TWI655235B - Composition for basement membrane formation and self-organizing lithography process - Google Patents

Composition for basement membrane formation and self-organizing lithography process Download PDF

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TWI655235B
TWI655235B TW103145264A TW103145264A TWI655235B TW I655235 B TWI655235 B TW I655235B TW 103145264 A TW103145264 A TW 103145264A TW 103145264 A TW103145264 A TW 103145264A TW I655235 B TWI655235 B TW I655235B
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小松裕之
成岡岳彥
峯岸信也
酒井香織
永井智樹
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日商Jsr股份有限公司
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    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers

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Abstract

發明的目的為提供能夠良好地藉由自我組織化形成相分離構造、且形成矩形的圖型之基底膜形成用組成物。 An object of the present invention is to provide a composition for forming a base film capable of forming a phase-separated structure by self-organization and forming a rectangular pattern.

發明係一種基底膜形成用組成物,其係於自我組織化微影製程中,用以形成配置於含有矽原子之層與自我組織化膜之間的基底膜之組成物,其含有具有可與Si-OH或Si-H反應之基的化合物、及溶劑,且上述基底膜之與純水的後退接觸角為70°以上且90°以下。作為上述化合物,較佳為以下述式(1)表示。式(1)中,A為(m+n)價之連結基。D為碳數10以上之1價有機基。E係可與Si-OH或Si-H反應之基。m及n係分別獨立地為1~200之整數。 The invention relates to a composition for forming a base film, which is used in a self-organizing lithography process to form a base film which is arranged between a layer containing a silicon atom and a self-organizing film. A Si-OH or Si-H-reactive compound, and a solvent, and the receding contact angle of the base film with pure water is 70 ° or more and 90 ° or less. The compound is preferably represented by the following formula (1). In formula (1), A is a (m + n) -valent linking group. D is a monovalent organic group having 10 or more carbon atoms. E is a radical that can react with Si-OH or Si-H. m and n are each independently an integer of 1 to 200.

Description

基底膜形成用組成物及自我組織化微影製程 Composition for basement membrane formation and self-organizing lithography process

本發明係關於基底膜形成用組成物及自我組織化微影製程。 The invention relates to a composition for forming a base film and a self-organizing lithography process.

伴隨著半導體裝置、液晶裝置等之各種電子裝置構造之微細化,要求微影製程中圖型的微細化。目前,例如可使用ArF準分子雷射形成線寬90nm左右的微細圖型,但正要求進一步微細之圖型形成。 Along with the miniaturization of various electronic device structures such as semiconductor devices and liquid crystal devices, the miniaturization of patterns in photolithography processes is required. Currently, for example, an ArF excimer laser can be used to form a fine pattern with a line width of about 90 nm, but further fine pattern formation is required.

對於上述要求,提出了自發地形成有序圖型(ordered pattern)之利用了所謂自我組織化所成之相分離構造的自我組織化微影製程。作為該自我組織化微影製程,已知有使用使具有一性質之單體化合物、及與其性質相異之單體化合物予以共聚合而成的嵌段共聚物,藉由自我組織化來形成超微細圖型之方法(參照日本特開2008-149447號公報、日本特表2002-519728號公報及日本特開2003-218383號公報)。依照此方法,因為係藉由使含有上述嵌段共聚物之膜退火,而使具有相同性質之聚合物構造彼此傾向集結,故可自我整合地形成圖型。又,亦已知 使用含有性質互異之複數聚合物的組成物,藉由使其自我組織化而形成微細圖型之方法(參照美國專利公開2009/0214823號說明書及日本特開2010-58403號公報)。 In response to the above requirements, a self-organized lithography process that spontaneously forms an ordered pattern and uses a phase separation structure formed by a so-called self-organization is proposed. As this self-organizing lithography process, it is known to use a block copolymer obtained by copolymerizing a monomer compound having one property and a monomer compound having a property different from that of the block copolymer. Method of fine pattern (refer to Japanese Patent Application Publication No. 2008-149447, Japanese Patent Application Publication No. 2002-519728, and Japanese Patent Application Publication No. 2003-218383). According to this method, since the film containing the above-mentioned block copolymer is annealed, the polymer structures having the same properties tend to be aggregated with each other, so that a pattern can be formed by self-integration. Also known A method of forming a fine pattern by self-organizing a composition containing a plurality of polymers with mutually different properties (refer to US Patent Publication No. 2009/0214823 and Japanese Patent Application Publication No. 2010-58403).

於該自我組織化微影製程中,已知藉由將含有自我組織化之聚合物等之成分的膜,形成於其他層上,而會有藉由上述自我組織化而有效地發生相分離的情況。關於該上述層係進行有各種探討,而認為使用含有嵌段共聚物之組成物進行自我組織化時,藉由適切地控制上述層之表面自由能,可形成各種相分離構造(參照日本特開2008-36491號公報及日本特開2012-174984號公報)。但是,該等之習知方法中,尚未達到良好地以自我組織化形成相分離構造、且形成矩形的圖型。 In this self-organized lithography process, it is known that by forming a film containing a component such as a self-organized polymer on other layers, phase separation can occur effectively by the self-organization described above. Happening. Various investigations have been conducted on the above-mentioned layer system. When self-organizing using a composition containing a block copolymer, it is thought that various phase separation structures can be formed by appropriately controlling the surface free energy of the above-mentioned layers (see Japanese Patent Application Laid-Open) (2008-36491 and Japanese Patent Application Publication No. 2012-174984). However, in these conventional methods, it has not yet been possible to form a phase-separated structure with good self-organization and form a rectangular pattern.

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2008-149447號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2008-149447

[專利文獻2]日本特表2002-519728號公報 [Patent Document 2] Japanese Patent Publication No. 2002-519728

[專利文獻3]日本特開2003-218383號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2003-218383

[專利文獻4]美國專利出願公開2009/0214823號說明書 [Patent Document 4] US Patent Publication No. 2009/0214823

[專利文獻5]日本特開2010-58403號公報 [Patent Document 5] Japanese Patent Laid-Open No. 2010-58403

[專利文獻6]日本特開2008-36491號公報 [Patent Document 6] Japanese Patent Laid-Open No. 2008-36491

[專利文獻7]日本特開2012-174984號公報 [Patent Document 7] Japanese Patent Laid-Open No. 2012-174984

本發明係基於如以上之實情而為者,其目的在於提供能夠良好地藉由自我組織化形成相分離構造、且形成矩形的圖型之基底膜形成用組成物。 The present invention is based on the above facts, and an object thereof is to provide a composition for forming a base film which can form a phase separation structure by self-organization and form a rectangular pattern.

為了解決上述課題而為的發明,係基底膜形成用組成物,其係於自我組織化微影製程中,用以形成配置於含有矽原子之層(以下亦稱為「第1層」)與自我組織化膜之間的基底膜之組成物,該組成物含有具有可與Si-OH或Si-H反應之基的化合物(以下亦稱為「[A]化合物」)、及溶劑(以下亦稱為「[B]溶劑」),且上述基底膜之與純水的後退接觸角為70°以上且90°以下。 An invention for solving the above-mentioned problems is a composition for forming a base film, which is used in a self-organized lithography process to form a layer containing silicon atoms (hereinafter also referred to as "the first layer") and A composition of a basement film between self-organizing films, the composition containing a compound having a group capable of reacting with Si-OH or Si-H (hereinafter also referred to as "[A] compound"), and a solvent (hereinafter It is called "[B] solvent"), and the receding contact angle of the base film with pure water is 70 ° or more and 90 ° or less.

為了解決上述課題而為之另一發明,係自我組織化微影製程,其係具備於含有矽原子之第1層上藉由基底膜形成用組成物形成基底膜之步驟、於上述基底膜之與上述第1層相反側的面形成自我組織化膜之步驟、及去除上述自我組織化膜之至少一部分的相之步驟,且上述基底膜形成用組成物為該基底膜形成用組成物。 Another invention for solving the above-mentioned problems is a self-organized lithography process, which includes a step of forming a base film from a base film-forming composition on a first layer containing silicon atoms, and A step of forming a self-organizing film on a surface opposite to the first layer, and a step of removing a phase of at least a part of the self-organizing film; and the composition for forming a base film is the composition for forming a base film.

此處,「有機基」係指含有至少1個碳原子之基。「烴基」係包含鏈狀烴基、脂環式烴基及芳香族烴基。該「烴基」可為飽和烴基亦可為不飽和烴基。 Here, the "organic group" means a group containing at least one carbon atom. The "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "hydrocarbon group" may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

測定後退接觸角時之「基底膜」,係指於矽晶圓使該基底膜形成用組成物予以塗膜而成膜,以ArF光曝光後,於100℃燒成120秒所形成者。 The "base film" when measuring the receding contact angle refers to a film formed by coating the base film-forming composition on a silicon wafer and exposing it with ArF light, followed by firing at 100 ° C for 120 seconds.

依照本發明之基底膜形成用組成物及自我組織化微影製程,能夠良好地藉由自我組織化形成相分離構造、且形成矩形的圖型。因此,此等可適合使用於要求進一步微細化之半導體裝置、液晶裝置等之各種電子裝置製造中的微影製程。 The composition for forming a base film and the self-organizing lithography process according to the present invention can form a phase-separated structure and form a rectangular pattern by self-organization. Therefore, these can be suitably used in the lithography process in the manufacture of various electronic devices such as semiconductor devices and liquid crystal devices that require further miniaturization.

101‧‧‧基板 101‧‧‧ substrate

102‧‧‧基底膜 102‧‧‧ basement membrane

103‧‧‧預圖型 103‧‧‧ pre-pattern

104‧‧‧塗膜 104‧‧‧coating film

105‧‧‧自我組織化膜 105‧‧‧self-organizing membrane

105a‧‧‧構成自我組織化膜之一方的相 105a‧‧‧ Phases that form one of the self-organizing membranes

105b‧‧‧構成自我組織化膜之另一方的相 105b‧‧‧ The other phase that forms the self-organizing membrane

[圖1]顯示本發明之自我組織化微影製程中,形成基底膜後之狀態的一例之示意圖。 [Fig. 1] A schematic diagram showing an example of a state after forming a base film in the self-organized lithography process of the present invention.

[圖2]顯示本發明之自我組織化微影製程中,於基底膜上形成預圖型(pre-pattern)後之狀態的一例之示意圖。 [Fig. 2] A schematic diagram showing an example of a state after a pre-pattern is formed on a base film in the self-organized lithography process of the present invention.

[圖3]顯示本發明之自我組織化微影製程中,於以預圖型所分隔的基底膜上之區域,塗佈自我組織化組成物後之狀態的一例之示意圖。 [FIG. 3] A schematic diagram showing an example of a state after the self-organized composition is applied to the area on the base film separated by a pre-pattern in the self-organized lithography process of the present invention.

[圖4]顯示本發明之自我組織化微影製程中,於以預圖型所分隔的基底膜上之區域,形成具有自我組織化所致之相分離構造的膜後之狀態的一例之示意圖。 [Fig. 4] A schematic diagram showing an example of the state after forming a film having a phase separation structure due to self-organization in a region on a base film separated by a pre-pattern in the self-organized lithography process of the present invention .

[圖5]顯示本發明之自我組織化微影製程中,去除自我組織化膜之一部分的相及預圖型後之狀態的一例之示意圖。 FIG. 5 is a schematic diagram showing an example of a phase and a pre-patterned state of a part of the self-organized film in the self-organized lithography process of the present invention.

以下,詳細說明本發明之基底膜形成用組成物及自我組織化微影製程之實施形態。 Hereinafter, embodiments of the base film-forming composition and the self-organizing lithography process according to the present invention will be described in detail.

<基底膜形成用組成物> <Composition for forming basement film>

該基底膜形成用組成物,係於自我組織化微影製程中,用以形成配置於含有矽原子之層與自我組織化膜之間的基底膜之組成物,亦即,係用於形成自我組織化膜之第1層的基底膜形成者。該基底膜形成用組成物,係含有[A]化合物、及[B]溶劑。又,該基底膜形成用組成物,亦可具有[C]酸產生劑作為適合成分,在不損及本發明之效果的範圍內,亦可含有其他任意成分。又,[A]「化合物」中,除了聚合物以外,亦包含比較低分子量之寡聚物、具有烴鏈之物質等。以下說明各成分。 The composition for forming a base film is a composition for forming a base film disposed between a layer containing silicon atoms and a self-organizing film in a self-organizing lithography process, that is, forming a self Formation of the basement membrane of the first layer of a structured membrane. This composition for forming a base film contains a [A] compound and a [B] solvent. The composition for forming a base film may have a [C] acid generator as a suitable component, and may contain other optional components within a range that does not impair the effects of the present invention. [A] The "compound" includes, in addition to polymers, oligomers having a relatively low molecular weight, substances having a hydrocarbon chain, and the like. Each component is explained below.

[[A]化合物] [[A] Compound]

[A]化合物,係具有可與Si-OH或Si-H反應之基的化合物。依照該基底膜形成用組成物,[A]化合物,藉由具有可與Si-OH或Si-H反應之基,因例如空氣中之氧、水等之作用,可與其表面具有Si-OH或Si-H之第1層的表 面堅固地結合。其理由係推測如以下。第1層係因例如空氣中之氧、水等之作用,於其表面形成具有Si-OH或Si-H之基。因此,[A]化合物於基底膜內,化合物彼此凝集而均勻分布。又,藉由使上述基底膜與純水的後退接觸角為70°以上且90°以下,可良好地藉由自我組織化形成相分離構造。其結果,藉由使用該基底膜形成用組成物,可良好地藉由自我組織化形成相分離構造及矩形之圖型。 [A] Compound is a compound having a group capable of reacting with Si-OH or Si-H. According to the composition for forming a base film, the compound [A] has a group capable of reacting with Si-OH or Si-H, and can have Si-OH or Table of Si-H Layer 1 The faces are firmly joined. The reason is presumed as follows. The first layer is formed of a group having Si-OH or Si-H on its surface due to, for example, oxygen and water in the air. Therefore, the [A] compound is in the basement membrane, and the compounds are agglomerated and uniformly distributed. In addition, by setting the receding contact angle of the base film and pure water to be 70 ° or more and 90 ° or less, a phase separation structure can be favorably formed by self-organization. As a result, by using the composition for forming a base film, a phase separation structure and a rectangular pattern can be favorably formed by self-organization.

作為上述可與Si-OH或Si-H反應之基,可列舉例如羥基、羧基、胺基、環氧基(環氧乙烷基、氧雜環丁烷基)、烷氧基、下述式(2)表示之基等。 Examples of the group capable of reacting with Si-OH or Si-H include a hydroxyl group, a carboxyl group, an amine group, an epoxy group (oxiranyl group, oxetanyl group), an alkoxy group, and the following formula (2) The base of expression.

【化1】RB 3-aRA aSi- (2) [Chemical 1] R B 3-a R A a Si- (2)

上述式(2)中,RA係碳數1~20之1價烴基。RB係碳數1~20之1價氧烴基或鹵素原子。a係0~2之整數。惟,RA及RB分別有複數個時,複數個RA及複數個RB分別可相同亦可相異。 In the formula (2), R A is a monovalent hydrocarbon group having 1 to 20 carbon atoms. R B is a monovalent oxygen hydrocarbon group or a halogen atom having 1 to 20 carbon atoms. a is an integer from 0 to 2. However, when there are plural R A and R B , the plural R A and plural R B may be the same or different.

上述RA中之碳數1~20之1價烴基,可列舉例如碳數1~20之1價鏈狀烴基、碳數3~20之1價脂環式烴基、碳數6~20之1價芳香族烴基等。 Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in the R A include monovalent chain hydrocarbon groups having 1 to 20 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and 1 to 6 carbon atoms. Valence aromatic hydrocarbon group and the like.

上述1價鏈狀烴基,可列舉例如甲基、乙基、n-丙基、i-丙基、n-丁基、i-丁基、sec-丁基、t-丁基等之烷基;乙烯基、丙烯基、丁烯基等之烯基; 乙炔基、丙炔基、丁炔基等之炔基等。 Examples of the monovalent chain hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, and t-butyl; Alkenyl groups such as vinyl, propenyl, butenyl; Alkynyl groups such as ethynyl, propynyl, butynyl and the like.

上述1價脂環式烴基,可列舉例如環丙基、環丁基、環戊基、環己基、降莰基、金剛烷基、三環癸基、四環十二烷基等之環烷基;環丙烯基、環丁烯基、環戊烯基、環己烯基、降莰烯基、三環癸烯基等之環烯基等。 Examples of the monovalent alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, tricyclodecyl, and tetracyclododecyl. ; Cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, tricyclodecenyl, and other cycloalkenyl groups.

上述1價芳香族烴基,可列舉例如苯基、甲苯基、二甲苯基、均三甲苯基、萘基、蒽基等之芳基;苄基、苯乙基、苯基甲基、萘基甲基、蒽基甲基等之芳烷基等。 Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, and anthracenyl; benzyl, phenethyl, phenylmethyl, and naphthylmethyl And aralkyl groups such as anthrylmethyl and the like.

作為上述RA,此等之中,較佳為1價鏈狀烴基、更佳為烷基、又更佳為甲基。 Among the above-mentioned R A , a monovalent chain hydrocarbon group is preferred, an alkyl group is more preferred, and a methyl group is more preferred.

