロムマスクブランクは、金属
クロムをターゲツトとして、ArガスにN2ガスを
混入した雰囲気中でスパツタリングにより透明基
板上に形成されるが、第３図の曲線ａに示すよう
に、透明基板（寸法10cm□×1.5mmtのソーダライ
ムガラス）における平坦度変化量を１μｍ以下に
するには、クロム窒化膜を形成するためのガス雰
囲気としてN2ガス含有率を30％以上にする必要
がある。 A chromium mask blank by this method is formed on a transparent substrate by sputtering in an atmosphere containing Ar gas and N2 gas, using metallic chromium as a target. In order to reduce the variation in flatness of the glass (soda lime glass with dimensions 10 cm x 1.5 mm t ) to 1 μm or less, the N2 gas content must be at least 30% as the gas atmosphere for forming the chromium nitride film. be.
一方、このようなN2ガス含有率を多くする
と、スパツタリングにおいて減圧したガス雰囲気
中でガスプラズマをつくる際のガスプラズマの不
安定や、更に、イオン化したガスを対向電極にあ
るターゲツト（クロム）に当てて、そこからクロ
ム原子をたたき出し、その原子が活性化された
N2ガスと反応してクロム窒化膜が形成される
が、その際の膜の不安定性等により、ピンホール
が生じやすい。本例のN2ガス含有率が40％であ
るクロム窒化膜のピンホール不良率（１cm2当0.05
個以上発生したピンホールを有するブランクスの
割合）は38％であつた。 On the other hand, increasing the N 2 gas content may cause instability of the gas plasma when it is created in a reduced pressure gas atmosphere during sputtering, and may also cause the ionized gas to reach the target (chromium) on the counter electrode. When hit, a chromium atom was knocked out of it, and that atom was activated.
A chromium nitride film is formed by reacting with N 2 gas, but pinholes are likely to occur due to instability of the film at that time. In this example, the pinhole defect rate of the chromium nitride film with a N2 gas content of 40% (0.05 per cm2)
The percentage of blanks with more than one pinhole was 38%.
勿論、このようなピンホール不良率を低減する
ために、N2ガス含有率を少なくすればよいが、
この場合、透明基板の平坦度変化量が曲線ａで示
すように増大し、前述した(1)項を満足しなくなつ
てしまう。 Of course, in order to reduce the pinhole defect rate, the N2 gas content can be reduced, but
In this case, the amount of change in flatness of the transparent substrate increases as shown by curve a, and the above-mentioned item (1) is no longer satisfied.
したがつて、従来のクロムマスクブランクは、
前述した２項目を同時に満足することができなか
つた。 Therefore, traditional chrome mask blanks are
It was not possible to satisfy the two items mentioned above at the same time.
本発明の目的は、従来このように両立しがたか
つた２項目を満足するクロムマスクブランクを提
供することである。 An object of the present invention is to provide a chrome mask blank that satisfies these two conditions that have conventionally been incompatible.
このような目的を達成させるため、本発明は、
透明基板上に、金属クロム（Cr）と窒化クロム
（CrxNy）と酸化窒化クロム（CrxOyNz）の混合
物からなる膜を形成していることを特徴とするク
ロムマスクブランクを必須構成としている。 In order to achieve such an objective, the present invention
The essential component is a chromium mask blank, which is characterized by forming a film made of a mixture of metal chromium (Cr), chromium nitride (CrxNy), and chromium oxynitride (CrxOyNz) on a transparent substrate.
以下、本発明を第２図の実施例図面を参照して
説明する。 Hereinafter, the present invention will be explained with reference to the embodiment drawing of FIG.
表面を精密研磨したソーダライムガラスを素材
にした透明基板１上に、圧力１×10-3（Torr）
に減圧したアルゴン（Ar）70％、窒素（N2）25
％及び一酸化窒素（NO）５％の混合ガス雰囲気
中でガスプラズマをつくり、イオン化したアルゴ
ンガスをクロム・ターゲツトに当てて、そこから
クロム原子をたたき出し、そのクロム原子が活性
化された窒素及び一酸化窒素のガスと反応して、
金属クロム（Cr）と窒化クロム（CrxNy）と酸
化窒化クロム（CrxOyNz）の混合物から成る膜
４を被覆形成して、第２図に示すようにクロムマ
スクブランクを製作した。本例のクロムマスクブ
ランク（実施例１）における透明基板１の平坦度
変化量は0.4（μｍ）であり、ピンホール不良率
は14％であつた。 A pressure of 1×10 -3 (Torr) is applied to a transparent substrate 1 made of soda lime glass with a precisely polished surface.
