TWI286670B - Positive resist composition and resist pattern formation method - Google Patents
Positive resist composition and resist pattern formation method Download PDFInfo
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- TWI286670B TWI286670B TW93138146A TW93138146A TWI286670B TW I286670 B TWI286670 B TW I286670B TW 93138146 A TW93138146 A TW 93138146A TW 93138146 A TW93138146 A TW 93138146A TW I286670 B TWI286670 B TW I286670B
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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1286670 (1) 九、發明說明 【發明所屬之技術領域】 -本發明係有關正型光阻組成物及光阻圖塑 法。 本申請書係針對2003年12月15日所申請之 416,584號主張優先權，且援用其內容。 【先前技術】 近年來隨著微影技術進步，而促使半導體方 顯示之製.造技術急速微細化。該微細化方法一艇 光光源短波長化。具體而言，先前係使用g線、 之紫外線，但現在係導入KrF激元激光（ 248iim) 又，已知的符合可再現微細尺寸之圖型的高 件之光阻材料如，含有酸作用下可增加鹼可溶性 脂，及曝光下會產酸之酸發生劑的化學加強型正 成物。 一般最常使用之酸發生劑爲鎰鹽。該鎗鹽之 (酸）幾乎全爲鏈狀氟化烷基磺酸離子，至於其 酸性度問題而幾乎未使用。該氟化烷基之烷基鏈 阻膜中酸之擴散長度，故以碳數長爲佳，但烷I 以上之氟化烷基磺酸對安全性存在疑問，故目前 限用。因此不使用該長鏈之氟化烷基磺酸下，需 中擴散長度較短之酸發生劑。 另外近年來隨著半導體元件之急劇微細化， !之形成方 特願2003- i件及液晶 t爲，使曝 i線所代表 〇 ί解像性條 :之基本樹 型光阻組 陰離子部 他酸因有 可控制光 I爲碳數4 係世界性 求光阻膜 而需求細 -6 - (2) 1286670 微之解像性。特別是形成對空間部尺寸之光阻線部尺寸的 比低於1，例如對空間部尺寸之光阻線尺寸的比爲1 /9般孤 立線圖時，需提升解像性。 又，同時形成存在上述孤立線圖型部（疏圖型部）， 及對空間部尺寸之光阻線部尺寸的比爲1以上，例如對空 間部尺寸之光阻線部尺寸的比爲1/1般線與空間（L&S )圖 型部（密圖型部）之疏密混合圖型的步驟中，會產生疏圖 型部與密圖型部之光阻圖型尺寸差，即造成效果接近之問 題，故對先前光阻劑難抑制該效果接近之問題寄望於改善 〇 另外隨著半導體元素之急劇微細化，會產生線縫粗糙 (LER)之深切問題，故寄望於改善。 本發明者們曾提案具有優良孤立線圖型之解像性，且 能抑制疏密混合圖型之效果接近的化學加強型正型光阻組 成物用，主鏈具有含特定4元共聚物之（甲基）丙烯酸酯 所衍生物的單位，及以酸作用下對鹼可增加溶解性之樹脂 成分爲基本樹脂的正型光阻組成物（參考專利文獻1 )。 雖然含有專利文獻1所記載之4元共聚物的正型光阻組 成物具有優良之孤立線圖型的解像性，但對上述L& S圖型 之解像性，及清圖型，即對光阻線部尺寸之空間部尺寸的 比低於1般孤立空間圖型之解像性仍不足。因此寄望於提 升該圖型之解像性。又，寄望於更進一步改善含該4元共 聚物之正型光阻組成物的線緣粗糙度。 (專利文獻1)特開2 003 - 1 673 47號公報 (3) 1286670 【發明內容】 〔發明所欲解決之課題〕 有鑑於上述本發明之課題爲，提供能減少LER及具有 優良之解像性，特別是L&S圖型及孤立空間圖型之解像性 的正型光阻組成物，以及使用該光阻組成物之光阻圖型的 形成方法。 〔解決課題之方法〕 經本發明者們專心檢討後發現，組合使用上述4元共 聚物及特定酸發生劑時可解決上述課題。 本發明係基於上述見解而完成，即，本發明之第1態 樣（aspect )係特徵爲，含有（A)酸作用下可增加鹼可 溶性之樹脂成分，及（B)曝光下會產酸之酸發生劑成分 的正型光阻組成物中， 樹脂成分（A)爲含有，具有含單環式或多環式基之 酸解離性溶解抑制基的（甲基）丙烯酸酯所衍生之構成單 位（al)，具有含內酯之單環式或多環式基的（甲基）丙 烯酸酯所衍生的構成單位（a2)，具有含羥基之多環式基 的（甲基）丙烯酸酯所衍生之構成單位（a3)及構成單位 (a2 ) 、（ a3 )以外之具有含多環式基非酸解離性溶解抑 制基的（甲基）丙烯酸酯所衍生之構成單位（a4 )的共聚 合物。 酸發生劑成分（B )爲，含有下列一般式（b· 1 )或（ -8 - (4) 1286670 b-2 )所示至少一種之銃化合物的正型光阻組成物1286670 (1) Description of the Invention [Technical Field of the Invention] - The present invention relates to a positive resist composition and a photoresist pattern. This application claims priority to 416,584, filed on Dec. 15, 2003, and the content thereof is incorporated. [Prior Art] In recent years, with the advancement of lithography technology, the manufacturing technology of semiconductor display has been rapidly reduced. This miniaturization method is a short-wavelength light source of a boat. Specifically, the g-ray and the ultraviolet ray are used in the past, but now a KrF excimer laser (248iim) is introduced, and a high-resistance photoresist material which conforms to a pattern capable of reproducing a fine size, for example, contains an acid. It can increase the alkali-soluble fat and the chemically-enhanced positive form of the acid generator which will produce acid under exposure. The most commonly used acid generator is the cerium salt. The (acid) of the gun salt is almost entirely a chain-like fluorinated alkylsulfonate ion, and it is hardly used as far as its acidity is concerned. The length of the acid in the alkyl chain-blocking film of the fluorinated alkyl group is preferably as long as the number of carbon atoms, but the fluorinated alkylsulfonic acid having an alkane I or more has doubts about the safety, and is currently limited. Therefore, in the case of not using the long-chain fluorinated alkylsulfonic acid, an acid generator having a short diffusion length is required. In addition, in recent years, with the sharp miniaturization of semiconductor components, the formation of the product is intended to be the 2003-i piece and the liquid crystal t, so that the exposed line represents the 解ί resolution strip: the basic tree type resistive group anion part The acid has a controllable light I as a carbon number 4 system for the global photoresist film and requires a fine -6 - (2) 1286670 micro resolution. In particular, when the ratio of the size of the photoresist line portion to the size of the space portion is less than 1, for example, the ratio of the size of the photoresist line to the size of the space portion is 1 / 9, the resolution is required to be improved. Further, the ratio of the size of the photoresist line portion having the size of the space portion is 1 or more, and the ratio of the size of the photoresist portion to the size of the space portion is 1 at the same time. In the step of densely mixing the pattern of the line and space (L&S) pattern portion (dense pattern portion), the size difference of the photoresist pattern between the thin pattern portion and the dense pattern portion is generated, that is, The problem is close to the effect, so the problem that the previous photoresist is difficult to suppress the effect is expected to improve. In addition, as the semiconductor element is sharply miniaturized, the problem of deep crease (LER) is generated, so it is hoped that improve. The present inventors have proposed a chemically-reinforced positive-type photoresist composition having an excellent resolution of an isolated line pattern and capable of suppressing the effect of a dense and mixed pattern, and the main chain has a specific 4-member copolymer. A unit of a derivative of (meth) acrylate and a positive-type photoresist composition in which a resin component which can increase solubility in a base by an acid is a base resin (refer to Patent Document 1). The positive-type resist composition containing the quaternary copolymer described in Patent Document 1 has an excellent resolution of an isolated line pattern, but the resolution of the above-mentioned L&S pattern and the clearing type, that is, The resolution of the size of the space portion of the size of the photoresist line portion is still insufficient for the resolution of the isolated space pattern. Therefore, it is hoped to improve the resolution of this pattern. Further, it is expected to further improve the line edge roughness of the positive resist composition containing the quaternary copolymer. [Patent Document 1] JP-A-2002- 1 673 47 (3) 1286670 [Problem to be Solved by the Invention] In view of the above-described problems of the present invention, it is possible to provide a LER-reducing and excellent resolution. And a positive resistive composition of an L&S pattern and an isolated spatial pattern, and a method of forming a photoresist pattern using the photoresist composition. [Means for Solving the Problems] The inventors of the present invention have intensively reviewed and found that the above problems can be solved by using the above-mentioned quaternary copolymer and a specific acid generator in combination. The present invention has been accomplished based on the above findings, that is, the aspect of the present invention is characterized in that it contains (A) a resin component which increases alkali solubility under the action of an acid, and (B) an acid which is produced under exposure. In the positive resist composition of the acid generator component, the resin component (A) is a constituent unit derived from a (meth) acrylate having an acid dissociable dissolution inhibiting group containing a monocyclic or polycyclic group. (al) a constituent unit (a2) derived from a (meth) acrylate having a monocyclic or polycyclic group containing a lactone, derived from a (meth) acrylate having a polycyclic group having a hydroxyl group a copolymer of a constituent unit (a4) derived from a (meth) acrylate having a polycyclic group-based non-acid dissociable dissolution inhibiting group other than the constituent unit (a3) and constituent units (a2) and (a3) . The acid generator component (B) is a positive photoresist composition containing at least one of the following compounds of the formula (b-1) or (8-(4) 1286670 b-2)
R2- .(b-1)R2- .(b-1)
·· (b - 2) (式中，X爲至少一個氫原子受氟原子取代之碳數2至6的 伸烷基；Y及Z各自獨立爲至少一個氫原子受氟原子取代之 碳數1至10的烷基；R1至R3各自獨立爲芳基或烷基，且R1 至R3中至少一個爲芳基）。 本發明之第2態樣（aspect )係特徵爲，使用上述正型 光阻組成物於基板上形成光阻膜後，對光阻膜進行選擇性 曝光處理，再鹼顯像以形成光阻圖型的光阻圖型之形成方 又，本發明中「含有內酯之單環式基或多環式基」係 指，內酯環所形成之單環式基或具有內酯環之多環式基。 此時該內酯環係指，含有- C0-0 -構造之一個環，且以該環 爲第1個環。因此可爲僅由內酯環形成之含內酯單環式基 ，或具有其他環構造且無關其構造之含內酯多環式基。本 發明之「構成單位」係指，構成聚合物之單體單位。「（ 甲基）丙烯酸酯所衍生之構成單位」係指，本說明書中下 列一般式（5 )所示單位中，R爲氫原子之丙烯酸酯所衍生 -9- (5) 1286670 的構成單位，R爲甲基之甲基丙烯酸酯所衍生的構成單位 ，及R爲碳原子數2至5之低級烷基，具體例如乙基、丙基 、異丙基、η-丁基、異丁基、tert-丁基、戊基、異戊基、 新戊基等直鏈狀或支鏈狀之烷基的構成單位總稱。· (b - 2) (wherein X is an alkylene group having 2 to 6 carbon atoms substituted with at least one hydrogen atom by a fluorine atom; Y and Z are each independently a carbon number substituted by at least one hydrogen atom by a fluorine atom An alkyl group of 10; R1 to R3 are each independently an aryl group or an alkyl group, and at least one of R1 to R3 is an aryl group). A second aspect of the present invention is characterized in that after forming a photoresist film on a substrate by using the above-mentioned positive-type photoresist composition, the photoresist film is selectively exposed to light, and then alkali-developed to form a photoresist pattern. The formation of a type of photoresist pattern, the "monocyclic or polycyclic group containing a lactone" in the present invention means a monocyclic group formed by a lactone ring or a polycyclic ring having a lactone ring. Formula. In this case, the lactone ring means a ring containing a -C0-0 - structure, and the ring is the first ring. Thus, it may be a lactone-containing monocyclic group formed only of a lactone ring, or a lactone-containing polycyclic group having a different ring structure and irrelevant structure. The "constituting unit" of the present invention means a monomer unit constituting a polymer. The "constituting unit derived from (meth) acrylate" means a constituent unit derived from -9-(5) 1286670 derived from an acrylate of a hydrogen atom in the unit represented by the following general formula (5) in the present specification. R is a constituent unit derived from a methyl methacrylate, and R is a lower alkyl group having 2 to 5 carbon atoms, specifically, for example, ethyl, propyl, isopropyl, η-butyl, isobutyl, A general term for the constituent units of a linear or branched alkyl group such as tert-butyl, pentyl, isopentyl or neopentyl.
