JPH08179495A - Pellicle and production thereof - Google Patents

Pellicle and production thereof

Info

Publication number
JPH08179495A
JPH08179495A JP10356495A JP10356495A JPH08179495A JP H08179495 A JPH08179495 A JP H08179495A JP 10356495 A JP10356495 A JP 10356495A JP 10356495 A JP10356495 A JP 10356495A JP H08179495 A JPH08179495 A JP H08179495A
Authority
JP
Japan
Prior art keywords
pellicle
pellicle film
frame
film
adhesive
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
Application number
JP10356495A
Other languages
Japanese (ja)
Other versions
JP3429898B2 (en
Inventor
Yuichi Hamada
裕一 浜田
Satoshi Kawakami
聡 川上
Susumu Shirasaki
享 白崎
Akihiko Nagata
愛彦 永田
Shu Kashida
周 樫田
Yoshihiro Kubota
芳宏 久保田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Priority to JP10356495A priority Critical patent/JP3429898B2/en
Publication of JPH08179495A publication Critical patent/JPH08179495A/en
Application granted granted Critical
Publication of JP3429898B2 publication Critical patent/JP3429898B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

PURPOSE: To obtain a pellicle with a tightly bonded film free from wrinkles and strains. CONSTITUTION: In a process for bonding a pellicle film to a frame with an adhesive made of the same polymer as the pellicle film, the pellicle film is allowed to adhere to the frame with the adhesive, a soln. prepd. by dissolving the same polymer as the polymer of the pellicle film in an org. solvent is applied on the pellicle film and they are heated to bond the pellicle film to the frame.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明はLSI、超LSIなどの
半導体装置あるいは液晶表示板を製造する際のゴミよけ
として使用される、実質的に 500nm以下の光を用いる露
光方式における帯電防止されたペリクル及びその製造方
法に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as an anti-dust when manufacturing a semiconductor device such as an LSI or VLSI, or a liquid crystal display panel, and is used to prevent electrostatic charge in an exposure system using light of substantially 500 nm or less. And a manufacturing method thereof.

【0002】[0002]

【従来の技術】LSI、超LSIなどの半導体装置ある
いは液晶表示板などの製造においては、半導体ウェハー
あるいは液晶表示板に光を照射してパターニングを作成
するのであるが、この場合に用いる露光原版(マスクま
たはレチクルとも呼ばれる)にゴミが付着していると、
このゴミが光を吸収したり、光を曲げてしまうため、転
写したパターニングが変形したり、エッジががさついた
ものとなるほか、下地が黒く汚れ寸法、品質、外観など
が損なわれるという問題があった。
2. Description of the Related Art In the manufacture of semiconductor devices such as LSI and VLSI, or liquid crystal display plates, etc., a semiconductor wafer or liquid crystal display plate is irradiated with light to form a pattern. If there is dust on the mask (also called reticle),
Since this dust absorbs light or bends light, the transferred patterning may be deformed, edges may be rough, and the background may be black and stains, quality, and appearance may be impaired. It was

【0003】このため、これらの作業は通常クリーンル
ームで行われているが、このクリーンルーム内でも露光
原版を常に清浄に保つことが難しいので、露光原版の表
面にゴミよけのための露光用の光をよく通過させるペリ
クルを貼着する方式が一般的に取られている。この場
合、ゴミは露光原版の表面には直接付着せずペリクル上
に付着するため、リソグラフィー時に焦点を露光原版の
パターン上に合わせておけば、ペリクル上のゴミは転写
に無関係となる。このペリクルの構造は、紫外線をよく
通過させるニトロセルロース、酢酸セルロース、プロピ
オン酸セルロースなどのセルロース系ポリマーや、非晶
質フッ素系ポリマーなどの薄膜と、アルミニウム、ステ
ンレス、プラスチックスなどの材質からなるペリクルフ
レームとをフレームの上部にペリクル膜の良溶媒を塗布
し、風乾する(特開昭 58-219023号公報参照)か、アク
リル樹脂やエポキシ樹脂などの接着剤で接着したもの
(米国特許第 4861402号、特公昭 63-27707 号公報参
照)である。また、ペリクルフレームの下部には露光原
版にペリクルを固定するために、ポリブテン樹脂、ポリ
酢酸ビニル樹脂、アクリル樹脂などからなる粘着層を設
け、更にその粘着層の表面に、粘着層の保護を目的とし
たセパレーターを貼り合わせた構造となっている。
For this reason, these operations are usually carried out in a clean room, but it is difficult to always keep the exposure original plate clean even in this clean room. Therefore, the surface of the exposure original plate is exposed to light for exposure to prevent dust. A method of sticking a pellicle that allows the material to pass through is commonly used. In this case, since dust is not directly attached to the surface of the exposure original plate but is attached to the pellicle, if the focus is set on the pattern of the exposure original plate during lithography, the dust on the pellicle becomes unrelated to the transfer. The structure of this pellicle is a pellicle made of a material such as a cellulose-based polymer such as nitrocellulose, cellulose acetate, or cellulose propionate that transmits ultraviolet rays well, a thin film such as an amorphous fluoropolymer, and a material such as aluminum, stainless steel, or plastics. The frame and the top of the frame are coated with a good solvent for the pellicle film and air-dried (see Japanese Patent Laid-Open No. 58-219023) or bonded with an adhesive such as acrylic resin or epoxy resin (US Pat. No. 4861402). , Japanese Patent Publication No. 63-27707). In addition, an adhesive layer made of polybutene resin, polyvinyl acetate resin, acrylic resin, etc. is provided under the pellicle frame to fix the pellicle to the exposure master plate, and the surface of the adhesive layer further protects the adhesive layer. It has a structure in which separators are attached.

