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

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Publication number
JPH1152102A
JPH1152102A JP21105897A JP21105897A JPH1152102A JP H1152102 A JPH1152102 A JP H1152102A JP 21105897 A JP21105897 A JP 21105897A JP 21105897 A JP21105897 A JP 21105897A JP H1152102 A JPH1152102 A JP H1152102A
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Prior art keywords
optical member
protective film
formed
optical
excimer laser
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JP21105897A
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Japanese (ja)
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Norio Kaneko
Izumi Motoyama
いづみ 元山
則夫 金子
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Nikon Corp
株式会社ニコン
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites

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 The present invention relates to an optical member for excimer lasers, relates temporary protection method, in particular the optical member is used in an optical system of the 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。 BACKGROUND OF THE INVENTION Not only the optical member for projection exposure apparatus, members classified into optical members, the presence of foreign material adhering to the surface, causes such as a transmission rate reduction and illuminance unevenness of light, optical should have originally because the performance can not be obtained, various measures have been taken. 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 The member hating cloudiness due mainly water droplets such as windshield glasses lenses and automobile, or coated with a surfactant-containing anti-fogging agent in the top layer (JP-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。 0876 JP), the surface roughness increases the wettability by increasing the surface area in the crude to be or antifogging (JP 55-154348 JP), a material and a hydrophobic polymer having a fluorine reversed method of preventing the adhesion of water droplets by coating (JP 54-74291 JP) have also been taken to. 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 Also, members dislike adhesion of organic contaminants, such water as well as an optical member incorporated in a camera or a projection exposure apparatus, by forming a titanium oxide film is a photocatalyst action decomposing organic pollutants with or (JP-a-08-313705), or attempt reduction of contaminants by reducing the densely deposited surface a silicon oxide film, contaminated by depositing the organic film having a fluorocarbon group substance and it had reduced adhesion (JP-a-6-53
24号公報)。 24 JP).

【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。 [SUMMARY OF THE INVENTION However, the above conventional technique has been pointed out the following problems. 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、 Or applying a surface active agent in the top layer, the method of increasing the wettability by increasing the surface area and the surface roughness rough, will exist many moisture on the surface by the effect of moisture as an adsorbent foreign matter or deposited, moisture present on the surface not only degrade eroding an optical member,
短波長の光の透過率が低下するという問題もあった。 Short-wavelength light transmittance was also lowered. 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。 Also, coating with the hydrophobic polymer is poor in durability of the film itself, since become easily decomposed not only transmits light in a short wavelength side, it's become a source of contamination.

【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 [0004] Although permeability to relatively long wavelength of light, such as titanium oxide film i-line (365 nm) high, 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。 Because rF and not short wavelength absorbing light transmitted through such as ArF laser, KrF and ArF, X-rays or an electron beam in a projection exposure apparatus whose light source is capable of supplying the necessary amount of light in the photoresist curing Whilst not only lowering the imaging performance, under the use of long, destruction of coat film occurs, it is forced to the lens exchange heat or the like generated by the absorption of light of the titanium oxide film.

【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。 [0005] In the densification of the silicon oxide film, the surface area of ​​the optical member is reduced, a decrease in pollutant deposition amount is expected, for the removal of contaminants attached because no antifogging property to the silicon oxide film itself effect can not be expected. 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 Similarly organic material film is a titanium oxide film having a fluorocarbon group, i-ray (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、 Although high permeability to relatively long wavelength of light, such as 65 nm), KrF or ArF laser, X-rays,
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。 Not only it does not absorb transmits light length short such as electron-line, KrF and ArF lasers, X-rays, a problem that organic film itself having a fluorocarbon group is decomposed by irradiation of electron beams was It 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、 On the other hand, as a method for removing contaminants such as organic substances adhering to the surface of the optical member, the light wash is used,
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。 When the organic substance or the like and the optical member surface is the surface alteration of the optical member by chemical reaction, by light cleaning, there is a problem that can not be removed. 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。 SUMMARY OF THE INVENTION In view of these problems, to suppress the deposition of contaminants such as organic substances, and the transmittance is not reduced when used is incorporated in the optical system, which can ensure the exposure light an optical member, and to provide methods of use thereof.

