TW201841998A - Composition for silicon-containing-film formation, silicon-containing film, pattern formation method, and polysiloxane - Google Patents
Composition for silicon-containing-film formation, silicon-containing film, pattern formation method, and polysiloxane Download PDFInfo
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- TW201841998A TW201841998A TW107106814A TW107106814A TW201841998A TW 201841998 A TW201841998 A TW 201841998A TW 107106814 A TW107106814 A TW 107106814A TW 107106814 A TW107106814 A TW 107106814A TW 201841998 A TW201841998 A TW 201841998A
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Abstract
Description
本發明是有關於一種含矽膜形成用組成物、含矽膜、圖案形成方法及聚矽氧烷。The present invention relates to a composition for forming a ruthenium-containing film, a ruthenium-containing film, a pattern formation method, and a polyoxyalkylene.
於半導體元件等的圖案形成時,多使用抗蝕劑製程,即,對經由有機系的抗反射膜及含矽膜而積層於被加工基板上的抗蝕劑膜進行曝光·顯影,將所得的抗蝕劑圖案作為遮罩而進行蝕刻。近年來,隨著抗蝕劑圖案的微細化,抗蝕劑圖案的塌壞、遮罩圖案的蝕刻選擇性的下降等成為問題。此處,自先前以來關於改善抗蝕劑圖案的塌壞或遮罩圖案的蝕刻選擇性的含矽膜用材料、以及使用所述含矽膜用材料而於基板上形成圖案的方法進行了研究(參照日本專利特開2004-310019號公報及國際公開第2012/039337號)。 [現有技術文獻] [專利文獻]In the formation of a pattern of a semiconductor element or the like, a resist process is used, that is, exposure and development are performed on a resist film laminated on a substrate to be processed via an organic antireflection film and a ruthenium containing film. The resist pattern is etched as a mask. In recent years, as the resist pattern is miniaturized, the collapse of the resist pattern and the decrease in the etching selectivity of the mask pattern have become problems. Here, a material for a ruthenium-containing film which improves etching selectivity of a resist pattern or an etching pattern of a mask pattern, and a method of forming a pattern on a substrate using the material for a ruthenium-containing film have been studied. (Refer to Japanese Patent Laid-Open No. 2004-310019 and International Publication No. 2012/039337). [Prior Art Document] [Patent Literature]
[專利文獻1]日本專利特開2004-310019號公報 [專利文獻2]國際公開第2012/039337號[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-310019 [Patent Document 2] International Publication No. 2012/039337
[發明所欲解決之課題] 然而,若抗蝕劑圖案的微細化為線寬40 nm以下,則所述先前的含矽膜無法滿足該些要求。另外,於將抗蝕劑圖案作為遮罩而形成含矽膜的圖案後,在藉由氟系氣體等所引起的電漿蝕刻去除含矽膜時,有被加工基板受到損傷的問題,因此亦必須提高含矽膜的去除性。[Problems to be Solved by the Invention] However, if the refinement of the resist pattern is 40 nm or less in line width, the above-described ruthenium-containing film cannot satisfy these requirements. In addition, when the ruthenium-containing film is removed by plasma etching by a fluorine-based gas or the like after the resist pattern is formed as a mask, the substrate to be processed is damaged. The removal of the ruthenium containing film must be improved.
本發明是基於所述情況而成,其目的在於提供一種含矽膜形成用組成物、含矽膜、圖案形成方法及聚矽氧烷,所述含矽膜形成用組成物可形成維持氟系氣體所引起的蝕刻去除性、且抗蝕劑圖案的塌壞抑制性優異的含矽膜。 [解決課題之手段]The present invention has been made in view of the above circumstances, and an object thereof is to provide a composition for forming a ruthenium-containing film, a ruthenium-containing film, a pattern formation method, and a polysiloxane, which can form a fluorine-maintaining composition. A ruthenium-containing film excellent in etching removability by gas and excellent in suppressing collapse resistance of a resist pattern. [Means for solving the problem]
為了解決所述課題而成的發明是一種含矽膜形成用組成物,其含有:具有下述式(1)所表示的基的聚矽氧烷、及溶媒。 [化1](式(1)中,L為單鍵或碳數1~20的(n+1)價的有機基。E為下述式(2-1)或式(2-2)所表示的基。n為1~3的整數。於n為2以上的情況下,L為有機基,多個E相同或不同。*表示與所述聚矽氧烷中的矽原子鍵結的部位) [化2](式(2-1)中,R1 為單鍵或碳數1~20的二價有機基。Y1 為經取代或未經取代的碳數6~20的芳基或者至少一個氫原子經拉電子性基取代的碳數1~20的一價脂肪族烴基。 式(2-2)中,R2 為碳數1~20的一價有機基。Y2 為經取代或未經取代的碳數6~20的芳烴二基或者至少一個氫原子經拉電子性基取代的碳數1~20的二價脂肪族烴基)In order to solve the problem, the invention is a composition for forming a ruthenium-containing film, which comprises a polysiloxane having a group represented by the following formula (1) and a solvent. [Chemical 1] (In the formula (1), L is a single bond or an (n+1)-valent organic group having 1 to 20 carbon atoms. E is a group represented by the following formula (2-1) or (2-2). n is an integer of 1 to 3. When n is 2 or more, L is an organic group, and a plurality of E are the same or different. * indicates a site bonded to a ruthenium atom in the polysiloxane. ] (In the formula (2-1), R 1 is a single bond or a divalent organic group having 1 to 20 carbon atoms. Y 1 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or at least one hydrogen atom A monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted by an electron-donating group. In the formula (2-2), R 2 is a monovalent organic group having 1 to 20 carbon atoms. Y 2 is substituted or unsubstituted. a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted with an alkyl group having 6 to 20 carbon atoms or at least one hydrogen atom via an electron withdrawing group)
為了解決所述課題而成的另一發明為一種含矽膜,其是由該含矽膜形成用組成物所形成。Another invention to solve the above problems is a ruthenium-containing film formed of the ruthenium-containing film-forming composition.
為了解決所述課題而成的進而另一發明為一種圖案形成方法,其包括:藉由該含矽膜形成用組成物的塗敷而於基板的上側形成含矽膜的步驟;以及於所述含矽膜上形成圖案的步驟。According to still another aspect of the invention, there is provided a pattern forming method comprising: a step of forming a ruthenium-containing film on an upper side of a substrate by application of the composition for forming a ruthenium-containing film; The step of forming a pattern on the ruthenium film.
為了解決所述課題而成的進而另一發明為一種聚矽氧烷,其具有所述式(1)所表示的基。 [發明的效果]Still another invention to solve the above problems is a polysiloxane having a group represented by the formula (1). [Effects of the Invention]
根據本發明的含矽膜形成用組成物及圖案形成方法,可形成維持氟系氣體所引起的蝕刻去除性、且抗蝕劑圖案的塌壞抑制性優異的含矽膜,另外,可形成對抗蝕劑圖案形成步驟中的鹼性顯影液的耐性優異且鹼性過氧化氫水所引起的剝離性優異的含矽膜。進而,本發明的含矽膜形成用組成物的保存穩定性亦優異。本發明的含矽膜維持氟系氣體所引起的蝕刻去除性,且抗蝕劑圖案的塌壞抑制性優異,另外,對抗蝕劑圖案形成步驟中的鹼性顯影液的耐性優異且鹼性過氧化氫水所引起的剝離性優異。本發明的聚矽氧烷可較佳地用作該含矽膜形成用組成物的聚矽氧烷成分。因此,該些可較佳地用於多層抗蝕劑製程,可較佳地用於今後預計進一步進行微細化的半導體器件的製造等。According to the ruthenium-containing film-forming composition and the pattern forming method of the present invention, it is possible to form a ruthenium-containing film which is excellent in the etch-eliminability by the fluorine-based gas and has excellent collapse resistance of the resist pattern, and can form a confrontation. The ruthenium-containing film which is excellent in the resistance of the alkaline developing solution in the etchant pattern forming step and excellent in the peeling property by the alkaline hydrogen peroxide water. Further, the composition for forming a ruthenium-containing film of the present invention is also excellent in storage stability. The ruthenium-containing film of the present invention maintains the etching removability by the fluorine-based gas, and is excellent in the collapse suppressing property of the resist pattern, and is excellent in the resistance to the alkaline developing solution in the resist pattern forming step and is alkaline. Excellent in peeling properties due to hydrogen peroxide water. The polyoxyalkylene of the present invention can be preferably used as the polyoxymethane component of the composition for forming a ruthenium-containing film. Therefore, these can be preferably used for a multilayer resist process, and can be preferably used for the manufacture of a semiconductor device in which further miniaturization is expected in the future.
以下,對本發明的含矽膜形成用組成物、聚矽氧烷、含矽膜及圖案形成方法的實施形態進行說明。Hereinafter, embodiments of the composition for forming a ruthenium-containing film of the present invention, a polysiloxane, a ruthenium-containing film, and a pattern formation method will be described.
<含矽膜形成用組成物> 該含矽膜形成用組成物含有:具有式(1)所表示的基的聚矽氧烷(以下,亦稱為「[A]聚矽氧烷」)、及溶媒(以下,亦稱為「[B]溶媒」)。該含矽膜形成用組成物亦可於無損本發明的效果的範圍內含有任意成分。以下,對各成分進行說明。<The composition for forming a ruthenium-containing film> The composition for forming a ruthenium-containing film contains a polysiloxane having a group represented by the formula (1) (hereinafter also referred to as "[A] polyoxane"), And solvent (hereinafter also referred to as "[B] solvent"). The composition for forming a ruthenium-containing film may contain an optional component insofar as the effects of the present invention are not impaired. Hereinafter, each component will be described.
<[A]聚矽氧烷> [A]聚矽氧烷為具有下述式(1)所表示的基(以下,亦稱為「基(I)」)的聚矽氧烷。<[A] Polyoxane> [A] Polyoxyalkylene is a polyoxyalkylene having a group represented by the following formula (1) (hereinafter also referred to as "base (I)").
[化3] [Chemical 3]
所述式(1)中,L為單鍵或碳數1~20的(n+1)價的有機基。E為下述式(2-1)或式(2-2)所表示的基(以下,亦稱為「基(II-1)或基(II-2)」)。n為1~3的整數。於n為2以上的情況下,L為有機基,多個E相同或不同。*表示與所述聚矽氧烷中的矽原子鍵結的部位。In the formula (1), L is a single bond or an (n+1)-valent organic group having 1 to 20 carbon atoms. E is a group represented by the following formula (2-1) or formula (2-2) (hereinafter, also referred to as "base (II-1) or group (II-2)"). n is an integer of 1-3. When n is 2 or more, L is an organic group, and a plurality of E are the same or different. * indicates a site bonded to a ruthenium atom in the polyoxyalkylene.
[化4] [Chemical 4]
所述式(2-1)中,R1 為單鍵或碳數1~20的二價有機基。Y1 為經取代或未經取代的碳數6~20的芳基或者至少一個氫原子經拉電子性基取代的碳數1~20的一價脂肪族烴基。 所述式(2-2)中,R2 為碳數1~20的一價有機基。Y2 為經取代或未經取代的碳數6~20的芳烴二基或者至少一個氫原子經拉電子性基取代的碳數1~20的二價脂肪族烴基。In the formula (2-1), R 1 is a single bond or a divalent organic group having 1 to 20 carbon atoms. Y 1 is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted with at least one hydrogen atom via an electron withdrawing group. In the formula (2-2), R 2 is a monovalent organic group having 1 to 20 carbon atoms. Y 2 is a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which is substituted with an alkylene group having 6 to 20 carbon atoms or at least one hydrogen atom via an electron withdrawing group.
該含矽膜形成用組成物藉由含有[A]聚矽氧烷及[B]溶媒,可形成維持氟系氣體所引起的蝕刻去除性、且抗蝕劑圖案的塌壞抑制性優異、並且對抗蝕劑圖案形成步驟中的鹼性顯影液的耐性優異且鹼性過氧化氫水所引起的剝離性優異的含矽膜,進而保存穩定性亦優異。藉由該含矽膜形成用組成物具備所述構成而起到所述效果的理由未必明確,但例如可推測為以下所述。即,該含矽膜形成用組成物的[A]聚矽氧烷具有包含鍵結有拉電子性基等的磺酸酯結構的基(I)。所述磺酸酯結構鍵結有拉電子性基等,因此不論於常溫下,還是進行加熱,均不易開裂。因此,該含矽膜形成用組成物的保存穩定性優異,且所形成的含矽膜對於鹼性顯影液的耐性優異。另外,所述碸酯結構藉由鹼性過氧化氫水開裂而產生磺基,因此含矽膜成為鹼性過氧化氫水所引起的剝離性優異者。The composition for forming a ruthenium-containing film can form an etching removal property by maintaining a fluorine-based gas by containing [A] a polysiloxane and a solvent of [B], and is excellent in collapse suppressability of a resist pattern, and The antimony-containing film which is excellent in resistance to the alkaline developing solution in the resist pattern forming step and excellent in peeling property due to alkaline hydrogen peroxide water is further excellent in storage stability. The reason why the composition for forming a ruthenium-containing film has the above-described configuration and the above-described effects are not necessarily clear, but it can be estimated as follows. In other words, the [A] polysiloxane having the composition for forming a ruthenium film has a group (I) having a sulfonate structure in which an electron withdrawing group or the like is bonded. Since the sulfonate structure is bonded to an electron-donating group or the like, it is not easily cracked regardless of the temperature at normal temperature or heating. Therefore, the composition for forming a ruthenium-containing film is excellent in storage stability, and the formed ruthenium-containing film is excellent in resistance to an alkaline developer. Further, since the oxime ester structure is cleaved by alkaline hydrogen peroxide water to generate a sulfo group, the ruthenium-containing film is excellent in releasability due to alkaline hydrogen peroxide water.
[基(I)] 作為所述式(1)的L所表示的碳數1~20的(n+1)價的有機基,可列舉:碳數1~20的(n+1)價的烴基、該烴基的碳-碳間包含含二價雜原子的基的基(α)、所述烴基及所述基(α)所具有的氫原子的一部分或全部經含一價雜原子的基取代而成的基等。[Base (I)] The (n+1)-valent organic group having 1 to 20 carbon atoms represented by L in the formula (1) includes (n+1) valence of 1 to 20 carbon atoms. a hydrocarbon group, a carbon-carbon group containing a divalent hetero atom-containing group (α), a part or all of a hydrogen atom possessed by the hydrocarbon group and the group (α), and a monovalent hetero atom-containing group Substituted bases, etc.
作為碳數1~20的(n+1)價的烴基,例如可列舉:碳數1~20的(n+1)價的鏈狀烴基、碳數3~20的(n+1)價的脂環式烴基、碳數6~20的(n+1)價的芳香族烴基等。Examples of the (n+1)-valent hydrocarbon group having 1 to 20 carbon atoms include a (n+1)-valent chain hydrocarbon group having 1 to 20 carbon atoms and a (n+1)-valent carbon number of 3 to 20 carbon atoms. An alicyclic hydrocarbon group, an (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or the like.
作為碳數1~20的(n+1)價的鏈狀烴基,例如可列舉將甲烷、乙烷、丙烷、丁烷等烷烴、乙烯、丙烯、丁烯等烯烴、乙炔、丙炔、丁炔等炔烴等所具有的2個~4個氫原子去除而成的基等。Examples of the (n+1)-valent chain hydrocarbon group having 1 to 20 carbon atoms include an alkane such as methane, ethane, propane or butane, an olefin such as ethylene, propylene or butylene, acetylene, propyne or butyne. A group obtained by removing two to four hydrogen atoms such as an alkyne or the like.
作為碳數3~20的(n+1)價的脂環式烴基,例如可列舉將環戊烷、環己烷等環烷烴、降冰片烷、金剛烷、三環癸烷等橋聯環飽和烴等脂環式飽和烴、環戊烯、環己烯等環烯烴、降冰片烯、三環癸烯等橋聯環不飽和烴等脂環式不飽和烴等所具有的2個~4個氫原子去除而成的基等。Examples of the (n+1)-valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a saturated ring such as cyclopentane such as cyclopentane or cyclohexane, norbornane, adamantane or tricyclodecane. 2 to 4 of alicyclic unsaturated hydrocarbons such as alicyclic saturated hydrocarbons such as hydrocarbons, cycloolefins such as cyclopentene and cyclohexene, alicyclic unsaturated hydrocarbons such as bridged cyclic unsaturated hydrocarbons such as norbornene and tricyclodecene A base obtained by removing a hydrogen atom.
作為碳數6~20的(n+1)價的芳香族烴基,例如可列舉將苯、甲苯、乙基苯、二甲苯、萘、甲基萘、蒽、甲基蒽等芳烴所具有的2個~4個芳香環上的氫原子或2個~4個芳香環上及烷基上的氫原子去除而成的基等。Examples of the (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms include an aromatic hydrocarbon such as benzene, toluene, ethylbenzene, xylene, naphthalene, methylnaphthalene, anthracene or methyl anthracene. A hydrogen atom on one to four aromatic rings or a group in which two to four aromatic rings and a hydrogen atom on an alkyl group are removed.
