TW201420553A - Photoresist composition, method for forming resist pattern, and acid generator - Google Patents
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Abstract
Description
本發明係關於光阻組成物、阻劑圖型形成方法及酸產生劑。 The present invention relates to a photoresist composition, a resist pattern formation method, and an acid generator.
以積體電路元件之製造為代表之微細加工領域中,過去係利用含有具有酸解離性基之聚合物之光阻組成物於基板上形成阻劑膜,且介隔遮罩圖型對該阻劑膜以準分子雷射光等短波長之曝光光進行曝光,且以顯像液去除曝光部而形成微細之阻劑圖型。此時,係利用光阻組成物中含有藉由曝光而產生酸之酸產生劑,藉由其酸之作用而提高感度之化學增幅型阻劑。然而,目前,隨著積體電路之高積體化、高速化等微影術之進步,而要求可形成更微細阻劑圖型之光阻組成物。另外,伴隨於此,光阻組成物不僅要求上述解像性優異,亦要求圖型之剖面形狀之矩形性優異,顯示圖型寬度之遮罩尺寸依存性之MEEF(遮罩誤差增強係數(Mask Error Enhancement Factor))性能優異。 In the field of microfabrication represented by the manufacture of integrated circuit components, in the past, a resist film having a polymer having an acid dissociable group was used to form a resist film on a substrate, and the mask pattern was blocked. The film is exposed to exposure light of a short wavelength such as excimer laser light, and the exposed portion is removed by a developing solution to form a fine resist pattern. In this case, a chemically amplified resist which enhances sensitivity by the action of an acid is used in the photoresist composition containing an acid generator which generates an acid by exposure. However, at present, with the advancement of lithography such as high integration and high speed of integrated circuits, it is required to form a photoresist composition having a finer resist pattern. In addition, the photoresist composition is required to have excellent resolution, and it is required to have excellent cross-sectional shape of the pattern, and the MEEF (mask error enhancement coefficient (Mask) of the mask size dependence of the pattern width is displayed. Error Enhancement Factor)) Excellent performance.
對於該等要求,已開發出含有各種酸產生劑 之光阻組成物(參照特開2007-145803號公報及國際公開第2011/104127號)。然而,愈來愈朝向阻劑圖型之微細化發展之今日,要求更優異之MEEF性能。另外,針對上述光阻組成物,所形成之阻劑圖型有頂端損失(top loss)等之傾向,其剖面形狀之矩形性亦不足。而且,隨著阻劑膜之薄膜化,亦要求阻劑圖型具有優異之蝕刻耐性。 For these requirements, various acid generators have been developed The photoresist composition (see JP-A-2007-145803 and International Publication No. 2011/104127). However, more and more towards the development of the refinement of the resist pattern today requires more excellent MEEF performance. Further, in the resist composition described above, the resist pattern formed tends to have a top loss or the like, and the rectangular shape of the cross-sectional shape is also insufficient. Moreover, as the resist film is thinned, the resist pattern is also required to have excellent etching resistance.
〔專利文獻1〕特開2007-145803號公報 [Patent Document 1] JP-A-2007-145803
〔專利文獻2〕國際公開第2011/104127號 [Patent Document 2] International Publication No. 2011/104127
本發明係基於以上情況而完成者,其目的係提供一種可形成MEEF性能優異、剖面形狀之矩形性及蝕刻耐性優異之阻劑圖型之光阻組成物。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a resist composition which can form a resist pattern having excellent MEEF performance, a rectangular shape in cross-sectional shape, and excellent etching resistance.
用以解決上述課題之發明係一種光阻組成物,其係含有具有含酸解離性基之構造單位的聚合物(以下亦稱為「〔A〕聚合物」)、及 含以下述式(1)表示之化合物(以下亦稱為「化合物(1)」)的酸產生劑(以下亦稱為「〔B〕酸產生劑」),【化1】R1-SO2O-R2-SO3 - Q+ (1) The invention for solving the above problems is a photoresist composition containing a polymer having a structural unit containing an acid-dissociable group (hereinafter also referred to as "[A] polymer"), and a formula (1) An acid generator (hereinafter also referred to as "the compound (1)")) (hereinafter referred to as "[B] acid generator"), [Chem. 1] R 1 -SO 2 OR 2 -SO 3 - Q + (1)
(式(1)中,R1為取代或非取代之碳數1~30之1價烴基或取代或非取代之環原子數3~30之1價雜環基,R2為碳數1~30之烷烴二基或氟數小於碳數之碳數2~30之氟化烷烴二基,Q+為1價之光分解性有機陽離子)。 (In the formula (1), R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms or a substituted or unsubstituted monovalent heterocyclic group having 3 to 30 ring atoms, and R 2 is a carbon number 1~ 30 alkanediyl or a fluorinated alkanediyl group having a fluorine number of less than 2 to 30 carbon atoms, and Q + is a monovalent photodecomposable organic cation).