【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 A solution for the present invention is intended to apply as an advantage the problem of organic film having the carbon fluoride group, using the organic film having the fluorocarbon group as a protective film, optical preventing contaminants adhesion between the end of production of the member to the optical member incorporation completion of the projection exposure apparatus, after the optical member incorporation completion of the projection exposure apparatus, in which the protective film is removed.

【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 [0008] The present invention includes the steps of forming "suppressing protective film 3 adhesion of contaminants to the top layer of the substrate 1, the optical thin film 2 is formed for the excimer laser in the first, the protective film 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 providing temporary protection method (claim 1) "in excimer laser optical member, characterized by and a step of removing by irradiation of ultraviolet rays.

【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、 [0009] The optical member in the temporary protection method according to claim 1 is transported, in the assembly process of the optical system, by suppressing protective film adhesion of contaminants provided in the uppermost layer,
有機物質等の汚染物質の付着を抑制することができる。 It is possible to suppress the adhesion of contaminants such as organic substances.
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。 Also, after incorporating the optical element in the optical system, before using the optical system, since the protective film is removed by ultraviolet rays, the transmittance does not decrease, it is possible to secure a sufficient exposure amount.

【0010】また、本発明は、第二に「前記保護膜3 Further, the present invention, the second to "the protective film 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。 Includes fluorocarbon group 3a, it provides a temporary protection method (claim 2) "according to claim 1, characterized by being formed through a siloxane bond 3b. また、本発明は、 In addition, the present invention is,
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 top layer of the "substrate 1 optical thin film 2 is formed for the excimer laser in the third, contaminant deposition of the suppression, the optical member for excimer lasers made formed protective film 3 can be removed by UV irradiation ( providing claim 3). "

【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、 [0011] The optical member according to claim 3, wherein suppresses adhesion of contaminants to the top layer, the protective layer removable is provided by ultraviolet irradiation, transportation, in the assembly process of the optical system, organic matter it is possible to suppress the deposition of contaminants, after incorporating the optical element in the optical system,
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。 Before using the optical system, the protective film is removed by ultraviolet irradiation, without decreasing the transmittance, it is possible to secure a sufficient exposure amount.

【0012】また、本発明は、第四に「前記保護膜3 Further, the present invention is "the protective film 3 on the fourth
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。 Includes fluorocarbon group 3a, provides an excimer laser optical member (claim 4) "according to claim 3, characterized by being formed through a siloxane bond 3b.
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 Further, the present invention includes an illumination optical system 21 for illuminating the "mask R Fifth, the pattern formed on the mask R substrate 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。 A projection optical system 25 for projecting and exposing the top, in the initialization method of a projection exposure apparatus having a, the formed mask R pattern before projection exposure onto the substrate W, is incorporated in the optical system other optical member placing the uppermost two formed other pollutants Roh attached wo suppress the protective film 3 wo, ultraviolet field irradiation Niyori removal to stage wo with other matters wo feature door to the projection exposure apparatus Roh initial mosquito method (claim 5). " 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。 [0013] Since the protective film on the uppermost layer of the optical member incorporated in an optical system of a projection exposure apparatus according to claim 5, wherein for preventing adhesion of contaminants such as organic substances are provided, by adhering during the assembly process Aro will adhere to the suppression of contaminant organic matter and water droplets, until incorporation into the projection exposure apparatus of the optical member, it is possible to maintain the cleanliness of the optical member surface.
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。 Therefore, organic substances and the optical member surface is not be altered surface of the optical member by a chemical reaction.

【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、 Further, the protective film provided on the uppermost layer of the optical member, so that can be removed by UV irradiation,
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、 The pattern formed on the mask prior to the projection exposure onto the substrate by the exposure light, by removing by using an exposure light,
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。 Preventing a reduction transmittance of the optical system due to the provision of the protective film on the uppermost layer of the optical member, it is possible to supply a necessary amount of light at the photoresist curing.

