JPH1152102A - Optical member for excimer laser, its temporarily protecting method and projection aligner - Google Patents

Optical member for excimer laser, its temporarily protecting method and projection aligner

Info

Publication number
JPH1152102A
JPH1152102A JP9211058A JP21105897A JPH1152102A JP H1152102 A JPH1152102 A JP H1152102A JP 9211058 A JP9211058 A JP 9211058A JP 21105897 A JP21105897 A JP 21105897A JP H1152102 A JPH1152102 A JP H1152102A
Authority
JP
Japan
Prior art keywords
optical member
protective film
excimer laser
film
optical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP9211058A
Other languages
Japanese (ja)
Inventor
Izumi Motoyama
いづみ 元山
Norio Kaneko
則夫 金子
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.)
Nikon Corp
Original Assignee
Nikon Corp
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 Nikon Corp filed Critical Nikon Corp
Priority to JP9211058A priority Critical patent/JPH1152102A/en
Publication of JPH1152102A publication Critical patent/JPH1152102A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

PROBLEM TO BE SOLVED: To prevent the lowering of the transmissivity of an optical system and to ensure sufficient exposure by forming a fluorocarbon group-contg. protective film on the top of an optical member and removing it before the projection exposure of a pattern formed on a mask to the surface of a substrate. SOLUTION: A chemically adsorbed monomolecular film (fluorocarbon group 3a-contg. protective film) 3 of a silane compd. having an alkoxysilyl or halogenated silyl group at one terminal and a fluorocarbon group 3a at the other terminal (fluorocarbon silane compd.) is formed on the top of an optical member 1 coated with an antireflection or reflection film 2 through M (metal)-O- Si bonds (siloxane bonds) 3b on the film 2. The resultant optical member is applied to a projection optical system and the protective film 3 on the top of the optical member 1 is removed with UV as light for exposure before the projection exposure of a pattern formed on a mask to the surface of a substrate. The surface of the optical member 1 can be made clean.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、エキシマレーザー
用光学部材、仮保護方法に関するものであり、特にその
光学部材は、投影露光装置の光学系に用いられる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical member for an excimer laser and a temporary protection method, and more particularly, the optical member is used for an optical system of a projection exposure apparatus.

【０００２】[0002]

【従来の技術】投影露光装置用光学部材に限らず、光学
部材に分類される部材は、表面に付着する異物の存在
が、光線の透過率低下や照度ムラ等の原因となり、本来
持つべき光学性能が得られなくなるため、種々の対策が
講じられてきた。眼鏡レンズや自動車のフロントガラス
といった主に水滴によるくもりを嫌う部材では、最上層
に界面活性剤含有防曇剤を塗布したり（特開昭５６−９
０８７６号公報）、表面粗さを粗にして表面積を大きく
することによって濡れ性を増加させて防曇したり（特開
昭５５−１５４３４８号公報）、逆にフッ素を有する物
質や疎水性ポリマーでコーティングすることによって水
滴の付着を防止する方法（特開昭５４−７４２９１号公
報）も採られてきた。また、カメラや投影露光装置に組
み込まれる光学部材のような水分だけでなく有機系汚染
物質の付着を嫌う部材には、光触媒である酸化チタン膜
を成膜し有機系汚染物質を分解する作用を備えたり（特
開平０８−３１３７０５号公報）、酸化珪素膜を緻密に
成膜し表面積を小さくすることによって汚染物質の減量
を試みたり、フッ化炭素基を有する有機物膜を成膜して
汚染物質との密着性を小さくしていた（特開平６−５３
２４号公報）。2. Description of the Related Art Not only optical members for a projection exposure apparatus, but also members classified as optical members, the presence of foreign matter adhering to the surface causes a reduction in light transmittance and uneven illuminance, etc. Various measures have been taken to prevent performance from being obtained. For members that do not like cloudiness mainly due to water droplets, such as spectacle lenses and automobile windshields, a surfactant-containing anti-fog agent may be applied to the uppermost layer (see JP-A-56-9).
No. 0876), increasing the surface area by increasing the surface roughness to increase the wettability to prevent fogging (Japanese Patent Application Laid-Open No. 55-154348), or conversely using a substance containing fluorine or a hydrophobic polymer. A method of preventing adhesion of water droplets by coating (Japanese Patent Application Laid-Open No. 54-74291) has also been adopted. In addition, for members that do not want to adhere not only to water but also to organic contaminants such as optical members incorporated in cameras and projection exposure equipment, a titanium oxide film as a photocatalyst is formed to decompose organic contaminants. (Japanese Patent Application Laid-Open No. 08-313705), attempts to reduce contaminants by forming a silicon oxide film densely and reducing the surface area, or forming an organic film having a fluorocarbon group to form contaminants (Japanese Unexamined Patent Publication No. 6-53)
No. 24).

【０００３】[0003]

【発明が解決しようとする課題】しかしながら、上記従
来の技術には以下のような問題点が指摘されている。最
上層に界面活性剤を塗布したり、表面粗さを粗にし表面
積を大きくすることによって濡れ性を増加させる方法で
は、その効果により表面に水分が多く存在することにな
り、水分を吸着剤として異物が付着したり、表面に存在
する水分が光学部材を浸食して劣化させるだけでなく、
短波長の光の透過率が低下するという問題もあった。ま
た、疎水性ポリマーによるコーティングは膜自体の耐久
性に乏しく、短波長側の光を透過しないだけでなく容易
に分解してしまうため、汚染源になってしまうのであ
る。However, the following problems have been pointed out in the above prior art. In the method of increasing the wettability by applying a surfactant to the top layer or increasing the surface area by roughening the surface roughness, the effect causes a large amount of moisture on the surface, and the moisture is used as an adsorbent In addition to foreign substances adhering and moisture existing on the surface eroding and degrading optical members,
There is also a problem that the transmittance of short-wavelength light decreases. Further, coating with a hydrophobic polymer has poor durability of the film itself, and not only does not transmit light on the short wavelength side, but also easily decomposes, and thus becomes a contamination source.

