TW200804989A - Method for forming resist pattern - Google Patents
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- TW200804989A TW200804989A TW96114834A TW96114834A TW200804989A TW 200804989 A TW200804989 A TW 200804989A TW 96114834 A TW96114834 A TW 96114834A TW 96114834 A TW96114834 A TW 96114834A TW 200804989 A TW200804989 A TW 200804989A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70216—Mask projection systems
- G03F7/70341—Details of immersion lithography aspects, e.g. exposure media or control of immersion liquid supply
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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200804989 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於適合使用於製造集成電路爲首 工領域之光阻圖型的形成方法。詳言之,係關於 度高’可形成更微細之光阻圖型之光刻技術的液 • 光阻圖型的形成方法。 【先前技術】 近年來,集成電路的微細化爲朝向發展一途 成電路所用之投影曝光裝置中,解像度R及焦點 以下述式(i)及下述式(ii)表示,作爲曝光光 線的波長λ愈短,且投影透鏡之開口數n A値愈 像度R (最小解像尺寸)値愈小,可令解像度提 ,投影曝光裝置中之曝光光源的短波長化與投影 開口數化爲加速度地進行。 ❿ R = k1 · λ /NA : ( i) (5=k2·久 /ΝΑ2 : (ii) (但,R :解像度、5 :集點深度、A :曝光光 、N A :投影透鏡之開口數、k 1、k2 :處理係數) 此外,作爲提高解像度之光刻技術,亦已知 之手法。液浸曝光爲以中介存在比空氣更高折射 (液浸液)的狀態下,對於光阻膜照射射線,令 之微細加 利用解像 浸曝光之 。製造集 深度δ爲 源之放射 大,則解 高。因此 透鏡的高 源之波長 〇 液浸曝光 率之液體 其光阻膜 -5- 200804989 (2) 曝光之手法。即,通常爲在以空氣和氮氣所充滿之投影透 鏡與光阻膜之間的空間,以液浸液充滿的狀態下進行曝光 〇 投影透鏡與光阻膜間之空間爲以折射率η之液浸液所 充滿時之解像度R及焦點深度6,爲以下述式(iii )及下 述式(iv )表示。即,經由使用折射率η的液浸液,令解 像度R (最小解像尺寸)之値爲1 /η,提高解像度,加上 可將焦點深度· 6擴大,改善至η倍。例如,使用ArF激元 雷射(波長又:193 nm )作爲光源,並且使用於其波長入 中之折射率η爲1.4 4之水作爲液浸液時,與中介存在空 氣和氮氣之非液浸情況相比較,解像度R (最小解像尺寸 )爲提高至1/1.44 ( 69.4% ),且焦點深度5爲擴大,改 善至1.4 4倍。 R = k 1 · ( λ/η) /ΝΑ : (iii) 5=k2· ηλ/ΝΑ2 : (iv) (但,n :折射率’關於R、d、λ、N A、k 1、k 2爲與式 (i )及式(i i )之但書同義)。 此類液浸曝光之技術爲微細加工,特別爲用以1 〇nm 單位之微細加工的光刻技術型式被認爲係爲必須之手法, 即亦已揭示液浸曝光用之投影曝光裝置(例如,參照專利 文獻1 )。 但是,於液浸曝光中,因爲液浸液爲直接接觸光阻膜 -6 - 200804989 (3) ,故經由浸透光阻膜的液浸液引起無法預期的化學反應, 被指出恐對光阻性能造成不良影響(例如,參照專利文獻 2) ° 於是,提案於光阻膜之表面形成對於液浸液具有耐性 ~ 之保護膜的狀態下進行液浸曝光,其次曝光後進行加熱處 - 理後將保護膜剝離形成光阻圖型之方法(例如,參照專利 文獻3及4)。 ^ [專利文獻1]特開平1 1 - 1 76727號公報 [專利文獻2]特開平2005-2683 82號公報 [專利文獻3 ]特開平2 0 0 5 - 2 5 0 5 1 1號公報 [專利文獻4]特開平2005-264 1 3 1號公報 【發明內容】 但是,專利文獻3及4所記載之光阻圖型形成方法, 具有保護膜浸透,起因於殘存之液浸液,於光阻圖型上殘 • 留液滴痕之缺陷(水痕缺陷)、和光阻圖型的寬度變粗且 反而產生變細之缺陷(圖型不良缺陷)的課題。即,專利 文獻3及4所記載之光阻圖型形成方法,雖可期待形成高 解像度之光阻圖型,但於產生水痕缺陷和圖型不良缺陷之 ’ 方面,則仍未令人充分滿足,要求進一步改良。 如以上所說明般,現在之情況,作爲可有效抑制水痕 缺陷和圖型不良缺陷之發生,並且可形成高解像度之光阻 圖型的對策仍未被揭示,且急切期望此類對策。 本發明爲解決如上述先前技術之課題而完成者,係爲 -7 - 200804989 (4) 提供有效抑制水痕缺陷和圖型不良缺陷之發生, 成高解像度之光阻圖型的光阻圖型形成方法。 本發明者等人爲了解決如前述之先前技術的 檢討之結果,發現將光阻膜經液浸液所保護的保 ' 光阻膜曝光後,且於曝光後加熱處理(PEB )前 • 膜表面預先剝離,其後,經由進行曝光後加熱處 ,則可解決前述課題,並且完成本發明。具體而 ^ 以下之光阻圖型形成方法。 [1] 一種光阻圖型之形成方法,其爲具備藉由 比空氣之折射率更高之液體(液浸液)的狀態下 阻膜照射放射線,則可令此光阻膜曝光之液浸曝 光阻圖型之形成方法,其特徵爲於基板表面形成 膜,並於此光阻膜表面形成對於前述液浸液具有 護膜,且於中介存在前述液浸液之狀態下對光阻 射線,則可令前述光阻膜曝光,並將前述保護膜 m 阻膜表面剝離後,進行曝光後加熱處理及顯像, 圖型。 [2] 如前述[1]之光阻圖型之形成方法,其爲 樹脂形成前述保護膜,並且使用有機溶劑進行前 ' 的剝離。 [3] 如前述[2]之光阻圖型之形成方法,其中 述保護膜之前述脂溶性樹脂,爲以含有下述一 I 及下述一般式(2 )所組成群中選出至少一種之 的聚合物作爲構成成分。 並且可形 課題致力 護膜,於 ,由光阻 理、顯像 言,提供 中介存在 ,對於光 光步驟的 前述光阻 耐性的保 膜照射放 由前述光 取得光阻 以脂溶性 述保護膜 ,形成前 J 式(1 ) 重複單位 - 8- 200804989 (5) 【化1】200804989 (1) Description of the Invention [Technical Field] The present invention relates to a method of forming a photoresist pattern suitable for use in the manufacture of integrated circuits. In particular, it is a method for forming a liquid/resist pattern of a lithography technique that can form a finer photoresist pattern. [Prior Art] In recent years, the miniaturization of integrated circuits has been made into a projection exposure apparatus for developing a circuit, and the resolution R and the focus are expressed by the following formula (i) and the following formula (ii) as the wavelength λ of the exposure light. The shorter the distance, the smaller the number of apertures of the projection lens n A, the smaller the resolution R (the minimum resolution size), the lower the resolution, the shorter the wavelength of the exposure light source and the number of projection openings in the projection exposure apparatus. get on. ❿ R = k1 · λ /NA : ( i) (5=k2·久/ΝΑ2 : (ii) (However, R: resolution, 5: set depth, A: exposure light, NA: number of openings of the projection lens, k 1 , k2 : processing coefficient) In addition, as a lithography technique for improving the resolution, a method is also known. The immersion exposure is a medium in which a refracting film is irradiated with a higher refractive index (liquid immersion liquid) than air. Let it be finely applied by using the solution immersion exposure. The set depth δ is the source of the large radiation, then the solution is high. Therefore, the high source wavelength of the lens 〇 liquid immersion exposure liquid of the photoresist film -5 - 200804989 (2 The method of exposure, that is, the space between the projection lens and the photoresist film which is filled with the liquid immersion liquid in a space filled with the projection lens and the photoresist film filled with air and nitrogen is usually The resolution R and the depth of focus 6 when the liquid immersion liquid having the refractive index η is full are expressed by the following formula (iii) and the following formula (iv). That is, the resolution R is obtained by using the liquid immersion liquid having the refractive index η. The minimum resolution size is 1 / η, which improves the resolution, plus the depth of focus · 6 is expanded and improved to η times. For example, when an ArF excimer laser (wavelength: 193 nm) is used as a light source, and water having a refractive index η of 1.4 4 in its wavelength is used as a liquid immersion liquid, Compared with the non-liquid immersion condition of air and nitrogen, the resolution R (minimum resolution size) is increased to 1/1.44 (69.4%), and the depth of focus 5 is expanded to 1.4 times. R = k 1 · ( λ / η ) / ΝΑ : (iii) 5 = k2 · ηλ / ΝΑ 2 : (iv) (however, n : refractive index ' with respect to R, d, λ, NA, k 1 , k 2 and equation (i) And the formula (ii) is synonymous.) The technique of such immersion exposure is microfabrication, especially for the lithography type of microfabrication in units of 1 〇 nm. It is considered to be a necessary method. A projection exposure apparatus for immersion exposure is disclosed (for example, refer to Patent Document 1). However, in the immersion exposure, since the liquid immersion liquid is in direct contact with the photoresist film -6 - 200804989 (3), the light-shielding film is immersed through the immersion film. The liquid immersion liquid causes an unpredictable chemical reaction and is pointed out to have an adverse effect on the photoresist performance (for example, refer to Patent Document 2) It is proposed to perform liquid immersion exposure in a state where a protective film having resistance to a liquid immersion liquid is formed on the surface of the photoresist film, and then, after the exposure, the protective film is peeled off to form a photoresist pattern (for example, Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei. No. 2005-264. The remaining liquid immersion liquid has a problem of residual defects in the resist pattern, defects in the water droplets (water mark defects), and a defect in which the width of the photoresist pattern becomes thick and conversely becomes thin (defective pattern defects). In other words, the photoresist pattern forming method described in Patent Documents 3 and 4 can be expected to form a high-resolution photoresist pattern, but it is still insufficient in terms of water mark defects and pattern defects. Satisfied, requires further improvement. As described above, in the present case, as a countermeasure against the occurrence of water mark defects and pattern defects, and the formation of a high-resolution photoresist pattern, the countermeasures have not been disclosed, and such countermeasures are urgently desired. The present invention is directed to solving the problems of the prior art described above, and is -7 - 200804989 (4) providing a photoresist pattern that effectively suppresses the occurrence of water mark defects and pattern defects, and forms a high resolution photoresist pattern. Forming method. The inventors of the present invention have found that after the exposure of the photoresist film protected by the liquid immersion liquid, and after the post-exposure heat treatment (PEB) in order to solve the results of the prior art review as described above, the film surface The present invention can be solved by preliminarily peeling off, and thereafter, by performing the post-exposure heating, the above problems can be solved. Specifically, the following method for forming a photoresist pattern. [1] A method for forming a photoresist pattern, which is characterized in that the resist film is irradiated with radiation by a liquid (liquid immersion liquid) having a higher refractive index than air, and the resist film can be exposed to immersion exposure. A method for forming a resist pattern, which is characterized in that a film is formed on a surface of the substrate, and a film is formed on the surface of the photoresist film for the liquid immersion liquid, and the photoresist is irradiated in a state in which the liquid immersion liquid is interposed. The photoresist film may be exposed, and the surface of the protective film m is peeled off, and then subjected to post-exposure heat treatment and development, and a pattern. [2] The method for forming a photoresist pattern according to the above [1], wherein the protective film is formed of a resin, and the front side is peeled off using an organic solvent. [3] The method for forming a photoresist pattern according to the above [2], wherein the lipophilic resin of the protective film is at least one selected from the group consisting of the following one I and the following general formula (2); The polymer acts as a constituent. Further, the shape-sensitive problem is to protect the film, and it is provided by photo-resistance and image-sensing, and the film-preserving film for the photoresistance of the light-lighting step is made of the light-receiving photoresist to provide a fat-soluble protective film. Forming the former J formula (1) repeat unit - 8- 200804989 (5) [Chemical 1]