作為構成含有二價及一價雜原子的基的雜原子,例如可列舉:氧原子、氮原子、硫原子、磷原子、矽原子、鹵素原子等。作為鹵素原子,例如可列舉:氟原子、氯原子、溴原子、碘原子等。Examples of the hetero atom constituting the group containing a divalent or monovalent hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a ruthenium atom, and a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
作為含二價雜原子的基,例如可列舉:-O-、-CO-、-S-、-CS-、-NR'-、將該些中的兩個以上組合而成的基等。R'為氫原子或一價烴基。該些中,較佳為-O-及-S-。Examples of the divalent hetero atom-containing group include -O-, -CO-, -S-, -CS-, and -NR'-, and a combination of two or more of these. R' is a hydrogen atom or a monovalent hydrocarbon group. Among these, -O- and -S- are preferred.
作為含一價雜原子的基,例如可列舉:氟原子、氯原子、溴原子、碘原子等鹵素原子、羥基、羧基、氰基、胺基、巰基等。該些中,較佳為鹵素原子,更佳為氟原子。Examples of the group having a monovalent hetero atom include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a hydroxyl group, a carboxyl group, a cyano group, an amine group or a fluorenyl group. Among these, a halogen atom is preferred, and a fluorine atom is more preferred.
作為所述式(1)的n,較佳為1及2,更佳為1。n as the formula (1) is preferably 1 or 2, more preferably 1.
作為L,較佳為(n+1)價的烴基及於所述烴基的碳-碳間包含含二價雜原子的基的基,更佳為(n+1)價的鏈狀烴基或芳香族烴基以及於該些烴基的碳-碳間包含含二價雜原子的基的基。於n為1的情況下,作為L,進而佳為烷烴二基、於烷烴二基的碳-碳間包含-O-或-S-的基、以及芳烴二基,尤佳為甲烷二基、乙烷二基、丙烷二基、甲烷二基巰基甲烷二基、甲烷二基巰基乙烷二基、乙烷二基巰基乙烷二基、丙烷二基巰基甲烷二基、丙烷二基巰基乙烷二基、甲烷二基氧基甲烷二基、甲烷二基氧基乙烷二基、乙烷二基氧基甲烷二基、乙烷二基氧基乙烷二基、丙烷二基氧基甲烷二基、丙烷二基氧基乙烷二基及苯二基。The L is preferably a (n+1)-valent hydrocarbon group and a group containing a divalent hetero atom-containing group between the carbon-carbons of the hydrocarbon group, more preferably a (n+1)-valent chain hydrocarbon group or aroma. The group hydrocarbon group and the group containing a group containing a divalent hetero atom between the carbon and carbon of the hydrocarbon group. In the case where n is 1, as L, further preferably an alkanediyl group, a group containing -O- or -S- between carbon-carbons of an alkanediyl group, and an aromatic hydrocarbon diyl group, particularly preferably a methane diyl group, Ethane diyl, propane diyl, methane diyl fluorenyl methane diyl, methane diyl decyl ethane diyl, ethane diyl decyl ethane diyl, propane diyl fluorenyl methane diyl, propane diyl decyl ethane Diyl, methanediyloxymethanediyl, methanediyloxyethanediyl, ethanediyloxymethanediyl, ethanediyloxyethanediyl, propanediyloxymethane a base, a propane diyloxyethanediyl group, and a phenyldiyl group.
若L為於烴基的碳-碳間包含含二價雜原子的基的基,則可進一步提高含矽膜的氟系氣體所引起的蝕刻去除性。When L is a group containing a group containing a divalent hetero atom between carbon-carbons of a hydrocarbon group, the etching removeability by the fluorine-containing gas containing a ruthenium film can be further improved.
[基(II-1)] 作為所述式(2-1)的R1 所表示的碳數1~20的二價有機基,例如可列舉作為所述L的(n+1)價的有機基而例示者中n為1的基等。[Base (II-1)] The divalent organic group having 1 to 20 carbon atoms represented by R 1 in the above formula (2-1) is, for example, an organic compound of the (n+1) valence of L described above. In the example, n is a group of 1 or the like.
作為R1 ,較佳為單鍵。As R 1 , a single bond is preferred.
作為所述式(2-1)的Y1 所表示的經取代或未經取代的碳數6~20的芳基中的芳基,例如可列舉:苯基、苄基、甲苯基、二甲苯基、萘基、蒽基等。Examples of the aryl group in the substituted or unsubstituted aryl group having 6 to 20 carbon atoms represented by Y 1 of the formula (2-1) include a phenyl group, a benzyl group, a tolyl group, and a xylene group. Base, naphthyl, anthracenyl and the like.
作為Y1 的所述芳基的取代基,例如可列舉:氟原子、氯原子、溴原子、碘原子等鹵素原子、羥基、氰基、硝基、醯基、醯氧基、烴基、氧烴基等。該些中,就拉電子性的觀點而言,較佳為鹵素原子、氰基、硝基、醯基及醯氧基,更佳為鹵素原子,進而佳為氟原子。Examples of the substituent of the aryl group of Y 1 include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a hydroxyl group, a cyano group, a nitro group, a decyl group, a decyloxy group, a hydrocarbon group, and an oxyhydrocarbyl group. Wait. Among these, from the viewpoint of electron pullability, a halogen atom, a cyano group, a nitro group, a fluorenyl group and a decyloxy group are preferred, and a halogen atom is more preferred, and a fluorine atom is preferred.
作為所述Y1 的經取代或未經取代的碳數6~20的芳基,較佳為苯基、萘基、蒽基、氟苯基、氯苯基、三氟苯基、五氟苯基、氟苄基及二氟苄基,更佳為苯基、氟苯基及氟苄基,進而佳為苯基及氟苯基。The substituted or unsubstituted aryl group having 6 to 20 carbon atoms of the Y 1 is preferably a phenyl group, a naphthyl group, an anthranyl group, a fluorophenyl group, a chlorophenyl group, a trifluorophenyl group or a pentafluorobenzene. The group is preferably a phenyl group, a fluorophenyl group or a fluorobenzyl group, more preferably a phenyl group or a fluorophenyl group.
作為所述式(2-1)的Y1 所表示的至少一個氫原子經拉電子性基取代的碳數1~20的一價脂肪族烴基(以下,亦稱為「拉電子性基取代脂肪族烴基」)中的脂肪族烴基,例如可列舉作為所述L的碳數1~20的(n+1)價的鏈狀烴基、碳數3~20的(n+1)價的脂環式烴基而例示者中於n為1的二價基中加入一個氫原子而成的基等。a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted with at least one hydrogen atom represented by Y 1 of the formula (2-1) via an electron withdrawing group (hereinafter, also referred to as "electron-based substituted fat" The aliphatic hydrocarbon group in the hydrocarbon group ") may, for example, be a (n+1)-valent chain hydrocarbon group having 1 to 20 carbon atoms as the L, and an (n+1)-valent alicyclic ring having 3 to 20 carbon atoms. In the exemplified hydrocarbon group, a group in which a hydrogen atom is added to a divalent group in which n is 1 is exemplified.
作為Y1 的拉電子性基取代脂肪族烴基中的拉電子性基,例如可列舉:鹵素原子、氰基、硝基、碳數1~10的鹵化烴基、碳數1~10的具有-O-的基、碳數1~10的具有-SO-的基、碳數1~10的具有-SO2 -的基、碳數1~10的具有-CO-的基、碳數1~10的具有-COO-的基等。Examples of the electron withdrawing group in the aliphatic group-substituted aliphatic hydrocarbon group of Y 1 include a halogen atom, a cyano group, a nitro group, a halogenated hydrocarbon group having 1 to 10 carbon atoms, and a -O having 1 to 10 carbon atoms. - a group having a -SO- group having 1 to 10 carbon atoms, a group having -SO 2 - having 1 to 10 carbon atoms, a group having -CO- having 1 to 10 carbon atoms, and a carbon number of 1 to 10 A group having -COO- or the like.
作為鹵素原子,例如可列舉:氟原子、氯原子、溴原子、碘原子等。Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
作為碳數1~10的鹵化烴基,一價基例如可列舉氟甲基、二氟甲基、三氟甲基、三氯甲基、三氟乙基、六氟異丙基、五氟正丙基、九氟正丁基等鹵化鏈狀烴基等。Examples of the halogenated hydrocarbon group having 1 to 10 carbon atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a trifluoroethyl group, a hexafluoroisopropyl group, and a pentafluoro-n-propyl group. A halogenated chain hydrocarbon group such as a hexafluoro-n-butyl group or the like.
作為碳數1~10的具有-O-的基,一價基例如可列舉:甲氧基、環己氧基、苯氧基等氧烴基、羥基苯基等羥基芳香族烴基、四氫呋喃基、四氫吡喃基等環狀醚基等。Examples of the monovalent group having a carbon number of 1 to 10 and having a -O- group include an oxy group such as a methoxy group, a cyclohexyloxy group or a phenoxy group, a hydroxyaromatic hydrocarbon group such as a hydroxyphenyl group, a tetrahydrofuranyl group or the like. A cyclic ether group such as a hydropyranyl group or the like.
作為碳數1~10的具有-SO-的基,一價基例如可列舉:甲基磺酸氧基、苯基磺酸氧基等磺酸氧基烴基、S-氧代四氫硫代苯基等環狀磺酸氧基等。Examples of the monovalent group having a carbon number of 1 to 10 and having a -SO- group include a sulfonic acidoxy group such as a methylsulfonic acid group or a phenylsulfonic acid group, and a S-oxotetrahydrothiobenzene group. A cyclic sulfonic acid oxy group or the like.
作為碳數1~10的具有-SO2 -的基,一價基例如可列舉:甲基磺醯基、苯基磺醯基等磺醯基烴基、S-二氧代四氫硫代苯基等環狀磺醯基等。As having 1 to 10 carbon atoms is -SO 2 - group is, for example, a monovalent group include: methyl acyl sulfo, acyl and the like sulfo sulfo phenyl acyl hydrocarbyl, S- dioxo-tetrahydro-thiophenyl Such as a cyclic sulfonyl group and the like.
作為碳數1~10的具有-CO-的基,一價基例如可列舉:甲醯基、乙醯基、苯甲醯基等醯基、氧代環己基、氧代金剛烷基等環狀酮基等。Examples of the monovalent group having a carbon number of 1 to 10 and having a -CO- group include a fluorenyl group such as a mercapto group, an ethenyl group or a benzamidine group, an oxocyclohexyl group or an oxoadamantyl group. Keto group and the like.
作為碳數1~10的具有-COO-的基,一價基例如可列舉:甲醯氧基、乙醯氧基、苯甲醯氧基等醯氧基、甲氧基羰基、苯氧基羰基等羰氧基烴基、丁內酯-基、降冰片烷內酯-基等包含內酯結構的基等。Examples of the monomethyl group having a carbon number of 1 to 10 and having a -COO- group include a decyloxy group such as a methyl methoxy group, an ethoxycarbonyl group or a benzyl methoxy group, a methoxycarbonyl group or a phenoxycarbonyl group. A group containing a lactone structure, such as a carbonyloxy hydrocarbon group, a butyrolactone-based group, a norbornane lactone-based group, or the like.
作為拉電子性基,一價基較佳為鹵素原子、氰基、碳數1~10的鹵化烴基、碳數1~10的具有-O-的基、碳數1~10的具有-SO-的基、碳數1~10的具有-SO2 -的基、碳數1~10的具有-CO-的基及碳數1~10的具有-COO-的基,更佳為氟原子、氯原子、氰基、氟化烴基、氧烴基、醯基、羰氧基烴基及磺醯基烴基,進而佳為氟原子、氯原子、氰基、氟化烷基、烷氧基、烷基羰基、烷氧基羰基及烷基磺醯基,尤佳為氟原子、氯原子、氰基、三氟甲基、甲氧基、乙醯基、甲氧基羰基及甲基磺醯基。The electron-donating group is preferably a halogen atom, a cyano group, a halogenated hydrocarbon group having 1 to 10 carbon atoms, a group having -O- having 1 to 10 carbon atoms, and -SO- having 1 to 10 carbon atoms. a group having a -SO 2 - group having 1 to 10 carbon atoms, a group having -CO- having 1 to 10 carbon atoms, and a group having -COO- having 1 to 10 carbon atoms, more preferably a fluorine atom or a chlorine atom. An atom, a cyano group, a fluorinated hydrocarbon group, an oxyhydrocarbyl group, a fluorenyl group, a carbonyloxy hydrocarbon group, and a sulfonyl hydrocarbon group, and more preferably a fluorine atom, a chlorine atom, a cyano group, a fluorinated alkyl group, an alkoxy group, an alkylcarbonyl group, The alkoxycarbonyl group and the alkylsulfonyl group are particularly preferably a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a methoxy group, an ethyl fluorenyl group, a methoxycarbonyl group or a methylsulfonyl group.
認為若於基(I)中包含氟原子作為拉電子性基等,則由[A]聚矽氧烷形成的含矽膜與形成於其上側的抗蝕劑圖案、尤其是藉由鹼顯影而形成的正型的抗蝕劑圖案的密接性進一步提高,抗蝕劑圖案的塌壞抑制性進一步提高。若[A]聚矽氧烷包含氟原子,則氟系氣體所引起的蝕刻去除性進一步提高。另外,若[A]聚矽氧烷包含氟原子,則可提高使用極紫外線(Extreme Ultraviolet,EUV)時的感放射線性樹脂組成物的感度。It is considered that when a fluorine atom is contained in the base (I) as an electron-donating group or the like, the ruthenium-containing film formed of [A] polysiloxane and the resist pattern formed on the upper side thereof, in particular, by alkali development The adhesion of the formed positive resist pattern is further improved, and the collapse inhibition property of the resist pattern is further improved. When the [A] polyoxyalkylene contains a fluorine atom, the etching removability by the fluorine-based gas is further improved. Further, when the [A] polyoxyalkylene contains a fluorine atom, the sensitivity of the radiation sensitive resin composition when Extreme Ultraviolet (EUV) is used can be improved.
作為Y1 的拉電子性基取代脂肪族烴基,例如可列舉下述式(4-1)所表示的基等。The alkyl group represented by the following formula (4-1) and the like are exemplified as the electron-donating group-substituted aliphatic hydrocarbon group of Y 1 .
[化5] [Chemical 5]
所述式(4-1)中,R4 ~R8 分別獨立地為氫原子、碳數1~18的一價烴基或一價拉電子性基。p為0或1。其中,於p為0的情況下,R6 ~R8 中的至少一個為拉電子性基。於p為1的情況下,R4 ~R8 中的至少一個為拉電子性基。In the formula (4-1), R 4 to R 8 each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent electron-donating group. p is 0 or 1. However, when p is 0, at least one of R 6 to R 8 is an electron withdrawing group. When p is 1, at least one of R 4 to R 8 is an electron withdrawing group.
作為R4 ~R8 ,較佳為氫原子、甲基、氟原子、氯原子、氰基、三氟甲基、甲氧基、甲氧基羰基、甲基磺醯基及乙醯氧基。R 4 to R 8 are preferably a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a methoxy group, a methoxycarbonyl group, a methylsulfonyl group or an ethoxy group.
作為Y1 ,較佳為拉電子性基取代脂肪族烴基。As Y 1 , an electron-donating group is preferably substituted for the aliphatic hydrocarbon group.
[基(II-2)] 作為所述式(2-2)的R2 所表示的碳數1~20的一價有機基,例如可列舉作為所述L的(n+1)價的有機基而例示者中於n為1的二價有機基中加入一個氫原子而成的基等。該些中,較佳為一價烴基,更佳為一價鏈狀烴基,進而佳為烷基,尤佳為甲基及乙基。[Base (II-2)] The monovalent organic group having 1 to 20 carbon atoms represented by R 2 in the formula (2-2), for example, may be exemplified as the (n+1)-valent organic group of the above-mentioned L. In the example, a group in which a hydrogen atom is added to a divalent organic group in which n is 1 is used. Among these, a monovalent hydrocarbon group is preferred, a monovalent chain hydrocarbon group is more preferred, and an alkyl group is further preferred, and a methyl group and an ethyl group are particularly preferred.
作為作為所述式(2-2)的Y2 所表示的經取代或未經取代的碳數6~20的芳烴二基中的芳烴二基,例如可列舉:苯二基、甲苯二基、二甲苯二基、萘二基、蒽二基等。該些中較佳為苯二基。Examples of the substituted or unsubstituted aromatic hydrocarbon diyl group having 6 to 20 carbon atoms represented by Y 2 of the above formula (2-2) include a benzenediyl group and a toluenediyl group. Xylene diyl, naphthalenediyl, anthracenyl and the like. Among these, a benzenediyl group is preferred.