上述RB中之碳數1~20之1價氧烴基,可列舉例如氧原子鍵結於作為上述RA之碳數1~20之1價烴基所例示者而得之基等。此等之中,較佳為氧原子鍵結於1價鏈狀烴基而得之基、更佳為烷氧基、又更佳為甲氧基。 Examples of the monovalent oxyhydrocarbon group having 1 to 20 carbon atoms in the aforementioned R B include, for example, a group obtained by exemplifying an oxygen atom bonded to the monovalent hydrocarbon group having 1 to 20 carbon atoms in the aforementioned R A. Among these, a group in which an oxygen atom is bonded to a monovalent chain hydrocarbon group is preferable, an alkoxy group is more preferable, and a methoxy group is more preferable.

上述鹵素原子,可列舉例如氟原子、氯原子、溴原子、碘原子等。此等之中,較佳為氯原子。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom is preferred.

上述a較佳為0或1、更佳為0。 The a is preferably 0 or 1, and more preferably 0.

上述可與Si-OH或Si-H反應之基,較佳為羥基、烷氧基、及上述式(2)表示之基。 The above-mentioned group capable of reacting with Si-OH or Si-H is preferably a hydroxyl group, an alkoxy group, and a group represented by the above formula (2).

上述基底膜之與純水的後退接觸角的下限,較佳為71°、更佳為72°、又更佳為73°、特佳為74°。另 一方面,上述後退接觸角之上限,較佳為87°、更佳為84°、又更佳為81°、特佳為78°。藉由使上述後退接觸角成為上述範圍,係有可更良好地藉由自我組織化形成相分離構造,且可形成更加矩形的圖型之傾向。 The lower limit of the receding contact angle of the base film with pure water is preferably 71 °, more preferably 72 °, still more preferably 73 °, and particularly preferably 74 °. another On the one hand, the upper limit of the receding contact angle is preferably 87 °, more preferably 84 °, still more preferably 81 °, and particularly preferably 78 °. By making the receding contact angle into the above-mentioned range, there is a tendency that a phase separation structure can be formed better by self-organization, and a more rectangular pattern can be formed.

[A]化合物,較佳為下述式(1)表示之化合物。 [A] The compound is preferably a compound represented by the following formula (1).

上述式(1)中,A為(m+n)價之連結基。D為碳數10以上之1價有機基。E為可與Si-OH或Si-H反應之基。m及n係分別獨立地為1~200之整數。惟,m為2以上時,複數個D可相同亦可相異,2個以上之D亦可互相鍵結。n為2以上時,複數個E可相同亦可相異。 In the formula (1), A is a (m + n) -valent linking group. D is a monovalent organic group having 10 or more carbon atoms. E is a group capable of reacting with Si-OH or Si-H. m and n are each independently an integer of 1 to 200. However, when m is 2 or more, a plurality of Ds may be the same or different, and two or more Ds may be bonded to each other. When n is 2 or more, a plurality of E may be the same or different.

上述A表示之(m+n)價之連結基,只要係連結上述E表示之基與上述D表示之1價有機基之基,則無特殊限定,可列舉例如碳數1~30之有機基、下述式(3)表示之基。 The (m + n) -valent linking group represented by the above A is not particularly limited as long as it is a linking the base represented by the E with the monovalent organic group represented by the D, and examples thereof include organic groups having 1 to 30 carbon atoms. A base represented by the following formula (3).

式(3)中,Q係(m+n)價之矽數2~100之聚矽氧烷構造。T係與Q之矽原子以碳原子或氧原子進行鍵結之碳數1~30之2價有機基。m及n係與上述式(1)相同意 義。*1係表示鍵結於上述式(1)中之E的部位。*2係表示鍵結於上述式(1)中之D的部位。 In formula (3), the Q series (m + n) has a polysiloxane structure with a silicon number of 2 to 100. T is a divalent organic group having 1 to 30 carbon atoms bonded to a silicon atom of Q by a carbon atom or an oxygen atom. m and n have the same meanings as in the above formula (1). * 1 indicates a site bonded to E in the above formula (1). * 2 indicates a site bonded to D in the above formula (1).

上述Q表示之聚矽氧烷構造,只要係具有矽氧烷鍵(-Si-O-)之構造,則無特殊限定,可列舉例如來自包含下述式(5)表示之水解性矽烷化合物之化合物的水解縮合物之構造等。 The polysiloxane structure represented by the above Q is not particularly limited as long as it has a structure having a siloxane bond (-Si-O-), and examples thereof include those derived from a hydrolyzable silane compound represented by the following formula (5) Structure of hydrolysis condensate of compounds.

【化4】RC cSi X4-c (5) [Chem 4] R C c Si X 4-c (5)

上述式(5)中,RC為氫原子或1價有機基。X為鹵素原子或-ORD。RD為1價有機基。c為0~3之整數。惟,RC及X分別有複數個時,複數個RC可相同亦可相異,複數個X可相同亦可相異。 In the formula (5), R C is a hydrogen atom or a monovalent organic group. X is a halogen atom or -OR D. R D is a monovalent organic group. c is an integer from 0 to 3. However, when there are plural R C and X, the plural R C may be the same or different, and the plural X may be the same or different.

上述RC表示之1價有機基,可列舉例如碳數1~30之1價烴基、包含於該烴基之碳-碳間具有雜原子之基的含有雜原子之基、上述烴基及含有雜原子之基所具有之氫原子的一部分或全部被取代基取代之基等。 Examples of the monovalent organic group represented by the aforementioned R C include, for example, a monovalent hydrocarbon group having 1 to 30 carbon atoms, a heteroatom-containing group containing a heteroatom group between carbon and carbon contained in the hydrocarbon group, the hydrocarbon group, and a heteroatom-containing group A group in which a part or all of a hydrogen atom possessed by a substituent is substituted with a substituent, and the like.

上述碳數1~30之1價烴基,可列舉例如碳數1~30之1價鏈狀烴基、碳數3~30之1價脂環式烴基、碳數6~30之1價芳香族烴基等。 Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms include a monovalent chain hydrocarbon group having 1 to 30 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Wait.

上述1價鏈狀烴基,可列舉例如甲基、乙基、n-丙基、i-丙基、n-丁基、i-丁基、sec-丁基、t-丁基等之烷基;乙烯基、丙烯基、丁烯基等之烯基; 乙炔基、丙炔基、丁炔基等之炔基等。 Examples of the monovalent chain hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, and t-butyl; Alkenyl groups such as vinyl, propenyl, butenyl; Alkynyl groups such as ethynyl, propynyl, butynyl and the like.

上述1價脂環式烴基,可列舉例如環丙基、環丁基、環戊基、環己基、降莰基、金剛烷基、三環癸基、四環十二烷基等之環烯基;環丙烯基、環丁烯基、環戊烯基、環己烯基、降莰烯基、三環癸烯基等之環烯基等。 Examples of the monovalent alicyclic hydrocarbon group include cycloalkenyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, tricyclodecyl, and tetracyclododecyl. ; Cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornenyl, tricyclodecenyl, and other cycloalkenyl groups.

上述1價芳香族烴基,可列舉例如苯基、甲苯基、二甲苯基、均三甲苯基、萘基、蒽基等之芳基;苄基、苯乙基、苯基甲基、萘基甲基、蒽基甲基等之芳烷基等。 Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, and anthracenyl; benzyl, phenethyl, phenylmethyl, and naphthylmethyl And aralkyl groups such as anthrylmethyl and the like.

上述具有雜原子之基的雜原子,可列舉例如氧原子、氮原子、硫原子、磷原子等。 Examples of the hetero atom having a hetero atom group include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.

上述具有雜原子之基,可列舉例如-O-、-CO-、-NR’-、-S-、-CS-等。上述R’為碳數1~20之1價烴基。 Examples of the heteroatom-containing group include -O-, -CO-, -NR'-, -S-, -CS- and the like. The R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms.

上述取代基,可列舉例如氟原子、氯原子、溴原子、碘原子等之鹵素原子;羥基、羧基、氰基、硝基等。 Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group, a carboxyl group, a cyano group, and a nitro group.

上述RD表示之1價有機基,可列舉例如與作為上述RC之1價有機基所例示者相同之基等。 Examples of the monovalent organic group represented by R D include the same groups as those exemplified as the monovalent organic group of R C described above.

上述式(5)表示之水解性矽烷化合物,c為0時係4官能性矽烷、c為1時係3官能性矽烷、c為2時係2官能性矽烷、c為3時係1官能性矽烷。就c而言, 此等之中,較佳為0及1、更佳為1。 The hydrolyzable silane compound represented by the formula (5), when c is 0, it is a 4-functional silane, c is 1, it is a trifunctional silane, c is 2, it is a bifunctional silane, and c is 3, it is a monofunctional Silane. As far as c is concerned, Among these, 0 and 1, and 1 are more preferable.

上述式(5)表示之水解性矽烷化合物,可列舉例如四甲氧基矽烷、四乙氧基矽烷等之4官能性矽烷;甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三i-丙氧基矽烷、甲基三n-丁氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、乙基三i-丙氧基矽烷、乙基三n-丁氧基矽烷、n-丙基三甲氧基矽烷、n-丙基三乙氧基矽烷、n-丁基三甲氧基矽烷、n-丁基三乙氧基矽烷、n-己基三甲氧基矽烷、n-己基三乙氧基矽烷、癸基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、4-甲基苯基三甲氧基矽烷、4-甲基苯基三乙氧基矽烷、4-t-丁氧基苯乙基三乙氧基矽烷、1-(t-丁氧基苯基)乙基三乙氧基矽烷、t-丁氧基苯基三乙氧基矽烷、p-羥基苯基三甲氧基矽烷、1-(p-羥基苯基)乙基三甲氧基矽烷、2-(p-羥基苯基)乙基三甲氧基矽烷、4-羥基-5-(p-羥基苯基羰氧基)戊基三甲氧基矽烷、三氟甲基三甲氧基矽烷、三氟甲基三乙氧基矽烷、3,3,3-三氟丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷 等之3官能性矽烷;二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二乙醯氧基矽烷、二n-丁基二甲氧基矽烷、二苯基二甲氧基矽烷等之2官能性矽烷;三甲基甲氧基矽烷、三n-丁基乙氧基矽烷等之1官能性矽烷等。此等可單獨使用,亦可合併使用2種以上。 Examples of the hydrolyzable silane compound represented by the formula (5) include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyl Tri-i-propoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrii-propoxysilane, ethyltrin-butoxy Silane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n -Hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methylpropylene Methoxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 4-methylphenyltrimethoxysilane, 4-methylphenyltriethoxysilane, 4-t-butoxyphenethyltriethoxysilane, 1- (t-butoxyphenyl) ethyltriethoxysilane, t-butyl Oxyphenyltriethoxy Silane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silyl, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane 3-functional silane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, di-n-butyldimethoxysilane, diphenyldisiloxane Bifunctional silanes such as methoxysilane; monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane. These can be used alone or in combination of two or more.

作為聚矽氧烷構造,只要係不損及本發明之效果,可為鏈狀構造、可為面狀構造等之2次元構造、亦可為倍半矽氧烷構造等之3次元構造。 As the polysiloxane structure, as long as the effect of the present invention is not impaired, the structure may be a two-dimensional structure such as a chain structure, a planar structure, or a three-dimensional structure such as a silsesquioxane structure.

上述式(3)中之Q之矽數,係2~100、較佳為2~50、更佳為2~20。 The silicon number of Q in the above formula (3) is 2 to 100, preferably 2 to 50, and more preferably 2 to 20.

上述式(3)中之T表示之與Q之矽原子以碳原子或氧原子進行鍵結之碳數1~30之2價有機基,可列舉例如-R1-*2、-O-R2-*2等。上述R1及R2,係分別獨立地為碳數1~30之2價有機基。上述*2,係與上述式(3)相同意義。 The divalent organic group of 1 to 30 carbon atoms having a carbon atom or an oxygen atom bonded to the silicon atom of Q represented by T in the above formula (3) can be exemplified by -R 1- * 2 , -OR 2- * 2 etc. The R 1 and R 2 are each independently a divalent organic group having 1 to 30 carbon atoms. The above * 2 has the same meaning as the above formula (3).

上述R1及R2表示之碳數1~30之2價有機基,可列舉例如碳數1~30之2價鏈狀烴基、碳數3~30之2價脂環式烴基、碳數6~30之2價芳香族烴基、於上述2價烴基之構造中包含氧原子、氮原子、硫原子等之雜原子之基等。 Examples of the divalent organic group having 1 to 30 carbon atoms represented by R 1 and R 2 include a divalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, and 6 carbon atoms. A divalent aromatic hydrocarbon group of ~ 30, a group containing a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, and the like in the structure of the divalent hydrocarbon group.

上述2價鏈狀烴基,可列舉例如甲烷二基、乙烷二基、n-丙烷二基、i-丙烷二基、n-丁烷二基、i-丁烷二基、n-戊烷二基、i-戊烷二基、n-己烷二基、i-己烷二基 等。 Examples of the divalent chain hydrocarbon group include methanediyl, ethanediyl, n-propanediyl, i-propanediyl, n-butanediyl, i-butanediyl, and n-pentanediyl. , I-pentanediyl, n-hexanediyl, i-hexanediyl Wait.

上述2價脂環式烴基,可列舉例如環丙烷二基、環丁烷二基、環戊烷二基、環己烷二基、環辛烷二基、降莰烷二基、金剛烷二基等。 Examples of the divalent alicyclic hydrocarbon group include cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, norbornanediyl, and adamantanediyl. Wait.

上述2價芳香族烴基,可列舉例如伸苯基、伸萘基、伸蒽基、甲苯二基、苯基乙烷二基、二甲苯二基等。 Examples of the divalent aromatic hydrocarbon group include phenylene, naphthyl, anthracene, tolyldiyl, phenylethanediyl, and xylylenediyl.

上述於2價烴基之構造中包含雜原子之基,可列舉例如3-丁氧基丙烷-1,2-二基等。 Examples of the aforementioned heteroatom-containing group in the structure of the divalent hydrocarbon group include 3-butoxypropane-1,2-diyl.

上述R1及R2之碳數,係1~30、較佳為1~20、更佳為1~10。 The carbon numbers of R 1 and R 2 are 1 to 30, preferably 1 to 20, and more preferably 1 to 10.

上述式(1)中之D表示之碳數10以上之1價有機基,可列舉例如作為上述式(5)之RC所例示之1價有機基當中之碳數10以上者等。 Examples of the monovalent organic group having a carbon number of 10 or more represented by D in the formula (1) include, for example, those having a carbon number of 10 or more among the monovalent organic groups exemplified as R C in the formula (5).

上述D之有機基之碳數的下限,較佳為10、更佳為20、又更佳為50、特佳為100。上述碳數的上限,較佳為10,000、更佳為5,000、又更佳為2,000、特佳為1,000。 The lower limit of the carbon number of the organic group of D is preferably 10, more preferably 20, still more preferably 50, and particularly preferably 100. The upper limit of the carbon number is preferably 10,000, more preferably 5,000, still more preferably 2,000, and particularly preferably 1,000.

上述D表示之有機基,較佳為具有鏈狀構造之有機鏈,可列舉例如含有由使乙烯基單體等聚合而得之碳-碳鍵所成的聚合鏈之基、寡聚物鏈、烴鏈、聚環氧烷鏈等。「由使乙烯基單體等聚合而得之碳-碳鍵所成的聚合鏈」,係指以藉由聚合反應、接枝反應等而形成之碳-碳鍵所構成之鏈(以下亦稱為接枝鏈)。上述聚合鏈可列舉例如高分子鏈、寡聚物鏈等。 The organic group represented by D is preferably an organic chain having a chain structure, and examples thereof include a group containing a polymer chain formed from a carbon-carbon bond obtained by polymerizing a vinyl monomer or the like, an oligomer chain, Hydrocarbon chain, polyalkylene oxide chain, etc. A "polymeric chain formed by carbon-carbon bonds obtained by polymerizing vinyl monomers and the like" refers to a chain composed of carbon-carbon bonds formed by polymerization reaction, graft reaction, etc. (hereinafter also referred to as For grafting chains). Examples of the polymer chain include a polymer chain and an oligomer chain.

上述式(1)中之D,就製造容易性之觀點而言,較佳為含有由碳-碳鍵所成之聚合鏈之基、更佳為含有乙烯基聚合鏈之基。此等之中,就製造容易性之觀點而言較佳為高分子鏈。構成上述聚合鏈之構造單位可為1種或2種以上,上述聚合鏈可為直鏈狀亦可為分支狀,具有2種以上之構造單位時,各構造單位可為隨機狀亦可為嵌段狀。 From the viewpoint of ease of production, D in the above formula (1) is preferably a group containing a polymer chain formed by a carbon-carbon bond, and more preferably a group containing a vinyl polymer chain. Among these, a polymer chain is preferred from the viewpoint of ease of production. The structural unit constituting the above-mentioned polymerization chain may be one type or two or more types. The above-mentioned polymerization chain may be linear or branched. When there are two or more types of structural units, each structural unit may be random or embedded. Segment.