【０００４】酸化チタン膜はｉ線（３６５ｎｍ）のよう
な比較的長波長側の光に対する透過性は高いものの、Ｋ
ｒＦ及びＡｒＦレーザーのような短波長の光を吸収し透
過させないため、ＫｒＦやＡｒＦ、エックス線、電子線
等を光源とする投影露光装置においては、フォトレジス
ト硬化に必要な光量を供給することができなくなり、結
像性能を落とすだけでなく、長時間の使用下では、酸化
チタン膜の光の吸収により発生する熱等でコート膜の破
壊が生じ、レンズ交換を余儀なくされる。Although the titanium oxide film has a high transmittance for light having a relatively long wavelength such as i-line (365 nm), it has a high transmittance.
In order to absorb and not transmit short-wavelength light such as rF and ArF lasers, a projection exposure apparatus using KrF, ArF, X-ray, electron beam or the like as a light source can supply a light amount necessary for curing a photoresist. In addition to deteriorating the imaging performance, the coating film is destroyed by the heat or the like generated by the absorption of light of the titanium oxide film when used for a long time, and the lens must be replaced.

【０００５】また、酸化珪素膜の緻密化では、光学部材
の表面積が小さくなるため、汚染物質付着量の減少が見
込めるが、酸化珪素膜自体に防曇性が無いため付着した
汚染物質の除去に関しては効果が期待できない。フッ化
炭素基を有する有機物膜は酸化チタン膜同様、ｉ線（３
６５ｎｍ）のような比較的長波長側の光に対する透過性
は高いものの、ＫｒＦやＡｒＦレーザー、エックス線、
電子線のような短波長の光を吸収し透過させないだけで
なく、ＫｒＦ及びＡｒＦレーザー、エックス線、電子線
等の照射によってフッ化炭素基を有する有機物膜自体が
分解してしまうという問題点があった。In the case of densification of the silicon oxide film, the surface area of the optical member is reduced, so that the amount of contaminants attached can be expected to decrease. However, since the silicon oxide film itself has no antifogging property, it is necessary to remove the contaminants attached. Cannot be expected to be effective. The organic film having a fluorocarbon group is the same as the titanium oxide film in the i-line (3
65 nm), but has a high transmittance for light having a relatively long wavelength, such as KrF or ArF laser, X-ray,
In addition to absorbing and not transmitting short-wavelength light such as an electron beam, there is a problem that an organic material film having a fluorocarbon group itself is decomposed by irradiation with a KrF or ArF laser, X-ray, electron beam or the like. Was.

【０００６】一方、光学部材の表面に付着した有機物等
の汚染物質の除去方法として、光洗浄が用いられるが、
有機物質等と光学部材表面が化学反応して光学部材の表
面が変質した場合には、光洗浄によっては、除去するこ
とができないという問題がある。そこで、本発明は、こ
れらの問題点に鑑み、有機物等の汚染物質の付着を抑制
し、かつ光学系に組み込んで使用する場合に透過率が低
下せず、露光光を確保することが可能な光学部材、その
使用方法を提供することを目的とする。On the other hand, light cleaning is used as a method for removing contaminants such as organic substances attached to the surface of an optical member.
When the surface of the optical member is altered due to a chemical reaction between the organic material and the surface of the optical member, there is a problem that the surface cannot be removed by light cleaning. Therefore, the present invention has been made in view of these problems, and suppresses the attachment of contaminants such as organic substances, and does not decrease the transmittance when used by being incorporated into an optical system, and can secure exposure light. It is an object to provide an optical member and a method for using the same.

【０００７】[0007]

【課題を解決するための手段】本発明では前記フッ化炭
素基を有する有機物膜の問題点を利点として応用するも
のであり、上記フッ化炭素基を有する有機物膜を保護膜
として使用し、光学部材の製造終了から投影露光装置内
への光学部材組み込み完了までの間の汚染物質付着を防
止し、投影露光装置内への光学部材組み込み完了後、保
護膜を除去するものである。In the present invention, the problem of the organic film having a fluorocarbon group is applied as an advantage. The organic film having a fluorocarbon group is used as a protective film, The purpose is to prevent contaminants from adhering during the period from the end of the manufacture of the member to the completion of the incorporation of the optical member into the projection exposure apparatus, and after the incorporation of the optical member into the projection exposure apparatus, remove the protective film.

【０００８】本発明は、第一に「エキシマレーザー用の
光学薄膜２が形成された基板１の最上層に汚染物質の付
着を抑制する保護膜３を形成する工程と、前記保護膜３
を紫外線の照射により除去する工程と、を有すること特
徴とするエキシマレーザー用光学部材の仮保護方法（請
求項１）」を提供する。The present invention firstly comprises a step of forming a protective film 3 for suppressing the attachment of contaminants on the uppermost layer of the substrate 1 on which the optical thin film 2 for excimer laser is formed;
And a method of temporarily protecting the optical member for excimer laser (claim 1).