CF3-P\ OH CF3 (1) (2) [但,於一般式(1)或(2)中,R1爲表示氫、甲基或三 氟甲基,R2爲表示二價之有機基,R3爲表示碳數4〜20個 之脂環式烴基或其衍生物]。 本發明之光阻圖型之形成方法爲有效抑制水痕缺陷和 圖型不良缺陷之發生,並且可形成高解像度之光阻圖型。 【實施方式】 以下,具體說明關於實施本發明之光阻圖型形成方法 之最佳形態。但,本發明爲包含具備此發明特定事項之全 部的實施形態,並非被限定於以下所示的實施形態。另外 ,本說明書中,所謂「(甲基)丙烯酸酯」時,爲意指包 含丙烯酸酯或甲基丙烯酸酯兩者之槪念。 本發明之光阻圖型之形成方法爲具備透過比空氣更高 折射率之液體(液浸液),對光阻膜照射放射線,令光阻 膜曝光之液浸曝光步驟之光阻圖型的形成方法,於基板表 面形成光阻膜,並於此光阻膜表面形成對於液浸液具有耐 -9- 200804989 (6) 性的保護膜,且中介存在液浸液並照射放射線,則可令光 阻膜曝光,並將保—護膜由光阻膜表面剝離後,進行曝光後 加熱處理及顯像,形成光阻圖型。 、 Π]光阻膜之形成: * 本發明之光阻圖型之形成方法中,首先,於基板表面 形成光阻膜。 π-l]基板: 基板通常爲使用矽晶圓、經鋁覆被之矽晶圓等。爲了 以最大極限引出光阻膜的特性,預先,於基板表面形成有 機系或無機系之防止反射膜亦爲較佳形態之一(例如,參 照特公平6- 1 2452號公報等)。 [1-2]光阻膜(敏放射性樹脂組成物): • 形成光阻膜之物質種類並無特別限制,可由以往形成 光阻膜所用之物質中,根據光阻的使用目的適當選擇使用 即可。 但,於本發明之光阻圖型之形成方法中,使用含有產 * 酸劑之增強化學型光阻材料,特別,正型光阻材料爲佳。 增強化學型之正型光阻材料可列舉例如含有酸解離性基修 飾鹼可溶性樹脂(A成分)、和敏放射線性產酸劑(B成 分)作爲必須成分之敏放射線性的樹脂組成物等。此類樹 脂組成物爲經由放射線照射(曝光)而由產酸劑發生酸, -10- 200804989 (7) 並且藉由此發生酸之作用,令保護樹脂之酸性基(例如, 羧基)的酸解離性基解離,露出酸性基。因此,光阻曝光 部之鹼溶解性變高,且其曝光部爲經由鹼顯像液而被溶解 、除去,形成正型之光阻圖型。 , [1-2A]酸解離性基修飾鹼可溶性樹脂(A成分) 所謂「酸解離性基修飾鹼可溶性樹脂」爲具有酸性基 $ ,且此酸性基的至少一部分爲經由酸解離性基所保護的樹 脂。此樹脂爲在樹脂中之至少一部分酸性基經由酸解離性 基保護之狀態下,顯示出鹼不溶性或鹼難溶性,但若經由 酸之作用令酸解離性基解離,則酸性基露出並且爲顯示出 鹼可溶性的樹脂。 另外,所謂「鹼不溶性或鹼難溶性」爲意指由含有酸 解離性基修飾鹼可溶性樹脂(A成分)、和敏放射線性產 酸劑(B成分)之敏放射線性樹脂組成物所得之光阻膜, m 形成光阻圖型時使用之鹼顯像條件下,將僅以酸離性基修 飾鹼可溶性樹脂代替此光阻膜所得之被膜予以顯像之情形 中,其被膜之初期被膜的50%以上爲於顯像後殘存的性質 〇 * 「酸性基」若爲顯示酸性之官能基則無特別限制。可 列舉例如,酚性羥基、羧基或磺酸基等。其中,由提高對 於鹼之溶解性之效果高的理由而言,以酚性羥基、羧基等 爲佳。酸解離性基修飾鹼可溶性樹脂可於其中僅具有一種 酸性基者即可,且亦可具有二種以上之酸性基者。 -11 - 200804989 (8) 相當於A成分所含有之酸解離性基的具體構造,可列 舉例如含有含下述一般式(3)所示之骨架之重複單位( 以下,稱爲「重複單k ( 1 )」作爲必須成分的聚合物。 【化2】CF3-P\ OH CF3 (1) (2) [However, in the general formula (1) or (2), R1 represents hydrogen, methyl or trifluoromethyl, and R2 represents a divalent organic group, R3 To represent an alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof]. The method for forming the photoresist pattern of the present invention is effective for suppressing the occurrence of water mark defects and pattern defects, and can form a high resolution photoresist pattern. [Embodiment] Hereinafter, a best mode for forming a photoresist pattern of the present invention will be specifically described. However, the present invention is an embodiment including all of the specific matters of the invention, and is not limited to the embodiments described below. In the present specification, the term "(meth)acrylate" means the concept of containing both acrylate or methacrylate. The method for forming the photoresist pattern of the present invention is a photoresist pattern having a liquid immersion exposure step of exposing the photoresist to a liquid having a higher refractive index than air (liquid immersion liquid), irradiating the photoresist film with radiation, and exposing the photoresist film. a method for forming a photoresist film on the surface of the substrate, and forming a protective film having a resistance to liquid immersion liquid on the surface of the photoresist film, and intervening the liquid immersion liquid and irradiating the radiation, The photoresist film is exposed, and the protective film is peeled off from the surface of the photoresist film, and then subjected to post-exposure heat treatment and development to form a photoresist pattern. Π] Formation of a photoresist film: * In the method for forming a photoresist pattern of the present invention, first, a photoresist film is formed on the surface of the substrate. Π-l] Substrate: The substrate is usually a germanium wafer, an aluminum-coated silicon wafer, or the like. In order to extract the characteristics of the photoresist film at the maximum limit, it is also preferable to form a film-based or inorganic anti-reflection film on the surface of the substrate in advance (for example, see Japanese Patent Publication No. Hei 6-22452). [1-2] Photoresist film (sensitive radioactive resin composition): • The type of the material for forming the photoresist film is not particularly limited, and may be appropriately selected and used according to the purpose of use of the photoresist, among the materials used for forming the photoresist film. can. However, in the method for forming a photoresist pattern of the present invention, a reinforced chemical resist material containing an acid generator is used, and a positive resist material is particularly preferable. The positive-type resistive material of the reinforced chemical type may, for example, be a radiation-sensitive resin composition containing an acid-dissociable base-modified alkali-soluble resin (component A) and a radiation-sensitive linear acid generator (component B) as essential components. Such a resin composition is an acid generated by an acid generator by radiation irradiation (exposure), -10- 200804989 (7) and by the action of an acid thereby, the acid group of the protective resin (for example, a carboxyl group) is dissociated. The base is dissociated to reveal an acidic group. Therefore, the alkali solubility of the photoresist exposed portion is increased, and the exposed portion is dissolved and removed via the alkali developing solution to form a positive resist pattern. [1-2A] Acid dissociable group-modified alkali-soluble resin (component A) The "acid-dissociable group-modified alkali-soluble resin" has an acidic group, and at least a part of the acidic group is protected by an acid-dissociable group. Resin. This resin exhibits an alkali-insoluble or alkali-insoluble property in a state in which at least a part of the acidic groups of the resin are protected by an acid-dissociable group. However, if the acid-dissociable group is dissociated by the action of an acid, the acidic group is exposed and displayed. An alkali soluble resin is obtained. In addition, the term "alkali-insoluble or alkali-insoluble" means light obtained from a radiation-sensitive resin composition containing an acid-dissociable group-modified alkali-soluble resin (component A) and a radiation-sensitive linear acid generator (component B). In the case where the film formed by the photoresist film is replaced by an acid-soluble modified alkali-soluble resin, the film is formed by the initial film of the film. 50% or more is a property remaining after development 〇* "Acid group" is not particularly limited as long as it is an acidic group. For example, a phenolic hydroxyl group, a carboxyl group or a sulfonic acid group may, for example, be mentioned. Among them, a phenolic hydroxyl group, a carboxyl group or the like is preferred for the reason that the effect of improving the solubility to alkali is high. The acid-dissociable group-modified alkali-soluble resin may have only one acidic group in it, and may have two or more kinds of acidic groups. -11 - 200804989 (8) The specific structure of the acid dissociable group which is contained in the component A is, for example, a repeating unit containing a skeleton represented by the following general formula (3) (hereinafter referred to as "repeated single k" (1) "Polymer as an essential component."
(3) [於前述一般式(3 )中’ R4爲分別表示相同或相異之碳·數 4〜20個之一價脂環式烴基或其衍生物、碳數^4個之直 鏈狀或分支狀烷基、R4彼此爲相互結合,且形成碳數 4〜20個之脂環式烴基或其衍生物亦可。但,R4爲包含至 少一個前述脂環式烴基或其衍生物,或者包含R·4彼此爲 相互結合,形成碳數4〜20個之脂環式烴基或其衍生物的 構造]。 A成分爲上述一般式(3)所示之骨架中’以含有下 述一般式(3a)〜(3d)所示骨架者爲佳。 一 12- 200804989 (9) 3 化 c=lo- R5 oR5(3) [In the above general formula (3), 'R4 is a linear or a mixture of 4 to 20 one-valent alicyclic hydrocarbon groups or derivatives thereof, and a linear number of 4 carbon atoms, respectively. Further, the branched alkyl group and R4 may be bonded to each other, and an alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof may be formed. However, R4 is a structure containing at least one of the aforementioned alicyclic hydrocarbon groups or derivatives thereof, or R.4 which is bonded to each other to form an alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof. The component A is in the skeleton represented by the above general formula (3), and it is preferable to include a skeleton represented by the following general formulas (3a) to (3d).一 12- 200804989 (9) 3 Turn c=lo- R5 oR5
CIOCIO
oR5、 II V / CIOICoR5, II V / CIOIC
OR5 II CIO mOR5 II CIO m
I (3b \^/ (3d [於前述一般式(3 a )〜(3 d )中,R 爲分別相同或相異表 示碳數1〜4個之直鏈狀或分支狀之烷基,m爲表示0或1 ] 〇 前述重複單位(1 )之主鏈構造並無特別限定,但以 (甲基)丙烯酸酯或α -三氟丙烯酸酯之構造爲佳。 前述重複單位(1 )之具體構造以(甲基)丙烯酸2-甲基金剛烷基-2-基酯、(甲基)丙烯酸2 =乙基金剛烷基-2-基酯、(甲基)丙烯酸-2-甲基雙環[2.2.1]庚-2-基酯、 (甲基)丙烯酸-2-乙基雙環[2.2_1]庚-2-基酯、(甲基) 丙烯酸1-(雙環[2.2.1]庚-2-基)-1-甲基乙基酯、(甲基 )丙烯酸1 -(金剛烷-1 -基)-1 -甲基乙基酯、(甲基)丙 烯酸1-甲基-1-環戊酯、(甲基)丙烯酸1-乙基-1-環戊酯 、(甲基)丙烯酸1-甲基-1-環己酯、(甲基)丙烯酸1-乙基-1-環己酯等爲佳。 酸性基之至少一部分爲經酸解離性基所保護之狀態下 -13- 200804989 (10) 顯示鹼不溶性或鹼難溶性,只要具有經由酸作用將酸解離 性基解離露出酸性基且顯示鹼可溶性之性質,則A成分之 構造並無特別限定。因此,A成分並不限於含有重複單位 (1)的聚合物,可由以往,此類用途所使用之樹脂中, ^ 根據目的適當選擇即可。 * 於A成分爲含有重複單位(1 )之情形中,·可爲一種 重複單位(1 )之單聚物,且亦可爲二種以上之重複單位 (1 )的共聚物,並且除了重複單位(1 )以外,含有重複 單位(1 )以外之重複單位的聚合物亦可。重複單位(1 ) 之含有率,相對於全部重複單位,通常,爲〇〜70莫耳%、 15〜60莫耳%爲佳,且以20〜50莫耳%爲更佳。重複單位( 1 )之含有率若超過70莫耳%,則恐曝光充裕度惡化。 另外,構成A成分之聚合物,若至少一部分之酸性基 爲經由酸解離性基予以保護即可,且全部酸性基並非必要 受到酸解離性基所保護。酸解離性基之導入率(相對於構 m 成A成分之聚合物中之酸性基與酸解離性基之合計數之酸 解離性基數的比例),爲根據酸解離性基之種類和作爲基 劑之聚合物種類而異。但,前述導入率爲5〜100%之範圍 爲佳,且以10〜100%之範圍爲更佳。 ^ 關於構成A成分之聚合物的分子量範圍並無特別限定 ,可視需要作成各種分子量之範圍。以膠滲透層析(GPC )所測定之換算成聚苯乙烯之質量平均分子量(有時記述 爲「Mw」)通常爲1,000〜100,〇〇〇,且以1,〇〇〇〜30,000爲 佳,以1,000〜20,000爲更佳。經由作成此類範圍,則可取 -14- 200804989 (11) 得耐熱性,顯像性優良的光阻。另一方面,若構成A成分 之聚合物的Mw爲未滿1,〇〇〇,則所得光阻之耐熱性有不 夠充分之傾向。又,若M w爲超過1 0 0,0 0 0,則恐令所得 光阻的顯像性降低。 ~ 又,關於換算成聚苯乙烯之質量平均分子量Mw與 - GPC所測定之換算成聚苯乙烯之數平均分子量(有時記述 爲「Μη」)之比(Mw/Mn )亦無特別限定,可視需要作 0 成各種分子量之範圍。Mw/Mn之値通常爲1〜5,且以1〜3 爲佳。經由作成此類範圍,則可取得解像度優良之光阻。 [1-2B]敏放射線性產酸劑(B成分): 「敏放射線性產酸劑」爲感應放射線而發生酸的添加 劑。B成分爲經由放射線照射(曝光)而發生酸,且經由 其發生之酸,令保護樹脂酸性基(例如,羧基)的酸解離 性基解離,且酸性基露出。因此,提高光阻之曝光部的鹼 m 溶解性,且經由鹼顯像可形成正型之光阻圖型。 只要具有如上述之性質,則B成分之構造並無特別限 定。因此,可由以往,此類用途中所用之物質中,根據目 的適當選擇即可。可使用例如碘鎗鹽、锍鹽、鳞鹽、重氮 ' 鐵鹽、吡啶鑰鹽等之鐵鹽化合物,含有鹵烷基之烴類化合 物,含有鹵烷基之雜環式化合物等之含鹵素化合物,1,3 -二酮基-2 -重氮化合物、重氮苯醌化合物、重氮萘醌化合物 等之重氮酮化合物;^ -酮基楓、Θ -磺醯諷、和此等化合 物之α -重氮化合物等之楓化合物和磺酸化合物等。 -15- 200804989 (12) 其中,亦以使用下述一般式(4)所示構造之銃鹽爲 佳。 【化4】I (3b \^/ (3d [in the above general formula (3 a ) to (3 d ), R is a linear or branched alkyl group having the same or different carbon number of 1 to 4, m The structure of the main chain of the above repeating unit (1) is not particularly limited, but it is preferably a structure of (meth) acrylate or α-trifluoroacrylate. The specific unit of the above repeating unit (1) Constructed with 2-methyladamantyl-2-yl (meth)acrylate, 2 =ethyladamantyl-2-yl (meth)acrylate, 2-methylbicyclo(methyl)acrylate [ 2.2.1] Hept-2-yl ester, 2-ethylbicyclo[2.2_1]hept-2-yl (meth)acrylate, 1-(bicyclo[2.2.1]heptane-2(meth)acrylate -yl)-1-methylethyl ester, 1-(adamantan-1 -yl)-1-methylethyl (meth)acrylate, 1-methyl-1-cyclopentyl (meth)acrylate Ester, 1-ethyl-1-cyclopentyl (meth)acrylate, 1-methyl-1-cyclohexyl (meth)acrylate, 1-ethyl-1-cyclohexyl (meth)acrylate, etc. Preferably, at least a portion of the acidic group is protected by an acid-dissociable group - 13 - 200804989 (10) showing an alkali-insoluble or alkali The solubility is not particularly limited as long as it has a property of dissociating the acid dissociable group to expose an acidic group by an acid action and exhibiting alkali solubility. Therefore, the component A is not limited to a polymer containing a repeating unit (1). In the case of the resin used in such a use, it may be appropriately selected according to the purpose. * In the case where the component A is a repeating unit (1), it may be a monomer of a repeating unit (1), and Further, a copolymer of two or more kinds of repeating units (1) may be used, and a polymer having a repeating unit other than the repeating unit (1) may be used in addition to the repeating unit (1). The content of the repeating unit (1), Relatively speaking, all of the repeating units are usually 〇70% by mole, 15% to 60% by mole, and more preferably 20 to 50% by mole. The repeating unit (1) is more than 70 moles. %, the exposure margin may be deteriorated. Further, at least a part of the acidic groups of the polymer constituting the component A may be protected by the acid dissociable group, and all the acidic groups are not necessarily protected by the acid dissociable group. Dissociation