上述式(1)中之D,亦佳為含有硫原子之基。上述式(1)中之D為含有硫原子之基時,較佳為上述式(1)中之D與A係透過上述硫原子而鍵結。 D in the above formula (1) is also preferably a group containing a sulfur atom. When D in the formula (1) is a group containing a sulfur atom, it is preferable that D and A in the formula (1) are bonded through the sulfur atom.

A為碳數1~30之有機基、且n為1~10之整數時,作為上述式(1)中之E,於此等之中,由可更加抑制於[A]化合物之第1層上的分布不均之觀點而言,較佳為羥基、及上述式(2)表示之基。 When A is an organic group having 1 to 30 carbon atoms and n is an integer of 1 to 10, as E in the above formula (1), among these, the first layer of the compound [A] can be more suppressed. From the viewpoint of uneven distribution, a hydroxyl group and a group represented by the above formula (2) are preferred.

[A]化合物,可具有1個之上述式(1)中E表示之可與Si-OH或Si-H反應之基、亦可具有2個以上之可與Si-OH或Si-H反應之基。 [A] The compound may have one of the groups represented by E in the above formula (1) that can react with Si-OH or Si-H, or two or more compounds that can react with Si-OH or Si-H base.

又,作為上述式(1)中之E,當A表示之連結基為上述式(3)表示之基時,於此等之中,就可更加與Si-OH或Si-H反應之基的觀點而言,較佳為羥基、及烷氧基。 In addition, as E in the above formula (1), when the linking group represented by A is the group represented by the above formula (3), among these, the group which can react with Si-OH or Si-H more From a viewpoint, a hydroxyl group and an alkoxy group are preferable.

上述式(1)中之m及n,係1~100之整數、較佳為1~50之整數、更佳為1~20之整數。 M and n in the above formula (1) are integers of 1 to 100, preferably integers of 1 to 50, and more preferably integers of 1 to 20.

上述式(1)中之A為碳數1~30之有機基 時,[A]化合物,較佳為於上述式(1)中之E表示之基以外,不具有含活性氫之基。[A]化合物若於上述式(1)中之E表示之基以外,具有含活性氫之基時,會有後退接觸角變低的傾向。 A in the above formula (1) is an organic group having 1 to 30 carbon atoms In this case, the compound [A] preferably has no active hydrogen-containing group in addition to the group represented by E in the formula (1). [A] If the compound has an active hydrogen-containing group other than the group represented by E in the formula (1), the receding contact angle tends to be low.

上述式(1)表示之[A]化合物,可列舉例如下述式(6)表示之化合物等。 Examples of the compound [A] represented by the formula (1) include compounds represented by the following formula (6).

上述式(6)中,A、E、m及n係與上述式(1)相同意義。D’為碳數10以上之1價有機基。惟,m為2以上時,複數個D’可相同亦可相異,2個以上之D’亦可互相鍵結。 In the formula (6), A, E, m, and n have the same meanings as in the formula (1). D 'is a monovalent organic group having 10 or more carbon atoms. However, when m is 2 or more, a plurality of D's may be the same or different, and two or more D's may be bonded to each other.

上述D’表示之碳數10以上之1價有機基,可列舉例如與作為上述D表示之碳數10以上之1價有機基所例示者相同之基等。 Examples of the monovalent organic group having a carbon number of 10 or more represented by D 'include the same groups as those exemplified as the monovalent organic group of 10 or more carbon atoms represented by D.

[A]化合物為上述式(6)表示,A為碳數1~30之有機基、且D’為有機鏈時,上述式(6)中之硫原子可鍵結於此有機鏈之末端,亦可鍵結於末端以外。此處,「有機鏈之末端」,係指位於構成有機鏈之原子鏈當中最長者之一端的原子。 [A] The compound is represented by the above formula (6), when A is an organic group having 1 to 30 carbon atoms, and D 'is an organic chain, the sulfur atom in the above formula (6) may be bonded to the end of the organic chain, It can also be bonded outside the end. Here, "the end of the organic chain" refers to an atom located at one end of the longest of the atomic chains constituting the organic chain.

上述式(6)表示之[A]化合物,由可更加抑制於[A]化合物之第1層上的分布不均之觀點而言,較佳為具有1個之可與Si-OH或Si-H反應之基,更佳為D’係 有機鏈、且硫原子鍵結於此有機鏈之末端。此時,[A]化合物係有於第1層上配置排列為刷(brush)狀之傾向。 From the viewpoint that the [A] compound represented by the above formula (6) can further suppress the uneven distribution on the first layer of the [A] compound, it is preferable to have one compound capable of interacting with Si-OH or Si- H reaction base, more preferably D 'system The organic chain has a sulfur atom bonded to the end of the organic chain. At this time, the [A] compound tends to be arranged in a brush shape on the first layer.

作為[A]化合物之含量之下限,係該基底膜形成用組成物之全部固體成分中,較佳為70質量%、更佳為80質量%、又更佳為85質量%。再者,[A]化合物可單獨使用亦可合併使用2種以上。 As the lower limit of the content of the [A] compound, it is preferably 70% by mass, more preferably 80% by mass, and even more preferably 85% by mass of the total solid content of the base film-forming composition. The [A] compound may be used alone or in combination of two or more.

[[A]化合物之製造方法] [Method for producing [A] compound]

[A]化合物之製造方法,可列舉例如自由基聚合、使用鏈轉移劑之自由基聚合、原子移動自由基聚合(ATRP)等之活性自由基聚合、陽離子聚合、陰離子聚合等之聚合法、周知之有機化合物之合成方法等。此等之中,就製造容易性之觀點而言,較佳為使用鏈轉移劑之自由基聚合。 [A] A method for producing the compound includes, for example, radical polymerization, radical polymerization using a chain transfer agent, living radical polymerization such as atomic radical polymerization (ATRP), cationic polymerization, anionic polymerization, and other known polymerization methods. Methods for the synthesis of organic compounds. Among these, in terms of ease of production, radical polymerization using a chain transfer agent is preferred.

[A]化合物,例如為上述式(1)表示、且上述式(1)中之D包含硫原子時,更具體而言,上述式(6)表示者,係為例如將乙烯基單體於下述式(4)表示之鏈轉移劑存在下進行自由基聚合而成者等,例如可藉由具備將乙烯基單體於下述式(4)表示之鏈轉移劑存在下進行自由基聚合之步驟的製造方法而得到。 [A] The compound is, for example, when the formula (1) is represented and D in the formula (1) contains a sulfur atom. More specifically, the compound represented by the formula (6) is, for example, a vinyl monomer in Those obtained by performing radical polymerization in the presence of a chain transfer agent represented by the following formula (4), and the like, for example, can be provided with a radical polymerization in the presence of a chain transfer agent represented by the following formula (4) Step manufacturing method.

上述式(4)中,A、E、m及n係與上述式 (1)相同意義。 In the above formula (4), A, E, m and n are the same as the above formula (1) The same meaning.

上述鏈轉移劑,可遵照周知之製造方法合成、亦可使用商業上可獲得之市售品。 The above-mentioned chain transfer agent may be synthesized in accordance with a known manufacturing method, or a commercially available product may be used.

上述鏈轉移劑,可藉由例如具備使具有巰基之矽烷化合物與不具有巰基之矽烷化合物在酸或鹼存在下反應之步驟的製造方法等而得到。 The said chain transfer agent can be obtained by the manufacturing method etc. which have a process which makes the silane compound which has a mercapto group and the silane compound which does not have a mercapto group react in presence of an acid or a base.

上述具有巰基之矽烷化合物,可列舉例如3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷等。此等之中,較佳為3-巰基丙基三甲氧基矽烷。 Examples of the mercapto-containing silane compound include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane. Among these, 3-mercaptopropyltrimethoxysilane is preferred.

上述不具有巰基之矽烷化合物,可列舉例如n-丁基三甲氧基矽烷、甲基三甲氧基矽烷、二甲基二甲氧基矽烷、苯基三甲氧基矽烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、苯基三乙氧基矽烷、n-己基三甲氧基矽烷、n-己基三乙氧基矽烷、n-癸基三甲氧基矽烷、三氟丙基三甲氧基矽烷等。此等之中,較佳為n-丁基三甲氧基矽烷、及甲基三甲氧基矽烷。 Examples of the silane compound having no mercapto group include n-butyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and methyltriethoxysilane. , Dimethyldiethoxysilane, phenyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-decyltrimethoxysilane, trifluoropropyltrimethoxy Silane and so on. Among these, n-butyltrimethoxysilane and methyltrimethoxysilane are preferred.

上述酸可列舉例如草酸、鹽酸、硫酸等。此等之中,較佳為草酸。上述鹼可列舉例如氫氧化鈉等之氫氧化鹼、三乙基胺等之胺化合物等之含有氮之化合物等。 Examples of the acid include oxalic acid, hydrochloric acid, and sulfuric acid. Among these, oxalic acid is preferred. Examples of the base include nitrogen-containing compounds such as alkali hydroxides such as sodium hydroxide and amine compounds such as triethylamine.

上述鏈轉移劑之以凝膠滲透層析(GPC)所得之聚苯乙烯換算之重量平均分子量(Mw)的下限,較佳為100、更佳為200、又更佳為300。上述鏈轉移劑之Mw的上限,較佳為20,000、更佳為15,000、又更佳為10,000。藉由使上述鏈轉移劑之Mw成為上述範圍,會有 更減低上述鏈轉移劑之分布不均的傾向。 The lower limit of the polystyrene-equivalent weight average molecular weight (Mw) of the chain transfer agent obtained by gel permeation chromatography (GPC) is preferably 100, more preferably 200, and still more preferably 300. The upper limit of the Mw of the chain transfer agent is preferably 20,000, more preferably 15,000, and even more preferably 10,000. By setting the Mw of the chain transfer agent to the above range, there will be The tendency of uneven distribution of the chain transfer agent is further reduced.

上述鏈轉移劑之以凝膠滲透層析(GPC)所得之聚苯乙烯換算之數平均分子量(Mn)的下限,較佳為50、更佳為100、又更佳為150。上述鏈轉移劑之Mn的上限,較佳為10,000、更佳為7,500、又更佳為5,000。藉由使上述鏈轉移劑之Mn成為上述範圍,會有更減低上述鏈轉移劑之分布不均的傾向。 The lower limit of the polystyrene-equivalent number average molecular weight (Mn) of the chain transfer agent obtained by gel permeation chromatography (GPC) is preferably 50, more preferably 100, and even more preferably 150. The upper limit of the Mn of the chain transfer agent is preferably 10,000, more preferably 7,500, and still more preferably 5,000. When the Mn of the chain transfer agent is in the above range, the distribution unevenness of the chain transfer agent tends to be further reduced.

相對於上述鏈轉移劑之以GPC所得之聚苯乙烯換算之數平均分子量(Mn)而言,Mw之比(Mw/Mn)的下限,較佳為1。上述鏈轉移劑之Mw/Mn的上限,較佳為5、更佳為4、又更佳為3。 The lower limit of the Mw ratio (Mw / Mn) is preferably 1 with respect to the polystyrene-equivalent number average molecular weight (Mn) of the chain transfer agent obtained by GPC. The upper limit of Mw / Mn of the chain transfer agent is preferably 5, more preferably 4, and even more preferably 3.

本說明書中,重量平均分子量(Mw)及數平均分子量(Mn),係藉由使用GPC管柱(東曹公司之「G2000HXL」2根、「G3000HXL」1根及「G4000HXL」1根),以流量:1.0mL/分鐘、溶出溶劑:四氫呋喃、管柱溫度:40℃之分析條件,藉由以單分散聚苯乙烯為標準之凝膠滲透層析(GPC)來測定者。 In this manual, the weight average molecular weight (Mw) and number average molecular weight (Mn) are based on the use of GPC columns (two "G2000HXL" from Tosoh Corporation, one "G3000HXL", and one "G4000HXL") from Flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C. Analytical conditions were determined by gel permeation chromatography (GPC) using monodisperse polystyrene as the standard.

上述乙烯基單體、即賦予上述式(1)中之D’表示之接枝鏈的乙烯基單體,可列舉例如乙烯、丙烯、丁烯、戊烯、己烯、庚烯等之烯烴系單體;苯乙烯、乙烯基萘、乙烯基聯苯、α-甲基苯乙烯等之乙烯基芳香族系單體;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲 基)丙烯酸n-丙酯、(甲基)丙烯酸i-丙酯、(甲基)丙烯酸n-丁酯、(甲基)丙烯酸i-丁酯、(甲基)丙烯酸t-丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸2-乙醯乙醯氧基乙酯等之脂肪族(甲基)丙烯酸酯;(甲基)丙烯酸環丙酯、(甲基)丙烯酸環丁酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸降莰酯、(甲基)丙烯酸金剛烷酯等之脂環式(甲基)丙烯酸酯;(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯等之芳香族(甲基)丙烯酸酯;氟乙烯、氯乙烯、溴乙烯、碘乙烯、偏二氟乙烯、偏二氯乙烯等之鹵素系單體;(甲基)丙烯酸、馬來酸等之羧酸系單體;具有酸酐基、磷酸基、磺酸基、羥基、醛基、胺基、醯胺基、環氧基、乙醯乙醯氧基、異氰酸酯基、異硫氰酸酯基等之極性基之單體等。 Examples of the vinyl monomer, that is, a vinyl monomer imparting a graft chain represented by D ′ in the formula (1) include olefins such as ethylene, propylene, butene, pentene, hexene, and heptene. Monomers; vinyl aromatic monomers such as styrene, vinylnaphthalene, vinylbiphenyl, α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, (formaldehyde) N-propyl acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, (formyl) Base) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Aliphatic (meth) acrylates such as acetoacetoxyethyl; cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, (formyl) Cyclohexyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, etc. (Meth) acrylates; aromatic (meth) acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, and naphthyl (meth) acrylate; vinyl fluoride, vinyl chloride, bromoethylene, Halogen monomers such as iodoethylene, vinylidene fluoride, and vinylidene chloride; carboxylic acid monomers such as (meth) acrylic acid and maleic acid; have acid anhydride, phosphate, sulfonic, hydroxyl, and aldehyde Group, amino group, amido group, The monomers of group a polar group, acetyl acetyl group, an isocyanate group, an isothiocyanate group.

作為乙烯基單體,於此等之中就[A]化合物更加分布不均之觀點而言,較佳為乙烯基芳香族系單體、脂肪族(甲基)丙烯酸酯、及芳香族(甲基)丙烯酸酯;更佳為苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸環己酯、及甲基丙烯酸二環戊酯。 As the vinyl monomer, among these, from the viewpoint that the [A] compound is more unevenly distributed, a vinyl aromatic monomer, an aliphatic (meth) acrylate, and an aromatic (formaldehyde) are preferred. Acrylate); more preferably styrene, methyl methacrylate, cyclohexyl methacrylate, and dicyclopentyl methacrylate.

例如,作為乙烯基單體而言,藉由調整具有極性者與非極性者的使用比例等,可合成可使藉由該基底膜形成用組成物所形成之膜的後退接觸角成為特定範圍的[A]化合物。 For example, as a vinyl monomer, it is possible to synthesize a receding contact angle of a film formed by the base film-forming composition to a specific range by adjusting the use ratio of a person having polarity to a person having non-polarity. [A] Compound.

自由基聚合起始劑,可列舉例如偶氮雙異丁腈(AIBN)、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮雙(2-環丙基丙腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、二甲基2,2’-偶氮雙異丁酸酯、2,2’-偶氮雙(2-甲基丙腈)等之偶氮系自由基起始劑;苄醯基過氧化物、t-丁基氫過氧化物、異丙苯氫過氧化物、己酸t-丁基過氧基-2-乙酯等之過氧化物系自由基起始劑等。此等可單獨使用,亦可合併使用2種以上。 Examples of the radical polymerization initiator include azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2 ' -Azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl2,2'-azobisisobutyrate, Azo radical initiators such as 2,2'-azobis (2-methylpropionitrile); benzamidine peroxide, t-butyl hydroperoxide, cumene hydroperoxide , T-butylperoxy-2-ethylhexanoate, and other peroxide-based radical initiators. These can be used alone or in combination of two or more.

作為自由基聚合起始劑,此等之中,較佳為2,2’-偶氮雙(2-甲基丙腈)、己酸t-丁基過氧基-2-乙酯、及2,2’-偶氮雙(2,4-二甲基戊腈)。 As the radical polymerization initiator, among these, 2,2'-azobis (2-methylpropionitrile), t-butylperoxy-2-ethylhexanoate, and 2 , 2'-Azobis (2,4-dimethylvaleronitrile).