用以解決上述課題之另一發明係一種阻劑圖型形成方法,其具有下列步驟:形成阻劑膜之步驟,使上述阻劑膜曝光之步驟,及使上述經曝光之阻劑膜顯像之步驟,且藉由該光阻組成物來形成上述阻劑膜。 Another invention for solving the above problems is a resist pattern forming method having the steps of: forming a resist film, exposing the resist film, and developing the exposed resist film And a step of forming the above-mentioned resist film by the photoresist composition.
用以解決上述課題之另一發明係一種酸產生劑,其含有以下述式(1)表示之化合物,【化2】R1-SO2O-R2-SO3 - Q+ (1) Another invention for solving the above problems is an acid generator containing a compound represented by the following formula (1): R 2 -SO 2 OR 2 -SO 3 - Q + (1)
(式(1)中,R1為取代或非取代之碳數1~30之1價烴基或取代或非取代之環原子數3~30之1價雜環基,R2為碳數1~30之烷烴二基或氟數小於碳數之碳數2~30之氟化烷烴二基,Q+為1價之光分解性有機陽離子)。 (In the formula (1), R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms or a substituted or unsubstituted monovalent heterocyclic group having 3 to 30 ring atoms, and R 2 is a carbon number 1~ 30 alkanediyl or a fluorinated alkanediyl group having a fluorine number of less than 2 to 30 carbon atoms, and Q + is a monovalent photodecomposable organic cation).
此處,所謂「烴基」係指以碳原子與氫原子構成之基,且分類成「鏈狀烴基」、「脂環式烴基」及「芳香族烴基」。所謂「鏈狀烴基」係指不含環狀構造,僅以鏈狀構造構成之烴基。所謂「脂環式烴基」係指僅含脂環式構造作為環構造之烴基。但,未必僅以脂環構造構成,其一部分亦可含鏈狀構造。所謂「芳香族烴基」係指含芳香環構造作為環構造之烴基。但,未必僅以芳香環構造構成,其一部分亦可含脂環構造或鏈狀構造。上述鏈狀烴基及鏈狀構造可為直鏈狀,亦可為分支狀。 Here, the "hydrocarbon group" means a group consisting of a carbon atom and a hydrogen atom, and is classified into a "chain hydrocarbon group", an "alicyclic hydrocarbon group", and an "aromatic hydrocarbon group". The "chain hydrocarbon group" means a hydrocarbon group which does not contain a cyclic structure and has only a chain structure. The "alicyclic hydrocarbon group" means a hydrocarbon group having only an alicyclic structure as a ring structure. However, it is not necessarily composed only of an alicyclic structure, and a part thereof may have a chain structure. The "aromatic hydrocarbon group" means a hydrocarbon group having an aromatic ring structure as a ring structure. However, it is not necessarily composed only of an aromatic ring structure, and a part thereof may have an alicyclic structure or a chain structure. The chain hydrocarbon group and the chain structure may be linear or branched.
「雜環基」為與脂環式烴基或芳香族烴基相同之環構造,且含有碳以外之原子作為環構成原子之基。碳以外之原子列舉為1個以上之例如硫、氮、氧等雜原子。雜環基可為單環式,亦可為多環式,且,可為芳香族雜環基,亦可為脂肪族雜環基。但,未必僅以雜環構造構成,其一部分亦可含脂環構造、芳香族環構造、鏈狀構造等。上述鏈狀構造可為直鏈狀,亦可為分支狀。 The "heterocyclic group" is a ring structure identical to an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and contains an atom other than carbon as a ring constituting atom. The atom other than carbon is exemplified by one or more hetero atoms such as sulfur, nitrogen, and oxygen. The heterocyclic group may be a monocyclic ring or a polycyclic ring, and may be an aromatic heterocyclic group or an aliphatic heterocyclic group. However, it is not necessarily composed only of a heterocyclic structure, and a part thereof may contain an alicyclic structure, an aromatic ring structure, a chain structure, or the like. The chain structure may be linear or branched.