The ratio of the introduction rate of the base (the ratio of the acid dissociable group of the acid group to the acid dissociable group in the polymer of the component A) is based on the type of the acid dissociable group and the polymerization as a base However, the introduction ratio is preferably in the range of 5 to 100%, and more preferably in the range of 10 to 100%. ^ The molecular weight range of the polymer constituting the component A is not particularly limited, and may be optionally required. The range of various molecular weights is determined. The mass average molecular weight (sometimes referred to as "Mw") converted into polystyrene measured by gel permeation chromatography (GPC) is usually 1,000 to 100, 〇〇〇, and is 1 , 〇〇〇 ~ 30,000 is better, with 1,000 ~ 20,000 as better. By making such a range, it is preferable to use -14-200804989 (11) to obtain a light resistance excellent in heat resistance and development. On the other hand, when the Mw of the polymer constituting the component A is less than 1, the heat resistance of the obtained photoresist tends to be insufficient. Further, if M w is more than 100 and 0 0 0, the development of the obtained photoresist may be lowered. In addition, the ratio (Mw/Mn) of the mass average molecular weight Mw converted to polystyrene to the number average molecular weight (may be described as "Μη") in terms of polystyrene measured by - GPC is not particularly limited. It can be made into a range of various molecular weights as needed. The enthalpy of Mw/Mn is usually from 1 to 5, and preferably from 1 to 3. By forming such a range, it is possible to obtain a photoresist having excellent resolution. [1-2B] Sensitive radioactive acid generator (component B): The "sensitizing radioactive acid generator" is an acid additive that induces radiation. The component B is an acid which generates an acid by radiation (exposure), and an acid generated therethrough dissociates the acid dissociable group of the acidic group (for example, a carboxyl group) of the protective resin, and the acidic group is exposed. Therefore, the alkali m solubility of the exposed portion of the photoresist is improved, and a positive resist pattern can be formed via alkali development. The structure of the component B is not particularly limited as long as it has the above properties. Therefore, it can be appropriately selected according to the purpose of the materials used in such applications. For example, an iron salt compound such as an iodine salt, a phosphonium salt, a scale salt, a diazo' iron salt or a pyridyl salt, a halogenated alkyl hydrocarbon compound, a haloalkyl group-containing heterocyclic compound or the like may be used. a compound, a 1,3 -diketo-2 -diazo compound, a diazonium phthalide compound, a diazonaphthene compound, or the like; a ketone maple, a sulfonium sulfonate, and the like A maple compound such as an α-diazo compound or a sulfonic acid compound. -15- 200804989 (12) Among them, an onium salt having a structure represented by the following general formula (4) is also preferred. 【化4】
R8 [於前述一般式(4)中,R6爲表示氫原子、氟原子、羥基 、碳數1〜10個之直鏈狀或分支狀烷基、碳數1〜10個之直 鏈狀或分支狀烷氧基、碳數2〜11個之直鏈狀或分支狀烷 氧羰基,R7爲表示碳數1〜10個之直鏈或分支狀烷基、烷 氧基、碳數1〜1 0個之直鏈狀、分支狀、環狀鏈烷磺醯基 、r爲表示0〜10之整數。R8爲分別相同或相異表示碳數 1〜1 〇個之直鏈狀或分支狀烷基,亦可經取代之苯基,亦可 φ 經取代之萘基,R8彼此爲相互結合形成碳數2〜1 0個之環 構造或其衍生物亦可。k爲表示0〜2之整數,R9爲表示氟 原子或亦可經取代之碳數1〜1 2個之烴基,η爲表示1〜1 0 之整數]。 Β成分可單獨使用前述之各種產酸劑,且亦可倂用二 種以上。Β成分之配合量爲根據欲賦予至光阻之特性而適 當設定即可,相對於Α成分1〇〇質量份,通常爲0.1〜20 質量份,且以〇 · 5〜1 0質量份爲佳。經由作成此類範圍, 則可取得敏感度、顯像性優良的光阻。另一方面,若B成 -16- 200804989 (13) 分之配合量未滿0.1質量份,則有令敏感度及顯像性降低 之傾向。又,若超過20質量份,則對於放射線的透明恪 降低,且有難以取得矩形之光阻圖型的傾向。 [1-2C]添加劑: ' 於敏放射線性樹脂組成物中,視需要,亦可配合A成 分、B成分以外之添加劑,例如,酸擴散抑制劑,具有酸 φ 解離性基之脂環族添加劑、增感劑、界面活性劑等。 「酸擴散抑制劑」爲抑制經由曝光而由產酸劑等所產 生之酸於光阻膜中的擴散現象,並且具有抑制非曝光領域 中之不佳化學反應之作用的添加劑。經由配合酸擴散抑制 劑,則可提高敏放射線性樹脂組成物的貯藏安定性。又, 經由配合酸擴散抑制劑,則可提高光阻的解像度,並且可 抑制曝光至顯像處理爲止之拉住時間(PED )變動所造成 之光阻圖型的線寬變化。其結果,具有取得處理安定性極 ^ 爲優良之敏放射線性樹脂組成物。 酸擴散抑制劑以不會經由光阻圖型之形成步驟中的曝 光和加熱處理變化成鹼性的含氮有機化合物爲佳。含氮有 機化合物可列舉例如烷胺類、環烷胺類、芳香族胺類、烷 ' 醇胺類等之三級胺化合物,含有N -第三丁氧羰基之胺基 化合物等之含有醯胺基之化合物;氫氧化四正丙基銨、氫 氧化四正丁基胺等之氫氧化四級銨化合物;吡啶類、哌哄 類、咪唑類等之含氮雜環化合物等。此類酸擴散抑制劑可 單獨使用一種,且亦可倂用二種以上。 -17- 200804989 (14) 前述酸擴散抑制劑的配合量,相對於A成分1 00質量 份,通常爲10質量份以下,且以0.001 —10質量份爲佳, 以0.005〜5質量份爲更佳。若前述酸擴散抑制劑之配合量 爲1 0質量份以下,則可提高作爲光阻劑之敏感度和曝光 部之顯像性故爲佳。又,若前述酸擴散抑制劑之配合量爲 • 0.001質量份以上,則可根據處理條件,抑制作爲光阻之 圖型形狀和尺寸忠實度降低,故爲佳。 φ 「具有酸解離性基之脂環族添加劑」爲顯示出令乾式 蝕刻耐性、圖型形狀、與基板之接黏性等進一步改善作用 的成分。前述脂環族添加劑可列舉例如1 -金剛烷羧酸、2-金剛烷酮等之金剛烷衍生物類;脫氧膽酸第三丁酯、脫氧 膽酸第三丁氧羰基甲酯等之脫氧膽酸酯類;三膽酸第三丁 酯、三膽酸第三丁氧羰基甲酯等之三膽酸酯類;己二酸二 甲酯、己二酸二乙酯等之烷基羧酸酯類;3-[2-羥基-2,2-雙 (三氟甲基)乙基]四環[4·4.0·12·5·17,10]十二烷等。 _ 前述脂環族添加劑可單獨使用一種,且亦可倂用二種 以上。前述脂環族添加劑之配合量由提高光阻之耐熱性的 觀點而言,則相對於Α成分100質量份,以5 〇質量份以 下爲佳,且以3 0質量份以下爲更佳。若前述脂環族添加 劑之配合量爲超過5 0質量份,則光阻之耐熱性有不夠充 分之傾、向。 「增感劑」爲吸收放射線的能量,並將其能量傳達到 B成分,顯示出令酸之產量增加的作用,且具有提高敏放 射線性樹脂組成物之表觀敏感度的效果。 -18- 200804989 (15) 增感劑可列舉例如咔唑類、乙醯苯類、二苯酮類、萘 類、酚類、雙乙醯、曙-紅、孟加拉玫瑰、芘類、蒽類、吩 噻哄類等。此些增感劑可單獨使用一種,且亦可倂用二種 以。增感劑之配合量,相對於A成分1 〇〇質量份,以5 〇 質量份以下爲佳。 ' 「界面活性劑」爲顯示出改良塗佈性、線痕性、顯像 性等作用的成分。界面活性劑可使用陰離子系、陽離子系 φ 、非離子系或兩性之界面活性劑之任一者,但以使用非離 子系界面活性劑爲佳。非離子系界面活性劑可列舉例如聚 氧乙烯高級烷醚類、聚氧乙烯高級烷基苯醚類、聚乙二醇 之高級脂肪酸二酯類等,以及以下均以商品名之「KP」( 信越化學工業公司製)、「Polyflow」(共榮社油脂化學 工業公司製)、「Efutop」 (TokemProdncts 公司製)、 「Megafac」(大日本油墨化學工業公司製)、r Fl〇ride 」(住友3M公司製)、「Asahignard」及「Sufuron」( _ 旭硝子公司製)等之各系列等。 此等界面活性劑可單獨使用一種,且亦可混合使用二 , 種以上。界面活性劑之配合量爲相對於敏放射線性樹脂組 成物中之全樹脂成分1 00質量份,通常爲2質量份以下, ^ 且以1 . 5質量份以下爲佳,以1質量份以下爲更佳。 於敏放射線性樹脂組成物中,爲了令曝光部之潛像可 視化、緩和曝光時的暈光作用,亦可配合染料和顏料,且 爲了改善與基板之接黏性亦可配合接黏輔助劑。除了上述 之添加劑以外,亦可列舉防暈劑、保存安定化劑、消泡劑 -19- 200804989 (16)R8 [In the above general formula (4), R6 is a linear or branched alkyl group having a hydrogen atom, a fluorine atom, a hydroxyl group, a carbon number of 1 to 10, or a linear or branched carbon number of 1 to 10. Alkoxy group, a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms, and R 7 is a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group, and a carbon number of 1 to 1 0. One of a linear, branched, or cyclic alkanesulfonyl group, and r is an integer representing from 0 to 10. R8 is a linear or branched alkyl group having the same or different carbon number of 1 to 1 carbon atoms, and may be substituted phenyl or φ substituted naphthyl group, and R8 is bonded to each other to form a carbon number. 2 to 10 ring structures or derivatives thereof may also be used. k is an integer representing 0 to 2, R9 is a fluorine atom or a hydrocarbon group which may be substituted with 1 to 12 carbon atoms, and η is an integer representing 1 to 10]. The above-mentioned various acid generators may be used alone or in combination of two or more. The amount of the ruthenium component to be added is appropriately set according to the properties to be imparted to the photoresist, and is usually 0.1 to 20 parts by mass based on 1 part by mass of the bismuth component, and preferably 〇 5 to 10 parts by mass. . By forming such a range, it is possible to obtain a photoresist having excellent sensitivity and developability. On the other hand, if the blending amount of B is -16 - 200804989 (13) is less than 0.1 part by mass, the sensitivity and developability tend to be lowered. In addition, when it exceeds 20 parts by mass, the transparency 放射 of the radiation is lowered, and it is difficult to obtain a rectangular photoresist pattern. [1-2C] Additive: 'In the sensitive radiation linear resin composition, if necessary, additives other than the A component and the B component may be blended, for example, an acid diffusion inhibitor, an alicyclic additive having an acid φ dissociable group. , sensitizers, surfactants, etc. The "acid diffusion inhibitor" is an additive which suppresses the diffusion of an acid generated by an acid generator or the like in the photoresist film by exposure, and has an effect of suppressing a poor chemical reaction in the non-exposure field. By incorporating an acid diffusion inhibitor, the storage stability of the radiation sensitive resin composition can be improved. Further, by blending the acid diffusion inhibitor, the resolution of the photoresist can be improved, and the change in the line width of the resist pattern due to the change in the pull-in time (PED) until the development process is suppressed can be suppressed. As a result, it has a sensitive radiation linear resin composition which is excellent in handling stability. The acid diffusion inhibitor is preferably a nitrogen-containing organic compound which does not change to alkali by exposure and heat treatment in the formation step of the photoresist pattern. Examples of the nitrogen-containing organic compound include a tertiary amine compound such as an alkylamine, a cycloalkylamine, an aromatic amine, or an alkane alcoholamine, and a guanamine containing an N-tert-butoxycarbonyl group-based amine compound or the like. a compound of a base; a tetra-ammonium hydroxide compound such as tetra-n-propylammonium hydroxide or tetra-n-butylamine hydroxide; a nitrogen-containing heterocyclic compound such as a pyridine, a piperidine or an imidazole. Such an acid diffusion inhibitor may be used alone or in combination of two or more. -17- 200804989 (14) The amount of the acid diffusion inhibitor is usually 10 parts by mass or less, and preferably 0.001 to 10 parts by mass, and 0.005 to 5 parts by mass, based on 100 parts by mass of the component A. good. When the amount of the acid diffusion inhibitor is 10 parts by mass or less, the sensitivity as a photoresist and the development of the exposed portion can be improved. In addition, when the amount of the acid-diffusion inhibitor is 0.001 parts by mass or more, it is preferable to suppress the decrease in the shape and dimensional fidelity as a resist depending on the processing conditions. φ "The alicyclic additive having an acid-dissociable group" is a component which exhibits a further improvement in dry etching resistance, pattern shape, adhesion to a substrate, and the like. Examples of the alicyclic additive include adamantane derivatives such as 1-adamantanecarboxylic acid and 2-adamantanone; deoxycholate such as deoxycholic acid tert-butyl ester and deoxycholic acid third butoxycarbonyl methyl ester; Acid esters; tricholates such as tributyl cholesterate, tributyloxycarbonyl methyl trisulphate; alkyl carboxylates such as dimethyl adipate, diethyl adipate, etc. Class; 3-[2-hydroxy-2,2-bis(trifluoromethyl)ethyl]tetracyclo[4·4.0·12·5·17,10]dodecane and the like. _ The above alicyclic additive may be used alone or in combination of two or more. The blending amount of the above-mentioned alicyclic additive is preferably 5 parts by mass or less, and more preferably 30 parts by mass or less, based on 100 parts by mass of the bismuth component, from the viewpoint of improving the heat resistance of the photoresist. When the amount of the alicyclic additive is more than 50 parts by mass, the heat resistance of the photoresist is insufficiently sufficient. The "sensitizer" is an energy that absorbs radiation and transmits its energy to the component B, exhibits an effect of increasing the yield of the acid, and has an effect of improving the apparent sensitivity of the composition of the radioactive resin. -18- 200804989 (15) Examples of the sensitizer include oxazoles, acetophenones, benzophenones, naphthalenes, phenols, diacetamidines, anthracene-red, bengal roses, anthraquinones, anthraquinones, Phenothiazines and the like. These sensitizers may be used alone or in combination of two. The amount of the sensitizer is preferably 5 parts by mass or less based on 1 part by mass of the component A. The "surfactant" is a component that exhibits effects such as improved coatability, line traceability, and development. As the surfactant, any of an anionic, cationic φ, nonionic or amphoteric surfactant may be used, but a nonionic surfactant is preferably used. Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol, and the following are commercially available under the trade name "KP" ( "Shin-Etsu Chemical Co., Ltd.", "Polyflow" (manufactured by Kyoei Oil & Fat Chemical Industry Co., Ltd.), "Efutop" (manufactured by TokemProdncts Co., Ltd.), "Megafac" (made by Dainippon Ink Chemical Industry Co., Ltd.), r Fl〇ride" (Sumitomo Each series such as "3M company", "Asahignard" and "Sufuron" (_ Asahi Glass Co., Ltd.). These surfactants may be used alone or in combination of two or more. The blending amount of the surfactant is preferably 1 part by mass or less based on the total resin component in the radiation sensitive resin composition, and is preferably 1.5 parts by mass or less, and 1 part by mass or less. Better. In the radiation-sensitive linear resin composition, in order to visualize the latent image of the exposed portion and to alleviate the blooming effect during exposure, a dye and a pigment may be blended, and a tackifier may be blended for the purpose of improving the adhesion to the substrate. In addition to the above additives, anti-corona agents, storage stabilizers, and antifoaming agents may also be cited. -19- 200804989 (16)
[1-2D]溶劑: 於敏放射線性樹脂組成物中,除了 A成分、B 各種添加劑以外,亦可配合溶劑。經由配合溶劑, 高對基板塗佈敏放射線性樹脂組成物時的塗佈性。 「溶劑」之種類並無特別限定,可列舉例如2· 3-甲基-2-丁酮等之直鏈狀或分支狀之酮類;環戊酮 基環戊酮等之環狀酮類;丙二醇單甲醚醋酸酯等之 單烷醚醋酸酯類;2-羥基丙酯甲酯等之2-羥基丙酸 ;3-甲氧基丙酸甲酯等之3-烷氧基丙酸烷酯類以外 舉r -丁內酯等。此等溶劑可單獨可混合使用二種 [1-3]光阻膜之形成: 光阻膜爲例如於A成分、B成分,各種添加劑 0 溶劑,將其全固形成分濃度調整至5〜50質量%,並 3 Onm左右之濾紙將此溶液過濾調製塗佈液,且將 液使用迴轉塗佈、流涎塗佈、輥塗佈等之先前公知 方法於基板上塗佈則可形成。此光阻膜爲了令溶劑 亦可進行預備锻燒(以下,有時記述爲「PB」)。 形成光阻膜時,塗佈液可自行調製,且亦可使用市 阻溶液作爲塗佈液。 [2]保護膜之形成: 成分、 則可提 丁酮、 、3-甲 丙二醇 烷酯類 ,可列 上0 中加入 以孔徑 此塗佈 的塗佈 揮發, 另外, 售之光 -20- 200804989 (17) 本發明之方法爲如上述形成光阻膜後, 面形成對於液浸液具有耐性的保護膜。經由 則可於液浸液曝光時,防止液浸液與光阻膜 有效防止因液浸之浸透令光阻膜的光刻性能 * 有效防止由光阻膜溶出之成分令投影曝光裝 * 污染的事態。 保護膜爲由可形成對於液浸液(例如, I 之膜,加上液浸曝光後可容易剝離之材料所 常爲以樹脂形成。另外,所謂「對於液浸液 指根據後述對於水之安定性評價方法測定時 初期膜厚的3%以內。 [安定性評價試驗] (1 ):使用 C 〇 a t e r / D e v e 1 ο p e r ( 1 ) CLEAN TRACK ACT8、東京 Electron 公司製 φ 晶圓上,將形成保護膜用塗佈液(令形成保 解於溶劑者)旋轉塗佈,並以90 °C、60秒 PB,形成膜厚90nm之保護膜。使用光千擾 置(商品名:λ SVM-2010、大日本 Screen * 測定此保護膜(當初膜厚)。 (2):其次,於形成此保護膜之晶圓 Coater/Developer ( 1 )之清洗管嘴令超純水 後,以迴轉數4000rpm振動甩開15秒鐘, 。再度測定此時保護膜之膜厚,算出保護膜 於此光阻膜表 形成保護膜, 直接接觸,可 降低,並且可 置之透鏡受到 純水等)安定 形成爲佳,通 安定」’爲意 之膜厚變化在 (商品名: ),於8吋矽 護膜用樹脂溶 鐘之條件進行 式膜厚測定裝 製造公司製) 表面,由前述 吐出 6 0秒鐘 進行旋轉乾燥 的膜厚變化( -21 - 200804989 (18) 已減少之膜厚)。相對於當初膜厚所減少之膜厚比率若爲 3%以內,則評價爲「對於液浸液安定」。 形成保護膜之樹脂(形成保護膜用樹脂)只要具有如 上述之性質,則其構造並無特別限定。因此,形成保護膜 用樹脂可由先前於此類用途中所用之樹脂中,根據目的適 • 當選擇即可。但,於本發明之方法中,使用脂溶性之樹脂 作爲形成保護膜用樹脂爲佳。若以脂溶性樹脂形成保護膜 φ ,則可使用有機溶劑將保護膜剝離,且於液浸曝光後,鹼 顯像前,可僅剝離保護膜。即,因爲於曝光後加熱處理和 顯像前進行保護膜之剝離,故可有效防止起因於保護膜浸 透液浸液之水痕缺陷和圖型不良缺陷。另外,此脂溶性樹 脂只要對於有機溶劑具有溶解性,則亦可爲鹼中可溶性的 樹脂。 脂溶性樹脂爲例如以含有下述一般式(1 )及下述一 般式(2 )所組成群中選出至少一種重複單位之聚合物作 $ 爲構成成分的樹脂爲佳。此些樹脂因於其構造中具有三氟 甲基和碳數4〜20個之脂環式烴基,故可形成對於泛用作 _ 爲液浸液之純水具有耐性的保護膜,加上因爲脂溶性高, 故例如可經由高級醇、多元醇、烷基醋酸酯、烷醚等之有 機溶劑輕易剝離。 -22 - 200804989 (19) 【化5】 R1[1-2D] Solvent: In addition to the components A and B, the solvent may be blended with the solvent. The coating property when the radiation sensitive linear resin composition is applied to the substrate is high through the compounding solvent. The type of the "solvent" is not particularly limited, and examples thereof include a linear or branched ketone such as 2/3-methyl-2-butanone; and a cyclic ketone such as cyclopentanonecyclopentanone; a monoalkyl ether acetate such as propylene glycol monomethyl ether acetate; 2-hydroxypropionic acid such as 2-hydroxypropyl methyl ester; and 3-alkoxypropionic acid alkyl ester such as methyl 3-methoxypropionate Excluding r-butyrolactone and the like. These solvents may be used alone to form a mixture of two [1-3] photoresist films: the photoresist film is, for example, a component A, a component B, various additives, 0 solvent, and the total solid concentration is adjusted to 5 to 50 mass. %, and about 3 Onm filter paper This solution is filtered to prepare a coating liquid, and the liquid can be formed by coating the liquid on a substrate by a conventionally known method such as rotary coating, flow coating, roll coating, or the like. This resist film may be subjected to preliminary calcination (hereinafter, referred to as "PB") in order to allow the solvent to be used. When the photoresist film is formed, the coating liquid can be self-modulated, and a barrier solution can also be used as the coating liquid. [2] Formation of protective film: Ingredients, but can be butanone, 3-methylpropanediol alkyl ester, can be listed as 0 in the coating with the pore size of the coating volatilization, in addition, sold in the light -20- 200804989 (17) The method of the present invention is to form a protective film having resistance to a liquid immersion liquid after forming a photoresist film as described above. Through the exposure of the liquid immersion liquid, the liquid immersion liquid and the photoresist film are prevented from effectively preventing the lithographic performance of the photoresist film due to the immersion of the liquid immersion*. Effectively preventing the component eluted by the photoresist film from contaminating the projection exposure device* situation. The protective film is formed of a resin which can be formed into a liquid immersion liquid (for example, a film of I, which can be easily peeled off after immersion exposure. Further, "the liquid immersion liquid refers to the stability of water according to the following. The evaluation method is within 3% of the initial film thickness. [Stability evaluation test] (1): Use C 〇ater / D eve 1 ο per ( 1 ) CLEAN TRACK ACT8, φ wafer made by Tokyo Electron Co., Ltd. A coating liquid for a protective film (which is formed into a solvent) was spin-coated, and a protective film having a film thickness of 90 nm was formed at 90 ° C for 60 seconds PB. The light was disturbed (trade name: λ SVM- 2010, Dainippon Screen * Determine the protective film (initial film thickness). (2): Secondly, after the cleaning nozzle of the Coater/Developer (1) wafer forming the protective film is made of ultrapure water, the number of revolutions is 4000 rpm. The vibration is opened for 15 seconds, and the film thickness of the protective film is measured again, and the protective film is formed on the resist film surface to form a protective film, which is directly contacted, and can be lowered, and the lens can be stabilized by pure water or the like. Good, Tong'an Ding' In the case of (product name: ), the film thickness measurement was carried out under the conditions of a resin-melting clock for a film of 8 )), and the film thickness of the surface was rotated by the above-described discharge for 60 seconds (-21 - 200804989 (18) Reduced film thickness). When the ratio of the film thickness which is reduced by the film thickness is within 3%, it is evaluated as "the stability of the liquid immersion liquid". The resin forming the protective film (the resin for forming the protective film) is not particularly limited as long as it has the above properties. Therefore, the resin for forming the protective film can be selected from the resins previously used in such applications, depending on the purpose. However, in the method of the present invention, a fat-soluble resin is preferably used as the resin for forming a protective film. When the protective film φ is formed of a fat-soluble resin, the protective film can be peeled off using an organic solvent, and after the liquid immersion exposure, only the protective film can be peeled off before the alkali image is developed. That is, since the protective film is peeled off after the post-exposure heat treatment and development, it is possible to effectively prevent water mark defects and pattern defects caused by the protective film impregnation liquid immersion liquid. Further, the fat-soluble resin may be a resin soluble in alkali as long as it has solubility in an organic solvent. The fat-soluble resin is preferably a resin containing, as a constituent component, a polymer having at least one repeating unit selected from the group consisting of the following general formula (1) and the following general formula (2). These resins have a trifluoromethyl group and an alicyclic hydrocarbon group having 4 to 20 carbon atoms in the structure, so that a protective film which is resistant to pure water which is widely used as a liquid immersion liquid can be formed, and Since it has high fat solubility, it can be easily peeled off, for example, by an organic solvent such as a higher alcohol, a polyhydric alcohol, an alkyl acetate, or an alkyl ether. -22 - 200804989 (19) 【化5】 R1
+CH 2·+CH 2·
(2) (1) [但,於一般式(1 )或(2 )中,R1爲表示氫、甲基或三 氟甲基,R2爲表示二價之有機基,R3爲表示碳數4〜20個 之脂環式烴基或其衍生物。 一般式(1 )中,R2所示之「二價之有機基」可列舉 例如二價之烴基、伸烷基二元醇基、伸烷基酯基般之含有 碳原子、氫原子以外之原子的二價有機基等。其中亦以直 鏈狀、分支狀或環狀之二價烴基爲佳,且以直鏈狀或分支 狀之飽和烴基、單環式烴環基或交聯環式烴環基等爲更佳 「直鏈狀或分支狀之飽和烴基」以亞甲基、伸乙基、 1,2-伸丙基、1,3-伸丙基、伸丁基、伸戊基、伸己基、伸 庚基、伸辛基、伸壬基、伸癸基、伸--烷基、伸十二院 基、伸十三烷基、伸十四烷基、伸十五烷基、伸十六院基 、伸十七烷基、伸十八烷基或伸十九烷基等之直鏈狀伸院 基,1-甲基-1,3 -伸丙基、2 -甲基-1,3 -伸丙基、2 -甲基- i,2_ 伸丙基、1-甲基-1,4-伸丁基或2 -甲基-1,4 -伸丁基等之分支 狀伸烷基;亞乙基、亞丙基或2-亞丙基等之亞院基等爲合 -23- 土 ..... 口 200804989 (20) 適。 「單環式烴環基」爲碳數3〜10個之伸魯烷基,-具體 而言以1,3-伸環丁基、1,3-伸環戊基、1,4-伸環己基、l,5- 伸環辛基等爲合適。「交聯環式烴環基」爲碳數4〜30個 * 且環數爲2〜4個之烴環基,具體而言以1,4-伸原冰片基、 , 2,5-伸原冰片基等之伸原冰片基;1,5-伸金剛烷基、2,6-伸 金剛烷基等之伸金剛烷基等爲合適。 φ 「二價之有機基」亦可結合此些官能基者。例如,於 「二價之有機基」爲於其構造中具有單環式烴環基或交聯 環式烴環基之情形中,於其基之終端,作爲與重複單位( 1 )之雙(三氟甲基)-羥甲基間之間隔件,以結合碳數 1〜4個之直鏈狀伸烷基的構造爲佳。 於以上說明之「二價之取代基」中,以含有2,5-伸 原冰片基之二價烴基、1,2-伸乙基或伸丙基爲佳。 於一般式(2 )中,R3之碳數4〜20個之脂環式烴基可 • 列舉例如,原冰片烷、三環癸烷、四環十二烷、金剛烷、 和來自環丁烷、環戊烷、環己烷、環庚烷、環辛烷等之環 鏈烷類之脂環式烴基;將此些脂環式烴基之氫原子,例如 ,以甲基、乙基、正丙基、異丙基、正丁基、2-甲基丙基 ' 、1-甲基丙基、第三丁基等之碳數1〜4個之直鏈狀、分支 狀或環狀烷基之一種以上或一個以上所取代之基等。此些 脂環式烴基中,以來自原冰片烷、三環癸烷、四環十二烷 、金剛烷、環戊烷或環己烷之脂環式烴基,和令此些脂環 式烴基之氫原子經前述烷基所取代之基等爲佳。 -24- 200804989 (21) 用以形成保護膜之脂溶性樹脂,即使未含有全部之重 複單位(1 )或重複單位(2 )亦可,— 且亦可僅含有一種, 含有二種以上亦可。又,亦可含有重複單位(丨)或重複 單位(2 )以外之重複單位。但,重複單位(〗)與重複單 位(2 )之總含有率,相對於全部重複單位,以5 0〜1 00莫 ‘ 耳%爲佳,且以60〜100莫耳%爲更佳,以70〜100莫耳%爲 特佳。若重複單位(1 )與重複單位(2 )之總含有率爲5 0 φ 莫耳%以下,則恐無法充分表現作爲保護膜的特性。 關於形成保護膜之脂溶性樹脂的分子量範圍並無特別 限定,視需要可作成各種的分子量範圍。以膠滲透層析( GPC )測定之換算成聚苯乙烯之質量平均分子量(有時記 述爲 「Mw」),通常爲 2,000〜200,000 ,且以 2,500〜1 00,000爲佳,以3,000〜50,000爲更佳。經由作成 此類範圍,則具有可形成對於有機溶劑之溶解性優良,並 且耐水性及機械特性高之保護膜的優點。另一方面,若形 _ 成保護膜之脂溶性樹脂的Mw爲未滿2,000,則恐無法形 成耐水性及機械特性高的保護膜。又,若Mw爲超過 200,000,則恐對於有機溶劑的溶解性降低。 另外,用以形成保護膜之脂溶性樹脂以鹵素、金屬等 雜質愈少愈佳,如此,可更加改善作爲保護膜的塗佈性和 對於有機溶劑的均勻溶解性。樹脂之精製法可列舉例如, 水洗、溶液萃取等之化學性精製法’和此些化學性精製法 與超過濾、離心等之物理性精製法組合的精製法等。用以 形成保護膜之脂溶性樹脂可單獨使用一種,且亦可混合使 -25- 200804989 (22) 用二種以上。 