【0004】[0004]

【発明が解決しようとする課題】このペリクルの使用に
当って直接露光光源(g線、i線などの紫外線、または
エキシマレーザー光)に照射されるのはペリクル膜であ
るが、このペリクル膜をペリクルフレームに固着させる
接着剤にもこの露光光源の一部が照射されるおそれがあ
るために、この接着剤についても耐久性が重要な性質と
され、この接着剤は厚さが数ミクロンの超薄膜であるペ
リクル膜を常に張った状態でペリクルフレームに接着さ
せておくことが必要であることから、ペリクルの性能上
重要な材料とされている。しかし、従来使用されている
アクリル系接着剤やエポキシ系接着剤は接着強度が不十
分であったり、接着面積が一定しないために、シワが発
生するなどの信頼性に欠けるもので、さらにこれらの接
着剤は露光光源による劣化が激しく、ある程度使用する
と接着剤が固化、分解してこれがゴミの発生源となり、
さらにペリクル膜の張力変化で膜が剥離したり、亀裂を
起こすという欠点があり、特にペリクル膜の材料として
非晶質のフッ素系ポリマーを用いた場合には、フッ素系
ポリマーが離型性に優れているためにアクリル系接着剤
やエポキシ系接着剤では実用的な接着力を得ることが不
可能であるという問題点もある。
In using this pellicle, it is the pellicle film that is directly irradiated with the exposure light source (ultraviolet rays such as g-line, i-line, or excimer laser beam). Since the adhesive that is fixed to the pellicle frame may also be irradiated with part of this exposure light source, durability is an important property for this adhesive as well. Since it is necessary to bond the pellicle film, which is a thin film, to the pellicle frame in a state where the pellicle film is always stretched, it is an important material for the performance of the pellicle. However, acrylic adhesives and epoxy adhesives that have been conventionally used have insufficient adhesive strength, or the adhesive area is not constant, so that wrinkles, etc. are not reliable, and further The adhesive is severely deteriorated by the exposure light source, and when used to some extent, the adhesive solidifies and decomposes, which becomes a source of dust,
In addition, there is a drawback that the film peels off or cracks due to the change in tension of the pellicle film, and especially when an amorphous fluoropolymer is used as the material of the pellicle film, the fluoropolymer has excellent releasability. Therefore, there is a problem in that it is impossible to obtain a practical adhesive force with an acrylic adhesive or an epoxy adhesive.

【0005】そこで、本発明者らは非晶質のフッ素系ポ
リマーを用いたペリクル膜の接着剤としてペリクル膜と
同一もしくは類似の構造をもつフッ素系接着剤を用い
て、ガラス転移温度付近またはそれ以上に加熱すると、
ペリクル膜と接着剤が強固に接着するということを提案
した(特開平 6-67409号公報参照)が、この場合には膜
とフレームとを接着するときに、十分な接着強度を得る
ためにこれをペリクル膜形成ポリマーのガラス転移温度
以上に加熱すると、膜自体にシワや歪みが発生し易く、
それを防止するためにこの加熱温度をガラス転移温度以
下とすると、接着強度が不十分になるという不利のある
ことが確認された。
Therefore, the present inventors have used a fluorine-based adhesive having the same or similar structure as that of the pellicle film as an adhesive for the pellicle film using an amorphous fluorine-based polymer, and at or near the glass transition temperature. When heated above,
It has been proposed that the pellicle film and the adhesive bond firmly (see Japanese Patent Laid-Open No. 6-67409). However, in this case, in order to obtain sufficient adhesion strength when bonding the film and the frame, When heated above the glass transition temperature of the pellicle film-forming polymer, wrinkles and distortions tend to occur in the film itself,
It has been confirmed that if the heating temperature is set to the glass transition temperature or lower in order to prevent this, the adhesive strength becomes insufficient.