【０００９】請求項１記載の仮保護方法における光学部
材は、運搬、光学系への組み立て工程において、最上層
に設けられた汚染物質の付着を抑制する保護膜により、
有機物質等の汚染物質の付着を抑制することができる。
また、光学部材を光学系に組み込んだ後、光学系を使用
する前に、前記保護膜を紫外線により除去するので、透
過率は低下せず、充分な露光量を確保することができ
る。In the provisional protection method according to the first aspect, the optical member is provided with a protective film provided on the uppermost layer for suppressing adhesion of contaminants in a transportation and assembling process to the optical system.
Adhesion of contaminants such as organic substances can be suppressed.
Further, since the protective film is removed by ultraviolet rays after the optical member is incorporated in the optical system and before the optical system is used, the transmittance is not reduced and a sufficient exposure amount can be secured.

【００１０】また、本発明は、第二に「前記保護膜３
は、フッ化炭素基３ａを含み、シロキサン結合３ｂを介
して形成されてなることを特徴とする請求項１記載の仮
保護方法（請求項２）」を提供する。また、本発明は、
第三に「エキシマレーザー用の光学薄膜２が形成された
基板１の最上層に、汚染物質の付着を抑制し、紫外線照
射により除去可能な保護膜３が形成されてなるエキシマ
レーザー用光学部材（請求項３）」を提供する。The present invention also relates to a second aspect of the invention.
(1) comprises a fluorocarbon group 3a and is formed via a siloxane bond 3b. Also, the present invention
Thirdly, an “optical member for excimer laser, in which a protective film 3 that suppresses adhesion of contaminants and is removable by ultraviolet irradiation is formed on the uppermost layer of the substrate 1 on which the optical thin film 2 for excimer laser is formed ( Claim 3) "is provided.

【００１１】請求項３記載の光学部材は、最上層に汚染
物質の付着を抑制し、紫外線照射により除去可能な保護
膜が設けられているので、運搬、光学系への組み立て工
程において、有機物等の汚染物質の付着を抑制すること
ができるとともに、光学部材を光学系に組み込んだ後、
光学系を使用する前に、前記保護膜を紫外線照射により
除去することにより、透過率を低下させずに、充分な露
光量を確保することができる。In the optical member according to the third aspect of the present invention, since a protective film which suppresses the attachment of contaminants and which can be removed by irradiating ultraviolet rays is provided on the uppermost layer, organic substances and the like can be used in the transportation and assembly steps to the optical system. After incorporating the optical member into the optical system,
By removing the protective film by irradiating ultraviolet rays before using the optical system, a sufficient exposure amount can be secured without lowering the transmittance.

【００１２】また、本発明は、第四に「前記保護膜３
は、フッ化炭素基３ａを含み、シロキサン結合３ｂを介
して形成されてなることを特徴とする請求項３記載のエ
キシマレーザー用光学部材（請求項４）」を提供する。
また、本発明は、第五に「マスクＲを照明する照明光学
系２１と、前記マスクＲに形成されたパターンを基板Ｗ
上に投影露光するための投影光学系２５と、を具備する
投影露光装置の初期化方法において、前記マスクＲに形
成されたパターンを基板Ｗ上に投影露光する前に、前記
光学系に組み込まれた光学部材の最上層に形成された汚
染物質の付着を抑制する保護膜３を、紫外線の照射によ
り除去する段階を備えたことを特徴とする投影露光装置
の初期化方法（請求項５）」を提供する。Further, the present invention is directed to a fourth aspect of the present invention, namely, "the protective film 3".
The present invention provides an optical member for an excimer laser according to claim 3, wherein the optical member includes a fluorocarbon group 3 a and is formed via a siloxane bond 3 b.
In addition, the present invention provides, fifthly, an illumination optical system 21 for illuminating the mask R and a pattern formed on the mask R by the substrate W
A projection optical system 25 for projecting and exposing the light onto the substrate W, wherein the pattern formed on the mask R is incorporated into the optical system before the pattern is exposed on the substrate W. A step of removing the protective film 3 formed on the uppermost layer of the optical member, which suppresses the adhesion of contaminants, by irradiating ultraviolet rays, wherein the method comprises the steps of: I will provide a.

【００１３】請求項５記載の投影露光装置の光学系に組
み込まれた光学部材の最上層には有機物等の汚染物質の
付着を防止する保護膜が設けられているので、組み立て
工程中付着するであろう有機物や水滴等の汚染物質の付
着を抑制し、光学部材の投影露光装置への組み込みまで
の間、光学部材表面の清浄性を維持することができる。
そのため、有機物質等と光学部材表面が化学反応して
光学部材の表面が変質することがない。According to a fifth aspect of the present invention, a protective film for preventing the attachment of contaminants such as organic substances is provided on the uppermost layer of the optical member incorporated in the optical system of the projection exposure apparatus. Adhesion of contaminants such as organic substances and water droplets which may be suppressed can be suppressed, and cleanliness of the optical member surface can be maintained until the optical member is incorporated into the projection exposure apparatus.
Therefore, the surface of the optical member is not deteriorated due to a chemical reaction between the organic material and the surface of the optical member.

【００１４】また、光学部材の最上層に設けられた保護
膜は、紫外線照射によって除去することが可能なので、
露光光によりマスクに形成されたパターンを基板上に投
影露光する前に、露光光を用いて除去することにより、
光学部材の最上層に保護膜を設けることによる光学系の
透過率低下を防止し、フォトレジスト硬化時に必要な光
量を供給することができる。Further, since the protective film provided on the uppermost layer of the optical member can be removed by irradiation with ultraviolet light,
Before projecting and exposing the pattern formed on the mask by exposure light onto the substrate, by removing using exposure light,
By providing a protective film on the uppermost layer of the optical member, it is possible to prevent a decrease in transmittance of the optical system and to supply a necessary amount of light at the time of curing the photoresist.