使用於聚合之溶劑,可列舉例如n-戊烷、n-己烷、n-庚烷、n-辛烷、n-壬烷、n-癸烷等之烷類;環己烷、環庚烷、環辛烷、十氫萘、降莰烷等之環烷類;苯、甲苯、二甲苯、乙基苯、異丙苯等之芳香族烴類;氯丁烷類、溴己烷類、二氯乙烷類、六亞甲基二溴化 物、氯苯等之鹵化烴類;乙酸乙酯、乙酸n-丁酯、乙酸i丁酯、丙酸甲酯等之飽和羧酸酯類;丙酮、甲基乙基酮、4-甲基-2-戊酮、2-庚酮等之酮類;四氫呋喃、二甲氧基乙烷類、二乙氧基乙烷類等之醚類;甲醇、乙醇、1-丙醇、2-丙醇、4-甲基-2-戊醇等之醇類等。此等可單獨使用,亦可合併使用2種以上。 Examples of the solvent used for polymerization include alkane such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cyclohexane and cycloheptane , Cyclooctane, decalin, norbornane, etc .; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, etc .; chlorobutane, bromohexane, two Ethyl chloride, hexamethylene dibromide Compounds, chlorobenzene and other halogenated hydrocarbons; ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate and other saturated carboxylic acid esters; acetone, methyl ethyl ketone, 4-methyl- Ketones such as 2-pentanone, 2-heptanone; ethers such as tetrahydrofuran, dimethoxyethane, diethoxyethane; methanol, ethanol, 1-propanol, 2-propanol, Alcohols such as 4-methyl-2-pentanol and the like. These can be used alone or in combination of two or more.

作為使用於聚合之溶劑,此等之中,較佳為酮類、更佳為甲基乙基酮。 Among the solvents used for polymerization, ketones are preferred, and methyl ethyl ketone is more preferred.

聚合之反應溫度之下限,較佳為40℃、更佳為50℃。上述反應溫度之上限,較佳為150℃、更佳為120℃。另一方面,反應時間之下限,較佳為1小時。反應時間之上限,較佳為48小時、更佳為24小時。 The lower limit of the polymerization reaction temperature is preferably 40 ° C, more preferably 50 ° C. The upper limit of the reaction temperature is preferably 150 ° C, and more preferably 120 ° C. On the other hand, the lower limit of the reaction time is preferably 1 hour. The upper limit of the reaction time is preferably 48 hours, and more preferably 24 hours.

聚合後之反應溶液,考慮操作面,較佳為以丙二醇單甲基醚乙酸酯等之溶劑,以固體成分之濃度計稀釋為5質量%以上且15質量%以下之溶液。 The reaction solution after polymerization is preferably a solution diluted with 5% to 15% by mass based on the concentration of the solid content in a solvent such as propylene glycol monomethyl ether acetate in consideration of the operation surface.

上述式(1)表示之[A]化合物,較佳為具有含有由碳-碳鍵所成之聚合鏈之基,作為D之有機基。該含有聚合鏈之基,可列舉含有高分子鏈之基、含有寡聚物鏈之基等。此等之中,由更加抑制[A]化合物之分布不均的觀點而言,較佳為含有高分子鏈之基、更佳為含有由乙烯基單體所形成之高分子鏈之基。亦即,作為[A]化合 物,較佳為具有由乙烯基單體所形成之接枝鏈的接枝聚合物。 The compound [A] represented by the above formula (1) preferably has a group containing a polymer chain formed by a carbon-carbon bond as an organic group of D. Examples of the polymer chain-containing group include a polymer chain-containing group and a oligomer chain-containing group. Among these, from the viewpoint of further suppressing the uneven distribution of the [A] compound, a group containing a polymer chain is more preferable, and a group containing a polymer chain formed of a vinyl monomer is more preferable. That is, as [A] It is preferably a graft polymer having a graft chain formed from a vinyl monomer.

[A]化合物之以凝膠滲透層析(GPC)所得之聚苯乙烯換算之重量平均分子量(Mw)的下限,較佳為1,000、更佳為2,000、又更佳為3,000。上述Mw之上限,較佳為50,000、更佳為30,000、又更佳為20,000。藉由使[A]化合物之Mw成為上述範圍,會有更減低[A]化合物之分布不均的傾向。 [A] The lower limit of the polystyrene-equivalent weight average molecular weight (Mw) of the compound obtained by gel permeation chromatography (GPC) is preferably 1,000, more preferably 2,000, and even more preferably 3,000. The upper limit of the Mw is preferably 50,000, more preferably 30,000, and even more preferably 20,000. When the Mw of the [A] compound falls within the above range, the distribution unevenness of the [A] compound tends to be further reduced.

[A]化合物之以凝膠滲透層析(GPC)所得之聚苯乙烯換算之數平均分子量(Mn)的下限,較佳為900、更佳為1,900、又更佳為2,900。上述Mn之上限,較佳為49,000、更佳為29,000、又更佳為19,000。藉由使[A]化合物之Mw成為上述範圍,會有更減低[A]化合物之分布不均的傾向。 [A] The lower limit of the polystyrene-equivalent number average molecular weight (Mn) of the compound obtained by gel permeation chromatography (GPC) is preferably 900, more preferably 1,900, and still more preferably 2,900. The upper limit of the Mn is preferably 49,000, more preferably 29,000, and even more preferably 19,000. When the Mw of the [A] compound falls within the above range, the distribution unevenness of the [A] compound tends to be further reduced.

相對於[A]化合物之以GPC所得之聚苯乙烯換算之數平均分子量(Mn)而言,Mw之比(Mw/Mn)的下限,較佳為1。上述Mw/Mn之上限,較佳為5、更佳為3、又更佳為2.5。 The lower limit of the Mw ratio (Mw / Mn) is preferably 1 relative to the polystyrene-equivalent number average molecular weight (Mn) of the [A] compound obtained by GPC. The upper limit of the Mw / Mn is preferably 5, more preferably 3, and even more preferably 2.5.

[[B]溶劑] [[B] Solvent]

該基底膜形成用組成物係含有[B]溶劑。上述[B]溶劑,可列舉例如醇系溶劑、醚系溶劑、酮系溶劑、醯胺系溶劑、酯系溶劑、烴系溶劑等。 This composition for base film formation contains a [B] solvent. Examples of the [B] solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amidine-based solvents, ester-based solvents, and hydrocarbon-based solvents.

醇系溶劑,可列舉例如 4-甲基-2-戊醇、n-己醇等之碳數1~18之脂肪族單元醇系溶劑;環己醇等之碳數3~18之脂環式單元醇系溶劑;1,2-丙二醇等之碳數2~18之多元醇系溶劑;丙二醇單甲基醚等之碳數3~19之多元醇部分醚系溶劑等。 Examples of the alcohol-based solvent include 4-methyl-2-pentanol, n-hexanol and other aliphatic unit alcohol solvents having 1 to 18 carbons; cyclohexanol and other cycloaliphatic unit alcohol solvents having 3 to 18 carbons; 1, 2-Propylene glycol and other polyhydric alcohol solvents having 2 to 18 carbons; Propylene glycol monomethyl ether and other polyhydric alcohol partial ether solvents such as 3 to 19 carbons.

醚系溶劑,可列舉例如二乙基醚、二丙基醚、二丁基醚、二戊基醚、二異戊基醚、二己基醚、二庚基醚等之二烷基醚系溶劑;四氫呋喃、四氫吡喃等之環狀醚系溶劑;二苯基醚、苯甲醚等之含有芳香環之醚系溶劑等。 Examples of the ether-based solvent include dialkyl ether-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisopentyl ether, dihexyl ether, and diheptyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; ether solvents containing aromatic rings such as diphenyl ether and anisole.

酮系溶劑,可列舉例如丙酮、甲基乙基酮、甲基-n-丙基酮、甲基-n-丁基酮、二乙基酮、甲基-iso-丁基酮、2-庚酮、乙基-n-丁基酮、甲基-n-己基酮、二-iso-丁基酮、三甲基壬酮等之鏈狀酮系溶劑:環戊酮、環己酮、環庚酮、環辛酮、甲基環己酮等之環狀酮系溶劑:2,4-戊二酮、丙酮基丙酮、苯乙酮等。 Examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, and 2-heptane Ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethyl nonanone and other chain ketone solvents: cyclopentanone, cyclohexanone, cycloheptan Cyclic ketone solvents such as ketone, cyclooctanone, methylcyclohexanone: 2,4-pentanedione, acetone acetone, acetophenone, etc.

醯胺系溶劑,可列舉例如N,N’-二甲基四氫咪唑酮、N-甲基吡咯啶酮等之環狀醯胺系溶劑;N-甲基甲醯胺、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基丙醯胺等之鏈狀醯胺系溶劑等。 Examples of the amidine solvents include cyclic amidine solvents such as N, N'-dimethyltetrahydroimidazolone and N-methylpyrrolidone; N-methylformamide, N, N-di Methylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropylamine, etc. Amidamine-based solvents and the like.

酯系溶劑,可列舉例如 乙酸丁酯、乳酸乙酯、乙酸丁氧基甲酯等之單羧酸酯系溶劑;丙二醇乙酸酯等之多元醇羧酸酯系溶劑;丙二醇單甲基醚乙酸酯等之多元醇部分醚羧酸酯系溶劑;草酸二乙酯等之多元羧酸二酯系溶劑;碳酸二甲酯、碳酸二乙酯等之碳酸酯系溶劑等。 Examples of the ester-based solvent include Monocarboxylic acid ester solvents such as butyl acetate, ethyl lactate, butoxymethyl acetate; polyol carboxylic acid ester solvents such as propylene glycol acetate; polyhydric alcohol portions such as propylene glycol monomethyl ether acetate Ether carboxylic acid ester-based solvents; polycarboxylic acid diester-based solvents such as diethyl oxalate; carbonate-based solvents such as dimethyl carbonate and diethyl carbonate.

烴系溶劑,可列舉例如n-戊烷、n-己烷等之碳數5~12之脂肪族烴系溶劑;甲苯、二甲苯等之碳數6~16之芳香族烴系溶劑等。 Examples of the hydrocarbon-based solvent include aliphatic hydrocarbon-based solvents having 5 to 12 carbon atoms such as n-pentane and n-hexane; aromatic hydrocarbon-based solvents having 6 to 16 carbon atoms such as toluene and xylene.

此等可單獨使用,亦可合併使用2種以上。 These can be used alone or in combination of two or more.

作為[B]溶劑,於此等之中,較佳為醇系溶劑、酯系溶劑、及酮系溶劑;更佳為碳數3~19之多元醇部分醚系溶劑、單羧酸酯系溶劑、及環狀酮系溶劑;又更佳為丙二醇單甲基醚乙酸酯、乙酸丁氧基甲酯、乙酸丁酯、及環己酮。 As the [B] solvent, among these, alcohol-based solvents, ester-based solvents, and ketone-based solvents are preferred; polyhydric alcohol partial ether-based solvents and monocarboxylic acid ester-based solvents having a carbon number of 3 to 19 are more preferred. And cyclic ketone solvents; more preferred are propylene glycol monomethyl ether acetate, butoxymethyl acetate, butyl acetate, and cyclohexanone.

[B]溶劑之含量的下限,相對於[A]化合物100質量份而言,較佳為500質量份、更佳為1,000質量份、又更佳為2,000質量份。另一方面,[B]溶劑之含量的上限,相對於[A]化合物100質量份而言,較佳為50,000質量份、更佳為30,000質量份、又更佳為20,000質量份。藉由使[B]溶劑之含量成為上述範圍,可使[A]化合物更加分散於[B]溶劑中。 The lower limit of the content of [B] the solvent is preferably 500 parts by mass, more preferably 1,000 parts by mass, and even more preferably 2,000 parts by mass with respect to 100 parts by mass of the [A] compound. On the other hand, the upper limit of the content of the [B] solvent is preferably 50,000 parts by mass, more preferably 30,000 parts by mass, and still more preferably 20,000 parts by mass relative to 100 parts by mass of the [A] compound. By making the content of the [B] solvent into the above range, the [A] compound can be more dispersed in the [B] solvent.

[[C]酸產生劑] [[C] Acid generator]

[C]酸產生劑係藉由曝光或加熱而產生酸的成分。該基底膜形成用組成物,藉由含有[C]酸產生劑,可促進[A]化合物與Si-OH或Si-H之反應,其結果,可更加抑制[A]化合物之分布不均,更良好地藉由自我組織化來形成相分離構造,且形成更加矩形的圖型。 [C] The acid generator is a component that generates an acid by exposure or heating. The composition for forming a base film can promote the reaction between the [A] compound and Si-OH or Si-H by containing a [C] acid generator. As a result, the uneven distribution of the [A] compound can be further suppressed. Phase separation structure is better formed by self-organization, and a more rectangular pattern is formed.

[C]酸產生劑,可列舉例如三苯基鋶三氟甲磺酸鹽、三苯基鋶2-(金剛烷-1-基羰氧基)-1,1,3,3,3-五氟丙烷-1-磺酸鹽、三苯基鋶降莰烷磺內酯-2-基氧羰基二氟甲磺酸鹽、三苯基鋶哌啶-1-基磺醯基-1,1,2,2,3,3-六氟丙烷-1-磺酸鹽、三苯基鋶金剛烷-1-基氧羰基二氟甲磺酸鹽、4-環己基苯基二苯基鋶樟腦磺酸鹽、4-甲烷磺醯基苯基二苯基鋶九氟-n-丁磺酸鹽、三苯基鋶2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙烷-1-磺酸鹽等之鋶鹽;1-(4-n-丁氧基萘-1-基)四氫噻吩鎓三氟甲磺酸鹽、1-(6-n-丁氧基萘-1-基)四氫噻吩鎓2-雙環[2.2.1]庚-2-基-1,1,2,2-四氟乙烷-1-磺酸鹽、1-(3,5-二甲基-4-羥基苯基)四氫噻吩鎓樟腦磺酸鹽等之四氫噻吩鎓鹽;N-(三氟甲烷磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-(樟腦磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧醯亞胺等之N-磺醯氧基醯亞胺化合物;二苯基錪三氟甲磺酸鹽、雙(4-t-丁基苯基)錪三氟甲磺酸鹽、雙(4-t-丁基苯基)錪九氟-n-丁磺酸鹽、4-甲 氧基苯基苯基錪樟腦磺酸鹽等之錪鹽等。 [C] Examples of the acid generator include triphenylsulfonium triflate, triphenylsulfonium 2- (adamantane-1-ylcarbonyloxy) -1,1,3,3,3-penta Fluoropropane-1-sulfonate, triphenylphosphonium norbornane sultone-2-yloxycarbonyl difluoromethanesulfonate, triphenylphosphonium piperidin-1-ylsulfonyl-1,1, 2,2,3,3-hexafluoropropane-1-sulfonate, triphenylphosphonium adamantane-1-yloxycarbonyl difluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium camphorsulfonic acid Salt, 4-methanesulfonylphenyldiphenylsulfonium nona-n-butanesulfonate, triphenylsulfonium 2- (bicyclo [2.2.1] hept-2-yl) -1,1,2, Sulfonium salts such as 2-tetrafluoroethane-1-sulfonate; 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothienium trifluoromethanesulfonate, 1- (6-n -Butoxynaphthalen-1-yl) tetrahydrothienylium 2-bicyclo [2.2.1] heptan-2-yl-1,1,2,2-tetrafluoroethane-1-sulfonate, 1- ( Tetrahydrothienium salts such as 3,5-dimethyl-4-hydroxyphenyl) tetrahydrothienium camphorsulfonate; N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxyfluorenimine, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyfluorenimine, etc. Sulfonium imine compounds; diphenylsulfonium triflate, bis (4 -t-butylphenyl) fluorene triflate, bis (4-t-butylphenyl) fluorene nonafluoro-n-butanesulfonate, 4-formyl The sulfonium salt of oxyphenylphenyl camphor sulfonate and the like.

此等可單獨使用,亦可合併使用2種以上。 These can be used alone or in combination of two or more.

[C]酸產生劑中所含的陰離子種類,較佳為氟化磺酸陰離子。 [C] The type of anions contained in the acid generator is preferably a fluorinated sulfonic acid anion.

[C]酸產生劑中所含的陽離子種類,較佳為鋶陽離子、及錪陽離子。 [C] The type of cations contained in the acid generator is preferably a sulfonium cation and a sulfonium cation.

[C]酸產生劑較佳為鋶鹽、及錪鹽。 [C] The acid generator is preferably a sulfonium salt and a sulfonium salt.

該基底膜形成用組成物含有[C]酸產生劑時,[C]酸產生劑之含量的下限,相對於[A]化合物100質量份而言,較佳為0.1質量份、更佳為0.5質量份。另一方面,[C]酸產生劑之含量的上限,相對於[A]化合物100質量份而言,較佳為30質量份、更佳為20質量份。藉由使[C]酸產生劑之含量成為上述範圍,可更加抑制[A]化合物之分布不均,其結果,可更良好地藉由自我組織化來形成相分離構造,且形成更加矩形的圖型。 When the base film forming composition contains a [C] acid generator, the lower limit of the content of the [C] acid generator is preferably 0.1 parts by mass and more preferably 0.5 relative to 100 parts by mass of the [A] compound. Parts by mass. On the other hand, the upper limit of the content of the [C] acid generator is preferably 30 parts by mass and more preferably 20 parts by mass relative to 100 parts by mass of the [A] compound. By making the content of the [C] acid generator into the above range, the uneven distribution of the [A] compound can be further suppressed, and as a result, a phase separation structure can be formed by self-organization, and a more rectangular shape can be formed. Pattern.

[其他任意成分] [Other optional ingredients]

該基底膜形成用組成物,於上述成分以外,亦可含有其他任意成分。上述其他任意成分,可列舉例如界面活性劑等。 The composition for forming a base film may contain other optional components in addition to the above-mentioned components. Examples of the other optional components include a surfactant and the like.