【0006】[0006]

【課題を解決するための手段】本発明はこのような不利
を解決したペリクル及びその製造方法に関するもので、
これはペリクル膜とフレームを該ペリクル膜と同等のポ
リマーからなる接着剤を用いて接着する工程において、
該ペリクル膜と該フレームを該接着剤を介して密着させ
たのち、該ペリクル膜と同等のポリマーを溶解した有機
溶剤溶液を該ペリクル膜の上から該フレーム上面の形に
合せて塗布し、加熱して該ペリクル膜と該フレームを接
着してなることを特徴とするものである。
SUMMARY OF THE INVENTION The present invention relates to a pellicle and a method for manufacturing the pellicle, in which such disadvantages are solved.
This is because in the process of bonding the pellicle film and the frame with an adhesive made of the same polymer as the pellicle film,
After the pellicle film and the frame are brought into close contact with each other via the adhesive, an organic solvent solution in which a polymer equivalent to the pellicle film is dissolved is applied from above the pellicle film in conformity with the shape of the upper surface of the frame and heated. Then, the pellicle film and the frame are bonded to each other.

【0007】すなわち、本発明者らはペリクル膜とフレ
ームが強固に接着され、接着後もシワや歪みなどの発生
しないペリクルを開発すべく種々検討した結果、これに
ついてはペリクル膜とフレームを該ペリクル膜と同等の
ポリマーからなる接着剤を用いて接着するときに、ペリ
クル膜とフレームを該接着剤で密着後、該ペリクル膜と
同等のポリマーを溶解した有機溶剤溶液を該ペリクル膜
の上から該フレーム上面の形に合せて塗布し、加熱して
ペリクル膜とフレームを接着してなるものであることか
ら、ペリクル膜とフレームが強く接着されたものとなる
ことを見出すと共に、接着剤による接着および溶液の乾
燥の際に、膜に加える温度もこのポリマーのガラス転移
温度以下でよいので、接着後このペリクル膜にシワや歪
みの発生することがないということを確認して本発明を
完成させた。以下にこれをさらに詳述する。
That is, the inventors of the present invention have conducted various studies to develop a pellicle in which the pellicle film and the frame are firmly bonded and wrinkles and distortion do not occur even after bonding. As a result, the pellicle film and the frame are When using an adhesive composed of a polymer equivalent to the film, the pellicle film and the frame are adhered to each other with the adhesive, and then an organic solvent solution in which a polymer equivalent to the pellicle film is dissolved is applied from above the pellicle film. It is found that the pellicle film and the frame are strongly adhered to each other because the pellicle film and the frame are adhered to each other by applying them according to the shape of the upper surface of the frame and heating them to bond them together. When the solution is dried, the temperature applied to the film may be below the glass transition temperature of this polymer, so wrinkles and distortions may occur in this pellicle film after adhesion. It was completed by the present invention confirmed that there is no. This will be described in more detail below.

【0008】[0008]

【作用】本発明はペリクル及びその製造方法に関するも
のであり、これは上記したようにペリクル膜とフレーム
を該ペリクル膜と同等のポリマーからなる接着剤を用い
て接着する工程において、ペリクル膜とフレームを該接
着剤で密着後該ペリクル膜と同様のポリマーを溶解した
溶液を該ペリクル膜の上から塗布し、加熱してペリクル
膜とフレームを接着させることを特徴とするものであ
り、これによればペリクルにはペリクル膜とフレームと
が強く接着されており、このペリクル膜にはシワや歪み
の発生することもないという有利性が与えられる。
The present invention relates to a pellicle and a method for producing the pellicle, which is used in the step of adhering the pellicle film and the frame with an adhesive made of a polymer equivalent to the pellicle film as described above. Is adhered with the adhesive and then a solution in which a polymer similar to that of the pellicle film is dissolved is applied from above the pellicle film, and the pellicle film and the frame are adhered by heating. For example, the pellicle film and the frame are strongly adhered to the pellicle, and this pellicle film is advantageous in that wrinkles and distortion do not occur.