【００１５】保護膜は再汚染物質と成りうる分量が光学
部材表面に形成されていない上に、分解により低分子化
し気化するため、投影露光装置の鏡筒内に存在しても光
学特性に何ら影響を与えることはない。また、本発明
は、第六に「前記保護膜３は、フッ化炭素基３ａを含
み、シロキサン結合３ｂを介して形成されてなることを
特徴とする請求項５記載の投影露光装置の初期化方法
（請求項６）」を提供する。The protective film does not have an amount that can become a re-contaminant on the surface of the optical member and has a low molecular weight due to decomposition and is vaporized. Has no effect. In the sixth aspect of the present invention, the initialization of the projection exposure apparatus according to claim 5, wherein the protective film 3 includes a fluorocarbon group 3a and is formed via a siloxane bond 3b. A method (claim 6) is provided.

【００１６】[0016]

【発明の実施の形態】以下、本発明にかかる実施形態の
光学部材を図面を参照しながら説明する。図１は、本発
明にかかる実施形態の光学部材の概略断面図である。本
発明にかかる実施形態の光学部材は、反射防止膜又は反
射膜２が形成された光学部材１上に、一端にアルコキシ
シリル基又はハロゲン化シリル基を有し、他端にフッ化
炭素基３ａを有するシラン系化合物（以下、フッ化炭素
シラン系化合物という）の化学吸着単分子膜（フッ化炭
素基３ａを含んだ保護膜）３が反射防止膜又は反射膜２
と（Ｍ（メタル）−Ｏ−Ｓｉ）の形態の結合（シロキサ
ン結合）３ｂを介して形成されている。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an optical member according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view of an optical member according to an embodiment of the present invention. The optical member according to the embodiment of the present invention has an alkoxysilyl group or a halogenated silyl group at one end on the optical member 1 on which the antireflection film or the reflection film 2 is formed, and a fluorocarbon group 3a at the other end. A monolayer (a protective film containing a fluorocarbon group 3a) 3 of a silane-based compound (hereinafter referred to as a fluorocarbon silane-based compound) having
And (M (metal) -O-Si) bond (siloxane bond) 3b.

【００１７】光学部材１の材料としては、石英ガラス、
蛍石等が用いられる。フッ化炭素シラン系化合物として
は、 ＣＦ3ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3 ＣＦ3ＣＨ2ＣＨ2ＳｉＣｌ3 ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2ＳｉＣｌ3 ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3 ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3 ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2ＳｉＣｌ3 ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2ＳｉＣＨ3Ｃｌ2 ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2ＳｉＣＨ3（ＯＣＨ3）2 等が挙げられるが、フッ化炭素基３ａと光学薄膜と反応
する反応性基を有する化合物であれは、これに限定され
ない。The material of the optical member 1 is quartz glass,
Fluorite or the like is used. Examples of the fluorocarbon silane-based compound include CF 3 CH 2 CH 2 Si (OCH 3 ) 3 CF 3 CH 2 CH 2 SiCl 3 CF 3 (CF 2 ) 5 CH 2 CH 2 SiCl 3 CF 3 (CF 2 ) 5 CH 2 CH 2 Si (OCH 3) 3 CF 3 (CF 2) 7 CH 2 CH 2 Si (OCH 3) 3 CF 3 (CF 2) 7 CH 2 CH 2 SiCl 3 CF 3 (CF 2) 7 CH 2 CH 2 Examples include SiCH 3 Cl 2 CF 3 (CF 2 ) 7 CH 2 CH 2 SiCH 3 (OCH 3 ) 2 , and any compound having a reactive group that reacts with the fluorocarbon group 3a and the optical thin film is used. It is not limited to.

【００１８】特に、フッ化炭素シラン系化合物として
は、ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3が好
ましい。それは、Ｃ−Ｆ結合やＣ−Ｈ結合を多く含む化
合物は、これらの結合の分極率が低いことに起因して表
面自由エネルギー（表面の分子を内部に引きつける力）
が低くなる結果、各種の液体にぬれにくい特性を示す、
すなわち、高い撥水性を示すからである。 また、Ｃ−
Ｆ結合やＣ−Ｈ結合が多すぎると、液体物質の粘性が大
きくなり、逆に少なすぎると揮発性が大きくなり、取扱
い難くなるからである。Particularly, as the fluorocarbon silane-based compound, CF 3 (CF 2 ) 7 CH 2 CH 2 Si (OCH 3 ) 3 is preferable. Compounds containing many CF and CH bonds have low surface polar energies (the ability to attract surface molecules to the inside) due to the low polarizability of these bonds.
As a result, it shows properties that are difficult to wet with various liquids,
That is, high water repellency is exhibited. Also, C-
If the number of F bonds or C—H bonds is too large, the viscosity of the liquid substance increases, and if it is too small, the volatility increases and the handling becomes difficult.

【００１９】フッ化炭素シラン系化合物の炭素鎖の長さ
は、任意に選択可能であり、単分子膜の場合の膜厚は、
アルキル鎖の長さで決まる。次に、本発明にかかる実施
形態の光学部材の製造工程を示す。まず、光学部材１上
にエキシマレーザー用の反射防止膜又は反射膜２を形成
する。The length of the carbon chain of the fluorocarbon silane compound can be arbitrarily selected.
It is determined by the length of the alkyl chain. Next, a manufacturing process of the optical member according to the embodiment of the present invention will be described. First, an antireflection film or a reflection film 2 for excimer laser is formed on the optical member 1.