用以形成保護膜之脂溶性樹脂爲加入適當的有機溶劑 ,將其全固形成分濃度調整至0.1〜20質量%左右,並以孔 徑3 Onm左右之濾紙將此溶液過濾調製塗佈液,並且將此 塗佈液使用迴轉塗佈、流涎塗佈、輥塗佈等之先前公知的 塗佈方法於光阻膜上塗佈則可形成。此保護膜爲了令溶劑 揮發亦可進行煅燒。 調製上述塗佈液時所用之有機溶劑,可考慮脂溶性樹 脂之溶解性適當選擇,但以使用醇類爲佳,以使用一元醇 類爲更佳,以使用碳數爲1〜1 0個之一元醇類爲特佳。此 些有機溶劑爲脂溶性樹脂的溶解性優良,加上難引起與作 爲塗佈對象之光阻膜的層間混合,就對光刻性能造成不良 影響之可能性低方面爲佳。 「碳數1〜10個之一元醇」可列舉例如,甲醇、乙醇 、1 -丙醇、異丙醇、正丙醇、1 - 丁醇、2 - 丁醇、第三丁醇 、1-戊醇、2-戊醇、3-戊醇、正己醇、環己醇、2-甲基-2-丁醇、3 -甲基-2-丁醇、2 -甲基-1-丁醇、3 -甲基-1-丁醇、 2-甲基-1-戊醇、2-甲基-2-戊醇、2-甲基-3-戊醇、3-甲基-1-戊醇、3 -甲基-2-戊醇、3 -甲基-3-戊醇、4 -甲基-1-戊醇 、4-甲基-2-戊醇等之碳數1〜6個之一元醇類;2,2-二甲 基-3 -戊醇、2,3 -二甲基-3 -戊醇、2,4 -二甲基-3 -戊醇、4,4 -二甲基-2-戊醇、3-乙基-3-戊醇、1-庚醇、2-庚醇、3-庚醇 、2 -甲基-2 -己醇、2 -甲基-3 -己醇、5 -甲基-1 -己醇、5 -甲 基-2-己醇等之碳數7個之一元醇類;2-乙基-1-己醇、4- -26 - 200804989 (23) 甲基-3-庚醇、6-甲基-2_庚醇、1-辛醇、2-辛醇、3-辛醇、 2-丙基一 1-戊醇、2,4,4-三甲基-1-戊醇等之碳數8個之一元 醇類;2,6-二甲基-4-庚醇、3-乙基-2,2-二甲基-1-戊醇、1-壬醇、2-壬醇、3,5,5-三甲基-1-己醇等之碳數9個之一元 醇類;1-癸醇、2-癸醇、4-癸醇、3,7-二甲基-1-辛醇、 • 3,7 -二甲基-3 -辛醇等之碳數10個之一元醇類。於此些醇 類中,由低溫時難凝固,且於光阻膜難殘留之理由而言, ^ 以使用4-甲基-2-戊醇、丁醇、己醇或其混合溶劑爲佳。 於調製塗佈液之有機溶劑中,於調整對於光阻膜之塗 佈性的目的下,亦可混合其他溶劑。「其他溶劑」若由爲 了可將保護膜均勻塗佈,而可充分溶解形成保護膜用樹脂 ,且難溶解光阻膜之溶劑中適當選擇即可。 「其他溶劑」可列舉乙二醇、丙二醇等之多元醇類; 四氫呋喃、二噚烷等之環狀醚類;乙二醇單甲醚、乙二醇 單乙醚、乙二醇二甲醚、乙二醇二乙醚、二乙二醇單甲醚 m 、二乙二醇單乙醚、二乙二甲醚、二乙二醇二乙醚、二乙 二醇乙基甲醚、丙二醇單甲醚、丙二醇單乙醚等之多元醇 的烷醚類;乙二醇乙醚醋酸酯、二乙二醇乙醚醋酸酯、丙 二醇乙醚醋酸酯、丙二醇單甲醚醋酸酯等之多元醇的烷醚 _ 醋酸酯類;甲苯、二甲苯等之芳香族烴類;丙酮、甲基乙 基酮、甲基異丁基酮、環己酮、4-羥基-4-甲基-2-戊酮、 雙丙酮醇等之酮類;醋酸乙酯、醋酸丁酯、2-羥基丙酸乙 酯、2-羥基-2-甲基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、 乙氧基醋酸乙酯、羥基醋酸乙酯、2-羥基-3-甲基丁酸甲酯 -27- 200804989 (24) 、3 -甲氧基丙烯甲酸、3 -甲氧基丙酸乙酯、3 -乙氧基丙酸 乙酯、3 -乙氧基丙酸甲酯等之酯類;水等,其中,以使用 環狀醚類、多元醇之烷醚類、多元醇之烷醚醋酸酯類、酮 類、酯類、水爲佳。 ^ 有機溶劑可單獨使用一種,且亦可倂用二種以上,且 , 只要可維持溶劑的均勻性則亦可含有水。因爲低溫時難凝 固,且發揮難殘留於光阻膜的效果,故有機溶劑中之碳數 ^ 10個以下之一元醇含量相對於全溶劑爲10〜100質量%爲 佳,且以20〜100質量%爲更佳。 於上述塗佈液中,於提高塗佈性、消泡性、勻塗性等 之目的下,亦可配合界面活性劑。界面活性劑可使用以下 全部以商品名之BM- 1 000、BM-1 100 (以上,BM Chem公 司製),Mega fac F142D、同 F172、同 F173、同 F183 ( 以上,大日本油墨化學工業公司製)、Floride FC-135、 同FC-170C、同FC-430、同FC-431 (以上,住友3M公司 _ 製),Sufuron S-112、同 S-113、同 S-131、同 S=141、同 S-145 (以上,旭硝子公司製)、SH-28PA、同-190、同-193、SZ-6032、SF-8428 (以上,東雷 Dowconing Silicone 公司製)等之氟系界面活性劑。此些界面活性劑之配合量 * 相對於脂溶性樹脂1 00質量份爲5質量份以下爲佳。 保護膜之厚度爲儘可能接近λ /4m (但,λ :放射線 之波長、m :保護膜之折射率)的奇數倍爲佳。因係可令 光阻膜之上側界面的抑制反射效果變大。 -28- 200804989 (25) [3 ]液浸曝光: 本發明之方法爲具備在中介存在比空氣之折射率更高 之液體(液浸液)的狀態下,對光阻膜照射放射線,令此 光阻0吴曝光之液浸曝光的步驟。 液浸液若爲比空氣之折射率更高的液體即可,通常爲 • 使用水,且以使用純水爲佳。於中介存在此液浸液的狀態 下(即,於曝光裝置之透鏡與光阻膜之間注滿液浸液的狀 φ 態)’透過具有指定圖型之光罩照射放射線,令光阻膜曝 光。 液浸曝光時可使用的放射線,爲根據所使用之光阻膜 和保護膜之種類而適當選擇,可使用例如,可見光線;g 射線、i射線等之紫外線、激元雷射等之遠紫外線;同步 加速器放射線等之X射線;電子射線等之荷電粒子射線等 之各種放射線。其中,亦以使用 ArF激光雷射(波長 193ixm)或KrF激光雷射(波長248nm)爲佳。又,放射 0 線量等之曝光條件爲根據敏放射線性樹脂組成物之配合組 成、添加劑之種類等而適當設定。 [4]剝離保護膜: ' 光阻膜曝光後,將保護膜由前述光阻膜之表面剝離。 於本發明之方法中,其特徵爲在於曝光後加熱處理和顯像 前進行此保護膜的剝離。雖亦考慮在光阻膜之鹼顯像時剝 離保護膜,但經由在曝光後加熱處理和顯像前進行保護膜 之剝離,則可有效防止起因於浸透保護膜之液浸液的水痕 -29 - 200804989 (26) 缺陷和圖型不良缺陷。 剝離之方法並無特別限定,但以不損害光阻膜之光阻 型系性能的方法爲佳。例如,如已說明般之以脂溶性樹脂 形成保護膜’並且使用有機溶劑進行保護膜剝離之方法爲 • 佳。 • 保護膜剝離中所用之有機溶劑爲根據保護膜之組成而 異,但以一元醇爲佳,其中亦以碳數10個以下之一元醇 0 爲特佳。此類有機溶劑爲保護膜之溶解性優良,加上難因 與光阻膜之居間混合產生光刻性能之降低’故爲佳。 一元醇類中,由低溫時難凝固,即使使用於保護膜剝 離亦難殘留於光阻膜之理由而言,以4-甲基-2-戊醇、丁 醇、己醇或其混合溶劑爲佳。另外’ 一元醇亦可與其他有 機溶劑混合使用,但此混合溶劑之全質量中’一元醇爲含 有10〜100質量%爲佳,且以含有20〜100質量%爲佳。 保護膜剝離中所用之有機溶劑亦可含有酸。此時,酸 _ 以使用解離常數(pKa )爲5以下之化合物爲佳。解離常 數(pKa )爲超過5之化合物,有時顯像後之光阻圖型的 剖面形狀發生頭部擴張等之不適。 解離常數(pKa )爲5以下之化合物以有機酸爲佳, ' 且以分子內具有磺基(-so2oh)之磺酸類或具有羧基之羧 酸類爲更佳,以磺酸類爲特佳。磺酸類因解離常數(PKa )小,且酸性度高故適合使用。 磺酸可列舉甲烷磺酸、乙烷磺酸、丙烷磺酸、異丙烷 磺酸、丁烷磺酸、異丁烷磺酸、1,1 -二甲基乙烷磺酸、戊 -30- 200804989 (27) 烷磺酸' 1 -甲基丁烷磺酸、2 -甲基丁烷磺酸、3 -甲基丁烷 磺酸、新戊烷磺酸、己烷磺酸、奥烷-磺-酸、辛院磺酸、壬 烷磺酸、癸烷磺酸等之烷基磺酸類;苯磺酸、2_甲苯磺酸 .、3-甲苯磺酸、4-甲苯磺酸、4-乙基苯磺酸、4_丙基苯磺 酸、4· 丁基苯磺酸、4-(第三丁基)苯磺酸、2,5_二甲基 苯磺酸、2-来基磺酸、2,4-二硝基苯磺酸、4-氯基苯磺酸 、4-溴基苯磺酸、4-氟基苯磺酸、2,3,4,5,6-五氟苯磺酸、 0 4 -經基苯磺酸、4 -磺基苯甲酸、4 -磺基苯胺等之芳基磺酸 類、苄基磺酸、苯乙基磺酸等之芳烷基磺酸類,樟腦磺酸 等之環式磺酸類等。保護膜剝離中所用之有機溶劑可單獨 含有一種酸,且亦可含有二種以上之酸。 [5] 曝光後加熱處理: 於本發明之方法中,由光阻膜表面將保護膜剝離後’ 進行曝光後加熱處理(Post Exposure Bake,以下’有時 • 記述爲「PEB」)。經由進行PEB,則可提高光阻的解像 度、圖型形狀、顯像性等,故爲佳。PEB.的加熱條件爲根 據敏放射線性樹脂組成物的配合組成,添加劑的種類等而 異,但以30〜200°C爲佳,且以50〜150°C爲更佳。 [6] 顯像: 於本發明之方法中,進行曝光後加熱處理後,進行顯 像,取得光阻圖型形成體。例如,若由含有酸解離性基修 飾鹼可溶性樹脂、和敏放射線性產酸劑之敏放射線性樹脂 200804989 (28) 組成物所得的光阻膜時,則可經鹼顯像液予以顯像取得光 阻圖型形成體。 鹼顯像液可使用例如將氫氧化鈉、氫氧化鉀、碳酸鈉 、矽酸鈉、偏矽酸鈉、氨、乙基胺、正丙基胺、一乙基胺 、二-正丙基胺、三乙基胺、甲基二乙基胺、一甲基乙醇 - 胺、三乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、吡咯 哌啶、膽鹼、1,8-二吖雙環[5·4·0]-7-十一碳烯、1,5-二吖(2) (1) [However, in the general formula (1) or (2), R1 represents hydrogen, methyl or trifluoromethyl, R2 represents a divalent organic group, and R3 represents a carbon number of 4~ 20 alicyclic hydrocarbon groups or derivatives thereof. In the general formula (1), the "divalent organic group" represented by R2 may, for example, be a hydrocarbon such as a divalent hydrocarbon group, an alkylene glycol group or an alkyl ester group, and may contain a carbon atom or an atom other than a hydrogen atom. The divalent organic group and the like. Among them, a linear, branched or cyclic divalent hydrocarbon group is preferred, and a linear or branched saturated hydrocarbon group, a monocyclic hydrocarbon ring group or a crosslinked cyclic hydrocarbon ring group is preferred. a linear or branched saturated hydrocarbon group" is a methylene group, an extended ethyl group, a 1,2-propyl group, a 1,3-propanyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Stretching octyl, stretching base, stretching base, stretching - alkyl, stretching 12 yards, stretching tridecyl, stretching tetradecyl, stretching pentadecyl, stretching 16 yards, stretching ten a linear chain of pentaalkyl, octadecyl or hexadecyl, 1-methyl-1,3-propanyl, 2-methyl-1,3-propanyl, a branched alkyl group of 2-methyl-i, 2_ propyl, 1-methyl-1,4-butyl or 2-methyl-1,4-butylene; ethylene, arylene The sub-base of propyl or 2-propylene, etc. is -23- soil..... mouth 200804989 (20) suitable. The "monocyclic hydrocarbon ring group" is a condensed alkyl group having 3 to 10 carbon atoms, specifically, a 1,3-cyclopentene butyl group, a 1,3-cyclopentylene group, and a 1,4-stretched ring. Hexyl, l,5-cyclohexyl group and the like are suitable. "Crosslinked cyclic hydrocarbon ring group" is a hydrocarbon ring group having 4 to 30 carbon atoms* and a number of rings of 2 to 4, specifically, 1,4-extension borneol, 2,5-extension An borneol base such as a borneol base; a stretched adamantyl group such as 1,5-adamantyl, 2,6-adamantyl or the like is suitable. φ "Divalent organic group" can also be combined with such functional groups. For example, in the case where the "divalent organic group" has a monocyclic hydrocarbon ring group or a crosslinked cyclic hydrocarbon ring group in its structure, at the terminal of its group, it is a double with the repeating unit (1) ( The spacer between the trifluoromethyl)-hydroxymethyl group is preferably a structure in which a linear alkyl group having 1 to 4 carbon atoms is bonded. In the "divalent substituent" described above, a divalent hydrocarbon group having a 2,5-extension borneol group, a 1,2-extended ethyl group or a stretching propyl group is preferred. In the general formula (2), the alicyclic hydrocarbon group having 4 to 20 carbon atoms of R3 can be enumerated, for example, norbornane, tricyclodecane, tetracyclododecane, adamantane, and cyclobutane, An alicyclic hydrocarbon group of a cycloalkane such as cyclopentane, cyclohexane, cycloheptane or cyclooctane; a hydrogen atom of such an alicyclic hydrocarbon group, for example, a methyl group, an ethyl group, or a n-propyl group One of linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms, such as isopropyl, n-butyl, 2-methylpropyl', 1-methylpropyl or t-butyl. The base or the like substituted by the above or more. Among the alicyclic hydrocarbon groups, an alicyclic hydrocarbon group derived from ortho-norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane, and such an alicyclic hydrocarbon group A hydrogen atom or the like substituted by the aforementioned alkyl group is preferred. -24- 200804989 (21) The fat-soluble resin used to form the protective film may not contain all of the repeating units (1) or repeating units (2), and may contain only one type, and may contain two or more types. . Further, it may contain a repeating unit other than the repeating unit (丨) or the repeating unit (2). However, the total content ratio of the repeating unit (〗) and the repeating unit (2) is preferably from 50 to 100%, and more preferably from 60 to 100% by mole, based on the total repeating unit. 70 to 100% of the mole is especially good. When the total content of the repeating unit (1) and the repeating unit (2) is 5 0 φ mol% or less, the characteristics as a protective film may not be sufficiently exhibited. The molecular weight range of the fat-soluble resin forming the protective film is not particularly limited, and various molecular weight ranges can be produced as needed. The mass average molecular weight (sometimes referred to as "Mw") converted to polystyrene by gel permeation chromatography (GPC), usually 2,000 to 200,000, preferably 2,500 to 1,00,000, and 3,000 to 50,000. good. By forming such a range, there is an advantage that a protective film excellent in solubility in an organic solvent and having high water resistance and mechanical properties can be formed. On the other hand, if the Mw of the fat-soluble resin in the form of a protective film is less than 2,000, it is feared that a protective film having high water resistance and high mechanical properties cannot be formed. Further, when Mw is more than 200,000, the solubility in an organic solvent may be lowered. Further, the fat-soluble resin for forming the protective film is preferably as small as impurities such as halogen or metal, so that the coatability as a protective film and the uniform solubility to an organic solvent can be further improved. For the resin purification method, for example, a chemical purification method such as water washing or solution extraction, and a purification method in which the chemical purification method is combined with a physical purification method such as ultrafiltration or centrifugation. The fat-soluble resin used to form the protective film may be used singly or in combination of two or more kinds of -25-200804989 (22). The fat-soluble resin for forming a protective film is added to a suitable organic solvent, and the total solid concentration thereof is adjusted to about 0.1 to 20% by mass, and the solution is filtered to prepare a coating liquid with a filter paper having a pore diameter of about 3 Onm, and This coating liquid can be formed by coating on a photoresist film using a previously known coating method such as rotary coating, flow coating, roll coating, or the like. This protective film can be calcined in order to volatilize the solvent. The organic solvent used in the preparation of the above coating liquid can be appropriately selected in consideration of the solubility of the fat-soluble resin. However, it is preferred to use an alcohol, and it is more preferable to use a monohydric alcohol to use a carbon number of 1 to 10. Monohydric alcohols are particularly good. These organic solvents are excellent in solubility of the fat-soluble resin, and it is preferable that the interlayer of the photoresist film to be coated is difficult to be mixed, and the