作為Y2 的所述芳烴二基的取代基,例如可列舉作為所述Y1 的芳基的取代基而例示者等。該些中,較佳為鹵素原子,更佳為氟原子。Examples of the substituent of the aromatic hydrocarbon diradical group of Y 2 include, for example, a substituent of the aryl group of Y 1 . Among these, a halogen atom is preferred, and a fluorine atom is more preferred.
作為Y2 的拉電子性基取代脂肪族烴基,例如可列舉下述式(4-2)所表示的基等。The alkyl group represented by the following formula (4-2) is exemplified as the electron-donating group-substituted aliphatic hydrocarbon group of Y 2 .
[化6] [Chemical 6]
所述式(4-2)中,R9 ~R12 分別獨立地為氫原子、碳數1~18的一價烴基或一價拉電子性基。R13 為單鍵、碳數1~18的二價烴基或二價拉電子性基。q為0或1。其中,於q為0的情況下,R11 ~R13 中的至少一個為拉電子性基。於q為1的情況下,R9 ~R13 中的至少一個為拉電子性基。**表示與所述式(2-2)中的-O-鍵結的部位。In the formula (4-2), R 9 to R 12 each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent electron-donating group. R 13 is a single bond, a divalent hydrocarbon group having 1 to 18 carbon atoms or a divalent electron-donating group. q is 0 or 1. However, when q is 0, at least one of R 11 to R 13 is an electron withdrawing group. When q is 1, at least one of R 9 to R 13 is an electron withdrawing group. ** indicates a site bonded to -O- in the formula (2-2).
作為R9 ~R12 ,較佳為氫原子、甲基、氟原子、氯原子、三氟甲基、氰基、甲氧基、甲氧基羰基、甲基磺醯基及乙醯氧基。R 9 to R 12 are preferably a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a trifluoromethyl group, a cyano group, a methoxy group, a methoxycarbonyl group, a methylsulfonyl group or an ethoxy group.
作為R13 ,較佳為單鍵。As R 13 , a single bond is preferred.
作為q,較佳為1。As q, it is preferably 1.
作為Y2 ,較佳為經取代或未經取代的芳烴二基,更佳為經取代或未經取代的苯二基,進而佳為苯二基及氟苯二基。As Y 2 , a substituted or unsubstituted arene diyl group is preferred, and a substituted or unsubstituted phenyldiyl group is more preferred, and a phenyldiyl group and a fluorophenyldiyl group are further preferred.
[A]聚矽氧烷具有包含所述基(I)的式(3)所表示的第1結構單元(以下,亦稱為「結構單元(I)」)。[A]聚矽氧烷較佳為除了結構單元(I)以外進而具有後述式(5)所表示的第2結構單元(以下,亦稱為「結構單元(II)」)及/或後述式(6)所表示的第3結構單元(以下,亦稱為「結構單元(III)」),亦可於無損本發明的效果的範圍內具有結構單元(I)~結構單元(III)以外的其他結構單元。以下,對各結構單元進行說明。[A] Polyoxyalkylene has a first structural unit represented by the formula (3) containing the above-mentioned group (I) (hereinafter also referred to as "structural unit (I)"). [A] Polyoxyalkylene preferably has a second structural unit (hereinafter also referred to as "structural unit (II)") represented by the following formula (5) in addition to the structural unit (I), and/or a later formula (3) The third structural unit (hereinafter also referred to as "structural unit (III)") may have a structure other than the structural unit (I) to the structural unit (III) without departing from the effects of the present invention. Other structural units. Hereinafter, each structural unit will be described.
[結構單元(I)] 結構單元(I)為由下述式(3)所表示的結構單元。該含矽膜形成用組成物藉由[A]聚矽氧烷具有結構單元(I),可進一步提高對鹼性顯影液的耐性、抗蝕劑圖案的塌壞抑制性、鹼性過氧化氫水所引起的剝離性及保存穩定性。[Structural unit (I)] The structural unit (I) is a structural unit represented by the following formula (3). The composition for forming a ruthenium-containing film has a structural unit (I) by [A] polyoxyalkylene, which can further improve resistance to an alkaline developer, collapse inhibition of a resist pattern, and alkaline hydrogen peroxide. Peelability and storage stability caused by water.
[化7] [Chemistry 7]
所述式(3)中,Z為所述基(I)。R3 為不含-SO2 O-的碳數1~20的一價有機基、氫原子或羥基。m為0~2的整數。於m為2的情況下,兩個R3 相同或不同。In the formula (3), Z is the group (I). R 3 is a monovalent organic group having 1 to 20 carbon atoms, a hydrogen atom or a hydroxyl group which does not contain -SO 2 O-. m is an integer of 0 to 2. In the case where m is 2, the two R 3 are the same or different.
作為R3 所表示的不含-SO2 O-的碳數1~20的一價有機基,例如可列舉與所述式(2-2)的R2 的碳數1~20的一價有機基相同者等。The monovalent organic group having 1 to 20 carbon atoms which does not contain -SO 2 O- represented by R 3 may, for example, be a monovalent organic group having 1 to 20 carbon atoms of R 2 of the above formula (2-2). The same as the base.
作為R3 ,較佳為烷氧基及羥基。As R 3 , an alkoxy group and a hydroxyl group are preferred.
作為m,較佳為0及1,更佳為0。As m, it is preferably 0 and 1, more preferably 0.
作為提供結構單元(I)的單體,例如具有基(II-1)的單體可列舉下述式(i-1-1)~式(i-1-18)所表示的化合物(以下,亦稱為「化合物(i-1-1)~化合物(i-1-18)」),具有基(II-2)所表示的基的單體可列舉下述式(i-2-1)~式(i-2-3)所表示的化合物(以下,亦稱為「化合物(i-2-1)~化合物(i-2-3)」)等。The monomer having a structural unit (I), for example, a compound having a group (II-1), a compound represented by the following formula (i-1-1) to (i-1-18) (hereinafter, The compound (i-1-1) to the compound (i-1-18), and the monomer having a group represented by the group (II-2) is exemplified by the following formula (i-2-1). The compound represented by the formula (i-2-3) (hereinafter also referred to as "compound (i-2-1) to the compound (i-2-3)").
[化8] [化8]
[化9] [Chemistry 9]
[化10] [化10]
所述式(i-1-1)~式(i-1-18)及式(i-2-1)~式(i-2-3)中,R為碳數1~20的一價烴基。In the formula (i-1-1) to the formula (i-1-18) and the formula (i-2-1) to the formula (i-2-3), R is a monovalent hydrocarbon group having 1 to 20 carbon atoms. .
作為R的烴基,較佳為烷基,更佳為甲基及乙基。The hydrocarbon group of R is preferably an alkyl group, more preferably a methyl group and an ethyl group.
作為結構單元(I)的含有比例的下限,相對於構成[A]聚矽氧烷的所有結構單元,較佳為0.1莫耳%,更佳為1莫耳%,進而佳為2莫耳%,尤佳為5莫耳%,進而尤佳為8莫耳%。作為所述含有比例的上限,較佳為80莫耳%,更佳為50莫耳%,進而佳為30莫耳%,尤佳為20莫耳%。該含矽膜形成用組成物藉由將結構單元(I)的含有比例設為所述範圍,可進一步提高對鹼性顯影液的耐性、抗蝕劑圖案的塌壞抑制性、鹼性過氧化氫水所引起的剝離性及保存穩定性。The lower limit of the content ratio of the structural unit (I) is preferably 0.1 mol%, more preferably 1 mol%, and still more preferably 2 mol%, based on all structural units constituting the [A] polyoxyalkylene. More preferably, it is 5 mol%, and particularly preferably 8 mol%. The upper limit of the content ratio is preferably 80% by mole, more preferably 50% by mole, still more preferably 30% by mole, still more preferably 20% by mole. By setting the content ratio of the structural unit (I) to the above range, the composition for forming a ruthenium-containing film can further improve resistance to an alkaline developer, collapse inhibition of a resist pattern, and alkaline peroxidation. Peelability and storage stability caused by hydrogen water.
[結構單元(II)] 結構單元(II)為下述式(5)所表示的結構單元。該含矽膜形成用組成物藉由[A]聚矽氧烷具有結構單元(II),可進一步提高含矽膜的氧系氣體所引起的耐蝕刻性。[Structural unit (II)] The structural unit (II) is a structural unit represented by the following formula (5). The composition for forming a ruthenium-containing film has the structural unit (II) by [A] polyoxyalkylene, and the etching resistance by the oxygen-containing gas containing the ruthenium film can be further improved.
[化11] [11]
作為提供結構單元(II)的單體,例如 可列舉:四甲氧基矽烷、四乙氧基矽烷等四烷氧基矽烷、四氯矽烷、四溴矽烷等四鹵矽烷等。The monomer which provides the structural unit (II) may, for example, be a tetraalkyl decane such as tetramethoxy decane such as tetramethoxy decane or tetraethoxy decane, tetrachloro decane or tetrabromodecane such as tetrabromodecane.
於[A]聚矽氧烷具有結構單元(II)的情況下,作為結構單元(II)的含有比例的下限,相對於構成[A]聚矽氧烷的所有結構單元,較佳為1莫耳%,更佳為10莫耳%,進而佳為30莫耳%,尤佳為60莫耳%。作為所述含有比例的上限,較佳為95莫耳%,更佳為90莫耳%,進而佳為85莫耳%,尤佳為80莫耳%。該含矽膜形成用組成物藉由將結構單元(II)的含有比例設為所述範圍,可進一步提高含矽膜的對鹼性顯影液的耐性、氧系氣體所引起的耐蝕刻性。In the case where the [A] polyoxyalkylene has the structural unit (II), the lower limit of the content ratio of the structural unit (II) is preferably 1 mol with respect to all the structural units constituting the [A] polyoxyalkylene. The ear%, more preferably 10% by mole, and further preferably 30% by mole, more preferably 60% by mole. The upper limit of the content ratio is preferably 95% by mole, more preferably 90% by mole, still more preferably 85% by mole, still more preferably 80% by mole. By setting the content ratio of the structural unit (II) to the above range, the composition for forming a ruthenium-containing film can further improve the resistance to the alkaline developing solution and the etching resistance by the oxygen-based gas.
[結構單元(III)] 結構單元(III)為下述式(6)所表示的結構單元。該含矽膜形成用組成物藉由[A]聚矽氧烷具有結構單元(III),可調整含矽膜的各種特性。[Structural unit (III)] The structural unit (III) is a structural unit represented by the following formula (6). The composition for forming a ruthenium-containing film has a structural unit (III) by [A] polyoxyalkylene, and various characteristics of the ruthenium-containing film can be adjusted.
[化12] [化12]
所述式(6)中,RA 為不含-SO2 O-的碳數1~20的一價有機基。a為1或2。於a為2的情況下,兩個RA 相同或不同。In the formula (6), R A is a monovalent organic group having 1 to 20 carbon atoms which does not contain -SO 2 O-. a is 1 or 2. In the case where a is 2, the two R A are the same or different.
作為RA 所表示的不含-SO2 O-的碳數1~20的一價有機基,例如可列舉與所述式(2-2)的R2 的碳數1~20的一價有機基相同者等。該些中,較佳為烴基,更佳為鏈狀烴基及芳香族烴基,進而佳為烷基及芳基,尤佳為甲基、乙基、苯基及萘基。The monovalent organic group having 1 to 20 carbon atoms which does not contain -SO 2 O- represented by R A may, for example, be a monovalent organic group having 1 to 20 carbon atoms of R 2 of the above formula (2-2). The same as the base. Among these, a hydrocarbon group is preferred, a chain hydrocarbon group and an aromatic hydrocarbon group are more preferred, and an alkyl group and an aryl group are preferred, and a methyl group, an ethyl group, a phenyl group and a naphthyl group are particularly preferred.
作為a,較佳為1。As a, it is preferably 1.
作為提供結構單元(III)的單體,例如可列舉:甲基三甲氧基矽烷、苯基三乙氧基矽烷、二甲基二甲氧基矽烷、二苯基二乙氧基矽烷、甲基苯基二甲氧基矽烷、環己基三氯矽烷等。Examples of the monomer which provides the structural unit (III) include methyltrimethoxydecane, phenyltriethoxydecane, dimethyldimethoxydecane, diphenyldiethoxydecane, and methyl group. Phenyldimethoxydecane, cyclohexyltrichlorodecane, and the like.
於[A]聚矽氧烷具有結構單元(III)的情況下,作為結構單元(III)的含有比例的下限,相對於構成[A]聚矽氧烷的所有結構單元,較佳為0.1莫耳%,更佳為1莫耳%,進而佳為8莫耳%,尤佳為12莫耳%。作為所述含有比例的上限,較佳為80莫耳%,更佳為50莫耳%,進而佳為40莫耳%,進而尤佳為25莫耳%。In the case where the [A] polyoxyalkylene has the structural unit (III), the lower limit of the content ratio of the structural unit (III) is preferably 0.1 mol with respect to all structural units constituting the [A] polyoxyalkylene. The ear %, more preferably 1 mol%, and further preferably 8 mol%, particularly preferably 12 mol%. The upper limit of the content ratio is preferably 80 mol%, more preferably 50 mol%, still more preferably 40 mol%, and still more preferably 25 mol%.
[其他結構單元] [A]聚矽氧烷只要無損本發明的效果,則亦可具有所述結構單元(I)~結構單元(III)以外的結構單元作為其他結構單元。作為其他結構單元,例如可列舉:來源於六甲氧基二矽烷、雙(三甲氧基矽烷基)甲烷、聚二甲氧基甲基碳矽烷等含有多個矽原子的矽烷單體的結構單元等。於[A]聚矽氧烷具有其他結構單元的情況下,作為其他結構單元的含有比例的上限,相對於構成[A]聚矽氧烷的所有結構單元,較佳為10莫耳%,更佳為5莫耳%,進而佳為2莫耳%,尤佳為5莫耳%。[Other structural unit] [A] Polyoxyalkylene may have other structural units other than the structural unit (I) to the structural unit (III) as long as the effects of the present invention are not impaired. Examples of the other structural unit include a structural unit derived from a decane monomer containing a plurality of ruthenium atoms such as hexamethoxydioxane, bis(trimethoxydecyl)methane, or polydimethoxymethylcarbane. . In the case where the [A] polyoxyalkylene has other structural units, the upper limit of the content ratio of the other structural unit is preferably 10 mol%, more preferably 10 mol%, based on all structural units constituting the [A] polyoxyalkylene. Preferably, it is 5% by mole, and further preferably 2% by mole, and particularly preferably 5% by mole.
作為[A]聚矽氧烷的含量的下限,相對於該含矽膜形成用組成物的總固體成分,較佳為50質量%,更佳為80質量%,進而佳為90質量%,尤佳為95質量%。作為所述含量的上限,較佳為100質量%,較佳為99質量%,更佳為97質量%。所謂該含矽膜形成用組成物的總固體成分是指[B]溶媒以外的成分的總和。[A]聚矽氧烷可僅含有一種,亦可含有兩種以上。The lower limit of the content of the [A] polyoxane is preferably 50% by mass, more preferably 80% by mass, even more preferably 90% by mass, based on the total solid content of the composition for forming a ruthenium-containing film. Good is 95% by mass. The upper limit of the content is preferably 100% by mass, preferably 99% by mass, and more preferably 97% by mass. The total solid content of the composition for forming a ruthenium-containing film means the sum of components other than the solvent [B]. [A] The polyoxyalkylene may be contained alone or in combination of two or more.
作為[A]聚矽氧烷的重量平均分子量(Mw)的下限,較佳為1,000,更佳為1,300,進而佳為1,500,尤佳為1,700。作為所述Mw的上限,較佳為100,000,更佳為20,000,進而佳為7,000,尤佳為3,000。The lower limit of the weight average molecular weight (Mw) of [A] polyoxyalkylene is preferably 1,000, more preferably 1,300, still more preferably 1,500, still more preferably 1,700. The upper limit of the Mw is preferably 100,000, more preferably 20,000, still more preferably 7,000, and still more preferably 3,000.
本說明書中的[A]聚矽氧烷的Mw為使用東曹(Tosoh)公司的凝膠滲透層析(Gel Permeation Chromatography,GPC)管柱(「G2000HXL」2根、「G3000HXL」1根及「G4000HXL」1根),於流量:1.0 mL/min、溶出溶媒:四氫呋喃、管柱溫度:40℃的分析條件下,藉由以單分散聚苯乙烯作為標準的凝膠滲透層析(檢測器:示差折射計)而測定的值。The Mw of [A] polyoxane in this specification is a gel permeation chromatography (GPC) column of Tosoh Corporation (2 "G2000HXL", "G3000HXL" and 1" G4000HXL"1), under the conditions of flow rate: 1.0 mL/min, dissolution solvent: tetrahydrofuran, column temperature: 40 ° C, by gel permeation chromatography using monodisperse polystyrene as a standard (detector: The value measured by the differential refractometer.