【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。 [0015] On the protective film is quantity that can be the re-contamination is not formed on the optical member surface, for low molecular weight gasified by decomposition, any optical properties be present in a lens barrel of the projection exposure apparatus It is not affected. 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。 Further, the present invention is "the protective film 3 on the sixth, include fluorocarbon group 3a, the initialization of the projection exposure apparatus according to claim 5, characterized by being formed through a siloxane bond 3b a method (claim 6). "

【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。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, will be described with the optical member of the embodiment according to the present invention with reference to the drawings. 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。 Figure 1 is a schematic sectional view of an optical member of an embodiment according to the present invention. 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 The optical element of the embodiment according to the present invention, on the optical element 1 the antireflection film or the reflection film 2 is formed, has an alkoxysilyl group or a halogenated silyl group at one end, fluorocarbon group 3a at the other end silane compounds having a (hereinafter, referred to fluorocarbon silane compound) 3 anti-reflection film or reflective film 2 (the protective film containing fluorocarbon group 3a) chemical adsorption monomolecular film
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。 A coupling in the form of (M (metal) -O-Si) is formed via a (siloxane bond) 3b.

【0017】光学部材1の材料としては、石英ガラス、 [0017] As the material of the optical member 1, quartz glass,
蛍石等が用いられる。 Fluorite or the like is used. フッ化炭素シラン系化合物としては、 CF 3 CH 2 CH 2 Si(OCH 33 CF 3 CH 2 CH 2 SiCl 3 CF 3 (CF 25 CH 2 CH 2 SiCl 3 CF 3 (CF 25 CH 2 CH 2 Si(OCH 33 CF 3 (CF 27 CH 2 CH 2 Si(OCH 33 CF 3 (CF 27 CH 2 CH 2 SiCl 3 CF 3 (CF 27 CH 2 CH 2 SiCH 3 Cl 2 CF 3 (CF 27 CH 2 CH 2 SiCH 3 (OCH 32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 fluorocarbon silane compound, 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 SiCH 3 Cl 2 CF 3 (CF 2) 7 CH 2 CH 2 SiCH 3 (OCH 3) but 2 and the like, is any compound having a reactive group which reacts with fluorocarbon group 3a and the optical thin film, which but it is not limited to.

【0018】特に、フッ化炭素シラン系化合物としては、CF 3 (CF 27 CH 2 CH 2 Si(OCH 33が好ましい。 [0018] In particular, the fluorocarbon silane compound, CF 3 (CF 2) 7 CH 2 CH 2 Si (OCH 3) 3 is preferred. 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) It is a compound containing many C-F bonds and C-H bonds is due to the polarizability of these bonds is low surface free energy (force attracting molecules of the surface inside)
が低くなる結果、各種の液体にぬれにくい特性を示す、 Results is low, indicating a wetting hard characteristic to various liquids,
すなわち、高い撥水性を示すからである。 That is because exhibit high water repellency. また、C− In addition, 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。 When F bonds and C-H bonds is too large, the viscosity of the liquid substance is increased, and volatile increases too small Conversely, because difficult handling.

【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、 The length of the carbon chain of the fluorocarbon silane compound is arbitrarily selected, the thickness of the case of the monolayer,
アルキル鎖の長さで決まる。 Determined by the length of the alkyl chain. 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。 Next, the manufacturing process of the optical element of the embodiment according to the present invention. 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。 First, an antireflection film or the reflection film 2 of the excimer laser 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。 Next, to clean by washing the surface of the optical member 1 antireflection film or reflection film 2 is formed by raised or ultrasonic cleaning wipe with an organic solvent such as alcohol or acetone. 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。 Further, in order to clean and activate the optical member surface, it is effective to perform optical washed with excimer lamp (172 nm) and 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。 Next, as shown in FIG. 2, the optical member 1 of the antireflection film or with a reflective film 2 has a light wash is placed in a holder which is provided above in the closed container 4, a liquid fluorocarbon the container 7 filled with a silane compound 6 was placed on the lower side of the optical member 1. 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。 Figure 2 blade, the present invention similar to such an embodiment mounting the optical member mounting method for manufacturing Niokeru gas-phase process Roh process wo shown Figure out there.

【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。 [0022] The entire sealed container 4 was heated to 50 ° C. to 150 DEG ° C., to evaporate the liquid fluorocarbon silane compound 6. 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、 Thus, the vapor of the fluorocarbon silane molecule fills the space in the closed container 4, the surface of the optical member 1, formed antireflection film or reflection on alkoxysilyl group and the optical member 1 of the fluorocarbon silane hydroxyl group and react chemically with the oxide film 2 (natural oxide film can be a surface otherwise oxide),
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。 Chemisorption monomolecular film 3 of fluorocarbon silane to the entire surface of the optical member 1 (hereinafter, referred monomolecular film) is formed.