Argon (Ar) 70%, nitrogen ( N2 ) under reduced pressure to 25%
% and nitrogen monoxide (NO) in a mixed gas atmosphere, and ionized argon gas is applied to a chromium target to knock out chromium atoms, and the chromium atoms become activated nitrogen and Reacts with nitric oxide gas,
A chromium mask blank was produced as shown in FIG. 2 by coating it with a film 4 consisting of a mixture of metallic chromium (Cr), chromium nitride (CrxNy), and chromium oxynitride (CrxOyNz). In the chrome mask blank of this example (Example 1), the flatness variation of the transparent substrate 1 was 0.4 (μm), and the pinhole defect rate was 14%.
次に、前実施例の製法において、混合ガス比率
をアルゴン80％、窒素15％及び一酸化窒素５％に
したもの（実施例２）と、アルゴン90％、窒素５
％及び一酸化窒素５％にしたもの（実施例３）と
をそれぞれ製作した結果、実施例２及び３による
クロムマスクブランクにおける透明基板１の平坦
度変化量はそれぞれ0.5（μｍ）及び１（μｍ）
であり、ピンホール不良率はそれぞれ８％及び７
％であつた。その結果、N2ガス含有率に対する
透明基板１の平坦度変化量の特性は第３図の曲線
ｂに示される。 Next, in the manufacturing method of the previous example, the mixed gas ratio was 80% argon, 15% nitrogen, and 5% nitrogen monoxide (Example 2), and 90% argon, 5% nitrogen
% and 5% nitrogen monoxide (Example 3), the flatness changes of the transparent substrate 1 in the chrome mask blanks of Examples 2 and 3 were 0.5 (μm) and 1 (μm), respectively. )
The pinhole defect rates are 8% and 7, respectively.
It was %. As a result, the characteristic of the amount of change in flatness of the transparent substrate 1 with respect to the N 2 gas content is shown by curve b in FIG.
以上のとおり本発明によれば、活性化される混
合ガスとして従来の窒素の他に一酸化窒素を導入
して、金属クロムと窒化クロムと酸化窒化クロム
の混合物から成る膜を透明基板上に被覆すること
により、N2含有率を少なくしてピンホール不良
率を低減し、かつ透明基板の平坦度変化量も低減
することができた。 As described above, according to the present invention, nitrogen monoxide is introduced in addition to conventional nitrogen as a mixed gas to be activated, and a film made of a mixture of metallic chromium, chromium nitride, and chromium oxynitride is coated on a transparent substrate. By doing so, it was possible to reduce the N 2 content, reduce the pinhole defect rate, and also reduce the amount of change in flatness of the transparent substrate.
次に、本発明の変形例を挙げれば、先ず、一酸
化窒素（NO）に代えて一酸化二窒素（N2O）、三
酸化二窒素（N2O3）及び二酸化窒素（NO2）等の
酸化窒素でもよい。次に、本発明による金属クロ
ム（Cr）と窒化クロム（CrxNy）と酸化窒化ク
ロム（CrxOyNz）混合物からなる膜を形成した
クロムマスクブランクに対して、第１図ｂに示し
たように更に酸化クロム３を被覆してもよいし、
第１図ｃに示したように透明基板１との間に透明
導電膜1′を介在させて被覆してもよい。また、透
明基板１はソーダライムガラスの代わりに、アル
ミノボロシリケートガラス等の他の硝種のガラス
や合成石英でもよい。また更に、成膜方法として
スパツタリングの他に、真空蒸着、イオンプレー
テイングを使用してもよい。 Next, to give a modification of the present invention, first, instead of nitrogen monoxide (NO), dinitrogen monoxide (N 2 O), dinitrogen trioxide (N 2 O 3 ), and nitrogen dioxide (NO 2 ) are used. Nitrogen oxides such as Next, as shown in FIG. 1b, a chromium oxide mask blank was coated with a film made of a mixture of metal chromium (Cr), chromium nitride (CrxNy), and chromium oxynitride (CrxOyNz) according to the present invention. 3 may be covered,
As shown in FIG. 1c, a transparent conductive film 1' may be interposed and coated with the transparent substrate 1. Further, the transparent substrate 1 may be made of other types of glass such as aluminoborosilicate glass or synthetic quartz instead of soda lime glass. Furthermore, in addition to sputtering, vacuum evaporation or ion plating may be used as a film forming method.