[A]聚矽氧烷可藉由將與所述各結構單元相對應的水解性矽烷單體加以水解縮合的方法而獲得。認為藉由水解縮合反應,各水解性矽烷單體與種類無關而被導入聚矽氧烷中,所合成的[A]聚矽氧烷中的結構單元(I)~結構單元(III)及其他結構單元的含有比例與合成反應中使用的各單體化合物的使用量的比例通常相等。[A] Polyoxyalkylene can be obtained by a method of hydrolyzing and condensing a hydrolyzable decane monomer corresponding to each of the structural units. It is considered that each hydrolyzable decane monomer is introduced into the polyoxyalkylene by a hydrolysis condensation reaction, and the structural unit (I) to structural unit (III) and other components in the synthesized [A] polyaluminoxane are synthesized. The ratio of the content ratio of the structural unit to the amount of each monomer compound used in the synthesis reaction is usually equal.
<[B]溶媒> 該含矽膜形成用組成物含有[B]溶媒。作為[B]溶媒,例如可列舉:醇系溶媒、酮系溶媒、醚系溶媒、酯系溶媒、含氮系溶媒、水等。[B]溶媒可單獨使用一種或將兩種以上組合使用。<[B] Solvent> The composition for forming a ruthenium-containing film contains a [B] solvent. Examples of the [B] solvent include an alcohol-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, a nitrogen-containing solvent, and water. [B] The solvent may be used singly or in combination of two or more.
作為醇系溶媒,例如可列舉:甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇等單醇系溶媒;乙二醇、1,2-丙二醇、二乙二醇、二丙二醇等多元醇系溶媒等。Examples of the alcohol-based solvent include monool-based solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, 1,2-propanediol, diethylene glycol, and two. A polyol-based solvent such as propylene glycol.
作為酮系溶媒,例如可列舉:丙酮、甲基乙基酮、甲基-正丙基酮、甲基-異丁基酮、環己酮等。Examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-isobutyl ketone, and cyclohexanone.
作為醚系溶媒,例如可列舉:***、異丙醚、乙二醇二丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇二***、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、四氫呋喃等。Examples of the ether solvent include diethyl ether, diisopropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and propylene glycol. Monoethyl ether, propylene glycol monopropyl ether, tetrahydrofuran, and the like.
作為酯系溶媒,例如可列舉:乙酸乙酯、γ-丁內酯、乙酸正丁酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、二丙二醇單甲醚乙酸酯、二丙二醇單***乙酸酯、丙酸乙酯、丙酸正丁酯、乳酸甲酯、乳酸乙酯等。Examples of the ester-based solvent include ethyl acetate, γ-butyrolactone, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monomethyl ether. Acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethyl propionate , n-butyl propionate, methyl lactate, ethyl lactate and the like.
作為含氮系溶媒,例如可列舉:N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等。Examples of the nitrogen-containing solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
該些中,較佳為醚系溶媒及酯系溶媒,由於成膜性優異,因此更佳為具有二醇結構的醚系溶媒及酯系溶媒。Among these, an ether solvent and an ester solvent are preferred, and since it has excellent film formability, it is more preferably an ether solvent or an ester solvent having a diol structure.
作為具有二醇結構的醚系溶媒及酯系溶媒,例如可列舉:丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯等。該些中,尤佳為丙二醇單甲醚乙酸酯。Examples of the ether solvent and the ester solvent having a diol structure include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl acetate. Ether acetate and the like. Among these, propylene glycol monomethyl ether acetate is particularly preferred.
作為[B]溶媒中的具有二醇結構的醚系溶媒及酯系溶媒的含有率的下限,較佳為20質量%,更佳為60質量%,進而佳為90質量%,尤佳為100質量%。The lower limit of the content of the ether solvent and the ester solvent having a diol structure in the solvent of [B] is preferably 20% by mass, more preferably 60% by mass, still more preferably 90% by mass, and particularly preferably 100%. quality%.
作為該含矽膜形成用組成物中的[B]溶媒的含量的下限,較佳為80質量%,更佳為90質量%,進而佳為95質量%。作為所述含量的上限,較佳為99質量%,更佳為98質量%。The lower limit of the content of the [B] solvent in the composition for forming a ruthenium-containing film is preferably 80% by mass, more preferably 90% by mass, still more preferably 95% by mass. The upper limit of the content is preferably 99% by mass, and more preferably 98% by mass.
<任意成分> 該含矽膜形成用組成物亦可含有鹼性化合物、酸產生劑等任意成分。<Optional component> The composition for forming a ruthenium-containing film may contain an optional component such as a basic compound or an acid generator.
[鹼性化合物] 作為鹼性化合物(包含鹼產生劑),例如可列舉具有鹼性胺基的化合物、或藉由酸的作用或熱的作用而成為具有鹼性胺基的化合物的化合物(鹼產生劑)。更具體而言,可列舉:胺化合物、以及作為鹼產生劑的含醯胺基化合物、脲化合物、含氮雜環化合物等。於在該含矽膜形成用組成物中含有鹼性化合物的情況下,可促進該含矽膜形成用組成物的硬化,另外可進一步提高所得的含矽膜的對於酸性液的剝離性等。[Basic compound] Examples of the basic compound (including a base generator) include a compound having a basic amino group or a compound having a basic amine group by the action of an acid or heat (alkali) Producer). More specifically, an amine compound, a guanamine-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, etc. which are an alkali generator are mentioned. When the basic compound is contained in the composition for forming a ruthenium-containing film, the composition for forming the ruthenium-containing film can be promoted, and the peeling property of the obtained ruthenium-containing film with respect to the acidic liquid can be further improved.
作為所述胺化合物,例如可列舉:單(環)烷基胺類、二(環)烷基胺類、三(環)烷基胺類、經取代的烷基苯胺或其衍生物、乙二胺、N,N,N',N'-四甲基乙二胺、四亞甲基二胺、六亞甲基二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基醚、4,4'-二胺基二苯甲酮、4,4'-二胺基二苯基胺、2,2-雙(4-胺基苯基)丙烷、2-(3-胺基苯基)-2-(4-胺基苯基)丙烷、2-(4-胺基苯基)-2-(3-羥基苯基)丙烷、2-(4-胺基苯基)-2-(4-羥基苯基)丙烷、1,4-雙(1-(4-胺基苯基)-1-甲基乙基)苯、1,3-雙(1-(4-胺基苯基)-1-甲基乙基)苯、雙(2-二甲基胺基乙基)醚、雙(2-二乙基胺基乙基)醚、1-(2-羥基乙基)-2-咪唑啶酮、2-喹唑酮、N,N,N',N'-四(2-羥基丙基)乙二胺、N,N,N',N''N''-五甲基二乙三胺等。Examples of the amine compound include mono(cyclo)alkylamines, di(cyclo)alkylamines, tri(cyclo)alkylamines, substituted alkylanilines or derivatives thereof, and ethylene. Amine, N, N, N', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4' -diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3-Aminophenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4- Aminophenyl)-2-(4-hydroxyphenyl)propane, 1,4-bis(1-(4-aminophenyl)-1-methylethyl)benzene, 1,3-double (1 -(4-Aminophenyl)-1-methylethyl)benzene, bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether, 1-( 2-hydroxyethyl)-2-imidazolidinone, 2-quinazolidone, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N',N' 'N''-pentamethyldiethylenetriamine and the like.
作為所述含醯胺基化合物,例如可列舉:N-第三丁氧基羰基-4-羥基哌啶、N-第三丁氧基羰基-2-羧基-4-羥基吡咯啶、N-第三丁氧基羰基-2-羧基吡咯啶等含有N-第三丁氧基羰基的胺基化合物;N-第三戊氧基羰基-4-羥基哌啶等含有N-第三戊氧基羰基的胺基化合物;N-(9-蒽基甲氧基羰基)哌啶等含有N-(9-蒽基甲氧基羰基)的胺基化合物;甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、丙醯胺、苯甲醯胺、吡咯啶酮、N-甲基吡咯啶酮、N-乙醯基-1-金剛烷基胺等。Examples of the guanamine-containing compound include N-tert-butoxycarbonyl-4-hydroxypiperidine, N-tert-butoxycarbonyl-2-carboxy-4-hydroxypyrrolidine, and N- N-tert-butoxycarbonyl-containing amine compound such as tributoxycarbonyl-2-carboxypyrrolidine; N-third pentyloxycarbonyl-4-hydroxypiperidine and the like containing N-third pentyloxycarbonyl group Amine compound; N-(9-fluorenylmethoxycarbonyl)-containing amine compound such as N-(9-fluorenylmethoxycarbonyl) piperidine; formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N-A Pyrrolidone, N-ethinyl-1-adamantylamine, and the like.
作為所述脲化合物,例如可列舉:脲、甲基脲、1,1-二甲基脲、1,3-二甲基脲、1,1,3,3-四甲基脲、1,3-二苯基脲、三-正丁基硫脲等。Examples of the urea compound include urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, and 1,3. - Diphenylurea, tri-n-butylthiourea, and the like.
作為所述含氮雜環化合物,例如可列舉:咪唑類、吡啶類、哌嗪類、吡嗪、吡唑、噠嗪、喹唑啉、嘌呤、吡咯啶、哌啶、哌啶乙醇、3-(N-哌啶基)-1,2-丙二醇、嗎啉、4-甲基嗎啉、1-(4-嗎啉基)乙醇、4-乙醯基嗎啉、3-(N-嗎啉基)-1,2-丙二醇、1,4-二甲基哌嗪、1,4-二氮雜雙環[2.2.2]辛烷等。Examples of the nitrogen-containing heterocyclic compound include imidazoles, pyridines, piperazines, pyrazines, pyrazoles, pyridazines, quinazolines, anthracenes, pyrrolidines, piperidines, piperidines, and 3-mer (N-piperidinyl)-1,2-propanediol, morpholine, 4-methylmorpholine, 1-(4-morpholinyl)ethanol, 4-ethylmercaptomorpholine, 3-(N-morpholine Base)-1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, and the like.
本實施形態中,該些中,尤佳為含醯胺基化合物及含氮雜環化合物。作為含醯胺基化合物,更佳為含有N-第三丁氧基羰基的胺基化合物、含有N-第三戊氧基羰基的胺基化合物及含有N-(9-蒽基甲氧基羰基)的胺基化合物,進而佳為N-第三丁氧基羰基-4-羥基哌啶、N-第三丁氧基羰基-2-羧基-4-羥基吡咯啶、N-第三丁氧基羰基-2-羧基-吡咯啶、N-第三戊氧基羰基-4-羥基哌啶及N-(9-蒽基甲氧基羰基)哌啶。作為含氮雜環化合物,較佳為3-(N-哌啶基)-1,2-丙二醇。In the present embodiment, among these, a mercapto group-containing compound and a nitrogen-containing heterocyclic compound are particularly preferable. As the guanamine-containing compound, an amine compound containing an N-tert-butoxycarbonyl group, an amine compound containing an N-third pentyloxycarbonyl group, and an N-(9-fluorenylmethoxycarbonyl group) are more preferable. An amine compound, preferably N-tertoxycarbonyl-4-hydroxypiperidine, N-tert-butoxycarbonyl-2-carboxy-4-hydroxypyrrolidine, N-tert-butoxy Carbonyl-2-carboxy-pyrrolidine, N-third pentyloxycarbonyl-4-hydroxypiperidine and N-(9-fluorenylmethoxycarbonyl)piperidine. As the nitrogen-containing heterocyclic compound, 3-(N-piperidinyl)-1,2-propanediol is preferred.
於該含矽膜形成用組成物含有鹼性化合物的情況下,作為所述鹼性化合物的相對於[A]聚矽氧烷100質量份的含量,較佳為0.01質量份,更佳為0.1質量%,進而佳為0.5質量份,尤佳為1質量份。作為所述含量的上限,較佳為20質量份,更佳為10質量份,進而佳為5質量份。When the composition for forming a ruthenium-containing film contains a basic compound, the content of the basic compound relative to 100 parts by mass of the [A] polyoxane is preferably 0.01 parts by mass, more preferably 0.1 part by mass. The mass%, and more preferably 0.5 parts by mass, is particularly preferably 1 part by mass. The upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass, and still more preferably 5 parts by mass.
[酸產生劑] 酸產生劑為藉由紫外光的照射及/或加熱而產生酸的化合物。若該含矽膜形成用組成物含有酸產生劑,可促進硬化,其結果可進一步提高含矽膜的強度,可提高耐溶劑性或耐氧氣蝕刻性。酸產生劑可單獨使用一種或者組合使用兩種以上。[Acid Generator] The acid generator is a compound which generates an acid by irradiation and/or heating of ultraviolet light. When the composition for forming a ruthenium-containing film contains an acid generator, the curing can be promoted, and as a result, the strength of the ruthenium-containing film can be further improved, and solvent resistance or oxygen etching resistance can be improved. The acid generators may be used alone or in combination of two or more.
作為酸產生劑,例如可列舉鎓鹽化合物、N-磺醯氧基醯亞胺化合物等。Examples of the acid generator include an onium salt compound and an N-sulfonoxyquinone imine compound.
作為所述鎓鹽化合物,例如可列舉:鋶鹽、四氫噻吩鎓鹽、錪鹽、銨鹽等。Examples of the onium salt compound include an onium salt, a tetrahydrothiophene salt, an onium salt, and an ammonium salt.
作為鋶鹽,可列舉日本專利特開2014-037386號公報的段落[0110]中記載的鋶鹽,更具體而言可列舉:三苯基鋶三氟甲磺酸鹽、三苯基鋶九氟-正丁磺酸鹽、三苯基鋶2-雙環[2.2.1]庚-2-基-1,1,2,2-四氟乙磺酸鹽、4-環己基苯基二苯基鋶三氟甲磺酸鹽等。Examples of the onium salt include the onium salt described in paragraph [0110] of JP-A-2014-037386, and more specifically, triphenylsulfonium trifluoromethanesulfonate and triphenylsulfonium nonafluoride. - n-butanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylphosphonium Trifluoromethanesulfonate and the like.
作為四氫噻吩鎓鹽,可列舉日本專利特開2014-037386號公報的段落[0111]中記載的四氫噻吩鎓鹽,更具體而言可列舉:1-(4-正丁氧基萘-1-基)四氫噻吩鎓三氟甲磺酸鹽、1-(4-正丁氧基萘-1-基)四氫噻吩鎓九氟-正丁磺酸鹽、1-(4-正丁氧基萘-1-基)四氫噻吩鎓2-雙環[2.2.1]庚-2-基-1,1,2,2-四氟乙磺酸鹽等。Examples of the tetrahydrothiophene sulfonium salt include a tetrahydrothiophene sulfonium salt described in paragraph [0111] of JP-A-2014-037386, and more specifically, 1-(4-n-butoxynaphthalene- 1-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene nonafluoro-n-butanesulfonate, 1-(4-n-butyl) Oxynaphthalen-1-yl)tetrahydrothiophene 2-cyclobi[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and the like.
作為錪鹽,可列舉日本專利特開2014-037386號公報的段落[0112]中記載的錪鹽,更具體可列舉:二苯基錪三氟甲磺酸鹽、二苯基錪九氟-正丁磺酸鹽、二苯基錪2-雙環[2.2.1]庚-2-基-1,1,2,2-四氟乙磺酸鹽、雙(4-第三丁基苯基)錪九氟-正丁磺酸鹽等。Examples of the onium salt include the onium salt described in paragraph [0112] of JP-A-2014-037386, and more specifically, diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium nonafluoride-positive Butane sulfonate, diphenyl hydrazine 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis(4-t-butylphenyl)fluorene Nonafluoro-n-butanesulfonate and the like.
作為銨鹽,例如可列舉三甲基銨九氟-正丁磺酸鹽、三乙基銨九氟-正丁磺酸鹽等。Examples of the ammonium salt include trimethylammonium nonafluoro-n-butylsulfonate and triethylammonium nonafluoro-n-butanesulfonate.
作為N-磺醯氧基醯亞胺化合物,可列舉日本專利特開2014-037386號公報的段落[0113]中記載的N-磺醯氧基醯亞胺化合物,更具體而言可列舉:N-(三氟甲磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(九氟-正丁磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-雙環[2.2.1]庚-2-基-1,1,2,2-四氟乙磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺等。The N-sulfonyloxyimine compound described in paragraph [0113] of JP-A-2014-037386, and more specifically, N: -(Trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(nonafluoro-n-butylsulfonyloxy)bicyclo[2.2.1 G-8-ene-2,3-dicarboxy quinone imine, N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, and the like.