【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。 [0023] At this time, since the alkoxysilyl group or a halogenated silyl group at one end of the fluorocarbon silane molecule chemically bonded to the anti-reflection film on the optical member, the other end of the fluorocarbon silane molecules fluorocarbon group 3a of, is to be positioned on the surface side of the monolayer. 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。 As a method for forming the top layer in the protective film containing fluorocarbon group of the optical member, in addition to the vapor phase method, a fluorocarbon silane compound in the liquid is dispersed by the dispersion medium such as alcohol, after soaking several hours 10 minutes the substrate to complete siloxane bonds 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。 [0024] In addition to the method for deposition onto the substrate of the fluorocarbon silane compound by immersion, the method by coating, the method according to spraying, a method in accordance with the spin coating is used. 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。 Further, as a method for promoting a siloxane bond, to other methods of performing in a high temperature atmosphere, there is a method by electron beam irradiation or ultraviolet irradiation, or the like. 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 the case of using the vapor phase method, a monomolecular film, the substrate is evenly even large diameter, it can be uniformly formed.

【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。 The method of forming the protective film, it is preferable to employ a method corresponding to the shape and manufacturing process of the substrate. 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、 Since the protective film of an optical member according to the present invention, to prevent contamination by organic substances such as optical members in embedded process of the optical system,
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。 That is provided in order to prevent the reaction product can not be removed by light washed reaction contaminants such as optical thin film and an organic material formed on the optical member is formed, merely the protective film the role is a temporary protection of the optical element 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。 [0026] Therefore, when used in an optical system, it is necessary to remove the protective film. 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 As a method of removing in a state of incorporating the protective film in an optical system, an ultraviolet (400
nm〜100nm)を照射する方法が挙げられる。 nm to 100 nm) a method of irradiating the like a. 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、 That is, a quartz glass used as an optical member of the optical system, the transmittance of ultraviolet rays of fluorite, since 90% or more,
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。 It is irradiated with ultraviolet rays in the optical system, a protective film of all 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 Furthermore, KrF excimer laser as the ultraviolet (248 nm), ArF excimer laser (193
nm)を照射することが好ましい。 It is preferable to irradiate the nm). 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。 Figure 3 is a diagram showing the relationship between contact angle with the ArF excimer laser irradiation time in the optical member according to the present invention. ここでは、ArFエキシマレーザーとは、波長が193nm、パルス巾40n Here, the ArF excimer laser, wavelength 193 nm, pulse width 40n
secのエキシマレーザーである。 An excimer laser of sec.

【0028】図3から保護膜成膜直後の接触角は、約1 The contact angle immediately after the protective film forming from 3, about 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。 10 degrees de Al-moth ,, ArF excimer laser wo about 5 Funkan irradiated continue door, about 10 degrees squid two differ moth seen. 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。 Further, considering that the contact angle of the protective film before film formation of the optical member surface was about 30 degrees, not only the protective film at a very high speed is disengaged from the optical member surface, the optical over the initial state it can be seen that the member surface is made 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、F 2レーザー(157nm)のようにAr [0029] The present embodiment leaf emergence, ArF excimer laser irradiation Niyoru protective film field effect of removing only wo shows other moth, KrF excimer laser (248nm) Ya i line light (365nm) Roh Yo name ArF excimer laser (198nm) more wavelength Roh long light and, Ar as F 2 laser (157 nm)
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。 F also removal of the protective film with an excimer laser from the short wavelength light is possible. 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 that case demo 100nm~250nm field light wo selected other square moth a shorter period of time similar removal can be.

【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。 Furthermore, instead of forming a protective film containing fluorocarbon groups on the surface of the optical member, even if the protective film is formed of silicon oil, it is possible to suppress the adhesion of contaminants into an optical element. 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。 Figure 4 is a diagram showing a basic structure of a projection exposure apparatus according to the present invention. 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、 As shown in FIG. 4, a projection exposure apparatus according to the present invention comprises at least a wafer stage 23 for placing the coated substrate W (wafer) a photosensitive material,
露光光をマスク(レチクルR)に照射する照明光学系2 An illumination optical system 2 for irradiating the exposure light on a mask (reticle R)
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。 1, has a projection optical system 25 disposed between the light source 100, and the wafer W and reticle R excimer laser for supplying exposure light to the illumination optical system 21. 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。 The object plane of the projection optical system 25 (P1) is arranged so that the surface of the reticle R (pattern formation surface) comes, as in the image plane of the projection optical system 25 (P2), come the surface of the wafer W It is located.