[界面活性劑] [Interactive agent]

界面活性劑係可提高對基板等之第1層之塗佈性的成分。上述界面活性劑之含量的上限,相對於[A]化合物100 質量份而言,較佳為2質量份、更佳為1.5質量份。 A surfactant is a component which can improve the coating property to the 1st layer, such as a board | substrate. The upper limit of the content of the above-mentioned surfactant is relative to [A] Compound 100 In terms of parts by mass, 2 parts by mass is preferred, and 1.5 parts by mass is more preferred.

<基底膜形成用組成物之配製方法> <Preparation method of base film formation composition>

該基底膜形成用組成物,可藉由例如將[A]化合物、[B]溶劑、及依需要之[C]酸產生劑等以特定比例混合而配製。又,該基底膜形成用組成物之固體成分濃度的下限,較佳為0.01質量%、更佳為0.1質量%。上述固體成分濃度之上限,較佳為30質量%、更佳為10質量%。 The composition for forming a base film can be prepared, for example, by mixing a [A] compound, a [B] solvent, and a [C] acid generator as needed in a specific ratio. The lower limit of the solid content concentration of the base film-forming composition is preferably 0.01% by mass, and more preferably 0.1% by mass. The upper limit of the solid content concentration is preferably 30% by mass, and more preferably 10% by mass.

<自我組織化微影製程> <Self-organized lithography process>

自我組織化(Directed Self Assembly),係指不僅起因於來自外部要因的控制,而自發性地構築組織或構造的現象。藉由於特定之基底上,塗佈例如自我組織化組成物等,形成具有自我組織化所致之相分離構造的膜(自我組織化膜),可藉由將該自我組織化膜之一部分的相予以去除,形成自我組織化圖型。 Self-organization (Directed Self Assembly) refers to the phenomenon of spontaneously constructing an organization or structure not only caused by control from external factors. By coating, for example, a self-organizing composition on a specific substrate, a film (self-organizing film) having a phase separation structure due to self-organization is formed, and a phase of a part of the self-organizing film can be formed. It is removed to form a self-organizing pattern.

該自我組織化微影製程,例如係具備於含有矽原子之第1層上藉由基底膜形成用組成物形成基底膜之步驟(以下亦稱為「基底膜形成步驟」)、於上述基底膜之與上述第1層相反側的面形成自我組織化膜之步驟(以下亦稱為「自我組織化膜形成步驟」)、及去除上述自我組織化膜之至少一部分的相之步驟(以下亦稱為「去除步驟」),且上述基底膜形成用組成物係該基底膜形成用組成物。 The self-organizing lithography process includes, for example, a step of forming a base film from a base film-forming composition on a first layer containing silicon atoms (hereinafter also referred to as a "base film forming step"), A step of forming a self-organizing film on a surface opposite to the first layer (hereinafter also referred to as a "self-organizing film forming step"), and a step of removing at least a portion of the phase of the self-organizing film (hereinafter also referred to as It is a "removal step"), and the above-mentioned base film-forming composition is the base film-forming composition.

自我組織化微影製程,亦可於基底膜形成步驟與上述自我組織化膜形成步驟之間,亦即基底膜形成步驟後、自我組織化膜形成步驟前,具備於上述基底膜之與上述第1層相反側的面、例如於形成有上述基底膜之第1層上,使用預圖型形成用組成物來形成預圖型之步驟(以下亦稱為「預圖型形成步驟」)。 The self-organizing lithography process may also be provided between the above-mentioned base film and the above-mentioned first base film forming step and the above-mentioned self-organizing film forming step, that is, after the base film forming step and before the self-organizing film forming step. A step of forming a pre-pattern using a composition for forming a pre-pattern on a surface opposite to the first layer, for example, on the first layer on which the above-mentioned base film is formed (hereinafter also referred to as a "pre-pattern forming step").

該自我組織化微影製程,亦可於去除步驟後,具備使第1層圖型化之步驟(以下亦稱為「第1層圖型化步驟」)。以下,針對第1層為基板的情況時的各步驟,使用圖1~5來說明。 This self-organized lithography process may also include a step of patterning the first layer after the removal step (hereinafter also referred to as a "first layer patterning step"). Hereinafter, each step when the first layer is a substrate will be described using FIGS. 1 to 5.

[基底膜形成步驟] [Base film formation step]

本步驟中,於基板101上藉由基底膜形成用組成物來形成基底膜。藉由進行本步驟。如圖1所示般,可得到於基板101上具備基底膜102之基板101、即形成有基底膜之基板101。自我組織化膜105係於此基底膜102上層合而形成。自我組織化膜105中,藉由於形成相分離構造(微相(microdomain)構造)之時對基板101形成基底膜,成為可控制構造,可簡便且良好地形成自我組織化所致之相分離構造,可形成矩形的圖型等。 In this step, a base film is formed on the substrate 101 with a composition for forming a base film. By performing this step. As shown in FIG. 1, a substrate 101 including a base film 102 on a substrate 101, that is, a substrate 101 on which a base film is formed can be obtained. The self-organizing film 105 is formed by laminating the base film 102. In the self-organizing film 105, since a base film is formed on the substrate 101 when a phase separation structure (microdomain structure) is formed, it becomes a controllable structure, and a phase separation structure due to self-organization can be easily and well formed. , Can form rectangular patterns and so on.

自我組織化微影製程所用之基板101,只要含有矽原子,則無特殊限定,可列舉例如矽晶圓等之含有矽原子之基板、形成有矽氧烷膜之金屬基板等,此等之中較佳為含有矽原子之基板、更佳為矽晶圓。再者,基板101 通常係因空氣中之氧、水等之作用,於其表面具有Si-OH或Si-H。又,基板101亦能夠以硫酸等之酸進行表面處理,而於其表面具有Si-OH或Si-H。 The substrate 101 used in the self-organized lithography process is not particularly limited as long as it contains silicon atoms, and examples include substrates containing silicon atoms, such as silicon wafers, and metal substrates having a siloxane film. A substrate containing silicon atoms is preferred, and a silicon wafer is more preferred. Furthermore, the substrate 101 Usually it is Si-OH or Si-H on the surface due to the action of oxygen and water in the air. In addition, the substrate 101 may be surface-treated with an acid such as sulfuric acid, and may have Si-OH or Si-H on its surface.

上述基底膜形成方法並無特殊限定,可列舉例如將以旋轉塗佈法等之周知方法於基板101上塗佈該基底膜形成用組成物所形成之塗膜,予以加熱或曝光藉以硬化之方法等。該曝光所用之放射線,可列舉例如可見光線、紫外線、遠紫外線、X射線、電子束、γ射線、分子束、離子束等。 The above-mentioned base film forming method is not particularly limited, and examples thereof include a method in which a coating film formed by coating the base film-forming composition on a substrate 101 by a well-known method such as a spin coating method is heated and exposed to harden. Wait. Examples of the radiation used in this exposure include visible light, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, gamma rays, molecular beams, and ion beams.

加熱上述塗膜時的溫度之下限,較佳為100℃、更佳為120℃。上述溫度之上限,較佳為400℃、更佳為350℃。加熱上述塗膜時的時間之下限,較佳為10秒、更佳為30秒。上述時間之上限,較佳為600秒、更佳為300秒。藉由使形成基底膜時的加熱溫度及時間成為上述範圍,可更加抑制[A]化合物之分布不均。就加熱上述塗膜時的環境而言,並無特殊限定,可於空氣環境下、亦可於氮氣中等之惰性氣體環境下。又,加熱上述塗膜後,亦可進行溶劑洗淨。 The lower limit of the temperature when heating the coating film is preferably 100 ° C, and more preferably 120 ° C. The upper limit of the temperature is preferably 400 ° C, and more preferably 350 ° C. The lower limit of the time when the coating film is heated is preferably 10 seconds, and more preferably 30 seconds. The upper limit of the time is preferably 600 seconds, and more preferably 300 seconds. By setting the heating temperature and time during formation of the base film to the above ranges, the uneven distribution of the [A] compound can be further suppressed. The environment when the coating film is heated is not particularly limited, and it can be used in an air environment or an inert gas environment such as nitrogen. Moreover, after the said coating film is heated, you may wash it with a solvent.

上述基底膜102之平均膜厚的下限,較佳為0.5nm、更佳為1nm、又更佳為5nm。上述平均膜厚的上限,較佳為2,000nm、更佳為100nm、又更佳為50nm。 The lower limit of the average film thickness of the base film 102 is preferably 0.5 nm, more preferably 1 nm, and even more preferably 5 nm. The upper limit of the average film thickness is preferably 2,000 nm, more preferably 100 nm, and even more preferably 50 nm.

[預圖型形成步驟] [Pre-pattern forming step]

本步驟中,如圖2所示,係於上述基底膜102上使用 預圖型形成用組成物來形成預圖型103。藉由進行本步驟,可更加控制形成自我組織化膜105時之相分離,更良好地藉由自我組織化來形成相分離構造。亦即,形成自我組織化膜105之成分等當中,與預圖型103之側面的親和性高的成分等,係沿著預圖型103而形成相,親和性低的成分等,係於遠離預圖型103的位置形成相。藉此,可更良好地藉由自我組織化來形成相分離構造。又,可依預圖型103之材質、長度、厚度、形狀等,來細微地控制所形成之相分離構造。進一步地,預圖型103,亦可藉由部分曝光、雷射剝蝕等來進行部分改質。再者,就預圖型103而言,可配合最終欲形成的圖型來適當選擇,例如可使用線與間距(line and space)圖型、孔洞(hole)圖型、柱狀(pillar)圖型等。 In this step, as shown in FIG. 2, it is used on the base film 102 described above. The pre-pattern forming composition forms a pre-pattern 103. By performing this step, the phase separation at the time of forming the self-organizing film 105 can be more controlled, and the phase separation structure can be formed better by self-organizing. That is, among the components and the like forming the self-organizing film 105, the components and the like having high affinity with the side surface of the pre-pattern 103 form a phase along the pre-pattern 103, and the components and the like having low affinity are separated from each other The positions of the pre-pattern 103 form a phase. As a result, the phase separation structure can be formed better by self-organization. In addition, the phase separation structure formed can be finely controlled according to the material, length, thickness, shape, etc. of the pre-pattern 103. Further, the pre-pattern 103 may be partially modified by partial exposure, laser ablation, or the like. Furthermore, as for the pre-pattern pattern 103, it can be appropriately selected according to the pattern to be finally formed, for example, a line and space pattern, a hole pattern, and a pillar pattern can be used. Type and so on.

上述預圖型103之形成方法,可使用與周知之光阻圖型形成方法相同的方法。又,上述預圖型形成用之組成物,可使用以往之光阻膜形成用組成物。具體而言,作為預圖型103之形成方法,例如係使用JSR公司之「ARX2928JN」等之化學增幅型光阻組成物,於上述基底膜102上塗佈而形成光阻膜。之後,對上述光阻膜之期望的區域,透過特定圖型之遮罩照射放射線,進行曝光。上述放射線可列舉例如ArF準分子雷射光、KrF準分子雷射光等之遠紫外線、紫外線、X射線等之電磁波、電子束等之荷電粒子線等。此等之中,較佳為遠紫外線;更佳為ArF準分子雷射光、及KrF準分子雷射光;又更佳為ArF 準分子雷射光。之後,進行曝光後烘烤(PEB),使用鹼顯影液等之顯影液來進行顯影,可形成所期望的預圖型103。 As the method for forming the pre-pattern pattern 103, the same method as the well-known photoresist pattern formation method can be used. As the composition for forming the pre-pattern, the conventional composition for forming a photoresist film can be used. Specifically, as the method of forming the pre-pattern pattern 103, for example, a chemically amplified photoresist composition such as "ARX2928JN" from JSR Corporation is used to coat the base film 102 to form a photoresist film. Then, a desired area of the photoresist film is irradiated with radiation through a mask having a specific pattern to perform exposure. Examples of the radiation include far-ultraviolet rays such as ArF excimer laser light and KrF excimer laser light, electromagnetic waves such as ultraviolet rays and X-rays, and charged particle beams such as electron beams. Among these, far ultraviolet rays are preferred; ArF excimer laser light and KrF excimer laser light are more preferred; and ArF excimer laser light is further preferred. Excimer laser light. After that, post-exposure baking (PEB) is performed, and development is performed using a developer such as an alkali developer, to form a desired pre-pattern 103.

再者,亦可將上述預圖型103之表面進行疏水化處理或親水化處理。具體的處理方法,可列舉暴露於氫電漿一定時間之氫化處理等。藉由提高上述預圖型103之表面的疏水性或親水性,可促進上述自我組織化。 Furthermore, the surface of the pre-pattern 103 may be subjected to a hydrophobic treatment or a hydrophilic treatment. Specific treatment methods include hydrogenation treatment after exposure to a hydrogen plasma for a certain period of time. The self-organization can be promoted by increasing the hydrophobicity or hydrophilicity of the surface of the pre-pattern 103.

[自我組織化膜形成步驟] [Self-organizing film formation step]

本步驟中,係於上述基底膜102上形成自我組織化膜105。藉由進行本步驟,可得到於基底膜102上形成有自我組織化膜105的基板。該自我組織化膜105之形成,可例如藉由將含有可藉由自我組織化而形成相分離構造的成分之自我組織化組成物等塗佈於基底膜102上,以形成塗膜,並使該塗膜中之上述成分自我組織化等來進行。又,使用上述預圖型103的情況時,係如圖3所示,係於預圖型103之非層合區域,亦即以預圖型103所分隔的基底膜102上之區域,塗佈上述自我組織化組成物而形成塗膜,如圖4所示般,形成具有相分離構造之自我組織化膜105。 In this step, a self-organizing film 105 is formed on the base film 102. By performing this step, a substrate on which the self-organizing film 105 is formed on the base film 102 can be obtained. The self-organizing film 105 can be formed by, for example, applying a self-organizing composition containing a component capable of forming a phase separation structure by self-organizing to the base film 102 to form a coating film, and The aforementioned components in the coating film are self-organized and the like. In the case of using the pre-pattern 103, as shown in FIG. 3, it is applied to the non-layered area of the pre-pattern 103, that is, the area on the base film 102 separated by the pre-pattern 103, and applied. The self-organized composition is formed into a coating film, and as shown in FIG. 4, a self-organized film 105 having a phase separation structure is formed.

上述自我組織化膜105之形成時,藉由將上述自我組織化組成物塗佈於基底膜102上而形成塗膜後,進行退火等,可促進具有相同性質之部位彼此集結而自發地形成有序圖型即所謂自我組織化。藉此,於基底膜102 上形成具有相分離構造之自我組織化膜105。該相分離構造,較佳為沿著預圖型103而形成,更佳為藉由相分離所形成之界面,與預圖型103之側面呈大致平行。例如預圖型103為線圖型的情況時,與該預圖型103之親和性較高之成分等之相,係沿著預圖型103形成(105b),另一方之成分等之相,係於自預圖型103之側面起最遠離的部分,即於以預圖型103所分隔的區域之中央部分形成(105a),而形成交互配置有片(lamella)狀(板狀)之相的片狀相分離構造。預圖型103為孔洞圖型的情況時,係沿著預圖型103之孔洞側面,形成與預圖型103之親和性較高之成分等之相,於孔洞之中央部分形成另一方之成分等之相。又,預圖型103為柱狀圖型的情況時,係沿著預圖型103之柱狀的側面,形成與預圖型103之親和性較高之成分等之相,於遠離各自之柱狀的部分,形成另一方之成分等之相。藉由適當調整該預圖型103之柱狀間的距離、上述自我組織化組成物中之各聚合物等之成分的構造、摻合比率等,可形成所期望之相分離構造。再者,本步驟中所形成之相分離構造,係由複數的相所構成者,由此等相所形成之界面通常略呈垂直,但界面本身並不一定必須為明確。如此地,於基底膜102以外,藉由各化合物之成分的構造、摻合比率、預圖型103,可精密地控制所得到之相分離構造,得到更佳期望的微細圖型。 When the self-organizing film 105 is formed, the self-organizing composition is coated on the base film 102 to form a coating film, and then annealing is performed to promote the spontaneous formation of parts having the same properties. The sequence pattern is called self-organization. With this, the base film 102 A self-organizing film 105 having a phase separation structure is formed thereon. The phase separation structure is preferably formed along the pre-pattern 103, and more preferably, the interface formed by the phase separation is substantially parallel to the side surface of the pre-pattern 103. For example, when the pre-pattern 103 is a line pattern, the components with a higher affinity with the pre-pattern 103 are formed along the pre-pattern 103 (105b), and the other components are formed. It is the part farthest from the side of the pre-pattern 103, that is, formed in the central part of the area separated by the pre-pattern 103 (105a), and forms a lamella (plate-like) phase that is alternately arranged. Flake phase separation structure. When the pre-pattern 103 is a hole pattern, it forms along the side of the hole of the pre-pattern 103 to form a component with higher affinity with the pre-pattern 103, and forms the other component in the central part of the hole Equal phase. In the case where the pre-pattern 103 is a columnar pattern, it is formed along the side of the column of the pre-pattern 103 to form a component having a high affinity with the pre-pattern 103, and away from the respective columns. The shaped part forms a phase of the other component. By appropriately adjusting the distance between the columns of the pre-pattern 103, the structure of the components of each polymer and the like in the self-organizing composition, and the blending ratio, a desired phase separation structure can be formed. Moreover, the phase separation structure formed in this step is composed of a plurality of phases. The interface formed by the phases is usually slightly vertical, but the interface itself does not have to be clear. In this manner, with the exception of the base film 102, the structure of the components of each compound, the blending ratio, and the pre-pattern 103 can precisely control the phase separation structure obtained, and obtain a more desirable fine pattern.