於該含矽膜形成用組成物含有酸產生劑的情況下,作為所述酸產生劑的相對於[A]聚矽氧烷100質量份的含量,較佳為0.01質量份,更佳為0.1質量%,進而佳為0.5質量份,尤佳為1質量份。作為所述含量的上限,較佳為20質量份,更佳為10質量份,進而佳為5質量份。In the case where the composition for forming a ruthenium-containing film contains an acid generator, the content of the acid generator relative to 100 parts by mass of the [A] polyoxane is preferably 0.01 parts by mass, more preferably 0.1 part by mass. The mass%, and more preferably 0.5 parts by mass, is particularly preferably 1 part by mass. The upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass, and still more preferably 5 parts by mass.
該含矽膜形成用組成物亦可除了所述鹼性化合物及酸產生劑以外含有其他任意成分。作為其他任意成分,例如可列舉:界面活性劑、自由基產生劑、膠體狀二氧化矽、膠體狀氧化鋁、有機聚合物等。於該含矽膜形成用組成物含有其他任意成分的情況下,作為其含量的上限,相對於[A]聚矽氧烷100質量份,較佳為2質量份,更佳為1質量份。The composition for forming a ruthenium-containing film may contain other optional components in addition to the basic compound and the acid generator. Examples of other optional components include a surfactant, a radical generator, colloidal cerium oxide, colloidal alumina, and an organic polymer. In the case where the composition for forming a ruthenium-containing film contains other optional components, the upper limit of the content is preferably 2 parts by mass, more preferably 1 part by mass, per 100 parts by mass of the [A] polysiloxane.
<含矽膜形成用組成物的製備方法> 該含矽膜形成用組成物的製備方法並無特別限定,例如可藉由以下方式製備:將[A]聚矽氧烷、[B]溶媒及視需要的任意成分以既定的比例混合,較佳為利用孔徑0.2 μm的過濾器將所得的混合溶液過濾。<Method for Producing Composition Containing Antimony Film> The method for preparing the composition for forming a hafnium film is not particularly limited, and can be prepared, for example, by [A] polyoxane, [B] solvent, and The optional components are mixed in a predetermined ratio as needed, and it is preferred to filter the resulting mixed solution with a filter having a pore size of 0.2 μm.
作為該含矽膜形成用組成物的固體成分濃度的下限,較佳為0.01質量%,更佳為0.05質量%,進而佳為0.1質量%,尤佳為0.2質量%。作為所述固體成分濃度的上限,較佳為20質量%,更佳為10質量%,進而佳為5質量%,尤佳為3質量%。所謂該含矽膜形成用組成物的固體成分濃度,是藉由以下方式而算出的值(質量%):將含矽膜形成用組成物於250℃下煅燒30分鐘,藉此測定含矽膜形成用組成物中的固體成分的質量,將該固體成分的質量除以含矽膜形成用組成物的質量。The lower limit of the solid content concentration of the composition for forming a ruthenium-containing film is preferably 0.01% by mass, more preferably 0.05% by mass, still more preferably 0.1% by mass, still more preferably 0.2% by mass. The upper limit of the solid content concentration is preferably 20% by mass, more preferably 10% by mass, still more preferably 5% by mass, and particularly preferably 3% by mass. The solid content concentration of the composition for forming a ruthenium-containing film is a value (% by mass) calculated by calcining the composition for forming a ruthenium-containing film at 250 ° C for 30 minutes, thereby measuring the ruthenium-containing film. The mass of the solid component in the composition for formation, and the mass of the solid component is divided by the mass of the composition for forming a ruthenium film.
該含矽膜形成用組成物可較佳地用作作為多層抗蝕劑製程中的中間膜的含矽膜等的抗蝕劑製程中的膜形成材料,另外,亦可用於經過反轉製程所得的圖案(反轉圖案)的形成材料等抗蝕劑製程中的膜形成材料以外的用途。The composition for forming a ruthenium-containing film can be preferably used as a film-forming material in a resist process including a ruthenium film or the like as an intermediate film in a multilayer resist process, and can also be used in a reverse process. Uses other than the film forming material in the resist process such as the formation material of the pattern (reverse pattern).
<含矽膜> 由該含矽膜形成用組成物而獲得的含矽膜維持氟系氣體所引起的蝕刻去除性,且抗蝕劑圖案的塌壞抑制性優異,另外,對抗蝕劑圖案形成步驟中的鹼性顯影液的耐性優異且鹼性過氧化氫水所引起的剝離性優異。因此,該含矽膜形成用組成物可作為如下材料而較佳地使用,所述材料用以形成作為抗蝕劑製程、尤其是多層抗蝕劑製程中的中間膜的含矽膜。另外,於多層抗蝕劑製程中,可尤其較佳地用於較90 nm更微細的區域(ArF、液浸曝光中的ArF、F2 、EUV、奈米壓印等)中的使用多層抗蝕劑製程的圖案形成。<The ruthenium-containing film> The ruthenium-containing film obtained by the composition for forming a ruthenium film is excellent in the etch-resistance of the fluorine-based gas, and is excellent in the collapse resistance of the resist pattern, and is formed on the resist pattern. The alkaline developing solution in the step is excellent in resistance and excellent in peeling property due to alkaline hydrogen peroxide water. Therefore, the composition for forming a ruthenium-containing film can be preferably used as a material for forming a ruthenium-containing film which is an intermediate film in a resist process, particularly a multilayer resist process. In addition, in the multilayer resist process, it is particularly preferable to use a multilayer anti-friction in a finer region (ArF, F 2 , EUV, nanoimprint, etc.) in a finer region than 90 nm (ArF, F 2 , EUV, immersion exposure, etc.) Pattern formation of the etchant process.
所述含矽膜可藉由以下方式形成:將所述的該含矽膜形成用組成物塗敷於基板、有機下層膜等其他下層膜等的表面上,藉此形成塗膜,對該塗膜進行加熱處理而使其硬化。The ruthenium-containing film can be formed by applying the composition for forming a ruthenium-containing film to a surface of another underlayer film such as a substrate or an organic underlayer film, thereby forming a coating film. The film is heat treated to harden it.
作為塗敷該含矽膜形成用組成物的方法,例如可列舉旋轉塗敷法、輥塗法、浸漬法等。作為加熱處理的溫度的下限,較佳為50℃,更佳為70℃。作為所述溫度的上限,較佳為450℃,更佳為300℃。作為所形成的含矽膜的平均厚度的下限,較佳為10 nm,更佳為20 nm。作為所述平均厚度的上限,較佳為200 nm,更佳為150 nm。Examples of the method of applying the composition for forming a ruthenium-containing film include a spin coating method, a roll coating method, and a dipping method. The lower limit of the temperature for the heat treatment is preferably 50 ° C, more preferably 70 ° C. The upper limit of the temperature is preferably 450 ° C, more preferably 300 ° C. The lower limit of the average thickness of the formed ruthenium-containing film is preferably 10 nm, more preferably 20 nm. As the upper limit of the average thickness, it is preferably 200 nm, more preferably 150 nm.
<圖案形成方法> 該圖案形成方法包括:藉由該含矽膜形成用組成物的塗敷而於基板的上側形成含矽膜的步驟(以下,亦稱為「含矽膜形成步驟」);以及對所述含矽膜進行圖案化的步驟(以下,亦稱為「含矽膜圖案化步驟」)。<Pattern forming method> The pattern forming method includes a step of forming a ruthenium-containing film on the upper side of the substrate by the application of the ruthenium-containing film-forming composition (hereinafter also referred to as "the ruthenium-containing film forming step"); And a step of patterning the ruthenium-containing film (hereinafter also referred to as "film-containing patterning step").
根據該圖案形成方法,由於使用所述該含矽膜形成用組成物,因此可形成維持氟系氣體所引起的蝕刻去除性、且抗蝕劑圖案的塌壞抑制性優異的含矽膜,另外,可形成對抗蝕劑圖案形成步驟中的鹼性顯影液的耐性優異且鹼性過氧化氫水所引起的剝離性優異的含矽膜。According to the pattern forming method, since the composition for forming a ruthenium-containing film is used, it is possible to form a ruthenium-containing film which is excellent in the etch-removability of the fluorine-based gas and has excellent collapse resistance of the resist pattern, and It is possible to form a ruthenium-containing film which is excellent in resistance to an alkaline developer in the resist pattern forming step and excellent in peeling property due to alkaline hydrogen peroxide water.
所述含矽膜圖案化步驟亦可包括:於所述含矽膜的上側形成抗蝕劑圖案的步驟(以下,亦稱為「抗蝕劑圖案形成步驟」);以及將所述抗蝕劑圖案作為遮罩而對所述含矽膜進行蝕刻的步驟(以下,亦稱為「含矽膜蝕刻步驟」)。The ruthenium-containing film patterning step may further include a step of forming a resist pattern on the upper side of the ruthenium-containing film (hereinafter also referred to as "resist pattern formation step"); and the resist The step of etching the ruthenium-containing film as a mask (hereinafter also referred to as "ruthenium-containing film etching step").
該圖案形成方法亦可視需要於所述含矽膜形成步驟前進而包括於基板的上側形成有機下層膜的步驟(以下,亦稱為「有機下層膜形成步驟」)。另外,該圖案形成方法亦可於所述含矽膜形成步驟後進而包括去除所述含矽膜的步驟(以下,亦稱為「含矽膜去除步驟」)。該圖案形成方法通常於所述含矽膜圖案化步驟後包括將進行了圖案化的含矽膜作為遮罩並對基板進行蝕刻的步驟(以下,亦稱為「基板蝕刻步驟」)。以下,對各步驟進行說明。The pattern forming method may also include a step of forming an organic underlayer film on the upper side of the substrate (hereinafter also referred to as "organic underlayer film forming step") as needed in the ruthenium-containing film forming step. Further, the pattern forming method may further include a step of removing the ruthenium-containing film (hereinafter also referred to as "the ruthenium-containing film removal step") after the ruthenium-containing film formation step. The pattern forming method generally includes a step of etching the substrate by using the patterned ruthenium-containing film as a mask after the ruthenium-containing film patterning step (hereinafter also referred to as "substrate etching step"). Hereinafter, each step will be described.
<有機下層膜形成步驟> 本步驟中,於基板的上側形成有機下層膜。於該圖案形成方法中,視需要可進行有機下層膜形成步驟。<Organic Lower Film Forming Step> In this step, an organic underlayer film is formed on the upper side of the substrate. In the pattern forming method, an organic underlayer film forming step can be performed as needed.
於該圖案形成方法中,於進行有機下層膜形成步驟的情況下,於有機下層膜形成步驟後進行含矽膜形成步驟,於含矽膜形成步驟中,使用該含矽膜形成用組成物而於有機下層膜上形成含矽膜。In the pattern forming method, in the case of performing the organic underlayer film forming step, the ruthenium-containing film forming step is performed after the organic underlayer film forming step, and the ruthenium-containing film forming composition is used in the ruthenium-containing film forming step. A ruthenium-containing film is formed on the organic underlayer film.
作為所述基板,例如可列舉:氧化矽、氮化矽、氮氧化矽、聚矽氧烷等的絕緣膜、樹脂基板等。例如可使用藉由應用材料(AMAT)公司的「黑鑽(Black Diamond)」、陶氏化學(Dow Chemical)公司的「斯爾克(Silk)」、捷時雅(JSR)公司的「LKD5109」等而形成的經低介電質絕緣膜被覆的晶圓等的層間絕緣膜。作為該基板,亦可使用配線槽(淺槽)、插塞槽(通道)等經圖案化的基板。Examples of the substrate include an insulating film such as cerium oxide, cerium nitride, cerium oxynitride, or polyoxyalkylene, and a resin substrate. For example, "Black Diamond" by Applied Materials (AMAT), "Silk" by Dow Chemical, and "LKD5109" by JSR Corporation can be used. An interlayer insulating film such as a wafer coated with a low dielectric insulating film formed by the like. As the substrate, a patterned substrate such as a wiring groove (shallow groove) or a plug groove (channel) can be used.
所述有機下層膜與由該含矽膜形成用組成物所形成的含矽膜不同。有機下層膜為於抗蝕劑圖案形成中進一步彌補含矽膜及/或抗蝕劑膜所具有的功能,或為了獲得該些膜不具有的功能而賦予有所必需的既定功能(例如抗反射性、塗佈膜平坦性、對氟系氣體的高耐蝕刻性)的膜。The organic underlayer film is different from the ruthenium-containing film formed of the composition for forming a ruthenium-containing film. The organic underlayer film further compensates for the function of the ruthenium-containing film and/or the resist film in the formation of the resist pattern, or imparts a predetermined function (for example, anti-reflection) in order to obtain a function that the film does not have. A film of properties, coating film flatness, and high etching resistance to a fluorine-based gas.
作為有機下層膜,例如可列舉抗反射膜等。作為抗反射膜形成用組成物,例如可列舉捷時雅(JSR)公司的「NFC HM8006」等。Examples of the organic underlayer film include an antireflection film and the like. Examples of the composition for forming an antireflection film include "NFC HM8006" by JSR Corporation.
有機下層膜可藉由以下方式形成:藉由旋轉塗敷法等塗佈有機下層膜形成用組成物而形成塗膜後,進行加熱。The organic underlayer film can be formed by applying a composition for forming an organic underlayer film by a spin coating method or the like to form a coating film, followed by heating.
<含矽膜形成步驟> 本步驟中,藉由該含矽膜形成用組成物的塗敷而於基板的上側形成含矽膜。藉由本步驟,直接或經由有機下層膜等其他層而於基板上形成含矽膜。<The ruthenium-containing film formation step> In this step, a ruthenium-containing film is formed on the upper side of the substrate by the application of the ruthenium-containing film-forming composition. By this step, a ruthenium-containing film is formed on the substrate directly or via another layer such as an organic underlayer film.
含矽膜的形成方法並無特別限定,例如可列舉如下方法等:利用旋轉塗敷法等公知的方法於基板等上塗敷該含矽膜形成用組成物而形成塗膜,對該塗膜進行曝光及/或加熱而使其硬化而形成。The method of forming the ruthenium-containing film is not particularly limited, and for example, a coating film is formed by applying the composition for forming a ruthenium-containing film onto a substrate or the like by a known method such as a spin coating method, and the coating film is formed. It is formed by hardening and/or heating to harden it.
作為用於所述曝光的放射線,例如可列舉:可見光線、紫外線、遠紫外線、X射線、γ射線等電磁波、電子束、分子束、離子束等粒子束等。Examples of the radiation used for the exposure include electromagnetic waves such as visible rays, ultraviolet rays, far ultraviolet rays, X-rays, and gamma rays, particle beams such as electron beams, molecular beams, and ion beams.
作為對塗膜進行加熱時的溫度的下限,較佳為90℃,更佳為150℃,進而佳為200℃。作為所述溫度的上限,較佳為550℃,更佳為450℃,進而佳為300℃。作為所形成的含矽膜的平均厚度的下限,較佳為1 nm,更佳為10 nm,進而佳為20 nm。作為所述平均厚度的上限,較佳為20,000 nm,更佳為1,000 nm,進而佳為100 nm。The lower limit of the temperature at the time of heating the coating film is preferably 90 ° C, more preferably 150 ° C, and still more preferably 200 ° C. The upper limit of the temperature is preferably 550 ° C, more preferably 450 ° C, and still more preferably 300 ° C. The lower limit of the average thickness of the formed ruthenium-containing film is preferably 1 nm, more preferably 10 nm, and still more preferably 20 nm. The upper limit of the average thickness is preferably 20,000 nm, more preferably 1,000 nm, and still more preferably 100 nm.
<含矽膜圖案化步驟> 本步驟中,對所述含矽膜進行圖案化。藉由本步驟,含矽膜形成步驟中所形成的含矽膜經圖案化。作為對含矽膜進行圖案化的方法,例如可列舉包括抗蝕劑圖案形成步驟及含矽膜蝕刻步驟的方法。<Phase-containing film patterning step> In this step, the ruthenium-containing film is patterned. By this step, the ruthenium-containing film formed in the ruthenium-containing film formation step is patterned. As a method of patterning the ruthenium-containing film, for example, a method including a resist pattern forming step and a ruthenium-containing film etching step may be mentioned.
[抗蝕劑圖案形成步驟] 本步驟中,於所述含矽膜的上側形成抗蝕劑圖案。藉由本步驟,於含矽膜形成步驟中所形成的含矽膜的上側形成有抗蝕劑圖案。作為形成抗蝕劑圖案的方法,例如可列舉使用抗蝕劑組成物的方法、使用奈米壓印微影法的方法等的先前公知的方法等。所述抗蝕劑圖案通常由有機材料形成。[Resist Pattern Forming Step] In this step, a resist pattern is formed on the upper side of the ruthenium containing film. By this step, a resist pattern is formed on the upper side of the ruthenium-containing film formed in the ruthenium-containing film formation step. Examples of the method of forming the resist pattern include a conventionally known method such as a method using a resist composition, a method using a nanoimprint lithography method, and the like. The resist pattern is usually formed of an organic material.