【0009】本発明のペリクルの製造方法はペリクル膜
とフレームとを該ペリクル膜と同等のポリマーからなる
接着剤を用いて接着する際ペリクル膜とフレームを接着
剤で密着後、ペリクル膜と同等のポリマーを溶解した有
機溶媒溶液を用いてペリクル膜の上から塗布し、ペリク
ル膜をフレームに接着させたものである。このペリクル
膜は従来公知のいずれの種類のものであってもよく、こ
れにはニトロセルロース、酢酸セルロース、プロピオン
酸セルロース、非晶質のフッ素ポリマーとしてのパーフ
ルオロ(ブテニルビニルエーテル)重合体、テトラフル
オロエチレンとパーフルオロ(2,2−ジメチル−1,
3−ジオキソール)との共重合体などが例示され、これ
についてはこの接着剤を従来公知のアクリル樹脂やエポ
キシ樹脂の代わりに、ペリクル膜と同等のポリマーを使
用することも提案されており、これによってもかなり強
い接着強度が与えられるけれども、この場合には充分な
接着強度を得るためにはそのポリマーのガラス転移点以
上に加熱することが必要でその為にペリクル膜にしわや
歪が発生しやすいという問題があった。
According to the method of manufacturing a pellicle of the present invention, when the pellicle film and the frame are adhered to each other by using an adhesive made of a polymer equivalent to the pellicle film, the pellicle film and the frame are adhered to each other with the adhesive and then the pellicle film An organic solvent solution in which a polymer is dissolved is applied from above the pellicle film, and the pellicle film is adhered to the frame. This pellicle membrane may be of any conventionally known type, including nitrocellulose, cellulose acetate, cellulose propionate, perfluoro (butenyl vinyl ether) polymer as an amorphous fluoropolymer, and tetrapolymer. Fluoroethylene and perfluoro (2,2-dimethyl-1,
3-dioxole) and the like, and it is proposed to use a polymer equivalent to the pellicle film for this adhesive instead of the conventionally known acrylic resin or epoxy resin. Also gives a fairly strong adhesive strength, but in this case it is necessary to heat above the glass transition point of the polymer in order to obtain sufficient adhesive strength, which causes wrinkles and distortions in the pellicle film. There was a problem that it was easy.

【0010】しかし、この接着剤をこのペリクル膜と同
等のポリマーを溶解した有機溶剤溶液で溶解接着する
と、このものはペリクル膜と同等のポリマーを含んでい
るので、ペリクル膜との接着強度が上昇するし、粘度も
あるので、塗布の位置精度や溶解接着の際の溶解スピー
ドも安定し、このポリマーのガラス転移点以下の温度で
接着出来るのでペリクル膜にシワや歪みが発生すること
もなくなるという有利性が与えられる。
However, when this adhesive is dissolved and adhered in an organic solvent solution in which a polymer equivalent to this pellicle film is dissolved, since this adhesive contains a polymer equivalent to the pellicle film, the adhesive strength with the pellicle film increases. However, since it has viscosity, the position accuracy of application and the dissolution speed at the time of dissolution adhesion are stable, and since it can be adhered at a temperature below the glass transition point of this polymer, wrinkles and distortion will not occur in the pellicle film. Advantages are given.

【0011】なお、このものにおけるペリクル膜と同等
のポリマーを溶解した溶液中におけるポリマーの濃度
は、パーフルオロ(ブテニルビニルエーテル)重合体の
場合は1.0重量%未満ではこの溶液の粘度が 30cps未満
で塗布の際広がりすぎてしまい、位置精度が高めにくく
なるため、この濃度は1重量%以上とすることが必要で
あり、又15.0重量%を超える場合は溶液の粘度が上がっ
てしまいペリクル膜への浸透性が低下するため充分な接
着力が得られない。
The concentration of the polymer in the solution in which the polymer equivalent to the pellicle film is dissolved is less than 1.0% by weight in the case of the perfluoro (butenyl vinyl ether) polymer, and the viscosity of this solution is less than 30 cps. Since it spreads too much at the time of application and it is difficult to improve the position accuracy, it is necessary to set this concentration to 1% by weight or more. If it exceeds 15.0% by weight, the viscosity of the solution will increase and the pellicle film Sufficient adhesive strength cannot be obtained because the permeability decreases.

【0012】[0012]

【実施例】つぎに本発明の実施例、比較例をあげる。 実施例1 パーフルオロ(ブテニルビニルエーテル)重合体・サイ
トップCTXSタイプ[旭硝子(株)製商品名]をその
溶媒としての CT solv 180[旭硝子(株)製商品名]に
溶解して濃度5%(濃度は重量%を示す、以下同じ)の
溶液を調製した。ついで、この溶液を直径 200mm、厚さ
3mmの表面研磨した石英基板面に、スピンコーターを用
いて膜厚が0.84μmの透明膜を形成させ、 180℃で15分
間乾燥してペリクル膜を形成した。
EXAMPLES Next, examples and comparative examples of the present invention will be described. Example 1 Perfluoro (butenyl vinyl ether) polymer / CYTOP CTXS type [trade name of Asahi Glass Co., Ltd.] was dissolved in CT solv 180 (trade name of Asahi Glass Co., Ltd.) as a solvent to have a concentration of 5%. A solution (concentration indicates weight%, the same applies hereinafter) was prepared. Then, this solution was used to form a transparent film with a thickness of 0.84 μm using a spin coater on the surface of a quartz substrate having a diameter of 200 mm and a thickness of 3 mm, and dried at 180 ° C. for 15 minutes to form a pellicle film. .