possibility of adversely affecting the lithographic performance is low. Examples of the "1 to 10 carbon atoms of the carbon number" include methanol, ethanol, 1-propanol, isopropanol, n-propanol, 1-butanol, 2-butanol, tert-butanol, and 1-pentyl. Alcohol, 2-pentanol, 3-pentanol, n-hexanol, cyclohexanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, 3 -methyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3 -Methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, etc., having 1 to 6 carbon atoms ; 2,2-dimethyl-3-pentanol, 2,3-dimethyl-3-pentanol, 2,4-dimethyl-3-pentanol, 4,4-dimethyl-2- Pentanol, 3-ethyl-3-pentanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 5- 7-membered ones having a carbon number of methyl-1-hexanol or 5-methyl-2-hexanol; 2-ethyl-1-hexanol, 4--26 - 200804989 (23) methyl- 3-heptanol, 6-methyl-2-heptanol, 1-octanol, 2-octanol, 3-octanol, 2-propyl-1-pentanol, 2,4,4-trimethyl- 1-pentanol and the like, 8 carbon atoms, 2,6-dimethyl-4-heptanol, 3- a carbon number of one of the alcohols of 2,2-dimethyl-1-pentanol, 1-nonanol, 2-nonanol, 3,5,5-trimethyl-1-hexanol; 1-nonanol, 2-nonanol, 4-nonanol, 3,7-dimethyl-1-octanol, • 3,7-dimethyl-3-octanol, etc. class. Among these alcohols, it is preferable to use 4-methyl-2-pentanol, butanol, hexanol or a mixed solvent thereof for the reason that it is difficult to coagulate at a low temperature and it is difficult to remain in the photoresist film. In the organic solvent for preparing the coating liquid, other solvents may be mixed for the purpose of adjusting the coating property to the photoresist film. In the case where the protective film is uniformly applied, the "other solvent" can be sufficiently dissolved to form a resin for a protective film, and a solvent which is difficult to dissolve the photoresist film can be appropriately selected. Examples of the "other solvent" include polyhydric alcohols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethyl Glycol diethyl ether, diethylene glycol monomethyl ether m, diethylene glycol monoethyl ether, dimethyl dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol single An alkyl ether of a polyhydric alcohol such as diethyl ether; an alkyl ether of an alcohol such as ethylene glycol ethyl ether acetate, diethylene glycol diethyl ether acetate, propylene glycol ethyl ether acetate or propylene glycol monomethyl ether acetate; acetate; toluene; An aromatic hydrocarbon such as xylene; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone or diacetone alcohol; Ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxyl Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate-27- 200804989 (24), 3-methoxypropionic acid, ethyl 3-methoxypropionate, 3-ethoxypropionic acid An ester such as methyl 3-ethoxypropionate; water or the like, wherein a cyclic ether, an alkyl ether of a polyhydric alcohol, an alkyl ether acetate of a polyhydric alcohol, a ketone, an ester, or water is used. It is better. The organic solvent may be used singly or in combination of two or more kinds, and may contain water as long as the uniformity of the solvent can be maintained. Since it is difficult to coagulate at a low temperature and exhibits an effect of being hard to remain on the photoresist film, the carbon number of the organic solvent is preferably 10 to 100% by mass based on the total solvent, and is 20 to 100%. The mass % is better. In the above coating liquid, a surfactant may be blended for the purpose of improving coatability, defoaming property, leveling property, and the like. As the surfactant, the following BM-1 000, BM-1 100 (above, BM Chem), Mega fac F142D, F172, F173, and F183 (above, Dainippon Ink Chemical Industry Co., Ltd.) can be used. System), Floride FC-135, with FC-170C, with FC-430, with FC-431 (above, Sumitomo 3M Company _ system), Sufuron S-112, same S-113, same S-131, same S= 141. Fluorine-based surfactants such as S-145 (above, manufactured by Asahi Glass Co., Ltd.), SH-28PA, homo-190, homo-193, SZ-6032, and SF-8428 (above, manufactured by Dowconing Silicone Co., Ltd.) . The blending amount of the surfactants is preferably 5 parts by mass or less based on 100 parts by mass of the fat-soluble resin. The thickness of the protective film is preferably as close as possible to an odd multiple of λ / 4 m (however, λ: wavelength of radiation, m: refractive index of the protective film). The effect of suppressing reflection on the upper interface of the photoresist film is increased. -28- 200804989 (25) [3] Immersion exposure: The method of the present invention is to irradiate the photoresist film with radiation in a state in which a liquid (liquid immersion liquid) having a higher refractive index than air is present. The step of immersion exposure of photoresist 0 exposure. If the liquid immersion liquid is a liquid having a higher refractive index than air, it is usually • water is used, and pure water is preferably used. In the state in which the liquid immersion liquid is present (that is, in the state of being filled with the liquid immersion liquid between the lens of the exposure device and the photoresist film), the radiation is irradiated through the reticle having the specified pattern to make the photoresist film exposure. The radiation that can be used for the immersion exposure is appropriately selected depending on the type of the photoresist film and the protective film to be used, and for example, visible light rays, ultraviolet rays such as g-rays, i-rays, and ultraviolet rays such as excimer lasers can be used. ; X-rays such as synchrotron radiation; various kinds of radiation such as charged particle rays such as electron beams. Among them, ArF laser laser (wavelength 193ixm) or KrF laser laser (wavelength 248nm) is preferably used. Further, the exposure conditions such as the amount of the radiation line are appropriately set depending on the composition of the radiation-sensitive resin composition, the type of the additive, and the like. [4] Peeling protective film: After the photoresist film is exposed, the protective film is peeled off from the surface of the above-mentioned photoresist film. In the method of the present invention, it is characterized in that the protective film is peeled off after heat treatment after exposure and development. Although it is also considered to peel off the protective film during alkali development of the photoresist film, the peeling of the protective film by heat treatment after exposure and development can effectively prevent water marks caused by the liquid immersion liquid impregnated with the protective film - 29 - 200804989 (26) Defects in defects and patterns. The method of peeling is not particularly limited, but a method of not impairing the performance of the photoresist pattern of the photoresist film is preferred. For example, a method of forming a protective film by a fat-soluble resin as described above and performing peeling of the protective film using an organic solvent is preferable. • The organic solvent used for the release of the protective film varies depending on the composition of the protective film, but a monohydric alcohol is preferred, and one of the alcohols having a carbon number of 10 or less is particularly preferred. Such an organic solvent is excellent in solubility of a protective film, and it is preferable that the interdiction of the barrier film is mixed with the photoresist film to cause a decrease in lithographic performance. Among the monohydric alcohols, it is difficult to coagulate at a low temperature, and even if it is used for peeling off the protective film, it is difficult to remain in the photoresist film, and 4-methyl-2-pentanol, butanol, hexanol or a mixed solvent thereof is used. good. Further, the monohydric alcohol may be used in combination with other organic solvents, but the monohydric alcohol is preferably contained in an amount of 10 to 100% by mass, and preferably 20 to 100% by mass, based on the total mass of the mixed solvent. The organic solvent used in the release of the protective film may also contain an acid. In this case, the acid _ is preferably a compound having a dissociation constant (pKa) of 5 or less. A compound having a dissociation constant (pKa) of more than 5 may cause discomfort such as head expansion in the cross-sectional shape of the photoresist pattern after development. A compound having a dissociation constant (pKa) of 5 or less is preferably an organic acid, and a sulfonic acid having a sulfo group (-so2oh) or a carboxylic acid having a carboxyl group in the molecule is more preferable, and a sulfonic acid is particularly preferred. Sulfonic acids are suitable for use because of their small dissociation constant (PKa) and high acidity. The sulfonic acid may, for example, be methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, isopropanesulfonic acid, butanesulfonic acid, isobutanesulfonic acid, 1,1-dimethylethanesulfonic acid, pentyl-30-200804989 (27) alkanesulfonic acid '1-methylbutanesulfonic acid, 2-methylbutanesulfonic acid, 3-methylbutanesulfonic acid, neopentanesulfonic acid, hexanesulfonic acid, oxalic acid-sulfonate- Alkyl sulfonic acids such as acid, octane sulfonic acid, decane sulfonic acid, decane sulfonic acid, etc.; benzenesulfonic acid, 2-toluenesulfonic acid, 3-toluenesulfonic acid, 4-toluenesulfonic acid, 4-ethyl Benzenesulfonic acid, 4-propylbenzenesulfonic acid, 4·butylbenzenesulfonic acid, 4-(t-butyl)benzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2-mercaptosulfonic acid, 2,4-Dinitrobenzenesulfonic acid, 4-chlorobenzenesulfonic acid, 4-bromobenzenesulfonic acid, 4-fluorobenzenesulfonic acid, 2,3,4,5,6-pentafluorobenzenesulfonic acid , 0 4 - arylsulfonic acid such as benzenesulfonic acid, 4-sulfobenzoic acid or 4-sulfoaniline, aralkylsulfonic acid such as benzylsulfonic acid or phenethylsulfonic acid, camphorsulfonic acid Such as ring sulfonic acids and the like. The organic solvent used for the release of the protective film may contain an acid alone or may contain two or more kinds of acids. [5] Post-exposure heat treatment: In the method of the present invention, after the protective film is peeled off from the surface of the photoresist film, post-exposure heat treatment (Post Exposure Bake, hereinafter "may be described as "PEB"). By performing PEB, it is preferable to improve the resolution, pattern shape, development property, and the like of the photoresist. The heating condition of PEB. varies depending on the composition of the radiation-sensitive resin composition, the type of the additive, and the like, but is preferably 30 to 200 ° C, and more preferably 50 to 150 ° C. [6] Development: In the method of the present invention, after the post-exposure heat treatment, development is carried out to obtain a photoresist pattern-forming body. For example, when a photoresist film obtained from a composition containing an acid-dissociable group-modified alkali-soluble resin and a radiation-sensitive linear acid-sensitive resin of the radioactive acid generator, 200804989 (28), it can be imaged by an alkali developing solution. The photoresist pattern forms a body. As the alkali developing solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, monoethylamine, di-n-propylamine can be used. , triethylamine, methyldiethylamine, monomethylethanol-amine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrolidine, choline, 1,8-dioxin Bicyclo[5·4·0]-7-undecene, 1,5-diindole