作為使用抗蝕劑組成物的方法,例如可列舉如下方法等,其包括:藉由抗蝕劑組成物而於所述含含矽膜的上側形成抗蝕劑膜的步驟(以下,亦稱為「抗蝕劑膜形成步驟」);對所述抗蝕劑膜進行曝光的步驟(以下,亦稱為「曝光步驟」);以及對所述經曝光的抗蝕劑膜進行顯影的步驟(以下,亦稱為「顯影步驟」)。As a method of using the resist composition, for example, a method of forming a resist film on the upper side of the ruthenium-containing film by a resist composition (hereinafter, also referred to as a "resist film forming step"); a step of exposing the resist film (hereinafter also referred to as "exposure step"); and a step of developing the exposed resist film (hereinafter Also known as the "development step").
(抗蝕劑膜形成步驟) 本步驟中,藉由抗蝕劑組成物而於所述含矽膜的上側形成抗蝕劑膜。藉由本步驟而於含矽膜的上側形成抗蝕劑膜。(Resist Film Forming Step) In this step, a resist film is formed on the upper side of the ruthenium-containing film by a resist composition. A resist film is formed on the upper side of the ruthenium containing film by this step.
作為抗蝕劑組成物,例如可列舉:含有具有酸解離性基的聚合物及感放射線性酸產生劑的感放射線性樹脂組成物(化學增幅型抗蝕劑組成物)、包含鹼可溶性樹脂與醌二疊氮化物系感光劑的正型抗蝕劑組成物、含有鹼可溶性樹脂與交聯劑的負型抗蝕劑組成物等。該些中,較佳為感放射線性樹脂組成物。於使用感放射線性樹脂組成物的情況下,藉由利用鹼性顯影液進行顯影,可形成正型圖案,藉由利用有機溶媒顯影液進行顯影,可形成負型圖案。於形成抗蝕劑圖案時,亦可適宜使用作為形成微細圖案的方法的雙重圖案(double patterning)法、雙重曝光(double exposure)法等。Examples of the resist composition include a radiation-sensitive resin composition (chemically amplified resist composition) containing a polymer having an acid-dissociable group and a radiation-sensitive acid generator, and an alkali-soluble resin and A positive resist composition of a quinone diazide-based sensitizer, a negative resist composition containing an alkali-soluble resin and a crosslinking agent, and the like. Among these, a radiation sensitive resin composition is preferred. In the case of using a radiation sensitive resin composition, a positive pattern can be formed by development with an alkaline developer, and a negative pattern can be formed by development with an organic solvent developer. When forming a resist pattern, a double patterning method, a double exposure method, or the like as a method of forming a fine pattern may be suitably used.
感放射線性樹脂組成物中含有的聚合物除了包含酸解離性基的結構單元以外,亦可具有例如包含內酯結構、環狀碳酸酯結構及/或磺內酯結構的結構單元、包含醇性羥基的結構單元、包含酚性羥基的結構單元、包含氟原子的結構單元等。若所述聚合物具有包含酚性羥基的結構單元及/或包含氟原子的結構單元,則可提高於使用極紫外線(EUV)、電子束等作為曝光中的放射線時的感度。The polymer contained in the radiation sensitive resin composition may have, for example, a structural unit including a lactone structure, a cyclic carbonate structure, and/or a sultone structure, in addition to a structural unit containing an acid dissociable group, and an alcoholic property. A structural unit of a hydroxyl group, a structural unit containing a phenolic hydroxyl group, a structural unit containing a fluorine atom, and the like. When the polymer has a structural unit containing a phenolic hydroxyl group and/or a structural unit containing a fluorine atom, sensitivity when using extreme ultraviolet rays (EUV), an electron beam, or the like as radiation during exposure can be improved.
作為抗蝕劑組成物的固體成分濃度的下限,較佳為0.1質量%,較佳為1質量%。作為所述固體成分濃度的上限,較佳為50質量%,更佳為30質量%。作為抗蝕劑組成物,可較佳地使用利用孔徑0.2 μm左右的過濾器進行了過濾的抗蝕劑組成物。於該圖案形成方法中,亦可直接使用市售品的抗蝕劑組成物作為抗蝕劑組成物。The lower limit of the solid content concentration of the resist composition is preferably 0.1% by mass, preferably 1% by mass. The upper limit of the solid content concentration is preferably 50% by mass, and more preferably 30% by mass. As the resist composition, a resist composition which is filtered by a filter having a pore size of about 0.2 μm can be preferably used. In the pattern forming method, a resist composition of a commercially available product can be directly used as a resist composition.
作為抗蝕劑膜的形成方法,例如可列舉將抗蝕劑組成物塗敷於含矽膜上的方法等。作為抗蝕劑組成物的塗敷方法,例如可列舉旋轉塗敷法等先前的方法等。於塗敷抗蝕劑組成物時,以所得的抗蝕劑膜成為既定膜厚的方式調整所塗敷的抗蝕劑組成物的量。As a method of forming the resist film, for example, a method of applying a resist composition to a ruthenium-containing film or the like can be mentioned. The coating method of the resist composition is, for example, a conventional method such as a spin coating method. When the resist composition is applied, the amount of the applied resist composition is adjusted such that the obtained resist film has a predetermined film thickness.
關於抗蝕劑膜,可對抗蝕劑組成物的塗膜進行預烘烤,藉此使塗膜中的溶媒揮發而形成抗蝕劑膜。預烘烤的溫度是根據所使用的抗蝕劑組成物的種類等而適宜調整,作為預烘烤的溫度的下限,較佳為30℃,更佳為50℃。作為所述溫度的上限,較佳為200℃,更佳為150℃。Regarding the resist film, the coating film of the resist composition can be pre-baked, whereby the solvent in the coating film is volatilized to form a resist film. The prebaking temperature is appropriately adjusted depending on the type of the resist composition to be used and the like, and the lower limit of the prebaking temperature is preferably 30 ° C, more preferably 50 ° C. The upper limit of the temperature is preferably 200 ° C, more preferably 150 ° C.
(曝光步驟) 本步驟中,對所述抗蝕劑膜進行曝光。所述曝光例如是藉由透過光罩而選擇性地照射放射線而進行。(Exposure Step) In this step, the resist film is exposed. The exposure is performed, for example, by selectively irradiating radiation through a reticle.
用於曝光的放射線是根據抗蝕劑組成物中使用的酸產生劑的種類等而自可見光線、紫外線、遠紫外線、X射線、γ射線等電磁波、電子束、分子束、離子束等粒子束中適當選擇,該些中,較佳為遠紫外線及電子束,更佳為KrF準分子雷射光(248 nm)、ArF準分子雷射光(193 nm)、F2 準分子雷射光(波長157 nm)、Kr2 準分子雷射光(波長147 nm)、ArKr準分子雷射光(波長134 nm)、EUV(波長13 nm等)及電子束,進而佳為ArF準分子雷射光、EUV及電子束。另外,曝光的方法亦無特別限定,可依據先前公知的圖案形成中進行的方法而進行。The radiation used for exposure is a particle beam such as an electromagnetic wave such as a visible ray, an ultraviolet ray, a far ultraviolet ray, an X ray or a gamma ray, an electron beam, a molecular beam, or an ion beam, depending on the type of the acid generator used in the resist composition. Suitable choices, among them, far ultraviolet and electron beams, more preferably KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F 2 excimer laser light (wavelength 157 nm) ), Kr 2 excimer laser light (wavelength 147 nm), ArKr excimer laser light (wavelength 134 nm), EUV (wavelength 13 nm, etc.) and electron beam, and thus ArF excimer laser light, EUV and electron beam. Further, the method of exposure is not particularly limited, and it can be carried out according to a method previously performed in pattern formation.
(顯影步驟) 本步驟中,對所述經曝光的抗蝕劑膜進行顯影。藉此,形成抗蝕劑圖案。(Developing Step) In this step, the exposed resist film is developed. Thereby, a resist pattern is formed.
所述顯影可為鹼顯影,亦可為有機溶媒顯影。The development may be an alkali development or an organic solvent development.
作為鹼性顯影液,例如可列舉使氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨、乙基胺、正丙基胺、二乙基胺、二-正丙基胺、三乙基胺、甲基二乙基胺、二甲基乙醇胺、三乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、吡咯、哌啶、膽鹼、1,8-二氮雜雙環[5.4.0]-7-十一烯、1,5-二氮雜雙環[4.3.0]-5-壬烯等鹼性化合物中的至少一種溶解而成的鹼性水溶液等。另外,該些鹼性水溶液亦可為適量添加有例如甲醇、乙醇等醇類等水溶性有機溶媒、界面活性劑等的鹼性水溶液。Examples of the alkaline developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propyl. Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-di An aqueous alkaline solution obtained by dissolving at least one of a basic compound such as azabicyclo[5.4.0]-7-undecene or 1,5-diazabicyclo[4.3.0]-5-decene. Further, the alkaline aqueous solution may be an alkaline aqueous solution in which a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant is added in an appropriate amount.
作為有機溶媒顯影液,例如可列舉:以酮系溶媒、醇系溶媒、醯胺系溶媒、醚系溶媒、酯系溶媒等有機溶媒為主成分的溶液等。該些溶媒例如可列舉與作為所述[B]溶媒而例示的各溶媒相同的溶媒等。該些溶媒可為單獨一種,亦可混合使用多種。The organic solvent developing solution may, for example, be a solution containing an organic solvent such as a ketone solvent, an alcohol solvent, a guanamine solvent, an ether solvent or an ester solvent as a main component. Examples of the solvent include the same solvent as each of the solvents exemplified as the solvent (B). These solvents may be used singly or in combination of two or more.
於利用顯影液進行顯影後,較佳為進行清洗、乾燥,藉此可形成與光罩相對應的既定的抗蝕劑圖案。After development by a developing solution, it is preferable to carry out washing and drying, whereby a predetermined resist pattern corresponding to the mask can be formed.
[含矽膜蝕刻步驟] 本步驟中,將所述抗蝕劑圖案作為遮罩,對所述含矽膜進行蝕刻。更具體而言,藉由將所述抗蝕劑圖案形成步驟中形成的抗蝕劑圖案作為遮罩的一次或多次蝕刻,而獲得形成有圖案的含矽膜。[Antimony Film Etching Step] In this step, the resist pattern is used as a mask, and the germanium containing film is etched. More specifically, the patterned ruthenium-containing film is obtained by etching the resist pattern formed in the resist pattern forming step one or more times as a mask.
所述蝕刻可為乾式蝕刻,亦可為濕式蝕刻,但較佳為乾式蝕刻。The etching may be dry etching or wet etching, but is preferably dry etching.
乾式蝕刻例如可使用公知的乾式蝕刻裝置而進行。作為乾式蝕刻中使用的蝕刻氣體,可藉由被蝕刻的含矽膜的元素組成等適宜選擇,例如可使用:CHF3 、CF4 、C2 F6 、C3 F8 、SF6 等氟系氣體;Cl2 、BCl3 等氯系氣體;O2 、O3 、H2 O等氧系氣體;H2 、NH3 、CO、CO2 、CH4 、C2 H2 、C2 H4 、C2 H6 、C3 H4 、C3 H6 、C3 H8 、HF、HI、HBr、HCl、NO、NH3 、BCl3 等還原性氣體;He、N2 、Ar等惰性氣體等。該些氣體亦可混合使用。含矽膜的乾式蝕刻時,通常使用氟系氣體,可較佳地使用於其中混合有氧系氣體及惰性氣體的氣體。Dry etching can be performed, for example, using a known dry etching apparatus. The etching gas used in the dry etching can be suitably selected by the element composition of the ruthenium-containing film to be etched, and, for example, fluorine compounds such as CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 , and SF 6 can be used. a gas; a chlorine-based gas such as Cl 2 or BCl 3 ; an oxygen-based gas such as O 2 , O 3 or H 2 O; H 2 , NH 3 , CO, CO 2 , CH 4 , C 2 H 2 , C 2 H 4 , Reducing gases such as C 2 H 6 , C 3 H 4 , C 3 H 6 , C 3 H 8 , HF, HI, HBr, HCl, NO, NH 3 , BCl 3 ; inert gases such as He, N 2 , Ar, etc. . These gases can also be used in combination. In the dry etching of the ruthenium-containing film, a fluorine-based gas is usually used, and a gas in which an oxygen-based gas and an inert gas are mixed is preferably used.
<基板蝕刻步驟> 本步驟中,將所述進行了圖案化的含矽膜作為遮罩並對基板進行蝕刻。更具體而言,進行一次或多次蝕刻,而獲得進行了圖案化的基板,其中所述蝕刻以形成於所述含矽膜蝕刻步驟中所獲得的含矽膜上的圖案作為遮罩。<Substrate Etching Step> In this step, the patterned germanium-containing film is used as a mask and the substrate is etched. More specifically, one or more etchings are performed to obtain a patterned substrate, wherein the etching is performed as a mask with a pattern formed on the ruthenium-containing film obtained in the ruthenium-containing film etching step.
於在基板上形成有機下層膜的情況下,將含矽膜圖案作為遮罩並對有機下層膜進行蝕刻,藉此形成有機下層膜的圖案,然後將所述有機下層膜圖案作為遮罩並對基板進行蝕刻,藉此於基板上形成圖案。In the case where an organic underlayer film is formed on the substrate, the ruthenium-containing film pattern is used as a mask and the organic underlayer film is etched, thereby forming a pattern of the organic underlayer film, and then the organic underlayer film pattern is used as a mask and The substrate is etched to form a pattern on the substrate.
所述蝕刻可為乾式蝕刻,亦可為濕式蝕刻,但較佳為乾式蝕刻。The etching may be dry etching or wet etching, but is preferably dry etching.
於有機下層膜上形成圖案時的乾式蝕刻可使用公知的乾式蝕刻裝置而進行。作為乾式蝕刻中使用的蝕刻氣體,可藉由含氣體矽膜及被蝕刻的有機下層膜的元素組成等適宜選擇,例如可使用:CHF3 、CF4 、C2 F6 、C3 F8 、SF6 等氟系氣體;Cl2 、BCl3 等氯系氣體;O2 、O3 、H2 O等氧系氣體;H2 、NH3 、CO、CO2 、CH4 、C2 H2 、C2 H4 、C2 H6 、C3 H4 、C3 H6 、C3 H8 、HF、HI、HBr、HCl、NO、NH3 、BCl3 等還原性氣體;He、N2 、Ar等惰性氣體等,該些氣體亦可混合而使用。將含矽膜的圖案作為遮罩的有機下層膜的乾式蝕刻通常使用氧系氣體。The dry etching in forming a pattern on the organic underlayer film can be carried out using a known dry etching apparatus. The etching gas used in the dry etching can be suitably selected by an elemental composition of the gas-containing tantalum film and the organic underlayer film to be etched, and examples thereof include CHF 3 , CF 4 , C 2 F 6 , and C 3 F 8 . a fluorine-based gas such as SF 6 ; a chlorine-based gas such as Cl 2 or BCl 3 ; an oxygen-based gas such as O 2 , O 3 or H 2 O; H 2 , NH 3 , CO, CO 2 , CH 4 or C 2 H 2 , Reducing gases such as C 2 H 4 , C 2 H 6 , C 3 H 4 , C 3 H 6 , C 3 H 8 , HF, HI, HBr, HCl, NO, NH 3 , BCl 3 ; He, N 2 , An inert gas such as Ar may be used in combination. An oxygen-based gas is usually used for dry etching of an organic underlayer film in which a pattern containing a ruthenium film is used as a mask.
將有機下層膜圖案作為遮罩而於基板上形成圖案時的乾式蝕刻可使用公知的乾式蝕刻裝置而進行。作為乾式蝕刻中使用的蝕刻氣體,可藉由有機下層膜及被蝕刻的基板的元素組成等適宜選擇,例如可列舉與作為所述有機下層膜的乾式蝕刻中使用的蝕刻氣體而例示者為相同的蝕刻氣體等。亦可藉由多次不同的蝕刻氣體進行蝕刻。再者,於基板圖案形成步驟後,於基板上、抗蝕劑下層圖案上等殘留含矽膜的情況下,藉由進行後述的含矽膜去除步驟,可去除含矽膜。The dry etching in the case where the organic underlayer film pattern is patterned as a mask on a substrate can be performed using a known dry etching apparatus. The etching gas used for the dry etching can be appropriately selected by the elemental composition of the organic underlayer film and the substrate to be etched, and the like, for example, the same as the etching gas used for the dry etching of the organic underlayer film. Etching gas, etc. Etching can also be performed by multiple different etching gases. Further, in the case where the ruthenium-containing film remains on the substrate or the resist underlayer pattern after the substrate pattern forming step, the ruthenium-containing film can be removed by performing the ruthenium-containing film removal step to be described later.