【0013】つぎに、ペリクルフレームとしてのアルマ
イト処理をした 120mm角のアルミニウムフレームの上面
に、パーフルオロ(ブテニルビニルエーテル)重合体・
サイトップCTXSタイプ(前出)をその溶媒・ CT so
lv 180(前出)に溶解した10%濃度のフッ素ポリマー接
着剤を塗布し、 150℃で1時間乾燥して厚みが 0.2mmの
接着剤層を形成したのち、これに上記で得たペリクル膜
を3分間 100℃に加熱し押しつけて密着させ、この膜の
上からパーフルオロ(ブテニルビニルエーテル)重合体
・サイトップCTXSタイプ(前出)をその溶媒・ CT
solv 180(前出)に溶解した3%濃度のフッ素系ポリマ
ー溶液をペリクル膜の上よりフレームの上面の形に合せ
て塗布し、フレーム温度が 100℃になるように乾燥機で
10分間加熱乾燥してペリクル膜とペリクルフレームを接
着させたのち、余分な膜を取り除いたところ、外観が良
好で膜の接着強度が 150gf/cm2であるペリクルが得られ
た。
Next, a perfluoro (butenyl vinyl ether) polymer /
CYTOP CTXS type (above) is the solvent, CT so
Fluoropolymer adhesive with a concentration of 10% dissolved in lv 180 (above) was applied and dried at 150 ° C for 1 hour to form an adhesive layer with a thickness of 0.2 mm, and then the pellicle film obtained above Is heated to 100 ° C for 3 minutes and pressed to adhere, then perfluoro (butenyl vinyl ether) polymer / Cytop CTXS type (above) is used as the solvent / CT.
Apply a 3% concentration fluorine-based polymer solution dissolved in solv 180 (above) according to the shape of the upper surface of the frame from above the pellicle film, and dry with a dryer so that the frame temperature becomes 100 ° C.
After heating and drying for 10 minutes to bond the pellicle film and the pellicle frame, the excess film was removed, and a pellicle having a good appearance and a film adhesive strength of 150 gf / cm 2 was obtained.

【0014】実施例2 テトラフルオロエチレンとパーフルオロ(2,2−ジメ
チル−1,3−ジオキソール)との共重合体・テフロン
AF1600[米国デュポン社製商品名]をその溶剤・フロ
リナートFC−75[住友スリーエム(株)製商品名]に
溶解して濃度3%の溶液を調製し、この溶液を直径 200
mm、厚さ3mmの表面研磨した石英基板面に、スピンコー
ターを用いて膜厚が0.84μmの透明膜を形成させ、 180
℃で15分間乾燥してペリクル膜を形成させた。
Example 2 A copolymer of tetrafluoroethylene and perfluoro (2,2-dimethyl-1,3-dioxole), Teflon AF1600 [trade name of DuPont, USA] was used as its solvent, Fluorinert FC-75 [ Sumitomo 3M Co., Ltd. product name] to prepare a solution with a concentration of 3%, and this solution has a diameter of 200
The surface of a quartz substrate with a thickness of 3 mm and a thickness of 3 mm was polished to form a transparent film with a thickness of 0.84 μm using a spin coater.
Pellicle film was formed by drying at 15 ° C for 15 minutes.

【0015】ついで、ペリクルフレームとしてのアルマ
イト処理をした 120mm角のアルミニウムフレームの上面
に、上記したてテフロンAF1600(前出)をその溶媒・
フロリナートFC−75(前出)に溶解した濃度10%のフ
ッ素ポリマー接着剤を塗布し、 150℃で1時間乾燥し厚
みが 0.2mmの接着層を形成し、これに上記で得たペリク
ル膜を3分間 150℃で加熱し押しつけて密着させ、この
膜の上からフレーム上面の形に合わせて、上記したテフ
ロンAF1600(前出)をその溶媒・フロリナートFC−
75(前出)に溶解した濃度1%のフッ素系ポリマー溶液
を塗布し、フレーム温度が 150℃になるように乾燥機で
10分間加熱乾燥してペリクル膜とペリクルフレームを接
着させたのち、余分な膜を除去したところ、外観が良好
で膜の接着強度が 140gf/cm2であるペリクルが得られ
た。
Then, the above-mentioned Teflon AF1600 (above) is used as a solvent on the upper surface of a 120 mm square aluminum frame that has been anodized as a pellicle frame.
A fluoropolymer adhesive with a concentration of 10% dissolved in Fluorinert FC-75 (described above) was applied and dried at 150 ° C for 1 hour to form an adhesive layer with a thickness of 0.2 mm, on which the pellicle film obtained above was applied. Heat at 150 ° C for 3 minutes and press it into intimate contact to match the shape of the upper surface of the frame from the top of this film, and use the above-mentioned Teflon AF1600 (solvent) Fluorinert FC-
75% (described above) is coated with a 1% concentration of fluoropolymer solution and dried in a dryer so that the flame temperature is 150 ° C.
After heating and drying for 10 minutes to bond the pellicle film and the pellicle frame, the excess film was removed, and a pellicle having a good appearance and a film adhesive strength of 140 gf / cm 2 was obtained.