【００２０】次に、反射防止膜又は反射膜２が形成され
た光学部材１の表面をアルコールやアセトン等の有機溶
剤による拭き上げ又は超音波洗浄による洗浄により清浄
にする。また、光学部材表面を清浄かつ活性化させるた
めには、エキシマランプ（１７２ｎｍ）や低圧水銀ラン
プ（１８５ｎｍ、２５４ｎｍ）を用いて光洗浄を行うこ
とが有効である。Next, the surface of the optical member 1 on which the anti-reflection film or the reflection film 2 is formed is cleaned by wiping with an organic solvent such as alcohol or acetone or cleaning by ultrasonic cleaning. In order to clean and activate the optical member surface, it is effective to perform light cleaning using an excimer lamp (172 nm) or a low-pressure mercury lamp (185 nm, 254 nm).

【００２１】次に、図２に示すように、密閉容器４内の
上方に設けられたホルダーに光洗浄をした反射防止膜又
は反射膜２付きの前記光学部材１を設置し、液体フッ化
炭素シラン系化合物６で満たした容器７を前記光学部材
１の下側に設置した。図２は、本発明にかかる実施形態
の光学部材の製造方法における気相処理の工程を示す図
である。Next, as shown in FIG. 2, the optical member 1 provided with the anti-reflection film or the reflection film 2 which has been subjected to light cleaning is placed on a holder provided in the upper portion of the closed container 4 and the liquid fluorocarbon is provided. The container 7 filled with the silane compound 6 was placed below the optical member 1. FIG. 2 is a view illustrating a step of a gas phase treatment in the method for manufacturing an optical member according to the embodiment of the present invention.

【００２２】密閉容器４全体を５０℃〜１５０℃に加熱
し、液体フッ化炭素シラン系化合物６を蒸発させる。こ
れにより、フッ化炭素シラン分子の蒸気が密閉容器４内
の空間を満たし、前記光学部材１の表面で、フッ化炭素
シランのアルコキシシリル基と光学部材１上に形成され
た反射防止膜又は反射膜２の酸化物（酸化物以外の場合
は表面にできた自然酸化膜）の水酸基とが化学反応し、
光学部材１の表面全体にフッ化炭素シランの化学吸着単
分子膜３（以下、単分子膜という）が形成される。The whole closed container 4 is heated to 50 ° C. to 150 ° C. to evaporate the liquid fluorocarbon silane compound 6. As a result, the vapor of the fluorocarbon silane molecules fills the space in the closed vessel 4, and the alkoxysilyl group of the fluorocarbon silane and the antireflection film or the reflection film formed on the optical member 1 are formed on the surface of the optical member 1. Hydroxyl groups of oxides of the film 2 (natural oxide films formed on the surface in the case of other than oxides) chemically react with hydroxyl groups,
A chemically adsorbed monomolecular film 3 of fluorocarbon silane (hereinafter, referred to as a monomolecular film) is formed on the entire surface of the optical member 1.

【００２３】このとき、フッ化炭素シラン分子の一方の
端部のアルコキシシリル基又はハロゲン化シリル基が前
記光学部材上の反射防止膜と化学結合するため、フッ化
炭素シラン分子の他方の端部のフッ化炭素基３ａが、単
分子膜の表面側に位置することとなる。光学部材の最上
層にフッ化炭素基を含んだ保護膜を形成する方法とし
て、前記気相法の他に、フッ化炭素シラン系化合物をア
ルコールのような分散媒により分散させた液体中に、基
板を数１０分から数時間浸漬した後、高温雰囲気中でシ
ロキサン結合を完了させる。At this time, the alkoxysilyl group or the halogenated silyl group at one end of the fluorocarbon silane molecule is chemically bonded to the antireflection film on the optical member. Is located on the surface side of the monomolecular film. As a method of forming a protective film containing a fluorocarbon group on the uppermost layer of the optical member, in addition to the gas phase method, in a liquid in which a fluorocarbon silane-based compound is dispersed by a dispersion medium such as alcohol, After immersing the substrate for several tens of minutes to several hours, the siloxane bonding is completed in a high-temperature atmosphere.

【００２４】浸漬によるフッ化炭素シラン系化合物の基
板への成膜方法の他に、塗布による方法、吹き付けによ
る方法、スピンコートによる方法等が用いられる。ま
た、シロキサン結合の促進方法として、高温雰囲気中で
行う方法の他に、電子線照射や紫外線照射等による方法
がある。気相法を用いた場合は、単分子膜は、基板が大
口径であってもムラなく、均一に形成することができ
る。In addition to a method of forming a fluorocarbon silane-based compound on a substrate by immersion, a method of coating, a method of spraying, a method of spin coating, and the like are used. As a method for promoting siloxane bonding, there is a method using electron beam irradiation, ultraviolet irradiation, or the like, in addition to a method performed in a high-temperature atmosphere. When the vapor phase method is used, the monomolecular film can be uniformly formed without unevenness even if the substrate has a large diameter.