〔發明之效果〕 本發明之正型光阻組成物及光阻圖型之形成方法可形 成能減少LER及具有優良解像性，特別是L&S圖型及孤立 空間圖型之解像性的光阻圖型。 〔實施發明之最佳形態〕 下面將更詳說明本發明。 <<正型光阻組成物>> 本發明之正型光阻組成物爲，含有酸作用下可增加鹼 可溶性之樹脂成分（A )(以下稱爲（A )成分），及曝 光下會產酸之酸發生劑成分（B)(以下稱爲（B)成分） 之物。 本發明之特徵爲，含有（A)成分用含上述構成單位 -10- (6) 1286670 (al )至（a4 )的共聚物，及（B )成分用一般式（ 或（b-2 )所示至少一種之銃化合物。 組合該（A)成分及（B)成分可形成具有優良！ ，特別是L&S圖型及孤立空間圖型之解像性的光阻S 又，所得光阻圖型之形狀爲，具有優良之圖型側壁5 性的矩形性。另外可形成減少線緣粗糙度（LER ) ^ 圖型。又，形成該光阻圖型時可加大焦點深度幅寬 )。其中LER係指，顯像後光阻圖型中，例如形成， 空間圖型之側壁上的不均勻凹凸狀。 < (A )成分> (A )成分爲，具有所謂酸解離性溶解抑制基之 溶性物，因此曝光下可利用上述（B )成分所產生之 作用，使酸解離性溶解抑制基解離，而使（A )成分 由鹼不溶性轉變化鹼可溶性。故形成光阻圖型時介由 進行曝光，或曝光後進行加熱（PEB )時，可使曝光 化爲鹼可溶性，且維持未曝光部爲鹼不溶性，而於顯 形成正型光阻圖型。 構成單位（al)爲，具有含單環式或多環式基之 離性溶解抑制基的（甲基）丙烯酸酯所衍生之單位。 該單環式基如，由環鏈烷去除一個氫原子之基， 環戊基、環己基等脂肪族單環式基。多環式基如，二 烷、三環鏈烷、四環鏈烷等之金剛烷、降茨院、異冰 、三環癸烷、四環十二烷等聚環鏈烷中去除一個氫原 b-Ι ) U象性 丨型。 ί垂直 光阻 ：DOF 線與 鹼不 酸的 全體 圖罩 部轉 像後 酸解 例如 環鏈 片烷 子之 -11 - (7) 1286670 基，即脂肪族多環式基。又，ArF光阻劑中曾提案多數該 單環式基或多環式基，故本發明可隨著選用該單環式基或 多環式基，但就工業上易取性較佳爲金剛烷基、降茨基、 四環十二烷基等脂肪族多環式基。[Effects of the Invention] The positive-type photoresist composition and the pattern of forming a photoresist pattern of the present invention can form an image-reducing property capable of reducing LER and having excellent resolution, particularly L&S pattern and isolated space pattern. Photo resistive pattern. [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in more detail. <<Positive-type photoresist composition>> The positive-type photoresist composition of the present invention contains a resin component (A) (hereinafter referred to as (A) component) which can increase alkali solubility under the action of an acid, and An acid generator component (B) (hereinafter referred to as component (B)) which generates an acid under exposure. The present invention is characterized in that the component (A) contains a copolymer containing the above constituent units -10 (6) 1286670 (al ) to (a4 ), and the component (B) is represented by a general formula (or (b-2)). At least one of the ruthenium compounds is shown. Combining the (A) component and the (B) component can form a photoresist S having excellent resolution, in particular, an L&S pattern and an isolated spatial pattern, and the obtained photoresist pattern The shape of the shape is such that it has a rectangular shape with excellent pattern sidewalls, and a line edge roughness (LER) ^ pattern can be formed. Further, the focal depth width can be increased when the photoresist pattern is formed. The LER system refers to a non-uniform uneven shape on the side wall of the spatial pattern, for example, formed in the developed photoresist pattern. < (A) component> The component (A) is a soluble substance having a so-called acid dissociable dissolution inhibiting group. Therefore, the action of the component (B) can be used to dissociate the acid dissociable dissolution inhibitory group upon exposure. The component (A) is changed from alkali-insoluble to alkali-soluble. Therefore, when the photoresist pattern is formed by exposure or after heating (PEB) after exposure, exposure can be made alkali-soluble, and the unexposed portion can be made alkali-insoluble, and a positive photoresist pattern can be formed. The constituent unit (al) is a unit derived from a (meth) acrylate having a monocyclic or polycyclic group-based cleavage-suppressing group. The monocyclic group is, for example, a group in which a hydrogen atom is removed from a cycloalkane, an aliphatic monocyclic group such as a cyclopentyl group or a cyclohexyl group. A polycyclic group such as adamane, a tricycloalkane or a tetracycloalkane, such as adamantane, aztec, iso-ice, tricyclodecane, tetracyclododecane, etc. B-Ι) U-like sex type. ί Vertical photoresist: DOF line and alkali are not acid. The whole part of the mask is imaged by acid hydrolysis. For example, the cyclic chain of alkane -11 - (7) 1286670 base, that is, an aliphatic polycyclic group. Moreover, most of the monocyclic or polycyclic groups have been proposed in the ArF photoresist, so the present invention can be selected as the monocyclic or polycyclic group, but industrially preferred is the diamond. An aliphatic polycyclic group such as an alkyl group, a nordyl group or a tetracyclododecyl group.
如上述般，酸解離性溶解抑制基爲具有曝光前使（AAs described above, the acid dissociable dissolution inhibiting group has a pre-exposure (A)
)成分全體爲鹼不溶性之鹼溶解抑制性，但曝光下利用後 述（B)成分所產生之酸的作用會解離，而使（A)成分全 體變化爲鹼可溶性之物。 廣爲人知之該酸解離性溶解抑制基如，形成（甲基） 丙烯酸之羧基及環狀或鏈狀3級烷基酯之物。 構成單位（al )具有上述機能時，並無特別限制，可 隨意使用。具體上就優良解像性及耐乾蝕性等較佳爲，下 列一般式（1 ) 、 （ 2 )或（3 )中所選出至少一種之構成 單位。The whole component is an alkali-insoluble base dissolution inhibiting property, but the action of the acid generated by the component (B) described below is dissociated under exposure, and the component (A) is completely changed to an alkali-soluble one. The acid dissociable dissolution inhibiting group is widely known as a carboxyl group of (meth)acrylic acid and a cyclic or chain tertiary alkyl ester. When the constituent unit (al) has the above functions, it is not particularly limited and can be used arbitrarily. Specifically, it is preferable that the excellent resolution and the dry etching resistance are at least one selected from the following general formulas (1), (2) or (3).