【0016】実施例3 プロピオン酸セルロースをその溶媒としての2−ブタノ
ンに溶解して濃度5%の溶液を調製し、この溶液を直径
200mm、厚さ3mmの表面研磨した石英基板上に、スピン
コーターを用いて膜厚が 1.4μmの透明膜を形成させ、
150℃で20分間乾燥してペリクル膜を形成させた。
Example 3 Cellulose propionate was dissolved in 2-butanone as a solvent to prepare a solution having a concentration of 5%.
Using a spin coater to form a transparent film with a thickness of 1.4 μm on a quartz substrate with a surface of 200 mm and a thickness of 3 mm,
It was dried at 150 ° C. for 20 minutes to form a pellicle film.

【0017】ついで、アルマイト処理をした 120mm角の
アルミニウムフレームからなるペリクルフレームの上面
に、プロピオン酸セルロースをその溶媒としての2−ブ
タノンに溶解した濃度20%の接着剤溶液を塗布し、 150
℃で20分間乾燥して厚みが0.2mm の接着剤層を形成させ
たのち、これに上記で得たペリクル膜を3分間90℃に加
熱し押しつけて密着させ、この膜の上からフレーム上面
の形に合わせてプロピオン酸セルロースを2−ブタノン
に溶解した濃度2%の溶液を塗布し、フレーム温度が90
℃になるように乾燥機で10分間加熱乾燥しペリクル膜と
ペリクルフレームを接着させたのち、余分な膜を除去し
たところ、外観が良好で膜の接着強度が125gf/cm2であ
るペリクルが得られた。
Then, an adhesive solution having a concentration of 20% in which 2-propanate cellulose was dissolved in 2-butanone as a solvent was applied to the upper surface of a pellicle frame composed of an alumite-treated 120 mm square aluminum frame.
After drying at ℃ for 20 minutes to form an adhesive layer with a thickness of 0.2 mm, the pellicle film obtained above is heated at 90 ℃ for 3 minutes to make it adhere. Apply a solution of cellulose propionate dissolved in 2-butanone at a concentration of 2% according to the shape, flame temperature 90
The pellicle film and pellicle frame were bonded by heating and drying in a dryer at 10 ° C for 10 minutes, and then the excess film was removed.A pellicle with a good appearance and a film adhesion strength of 125 gf / cm 2 was obtained. Was given.

【0018】比較例1 パーフルオロ(ブテニルビニルエーテル)重合体・サイ
トップCTXSタイプ(前出)をその溶媒である CT so
lv 180(前出)に溶解して濃度5%の溶液を調製し、こ
の溶液を直径 200mm、厚さ3mmの表面研磨した石英基板
面に、スピンコーターを用いて膜厚が0.84μmの透明膜
を形成させ、 180℃で15分間乾燥してペリクル膜を形成
した。
Comparative Example 1 Perfluoro (butenyl vinyl ether) polymer / CYTOP CTXS type (supra) was used as its solvent CT so.
A solution with a concentration of 5% was prepared by dissolving it in lv 180 (described above), and this solution was applied to a surface-polished quartz substrate surface with a diameter of 200 mm and a thickness of 3 mm using a spin coater to form a transparent film with a thickness of 0.84 μm. Was formed and dried at 180 ° C. for 15 minutes to form a pellicle film.