【００２５】保護膜の形成方法は、基板の形状や製造工
程に応じた方法を採用することが好ましい。本発明にか
かる光学部材の保護膜は、光学系への組み込み工程にお
ける光学部材の有機物質等による汚染を防止するため、
すなわち光学部材上に形成された光学薄膜と有機物質等
の汚染物質が反応して光洗浄では除去できない反応物が
形成されることを防止するために設けられたものであ
り、あくまでもこの保護膜の役割は、光学部材表面の仮
保護である。It is preferable to adopt a method according to the shape of the substrate and the manufacturing process as the method of forming the protective film. The protective film of the optical member according to the present invention, in order to prevent contamination of the optical member by organic substances and the like in the process of incorporating into the optical system,
That is, it is provided in order to prevent the optical thin film formed on the optical member from reacting with a contaminant such as an organic substance to form a reactant which cannot be removed by light cleaning. The role is to temporarily protect the optical member surface.

【００２６】従って、光学系内で使用する場合には、こ
の保護膜を除去する必要がある。この保護膜を光学系に
組み込んだ状態で除去する方法として、紫外線（４００
ｎｍ〜１００ｎｍ）を照射する方法が挙げられる。すな
わち、光学系の光学部材として使用されている石英ガラ
ス、蛍石の紫外線の透過率は、９０％以上であるので、
紫外線を光学系に照射すれば、光学系を構成しているす
べての光学部材の保護膜を容易に除去することができ
る。Therefore, when used in an optical system, it is necessary to remove this protective film. As a method of removing the protective film in a state of being incorporated in the optical system, an ultraviolet ray (400
nm to 100 nm). That is, since the transmittance of ultraviolet rays of quartz glass and fluorite used as optical members of the optical system is 90% or more,
By irradiating the optical system with ultraviolet rays, the protective films of all the optical members constituting the optical system can be easily removed.

【００２７】さらに、紫外線としてＫｒＦエキシマレー
ザー（２４８ｎｍ）、ＡｒＦエキシマレーザー（１９３
ｎｍ）を照射することが好ましい。図３は、本発明にか
かる光学部材におけるＡｒＦエキシマレーザー照射時間
と接触角の関係を示す図である。ここでは、ＡｒＦエキ
シマレーザーとは、波長が１９３ｎｍ、パルス巾４０ｎ
ｓｅｃのエキシマレーザーである。Further, KrF excimer laser (248 nm) and ArF excimer laser (193 nm) are used as ultraviolet rays.
nm). FIG. 3 is a diagram showing the relationship between ArF excimer laser irradiation time and contact angle in the optical member according to the present invention. Here, the ArF excimer laser has a wavelength of 193 nm and a pulse width of 40 n.
sec excimer laser.

【００２８】図３から保護膜成膜直後の接触角は、約１
１０度であるが、、ＡｒＦエキシマレーザーを約５分間
照射し続けると、約１０度以下になることがわかる。ま
た、保護膜成膜前の光学部材表面の接触角が約３０度だ
ったことを考慮すると、非常に速い速度で保護膜が光学
部材表面から離脱しているだけでなく、初期状態以上に
光学部材表面が清浄になっていることがわかる。FIG. 3 shows that the contact angle immediately after the formation of the protective film is about 1
Although it is 10 degrees, it can be seen that when the ArF excimer laser is continuously irradiated for about 5 minutes, it becomes about 10 degrees or less. Also, considering that the contact angle of the optical member surface before the formation of the protective film was about 30 degrees, not only the protective film detached from the optical member surface at a very high speed, but also the optical It can be seen that the member surface is clean.

【００２９】本実施例では、ＡｒＦエキシマレーザー照
射による保護膜の除去効果のみを示したが、ＫｒＦエキ
シマレーザー（２４８ｎｍ）やｉ線光（３６５ｎｍ）の
ようなＡｒＦエキシマレーザー（１９８ｎｍ）より波長
の長い光や、Ｆ2レーザー（１５７ｎｍ）のようにＡｒ
Ｆエキシマレーザーより短波長の光でも保護膜の除去は
可能である。その場合でも１００ｎｍ〜２５０ｎｍの光
を選択した方がより短時間に除去できる。In this embodiment, only the effect of removing the protective film by the ArF excimer laser irradiation is shown. light and, Ar as F 2 laser (157 nm)
It is possible to remove the protective film even with light having a shorter wavelength than the F excimer laser. Even in that case, it is possible to remove the light in a shorter time by selecting the light of 100 nm to 250 nm.

【００３０】さらに、光学部材の表面にフッ化炭素基を
含む保護膜を形成する代わりに、シリコンオイルの保護
膜を形成しても、光学部材への汚染物質の付着を抑制す
ることができる。図４は、本発明にかかる投影露光装置
の基本構造を示した図である。図４に示すように、本発
明にかかる投影露光装置は、少なくとも、感光材を塗布
した基板Ｗ（ウエハ）を載置するウエハステージ２３、
露光光をマスク（レチクルＲ）に照射する照明光学系２
１、照明光学系２１に露光光を供給するためのエキシマ
レーザー等の光源１００、及びウエハＷとレチクルＲと
の間に配置される投影光学系２５を有する。投影光学系
２５の物体面（Ｐ１）には、レチクルＲの表面（パター
ン形成面）がくるように配置され、投影光学系２５の像
面（Ｐ２）には、ウエハＷの表面がくるように配置され
ている。Furthermore, instead of forming a protective film containing a fluorocarbon group on the surface of the optical member, a protective film made of silicon oil can be formed to suppress the adhesion of contaminants to the optical member. FIG. 4 is a diagram showing a basic structure of a projection exposure apparatus according to the present invention. As shown in FIG. 4, the projection exposure apparatus according to the present invention includes at least a wafer stage 23 on which a substrate W (wafer) coated with a photosensitive material is placed.
Illumination optical system 2 for irradiating exposure light to mask (reticle R)
1. It has a light source 100 such as an excimer laser for supplying exposure light to the illumination optical system 21, and a projection optical system 25 disposed between the wafer W and the reticle R. The surface (pattern forming surface) of the reticle R is arranged on the object plane (P1) of the projection optical system 25, and the surface of the wafer W is located on the image plane (P2) of the projection optical system 25. Are located.