雙環[4· 3.0]-5-壬烷等之鹼性化合物的至少一種予以溶解的 W 鹼水溶液爲佳。其中,以氫氧化四烷基銨類之水溶液爲適 於使用。 鹼性水溶液之濃度爲1 〇質量%以下爲佳,且以1〜1 〇 質量%爲更佳,以2〜5質量%爲特佳。若鹼性水溶液之濃 度爲1 0質量%以下,則可抑制非曝光部於鹼顯像液中溶解 •,故爲佳。 於鹼顯像液中,亦可適當配合使用界面活性劑。經由 φ 界面活性劑之添加,則具有提高顯像液對於光阻之濕潤性 的優點。 > 顯像爲例如將已曝光的光阻膜,於鹼顯像液中浸漬則 可進行。通常,顯像後,以水洗將鹼顯像液流洗,進行乾 ' 燥以取得光阻圖型成形體。 [實施例] 以下’使用實施例更加具體說明本發明之光阻圖型形 成體的製造方法。但’此些實施例不過爲示出本發明之一 -32- 200804989 (29) 部分的實施形態。即,本發明不應解釋爲被限定於 施例。 , [合成例1] 首先,根據以下之方法合成用以形成光阻膜的 離性基修飾鹼之可溶性樹脂。 預先,準備將下述化合物(M- 1 ) 5 3.93克(50 )、化合物(M-2 ) 3 5.3 8克(40莫耳% )、化合物 )10·69克(10莫耳%)溶解於2-丁酮200克, 2,2'-偶氮雙(2-甲基丙酸二甲酯)(聚合引發劑)5 的單體溶液。另一方面,於5 〇 〇毫升之三口燒瓶中 2-丁酮100克,吹掃氮氣3〇分鐘。吹掃氮氣後, 此三口燒瓶的內部攪拌一邊於8(rc中加熱,並使用 斗’將預先準備之上述單體溶液歷3小時滴下。將 下視爲聚合開始時間,並且實施6小時聚合反應。 此些實 經酸解 莫耳% 丨(M-3 再添加 • 58克 ’投入 一邊將 滴下漏 開始滴 【化6】It is preferred that at least one of the basic compounds such as bicyclo [4.3.0]-5-decane is dissolved in an aqueous solution of W alkali. Among them, an aqueous solution of a tetraalkylammonium hydroxide is suitably used. The concentration of the alkaline aqueous solution is preferably 1% by mass or less, more preferably 1 to 1% by mass, and particularly preferably 2 to 5% by mass. When the concentration of the alkaline aqueous solution is at most 10% by mass, it is preferable to prevent the non-exposed portion from being dissolved in the alkali developing solution. In the alkali imaging solution, a surfactant may be appropriately used. The addition of the φ surfactant improves the wettability of the developing solution to the photoresist. > Development is carried out, for example, by immersing the exposed photoresist film in an alkali developing solution. Usually, after development, the alkali developing solution is washed with water and dried to obtain a photoresist pattern shaped body. [Examples] Hereinafter, a method for producing a photoresist pattern type of the present invention will be described more specifically by way of examples. However, these embodiments are merely illustrative of one embodiment of the present invention - 32-200804989 (29). That is, the invention should not be construed as being limited to the embodiment. [Synthesis Example 1] First, a soluble resin for forming an ion-based modified base for forming a photoresist film was synthesized by the following method. In advance, the following compound (M-1) 5 3.93 g (50), compound (M-2) 3 5.3 8 g (40 mol%), and compound) 10.69 g (10 mol%) were dissolved in 200 g of 2-butanone, a monomer solution of 2,2'-azobis(dimethyl 2-methylpropionate) (polymerization initiator) 5. On the other hand, 100 g of 2-butanone was placed in a 5-inch flask of 5 ml, and nitrogen was purged for 3 minutes. After purging the nitrogen gas, the internal stirring of the three-necked flask was heated at 8 (rc, and the above-mentioned monomer solution prepared in advance was dropped for 3 hours using a bucket. The lower one was regarded as the polymerization start time, and the polymerization reaction was carried out for 6 hours. The actual acid hydrolysis of the mole % 丨 (M-3 added + 58 grams of 'put one side will drop the leak start to drop [Chemistry 6]
水口反應終了後,經由水冷將聚合溶液冷卻至 -33- 3 0,C 以 200804989 (30) 下爲止,並將此經冷卻之聚合溶液投入2000克之 將析出的白色粉末濾出。於濾出之白色粉末中加入 甲醇,並且以流漿狀態洗淨之操作重複2次後,’再 出白色粉末,並於50 °C中乾燥17小時,取得白色 聚合物(7 4克,產率7 4 % )。此聚合物爲M w爲 , Mw/Mn=1.70、13C-NMR分析之結果,來自化合物( 、化合物(M-2 )、化合物(M-3 )之各重複單位 ^ 率爲53.0: 37.2: 9.8(莫耳% )的共聚物。將此聚 爲丙烯酸系聚合物(A-1 )。另外,此聚合物中來 體之低分子量成分的含有量,相對於此聚合物1 〇〇 ,爲0 · 0 3質量%。 [合成例2] 其次,根據以下之方法合成用以形成保護膜的 樹脂。 0 預先,準備將甲基丙烯酸(三氟-2,三氟 羥基-4-戊基)酯93.91克(85莫耳%)溶解於異1 克的單體溶液(1 ),和將乙烯基磺酸6.09克(15 )溶解於異丙醇5 0克的單體溶液(2 )。另一方面 備温度計及滴下漏斗之5 0 0毫升三口燒瓶中,投入 氮雙-(2_甲基丙酸甲酯聚合引發劑)6.91克 醇2 0 〇克’並以氮氣吹掃3 〇分鐘。吹掃氮氣後, 內一邊以磁性攪拌子攪拌,一邊於8 0 °C中加熱,並 下漏斗,將預先準備之單體溶液(1 )歷2 0分鐘滴 甲醇, 400克 度,濾 粉末之 6900 ^ :M-1 ) 的含有 合物視 自各單 質量% 脂溶性 甲基-2-弓醇5 0 莫耳% ,於具 2,2,-偶 和異丙 將燒瓶 使用滴 下。滴 -34 - 200804989 (31) 下終了後,再繼續反應20分鐘,並將預先準備之單體溶 液(2)歷20分鐘滴下,再繼續反應1小時,冷卻至30°C 以下爲止則取得共聚液。 將上述共聚液於48 00克之水中再沈,攪拌3 0分鐘後 ,過濾。令所得之白色粉末溶解於1〇〇〇毫升之甲醇中, 並添加1 000毫升之正庚烷,並且重複4次分液之操作, 進行下層(甲醇層)之洗淨。將如此處理所得之下層溶劑 於4-甲基-2-戊醇中更換後,添加水,分液並進行分液洗 淨,再度,將溶劑於4-甲基-2-戊醇中更換。溶劑更換後 之試料的固形成分濃度爲由此樹脂溶液0.3克載放於鋁皿 ,並且於加熱至1 40°C之熱板上加熱2小時後之殘渣質量 算出,並且利用於其後之形成保護膜用塗佈液的調製和產 率計算。所得共聚物之Mw、Mw/Mn (分子量之分散度) 、產率(質量%)分別爲5 83 0、1.7、72%。 [敏放射線性樹脂組成物之調製]: 相對於合成例1之經酸解離性基修飾之鹼可溶性樹脂 1 〇〇質量份,添加作爲敏放射線性產酸劑之三苯锍九氟-正-丁烷磺酸酯1·5質量份、1(4 -正丁氧萘基)四氫硫苯 基三氟甲烷磺酸酯6質量份,作爲酸擴散抑制劑之Ν-丁 氧羰基吡略烷0.65質量份,作爲副溶劑之γ -丁內酯30質 量份,更且,添加作爲主溶劑之丙二醇單甲醚醋酸酯2 0 3 0 質量份,且將各成分混合作成均勻溶液。其後,使用孔徑 〇·2μιη之膜濾器過濾,則可調製敏放射線性樹脂紅成物所 -35- 200804989 (32) 構成的塗佈液(總固形成濃度約6質量%)。 [形成保護膜用塗佈液之調製]: 相對於合成例2所合成之脂溶性樹脂1 00質量份,加 ^ 入4-甲基-2-戊醇,將其全固形成分濃度調整至3.5質量% * ,並以孔徑〇·2μιη之濾紙過濾,調製形成保護膜用塗佈液 [保護膜剝離液之調製]: 調製含有0.075質量%樟腦磺酸的4-甲基-2-戊醇,並 以孔徑0.2 μιη之濾紙過濾,調製保護膜剝離液。 [評價方法]: 使用如上述所調製之敏放射線性樹脂組成物,形成保 護膜用塗佈液及保護膜剝離液,進行如下之評價。 (1 )強制水痕試驗: 使用 Coater/Developer ( 1 )(商品名:CLEAN TRACK ACT8,東京Electron公司製),於8吋矽晶圓上 ,將防止反射形成劑(商品名:ARC29A,Blower Science 公司製)予以旋轉塗佈,並以205 °C,60秒鐘之條件進行 PB,形成膜厚77nm的防止反射膜。其次,於此防止反射 膜之表面,將前述敏放射線性樹脂組成物所構成的塗佈液 予以旋轉塗佈,並以115°C,60秒鐘之條件進行PB,形 -36- 200804989 (33) 成膜厚15 Onm的光阻膜。更且,於此光阻膜表面,將前述 形成保護膜用塗佈液予以旋轉塗佈,並以9 0 °C,6 0秒鐘 之條件進行PB,形成膜厚90nm的保護膜。 其次,將形成保護膜的光阻膜,以ArF投影曝光裝置 (商品名:S306C,Nikkon 公司製),以 NA : 0.78, , Sigma : 0· 85,2/3 Ann之光學條件進行曝光,作成試驗用 晶圓。其後,使用吸移管將0.3微升之水滴,於此晶圓表 ^ 面四處加以標記並令其乾燥1 〇分鐘。 於實施例1中,預先,於前述保護膜剝離液中將保護 膜剝離,並以前述Coater/Developer ( 1 )之熱板,以115 °C,60秒鐘之條件進行PEB,並以同一 Coater/Developer (1 )之LD管嘴予以漿葉顯像60秒鐘後,以超純水洗滌 ,並再以迴轉數4000rpm振盪甩開15秒鐘,予以旋轉乾 燥。 另一方面,關於比較例,未將保護膜剝離並以實施例 1同樣之條件進行PEB後,於光阻膜之鹸顯像時將保護膜 剝離。目視如此處理所形成之光阻圖型,以吸移管標記水 滴之位置未殘留液滴痕(水痕)之情況判斷爲「良好」, 殘留之情況判斷爲「不良」。其結果示於表1。 表 1 強制水痕試驗 敏感度 圖型不良缺陷 圖型形狀 實施例1 良好 19mJ/cm2 良好 良好 比較例1 不良 19mJ/cm2 不良 良好 -37- 200804989 (34) (2 )敏感度: 使用 Coiter/Oevei〇p_er(2)(商品名:CLEAN TRACK ACT12,東京Electron公司製),於12吋矽晶圓 上,將防止反射形成劑(商品名:ARC29A,Blower ~ Science公司製)予以旋轉塗佈,並以205°C,60秒鐘之 , 條件進行PB,形成膜厚77nm的防止反射膜。將此物質使 用作爲基板。 ^ 其次,於基板之防止反射膜表面,將前述敏放射線性 樹脂組成物所構成的塗佈液予以旋轉塗佈,並以η 5 °c, 60秒鐘之條件進行PB,形成膜厚150nm的光阻膜。更且 ' ,於此光阻膜表面,將前述形成保護膜用塗佈液予以旋轉 塗佈,並以 90 °C,60秒鐘之條件進行PB,形成膜厚 90nm的保護膜。其次,將形成保護膜的光阻膜,以ArF 激元雷射曝光裝置(商品名:TWIN SCAN XT125〇i, ASML 公司製,證明條件;ΝΑΟ· 85,Sigma 0.93/0.69 ), φ 透過光罩圖型令其曝光。 其後,於實施例1中,預先,以前述保護膜剝離液將 保護膜剝離,並以1 1 5 °c,60秒鐘之條件進行ΡΕΒ,並且 以2.38質量%之氫氧化四甲基銨水溶液,以23°C顯像30 ^ 秒鐘,水洗,乾燥,形成正型之光阻圖型。 關於比較例1爲未將保護膜剝離並以實施例1同樣之 條件進行PEB後,於光阻膜之鹼顯像時將保護膜剝離。對 於如此處理所形成的光阻圖型,將線寬65nm之線/空間圖 型(1 L 1 S )以1 : 1之線寬形成的曝光量視爲最適曝光量 -38- 200804989 (35) ,並將此最適曝光量視爲敏感度。另外,於此測定 掃描型電子顯微鏡(商品名:S-93 80,日Ϊ Technology公司製)。其結果示於表i。 ' (3 )圖型不良缺陷檢查: • 使用 Coater/Dev eloper ( 2)(商品名: TRACK ACT12,東京 Electron 公司製),於 12 吋 $ 上,將防止反射膜形成劑(商品名:ARC 29A, Science公司製)予以旋轉塗佈,並以205 °C,60 條件進行PB,形成膜厚77nm的防止反射膜。將此 用作爲基板。 於前述基板之表面,實施敏放射線性樹脂組成 品名:ArF AR20 14J,JSR公司製)的圖型化。將 放射線性樹脂組成物於前述基板表面予以旋轉塗佈 1 15°C,60秒鐘之條件進行PB,形成膜厚150nm φ 膜。於此光阻膜表靣,將前述彫成保護膜用塗佈液 轉塗佈,並以90°C,60秒鐘之條件進行PB,形 3 2nm的保護膜。 將此形成保護膜的光阻膜,使用ArF激元雷射 ’ 置(商品名:TWIN SCAN XT 1 250i,ASML 公司製 條件;NA0.85,Sigma 0.93/0.69 ),透過光罩圖型 光。After the completion of the nozzle reaction, the polymerization solution was cooled to -33 - 30 by water cooling, C was taken up to 200804989 (30), and the cooled polymerization solution was poured into 2000 g of the precipitated white powder. Methanol was added to the filtered white powder, and the operation of washing in a slurry state was repeated twice, and then a white powder was again discharged and dried at 50 ° C for 17 hours to obtain a white polymer (74 g, produced). The rate is 7 4 %). The polymer was Mw, Mw/Mn=1.70, and 13C-NMR analysis. The repeating unit yield of the compound (, compound (M-2), compound (M-3) was 53.0: 37.2: 9.8 (Mole%) copolymer. This is a polyacrylic polymer (A-1). The content of the low molecular weight component of the polymer in the polymer is 0 with respect to the polymer 1 〇〇. 0. 3 mass%. [Synthesis Example 2] Next, a resin for forming a protective film was synthesized according to the following method: 0 In advance, chloroacrylic acid (trifluoro-2,trifluorohydroxy-4-pentyl) ester was prepared. 93.91 g (85 mol%) was dissolved in 1 g of the monomer solution (1), and 6.09 g (15) of vinylsulfonic acid was dissolved in 50 g of the monomer solution (2) of isopropanol. In a 500 ml three-necked flask equipped with a thermometer and a dropping funnel, nitrogen bis-(2-methylpropionate polymerization initiator) was charged with 6.91 g of alcohol 2 〇g' and purged with nitrogen for 3 Torr. After purging the nitrogen gas, the inner side is stirred with a magnetic stirrer, heated at 80 ° C, and the funnel is lowered, and the previously prepared monomer solution (1 ) is dripped for 20 minutes. The content of alcohol, 400 gram, 6900 ^ :M-1 of the filter powder is regarded as the % by mass of each of the fat-soluble methyl-2-cutinol, which is 2, 2, - even and different. C. Use the flask to drip. Drip-34 - 200804989 (31) After the end, the reaction was continued for another 20 minutes, and the previously prepared monomer solution (2) was dropped for 20 minutes, and the reaction was continued for another hour. After cooling to 30 ° C or less, copolymerization was carried out. liquid. The above copolymerization liquid was resuspended in 48,000 g of water, stirred for 30 minutes, and then filtered. The obtained white powder was dissolved in 1 ml of methanol, and 1 000 ml of n-heptane was added, and the liquid separation operation was repeated four times to carry out washing of the lower layer (methanol layer). After the solvent of the lower layer thus obtained was replaced with 4-methyl-2-pentanol, water was added thereto, and the mixture was separated and washed, and the solvent was replaced with 4-methyl-2-pentanol. The solid content concentration of the sample after solvent replacement was 0.3 g of the resin solution placed on the aluminum dish, and the mass of the residue was heated on a hot plate heated to 140 ° C for 2 hours, and was used for subsequent formation. Modulation and yield calculation of the coating liquid for protective film. Mw, Mw/Mn (degree of dispersion of molecular weight) and yield (% by mass) of the obtained copolymer were 583 0, 1.7, and 72%, respectively. [Preparation of Sensitive Radiation Resin Composition]: To a mass fraction of an alkali-soluble resin modified with an acid dissociable group of Synthesis Example 1, a triphenylsulfonium hexafluoride-positive-type as a sensitive radiogenic acid generator was added. 