【0019】ついで、ペリクルフレームとしてのアルマ
イト処理をした 120mm角のアルミニウムフレームの上面
に、パーフルオロ(ブテニルビニルエーテル)重合体・
サイトップCTXAタイプ(前出)を溶媒 CT solv 180
(前出)に溶解した10%濃度のフッ素ポリマー接着剤を
塗布し、 150℃で1時間乾燥し厚みが 0.2mmの接着剤層
を形成した後、これに上記で得たペリクル膜を3分間 1
00℃に加熱し押しつけ密着させ、この膜の上からフレー
ム上面の形に合わせて、溶媒 CT solv 100(前出)を塗
布し、フレーム温度が 100℃になるように乾燥機で10分
間加熱乾燥しペリクル膜とペリクルフレームを接着させ
たのち、余分な膜を取り除いたところ、得られたペリク
ルは塗布した CT solv 100(前出)の粘度が低すぎて、
フレーム端面の幅から溶媒がはみ出したために外観が悪
かった。なお膜の接着強度は 125gf/cm2であった。
Then, on the upper surface of the 120 mm square aluminum frame which was anodized as the pellicle frame, a perfluoro (butenyl vinyl ether) polymer.
CYTOP CTX A type (above) as solvent CT solv 180
A fluoropolymer adhesive with a concentration of 10% dissolved in (above) was applied and dried at 150 ° C for 1 hour to form an adhesive layer with a thickness of 0.2 mm, and then the pellicle film obtained above was applied for 3 minutes. 1
Heat to 00 ℃ and press them into close contact, apply the solvent CT solv 100 (described above) from the top of this film according to the shape of the top of the frame, and heat dry for 10 minutes with a dryer so that the frame temperature becomes 100 ℃. After adhering the pellicle film and pellicle frame, the excess film was removed, and the resulting pellicle had too low a viscosity of the applied CT solv 100 (described above),
The external appearance was poor because the solvent had overflowed from the width of the frame end face. The adhesive strength of the film was 125 gf / cm 2 .

【0020】比較例2 比較例1と同様の方法でパーフルオロ(ブテニルビニル
エーテル)重合体・サイトップCTXSタイプ(前出)
の0.84μmのペリクル膜を作製し、アルマイト処理をし
た 120mm角のアルミニウムフレームの上面に、パーフル
オロ(ブテニルビニルエーテル)重合体・サイトップC
TXAタイプ(前出)を溶媒 CT solv 180(前出)に溶
解した10%濃度のフッ素ポリマー接着剤を塗布し 150℃
で1時間乾燥し厚みが 0.2mmの接着剤層を形成した後、
これに上記で得たペリクル膜を3分間 100℃に加熱し押
しつけ密着させ、この膜の上からフレーム上面の形に合
わせて、パーフルオロ(ブテニルビニルエーテル)重合
体・サイトップCTXSタイプ(前出)をその溶媒 CT
solv 100(前出)に溶解した16%濃度のフッ素ポリマー
溶液を塗布し、フレーム温度が 100℃になるように乾燥
機で10分間加熱乾燥しペリクル膜とペリクルフレームを
接着させたのち、余分な膜を取り除いたところ、得られ
たペリクルは塗布した溶液の濃度が高すぎたために塗布
した場所が盛り上がって外観の悪いものとなり、また溶
液の溶解度が低かったために十分な接着強度が得られ
ず、接着強度も10gf/cm2以下であった。
Comparative Example 2 A perfluoro (butenyl vinyl ether) polymer / CYTOP CTXS type (described above) was prepared in the same manner as in Comparative Example 1.
A 0.84 μm pellicle film was prepared, and a perfluoro (butenyl vinyl ether) polymer / CYTOP C was applied to the upper surface of a 120 mm square aluminum frame that had been anodized.
TXA type (above) was dissolved in the solvent CT solv 180 (above) and applied with a 10% concentration fluoropolymer adhesive.
After drying for 1 hour to form an adhesive layer with a thickness of 0.2 mm,
The pellicle film obtained above was heated to 100 ° C. for 3 minutes to press it into close contact, and the perfluoro (butenyl vinyl ether) polymer / CYTOP CTXS type (see above ) Its solvent CT
Apply a 16% concentration fluoropolymer solution dissolved in solv 100 (described above), heat and dry for 10 minutes in a dryer so that the frame temperature becomes 100 ° C, and bond the pellicle membrane and pellicle frame. When the film was removed, the resulting pellicle had a too high concentration of the applied solution, resulting in a raised appearance at the applied place and poor appearance, and sufficient solubility was not obtained because the solubility of the solution was low, The adhesive strength was also 10 gf / cm 2 or less.