(式中，R爲氫原子或低級烷基；R1爲低級烷基） -12 - (8) 1286670(wherein R is a hydrogen atom or a lower alkyl group; R1 is a lower alkyl group) -12 - (8) 1286670
RR
…⑵ (式中，R爲氫原子或低級烷基；R2及R3各自獨立爲低級 烷基）(2) (wherein R is a hydrogen atom or a lower alkyl group; and R2 and R3 are each independently a lower alkyl group)
RR
• · .(3) (式中，R爲氫原子或低級烷基；R4爲3級烷基） 一般式（1 )所示構成單位爲，接鄰於（甲基）丙烯 酸之酯部上氧原子（-0-)的碳原子爲，金剛烷基般環骨 架上之3級烷基。 其中R爲氫原子、甲基或碳原子數2至5之低級烷基， 具體例如，乙基、丙基、異丙基、丁基、異丁基、tert- 丁基、戊基、異戊基、新戊基等低級之直鏈狀或支鏈狀烷 基。 又，R1如甲基、乙基、丙基、異丙基、η -丁基、異丁 -13 - (9) 1286670 基、tert-丁基、戊基、異戊基、新戊基等低級之直鏈狀或 支鏈狀烷基。R 1爲碳數2以上之烷基時，雖傾向酸解離性 高於甲基時而爲佳，但工業上最佳爲甲基及乙基。 一般式（2 )所示構成單位爲，接鄰於（甲基）丙烯 酸之酯部上氧原子（_0-)之碳原子爲3級烷基，且該烷基 中存在金剛烷基般環骨架。一般式（2)所示構成單位中 ，以同一般式（1)之定義，R2及R3各自獨立爲低級烷基， 即上述（^至（：5直鏈狀或支鏈狀院基。該基之酸解離性傾向 高於2-甲基-2-金剛烷基。又，工業上R2及R3較佳爲，同爲 甲基。 一般式（3)所示構成單位爲，接鄰於（甲基）丙烯 酸酯部以外之酯部上氧原子（-0-)的碳原子爲3級烷基， 且該酯部係以四環十二烷基般環骨架連結（甲基）丙烯酸 酯部。一般式（3)所示單位中，R同上述一般式（1)之 定義，R4爲tert-丁基、tert-戊基等3級烷基，較佳爲碳原 子數4或5之級烷基，又，工業上R4較佳爲tert-丁基。 上述一般式（1)至（3)所示構成單位中，就優良解 像性等佳爲一般式（1 )所示構成單位，且R1爲甲基或乙 基之物。 構成單位（a2)爲，具有含內酯單環或多環式基之（ 甲基）丙烯酸酯所衍生之構成單位。該內酯官能基可有效 提高本發明組成物所形成之光阻膜對基板的密合性，及提 高與顯像液之親水性。 構成單位（a2)可爲，同時具有內酯官能基及環基之 -14- 1286670 do) 隨意物，並無特別限制。具體之含內酯單環式基如，由 7-丁內酯中去除一個氫原子之基，又，含內酯之多環式 基如，由具有內酯基之二環鏈烷、三環鏈烷、四環鏈烷中 去除一個氫原子之基。其中就工業上易取性等特佳爲，由 具有下列構造式（6)之含內酯二環鏈烷，或具有構造式 (7)之含內醋三環鏈院中去除一個氫原子之基。• (3) (wherein R is a hydrogen atom or a lower alkyl group; and R4 is a 3-stage alkyl group). The unit of the formula (1) is an oxygen group attached to the ester of (meth)acrylic acid. The carbon atom of the atom (-0-) is a tertiary alkyl group on the adamantyl ring skeleton. Wherein R is a hydrogen atom, a methyl group or a lower alkyl group having 2 to 5 carbon atoms, and specifically, for example, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isethyl A lower linear or branched alkyl group such as a benzyl group or a neopentyl group. Further, R1 such as methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl-13 - (9) 1286670, tert-butyl, pentyl, isopentyl, neopentyl, etc. A linear or branched alkyl group. When R 1 is an alkyl group having 2 or more carbon atoms, it is preferable that the acid dissociation property is higher than that of the methyl group, but it is industrially preferred to be a methyl group and an ethyl group. The structural unit represented by the general formula (2) is such that the carbon atom adjacent to the oxygen atom (_0-) on the ester moiety of (meth)acrylic acid is a tertiary alkyl group, and an adamantyl ring skeleton is present in the alkyl group. . In the structural unit represented by the general formula (2), R2 and R3 are each independently a lower alkyl group as defined in the general formula (1), that is, the above (^ to (5 linear or branched). The acid dissociation tendency is higher than 2-methyl-2-adamantyl group. Further, in the industry, R2 and R3 are preferably the same as methyl. The general formula (3) is represented by a unit of The carbon atom of the oxygen atom (-0-) on the ester moiety other than the methyl acrylate moiety is a tertiary alkyl group, and the ester moiety is linked to a (meth) acrylate moiety by a tetracyclododecyl ring skeleton. In the unit of the general formula (3), R is the same as defined in the above general formula (1), and R4 is a tertiary alkyl group such as tert-butyl or tert-pentyl, preferably having a carbon number of 4 or 5. In the structural unit represented by the above general formulas (1) to (3), the alkyl group is preferably a structural unit represented by the general formula (1). And R1 is a methyl or ethyl group. The constituent unit (a2) is a constituent unit derived from a (meth) acrylate having a monocyclic or polycyclic group of a lactone. The lactone functional group can be effectively improved. This hair The adhesion of the photoresist film formed by the composition to the substrate, and the improvement of the hydrophilicity with the developing solution. The constituent unit (a2) may be a lactone functional group and a cyclic group of -14 to 1286670 do) The content of the monoester-containing monocyclic group is, for example, a group in which a hydrogen atom is removed from 7-butyrolactone, and the polycyclic group having a lactone is, for example, a lactone group. a group in which a hydrogen atom is removed from a bicycloalkane, a tricycloalkane or a tetracycloalkane. Among them, industrially preferable, etc., a lactone-containing bicyclic alkane having the following structural formula (6) Or a group having a hydrogen atom in the vinegar-tricyclic chain containing the structural formula (7).
又，具體之構成單位（a2)如，具有含內酯之單環烷 基或三環烷基的（甲基）丙烯酸酯所衍生之構成單位，更 具體之例如，下列一般式（8 )至（〗〇 )所示構成單位。 ~ 15 - (11)1286670 Η /Further, the specific constituent unit (a2) is, for example, a constituent unit derived from a (meth) acrylate having a monocyclic alkyl group or a tricycloalkyl group containing a lactone, and more specifically, for example, the following general formula (8) to (〗 〖) The constituent units shown. ~ 15 - (11)1286670 Η /
• · · (8)• · · (8)
(式中，R爲氫原子或低級烷基）(wherein R is a hydrogen atom or a lower alkyl group)
RR
鍵結位置存在5位或6位之異構物的混合物， (式中，R爲氫原子或低級烷基） -16 - (12) 1286670A 5- or 6-position mixture of isomers is present at the bonding site, (wherein R is a hydrogen atom or a lower alkyl group) -16 - (12) 1286670
(式中，R爲氫原子或低級院基） 上述一般式（8)至（10)所示構成單位中，就優良 之抑制性及降低效果接近等較佳爲，α碳具有酯鍵之一般 式（10)所示（甲基）丙烯酸的r-丁內酯，即7-丁內酯 之（甲基）丙烯酸酯所衍生的構成單位。 又，一般式（8) 、 （9)所示（甲基）丙烯酸之降茨 內酯，即降茨內酯之（甲基）丙烯酸酯所衍生的構成單位 ，可得良好之光阻圖型形狀，例如矩形性而爲佳。特佳爲 可得極高效果之一般式（9 )所示構成單位。 構成單位（a3)爲，具有含羥基多環式基之（甲基） 丙烯酸酯所衍生的構成單位，其因具有羥基之極性基，故 可提高樹脂成分（A )全體與顯像液之親水性，及提升曝 光部之鹼溶解性，因此可更進一步提升解像性。所使用之 多環式基可同上述構成單位（al)之多環式基。 該構成單位（a3)可爲含羥基之多環式基中隨意物， 並無特別限制。具體上就提升耐乾蝕性及使圖型剖面爲矩 形性之效果較佳爲含羥基之金剛烷基，特佳爲下列一般式 (4 )所示構成單位。 -17- (13) 1286670(In the formula, R is a hydrogen atom or a lower-grade courtyard group.) In the constituent units represented by the above general formulas (8) to (10), it is preferred that the excellent inhibitory property and the reducing effect are close to each other, and the α carbon has an ester bond. The constituent unit derived from the r-butyrolactone of (meth)acrylic acid represented by the formula (10), that is, the (meth) acrylate of 7-butyrolactone. Further, in the general formula (8), (9), the lowering of the (meth)acrylic acid, which is a constituent unit derived from the (meth) acrylate of the decanolide, can obtain a good photoresist pattern. The shape, for example, is rectangular. It is particularly preferable as a constituent unit represented by the general formula (9) which can obtain an extremely high effect. The constituent unit (a3) is a constituent unit derived from a (meth) acrylate having a hydroxyl group-containing polycyclic group, and since it has a polar group of a hydroxyl group, the hydrophilicity of the entire resin component (A) and the developing solution can be improved. And improve the alkali solubility of the exposed portion, so that the resolution can be further improved. The polycyclic group used may be the same as the above-mentioned polycyclic group constituting the unit (al). The constituent unit (a3) may be a random group of a hydroxyl group-containing polycyclic group, and is not particularly limited. Specifically, the effect of improving the dry etching resistance and the rectangular cross section of the pattern is preferably a hydroxyl group-containing adamantyl group, and particularly preferably a constituent unit represented by the following general formula (4). -17- (13) 1286670
(式中，R爲氫原子或低級烷基） 構成單位（a4 )爲，構成單位（a2 ) 、（ a3 )以外之 具有含多環式·基非酸解離性溶解抑制基的（甲基）丙烯酸 酯所衍生之構成單位。 該具有含多環式基非酸解離性溶解抑制基之（甲基） 丙烯酸酯所衍生的構成單位係指，具有提升曝光前後之（ A )成分全體的排水性，而抑制鹼溶解性之機能的構成單 位。即，該構成單位含有能降低曝光前（A)成分全體之 鹼溶解性，且曝光後不受（B )成分所產生之酸的作用而 解離，故有可降低構成單位（a 1 )之酸解離性溶解抑制基 解離後，使（A )成分全體變化爲鹼可溶性時（A )成分 全體之鹼溶解性，但不爲鹼不溶性之溶解抑制性的基。 因此構成單位（a4 )不同於構成單位（al )、構成單 位（a2 )及構成單位（a3 )。即，不具有構成單位（al ) 之酸解離性溶解抑制基，構成單位（a2 )之內酯基及構成 單位（a3 )之酸基中任何一種基。 所使用之構成單位（a4 )的多環式基可同構成單位（ -18- (14) 1286670 al )之多環式基。(wherein R is a hydrogen atom or a lower alkyl group). The constituent unit (a4) is a (meth) group having a polycyclic type-based non-acid dissociable dissolution inhibiting group other than the constituent units (a2) and (a3). The constituent unit derived from acrylate. The constituent unit derived from the (meth) acrylate having a polycyclic group-based non-acid dissociable dissolution inhibiting group means that it has the function of improving the drainage property of the entire component (A) before and after the exposure, and suppressing the alkali solubility. The constituent unit. In other words, the constituent unit contains an alkali which can reduce the alkali solubility of the entire component (A) before exposure, and is not dissociated by the action of the acid generated by the component (B) after the exposure, so that the acid of the constituent unit (a 1 ) can be lowered. After the dissociation dissolution inhibiting group is dissociated, the entire component (A) is changed to the alkali solubility of the entire component (A) when it is alkali-soluble, but it is not the alkali-insoluble dissolution-inhibiting group. Therefore, the constituent unit (a4) is different from the constituent unit (al), the constituent unit (a2), and the constituent unit (a3). Namely, it does not have an acid dissociable dissolution inhibiting group of the constituent unit (al), and constitutes any one of the lactone group of the unit (a2) and the acid group of the constituent unit (a3). The polycyclic group of the constituent unit (a4) used may be a polycyclic group of the constituent unit (-18-(14) 1286670 al).
所使用之構成單位（a4 )可爲多數已知的ArF正型光 阻材料，但就工業上易取性等較佳爲三環十二烷基（甲基 )丙烯酸酯、金剛烷基（甲基）丙烯酸酯、四環十二烷基 (甲基）丙烯酸酯、異冰片基（甲基）丙烯酸酯中所選出 至少1種所衍生之構成單位。該構成單位例如，下列一般 式（1 1 )至（1 4 )所示。其中就所得光阻圖型之形狀，例 如良好矩形性特佳爲一般式（1 1 )所示構成單位。The constituent unit (a4) used may be most known ArF positive-type photoresist materials, but tricyclododecyl (meth) acrylate or adamantyl group is preferred in terms of industrial easiness and the like. At least one of the constituent units derived from the acrylate, tetracyclododecyl (meth) acrylate, and isobornyl (meth) acrylate is selected. The constituent units are, for example, the following general formulas (1 1 ) to (1 4 ). Among them, the shape of the obtained resist pattern, for example, the good rectangular shape is particularly preferably a constituent unit represented by the general formula (1 1 ).