【0031】また、レチクルRは、レチクルステージ2 [0031] In addition, the reticle R, the reticle stage 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。 Arranged on 2 has a configuration of projecting exposure to the wafer W placed on the wafer stage 23 through a pattern the projection optical system 25 on the reticle R. レチクル交換系2 Reticle exchange system 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 00, performs insertion and removal and replacement of the reticle R set on the reticle stage 22, the reticle stage 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。 It has a function of transporting the reticle R between the 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。 [0032] The optical member according to an embodiment of the present invention is applied to a projection optical system 25, before the pattern formed on the mask to the projection exposure onto the substrate, exposing the protective film formed on the top surface of the optical member it is removed by ultraviolet rays as light, which makes it possible to the surface of the optical member clean. 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。 That is, before the pattern formed on the mask to the projection exposure onto the substrate, so to remove the protective film formed on the surface of the optical member, does not decrease the transmittance of the optical system, to ensure sufficient exposure 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 has been formed with the optical thin film for the excimer laser (antireflection film or reflection film) through a siloxane bond, because the siloxane bonds is a relatively strong bond, the protective film removing its there is a possibility to remain only binding moiety, no effect whatever on the transmittance of the exposure light is confirmed.

【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, according to the present invention, the optical member according to the present invention, since a protective film containing a fluorocarbon group on the uppermost surface, the adhesion of contaminants such as organic materials and water droplets adhering during the assembly process suppressing, until incorporation into the projection exposure apparatus of the optical member, it is possible to maintain the cleanliness of the optical member surface.

【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。 Further, after the integration into the projection exposure apparatus of an optical member according to the present invention, before the pattern formed on the mask to the projection exposure onto the substrate, since the protective film is removed by using an ultraviolet and the like, an optical system the transmittance of not reduced, it is possible to secure a sufficient exposure amount.

【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。 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。 It is a schematic sectional view showing a gas phase process step in the manufacturing method of the optical member in the present invention; FIG.

【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。 3 is a diagram showing the relationship between contact angle with the ArF excimer laser irradiation time 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。 It is a diagram showing a basic structure of a projection exposure apparatus in the present invention; FIG.

【符号の説明】 DESCRIPTION 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) 1 ... optical member 2 ... optical thin (antireflection film, reflection film) 3 ... monomolecular film 3a ... fluorocarbon group 3b ... siloxane (protective film having a fluorocarbon group) coupling 4 ... closed vessel 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】 [The claims]
  1. 【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。 Has a claim 1 wherein the step of forming the inhibiting protective film adhesion of the top layer to the contaminants of substrates optical thin film is formed for an excimer laser, and a step of removing by irradiating the protective layer of ultraviolet temporary protection method of an excimer laser optical member according to this and features.
  2. 【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。 Wherein said protective film comprises a fluorocarbon group, temporary protection method according to claim 1, characterized by being formed through a siloxane bond.
  3. 【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。 Wherein the top layer of the substrate which optical thin film for the excimer laser is formed, contaminants adhered to the suppression, excimer laser optical member made of formed capable protective film is removed by ultraviolet irradiation.
  4. 【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。 Wherein said protective film comprises a fluorocarbon group, an excimer laser optical member according to claim 3, characterized by being formed through a siloxane bond.
  5. 【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. A lighting optical system for illuminating the mask, in the initialization method of a projection exposure apparatus which a pattern formed on the mask comprises a projection optical system for projecting exposure onto the substrate, the mask a pattern formed prior to projection exposure onto the substrate, suppressing protective film adhesion of contaminants formed on the uppermost layer of the optical member incorporated in the optical system, comprising the step of removing by irradiation of ultraviolet light initialization method for a projection exposure apparatus, characterized in that the.
  6. 【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。 Wherein said protective film comprises a fluorocarbon group, initialization method of a projection exposure apparatus according to claim 5, characterized by being formed through a siloxane bond.
JP21105897A 1997-08-05 1997-08-05 Optical member for excimer laser, its temporarily protecting method and projection aligner Pending JPH1152102A (en)

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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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