【００３１】また、レチクルＲは、レチクルステージ２
２上に配置され、レチクルＲ上のパターンを投影光学系
２５を介してウエハステージ２３上に載置されたウエハ
Ｗに投影露光する構成となっている。レチクル交換系２
００は、レチクルステージ２２にセットされたレチクル
Ｒの挿脱及び交換を行うとともに、レチクルステージ２
２とレチクルカセットとの間でレチクルＲの搬送を行う
機能を有する。The reticle R is a reticle stage 2
2 and is configured to project and expose a pattern on a reticle R to a wafer W placed on a wafer stage 23 via a projection optical system 25. Reticle exchange system 2
00 performs insertion / removal and exchange of the reticle R set on the reticle stage 22 and the reticle stage 2
It has a function of carrying the reticle R between the reticle cassette 2 and the reticle cassette.

【００３２】本発明の実施形態にかかる光学部材を投影
光学系２５に適用し、マスクに形成されたパターンを基
板上に投影露光する前に、光学部材の最上面に形成され
た保護膜を露光光として紫外線により除去し、これによ
り、光学部材の表面を清浄にすることができる。すなわ
ち、マスクに形成されたパターンを基板上に投影露光す
る前に、光学部材の表面に形成された保護膜を除去する
ので、光学系の透過率が低下せず、充分な露光量を確保
することができる。The optical member according to the embodiment of the present invention is applied to the projection optical system 25, and before the pattern formed on the mask is projected and exposed on the substrate, the protective film formed on the uppermost surface of the optical member is exposed. The light is removed by ultraviolet rays, whereby the surface of the optical member can be cleaned. That is, the protective film formed on the surface of the optical member is removed before the pattern formed on the mask is projected and exposed on the substrate, so that the transmittance of the optical system does not decrease and a sufficient exposure amount is secured. be able to.

【００３３】保護膜は、エキシマレーザー用光学薄膜
（反射防止膜又は反射膜）とシロキサン結合を介して形
成されているが、そのシロキサン結合は比較的強い結合
であるので、保護膜除去において、その結合部分だけ残
留する可能があるが、露光光の透過率には何等影響しな
いことが確認されている。The protective film is formed with an optical thin film for an excimer laser (anti-reflection film or reflective film) via a siloxane bond. Since the siloxane bond is a relatively strong bond, the protective film is removed when the protective film is removed. Although it is possible that only the coupling portion remains, it has been confirmed that it has no effect on the transmittance of the exposure light.

【００３４】[0034]

【発明の効果】以上説明した通り、本発明にかかる光学
部材は、その最上面にフッ化炭素基を含む保護膜を設け
たので、組み立て工程中付着する有機物や水滴等の汚染
物質の付着を抑制し、光学部材の投影露光装置への組み
込みまでの間、光学部材表面の清浄性を維持することが
できる。As described above, the optical member according to the present invention is provided with the protective film containing a fluorocarbon group on the uppermost surface thereof, so that the adherence of contaminants such as organic substances and water droplets during the assembly process is prevented. The optical member surface can be kept clean until the optical member is incorporated into the projection exposure apparatus.

【００３５】また、本発明にかかる光学部材の投影露光
装置への組み込み後、マスクに形成されたパターンを基
板上に投影露光する前に、保護膜を紫外線等を用いて除
去するので、光学系の透過率は低下せず、充分な露光量
を確保することができる。After the optical member according to the present invention is incorporated in the projection exposure apparatus, the protective film is removed using ultraviolet light or the like before the pattern formed on the mask is projected and exposed on the substrate. Does not decrease, and a sufficient exposure amount can be secured.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明にかかる光学部材の概略断面図である。FIG. 1 is a schematic sectional view of an optical member according to the present invention.

【図２】本発明にかかる光学部材の製造方法における気
相処理の工程を示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing a step of a gas phase treatment in the method for manufacturing an optical member according to the present invention.

【図３】本発明にかかる光学部材におけるＡｒＦエキシ
マレーザー照射時間と接触角の関係を示す図である。FIG. 3 is a diagram showing a relationship between an ArF excimer laser irradiation time and a contact angle in the optical member according to the present invention.

【図４】本発明にかかる投影露光装置の基本構造を示し
た図である。FIG. 4 is a diagram showing a basic structure of a projection exposure apparatus according to the present invention.