<含矽膜去除步驟> 本步驟中,於所述含矽膜形成步驟後去除所述含矽膜。於在所述基板蝕刻步驟後進行本步驟的情況下,殘存於基板的上側的含矽膜被去除。另外,亦可對所述基板蝕刻步驟前的進行了圖案化或未進行圖案化的含矽膜進行本步驟。即,例如於在含矽膜的形成中產生不良情況的情況下,或者所述基板蝕刻步驟前的經圖案化的含矽膜產生不良情況的情況下,藉由進行本步驟,可不使基板廢棄而自含矽膜形成步驟再次重新進行。<The film containing ruthenium removal step> In this step, the ruthenium-containing film is removed after the ruthenium-containing film formation step. When this step is performed after the substrate etching step, the ruthenium containing film remaining on the upper side of the substrate is removed. Further, this step may be performed on the ruthenium-containing film which has been patterned or unpatterned before the substrate etching step. That is, for example, in the case where a defect occurs in the formation of the ruthenium-containing film, or in the case where the patterned ruthenium-containing film before the substrate etching step is defective, by performing this step, the substrate can be discarded. The self-containing ruthenium film forming step is repeated again.
作為去除所述含矽膜的方法,例如可列舉:對所述含矽膜進行乾式蝕刻的方法、使鹼性液或酸性液等液體與所述含矽膜接觸的方法等。作為所述液體,較佳為鹼性液體。Examples of the method for removing the ruthenium-containing film include a method of dry etching the ruthenium-containing film, a method of bringing a liquid such as an alkaline solution or an acidic liquid into contact with the ruthenium-containing film, and the like. As the liquid, an alkaline liquid is preferred.
所述乾式蝕刻可使用公知的乾式蝕刻裝置而進行。另外,作為乾式蝕刻時的源氣體,例如可使用:CHF3 、CF4 、C2 F6 、C3 F8 、SF6 等氟系氣體;Cl2 、BCl3 等氯系氣體等,該些氣體亦可混合而使用。The dry etching can be performed using a well-known dry etching apparatus. Further, as the source gas in the dry etching, for example, a fluorine-based gas such as CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 or SF 6 or a chlorine-based gas such as Cl 2 or BCl 3 can be used. Gas can also be mixed and used.
作為所述鹼性液,可列舉鹼性過氧化氫水等。更具體而言,尤佳為氨及過氧化氫的混合水溶液(25質量%氨水溶液/30質量%過氧化氫水溶液/水=1/2/40(質量比)混合水溶液(SC1))。於使用鹼性過氧化氫水的情況下,作為濕式剝離的方法,若為含矽膜與鹼性過氧化氫水等可於加熱條件下接觸一定時間的方法,則並無特別限定,例如可列舉:將具有含矽膜的基板浸漬於進行了加熱的鹼性過氧化氫水中的方法、於加熱環境下吹附鹼性過氧化氫水的方法、塗敷進行了加熱的鹼性過氧化氫水的方法等。可於該些的各方法後對基板進行水洗,並進行乾燥。Examples of the alkaline liquid include alkaline hydrogen peroxide water and the like. More specifically, a mixed aqueous solution of ammonia and hydrogen peroxide (25% by mass aqueous ammonia solution/30% by mass aqueous hydrogen peroxide solution/water=1/2/40 (mass ratio) mixed aqueous solution (SC1)) is preferable. In the case of using alkaline hydrogen peroxide water, the wet-peeling method is not particularly limited as long as it is a method in which a ruthenium-containing film and alkaline hydrogen peroxide water can be contacted under heating for a certain period of time, for example, for example. A method of immersing a substrate having a ruthenium-containing film in heated alkaline hydrogen peroxide water, a method of blowing alkaline hydrogen peroxide water in a heating environment, and applying a heated alkaline peroxidation Hydrogen water method, etc. The substrate may be washed with water and dried after each of the methods.
作為使用鹼性過氧化氫水進行含矽膜去除步驟時的溫度的下限,較佳為40℃,更佳為50℃。作為所述溫度的上限,較佳為90℃,更佳為80℃。The lower limit of the temperature at which the ruthenium-containing film removal step is carried out using alkaline hydrogen peroxide water is preferably 40 ° C, more preferably 50 ° C. The upper limit of the temperature is preferably 90 ° C, more preferably 80 ° C.
作為浸漬方法中的浸漬時間的下限,較佳為0.2分鐘,更佳為0.5分鐘。作為所述浸漬時間的上限,就抑制對基板的影響的觀點而言,較佳為30分鐘,更佳為20分鐘,進而佳為10分鐘,尤佳為5分鐘。 [實施例]The lower limit of the immersion time in the immersion method is preferably 0.2 minutes, more preferably 0.5 minutes. The upper limit of the immersion time is preferably 30 minutes, more preferably 20 minutes, and still more preferably 10 minutes, and particularly preferably 5 minutes, from the viewpoint of suppressing the influence on the substrate. [Examples]
以下,對實施例進行說明。再者,以下所示的實施例表示本發明的具代表性的實施例的一例,並不由此而狹隘地解釋本發明的範圍。Hereinafter, examples will be described. Further, the examples shown below show an example of a representative embodiment of the present invention, and the scope of the present invention is not construed as narrowly.
本實施例中的[A]聚矽氧烷的溶液中的固體成分濃度的測定及[A]聚矽氧烷的重量平均分子量(Mw)的測定是藉由下述方法而進行。The measurement of the solid content concentration in the solution of [A] polyoxane in the present example and the measurement of the weight average molecular weight (Mw) of [A] polyoxyalkylene were carried out by the following methods.
[[A]聚矽氧烷的溶液的固體成分濃度] 將0.5 g[A]聚矽氧烷的溶液於250℃下煅燒30分鐘,藉此測定所述溶液0.5 g中的固體成分的質量,算出[A]聚矽氧烷的溶液的固體成分濃度(質量%)。[[A] Solid Content Concentration of Solution of Polyoxane] A solution of 0.5 g of [A] polyoxane was calcined at 250 ° C for 30 minutes, thereby measuring the mass of the solid component in 0.5 g of the solution. The solid content concentration (% by mass) of the solution of [A] polyoxane was calculated.
[重量平均分子量(Mw)] 使用GPC管柱(東曹(Tosoh)公司的「G2000HXL」2根、「G3000HXL」1根、「G4000HXL」1根),於流量:1.0 mL/min、溶出溶媒:四氫呋喃、管柱溫度:40℃的分析條件下,藉由以單分散聚苯乙烯作為標準的凝膠滲透層析(檢測器:示差折射計)而測定。[Weight average molecular weight (Mw)] GPC column (2 pieces of "G2000HXL" from Tosoh, 1 "G3000HXL", and 1 "G4000HXL") were used, and the flow rate was 1.0 mL/min, and the solvent was dissolved: Tetrahydrofuran, column temperature: 40 ° C under analytical conditions, determined by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard.
[膜的平均厚度] 膜的平均厚度是使用分光橢圓偏振計(J.A.沃蘭姆(J. A. WOOLLAM)公司的「M2000D」)來測定。[Average Thickness of Film] The average thickness of the film was measured using a spectroscopic ellipsometer ("M2000D" by J.A. WOOLLAM).
<[A]聚矽氧烷的合成> 以下示出用於合成[A]聚矽氧烷的單體。 再者,於以下的合成例中,只要事先無特別說明,則質量份是指將所使用的單體的合計質量設為100質量份時的值。<Synthesis of [A] Polyoxane> The monomer for synthesizing [A] polyoxane is shown below. In the following synthesis examples, the mass parts are values when the total mass of the monomers to be used is 100 parts by mass, unless otherwise specified.
[化13] [Chemistry 13]
[化14] [Chemistry 14]
[合成例1](聚矽氧烷(A-1)的合成) 於反應容器中,將所述式(M-1)所表示的化合物、所述式(M-A1)所表示的化合物及所述式(M-A2)所表示的化合物以莫耳比率成為10/75/15(莫耳%)的方式溶解於丙二醇單***62質量份中,來製備單體溶液。將所述反應容器內設為60℃,一面進行攪拌,一面花20分鐘滴加9.1質量%乙二酸水溶液40質量份。將滴加開始設為反應的開始時間,實施4小時反應。反應結束後,將反應容器內冷卻至30℃以下。將52質量份丙二醇單***添加至進行了冷卻的反應溶液中後,使用蒸發器將藉由反應而生成的醇及剩餘的丙二醇單***去除,而獲得聚矽氧烷(A-1)的丙二醇單***溶液。聚矽氧烷(A-1)的Mw為1,800。所述聚矽氧烷(A-1)的丙二醇單***溶液的固體成分濃度為10.7質量%。[Synthesis Example 1] (Synthesis of Polyoxane (A-1)) The compound represented by the formula (M-1), the compound represented by the formula (M-A1), and the compound in the reaction container The compound represented by the formula (M-A2) was dissolved in 62 parts by mass of propylene glycol monoethyl ether so that the molar ratio became 10/75/15 (mol%) to prepare a monomer solution. While the inside of the reaction vessel was stirred at 60 ° C, 40 parts by mass of a 9.1% by mass aqueous solution of oxalic acid was added dropwise over 20 minutes. The start of the dropwise addition was set as the start time of the reaction, and the reaction was carried out for 4 hours. After completion of the reaction, the inside of the reaction vessel was cooled to 30 ° C or lower. After 52 parts by mass of propylene glycol monoethyl ether was added to the cooled reaction solution, the alcohol formed by the reaction and the remaining propylene glycol monoethyl ether were removed using an evaporator to obtain propylene glycol of polyoxyalkylene (A-1). A solution of diethyl ether. The Mw of the polyoxyalkylene (A-1) was 1,800. The solid content concentration of the propylene glycol monoethyl ether solution of the polyoxyalkylene (A-1) was 10.7% by mass.
[合成例2~合成例22](聚矽氧烷(A-2)~聚矽氧烷(A-20)及聚矽氧烷(a-1)及聚矽氧烷(a-2)的合成) 除了使用下述表1所示的種類及使用量的各單體以外,與合成例1同樣地獲得聚矽氧烷(A-2)~聚矽氧烷(A-20)及聚矽氧烷(a-1)及聚矽氧烷(a-2)的丙二醇單***溶液。將所得的[A]聚矽氧烷的溶液中的[A]聚矽氧烷的Mw及固體成分濃度(質量%)一併示於表1中。[Synthesis Example 2 to Synthesis Example 22] (polyoxane (A-2) to polyoxyalkylene (A-20) and polyoxyalkylene (a-1) and polyoxyalkylene (a-2) Synthesis) Polyoxane (A-2) to polyoxane (A-20) and polyfluorene were obtained in the same manner as in Synthesis Example 1 except that each of the types and amounts of the monomers shown in Table 1 below were used. A solution of oxyalkylene (a-1) and polydecane (a-2) in propylene glycol monoethyl ether. Table 1 shows the Mw of the [A] polyoxane in the obtained solution of the polyoxoxane and the solid content concentration (% by mass).
[表1]
<含矽膜形成用組成物的製備> 以下示出用於製備含矽膜形成用組成物的[A]聚矽氧烷以外的成分。<Preparation of a composition for forming a ruthenium film> A component other than the [A] polysiloxane which is used for preparing a composition for forming a ruthenium film is shown below.
[[B]溶媒] B-1:丙二醇單甲醚乙酸酯 B-2:丙二醇單***[[B] solvent] B-1: propylene glycol monomethyl ether acetate B-2: propylene glycol monoethyl ether
[實施例1] 將2.2質量份的作為[A]聚矽氧烷(固體成分)的(A-1)、作為[B]溶媒的(B-1)10質量份及(B-2)90質量份(亦包含[A]聚矽氧烷的溶液中所含的溶媒(B-2))混合,利用孔徑0.2 μm的過濾器對所得的溶液進行過濾,而製備含矽膜形成用組成物(J-1)。[Example 1] 2.2 parts by mass of (A-1) as [A] polyoxyalkylene (solid component), (B-1) 10 parts by mass of [B] solvent, and (B-2) 90 The mass fraction (also including the solvent (B-2) contained in the solution of [A] polyoxane) was mixed, and the obtained solution was filtered using a filter having a pore size of 0.2 μm to prepare a composition for forming a ruthenium-containing film. (J-1).
[實施例2~實施例20以及比較例1及比較例2] 除了使用下述表2所示的種類及調配量的各成分以外,與實施例1同樣地製備含矽膜形成用組成物(J-2)~含矽膜形成用組成物(J-20)及含矽膜形成用組成物(j-1)及含矽膜形成用組成物(j-2)。[Example 2 to Example 20, Comparative Example 1 and Comparative Example 2] A composition for forming a ruthenium-containing film was prepared in the same manner as in Example 1 except that each component of the type and the amount of the formulation shown in Table 2 below was used. J-2) to a composition for forming a ruthenium-containing film (J-20), a composition for forming a ruthenium-containing film (j-1), and a composition for forming a ruthenium-containing film (j-2).
<含矽膜的形成> 使用旋塗機(東京電子(Tokyo Electron)公司的「柯里塔克(CLEAN TRACK)ACT12」),藉由旋轉塗敷法將所述製備的各含矽膜形成用組成物塗敷於矽晶圓(基板)上。利用220℃的加熱板對所得的塗膜進行60秒加熱後,於23℃下冷卻60秒,藉此獲得表2的實施例1~實施例20以及比較例1及比較例2所示的形成有平均厚度35 nm的含矽膜的基板。<Formation of ruthenium-containing film> The prepared ruthenium-containing film was formed by a spin coating method using a spin coater ("CLEAN TRACK ACT12" by Tokyo Electron Co., Ltd.) The composition is applied to a tantalum wafer (substrate). The obtained coating film was heated by a hot plate at 220 ° C for 60 seconds, and then cooled at 23 ° C for 60 seconds, thereby obtaining the formations shown in Examples 1 to 20 of Table 2, and Comparative Example 1 and Comparative Example 2. A ruthenium-containing substrate having an average thickness of 35 nm.
<評價> 藉由下述方法來評價所述製備的含矽膜形成用組成物及所述形成的含矽膜的下述項目。將評價結果一併示於下述表2中。表2中的「-」表示不進行相應的評價。<Evaluation> The following items of the prepared ruthenium-containing film-forming composition and the formed ruthenium-containing film were evaluated by the following methods. The evaluation results are shown together in Table 2 below. The "-" in Table 2 indicates that the corresponding evaluation is not performed.
[對鹼性顯影液的耐性] 將形成有所述含矽膜的基板於2.38質量%氫氧化四甲基銨(TMAH)水溶液(20℃~25℃)中浸漬60秒,利用水進行清洗。測定浸漬前後的膜的平均厚度。 於將浸漬前的平均厚度設為T0 、浸漬後的平均厚度設為T1 的情況下,藉由下述式求出由TMAH水溶液浸漬所致的膜厚變化率(%)。 膜厚變化率(%)=│T1 -T0 │×100/T0 關於對鹼性顯影液的耐性,將膜厚變化率未滿1%的情形評價為「A」(良好),且將1%以上的情形評價為「B」(不良)。[Resistance to Alkaline Developer] The substrate on which the ruthenium film was formed was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) (20 ° C to 25 ° C) for 60 seconds, and washed with water. The average thickness of the film before and after the immersion was measured. When the average thickness before immersion was T 0 and the average thickness after immersion was T 1 , the film thickness change rate (%) by immersion in the TMAH aqueous solution was determined by the following formula. Film thickness change rate (%) = │ T 1 - T 0 │ × 100 / T 0 Regarding the resistance to the alkaline developer, the case where the film thickness change rate is less than 1% is evaluated as "A" (good), and The case of 1% or more was evaluated as "B" (bad).
[鹼性過氧化氫水所引起的剝離性] 將形成有所述含矽膜的基板於鹼性過氧化氫水(25質量%氨水溶液/30質量%過氧化氫水溶液/水=1/2/40(質量比)的混合液(SC1)、60℃~65℃)中浸漬5分鐘,利用水進行清洗。測定浸漬前後的膜的平均厚度。 於將浸漬前的平均厚度設為S0 、浸漬後的平均厚度設為S1 的情況下,藉由下述式求出由SC1浸漬所致的膜厚變化率(%)。 膜厚變化率(%)=(S0 -S1 )×100/S0 關於鹼性過氧化氫水所引起的剝離性,將膜厚變化率為99%以上的情形評價為「A」(良好),將未滿99%的情形評價為「B」(不良)。[Removability by Alkaline Hydrogen Peroxide Water] The substrate containing the ruthenium-containing film is formed in alkaline hydrogen peroxide water (25% by mass aqueous ammonia solution/30% by mass aqueous hydrogen peroxide solution/water = 1/2) The mixture was immersed in a /40 (mass ratio) mixed solution (SC1) at 60 ° C to 65 ° C for 5 minutes, and washed with water. The average thickness of the film before and after the immersion was measured. When the average thickness before immersion is S 0 and the average thickness after immersion is S 1 , the film thickness change rate (%) due to immersion in SC1 is obtained by the following formula. Film thickness change rate (%) = (S 0 - S 1 ) × 100 / S 0 Regarding the peeling property by alkaline hydrogen peroxide water, the case where the film thickness change rate is 99% or more is evaluated as "A" ( Good), the case of less than 99% is evaluated as "B" (bad).