鍵結位置存在5位或6位之異構體的混合物， (式中，R爲氫原子或低級烷基）A mixture of isomers at the 5-position or 6-position is present at the bonding position, (wherein R is a hydrogen atom or a lower alkyl group)
-19- (15) 1286670 (式中，R爲氫原子或低級烷基）-19- (15) 1286670 (wherein R is a hydrogen atom or a lower alkyl group)
RR
(式中，R爲氫原子或低級烷基） (A)成分較佳爲，構成單位（al)含有一般式（1) 所示構成單位、構成單位（a2 )含有一般式（9 )所示構 成單位、構成單位（a3)含有一般式（4)所示構成單位 及構成單位（a4)含有一般式（11)所示構成單位之共聚 物，即含有下列[化5]所記載之4種構成單位的共聚物。其 對LER及光阻圖型之矩形性特別佳。又，耐乾蝕性高於後 述樹脂而爲佳。(In the formula, R is a hydrogen atom or a lower alkyl group) The component (A) preferably has a constituent unit (al) containing a constituent unit represented by the general formula (1), and a constituent unit (a2) containing a general formula (9). The constituent unit and the constituent unit (a3) contain a copolymer having a structural unit represented by the general formula (4) and a constituent unit (a4) containing a constituent unit represented by the general formula (11), that is, four types described in the following [Chemical Formula 5] A copolymer of constituent units. It has a particularly good rectangular shape for LER and photoresist patterns. Further, the dry etching resistance is preferably higher than the later-described resin.
其中就上述優良效果較佳爲，構成單位（al)至（a4 )所形成之共聚物。 -20- (16) 1286670Among them, the above excellent effects are preferably such that the copolymer formed by the units (al) to (a4) is formed. -20- (16) 1286670
(式中，R爲氫原子或低級烷基；R5爲甲基或乙基） (A)成分中各構成單位（al)至（a4)之比率爲， 構成單位（a 1 ) 2 5至5 0莫耳°/❶，較佳爲3 〇至4 〇莫耳％，構 成單位（a2) 25至50莫耳。/。，較佳爲3〇至4〇莫耳％，構成 單位（a3) 10至30莫耳％，較佳爲1〇至2〇莫耳％，構成單 位（a4) 3至25莫耳％，較佳爲5至2〇莫耳％。該範圍內可 大幅提升所得的正型光阻組成物所形成之孤立圖型的焦點 深度幅寬’且可充分抑制而大幅減少效果接近。大幅超脫 該範圍時，恐降低解像性而不宜。 又’必要時本發明之正型光阻組成物中，形成（A ) 成分之各構成單位（al)至（a4)的單體中，可適當組合 、共聚合先前化學加強型正型光阻組成物中，提升耐乾蝕 性之基及具有酸非解離性之溶解抑制基用的丙烯酸衍生物 、甲基丙烯酸衍生物、甲基丙烯酸、烏來酸、富馬酸等可 成爲鹼可溶性用之具有乙烯性雙鍵的羧酸及已知之製造丙 -21 - (17) 1286670 烯樹脂用之單體等。 該丙烯酸衍生物如，丙烯酸萘酯、丙烯酸苄酯、丙烯 酸3-羰基環己酯、丙烯酸與萜品醇之酯、丙烯酸等3-溴丙 酮之酯等羧基之羥基受提升耐乾蝕性之基或酸非解離性取 代基保護的丙烯酸酯等。又，甲基丙烯酸衍生物如，對應 該丙烯酸衍生物之甲基丙烯酸的衍生物。 又，具有乙烯性雙鍵之羧酸如，丙烯酸、甲基丙烯酸 、烏來酸、富馬酸等。 已知之製造丙烯酸樹脂用的單體如，丙烯酸甲酯、丙 烯酸乙酯、丙烯酸丙酯、丙烯酸異丙酯、丙烯酸η-丁酯、 丙烯酸異丁酯、丙烯酸η-己酯、丙烯酸辛酯、丙烯酸2-乙 基己酯、丙烯酸月桂酯、丙烯酸2-羥基乙酯、丙烯酸2-羥 基丙酯等丙烯酸烷基酯及對應之甲基丙烯酸烷基酯等。 (A )成分中衍生各構成單位之單體例如可由，使用 偶氮雙異丁腈（AIBN )等自由基聚合引發劑之已知的自 由基聚合法等聚合而得。 (A)成分之質量平均分子量（利用凝膠滲透色譜法 之聚苯乙烯換算基準）較佳爲3 0000以下，更佳7500以下 。特佳爲4000至7200，最佳爲5000至6500。質量平均分子 量爲75 00以下時，可提升LER及減少鹼顯像時之顯像缺陷 〇 又，質量平均分子量爲4000以上時易合成（A)成分 。分散度較佳爲1·〇至5.0，更佳爲1.0至3.0。 (A )成分可由1種或2種以上之樹脂構成，例如上述 -22- (18) 1286670 構成單位（a 1 )至（a4 )所形成之共聚物可單獨或2種以 上混合使用。 本發明之（A)成分爲含有構成單位（al)至（a4) 之共聚物，故可提升孤立線圖型之焦點深度及減低效果接 近，因此對疏密兩圖型可形成忠實於圖罩之光阻圖型。 又，組合後述（B)成分時，可提升L&S圖型及孤立 空間圖型之解像性，且可提升該圖型之LER、形狀及焦點 深度等。 < (B )成分> 本發明之（B)成分的特徵爲，含有上述一般式（b-1 )或（b-2 )所示銃化合物（以下各自稱爲銃化合物1、銃 化合物2 )。 式（b-1 ) 、 （ b-2 )中，X爲至少一個氫原子受氟原 子取代之直鏈狀或支鏈狀伸烷基，該伸烷基之碳數爲2至6 ，較佳爲3至5，最佳爲碳數3。 Y、Z各自獨立爲至少一個氫原子受氟原子取代之直鏈 狀或支鏈狀烷基，該烷基爲碳數爲1至1〇，較佳爲1至7, 更佳爲1至3。X之伸烷基的碳數或Y、Z之烷基的碳數較小 時，對光阻溶劑可得良好溶解性而爲佳。 又，X之伸烷基或Y、Z之烷基中，受氟原子取代之氫 原子數愈多酸強度愈強，且可提升對200nm以下之高能量 光及電子線的透明性而爲佳。該伸院基或院基中之氟原子 比率，gp氟化率較佳爲70至100%，更佳爲90至100%，最 -23- (19) 1286670 佳爲全部氫原子受氟原子取代之全氟伸烷基或全氟烷基。 R1至R3各自獨立爲芳基或烷基。 R1至R3中至少一個爲芳基。R1至R3中又以二個以上爲 芳基較佳，最佳R1至R3全爲芳基。 R1至R3之芳基並無特別限制，例如可爲碳數6至2 0之 芳基中，可受或不受烷基、鹵原子等取代之苯基、萘基。 就可廉價合成較佳爲碳數6至10之芳基。 R1至R3之烷基並無特別限制，例如碳數1至10之直鏈 狀、支鏈狀環狀烷基等。就解像性優良觀點較佳爲碳數1 至5。具體例如，甲基、乙基、n-丙基、異丙基、丁基、 異丁基、η-戊基、環戊基、己基、環己基、壬基、癸基等 ，但就優良解像性及廉價合成觀點較佳如甲基。 其中R1至R3最佳爲，全爲苯基。 該銃化合物1、2可單獨使用或2種以上組合使用。 本發明之（Β)成分係提供具有優良之LER、解像性 、光阻圖型形狀、焦點深度等用，故需含有銃化合物1或2 〇 (Β )成分中，銃化合物1及2中所選出至少一種之比 率較佳爲，合計量爲（Β)成分全體之25至100質量％，更 佳爲30至100質量％。比率爲25質量％以上可得充分之本發 明的效果。 本發明之（Β )成分可含有先前化學加強型照相光阻 組成物所使用之已知的酸發生劑。該酸發生劑如多數已知 之碘_鹽、锍鹽等鐵鹽，或肟磺酸酯類、雙烷基或雙芳基 -24- (20) 1286670 磺醯二偶氮甲烷類、硝基苄基磺酸酯類、亞胺基磺酸酯_ 、二硕類等，並無特別限制。 其中又以含氟化烷基磺酸離子之陰離子的鑰鹽（以T 稱鐺鹽系酸發生劑）可得較強之酸強度而爲佳。 該鑰鹽系酸發生劑之陽離子如，可受甲基、乙基、$ 基、η-丁基、tert-丁基等低級烷基；甲氧基、乙氧基等低 級院氧基等取代之一或二苯基碘_及一、二或三苯基綺’ 二甲基（4-羥基萘基）銃等。 又，該鑰鹽系酸發生劑之陰離子較佳爲安全性高之碳 數1至7，更佳碳數1至3之直鏈狀烷基的部分或全部氫原子 受氟原子取代之氟化烷基磺酸離子。碳數7以下時可得較 高之磺酸強度。另外該氟化烷基磺酸離子之氟化率（烷基 中之氟原子比率）較佳爲10玉00%，更佳爲50至100%，特 佳爲能加強酸強度之全部氫原子受氟原子取代物。其具體 例如，三氟甲烷磺酸酯、七氟丙烷磺酸酯等。 上述鎗鹽系酸發生劑之具體例如，二苯基碘鎗之三氟 甲烷磺酸鹽或九氟丁烷磺酸鹽、雙（4-tert-丁基苯基）碘 鑰之三氟甲烷磺酸鹽或九氟丁烷磺酸鹽、三苯基銃之三氟 甲烷磺酸鹽、其七氟丙烷磺酸鹽或九氟丁烷磺酸鹽、三（ 4-甲基苯基）銃之三氟甲烷磺酸鹽、其七氟丙烷磺酸鹽或 九氟丁烷磺酸鹽、-苯基二甲基锍之三氟甲烷磺酸鹽、其 七氟丙烷磺酸鹽或九氟丁烷磺酸鹽、二苯基-甲基銃之三 氟甲烷磺酸鹽、其七氟丙烷磺酸鹽或九氟丁烷磺酸鹽等。 該鏺鹽系酸發生劑可單獨或2種以上混合使用。 -25- (21) 1286670 (B )成分係混合使用鑰鹽系酸發生劑與銃化合物1及 2中所選出之至少1種以上時，鑰鹽系酸發生劑之比率較佳 爲10至75質量％ ’更佳爲3〇至70質量％。添加該範圍內之 _鹽系酸發生劑時，可降低LER及顯像缺陷等。又，鑰鹽 系酸發生劑與銃化合物1及2中所選出之至少1種的混合比 率（質量比）爲1 : 9至9 : 1，較佳爲1 : 5至5 : 1，最佳爲1 : 2至 2 : 1。混合使用該比率下之酸發生劑時，有利於LER及顯像 缺陷。 (B )成分對（A )成分100質量份之比率爲0.1至30質 量份’較佳爲〇· 5至20質量份，更佳爲1至10質量份.。低於 該下限値時將無法形成像，又，超過3 0質量份時難得均勻 之溶液，而恐降低保存安定性。 < (C )成分> 本發明之正型光阻組成物可由，材料溶解於有機溶劑 (C )(以下稱爲（C )成分）而得。 (C )成分可爲，能溶解所使用之各成分而得均勻溶 液之物，即可適當選用先前化學加強型光阻物之溶劑用的 已知物中1種或2種以上之隨意物。 例如，7-丁內酯、丙酮、甲基乙基酮、環己酮、甲 基異戊基酮、2-庚酮等酮類；乙二醇、乙二醇-乙酸酯、二 乙二醇、二乙二醇-乙酸酯、丙二醇、丙二醇-乙酸酯、二 丙二醇或二丙二醇-乙酸酯之一甲基醚、一乙基醚、一丙 基醚、一丁基醚或一苯基醚等多種醇類及其衍生物；二噁 >26- (22) 1286670 烷等環式醚類；乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙 酯、乙酸丁酯、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲 酯、乙氧基丙酸乙酯等酯類等。該有機溶劑可單獨使用或 2種以上之混合溶劑。又，丙二醇-甲基醚乙酸酯（PGMEA )與極性溶劑之添加比，可於考量PGMEA與極性溶劑之相 溶性而適當選擇，較佳爲1:9至9:1，更佳爲2:8至8:1。 具體而言，所添加之極性溶劑爲乳酸乙酯（EL )時， PGMEA: EL之質量比較佳爲2:8至8:2，更佳爲3:7至7:3。 又，有機溶劑較佳如，其他之PGME A及EL中所選出至少 一種與7 - 丁內酯之混合溶劑。此時之混合.比中，前者與 後者之質量比較佳爲70:3 0至95:5。 (C )成分之使用量並無特別限制，可因應基板上等 能塗布之濃度下的塗膜壓而適當設定，一般係使光阻組成 物之固體成分濃度爲2至20質量％，較佳爲5至15質量％。 < (D )成分> 爲了提升本發明之正型光阻組成物的光阻圖型形狀、 置放經時安定性（post exposure stability of the latent image formed by the pattern wise exposure of resist layer )等，可添加隨意成分用之含氟有機化合物（D)(以下 稱爲（D )成分）。 該（D)成分曾有多種多樣之提案，故可隨意使用已 知之物，但較佳爲胺，特佳爲2級低級脂肪族胺及3級低級 脂肪族胺。 -27- (23) 1286670 該低級脂肪族胺係指，碳數5以下的烷基或烷基醇之 胺、2級3級胺如，三甲基胺、二乙基胺、三乙基胺、二-η· 丙基胺、三-η -丙基胺、三戊基胺、二乙醇胺、三乙醇胺、 三異丙·醇胺等，特佳爲三乙醇胺之3級烷醇胺。 其可單獨使用或2種以上組合使用。 (D)成分對（Α)成分1〇〇質量份之使用量一般爲 0.01至5.0質量份。 < (Ε)成分> 爲了防止因添加（D)成分而使敏感度惡化，及提升 光阻圖型之形狀及置放經時安定性等，可另含有隨意成分 用之有機羧酸、磷及含氧酸或其衍生物（Ε)(以下稱爲 (Ε)成分）。又，可倂用（D)成分及（Ε)成分或使用 任何一種。 有機羧酸較佳如，丙二酸、檸檬酸、蘋果酸、琥珀酸 、安息香酸、水楊酸等。 磷之含氧酸或其衍生物如，磷酸、磷酸二-心丁基酯、 磷酸二苯基酯等磷酸及其酯之衍生物；膦酸、膦酸二甲基 酯、膦酸-二-η-丁基酯、苯基膦酸、膦酸二苯基酯、膦酸 二苄基酯等膦酸或其酯之衍生物；次膦酸、苯基次膦酸等 次膦酸及其酯之衍生物，其中特佳爲膦酸。 (Ε)成分對（Α)成分每100質量份之使用率爲〇.01 至5.0質量份。 -28- (24) 1286670 〈其他隨意成分> 本發明之正型光阻組成物可依希望適當添加具混合性 之添加劑，例如改良光阻膜之性能用的附加性樹脂、提升 塗布性用之表面活性劑、溶解抑制劑、可塑劑、安定劑、 著色劑、防光暈劑等。 <<光阻圖型之形成方法>>(wherein R is a hydrogen atom or a lower alkyl group; R5 is a methyl group or an ethyl group). The ratio of each constituent unit (al) to (a4) in the component (A) is a constituent unit (a 1 ) 25 to 5 0 mol / ❶, preferably 3 〇 to 4 〇 mol %, constitutes the unit (a2) 25 to 50 m. /. Preferably, it is from 3 to 4 mol%, and the constituent unit (a3) is 10 to 30 mol%, preferably 1 to 2 mol%, and the constituent unit (a4) is 3 to 25 mol%. Good for 5 to 2% of Mo. Within this range, the depth of focus of the isolated pattern formed by the obtained positive resist composition can be greatly increased and can be sufficiently suppressed to greatly reduce the effect. When the range is greatly exceeded, it is not appropriate to reduce the resolution. Further, in the positive resist composition of the present invention, if necessary, a monomer which forms each of the constituent units (a1) to (a4) of the component (A) may be appropriately combined and copolymerized with a previously chemically strengthened positive resist. In the composition, an acrylic acid derivative, a methacrylic acid derivative, methacrylic acid, uric acid, fumaric acid or the like for improving the dry etching resistance and the dissolution inhibiting group having an acid non-dissociable property can be used for alkali solubility. A carboxylic acid having an ethylenic double bond and a monomer which is known to produce a C--21-(17) 1286670 olefin resin. The acrylic acid derivative such as naphthyl acrylate, benzyl acrylate, 3-carbonylcyclohexyl acrylate, an ester of acrylic acid and terpineol, an ester of a carboxyl group such as 3-bromoacetone such as acrylic acid, is promoted