就可藉由上述自我組織化而形成相分離構造的成分而言,只要係具有如此之性質,則無特殊限定,可 列舉例如嵌段共聚物、互不相溶之2種以上的聚合物之混合物等。此等之中,就可更良好地形成相分離構造的觀點而言,較佳為嵌段共聚物、更佳為由苯乙烯單位-甲基丙烯酸酯單位所成之嵌段共聚物、又更佳為由苯乙烯單位-甲基丙烯酸甲酯單位所成之二嵌段共聚物。 The components that can form a phase-separated structure by the above-mentioned self-organization are not particularly limited as long as they have such properties. Examples include block copolymers and mixtures of two or more polymers that are incompatible with each other. Among these, a block copolymer is more preferable from the viewpoint that a phase-separated structure can be formed more preferably, and a block copolymer composed of a styrene unit and a methacrylate unit is more preferable. The diblock copolymer is preferably a styrene unit-methyl methacrylate unit.

將上述自我組織化組成物塗佈於基板上形成塗膜104的方法並無特殊限定,可列舉例如將上述自我組織化組成物藉由旋轉塗佈法等予以塗佈之方法等。藉此,上述自我組織化組成物,係塗佈於上述基底膜102上之上述預圖型103間等,而形成塗膜104。 The method of applying the self-organizing composition to the substrate to form the coating film 104 is not particularly limited, and examples thereof include a method of applying the self-organizing composition by a spin coating method or the like. As a result, the self-organizing composition is applied to the pre-pattern 103 and the like on the base film 102 to form a coating film 104.

作為退火之方法,可列舉例如烘箱、加熱板等,較佳為於80℃以上且400℃以下之溫度、更佳為於80℃以上且300℃以下之溫度加熱的方法等。退火之時間的下限,較佳為10秒、更佳為30秒。退火之時間的上限,較佳為120分鐘、更佳為60分鐘。藉此所得之自我組織化膜105之平均膜厚的下限,較佳為0.1nm、更佳為0.5nm。上述平均膜厚之上限,較佳為500nm、更佳為100nm。 Examples of the annealing method include an oven, a hot plate, and the like, and a method of heating at a temperature of preferably 80 ° C. to 400 ° C., more preferably a temperature of 80 ° C. to 300 ° C., and the like. The lower limit of the annealing time is preferably 10 seconds, and more preferably 30 seconds. The upper limit of the annealing time is preferably 120 minutes, and more preferably 60 minutes. The lower limit of the average film thickness of the self-organizing film 105 thus obtained is preferably 0.1 nm, more preferably 0.5 nm. The upper limit of the average film thickness is preferably 500 nm, and more preferably 100 nm.

[去除步驟] [Removal steps]

本步驟中,如圖4及圖5所示,係將上述自我組織化膜105之至少一部分的相去除。藉由進行本步驟,可將上述自我組織化膜105所具有之相分離構造當中的一部分之相105a去除。使用藉由自我組織化而進行相分離後之各 相的蝕刻率之差等,可藉由蝕刻處理將一部分之相去除。此時,可將預圖型103同樣地或另外去除。將相分離構造當中之一部分的相105a及預圖型103去除後的狀態,係如圖5所示。 In this step, as shown in FIGS. 4 and 5, the phase of at least a part of the self-organizing film 105 is removed. By performing this step, a part of the phase 105a in the phase separation structure of the self-organizing film 105 can be removed. Use each phase separated by self-organization The difference in the etching rate of the phases can be removed by an etching process. In this case, the pre-pattern 103 may be removed in the same manner or separately. FIG. 5 shows a state where the phase 105a and the pre-pattern 103 of one part of the phase separation structure are removed.

上述自我組織化膜105所具有之相分離構造當中之一部分的相105a或預圖型103之去除方法,可列舉例如化學乾式蝕刻、化學濕式蝕刻等之反應性離子蝕刻(RIE);濺鍍蝕刻、離子束蝕刻等之物理蝕刻等之周知的方法。此等之中,較佳為反應性離子蝕刻(RIE);更佳為使用CF4、O2氣體等之化學乾式蝕刻;使用甲基異丁基酮(MIBK)、2-丙醇(IPA)等之有機溶劑、及氫氟酸等之液體蝕刻液的化學濕式蝕刻(濕式顯影)。 The method of removing the phase 105a or the pre-pattern 103 of a part of the phase separation structure of the self-organizing film 105 includes reactive ion etching (RIE) such as chemical dry etching, chemical wet etching, and sputtering; Well-known methods such as physical etching such as etching and ion beam etching. Among these, reactive ion etching (RIE) is preferred; chemical dry etching using CF 4 or O 2 gas is more preferred; methyl isobutyl ketone (MIBK) or 2-propanol (IPA) is used Chemical wet etching (wet development) of organic solvents such as organic solvents and liquid etching solutions such as hydrofluoric acid.

[第1層圖型化步驟(基板圖型化步驟)] [First layer patterning step (substrate patterning step)]

本步驟中,係形成基板圖型。藉由進行本步驟,能夠以由殘存之相分離膜的一部分之相105b所構成之圖型作為遮罩,藉由蝕刻基底膜102及基板來進行圖型化。對基板之圖型化結束後,作為遮罩所使用之相係藉由溶解處理等從基板上被去除,最終可得到經圖型化之基板(圖型)。該所得到之圖型,可列舉例如線與間距圖型、孔洞圖型等。上述蝕刻之方法,可使用與上述去除步驟同樣之方法,蝕刻氣體及蝕刻溶液,可依基底膜102及基板之材質而適當選擇。例如基板為矽材料時,可使用氟氯烷系氣體與SF4之混合氣體等。又,基板為金屬膜時,可使用 BCl3與Cl2之混合氣體等。藉由該自我組織化微影製程所得到之圖型,適合使用於半導體元件等,進一步地上述半導體元件係廣泛使用於LED、太陽電池等。 In this step, a substrate pattern is formed. By performing this step, the pattern can be patterned by etching the base film 102 and the substrate using the pattern composed of the phase 105b that is a part of the remaining phase separation membrane as a mask. After the patterning of the substrate is finished, the phase used as a mask is removed from the substrate by a dissolution process or the like, and finally a patterned substrate (pattern) can be obtained. Examples of the obtained patterns include line and pitch patterns, hole patterns, and the like. The above-mentioned etching method can be the same as the above-mentioned removal step. The etching gas and the etching solution can be appropriately selected depending on the materials of the base film 102 and the substrate. For example, when the substrate is a silicon material, a mixed gas of a chlorochloroethane gas and SF 4 can be used. When the substrate is a metal film, a mixed gas of BCl 3 and Cl 2 can be used. The pattern obtained by this self-organized lithography process is suitable for use in semiconductor devices and the like. Further, the above semiconductor devices are widely used in LEDs, solar cells, and the like.

就本實施形態而言,雖以第1層為基板的情況為例來說明,但第1層並無特殊限定,例如亦能夠以形成於基材上之含有矽原子之層作為第1層。 In this embodiment, although the case where the first layer is a substrate is used as an example, the first layer is not particularly limited. For example, a layer containing a silicon atom formed on a substrate can be used as the first layer.

又,就本實施形態而言,雖係藉由退火來形成具有相分離構造之膜,但自我組織化膜之形成方法並無特殊限定,可列舉例如不僅起因於來自外部要因的控制,而自發地形成的方法。 In addition, in this embodiment, although a film having a phase separation structure is formed by annealing, the method for forming a self-organizing film is not particularly limited, and examples thereof include spontaneity caused not only by control from external factors Ground formation method.

[實施例] [Example]

以下,基於實施例以具體地說明本發明,但本發明不受此等實施例限定。各種物性值之測定方法如以下所示。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. The measurement methods of various physical properties are shown below.

[重量平均分子量(Mw)及數平均分子量(Mn)] [Weight average molecular weight (Mw) and number average molecular weight (Mn)]

使用GPC管柱(東曹公司之「G2000HXL」2根、「G3000HXL」1根及「G4000HXL」1根),以流量:1.0mL/分鐘、溶出溶劑:四氫呋喃、管柱溫度:40℃之分析條件,藉由以單分散聚苯乙烯為標準之凝膠滲透層析(GPC)來測定。 Analytical conditions using GPC columns (two "G2000HXL", one "G3000HXL", and one "G4000HXL" from Tosoh Corporation), flow rate: 1.0 mL / min, dissolution solvent: tetrahydrofuran, column temperature: 40 ° C , Measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard.

[13C-NMR分析] [ 13 C-NMR analysis]

13C-NMR分析,係使用日本電子公司之「JNM-EX400」,使用DMSO-d6作為測定溶劑來進行。各構造單位之含有比例,係由於13C-NMR分析所得之光譜中對應於各構造單位的波峰面積比來算出。 13 C-NMR analysis was performed using "JNM-EX400" of Japan Electronics Corporation and DMSO-d 6 as a measurement solvent. The content ratio of each structural unit is calculated from the peak area ratio corresponding to each structural unit in the spectrum obtained by 13 C-NMR analysis.

<化合物、鏈轉移劑及聚合物之製造> <Manufacture of compounds, chain transfer agents, and polymers>

實施例及比較例中使用之鏈轉移劑、化合物及聚合物之製造方法係如以下所示。 The manufacturing methods of the chain transfer agent, compound, and polymer used in an Example and a comparative example are as follows.

[合成例1](化合物(A-1)之製造) [Synthesis Example 1] (Production of compound (A-1))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯51g(0.49mol)、甲基丙烯酸甲酯49g(0.49mol)及巰基-1,2-丙二醇3g(0.027mol)之混合溶液與作為自由基聚合起始劑之2,2’-偶氮雙(2,4-二甲基戊腈)3g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-1)的溶液。化合物(A-1)之Mw為7,285、Mn為5,465、Mw/Mn為1.33。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C and take 3 hours at the same temperature to add 100g of methyl ethyl ketone, 51g (0.49mol) of styrene, 49g (0.49mol) of methyl methacrylate, and 3g of mercapto-1,2-propanediol ( 0.027 mol) mixed solution with a mixed solution of 3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) and 100 g of methyl ethyl ketone as a radical polymerization initiator, and polymerized at this temperature 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-1). The Mw of the compound (A-1) was 7,285, the Mn was 5,465, and the Mw / Mn was 1.33.

[合成例2](化合物(A-2)之製造) [Synthesis Example 2] (Production of compound (A-2))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮 100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯46g(0.442mol)、甲基丙烯酸甲酯49g(0.489mol)、甲基丙烯酸環氧丙酯5g(0.035mol)及巰基-1,2-丙二醇3g(0.027mol)之混合溶液與2,2'-偶氮雙(2-甲基丙腈)3g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-2)的溶液。化合物(A-2)之Mw為6,715、Mn為4,874、Mw/Mn為1.38。 In a flask equipped with a cooling tube and a stirrer, feed methyl ethyl ketone 100 g were substituted with nitrogen. Heated to 85 ° C, and at the same temperature, it took 3 hours to add 100 g of methyl ethyl ketone, 46 g (0.442 mol) of styrene, 49 g (0.489 mol) of methyl methacrylate, and 5 g of glycidyl methacrylate ( 0.035mol) and a mixed solution of mercapto-1,2-propanediol 3g (0.027mol) and a mixed solution of 2,2'-azobis (2-methylpropionitrile) 3g and methyl ethyl ketone 100g Polymerize at temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-2). Compound (A-2) had Mw of 6,715, Mn of 4,874, and Mw / Mn of 1.38.

[合成例3](化合物(A-3)之製造) [Synthesis Example 3] (Production of compound (A-3))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下於甲基乙基酮100g、苯乙烯51g(0.49mol)、甲基丙烯酸甲酯49g(0.49mol)及巰基-1,2-丙二醇3g(0.027mol)之混合溶液中花費3小時各滴入日油公司之「Perbutyl O」(己酸t-丁基過氧基-2-乙酯)4g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-3)的溶液。化合物(A-3)之Mw為6,802、Mn為4,834、Mw/Mn為1.41。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C and mix at the same temperature with 100 g of methyl ethyl ketone, 51 g (0.49 mol) of styrene, 49 g (0.49 mol) of methyl methacrylate, and 3 g (0.027 mol) of mercapto-1,2-propanediol. It took 3 hours in the solution to drop into a mixed solution of 4 g of "Perbutyl O" (t-butylperoxy-2-ethyl hexanoate) and 100 g of methyl ethyl ketone, and polymerized at this temperature for 3 hours. . The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-3). The compound (A-3) had Mw of 6,802, Mn of 4,834, and Mw / Mn of 1.41.

[合成例4](化合物(A-4)之製造) [Synthesis Example 4] (Production of compound (A-4))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯48g(0.46mol)、甲基丙烯酸甲酯46g(0.46mol)、甲基丙烯酸環己酯6g(0.036mol)及9-巰基-1-壬醇4.9g(0.027mol)之混合溶液與2,2'-偶氮雙(2,4-二甲基戊腈)3g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-4)的溶液。化合物(A-4)之Mw為7,132、Mn為5,465、Mw/Mn為1.31。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and take 3 hours at the same temperature to add 100 g of methyl ethyl ketone, 48 g (0.46 mol) of styrene, 46 g (0.46 mol) of methyl methacrylate, and 6 g (0.036 of cyclohexyl methacrylate). mol) and 4.9 g (0.027 mol) of 9-mercapto-1-nonanol, 3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) and 100 g of methyl ethyl ketone The solution was polymerized while maintaining the temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-4). The compound (A-4) had Mw of 7,132, Mn of 5,465, and Mw / Mn of 1.31.

[合成例5](化合物(A-5)之製造) [Synthesis Example 5] (Production of compound (A-5))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯51g(0.49mol)、甲基丙烯酸甲酯49g(0.49mol)及3-巰基丙基三甲氧基矽烷5.3g(0.027mol)之混合溶液與2,2'-偶氮雙(2,4-二甲基戊腈)3g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此 所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-5)的溶液。化合物(A-5)之Mw為7,048、Mn為5,121、Mw/Mn為1.38。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and add 100 g of methyl ethyl ketone, 51 g (0.49 mol) of styrene, 49 g (0.49 mol) of methyl methacrylate, and 3-mercaptopropyltrimethoxysilane dropwise at the same temperature for 3 hours. A mixed solution of 5.3 g (0.027 mol) of a mixed solution with 3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) and 100 g of methyl ethyl ketone was polymerized at this temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Propylene glycol monomethyl ether acetate was added to the obtained material to obtain a solution containing 10% by mass of the compound (A-5). The compound (A-5) had Mw of 7,048, Mn of 5,121, and Mw / Mn of 1.38.

[合成例6](化合物(A-6)之製造) [Synthesis Example 6] (Production of compound (A-6))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯48g(0.46mol)、甲基丙烯酸甲酯46g(0.46mol)、甲基丙烯酸二環戊酯6g(0.027mol)及3-巰基丙基二甲氧基甲基矽烷4.9g(0.027mol)之混合溶液與2,2'-偶氮雙(2,4-二甲基戊腈)3g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-6)的溶液。化合物(A-6)之Mw為7,197、Mn為5,063、Mw/Mn為1.42。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and drop in 100g of methyl ethyl ketone, 48g (0.46mol) of styrene, 46g (0.46mol) of methyl methacrylate, and 6g of dicyclopentyl methacrylate at the same temperature for 3 hours. 0.027mol) and 3-mercaptopropyldimethoxymethylsilane 4.9g (0.027mol) mixed solution with 2,2'-azobis (2,4-dimethylvaleronitrile) 3g and methyl ethyl A mixed solution of 100 g of ketone was polymerized at this temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of Compound (A-6) in solution. Compound (A-6) had Mw of 7,197, Mn of 5,063, and Mw / Mn of 1.42.

[合成例7](化合物(A-7)之製造) [Synthesis Example 7] (Production of compound (A-7))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯51g(0.49mol)、甲基丙烯酸甲酯49g(0.49mol)及巰基十一烯5.5g(0.027mol)之混合溶液與2,2'-偶氮雙(2,4-二甲基戊 腈)3g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-7)的溶液。化合物(A-7)之Mw為7,201、Mn為5,114、Mw/Mn為1.41。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and take 3 hours at the same temperature to add 100g of methyl ethyl ketone, 51g (0.49mol) of styrene, 49g (0.49mol) of methyl methacrylate, and 5.5g (0.027mol of mercaptadecene). ) Mixed solution with 2,2'-azobis (2,4-dimethylpentane A mixed solution of 3 g of nitrile) and 100 g of methyl ethyl ketone was polymerized while maintaining the temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-7). The compound (A-7) had Mw of 7,201, Mn of 5,114, and Mw / Mn of 1.41.