第１図は従来のクロムマスクブランクを示す断
面図、第２図は本発明によるクロムマスクブラン
クを示す断面図、及び第３図はN2ガス含有率に
対する透明基板の平坦度変化量を示す特性図であ
る。
１……透明基板、１′……透明導電膜付き透明
基板、４……金属クロム（Cr）と窒化クロム
（CrxNy）と酸化窒化クロム（CrxOyNz）の混合
物からなる膜。
Fig. 1 is a cross-sectional view showing a conventional chrome mask blank, Fig. 2 is a cross-sectional view showing a chrome mask blank according to the present invention, and Fig. 3 is a characteristic showing the amount of change in flatness of a transparent substrate with respect to N2 gas content. It is a diagram. 1... Transparent substrate, 1'... Transparent substrate with a transparent conductive film, 4... Film made of a mixture of metal chromium (Cr), chromium nitride (CrxNy), and chromium oxynitride (CrxOyNz).
Claims (1)
ロム（CrxNy）と酸化窒化クロム（CrxOyNz）
の混合物から成る膜を形成していることを特徴と
するクロムマスクブランク。 ２ 窒素と酸化窒素を含むガス雰囲気中で、真空
蒸着、スパツタリング及びイオンプレーテイング
のいずれかにより、金属クロム（Cr）と窒化ク
ロム（CrxNy）と酸化窒化クロム（CrxOyNz）
の混合物からなる膜を透明基板上に形成すること
を特徴とするクロムマスクブランクの製造方法。[Claims] 1 Metallic chromium (Cr), chromium nitride (CrxNy), and chromium oxynitride (CrxOyNz) on a transparent substrate
A chrome mask blank characterized by forming a film consisting of a mixture of. 2. Metallic chromium (Cr), chromium nitride (CrxNy), and chromium oxynitride (CrxOyNz) are deposited by vacuum deposition, sputtering, or ion plating in a gas atmosphere containing nitrogen and nitrogen oxide.
A method for producing a chrome mask blank, comprising forming a film made of a mixture of the above on a transparent substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58199855A JPS6091356A (en) | 1983-10-25 | 1983-10-25 | Chromium mask blank and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58199855A JPS6091356A (en) | 1983-10-25 | 1983-10-25 | Chromium mask blank and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6091356A JPS6091356A (en) | 1985-05-22 |
| JPS6237384B2 true JPS6237384B2 (en) | 1987-08-12 |
Family
ID=16414767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58199855A Granted JPS6091356A (en) | 1983-10-25 | 1983-10-25 | Chromium mask blank and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6091356A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07305163A (en) * | 1994-05-10 | 1995-11-21 | Itochu Fine Chem Kk | Low-reflection chromium-base film |
| WO1997015866A1 (en) * | 1995-10-24 | 1997-05-01 | Ulvac Coating Corporation | Phase shift mask and method of manufacturing the same |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0765156B2 (en) * | 1985-10-09 | 1995-07-12 | セイコーエプソン株式会社 | Method for manufacturing exterior parts for watches |
| JPH0742568B2 (en) * | 1985-10-22 | 1995-05-10 | セイコーエプソン株式会社 | Exterior parts for watches |
| JP2524103B2 (en) * | 1985-10-22 | 1996-08-14 | セイコーエプソン株式会社 | Watch exterior parts |
| US5449547A (en) * | 1993-03-15 | 1995-09-12 | Teikoku Piston Ring Co., Ltd. | Hard coating material, sliding member coated with hard coating material and method for manufacturing sliding member |
| TW480367B (en) * | 2000-02-16 | 2002-03-21 | Shinetsu Chemical Co | Photomask blank, photomask and method of manufacture |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54153790A (en) * | 1978-05-25 | 1979-12-04 | Fujitsu Ltd | Chromium oxide layer formation |
| JPS57104141A (en) * | 1980-12-22 | 1982-06-29 | Dainippon Printing Co Ltd | Photomask and photomask substrate |
-
1983
- 1983-10-25 JP JP58199855A patent/JPS6091356A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54153790A (en) * | 1978-05-25 | 1979-12-04 | Fujitsu Ltd | Chromium oxide layer formation |
| JPS57104141A (en) * | 1980-12-22 | 1982-06-29 | Dainippon Printing Co Ltd | Photomask and photomask substrate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07305163A (en) * | 1994-05-10 | 1995-11-21 | Itochu Fine Chem Kk | Low-reflection chromium-base film |
| WO1997015866A1 (en) * | 1995-10-24 | 1997-05-01 | Ulvac Coating Corporation | Phase shift mask and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6091356A (en) | 1985-05-22 |
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