6 parts by mass of butane sulfonate, 6 parts by mass of 1 (4-n-butoxynaphthyl)tetrahydrothiophenyl trifluoromethanesulfonate, oxime-butoxycarbonylpyrrolidine as acid diffusion inhibitor 0.65 parts by mass, 30 parts by mass of γ-butyrolactone as a sub-solvent, and 2,300 parts by mass of propylene glycol monomethyl ether acetate as a main solvent were added, and the respective components were mixed to prepare a homogeneous solution. Thereafter, it is filtered by a membrane filter having a pore size of 〇·2 μm to prepare a coating liquid (total solid concentration concentration of about 6 mass%) of a radiation-sensitive resin red pigment-35-200804989 (32). [Preparation of coating liquid for forming a protective film]: To 100 parts by mass of the fat-soluble resin synthesized in Synthesis Example 2, 4-methyl-2-pentanol was added thereto, and the total solid content concentration was adjusted to 3.5. The mass % * was filtered through a filter paper having a pore size of 〇 2 μm to prepare a coating liquid for a protective film [Preparation of a protective film peeling liquid]: Preparation of 4-methyl-2-pentanol containing 0.075 mass% camphorsulfonic acid, The membrane was filtered through a filter paper having a pore size of 0.2 μm to prepare a protective film stripper. [Evaluation method]: The coating liquid for protective film and the protective film peeling liquid were formed using the photosensitive radiation resin composition prepared as described above, and the following evaluation was carried out. (1) Forced water mark test: Using Coater/Developer (1) (trade name: CLEAN TRACK ACT8, manufactured by Tokyo Electron Co., Ltd.), anti-reflection forming agent on 8 吋矽 wafer (trade name: ARC29A, Blower Science) The company was spin-coated, and PB was performed at 205 ° C for 60 seconds to form an antireflection film having a film thickness of 77 nm. Next, on the surface of the antireflection film, the coating liquid composed of the above-mentioned radiation sensitive resin composition was spin-coated, and PB was carried out at 115 ° C for 60 seconds, and the shape was -36-200804989 (33 ) A photoresist film with a film thickness of 15 Onm. Further, on the surface of the resist film, the coating liquid for forming a protective film was spin-coated, and PB was formed at 90 ° C for 60 seconds to form a protective film having a film thickness of 90 nm. Next, the photoresist film forming the protective film was exposed to an optical condition of NA: 0.78, Sigma: 0·85, 2/3 Ann by an ArF projection exposure apparatus (trade name: S306C, manufactured by Nikkon Co., Ltd.). Test wafer. Thereafter, 0.3 μl of water droplets were pipetted using a pipette and marked on the wafer surface and allowed to dry for 1 minute. In the first embodiment, the protective film was peeled off in the protective film peeling solution, and the PEB was subjected to the hot plate of the Coater/Developer (1) at 115 ° C for 60 seconds, and the same Coater was used. The LD nozzle of /Developer (1) was subjected to paddle image development for 60 seconds, then washed with ultrapure water, and shaken again at a revolution of 4000 rpm for 15 seconds, and then spin-dried. On the other hand, in the comparative example, after the protective film was peeled off and PEB was carried out under the same conditions as in Example 1, the protective film was peeled off during the development of the photoresist film. The pattern of the photoresist formed by the treatment was visually observed, and it was judged as "good" by the fact that the droplet mark (water mark) was not left at the position of the pipette mark, and the residual condition was judged as "poor". The results are shown in Table 1. Table 1 Forced water mark test sensitivity pattern defective defect pattern shape Example 1 Good 19 mJ/cm 2 Good good Comparative example 1 Bad 19 mJ/cm 2 Poor good -37- 200804989 (34) (2) Sensitivity: Using Coiter/Oevei 〇p_er(2) (trade name: CLEAN TRACK ACT12, manufactured by Tokyo Electron Co., Ltd.), and a spin-resistant forming agent (trade name: ARC29A, manufactured by Blower ~ Science Co., Ltd.) was spin-coated on a 12-inch wafer. PB was carried out under the conditions of 205 ° C for 60 seconds to form an antireflection film having a film thickness of 77 nm. This material was used as a substrate. ^ Next, the coating liquid composed of the above-mentioned radiation-sensitive resin composition is spin-coated on the surface of the antireflection film of the substrate, and PB is performed at η 5 ° C for 60 seconds to form a film thickness of 150 nm. Photoresist film. Further, on the surface of the photoresist film, the coating liquid for forming a protective film was spin-coated, and PB was formed at 90 ° C for 60 seconds to form a protective film having a film thickness of 90 nm. Next, a photoresist film forming a protective film is used as an ArF laser laser exposure apparatus (trade name: TWIN SCAN XT125〇i, manufactured by ASML, certified conditions; ΝΑΟ·85, Sigma 0.93/0.69), φ through the mask The pattern makes it exposed. Thereafter, in Example 1, the protective film was peeled off in advance by the protective film peeling liquid, and enthalpy was carried out at a temperature of 1 15 ° C for 60 seconds, and tetramethylammonium hydroxide was added in an amount of 2.38 mass%. The aqueous solution was developed at 23 ° C for 30 ^ seconds, washed with water and dried to form a positive photoresist pattern. In Comparative Example 1, after the protective film was peeled off and PEB was carried out under the same conditions as in Example 1, the protective film was peeled off during alkali development of the photoresist film. For the photoresist pattern formed by such processing, the exposure amount formed by the line/space pattern (1 L 1 S ) having a line width of 65 nm with a line width of 1:1 is regarded as an optimum exposure amount - 38 - 200804989 (35) And consider this optimum exposure as sensitivity. Further, a scanning electron microscope (trade name: S-93 80, manufactured by Nippon Technology Co., Ltd.) was measured here. The results are shown in Table i. ' (3) Pattern defect inspection: • Coater/Dev eloper (2) (trade name: TRACK ACT12, manufactured by Tokyo Electron Co., Ltd.), anti-reflective film forming agent at 12 吋$ (trade name: ARC 29A) , manufactured by Science Co., Ltd., spin-coated, and PB was carried out at 205 ° C, 60 to form an antireflection film having a film thickness of 77 nm. Use this as a substrate. A pattern of a radiation sensitive resin composition name: ArF AR20 14J, manufactured by JSR Co., Ltd. was applied to the surface of the substrate. The radiation-linear resin composition was spin-coated on the surface of the substrate at 1 15 ° C for 60 seconds to form a film having a film thickness of 150 nm φ. On the surface of the photoresist film, the above-mentioned coating liquid for engraving a protective film was applied by spin coating, and PB was formed at a temperature of 90 ° C for 60 seconds to form a protective film of 32 nm. The photoresist film forming the protective film was passed through a reticle pattern light using an ArF excimer laser (trade name: TWIN SCAN XT 1 250i, manufactured by ASML); NA 0.85, Sigma 0.93/0.69.
其後,於實施例1爲以前述保護膜剝離液將保 離,並以 Coater/Developer(2)的熱板,以 115°C 中使用 High CLEAN 矽晶圓 Blower 秒鐘之 物質使 物(商 前述敏 ,並以 的光阻 予以旋 成膜厚 曝光裝 ,證明 令其曝 護膜剝 ,6 0秒 -39 - 200804989 (36) 鐘之條件進行ΡΈΒ,並以Coater/Developer(2) 嘴予以漿葉顯像3 0秒鐘,以超純水洗滌後, 3 000rpm振盪甩開15秒鐘,予以旋轉乾燥。 關於比較例1爲未將保護膜剝離並以實施例 . 條件進行PEB後,於光阻膜之鹼顯像時將保護膜 ^ 將如此所形成之光阻圖型,使用一般名:缺 置(商品名·· KLA235 1,KLA-Tencor公司製)實 ^ 缺陷檢查,並以掃描型電子顯微鏡(商品名:S · 立計測器公司製)觀察所檢測出的缺陷,並且確 良缺陷(具體而言爲圖型細或粗的缺陷)的存在 出此圖型不良缺陷者視爲「不良」,未檢測出者 好」。其結果示於表1。 (4)圖型形狀: 以掃描型電子顯微鏡(商品名:S - 4 8 0 0,E φ Technology公司製)觀察65nm線/空間圖型的剖 並且如圖1所示般,測量光阻圖型中間的線寬 上方部的線寬 La,將 0.65 ^ ( La-Lb ) /Lb ^1.1 價爲「良好」,且此外評價爲「不良」。其結果 [評價結果]: 如表1之數據所闡明般,將保護膜由光阻膜 進行曝光後加熱處理及顯像之實施例1的光阻圖 之LD管 以迴轉數 1同樣之 剝離。 陷檢查裝 施晶圓的 93 60,日 認圖型不 。將檢測 視爲「良 3 立 High 面形狀, Lb,和膜 之範圍評 示於表1 剝離後, 型,於敏 -40- 200804989 (37) 感度、圖型形狀之任一種試驗中均顯示 亦未觀見水痕和圖型不良等之缺陷。 另一方面,曝光後加熱處理之後, 由光阻膜表面剝離之比較例1的光阻圖 圖型形狀顯不良好之結果,但發生水痕 • 陷。 [產業上之可利用性] 本發明之光阻圖型之形成方法,因 護膜表面殘存的大多數水滴,於PEB前 去,故可有效抑制起因於此水滴之水痕 陷的發生。因此,於微細加工之領域中 續發展微細化、高精細化、高集成化之 成電路元件的製造中可適當使用。 良好之結果。又, 顯像之前將保護膜 型,雖於敏感度, 和圖型不良等之缺 將液浸曝光時於保 之保護膜剝離時除 缺陷和圖型不良缺 ’特別,於急劇持 半導體裝置等之集 -41 -Thereafter, in the first embodiment, the protective film stripping solution is kept away, and a Coater/Developer (2) hot plate is used, and a high CLEAN 矽 wafer is used for a second time at 115 ° C. The aforementioned sensitivity, and the photoresist is rotated into a film thickness exposure package, which proves that the film is peeled off, and the condition of 60 seconds - 39 - 200804989 (36) clock is carried out, and the Coater/Developer (2) mouth is used. The paddle was imaged for 30 seconds, washed with ultrapure water, and shaken at 3,000 rpm for 15 seconds, and then spin-dried. Regarding Comparative Example 1, the protective film was not peeled off and PEB was subjected to the conditions of the examples. When the alkali film of the photoresist film is developed, the protective film is formed into the photoresist pattern thus formed, and the general name: the missing name (trade name · KLA235 1, manufactured by KLA-Tencor Co., Ltd.) is used for defect inspection, and scanning is performed. An electron microscope (trade name: S · Liji Co., Ltd.) observes the detected defects, and the presence of a defect (specifically, a thin or thick defect) is considered as a defective defect. "Poor", not detected is good. The results are shown in Table 1. (4) Shape: A section of the 65 nm line/space pattern was observed by a scanning electron microscope (trade name: S-4800, manufactured by E φ Technology Co., Ltd.) and the line in the middle of the photoresist pattern was measured as shown in FIG. The line width La of the upper portion of the width is 0.65 ^ ( La-Lb ) / Lb ^1.1 and the price is "good", and the evaluation is "bad". The result [evaluation result]: As illustrated by the data in Table 1, The LD tube of the resist pattern of the first embodiment in which the protective film was subjected to post-exposure heat treatment and development by the photoresist film was peeled off in the same manner as the number of revolutions 1. The inspection was performed on the wafer of 93 60, and the daily pattern was not. The test is regarded as "good 3 vertical shape, Lb, and the range of the film is shown in Table 1. After peeling, type, Yu Min-40-200804989 (37) In any test of the sensitivity and shape, On the other hand, after the post-exposure heat treatment, the shape of the resist pattern of Comparative Example 1 which was peeled off from the surface of the photoresist film was not good, but the water mark occurred. [Industrial Applicability] The method of forming the photoresist pattern of the present invention, Most of the water droplets remaining on the surface of the membrane are removed from the PEB, so that the occurrence of water marks caused by the water droplets can be effectively suppressed. Therefore, in the field of microfabrication, the development of miniaturization, high definition, and high integration has continued. It can be suitably used in the manufacture of circuit components. Good results. In addition, the film type will be protected before development, and the defects and the figure will be removed when the protective film is peeled off due to the lack of sensitivity and pattern. Type of defective 'special, in the set of semiconductor devices, etc. -41
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