依據本發明之光阻組成物及阻劑圖型形成方法,可一面發揮優異之MEEF性能,一面形成剖面形狀之矩形性及蝕刻耐性優異之阻劑圖型。且,本發明之酸產生劑可較好地使用作為該光阻組成物之成分。據此,該等可較好地使用於半導體裝置、液晶裝置等之各種電子裝置之微影步驟之圖型形成中。 According to the photoresist composition and the resist pattern forming method of the present invention, it is possible to form a resist pattern having excellent cross-sectional shape rectangularness and etching resistance while exhibiting excellent MEEF performance. Further, the acid generator of the present invention can be preferably used as a component of the photoresist composition. Accordingly, these can be preferably used in the pattern formation of the lithography step of various electronic devices such as semiconductor devices and liquid crystal devices.
該光阻組成物含有〔A〕聚合物及〔B〕酸產生劑。該光阻組成物亦可含有〔C〕酸擴散控制體、〔D〕含氟原子之聚合物、及〔E〕溶劑作為較適宜成分,在不損及本發明效果之範圍內,亦可含〔F〕偏在化促進劑等之其他任意成分。以下,針對各成分加以說明。 The photoresist composition contains the [A] polymer and the [B] acid generator. The resist composition may further contain a [C] acid diffusion controlling agent, [D] a fluorine atom-containing polymer, and [E] a solvent as suitable components, and may also contain a range which does not impair the effects of the present invention. [F] Other optional components such as a partialization accelerator. Hereinafter, each component will be described.
〔A〕聚合物為具有含酸解離性基之構造單位(以下亦稱為「構造單位(I)」)之聚合物。利用由後述之〔B〕酸產生劑產生之酸之作用,而改變〔A〕聚合物對顯像液之溶解性。因此,〔A〕聚合物係作為通常之基底聚合物發揮功能。又,所謂「基底聚合物」係指作為構成由光阻組成物所形成之阻劑圖型之聚合物的主成分之聚合物,較好係指相對於構成阻劑圖型之全部聚合物佔50質量%以上之聚合物。 [A] The polymer is a polymer having a structural unit containing an acid-dissociable group (hereinafter also referred to as "structural unit (I)"). The solubility of the [A] polymer in the developing solution is changed by the action of an acid produced by the [B] acid generator described later. Therefore, the [A] polymer functions as a usual base polymer. Further, the term "base polymer" means a polymer which is a main component of a polymer constituting a resist pattern formed by a photoresist composition, and preferably means a total of all polymers constituting a resist pattern. 50% by mass or more of the polymer.
〔A〕聚合物在不損及本發明效果之範圍內,除構造單位(I)以外,較好含有具有由內酯構造、環狀碳酸酯構造及磺內酯構造所組成群組選出之至少1種之構造單位(以下亦稱為「構造單位(II)」)。〔A〕聚合物可具有該等構造單位之各單獨1種或2種以上。〔A〕 聚合物可為無規共聚物,亦可為嵌段共聚物。 The polymer [A] preferably contains, in addition to the structural unit (I), at least a group selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure, within a range not impairing the effects of the present invention. One type of structural unit (hereinafter also referred to as "structural unit (II)"). The polymer [A] may have one or two or more of these structural units. [A] The polymer may be a random copolymer or a block copolymer.
構造單位(I)為含酸解離性基之構造單位。至於構造單位(I),只要含酸解離性基,則無特別限制。所謂「酸解離性基」為取代例如羥基、羧基等之氫原子的基,且在酸存在下解離之基。藉此,上述構造單位係藉由酸之作用而產生極性基。 The structural unit (I) is a structural unit containing an acid-dissociable group. As for the structural unit (I), there is no particular limitation as long as it contains an acid-dissociable group. The "acid dissociable group" is a group which is substituted with a hydrogen atom such as a hydroxyl group or a carboxyl group, and which is dissociated in the presence of an acid. Thereby, the above structural unit generates a polar group by the action of an acid.