[合成例8](化合物(A-8)之製造) [Synthesis Example 8] (Production of compound (A-8))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g及苯乙烯100g(1.00mol)之混合溶液與日油公司之「Perbutyl O」8g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-8)的溶液。化合物(A-8)之Mw為7,365、Mn為5,312、Mw/Mn為1.39。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and spend 3 hours at the same temperature, dropwise add a mixed solution of 100 g of methyl ethyl ketone and 100 g (1.00 mol) of styrene with 8 g of "Perbutyl O" and 100 g of methyl ethyl ketone. The solutions were mixed and polymerized at this temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-8). Compound (A-8) had Mw of 7,365, Mn of 5,312, and Mw / Mn of 1.39.

[合成例9](化合物(A-9)之製造) [Synthesis Example 9] (Production of compound (A-9))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g及甲基丙烯酸甲酯100g(1.00mol)之混合溶液與日油公司之「Perbutyl O」8g及 甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-9)的溶液。化合物(A-9)之Mw為7,732、Mn為5,862、Mw/Mn為1.32。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C and spend 3 hours at the same temperature, dropwise add a mixed solution of 100 g of methyl ethyl ketone and 100 g (1.00 mol) of methyl methacrylate and 8 g of "Perbutyl O" A mixed solution of 100 g of methyl ethyl ketone was polymerized at this temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-9). Compound (A-9) had Mw of 7,732, Mn of 5,862, and Mw / Mn of 1.32.

[合成例10](化合物(A-10)之製造) [Synthesis Example 10] (Production of compound (A-10))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯45g(0.43mol)、甲基丙烯酸甲酯43g(0.43mol)、甲基丙烯酸2-乙醯乙醯氧基乙酯12g(0.056mol)及3-巰基丙基三甲氧基矽烷5.3g(0.027mol)之混合溶液與2,2'-偶氮雙(2,4-二甲基戊腈)3g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-11)的溶液。化合物(A-11)之Mw為7,045、Mn為5,076、Mw/Mn為1.39。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and take 3 hours at the same temperature to add 100 g of methyl ethyl ketone, 45 g (0.43 mol) of styrene, 43 g (0.43 mol) of methyl methacrylate, and 2-ethyl acetoacetate methacrylate. A mixed solution of 12 g (0.056 mol) of ethoxyethyl and 5.3 g (0.027 mol) of 3-mercaptopropyltrimethoxysilane and 3 g of 2,2'-azobis (2,4-dimethylvaleronitrile) and A mixed solution of 100 g of methyl ethyl ketone was polymerized at this temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-11). Compound (A-11) had Mw of 7,045, Mn of 5,076, and Mw / Mn of 1.39.

[合成例11](鏈轉移劑(a-1)之製造) [Synthesis Example 11] (Production of chain transfer agent (a-1))

氮環境下,於三口燒瓶中饋入3-巰基丙基三甲氧基矽烷32.6g(0.166mol)及n-丁基三甲氧基矽烷31.9g (0.179mol),添加甲基異丁基酮100g使其溶解,將所得之溶液以磁攪拌器攪拌,同時加溫至60℃。於此溶液中,花費1小時連續地添加含1質量%之草酸的8.6g之草酸水溶液,於60℃進行4小時反應。之後,於減壓下餾去水、甲醇、甲基異丁基酮。將所得之生成物溶解於甲苯,以分液漏斗水洗3次,使用乾燥劑脫水,於減壓下餾去甲苯,然後以丙二醇單甲基醚乙酸酯稀釋,得到含10質量%之鏈轉移劑(a-1)的溶液。鏈轉移劑(a-1)之Mw為2,615、Mn為1,214、Mw/Mn為2.15。針對所得之鏈轉移劑進行IR光譜測定後,於3750cm-1確認到來自矽醇基之吸收。 In a nitrogen environment, 32.6 g (0.166 mol) of 3-mercaptopropyltrimethoxysilane and 31.9 g (0.179 mol) of n-butyltrimethoxysilane were fed into a three-necked flask, and 100 g of methyl isobutyl ketone was added to It was dissolved, and the resulting solution was stirred with a magnetic stirrer while warming to 60 ° C. To this solution, 8.6 g of an oxalic acid aqueous solution containing 1% by mass of oxalic acid was continuously added over 1 hour, and a reaction was performed at 60 ° C for 4 hours. Thereafter, water, methanol and methyl isobutyl ketone were distilled off under reduced pressure. The obtained product was dissolved in toluene, washed with water in a separatory funnel three times, dehydrated with a desiccant, and toluene was distilled off under reduced pressure, and then diluted with propylene glycol monomethyl ether acetate to obtain a chain transfer containing 10% by mass. Agent (a-1). Mw of the chain transfer agent (a-1) was 2,615, Mn was 1,214, and Mw / Mn was 2.15. After IR spectrum measurement was performed on the obtained chain transfer agent, absorption from a silanol group was confirmed at 3750 cm -1 .

[合成例12](鏈轉移劑(a-2)之製造) [Synthesis Example 12] (Production of chain transfer agent (a-2))

氮環境下,於三口燒瓶中饋入3-巰基丙基三甲氧基矽烷32.6g(0.166mol)及甲基三甲氧基矽烷24.4g(0.179mol),添加甲基異丁基酮100g使其溶解,將所得之溶液以磁攪拌器攪拌,同時加溫至60℃。於此溶液中,花費1小時連續地添加含1質量%之草酸的8.6g之草酸水溶液,於60℃進行4小時反應。之後,於減壓下餾去水、甲醇、甲基異丁基酮。將所得之生成物溶解於甲苯,以分液漏斗水洗3次,使用乾燥劑脫水,於減壓下餾去甲苯,然後以丙二醇單甲基醚乙酸酯稀釋,得到含10質量%之鏈轉移劑(a-2)的溶液。鏈轉移劑(a-2)之Mw為2,738、Mn為1,241、Mw/Mn為2.21。針對所得之鏈轉 移劑進行IR光譜測定後,於3750cm-1確認到來自矽醇基之吸收。 In a nitrogen environment, 32.6 g (0.166 mol) of 3-mercaptopropyltrimethoxysilane and 24.4 g (0.179 mol) of methyltrimethoxysilane were fed into a three-necked flask, and 100 g of methyl isobutyl ketone was added to dissolve the same. , The resulting solution was stirred with a magnetic stirrer while being heated to 60 ° C. To this solution, 8.6 g of an oxalic acid aqueous solution containing 1% by mass of oxalic acid was continuously added over 1 hour, and a reaction was performed at 60 ° C for 4 hours. Thereafter, water, methanol and methyl isobutyl ketone were distilled off under reduced pressure. The obtained product was dissolved in toluene, washed with water in a separatory funnel three times, dehydrated with a desiccant, and toluene was distilled off under reduced pressure, and then diluted with propylene glycol monomethyl ether acetate to obtain a chain transfer containing 10% by mass. Agent (a-2). Mw of the chain transfer agent (a-2) was 2,738, Mn was 1,241, and Mw / Mn was 2.21. After IR spectrum measurement was performed on the obtained chain transfer agent, absorption from a silanol group was confirmed at 3750 cm -1 .

[合成例13](化合物(A-11)之製造) [Synthesis Example 13] (Production of compound (A-11))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯51g(0.49mol)、甲基丙烯酸甲酯49g(0.49mol)及含10質量%之鏈轉移劑(a-1)的溶液30g之混合溶液與2,2'-偶氮雙(2-甲基丙腈)3g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-1)的溶液。化合物(A-1)之Mw為8,280、Mn為4,465、Mw/Mn為1.84。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and take 3 hours at the same temperature to add 100 g of methyl ethyl ketone, 51 g (0.49 mol) of styrene, 49 g (0.49 mol) of methyl methacrylate and 10% by mass of a chain transfer agent ( a-1) A mixed solution of 30 g of the solution, a mixed solution of 3 g of 2,2′-azobis (2-methylpropionitrile) and 100 g of methyl ethyl ketone, and the polymerization was maintained at this temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-1). Mw of the compound (A-1) was 8,280, Mn was 4,465, and Mw / Mn was 1.84.

[合成例14](化合物(A-12)之製造) [Synthesis Example 14] (Production of compound (A-12))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯51g(0.49mol)、甲基丙烯酸甲酯49g(0.49mol)及含10質量%之鏈轉移劑(a-1)的溶液30g之混合溶液與日油公司之「Perbutyl O」(己酸t-丁基過氧基-2-乙酯)4g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶 液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-2)的溶液。化合物(A-2)之Mw為7,880、Mn為4,267、Mw/Mn為1.85。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and take 3 hours at the same temperature to add 100 g of methyl ethyl ketone, 51 g (0.49 mol) of styrene, 49 g (0.49 mol) of methyl methacrylate and 10% by mass of a chain transfer agent ( a-1) Mixed solution of 30g of mixed solution with 4g of "Perbutyl O" (t-butylperoxy-2-ethylhexanoate) and 100g of methyl ethyl ketone of Nippon Oil Company, keep this temperature Polymerize for 3 hours. Dissolve the obtained compound The solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained product to obtain a compound (A- 2) Solution. The Mw of the compound (A-2) was 7,880, the Mn was 4,267, and the Mw / Mn was 1.85.

[合成例15](化合物(A-13)之製造) [Synthesis Example 15] (Production of compound (A-13))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯48g(0.46mol)、甲基丙烯酸甲酯46g(0.46mol)、甲基丙烯酸二環戊酯6g(0.027mol)及含10質量%之鏈轉移劑(a-2)的溶液30g之混合溶液與2,2'-偶氮雙(2-甲基丙腈)3g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-3)的溶液。化合物(A-3)之Mw為8,280、Mn為4,465、Mw/Mn為1.84。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and drop in 100g of methyl ethyl ketone, 48g (0.46mol) of styrene, 46g (0.46mol) of methyl methacrylate, and 6g of dicyclopentyl methacrylate at the same temperature for 3 hours. 0.027 mol) and a mixed solution containing 30 g of a solution containing 10% by mass of a chain transfer agent (a-2) and a mixture of 3 g of 2,2'-azobis (2-methylpropionitrile) and 100 g of methyl ethyl ketone The solution was polymerized while maintaining the temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-3). The compound (A-3) had Mw of 8,280, Mn of 4,465, and Mw / Mn of 1.84.

[合成例16](化合物(A-14)之製造) [Synthesis Example 16] (Production of compound (A-14))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯51g(0.49mol)、甲 基丙烯酸甲酯49g(0.49mol)及含10質量%之鏈轉移劑(a-2)的溶液30g之混合溶液與日油公司之「Perbutyl O」4g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-14)的溶液。化合物(A-4)之Mw為7,750、Mn為3,987、Mw/Mn為1.94。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and take 3 hours at the same temperature to add 100 g of methyl ethyl ketone, 51 g (0.49 mol) of styrene, A mixed solution of 49 g (0.49 mol) of methyl acrylate and 30 g of a solution containing 10% by mass of a chain transfer agent (a-2), and a mixed solution of 4 g of "Perbutyl O" and 100 g of methyl ethyl ketone from Nippon Oil Company, The polymerization was maintained at this temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-14). Compound (A-4) had Mw of 7,750, Mn of 3,987, and Mw / Mn of 1.94.

[合成例17](化合物(A-15)之製造) [Synthesis Example 17] (Production of compound (A-15))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯48g(0.46mol)、甲基丙烯酸甲酯46g(0.46mol)、甲基丙烯酸環己酯6g(0.036mol)、鏈轉移劑(a-3)(荒川化學工業公司之「Compoceran HBSQ105-9」及25質量%丙二醇單甲基醚乙酸酯溶液)12g之混合溶液與2,2'-偶氮雙(2-甲基丙腈)3g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-15)的溶液。化合物(A-5)之Mw為7,980、Mn為4,002、Mw/Mn為2.00。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and take 3 hours at the same temperature to add 100g of methyl ethyl ketone, 48g (0.46mol) of styrene, 46g (0.46mol) of methyl methacrylate, and 6g (0.036 of cyclohexyl methacrylate). mol), a chain transfer agent (a-3) ("Compoceran HBSQ105-9" of Arakawa Chemical Industry Co., Ltd. and 25% by mass of propylene glycol monomethyl ether acetate solution) and a mixed solution of 2,2'-azobis (2-methylpropionitrile) was a mixed solution of 3 g and 100 g of methyl ethyl ketone. Polymerization was carried out at this temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-15). Compound (A-5) had Mw of 7,980, Mn of 4,002, and Mw / Mn of 2.00.

[合成例18](化合物(A-16)之製造) [Synthesis Example 18] (Production of compound (A-16))

於具備冷卻管與攪拌機之燒瓶中,饋入甲基乙基酮100g,進行氮取代。加熱至85℃,於同溫度下花費3小時各滴入甲基乙基酮100g、苯乙烯51g(0.49mol)、甲基丙烯酸甲酯49g(0.49mol)、鏈轉移劑(a-3)(荒川化學工業公司之「Compoceran HBSQ105-9」及25質量%丙二醇單甲基醚乙酸酯溶液)12g之混合溶液與日油公司之「Perbutyl O」4g及甲基乙基酮100g之混合溶液,保持此溫度聚合3小時。將所得之化合物溶液以3L之甲醇進行沈澱精製,去除殘留單體、自由基聚合起始劑等,接下來於此所得到者當中添加丙二醇單甲基醚乙酸酯,得到含10質量%之化合物(A-16)的溶液。化合物(A-6)之Mw為7,807、Mn為3,869、Mw/Mn為2.02。 In a flask equipped with a cooling tube and a stirrer, 100 g of methyl ethyl ketone was fed, and nitrogen substitution was performed. Heat to 85 ° C, and take 3 hours at the same temperature to add 100g of methyl ethyl ketone, 51g (0.49mol) of styrene, 49g (0.49mol) of methyl methacrylate, and a chain transfer agent (a-3) ( Arakawa Chemical Industry Co., Ltd. "Compoceran HBSQ105-9" and a 25% by mass propylene glycol monomethyl ether acetate solution) 12g mixed solution with a Nippon Oil company "Perbutyl O" 4g and a methyl ethyl ketone 100g mixed solution, The polymerization was maintained at this temperature for 3 hours. The obtained compound solution was purified by precipitation with 3 L of methanol to remove residual monomers, radical polymerization initiators, and the like. Next, propylene glycol monomethyl ether acetate was added to the obtained solution to obtain 10% by mass of A solution of compound (A-16). The compound (A-6) had Mw of 7,807, Mn of 3,869, and Mw / Mn of 2.02.

[合成例19](嵌段共聚物(P-1)之製造) [Synthesis Example 19] (Production of block copolymer (P-1))

將500mL之燒瓶反應容器予以減壓乾燥後,於氮環境下,注入進行過蒸餾脫水處理之四氫呋喃200g,冷卻至-78℃。之後,注入sec-丁基鋰(sec-BuLi)之1N環己烷溶液0.27g,花費30分鐘滴下注入進行過蒸餾脫水處理之苯乙烯10.7g(0.103mol)。此時注意不要讓反應溶液之溫度成為-60℃以上。滴下結束後,進行30分鐘熟成後,進一步花費30分鐘滴下注入進行過蒸餾脫水處理之甲基丙烯酸甲酯10.3g(0.103mol),反應120分鐘。之後,注入甲醇1mL作為末端處理劑使其反應。將反應溶 液昇溫至室溫,將所得之反應溶液濃縮,以丙二醇甲基醚乙酸酯(PGMEA)取代後,注入草酸2質量%水溶液1,000g並攪拌、靜置後,去除下層之水層。重複此操作3次,去除Li鹽後,注入超純水1,000g並攪拌,去除下層之水層。重複此操作3次,去除草酸後,將溶液濃縮,滴入甲醇500g中,使聚合物析出。將經減壓過濾之聚合物以甲醇洗淨2次後,藉由於60℃減壓乾燥,得到白色的嵌段共聚物(P-1)20.5g。嵌段共聚物(P-1)之Mw為41,000、Mw/Mn為1.13。又,13C-NMR分析之結果,嵌段共聚物(P-1)中之苯乙烯單位之含有比例及甲基丙烯酸甲酯單位之含有比例分別為50.1(mol%)及49.9(mol%)。再者,嵌段共聚物(P-1)為二嵌段共聚物。 A 500 mL flask reaction container was dried under reduced pressure, and then 200 g of tetrahydrofuran subjected to distillation and dehydration treatment was injected under a nitrogen environment, and cooled to -78 ° C. Thereafter, 0.27 g of a 1N cyclohexane solution of sec-butyllithium (sec-BuLi) was injected, and 10.7 g (0.103 mol) of styrene subjected to distillation and dehydration treatment was dripped over 30 minutes. At this time, be careful not to let the temperature of the reaction solution become above -60 ° C. After the dropping was completed, after aging for 30 minutes, 10.3 g (0.103 mol) of methyl methacrylate subjected to distillation and dehydration treatment was added dropwise for 30 minutes, and reacted for 120 minutes. Thereafter, 1 mL of methanol was injected as a terminal treatment agent and reacted. The reaction solution was warmed to room temperature, and the obtained reaction solution was concentrated and substituted with propylene glycol methyl ether acetate (PGMEA). Then, 1,000 g of a 2% by mass oxalic acid aqueous solution was poured, and the mixture was left to stand, and then the lower aqueous layer was removed. This operation was repeated three times. After removing the Li salt, 1,000 g of ultrapure water was poured and stirred to remove the lower aqueous layer. This operation was repeated three times. After removing the oxalic acid, the solution was concentrated and dropped into 500 g of methanol to precipitate a polymer. The polymer filtered under reduced pressure was washed twice with methanol and then dried under reduced pressure at 60 ° C to obtain 20.5 g of a white block copolymer (P-1). The block copolymer (P-1) had Mw of 41,000 and Mw / Mn of 1.13. As a result of 13 C-NMR analysis, the content ratio of the styrene unit and the methyl methacrylate unit in the block copolymer (P-1) were 50.1 (mol%) and 49.9 (mol%), respectively. . The block copolymer (P-1) is a diblock copolymer.