to have a basis for improving dry etching resistance or An acid-non-dissociable substituent-protected acrylate or the like. Further, the methacrylic acid derivative is, for example, a derivative of methacrylic acid corresponding to the acrylic acid derivative. Further, a carboxylic acid having an ethylenic double bond such as acrylic acid, methacrylic acid, urethane, fumaric acid or the like. Monomers for producing acrylic resins are known, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, η-butyl acrylate, isobutyl acrylate, η-hexyl acrylate, octyl acrylate, acrylic acid. An alkyl acrylate such as 2-ethylhexyl ester, lauryl acrylate, 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate, and a corresponding alkyl methacrylate. The monomer derived from each constituent unit in the component (A) can be obtained, for example, by polymerization using a known radical polymerization method such as a radical polymerization initiator such as azobisisobutyronitrile (AIBN). The mass average molecular weight (polystyrene conversion standard by gel permeation chromatography) of the component (A) is preferably 30,000 or less, more preferably 7,500 or less. The best is 4000 to 7200, and the best is 5000 to 6500. When the mass average molecular weight is 75 00 or less, the LER can be improved and the development defects at the time of alkali development can be improved. 〇 Further, when the mass average molecular weight is 4,000 or more, the component (A) is easily synthesized. The degree of dispersion is preferably from 1.00 to 5.0, more preferably from 1.0 to 3.0. The component (A) may be composed of one or two or more kinds of resins. For example, the copolymer of the above-mentioned -22-(18) 1286670 constituent units (a1) to (a4) may be used singly or in combination of two or more. The component (A) of the present invention contains a copolymer of constituent units (al) to (a4), so that the depth of focus of the isolated line pattern can be improved and the effect of the reduction is close, so that the two patterns can form a faithful mask. Light resistance pattern. Further, when the component (B) described later is combined, the resolution of the L&S pattern and the isolated space pattern can be improved, and the LER, shape, and depth of focus of the pattern can be improved. <(B) component> The component (B) of the present invention is characterized by containing the above-described general formula (b-1) or (b-2) quinone compound (hereinafter each referred to as hydrazine compound 1, hydrazine compound 2) ). In the formulae (b-1) and (b-2), X is a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the carbon number of the alkyl group is 2 to 6, preferably. It is 3 to 5, and the optimum is 3 carbon atoms. Y and Z are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the alkyl group has a carbon number of 1 to 1 Torr, preferably 1 to 7, more preferably 1 to 3 . When the carbon number of the alkyl group of X or the carbon number of the alkyl group of Y and Z is small, it is preferred that the resist solvent has good solubility. Further, in the alkyl group of X or the alkyl group of Y and Z, the more the number of hydrogen atoms substituted by the fluorine atom, the stronger the acid strength, and the transparency of high-energy light and electron lines of 200 nm or less is preferably improved. . The ratio of fluorine atoms in the base or the courtyard base is preferably 70 to 100%, more preferably 90 to 100%, and most -23-(19) 1286670 is preferably replaced by fluorine atoms. Perfluoroalkylene or perfluoroalkyl. R1 to R3 are each independently an aryl group or an alkyl group. At least one of R1 to R3 is an aryl group. Further, two or more of R1 to R3 are preferably an aryl group, and most preferably R1 to R3 are all aryl groups. The aryl group of R1 to R3 is not particularly limited, and may be, for example, a phenyl group or a naphthyl group which may be substituted with an alkyl group, a halogen atom or the like in an aryl group having 6 to 20 carbon atoms. The aryl group preferably having a carbon number of 6 to 10 can be synthesized inexpensively. The alkyl group of R1 to R3 is not particularly limited, and examples thereof include a linear or branched cyclic alkyl group having 1 to 10 carbon atoms. The viewpoint of excellent resolution is preferably from 1 to 5 carbon atoms. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, η-pentyl, cyclopentyl, hexyl, cyclohexyl, decyl, decyl, etc., but excellent solutions Imagery and inexpensive synthetic views are preferred as methyl groups. Among them, R1 to R3 are most preferably all phenyl groups. The hydrazine compounds 1 and 2 may be used singly or in combination of two or more kinds. The (Β) component of the present invention provides excellent LER, resolution, photoresist pattern shape, depth of focus, etc., and therefore needs to contain a ruthenium compound 1 or 2 〇 (Β) component, 铳 compounds 1 and 2 The ratio of at least one selected is preferably from 25 to 100% by mass, more preferably from 30 to 100% by mass based on the total of the (Β) component. A ratio of 25% by mass or more can provide sufficient effects of the present invention. The (Β) component of the present invention may contain a known acid generator used in the prior chemically amplified photographic resist composition. The acid generator is, for example, most known iron salts such as iodine salts and barium salts, or sulfonium sulfonates, dialkyl or bisaryl-24-(20) 1286670 sulfonium diazomethanes, nitrobenzyl The sulfonate, the iminosulfonate, the second, and the like are not particularly limited. Among them, a key salt of an anion of a fluorine-containing alkylsulfonic acid ion (referred to as a sulfonium-based acid generator) is preferred to obtain a strong acid strength. The cation of the key salt acid generator may be replaced by a lower alkyl group such as a methyl group, an ethyl group, a benzyl group, a η-butyl group or a tert-butyl group; or a lower oxy group such as a methoxy group or an ethoxy group. One or diphenyliodine- and mono-, di- or triphenylphosphonium dimethyl (4-hydroxynaphthyl) anthracene and the like. Further, the anion of the key salt acid generator is preferably a highly safe carbon number of 1 to 7, and more preferably some or all of the hydrogen atoms of the linear alkyl group having 1 to 3 carbon atoms are substituted by fluorine atoms. Alkyl sulfonate ion. A higher sulfonic acid strength can be obtained with a carbon number of 7 or less. Further, the fluorination ratio of the fluorinated alkylsulfonic acid ion (the fluorine atom ratio in the alkyl group) is preferably 10 jade 00%, more preferably 50 to 100%, and particularly preferably all hydrogen atoms capable of strengthening the acid strength Fluorine atom substitution. Specific examples thereof include trifluoromethanesulfonate, heptafluoropropanesulfonate and the like. Specific examples of the above-mentioned gun salt acid generator include, for example, a triphenylmethanesulfonate or a nonafluorobutanesulfonate of a diphenyl iodine gun, and a tris(4-tert-butylphenyl) iodine trifluoromethanesulfonate. Acid salt or nonafluorobutane sulfonate, triphenylmethane trifluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate, tris(4-methylphenyl)phosphonium trifluoride Methanesulfonate, its heptafluoropropane sulfonate or nonafluorobutane sulfonate, triphenylmethanesulfonate of -phenyldimethylhydrazine, heptafluoropropane sulfonate or nonafluorobutane sulfonate, diphenyl a trifluoromethanesulfonate of a benzyl group, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate. These hydrazine salt-based acid generators may be used singly or in combination of two or more kinds. -25- (21) 1286670 (B) When the component is a mixture of a key salt generator and at least one selected from the group consisting of ruthenium compounds 1 and 2, the ratio of the key salt generator is preferably 10 to 75. The mass % ' is preferably from 3 to 70% by mass. When the _salt-based acid generator in this range is added, LER, development defects, and the like can be reduced. Further, the mixing ratio (mass ratio) of at least one selected from the key salt acid generator and the ruthenium compounds 1 and 2 is 1:9 to 9:1, preferably 1:5 to 5:1. For 1: 2 to 2: 1. When the acid generator at this ratio is used in combination, it is advantageous for LER and development defects. The ratio of the component (B) to 100 parts by mass of the component (A) is 0.1 to 30 parts by mass', preferably 5 to 20 parts by mass, more preferably 1 to 10 parts by mass. When the temperature is lower than the lower limit 値, the image cannot be formed, and when it exceeds 30 parts by mass, it is difficult to obtain a uniform solution, and the storage stability may be lowered. <(C) Component> The positive resist composition of the present invention can be obtained by dissolving a material in an organic solvent (C) (hereinafter referred to as a component (C)). The component (C) may be one which can dissolve a component to be used to obtain a homogeneous solution, and one or two or more kinds of known materials for a solvent of a previously chemically-reinforced photoresist can be suitably selected. For example, ketones such as 7-butyrolactone, acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, ethylene glycol-acetate, diethylene glycol Alcohol, diethylene glycol-acetate, propylene glycol, propylene glycol-acetate, dipropylene glycol or dipropylene glycol-acetate methyl ether, monoethyl ether, monopropyl ether, monobutyl ether or a a variety of alcohols and derivatives thereof such as phenyl ether; dioxin >26- (22) 1286670 alkane and other cyclic ethers; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, acetone An ester such as methyl ester, ethyl pyruvate, methyl methoxypropionate or ethyl ethoxypropionate. The organic solvent may be used singly or in combination of two or more. Further, the addition ratio of propylene glycol-methyl ether acetate (PGMEA) to the polar solvent can be appropriately selected in consideration of the compatibility of PGMEA with a polar solvent, and is preferably 1:9 to 9:1, more preferably 2: 8 to 8:1. Specifically, when the polar solvent to be added is ethyl lactate (EL), the mass of PGMEA: EL is preferably from 2:8 to 8:2, more preferably from 3:7 to 7:3. Further, the organic solvent is preferably, for example, a mixed solvent of at least one of 7-butyrolactone selected from other PGME A and EL. In this case, the quality of the former and the latter is preferably 70:30 to 95:5. The amount of the component (C) to be used is not particularly limited, and may be appropriately set in accordance with the coating film pressure at a concentration that can be applied on the substrate. Generally, the solid content concentration of the photoresist composition is from 2 to 20% by mass, preferably. It is 5 to 15% by mass. <Component (D)> In order to enhance the photoresist formation shape of the positive photoresist composition of the present invention, the post exposure stability of the latent image formed by the pattern wise exposure of resist layer Alternatively, a fluorine-containing organic compound (D) (hereinafter referred to as (D) component) for the optional component may be added. The (D) component has various proposals, so that the known one can be used arbitrarily, but it is preferably an amine, particularly preferably a grade 2 lower aliphatic amine and a grade 3 lower aliphatic amine. -27- (23) 1286670 The lower aliphatic amine means an alkyl group having a carbon number of 5 or less or an amine of an alkyl alcohol, a grade 2 tertiary amine such as trimethylamine, diethylamine or triethylamine. And di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine, triethanolamine, triisopropylethanolamine, etc., particularly preferably a tertiary alkanolamine of triethanolamine. They may be used singly or in combination of two or more. The amount of the component (D) to the (Α) component is usually 0.01 to 5.0 parts by mass. <(Ε)Component> In order to prevent the sensitivity from being deteriorated by the addition of the component (D), and to improve the shape of the photoresist pattern and the stability over time, it is possible to further contain an organic carboxylic acid for an optional component. Phosphorus and oxo acid or a derivative thereof (hereinafter referred to as (Ε) component). Further, the component (D) and the component (()) may be used or any one may be used. The organic carboxylic acid is preferably, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like. Phosphorus oxyacid or its derivatives such as phosphoric acid, di-butyl butyl phosphate, diphenyl phosphate and other derivatives of phosphoric acid and esters thereof; phosphonic acid, dimethyl phosphonate, phosphonic acid-di- a derivative of a phosphonic acid such as η-butyl ester, phenylphosphonic acid, diphenyl phosphonate or dibenzyl phosphonate or an ester thereof; phosphinic acid such as phosphinic acid or phenylphosphinic acid and an ester thereof A derivative thereof, particularly preferably a phosphonic acid. The use ratio of the (Ε) component to the (Α) component per 100 parts by mass is 〇.01 to 5.0 parts by mass. -28- (24) 1286670 <Other optional components> The positive-type resist composition of the present invention may be appropriately added with a mixture of additives as desired, for example, an additive resin for improving the properties of the photoresist film, and for improving coatability. Surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, and the like. <<Formation method of photoresist pattern>>
本發明之光阻圖型的形成方法如下所示。The method of forming the photoresist pattern of the present invention is as follows.
即，首，先以旋轉機等將上述正型光阻組成物塗布於矽 晶圓之基板上，以80至150 °C之溫度條件進行PAB (預烤 )40至120秒，較佳爲60至90秒，可形成光阻膜。其次利 用如ArF曝光裝置等介由所需之圖罩以ArF激元激光選擇性 曝光，再以80至15 0°C之溫度條件進行PEB (曝光後加熱） 40至120秒，較佳爲60至90秒。接著使用鹼顯像液，例如 0.1至10質量％四甲基銨羥化物水溶液進行顯像處理，可得 忠實於圖罩圖型之光阻圖型。 又，基板與光阻組成物之塗布層間可設置有機系或無 機系之防反射膜。 曝光用之波長並無特別限制，可使用ArF激元激光、 KrF激元激光、F2激元激光、EUV (極紫外線）、VUV ( 真空紫外線）、EB (電子線）、X線、軟X線等放射線。 本發明之光阻組成物特別適用於ArF激元激光。 【實施方式】 -29- (25) 1286670 實施例 下面將以實施例詳細說明本發明。 合成例1-1 將下列單體（al 1 ) ( a21 ) 、（ a31 )及（a41 )之混 合物0·25莫耳溶解於甲基乙基酮（MEK) 500ml中，再加 入AIBN O.Olmol，溶解後將所得溶液加熱至65至7°C。該 溫度下維持3小時後，將所得反應液注入攪拌中之異丙醇 3 L中，再過據分離所析出之固體物。將所得固體物溶解於 3 0 0ml之MEL中，再注入攪拌中之甲醇3L中，過濾分離所 析出之固體物後乾燥，得下列[化16]所示質量平均分子量 爲10000之樹脂1-1。 (all) ·· 2-甲基-2-金剛烷基甲基丙烯酸酯（相當於 一般式（1)中，R爲甲基且R1爲甲基之構成單位的單p) 4 0莫耳％ (a21): r-丁內酯甲基丙烯酸酯（相當於—般式（ 1 0 )中，R爲甲基之構成單位的單體）40莫耳。/。 (a3 1 ) : 3 -羥基-1 -金剛烷基甲基丙烯酸酯u 八 一般式（Ο中，R爲甲基之構成單位的單體）15莫耳％ (a41):三環癸基甲基丙烯酸酯（相當於〜般1 11)中，R爲甲基之構成單位的單體）5莫耳％ -30- (26) 1286670 [化 16]That is, first, the positive-type photoresist composition is applied onto a substrate of a germanium wafer by a rotary machine or the like, and PAB (pre-bake) is performed at a temperature of 80 to 150 ° C for 40 to 120 seconds, preferably 60. A photoresist film can be formed up to 90 seconds. Secondly, selective exposure is performed by ArF excimer laser through a mask such as an ArF exposure apparatus, and PEB (post-exposure heating) is carried out at a temperature of 80 to 150 ° C for 40 to 120 seconds, preferably 60. Up to 90 seconds. Subsequently, an alkali developing solution, for example, a 0.1 to 10% by mass aqueous solution of tetramethylammonium hydroxide is used for development processing, whereby a photoresist pattern faithful to the pattern of the mask can be obtained. Further, an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the photoresist composition. The wavelength for exposure is not particularly limited, and ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet ray), VUV (vacuum ultraviolet ray), EB (electronic line), X-ray, soft X-ray can be used. Wait for radiation. The photoresist composition of the present invention is particularly suitable for use in an ArF excimer laser. [Embodiment] -29-(25) 1286670 EXAMPLES Hereinafter, the present invention will be described in detail by way of examples. Synthesis Example 1-1 A mixture of the following monomers (al 1 ) ( a21 ), ( a31 ) and (a41 ) was dissolved in 500 ml of methyl ethyl ketone (MEK), and AIBN O. Olmol was further added. After dissolution, the resulting solution was heated to 65 to 7 °C. After maintaining at this temperature for 3 hours, the resulting reaction solution was poured into 3 L of isopropanol which was stirred, and the precipitated solid was separated. The obtained solid was dissolved in 300 ml of MEL, and then poured into 3 L of methanol stirred, and the precipitated solid was separated by filtration and dried to obtain a resin having a mass average molecular weight of 10,000 as shown in the following [Chemical Formula 16]. . (all) · 2-methyl-2-adamantyl methacrylate (corresponding to a single p in the general formula (1), R is a methyl group and R1 is a constituent unit of a methyl group) 4 0 mol% (a21): r-butyrolactone methacrylate (corresponding to a monomer of the general formula (10) wherein R is a constituent unit of a methyl group) 40 mol. /. (a3 1 ) : 3 -Hydroxy-1 -adamantyl methacrylate u VIII general formula (in the middle, R is a monomer of the methyl group) 15 mol% (a41): tricyclic mercapto In the acrylate (corresponding to ~11), R is a monomer of the methyl group) 5 mol% -30- (26) 1286670 [Chem. 16]
II /VII /V
PSPS
or ο cIP ό. ΌOr ο cIP ό. Ό
(式中 ’ p/q/r/s = 40 /40 /15 /5 (莫耳比）） 合成例1-2 问合成例1-1之組成及方法’侍質®平均分子量6900 之樹脂1-2。 合成例2 -1 除了以下列單體（al2 )及（a22 )取代（al〗）及（ a2 1 )，且各單體之組成（al2 ) / ( a22 ) / ( a31 ) / ( a41 )=40莫耳％/35莫耳％/15莫耳。/。/10莫耳。/〇以外，其他同合 成例1-1得下列[化17]所示質量平均分子量1 05 00之樹脂2-1 〇 (al2 ) : 2-乙基-2-金剛烷基甲基丙烯酸酯（相當於 一般式（1)中，R爲甲基且R1爲乙基之構成單位的單體） (a22 ):降茨烷內酯甲基丙烯酸酯（相當於一般式 (8)中，R爲甲基之構成單位的單體） -31 - (27) 1286670 [it 17](wherein p/q/r/s = 40 /40 /15 /5 (mr ratio)) Synthesis Example 1-2 Composition and method of Synthesis Example 1-1 'Servo® resin with an average molecular weight of 6900 1 -2. Synthesis Example 2 -1 except that (al) and (a2) were substituted with the following monomers (al2) and (a22), and the composition of each monomer (al2) / (a22) / ( a31 ) / ( a41 ) = 40 mol%/35 mol%/15 mol. /. /10 Moer. Other than the hydrazine, the same as in the synthesis example 1-1, the following phenol 2-1 (al2) having a mass average molecular weight of 1,500 00 as shown in the following [Chemical Formula 17]: 2-ethyl-2-adamantyl methacrylate ( Corresponding to the monomer of the general formula (1), wherein R is a methyl group and R1 is a constituent unit of an ethyl group) (a22): a reduced alkyl lactone methacrylate (corresponding to the general formula (8), R is Monomer of the constituent units of methyl) -31 - (27) 1286670 [it 17]
(式中，p/q/r/S = 40 /3 5 / 1 5 / 1 0 (莫耳比）） 合成例2-2 同合成例2-1之組成及方法得質量平均分子量6400之 樹脂2-2。(wherein, p/q/r/S = 40 /3 5 / 1 5 / 1 0 (mole ratio)) Synthesis Example 2-2 Composition and method of Synthesis Example 2-1 A resin having a mass average molecular weight of 6,400 was obtained. 2-2.
合成例3 - 1 除了以下列單體（a23 )取代（a22 )以外，其他同合 成例2得下列[化18]所示質量平均分子量7200之樹脂3-1。 (a23 ):降茨烷內酯甲基丙烯酸酯（相當於一般式 (9)中，R爲甲基之構成單位的單體） -32- (28) 1286670 [化 1 8 ]Synthesis Example 3 - 1 A resin 3-1 having a mass average molecular weight of 7,200 as shown in the following [Chemical Formula 18] was obtained except that the following monomer (a23) was substituted for (a22). (a23): Desperate lactone methacrylate (corresponding to a monomer of the general formula (9), R is a constituent unit of a methyl group) -32- (28) 1286670 [Chemical 1 8 ]
(式中，p/q/r/s = 40 /35 /15 /10 (莫耳比））(where p/q/r/s = 40 /35 /15 /10 (Morby))
合成例3-2 同合成例3-1之組成及方法得質量平均分子量1〇〇〇〇之 樹脂3 - 2。 實施例1 將合成例1-1所得之質量平均分子量10 〇〇〇之樹脂 100質量份’及（B)成分用之上述一般式（b-l)中X 爲碳數3且全部氫原子受氟原子取代之伸烷基，R I至R3爲 苯基之銃化合物（以下稱[化1 9]爲PAG1 ) 3.0質量份，及 (D )成分用之三乙醇胺〇·35質量份溶解於丙二醇-甲基醚 乙酸酯（PGMEA )與乳酸乙酯（el )之混合物（質量比 8 : 2 )中，得固體成分濃度8質量％之正型光阻組成物。 -33- (29) 1286670 [it 19]Synthesis Example 3-2 The composition and method of Synthesis Example 3-1 were obtained as a resin 3 - 2 having a mass average molecular weight of 1 Å. Example 1 100 parts by mass of the resin having a mass average molecular weight of 10 Å obtained in Synthesis Example 1-1 and the component (B) were used in the above general formula (b1), and X was a carbon number of 3 and all hydrogen atoms were subjected to fluorine atoms. Substituted alkylene group, RI to R3 is a phenyl ruthenium compound (hereinafter referred to as [Chem. 19] is PAG1) 3.0 parts by mass, and (D) component is used in the triethanolamine hydrazine·35 parts by mass in propylene glycol-methyl group. In a mixture (mass ratio of 8:2) of ether acetate (PGMEA) and ethyl lactate (el), a positive resist composition having a solid concentration of 8 mass% was obtained. -33- (29) 1286670 [it 19]
其次利用旋轉機將有機防反射膜組成物「ARC-29A」 (商品名，普流旺公司製）塗布於矽晶圓上，熱板上以 2 15°C燒烤6.0秒，乾燥後形成膜厚77nm之有機系防反射膜 。其後利用旋轉將上述正型光阻組成物塗布於防反射膜上 ，熱板上以120°C預烤（PAB ) 90秒，乾燥後形成膜厚 250nm之光阻層。 接著利用ArF曝光裝置NSR-S302 (尼康公司製，NA ( 開口數）=0.60，σ=0·55)，介由圖罩（二進劑）下選擇 φ 性照射A r F激元激光（1 9 3 n m )。 其後以1 3 0 °C、9 0秒之條件進行p E B處理，2 3 °C下再 以2.3 8質量％四甲基銨羥化物水溶液進行6 0秒之攪煉顯像 ，水洗2 0秒後乾燥，形成光阻圖型。 結果使用實施例1之正型光阻組成物時，將幅寬1 2 〇 n m 之線與空間爲1 ·· 1 〇 (間距1 3 2 0 n m )的圖罩複印爲線幅寬 80nm之曝光量Εορ (敏感度）爲25mJ/cm2。 又’所形成的幅寬80nm之孤立光阻圖型舄，頂端形狀 不圓且光阻線之側壁垂直的高矩形性物。 -34- (30) 1286670 另外求取表示所形成之圖型的LER尺度的3 σ，結果圖 型之3 σ爲5 · 0 n m。該3 σ係指，利用側長S Ε Μ (日立製作 所公司製，商品名「S-9220」）測定32處試料之光阻圖型 的幅寬後，由結果算出之標準偏差（σ )的3倍値（3 σ ) 。3 σ値愈小表示粗糙度愈低，可得均一幅寬之光阻圖型 〇 又，焦點深度幅（DOF )爲450nm。 另外逐次縮小圖罩之間距，以上述曝光量Εορ曝光後 ，所得線與空間之分離解像力爲間距24 Onm。該分離解像 力之値愈小表示光阻組成物之性能佳，且該評估法廣受業 者使用。 實施例2至18、比較例1至5 除了依表1所示更改（A)成分之種類、（B)成分之 種類及添加量（質量份）外，其他同實施例1調製正型光 阻組成物。 又，實施例9至12及比較例3中，將實施例1之PAB溫 度改爲l〇5°C，且PEB溫度改爲95°C。實施例13至18及比 較例4至5中，將實施例1之PAB 溫度改爲125°C，且PEB 溫度改爲1 1 5 °C。 -35- (31)1286670 s sa § —οςν d_ovl _0·ς Ιος d—ςι Ιος _8ς i s sms iig i §10vd8001 "go/imsuymsd umlsd 0S2 養V) ufi 1¾ 5 "gQ/i曰豸 codSYd un)10Yd 0801 11lgillg\ 1¾ i ς·< M\ieg/igv<N\ Glrisd dMDVd 0002 1丨1遝璉\ U雲親 500nm 450nm \ 450nm 450nm 450nm 500nm 450nm 450nm 450nm 1 450nm 450nm 500nm 1 450nm 1 450nm 500nm 500nm 450nm 500nm 450nm 一 1 一 一一 250 nmP 250 nmP 260 nmP 280 nmP 1 300 nmP 300 nmP 280 nmP 280 nmP 4.7 nm 260 nmP 4.8 nm 250 nmP 250 nmP 260 nmP 260 nmP 260 nmP 260 nmP 260 nmP 250 nmP 250 nmP 250 nmP 4.5 nm 1 4.6 nm 5.2 iim 4.5 nm 4.5 nm ΐ r~ 寸· 4.5 nm 4.4 nm 4.5 nm ' 4.6 nm 1 4.4 nm 6.2 nm 6.0 nm 6.5 nm 6.7 nm 6.7nm IS 蝤 _ 垂直 垂直 § s 垂直 i非常垂直 非常垂直 非常垂直 非常垂直 非常垂直 非常垂直1 Round Round Round Round Round - ,23ml/cm2 ; 28 mJ/cm2 25mJ/cm2 , 25 mJ/cm2 30 mJ/cm2 31 mJ/cm2 29 mJ/cm2 29 mJ/cm2 32 mJ/cm2 1 32 mi/cm2 30 mJ/cm2 30 mJ/cm2 30 mJ/cm2 28 mJ/cm2 20 mJ/cm2 22 mJ/cm2 26 mJ/cm2 30 mJ/cm2 30mJ/cm2 1 PAG2(1.5) 1 PAG2(1.5) 1 PAG2(1.5) 1 1 PAG2(1.5) I » • PAG2(1.5) 1 PAG3(3.0) PAG3(3.0) PAG3(3.0) PAG3(3.0) PAG3(3.0) 10000 PAG4(3.0) 6900 PAG1(3.0) 6900 PAGK1.5) PAG4(3.0) PAGK1.5) PAGK3.0) PAGK1.5) PAG4(3.0) PAG(3.0) 1 1 PAGK1.5) PAG4(3.0) PAG1(3.0) PAG1(1.5) PAG4(3.0) 1 雇 1 1 9 6900 10500 6400 6400 1 6400 1 7200 7200 _ 7200 10000 10000 I 10000 10000 6900 10500 7200 10000 樹脂1 -1 1 樹脂1-2 (N 1 ΰΐπ Π23 M 樹脂1-2 f—^ 1 <N m Π3Π M <N 1 (N m m 樹脂2-2 ΟΪ 1 (N Dm ΠΧ3 m 樹脂3-1 1樹脂3-1 樹脂3-1 樹脂3-2 樹脂3-2 樹脂3-2 樹脂1-1 樹脂1-2 1 <N m Π33 樹脂3-1 |樹脂3-2 丨實施例5 1 : 1實施例6 1 實施例7 1實施例8 1 1實施例9 i j實施例10 1實施例11 1 實施例12 實施例13 實施例14 實施例15 實施例16 實施例17 實施例18 比較例1 比較例2 比較例3 比較例4 s JJJ -u -36- (32) 1286670 表1中，PAG 2爲下列[化20]所示化合物，PAG 3爲下 列[化2 1]所示化合物，PAG 4爲下列[化22]所示化合物。 [化 20] PAG2Next, the organic anti-reflection film composition "ARC-29A" (trade name, manufactured by Puliuwang Co., Ltd.) was applied onto a silicon wafer by a rotary machine, and baked on a hot plate at 2 15 ° C for 6.0 seconds, and dried to form a film thickness. 77 nm organic anti-reflection film. Thereafter, the above-mentioned positive-type photoresist composition was applied onto an anti-reflection film by spin, pre-baked (PAB) at 120 ° C for 90 seconds on a hot plate, and dried to form a photoresist layer having a film thickness of 250 nm. Then, an ArF exposure apparatus NSR-S302 (manufactured by Nikon Corporation, NA (number of openings) = 0.60, σ = 0.55) was used, and a argon-irradiated A r F excimer laser was selected under the mask (dual-agent). 9 3 nm ). Thereafter, the p EB treatment was carried out under the conditions of 130 ° C and 90 seconds, and the mixture was stirred for 60 seconds with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23 ° C, and washed with water for 2 0. After a second, it is dried to form a photoresist pattern. As a result, when the positive-type photoresist composition of Example 1 was used, a pattern having a width of 1 2 〇 nm and a space of 1 ·· 1 〇 (pitch 1 3 2 0 nm) was copied as an exposure having a line width of 80 nm. The amount Εορ (sensitivity) is 25 mJ/cm2. Further, the isolated photoresist pattern having a width of 80 nm is formed, and the shape of the tip is not round and the side wall of the photoresist line is perpendicular to the high rectangular shape. -34- (30) 1286670 Further, 3 σ representing the LER scale of the formed pattern is obtained, and the resulting model 3 σ is 5 · 0 n m. The 3 σ is a standard deviation (σ ) calculated from the results by measuring the width of the resist pattern of 32 samples using the side length S Ε Μ (trade name “S-9220” manufactured by Hitachi, Ltd.). 3 times 値 (3 σ ). 3 The smaller the σ is, the lower the roughness is, and the uniform photoresist pattern is obtained. The depth of focus (DOF) is 450 nm. In addition, the distance between the masks is gradually reduced, and after the exposure amount Εορ is exposed, the separation resolution of the obtained line and space is a pitch of 24 Onm. The smaller the separation resolution, the better the performance of the photoresist composition, and the evaluation method is widely used by the industry. Examples 2 to 18 and Comparative Examples 1 to 5 In addition to the modification of the type of the component (A), the type of the component (B), and the amount of addition (parts by mass) as shown in Table 1, the positive resist was prepared in the same manner as in the first embodiment. Composition. Further, in Examples 9 to 12 and Comparative Example 3, the PAB temperature of Example 1 was changed to 10 °C, and the PEB temperature was changed to 95 °C. In Examples 13 to 18 and Comparative Examples 4 to 5, the PAB temperature of Example 1 was changed to 125 ° C, and the PEB temperature was changed to 1 15 °C. -35- (31)1286670 s sa § —οςν d_ovl _0·ς Ιος d—ςι Ιος _8ς is sms iig i §10vd8001 "go/imsuymsd umlsd 0S2 raise V) ufi 13⁄4 5 "gQ/i曰豸codSYd un 10Yd 0801 11lgillg\ 13⁄4 i ς·<M\ieg/igv<N\ Glrisd dMDVd 0002 1丨1遝琏\ U cloud pro 500nm 450nm \ 450nm 450nm 450nm 500nm 450nm 450nm 450nm 1 450nm 450nm 500nm 1 450nm 1 450nm 500nm 500nm 450nm 500nm 450nm 1-1111 250nmP 250 nmP 260 nmP 280 nmP 1 300 nmP 300 nmP 280 nmP 280 nmP 4.7 nm 260 nmP 4.8 nm 250 nmP 250 nmP 260 nmP 260 nmP 260 nmP 260 nmP 260 nmP 250 nmP 250 nmP 250 nmP 4.5 nm 1 4.6 nm 5.2 iim 4.5 nm 4.5 nm ΐ r~ inch · 4.5 nm 4.4 nm 4.5 nm ' 4.6 nm 1 4.4 nm 6.2 nm 6.0 nm 6.5 nm 6.7 nm 6.7 nm IS 蝤 _ vertical vertical § s vertical i very Vertical very vertical very vertical very vertical very vertical very vertical 1 Round Round Round Round - -, 23ml/cm2; 28 mJ/cm2 25mJ/cm2, 25 mJ/cm2 30 mJ/cm2 31 mJ/cm2 29 mJ/cm2 29 mJ/ Cm2 32 mJ/cm2 1 32 mi/cm2 30 mJ/cm2 30 mJ/cm2 30 mJ/cm2 28 m J/cm2 20 mJ/cm2 22 mJ/cm2 26 mJ/cm2 30 mJ/cm2 30mJ/cm2 1 PAG2(1.5) 1 PAG2(1.5) 1 PAG2(1.5) 1 1 PAG2(1.5) I » • PAG2(1.5) 1 PAG3(3.0) PAG3(3.0) PAG3(3.0) PAG3(3.0) PAG3(3.0) 10000 PAG4(3.0) 6900 PAG1(3.0) 6900 PAGK1.5) PAG4(3.0) PAGK1.5) PAGK3.0) PAGK1. 5) PAG4(3.0) PAG(3.0) 1 1 PAGK1.5) PAG4(3.0) PAG1(3.0) PAG1(1.5) PAG4(3.0) 1 Employment 1 1 9 6900 10500 6400 6400 1 6400 1 7200 7200 _ 7200 10000 10000 I 10000 10000 6900 10500 7200 10000 Resin 1 -1 1 Resin 1-2 (N 1 ΰΐπ Π23 M Resin 1-2 f—^ 1 <N m Π3Π M <N 1 (N mm Resin 2-2 ΟΪ 1 ( N Dm ΠΧ3 m resin 3-1 1 resin 3-1 resin 3-1 resin 3-2 resin 3-2 resin 3-2 resin 1-1 resin 1-2 1 <N m Π33 resin 3-1 | resin 3 - 2 丨 Embodiment 5 1 : 1 Embodiment 6 1 Embodiment 7 1 Embodiment 8 1 1 Embodiment 9 ij Embodiment 10 1 Embodiment 11 1 Embodiment 12 Example 13 Example 14 Example 15 Example 16 Implementation Example 17 Example 18 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 s JJJ -u -36- (32) 1286670 In Table 1, PAG 2 is a compound represented by the following [Chemical Formula 20], and PAG 3 is as follows The compound shown in [Chem. 2 1], PAG 4 is a compound represented by the following [Chem. 22]. [Chem. 20] PAG2
[化 21] PAG3[化 21] PAG3
-37- (33) 1286670 [化 22]-37- (33) 1286670 [Chem. 22]
同實施例1之方法評估實施例2至18及比較例1至5所得 之正型光阻組成物，結果倂記於表1。 又，表1中「Round」係指，空間部光阻側壁之光阻膜 表面附近的頂端形狀爲圓狀，且空間部之形狀爲圓錐狀。 由上述結果得知，實施例1至1 8之正型光阻組成物的 孤立空間圖型及L&S圖型之解像性高，且所形成之圖型形 狀良好，LER較小及DOF較大。其中又以使用樹脂3的實施 例13至1 8之正型光阻組成物的LER特佳。 以上爲說明本發明之較佳實施例，但本發明非限於該 實施例。不脫離本發明之要旨下，可附加、省略、取代或 變更其構成內容。本發明非受限於上述說明，但限定爲申 請專利範圍之範圍內。 »38-The positive resist compositions obtained in Examples 2 to 18 and Comparative Examples 1 to 5 were evaluated in the same manner as in Example 1. The results are shown in Table 1. Further, "Round" in Table 1 means that the shape of the tip end in the vicinity of the surface of the photoresist film on the side wall of the photoresist portion in the space portion is circular, and the shape of the space portion is conical. From the above results, it is found that the isolated space pattern of the positive-type photoresist compositions of Examples 1 to 18 and the L&S S pattern have high resolution, and the formed pattern shape is good, and the LER is small and DOF. Larger. Among them, the LER of the positive type resist composition of Examples 13 to 18 using the resin 3 was particularly preferable. The above is a description of the preferred embodiment of the invention, but the invention is not limited to the embodiment. The constituent elements may be added, omitted, substituted or changed without departing from the spirit of the invention. The present invention is not limited to the above description, but is limited to the scope of the patent application. »38-
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| JP2006078760A (en) * | 2004-09-09 | 2006-03-23 | Tokyo Ohka Kogyo Co Ltd | Resist composition for electron beam or euv (extreme ultraviolet radiation) and resist pattern forming method |
| JP4667278B2 (en) * | 2005-03-11 | 2011-04-06 | 富士フイルム株式会社 | Positive photosensitive composition and pattern forming method using the same |
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| JP5216892B2 (en) * | 2005-07-26 | 2013-06-19 | 富士フイルム株式会社 | Pattern forming method using positive resist composition |
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| JP2008026838A (en) * | 2006-06-23 | 2008-02-07 | Tokyo Ohka Kogyo Co Ltd | Positive resist composition and method for formation of resist pattern |
| US8252503B2 (en) * | 2007-08-24 | 2012-08-28 | Az Electronic Materials Usa Corp. | Photoresist compositions |
| JP2011008293A (en) * | 2010-09-15 | 2011-01-13 | Fujifilm Corp | Positive photosensitive composition and pattern forming method using the same |
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