【0021】[0021]

【発明の効果】本発明はペリクル及びその製造方法に関
するものであり、これは前記したようにペリクル膜とフ
レームを該ペリクル膜と同等のポリマーからなる接着剤
を用いて接着する工程において、ペリクル膜とフレーム
を接着剤で密着後、該ペリクル膜と同等のポリマーを溶
解した有機溶媒溶液を該ペリクル膜の上から塗布し加熱
して接着させることを特徴とするものであるが、これに
よればシワや歪みのない、強力に接着した膜を有するペ
リクルを得ることができる。
The present invention relates to a pellicle and a method for producing the pellicle, which is used in the step of adhering the pellicle film and the frame with an adhesive made of a polymer equivalent to the pellicle film as described above. And the frame are adhered to each other with an adhesive, and then an organic solvent solution in which a polymer equivalent to the pellicle film is dissolved is applied from above the pellicle film and heated to be adhered. It is possible to obtain a pellicle having a strongly adhered film without wrinkles or distortion.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 永田 愛彦 群馬県安中市磯部2丁目13番1号 信越化 学工業株式会社精密機能材料研究所内 (72)発明者 樫田 周 群馬県安中市磯部2丁目13番1号 信越化 学工業株式会社精密機能材料研究所内 (72)発明者 久保田 芳宏 群馬県安中市磯部2丁目13番1号 信越化 学工業株式会社精密機能材料研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Aihiko Nagata 2-13-1, Isobe, Annaka City, Gunma Prefecture Shin-Etsu Kagaku Kogyo Co., Ltd., Institute for Precision Materials (72) Inventor Shu Kashida Annaka City, Gunma Prefecture 2-13-1, Isobe Shin-Etsu Chemical Co., Ltd. Precision Materials Research Laboratory (72) Inventor Yoshihiro Kubota 2-1-1, Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Industry Co., Ltd.

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 ペリクル膜とフレームを該ペリクル膜と
同等のポリマーからなる接着剤を用いて接着する工程に
おいて、該ペリクル膜と該フレームを該接着剤を介して
密着させたのち、該ペリクル膜と同等のポリマーを溶解
した有機溶媒溶液を該ペリクル膜の上から該フレーム上
面の形に合わせて塗布し、加熱して該ペリクル膜と該フ
レームを接着してなることを特徴とするペリクル。
1. In the step of adhering the pellicle film and the frame with an adhesive made of a polymer equivalent to the pellicle film, the pellicle film and the frame are adhered to each other via the adhesive, and then the pellicle film is adhered. A pellicle characterized in that an organic solvent solution in which a polymer equivalent to the above is dissolved is applied from above the pellicle film according to the shape of the upper surface of the frame and heated to bond the pellicle film and the frame.
【請求項2】 ペリクル膜とフレームを該ペリクル膜と
同等のポリマーからなる接着剤を用いて接着する工程に
おいて、該ペリクル膜と該フレームを該接着剤を介して
密着させたのち、該ペリクル膜と同等のポリマーを溶解
した有機溶媒溶液を該ペリクル膜の上から該フレーム上
面の形に合わせて塗布し、加熱して該ペリクル膜と該フ
レームを接着することを特徴とするペリクルの製造方
法。
2. In the step of adhering the pellicle film and the frame using an adhesive made of a polymer equivalent to the pellicle film, the pellicle film and the frame are adhered to each other via the adhesive, and then the pellicle film is attached. A method for producing a pellicle, which comprises applying an organic solvent solution in which a polymer equivalent to the above is dissolved in conformity with the shape of the upper surface of the frame from above the pellicle film and heating to bond the pellicle film and the frame.
JP10356495A 1994-07-11 1995-04-27 Pellicle manufacturing method Expired - Fee Related JP3429898B2 (en)

Priority Applications (1)

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Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP15884594 1994-07-11
JP6-158845 1994-10-25
JP25993694 1994-10-25
JP6-259936 1994-10-25
JP10356495A JP3429898B2 (en) 1994-07-11 1995-04-27 Pellicle manufacturing method

Publications (2)

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JPH08179495A true JPH08179495A (en) 1996-07-12
JP3429898B2 JP3429898B2 (en) 2003-07-28

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ID=27310022

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0759576A2 (en) * 1995-07-27 1997-02-26 Micro Lithography, Inc. Method for making an optical pellicle
US5769984A (en) * 1997-02-10 1998-06-23 Micro Lithography, Inc. Optical pellicle adhesion system
US5772817A (en) * 1997-02-10 1998-06-30 Micro Lithography, Inc. Optical pellicle mounting system

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0759576A2 (en) * 1995-07-27 1997-02-26 Micro Lithography, Inc. Method for making an optical pellicle
EP0759576A3 (en) * 1995-07-27 1998-04-29 Micro Lithography, Inc. Method for making an optical pellicle
US5769984A (en) * 1997-02-10 1998-06-23 Micro Lithography, Inc. Optical pellicle adhesion system
US5772817A (en) * 1997-02-10 1998-06-30 Micro Lithography, Inc. Optical pellicle mounting system
KR19980070713A (en) * 1997-02-10 1998-10-26 옌융-차이 Optical pellicle mounting system
KR100529696B1 (en) * 1997-02-10 2006-03-16 마이크로 리쏘그래피 인코포레이티드 Optical pellicle bonding system

Also Published As

Publication number Publication date
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