<基底膜形成用組成物之配製> <Preparation of composition for basement film formation>

構成上述化合物(A-1)~(A-10)、(A-13)~(A-16)以外之基底膜形成用組成物之[B]溶劑及[C]酸產生劑係如以下所示。 The [B] solvent and [C] acid generator constituting the base film-forming composition other than the compounds (A-1) to (A-10) and (A-13) to (A-16) are as follows Show.

[[B]溶劑] [[B] Solvent]

B-1:丙二醇單甲基醚乙酸酯 B-1: Propylene glycol monomethyl ether acetate

B-2:乙酸丁氧基甲酯 B-2: Butoxymethyl acetate

B-3:乙酸丁酯 B-3: Butyl acetate

B-4:環己酮 B-4: Cyclohexanone

[[C]酸產生劑] [[C] Acid generator]

C-1:三苯基鋶2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙烷-1-磺酸鹽 C-1: Triphenylphosphonium 2- (bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethane-1-sulfonate

C-2:雙(4-t-丁基苯基)錪九氟-n-丁磺酸鹽 C-2: Bis (4-t-butylphenyl) fluorene nonafluoro-n-butanesulfonate

各化合物之構造係如以下所示。 The structure of each compound is shown below.

[實施例1](基底膜形成用組成物(D-1)之配製) [Example 1] (Preparation of composition (D-1) for base film formation)

混合作為含有[A]化合物之溶液的含有合成例1所得化合物(A-1)之溶液100質量份、作為[B]溶劑之(B-1)丙二醇單甲基醚乙酸酯9,895質量份、及作為[C]酸產生劑之(C-1)三苯基鋶2-(雙環[2.2.1]庚-2-基)-1,1,2,2-四氟乙烷-1-磺酸鹽5質量份,使其溶解而得到混合溶液。將所得之混合溶液以孔徑0.1μm之膜過濾器過濾,配製基底膜形成用組成物(D-1)。 100 parts by mass of a solution containing the compound (A-1) obtained in Synthesis Example 1 as a solution containing the [A] compound, 9,895 parts by mass of (B-1) propylene glycol monomethyl ether acetate as a [B] solvent, And (C-1) triphenylphosphonium 2- (bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethane-1-sulfonic acid as a [C] acid generator 5 parts by mass of the acid salt was dissolved to obtain a mixed solution. The obtained mixed solution was filtered through a membrane filter having a pore size of 0.1 μm to prepare a composition (D-1) for forming a base film.

[實施例2~15及比較例1~4](基底膜形成用組成物(D- 2)~(D-19)之配製) [Examples 2 to 15 and Comparative Examples 1 to 4] (Composition for formation of base film (D- 2) ~ (D-19) Preparation)

除了使用下述表1或表2所示種類及含量之各成分以外,係與實施例1相同方式,配製實施例2~15及比較例1~4之基底膜形成用組成物(D-2)~(D-19)。再者,表1及表2中之「-」表示未使用該成分。 A composition for forming a base film (D-2) of Examples 2 to 15 and Comparative Examples 1 to 4 was prepared in the same manner as in Example 1 except that components of the kinds and contents shown in Table 1 or Table 2 below were used. ) ~ (D-19). In addition, "-" in Tables 1 and 2 shows that this component is not used.

<自我組織化微影製程> <Self-organized lithography process>

使用所得之基底膜形成用組成物來形成形成有基底膜之第1基板,使用該形成有基底膜之第1基板來進行圖型形成。 A first substrate on which a base film is formed is formed using the obtained composition for forming a base film, and pattern formation is performed using the first substrate on which the base film is formed.

(1)圖型形成用自我組織化組成物之配製 (1) Formulation of self-organizing composition for pattern formation

將所得之嵌段共聚物(P-1)溶解於丙二醇單甲基醚乙酸酯(PGMEA),成為1質量%溶液。將此溶液以孔徑200nm之膜過濾器過濾,配製圖型形成用自我組織化組成物(E-1)。 The obtained block copolymer (P-1) was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to make a 1% by mass solution. This solution was filtered through a membrane filter having a pore size of 200 nm to prepare a self-organizing composition (E-1) for pattern formation.

(2)第1層之基底膜形成 (2) Formation of the base film of the first layer

使用所得之基底膜形成用組成物(D-1)~(D-19),於12吋矽晶圓之表面形成塗膜,以193nm之波長的ArF光曝光,於200℃燒成120秒。接下來,為了去除含未反應之聚合物的溶液,以丙二醇單甲基醚乙酸酯洗淨後,藉由於100℃使基板乾燥120秒,形成平均厚度10nm之塗膜。 Using the obtained base film-forming compositions (D-1) to (D-19), a coating film was formed on the surface of a 12-inch silicon wafer, exposed with ArF light having a wavelength of 193 nm, and fired at 200 ° C for 120 seconds. Next, in order to remove the solution containing the unreacted polymer, after washing with propylene glycol monomethyl ether acetate, the substrate was dried at 100 ° C. for 120 seconds to form a coating film having an average thickness of 10 nm.

[後退接觸角(RCA)之測定] [Measurement of receding contact angle (RCA)]

後退接觸角之測定,係使用接觸角計(KRUS公司之「DSA-10」),製成以基底膜形成用組成物形成有基底膜之基板(晶圓)後,迅速地於室溫:23℃、濕度:45%、常壓之環境下依下述順序進行。 The receding contact angle was measured using a contact angle meter ("DSA-10" by KRUS) to make a substrate (wafer) with a base film formed from a base film forming composition, and then quickly at room temperature: 23 ℃, humidity: 45%, under normal pressure in the following order.

首先,調整上述接觸角計之晶圓平台(wafer stage)位置,於該調整後的平台上設置上述晶圓。接著,於針中注入水,於上述經設置的晶圓上將針的位置微調為可形成水滴的初期位置。之後,由該針中排出水,於晶圓上形成25μL之水滴,由該水滴將針一時拉回,再度將針放下至初期位置,配置於水滴內。接著,以10μL/min之速度藉由針吸引水滴150秒,同時每秒測定接觸角1次,合計150次。其中,對於自接觸角之測定值穩定後的時間點起20秒(共20點)的接觸角,算出平均值,作為後退接觸角(單位:度(°))。所得之值示於表3。 First, adjust the wafer stage position of the contact angle meter, and set the wafer on the adjusted stage. Next, water is injected into the needle, and the position of the needle is fine-adjusted to the initial position where water droplets can be formed on the set wafer. Thereafter, water was discharged from the needle, and a 25 μL water droplet was formed on the wafer. The needle was temporarily pulled back by the water droplet, and the needle was lowered to the initial position again and placed in the water droplet. Then, the water droplet was sucked by the needle at a speed of 10 μL / min for 150 seconds, and the contact angle was measured once every second, for a total of 150 times. Here, an average value is calculated for a contact angle of 20 seconds (total of 20 points) from the time point when the measured value of the contact angle is stabilized, as the backward contact angle (unit: degree (°)). The obtained values are shown in Table 3.

(3)圖型之形成 (3) Formation of patterns

以於上述形成有基底膜之矽晶圓基板上所形成之自我組織化膜的平均膜厚成為30nm的方式,塗佈圖型形成用自我組織化組成物(E-1)後,於250℃加熱10分鐘使其相分離,形成具有微相構造之指紋樣式(fingerprint)後,以電漿處理進行乾式蝕刻,形成30nm節距(pitch)之凹凸圖型。 The self-organizing film (E-1) for pattern formation was applied so that the average thickness of the self-organizing film formed on the silicon wafer substrate on which the base film was formed was 30 nm, and then the temperature was 250 ° C. After heating for 10 minutes to separate the phases to form a fingerprint with a microphase structure, dry etching was performed by plasma treatment to form a bump pattern with a pitch of 30 nm.

針對上述形成之指紋樣式與圖型之截面,使用掃描型電子顯微鏡(日立製作所公司之「S-4800」)觀察,評估該指紋樣式中之相分離構造之良好性及圖型形狀之矩形性。以指紋樣式可確認到明確的相分離,無缺陷者為「A」(良好)、以相分離不完全或有缺陷者為「B」(不良)。圖型形狀係以可觀察到矩形的情況為「A」( 良好)、未溶解者等顯著等之未觀察到矩形的情況為「B」(不良)來評估。評估結果示於表3。 A cross-section of the fingerprint pattern and pattern formed as described above was observed with a scanning electron microscope ("S-4800" by Hitachi, Ltd.) to evaluate the goodness of the phase separation structure and the rectangularity of the pattern shape in the fingerprint pattern. A clear phase separation can be confirmed with a fingerprint pattern, with "A" (good) for non-defective, and "B" (bad) for incomplete or defective phase separation. The shape of the pattern is "A" ( A case where a rectangle was not observed significantly such as a good), undissolved person, etc. was evaluated as "B" (bad). The evaluation results are shown in Table 3.

由表3結果明顯可知,實施例中,形成有基底膜之第1基板表面的後退接觸角係為良好的範圍,指紋樣式之相分離構造良好,圖型形狀為矩形。另一方面,比較例中,可知形成有基底膜之第1基板表面的後退接觸角非為良好的範圍,指紋樣式之相分離構造非為良好,圖型形狀非為矩形。 It is clear from the results in Table 3 that in the examples, the receding contact angle of the first substrate surface on which the base film is formed is in a good range, the phase separation structure of the fingerprint pattern is good, and the pattern shape is rectangular. On the other hand, in the comparative example, it can be seen that the receding contact angle of the first substrate surface on which the base film is formed is not a good range, the phase separation structure of the fingerprint pattern is not good, and the pattern shape is not rectangular.

[產業上之可利用性] [Industrial availability]

依照本發明之基底膜形成用組成物及自我組 織化微影製程,能夠良好地藉由自我組織化形成相分離構造、且形成矩形的圖型。因此,此等可適合使用於要求進一步微細化之半導體裝置、液晶裝置等之各種電子裝置製造中之微影製程。 Composition for base film formation and self-group according to the present invention The weaving lithography process can form a phase separation structure and form a rectangular pattern by self-organization. Therefore, these can be suitably used in the lithography process in the manufacture of various electronic devices such as semiconductor devices and liquid crystal devices that require further miniaturization.

Claims (12)

一種基底膜形成用組成物,其係於自我組織化微影製程中用以形成配置於含有矽原子之層與自我組織化膜之間的基底膜之組成物,其係含有以下述式(1)表示的化合物、及溶劑,且上述基底膜之與純水的後退接觸角為70°以上且90°以下;式(1)中,A為(m+n)價之連結基,D為碳數10以上且含有硫原子之1價有機基,E為羥基、羧基、胺基、環氧基、烷氧基、或下述式(2)表示之基,m及n係分別獨立地為1~200之整數,惟,m為2以上時,複數個D可相同亦可相異,2個以上之D亦可互相鍵結,n為2以上時,複數個E可相同亦可相異,D與A係透過上述硫原子而鍵結;RB 3-aRA aSi- (2)式(2)中,RA為碳數1~20之1價烴基,RB為碳數1~20之1價氧烴基或鹵素原子,a為0~2之整數,惟,RA及RB分別有複數個時,複數個RA可相同亦可相異,複數個RB可相同亦可相異。A composition for forming a base film, which is a composition for forming a base film disposed between a layer containing a silicon atom and a self-organizing film in a self-organized lithography process, and comprises a composition represented by the following formula (1 ), A compound and a solvent, and the receding contact angle of the base film with pure water is 70 ° or more and 90 ° or less; In formula (1), A is a (m + n) -valent linking group, D is a monovalent organic group having 10 or more carbon atoms and containing a sulfur atom, and E is a hydroxyl group, a carboxyl group, an amine group, an epoxy group, and an alkoxy group. Or the base represented by the following formula (2), m and n are each independently an integer of 1 to 200, but when m is 2 or more, a plurality of D may be the same or different, and two or more D are also Can be bonded to each other. When n is 2 or more, a plurality of E may be the same or different. D and A are bonded through the sulfur atom; R B 3-a R A a Si- (2) Formula (2) in, R A is alkyl having 1 to 20 of a monovalent hydrocarbon group, R B is a carbon number of 1 to 20 of the monovalent oxygen-hydrocarbon group or a halogen atom, a is an integer of 0 to 2, the but, R A and R B each have a plurality of When a plurality of R A may be the same or different, a plurality of R B may be the same or different. 如請求項1之基底膜形成用組成物,其中,上述式(1)中之A為碳數1~30之有機基、n為1~10之整數。The composition for forming a base film according to claim 1, wherein A in the formula (1) is an organic group having 1 to 30 carbon atoms, and n is an integer of 1 to 10. 如請求項1之基底膜形成用組成物,其中,上述化合物,於上述式(1)中之E表示之基以外,不具有含活性氫之基。The composition for forming a base film according to claim 1, wherein the compound does not have a group containing active hydrogen other than the group represented by E in the formula (1). 如請求項1之基底膜形成用組成物,其中,上述式(1)中之E,係羥基或上述式(2)表示之基。The composition for forming a base film according to claim 1, wherein E in the formula (1) is a hydroxyl group or a group represented by the formula (2). 如請求項1之基底膜形成用組成物,其中,上述式(1)中之A,係下述式(3)表示之基,式(3)中,Q係(m+n)價之矽數2~100之聚矽氧烷構造,T係與Q之矽原子以碳原子或氧原子進行鍵結之碳數1~30之2價有機基,m及n係與上述式(1)相同意義,*1係表示鍵結於上述式(1)中之E的部位,*2係表示鍵結於上述式(1)中之D的部位。The composition for forming a base film according to claim 1, wherein A in the above formula (1) is a base represented by the following formula (3), In formula (3), Q is a polysiloxane structure having a silicon number of 2 to 100 (m + n), and T is a carbon atom having a carbon number of 1 to 30 and a silicon atom of Q bonded by a carbon atom or oxygen atom. Divalent organic groups, m and n have the same meanings as in the above formula (1), * 1 represents a site bonded to E in the above formula (1), and * 2 represents a site bonded to the above formula (1) Location of D. 如請求項5之基底膜形成用組成物,其中,上述式(1)中之E,為羥基、烷氧基或此等之組合。The composition for forming a base film according to claim 5, wherein E in the formula (1) is a hydroxyl group, an alkoxy group, or a combination thereof. 如請求項1之基底膜形成用組成物,其中,上述式(1)中之D,係含有由碳-碳鍵所成之聚合鏈之基。The composition for forming a base film according to claim 1, wherein D in the above formula (1) contains a group of a polymer chain formed by a carbon-carbon bond. 如請求項1之基底膜形成用組成物,其中,上述化合物,係使乙烯基單體於下述式(4)表示之鏈轉移劑存在下進行自由基聚合而成,式(4)中,A、E、m及n係與上述式(1)相同意義。The composition for forming a base film according to claim 1, wherein the compound is obtained by radical polymerization of a vinyl monomer in the presence of a chain transfer agent represented by the following formula (4), In Formula (4), A, E, m, and n have the same meanings as in Formula (1). 如請求項1之基底膜形成用組成物,其係進一步含有酸產生劑。The composition for forming a base film according to claim 1, further comprising an acid generator. 如請求項1之基底膜形成用組成物,其中,上述溶劑係包含酯系溶劑、酮系溶劑或此等之組合。The composition for forming a base film according to claim 1, wherein the solvent includes an ester-based solvent, a ketone-based solvent, or a combination thereof. 一種自我組織化微影製程,其係具備於含有矽原子之第1層上藉由基底膜形成用組成物形成基底膜之步驟、於上述基底膜之與上述第1層相反側的面形成自我組織化膜之步驟、及去除上述自我組織化膜之至少一部分的相之步驟,且上述基底膜形成用組成物為如請求項1之基底膜形成用組成物。A self-organizing lithography process comprising a step of forming a base film with a base film-forming composition on a first layer containing silicon atoms, and forming a self on a surface of the base film opposite to the first layer A step of organizing the film, and a step of removing at least a part of the phase of the self-organizing film; and the composition for forming a base film is the composition for forming a base film according to claim 1. 如請求項11之自我組織化微影製程,其中於上述基底膜形成步驟與上述自我組織化膜形成步驟之間,進一步具備於上述基底膜之與上述第1層相反側之面形成預圖型的步驟,且於上述自我組織化膜形成步驟中,係將上述自我組織化膜形成於上述預圖型之非層合區域。For example, the self-organized lithography process of claim 11, further comprising forming a pre-pattern on the side of the base film opposite to the first layer between the base film forming step and the self-organizing film forming step. Step, and in the step of forming the self-organizing film, the self-organizing film is formed on the non-layered region of the pre-pattern.
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