[塌壞抑制性(1)](ArF曝光中的抗蝕劑圖案的塌壞抑制性) 藉由使用所述旋塗機的旋轉塗敷法將有機下層膜形成用組成物(捷時雅(JSR)公司的「NFC HM8006」)塗敷於12吋矽晶圓上後,於250℃下進行60秒加熱處理,形成平均厚度100 nm的有機下層膜。藉由使用所述旋塗機的旋轉塗敷法將所述獲得的含矽膜形成用組成物塗敷於所述有機下層膜上,於220℃下進行60秒加熱處理後,於23℃下冷卻60秒,藉此形成平均厚度35 nm的含矽膜。繼而,藉由所述旋塗機將感放射線性樹脂組成物(捷時雅(JSR)公司的「ARF AR2772JN」)塗敷於該含矽膜上,於90℃下進行60秒加熱處理後,於23℃下冷卻30秒,藉此形成平均厚度100 nm的抗蝕劑膜。 繼而,使用ArF液浸曝光裝置(尼康(NIKON)公司的「S610C」),於NA:1.30、Dipole的光學條件下,介隔40 nm線/80 nm間距形成用的遮罩尺寸的遮罩進行曝光。於「里迪斯(Lithius)Pro-i」的加熱板上於100℃下進行60秒加熱處理,於23℃下冷卻30秒後,將2.38質量%TMAH水溶液作為顯影液進行30秒覆液顯影,利用水進行清洗。以2,000 rpm進行15秒旋轉乾燥,藉此獲得形成有40 nm線/80 nm間距的抗蝕劑圖案的評價用基板。 所述評價用基板的抗蝕劑圖案的測長及觀察時,使用掃描式電子顯微鏡(日立高新技術(Hitachi High-technologies)公司的「CG-4000」)。 於所述抗蝕劑圖案的形成中,階段性地增加曝光量並依次進行曝光,將與未確認到抗蝕劑圖案的塌壞的最大曝光量相對應的線寬定義為最小塌壞前尺寸(nm)而作為抗蝕劑圖案的塌壞抑制性的指標。關於塌壞抑制性(1),將最小塌壞前尺寸為32 nm以下的情形評價為「A」(良好),將超過32 nm且為38 nm以下的情形評價為「B」(稍良好),將超過38 nm的情形評價為「C」(不良)。[Sacking inhibition property (1)] (slack suppression property of resist pattern in ArF exposure) The composition for forming an organic underlayer film by spin coating using the spin coater (Jie Shiya ( JSR) "NFC HM8006" was applied to a 12-inch wafer and heat-treated at 250 ° C for 60 seconds to form an organic underlayer film having an average thickness of 100 nm. The obtained composition for forming a ruthenium-containing film was applied onto the organic underlayer film by a spin coating method using the spin coater, and subjected to heat treatment at 220 ° C for 60 seconds, at 23 ° C. It was cooled for 60 seconds, thereby forming a ruthenium-containing film having an average thickness of 35 nm. Then, the radiation-sensitive resin composition ("ARF AR2772JN" of JSR Corporation) was applied onto the ruthenium-containing film by the spin coater, and after heat treatment at 90 ° C for 60 seconds, The film was cooled at 23 ° C for 30 seconds, thereby forming a resist film having an average thickness of 100 nm. Then, an ArF immersion exposure apparatus ("S610C" of Nikon Corporation) was used to perform a mask size mask for forming a 40 nm line/80 nm pitch under the optical conditions of NA: 1.30 and Dipole. exposure. After heating on a hot plate of "Lithius Pro-i" at 100 ° C for 60 seconds, and cooling at 23 ° C for 30 seconds, a 2.38 mass % TMAH aqueous solution was used as a developing solution for 30 seconds. Wash with water. The substrate for evaluation was formed by spin drying at 2,000 rpm for 15 seconds, thereby obtaining a resist pattern having a pitch of 40 nm line/80 nm. A scanning electron microscope ("CG-4000" of Hitachi High-technologies Co., Ltd.) was used for the measurement and observation of the resist pattern of the evaluation substrate. In the formation of the resist pattern, the exposure amount is increased stepwise and exposure is sequentially performed, and the line width corresponding to the maximum exposure amount in which the collapse of the resist pattern is not confirmed is defined as the minimum pre-collapse size ( Nm) is used as an indicator of the collapse inhibition property of the resist pattern. Regarding the collapse inhibition property (1), the case where the minimum collapse size is 32 nm or less is evaluated as "A" (good), and the case where the value exceeds 32 nm and is 38 nm or less is evaluated as "B" (slightly good). The case of exceeding 38 nm was evaluated as "C" (bad).
[塌壞抑制性(2)](電子束曝光中的抗蝕劑圖案的塌壞抑制性) 藉由利用所述旋塗機的旋轉塗敷法將抗反射膜形成材料(捷時雅(JSR)公司的「HM8006」)塗敷於8吋矽晶圓上後,於250℃下進行60秒加熱,藉此形成平均厚度100 nm的抗反射膜。將含矽膜形成組成物塗敷於所述抗反射膜上,於220℃下進行60秒加熱後,於23℃下冷卻30秒,藉此形成平均厚度35 nm的含矽膜。 繼而,將後述感放射線性樹脂組成物塗敷於含矽膜上,於130℃下進行60秒加熱處理後,於23℃下冷卻30秒,藉此形成平均厚度50 nm的抗蝕劑膜。 所述感放射線性樹脂組成物藉由如下方式獲得,即,將具有源自4-羥基苯乙烯的結構單元(1)、源自苯乙烯的結構單元(2)及源自4-第三丁氧基苯乙烯的結構單元(3)(各結構單元的含有比例為(1)/(2)/(3)=65/5/30(莫耳%))的聚合物100質量份、作為感放射線性酸產生劑的三苯基鋶水楊酸鹽2.5質量份、與作為溶媒的乳酸乙酯1,500質量份及丙二醇單甲醚乙酸酯700質量份混合,利用孔徑0.2 μm的過濾器對所得的溶液進行過濾。 繼而,使用電子束描繪裝置(日立製作所公司的「HL800D」,輸出功率:50 KeV,電流密度:5.0安培/cm2 )對抗蝕劑膜照射電子束。於電子束的照射後,於110℃下對基板進行60秒加熱,繼而於23℃下冷卻60秒後,使用2.38質量%的TMAH水溶液(20℃~25℃),利用覆液法進行顯影後,利用水進行清洗,進行乾燥,藉此獲得形成有抗蝕劑圖案的評價用基板。 於形成所述抗蝕劑圖案時,將形成於線寬150 nm的1:1線與空間的曝光量設為最佳曝光量。 所述評價用基板的抗蝕劑圖案的測長及觀察時,使用掃描式電子顯微鏡(日立高新技術(Hitachi High-technologies)公司的「CG-4000」)。 關於塌壞抑制性(2),於所述最佳曝光量中,將未確認到圖案塌壞的情形評價為「A」(良好),將確認到圖案塌壞的情形評價為「B」(不良)。[Scatter suppression (2)] (slack suppression of resist pattern in electron beam exposure) Antireflection film forming material by spin coating using the spin coater (JSR) The company's "HM8006" was applied to an 8-inch wafer and heated at 250 ° C for 60 seconds to form an anti-reflection film having an average thickness of 100 nm. The ruthenium-containing film-forming composition was applied onto the anti-reflection film, heated at 220 ° C for 60 seconds, and then cooled at 23 ° C for 30 seconds, thereby forming a ruthenium-containing film having an average thickness of 35 nm. Then, the radiation-sensitive resin composition described later was applied onto a ruthenium-containing film, and heat-treated at 130 ° C for 60 seconds, and then cooled at 23 ° C for 30 seconds to form a resist film having an average thickness of 50 nm. The radiation sensitive resin composition is obtained by having a structural unit derived from 4-hydroxystyrene (1), a structural unit derived from styrene (2), and derived from 4-third 100 parts by mass of the structural unit (3) of oxystyrene (the content ratio of each structural unit is (1) / (2) / (3) = 65 / 5 / 30 (mol%)) 2.5 parts by mass of triphenylsulfonium salicylate of a radioactive acid generator, 1,500 parts by mass of ethyl lactate as a solvent, and 700 parts by mass of propylene glycol monomethyl ether acetate, and a filter having a pore size of 0.2 μm was used. The solution was filtered. Then, the resist film was irradiated with an electron beam using an electron beam drawing device ("HL800D" of Hitachi, Ltd., output: 50 KeV, current density: 5.0 amp/cm 2 ). After the irradiation of the electron beam, the substrate was heated at 110 ° C for 60 seconds, and then cooled at 23 ° C for 60 seconds, and then developed using a 2.38 mass % TMAH aqueous solution (20 ° C to 25 ° C) by a liquid coating method. The substrate for evaluation in which the resist pattern was formed was obtained by washing with water and drying. When the resist pattern is formed, an exposure amount of a 1:1 line and space formed at a line width of 150 nm is set as an optimum exposure amount. A scanning electron microscope ("CG-4000" of Hitachi High-technologies Co., Ltd.) was used for the measurement and observation of the resist pattern of the evaluation substrate. Regarding the collapse inhibition property (2), in the optimum exposure amount, the case where the pattern collapse was not confirmed was evaluated as "A" (good), and the case where the pattern collapse was confirmed was evaluated as "B" (bad) ).
[氟系氣體所引起的蝕刻去除性] 使用蝕刻裝置(東京電子(Tokyo Electron)公司的「塔卡翠絲(TACTRAS)」),於CF4 =200 sccm、PRESS.=75 mT、HF RF=250 W、LF RF=0 W、DCS=-150 V、RDC=50%、5 sec的條件下,對形成有所述獲得的含矽膜的基板進行蝕刻處理,根據處理前後的平均膜厚計算出蝕刻速度(nm/分鐘),評價氟系氣體所引起的蝕刻去除性。關於氟系氣體所引起的蝕刻去除性,將蝕刻速度為60(nm/分鐘)以上的情形評價為「A」(良好),將55(nm/分鐘)以上且未滿60(nm/分鐘)的情形評價為「B」(稍良好),將未滿55(nm/分鐘)的情形評價為「C」(不良)。[Etase removal by fluorine-based gas] Using an etching apparatus (TACTRAS of Tokyo Electron Co., Ltd.), CF 4 = 200 sccm, PRESS. = 75 mT, HF RF = Under the conditions of 250 W, LF RF=0 W, DCS=-150 V, RDC=50%, and 5 sec, the substrate on which the obtained ruthenium-containing film is formed is etched, and is calculated according to the average film thickness before and after the treatment. The etching rate (nm/min) was measured, and the etching removal property by the fluorine-based gas was evaluated. Regarding the etching removal property by the fluorine-based gas, the case where the etching rate is 60 (nm/min) or more is evaluated as "A" (good), and 55 (nm/min) or more and less than 60 (nm/min). The case was evaluated as "B" (slightly good), and the case of less than 55 (nm/min) was evaluated as "C" (bad).
[保存穩定性] 將所述製備的各含矽膜形成用組成物於-15℃及40℃下保管7日後,分別測定組成物中的[A]聚矽氧烷的重量平均分子量(Mw)。關於保存穩定性,將於-15℃下保管後的Mw與40℃下保管後的Mw的差未滿100的情形評價為「A」(良好),將100以上且未滿1,000的情形評價為「B」(稍良好),將1,000以上的情形評價為「C」(不良)。[Storage Stability] The composition for forming a ruthenium-containing film prepared as described above was stored at -15 ° C and 40 ° C for 7 days, and then the weight average molecular weight (Mw) of the [A] polyoxane in the composition was measured. . The storage stability was evaluated as "A" (good) when the difference between the Mw stored at -15 ° C and the Mw stored at 40 ° C was less than 100, and the case where 100 or more and less than 1,000 was evaluated as "B" (slightly good), the case of 1,000 or more was evaluated as "C" (bad).
[表2]
根據表2的結果可知,實施例的含矽膜形成用組成物可形成保存穩定性優異且對鹼性顯影液的耐性及鹼性過氧化氫水所引起的剝離性優異、氟系氣體所引起的蝕刻去除性優異、抗蝕劑圖案的塌壞抑制性優異的含矽膜。 一般來說,已知根據電子束曝光,顯示出與EUV曝光的情況相同的傾向,因此,根據實施例的含矽膜形成用組成物,推測即便於EUV曝光的情況下,抗蝕劑圖案的塌壞抑制性亦優異。 [產業上之可利用性]According to the results of Table 2, the composition for forming a ruthenium-containing film of the examples is excellent in storage stability, excellent in resistance to an alkaline developer, and excellent in peeling property due to alkaline hydrogen peroxide water, and is caused by a fluorine-based gas. A ruthenium-containing film which is excellent in etching removability and excellent in suppressing collapse resistance of a resist pattern. In general, it is known that the electron beam exposure shows the same tendency as in the case of EUV exposure. Therefore, according to the composition for forming a ruthenium film according to the embodiment, it is presumed that even in the case of EUV exposure, the resist pattern is The collapse inhibition is also excellent. [Industrial availability]
根據本發明的含矽膜形成用組成物及圖案形成方法,可形成維持氟系氣體所引起的蝕刻去除性、且抗蝕劑圖案的塌壞抑制性優異的含矽膜,另外,可形成對抗蝕劑圖案形成步驟中的鹼性顯影液的耐性優異且鹼性過氧化氫水所引起的剝離性優異的含矽膜。進而,本發明的含矽膜形成用組成物的保存穩定性亦優異。本發明的含矽膜維持氟系氣體所引起的蝕刻去除性,且對鹼性顯影液的耐性優異且鹼性過氧化氫水所引起的剝離性優異。本發明的聚矽氧烷可較佳地用作該含矽膜形成用組成物的聚矽氧烷成分。因此,該些可較佳地用於多層抗蝕劑製程,可較佳地用於今後預計進一步進行微細化的半導體器件的製造等。According to the ruthenium-containing film-forming composition and the pattern forming method of the present invention, it is possible to form a ruthenium-containing film which is excellent in the etch-eliminability by the fluorine-based gas and has excellent collapse resistance of the resist pattern, and can form a confrontation. The ruthenium-containing film which is excellent in the resistance of the alkaline developing solution in the etchant pattern forming step and excellent in the peeling property by the alkaline hydrogen peroxide water. Further, the composition for forming a ruthenium-containing film of the present invention is also excellent in storage stability. The ruthenium-containing film of the present invention maintains the etching removeability by the fluorine-based gas, and is excellent in resistance to an alkaline developer and excellent in peelability due to alkaline hydrogen peroxide water. The polyoxyalkylene of the present invention can be preferably used as the polyoxymethane component of the composition for forming a ruthenium-containing film. Therefore, these can be preferably used for a multilayer resist process, and can be preferably used for the manufacture of a semiconductor device in which further miniaturization is expected in the future.
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JPH03206461A (en) * | 1990-01-09 | 1991-09-09 | Fuji Photo Film Co Ltd | Photosensitive composition |
GB9124422D0 (en) * | 1991-11-14 | 1992-01-08 | Dow Corning | Radiation curable compositions |
JP4232276B2 (en) * | 1999-05-26 | 2009-03-04 | Jsr株式会社 | Hydrolyzable silane compound and method for producing the same |
JP5581225B2 (en) * | 2008-03-04 | 2014-08-27 | ダウ・コーニング・コーポレイション | Silsesquioxane resin |
JP5237743B2 (en) * | 2008-10-02 | 2013-07-17 | 東京応化工業株式会社 | Composition for forming a resist underlayer film |
WO2012114864A1 (en) * | 2011-02-24 | 2012-08-30 | 日産化学工業株式会社 | Silane compound and composition for formation of monolayer or multilayer using same |
KR102182360B1 (en) * | 2012-12-19 | 2020-11-24 | 닛산 가가쿠 가부시키가이샤 | Composition for forming silicon-containing resist underlayer film having cyclic diester group |
WO2016111210A1 (en) * | 2015-01-09 | 2016-07-14 | Jsr株式会社 | Composition for forming silicon-containing film and pattern forming method using said composition |
JP6455160B2 (en) * | 2015-01-14 | 2019-01-23 | Jsr株式会社 | Radiation-sensitive composition for forming cured film, cured film, display element and method for forming cured film |
-
2018
- 2018-02-19 WO PCT/JP2018/005724 patent/WO2018159356A1/en active Application Filing
- 2018-03-01 TW TW107106814A patent/TW201841998A/en unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11914295B2 (en) | 2018-11-21 | 2024-02-27 | Shin-Etsu Chemical Co., Ltd. | Thermosetting iodine- and silicon-containing material, composition containing the material for forming resist underlayer film for EUV lithography, and patterning process |
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