【符号の説明】[Explanation of symbols]

１・・・光学部材 ２・・・光学薄膜（反射防止膜、反射膜） ３・・・単分子膜（フッ化炭素基を有する保護膜） ３ａ・・・フッ化炭素基 ３ｂ・・・シロキサン結合 ４・・・密閉容器 ５・・・ホルダー ６・・・液体フッ化炭素シラン ７・・・容器 ２１・・・照明光学系 ２２・・・レチクルステージ ２３・・・ウエハステージ ２５・・・投影光学系 １００・・・光源 ２００・・・レチクル交換系 ３００・・・ステージ制御系 ４００・・・主制御部 Ｗ・・・基板（ウエハ） Ｒ・・・マスク（レチクル） DESCRIPTION OF SYMBOLS 1 ... Optical member 2 ... Optical thin film (antireflection film, reflection film) 3 ... Monomolecular film (protective film having a fluorocarbon group) 3a ... fluorocarbon group 3b ... siloxane Coupling 4 ... Closed container 5 ... Holder 6 ... Liquid fluorocarbon silane 7 ... Container 21 ... Illumination optical system 22 ... Reticle stage 23 ... Wafer stage 25 ... Projection Optical system 100 Light source 200 Reticle exchange system 300 Stage control system 400 Main control unit W Substrate (wafer) R Mask (reticle)

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】エキシマレーザー用の光学薄膜が形成され
た基板の最上層に汚染物質の付着を抑制する保護膜を形
成する工程と、 前記保護膜を紫外線の照射により除去する工程と、を有
すること特徴とするエキシマレーザー用光学部材の仮保
護方法。1. A method comprising: forming a protective film for suppressing adhesion of contaminants on an uppermost layer of a substrate on which an optical thin film for excimer laser is formed; and removing the protective film by irradiating ultraviolet rays. A method for temporarily protecting an optical member for an excimer laser. 【請求項２】前記保護膜は、フッ化炭素基を含み、シロ
キサン結合を介して形成されてなることを特徴とする請
求項１記載の仮保護方法。2. The temporary protection method according to claim 1, wherein the protective film contains a fluorocarbon group and is formed via a siloxane bond. 【請求項３】エキシマレーザー用の光学薄膜が形成され
た基板の最上層に、汚染物質の付着を抑制し、紫外線照
射により除去可能な保護膜が形成されてなるエキシマレ
ーザー用光学部材。3. An excimer laser optical member comprising a substrate on which an excimer laser optical thin film is formed, and a protective film which suppresses attachment of contaminants and which can be removed by ultraviolet irradiation. 【請求項４】前記保護膜は、フッ化炭素基を含み、シロ
キサン結合を介して形成されてなることを特徴とする請
求項３記載のエキシマレーザー用光学部材。4. An optical member for an excimer laser according to claim 3, wherein said protective film contains a fluorocarbon group and is formed via a siloxane bond. 【請求項５】マスクを照明する照明光学系と、 前記マスクに形成されたパターンを基板上に投影露光す
るための投影光学系と、を具備する投影露光装置の初期
化方法において、 前記マスクに形成されたパターンを基板上に投影露光す
る前に、前記光学系に組み込まれた光学部材の最上層に
形成された汚染物質の付着を抑制する保護膜を、紫外線
の照射により除去する段階を備えたことを特徴とする投
影露光装置の初期化方法。5. An initialization method for a projection exposure apparatus, comprising: an illumination optical system for illuminating a mask; and a projection optical system for projecting and exposing a pattern formed on the mask onto a substrate. Before projecting and exposing the formed pattern on the substrate, a step of removing a protective film for suppressing adhesion of contaminants formed on the uppermost layer of the optical member incorporated in the optical system by irradiating ultraviolet rays is provided. A method for initializing a projection exposure apparatus. 【請求項６】前記保護膜は、フッ化炭素基を含み、シロ
キサン結合を介して形成されてなることを特徴とする請
求項５記載の投影露光装置の初期化方法。6. The method according to claim 5, wherein the protective film contains a fluorocarbon group and is formed via a siloxane bond.
JP9211058A 1997-08-05 1997-08-05 Optical member for excimer laser, its temporarily protecting method and projection aligner Pending JPH1152102A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP9211058A JPH1152102A (en) 1997-08-05 1997-08-05 Optical member for excimer laser, its temporarily protecting method and projection aligner

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9211058A JPH1152102A (en) 1997-08-05 1997-08-05 Optical member for excimer laser, its temporarily protecting method and projection aligner

Publications (1)

Publication Number Publication Date
JPH1152102A true JPH1152102A (en) 1999-02-26

Family

ID=16599707

Family Applications (1)

Application Number Title Priority Date Filing Date
JP9211058A Pending JPH1152102A (en) 1997-08-05 1997-08-05 Optical member for excimer laser, its temporarily protecting method and projection aligner

Country Status (1)

Country Link
JP (1) JPH1152102A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6882406B2 (en) 2002-06-14 2005-04-19 Asml Netherlands B.V. Euv lithographic projection apparatus comprising an optical element with a self-assembled monolayer, optical element with a self-assembled monolayer, method of applying a self-assembled monolayer, device manufacturing method and device manufactured thereby
JP2011014929A (en) * 2004-06-21 2011-01-20 Nikon Corp Exposure device, exposure device member cleaning method, exposure device maintenance method, maintenance device, and device manufacturing method
US8810767B2 (en) 2004-06-21 2014-08-19 Nikon Corporation Exposure apparatus, method for cleaning member thereof, maintenance method for exposure apparatus, maintenance device, and method for producing device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6882406B2 (en) 2002-06-14 2005-04-19 Asml Netherlands B.V. Euv lithographic projection apparatus comprising an optical element with a self-assembled monolayer, optical element with a self-assembled monolayer, method of applying a self-assembled monolayer, device manufacturing method and device manufactured thereby
JP2011014929A (en) * 2004-06-21 2011-01-20 Nikon Corp Exposure device, exposure device member cleaning method, exposure device maintenance method, maintenance device, and device manufacturing method
US8810767B2 (en) 2004-06-21 2014-08-19 Nikon Corporation Exposure apparatus, method for cleaning member thereof, maintenance method for exposure apparatus, maintenance device, and method for producing device

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