作為酸解離性基,例如作為取代羥基之氫原子的基列舉為第三丁氧羰基、四氫吡喃基、四氫呋喃基、(硫四氫吡喃基胺磺胺醯基)甲基、(硫四氫呋喃基磺胺醯基)甲基、或烷氧基取代之甲基、烷基磺胺醯基取代甲基等,至於取代羧基之氫原子的基列舉為三級烷基等。烷氧基取代之甲基中之烷氧基(取代基)列舉為例如碳數1~4之烷氧基等。且,烷基磺胺醯基取代之甲基中之烷基(取代基)列舉為例如碳數1~4之烷基等。三級烷基之碳數較好為4~30,更好為4~20。且,三級烷基可為鏈狀烴基、脂環式烴基、脂環構造等之任一種。 As the acid-dissociable group, for example, a group as a hydrogen atom of a substituted hydroxyl group is exemplified by a third butoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a (thiotetrahydropyranylamine sulfonylamino)methyl group, (thiotetrahydrofuran). A methyl group or alkoxy group-substituted methyl group, an alkylsulfonyl group-substituted methyl group, and the like, and a group which substitutes a hydrogen atom of a carboxyl group is exemplified by a tertiary alkyl group. The alkoxy group (substituent group) in the methyl group substituted with an alkoxy group is, for example, an alkoxy group having 1 to 4 carbon atoms. Further, the alkyl group (substituent group) in the methyl group substituted with an alkylsulfonyl group is, for example, an alkyl group having 1 to 4 carbon atoms. The carbon number of the tertiary alkyl group is preferably from 4 to 30, more preferably from 4 to 20. Further, the tertiary alkyl group may be any of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an alicyclic structure.
至於上述構造單位(I)較好為以下述式(3)表示之構造單位。藉由使〔A〕聚合物具有上述構造單位,可容易地利用酸產生極性基,且可提高〔A〕聚合物與〔B〕酸產生劑之相溶性。 The structural unit (I) is preferably a structural unit represented by the following formula (3). By allowing the polymer [A] to have the above structural unit, the polar group can be easily produced by an acid, and the compatibility of the [A] polymer with the [B] acid generator can be improved.
上述式(3)中,R9為氫原子、氟原子、甲基或三氟甲基。R10為碳數1~10之鏈狀烴基。R11及R12各自獨立地表示碳數1~10之鏈狀烴基或碳數3~20之脂環式烴基,或此等基相互結合與該等所鍵結之碳原子一起構成之環碳數3~20之脂環構造。 In the above formula (3), R 9 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R 10 is a chain hydrocarbon group having 1 to 10 carbon atoms. R 11 and R 12 each independently represent a chain hydrocarbon group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a ring carbon in which the groups are bonded to each other and the carbon atoms bonded thereto Number 3~20 alicyclic structure.
上述R9就提高獲得上述構造單位之單體的共聚合性之觀點而言,以氫原子及甲基較佳,更好為甲基。 From the viewpoint of improving the copolymerizability of the monomer having the above structural unit, R 9 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
上述以R10、R11及R12表示之碳數1~10之鏈狀烴基列舉為例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、新戊基、第三戊基、正己基、異己基、正庚基、異庚基、正辛基、異辛基、正壬基、異壬基、正癸基、異癸基等烷基等。上述鏈狀烴基在該等中以碳數1~3之烷基較佳,更好為甲基、乙基、異丙基,又更好為甲基。 The above-mentioned chain hydrocarbon group having 1 to 10 carbon atoms represented by R 10 , R 11 and R 12 is exemplified by, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a second butyl group. , tert-butyl, n-pentyl, isopentyl, second amyl, neopentyl, third amyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, An alkyl group such as a fluorenyl group, an isodecyl group, a n-decyl group or an isodecyl group. The above-mentioned chain hydrocarbon group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, more preferably a methyl group.
上述以R11及R12表示之碳數3~20之1價脂環式烴基列舉為例如環丁基、環戊基、環己基、環庚基、環辛基等單環之脂環式烴基;降冰片基、異冰片基、金剛烷基、三環癸基、四環十二烷基等多環脂環式烴基等。上述脂環式烴基,於該等中,以環戊基、環己基、降冰片 基、異冰片基、金剛烷基較佳,更好為環戊基、金剛烷基。上述R11及R12之碳數較好為4~15,更好為4~12。 The monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 11 and R 12 is exemplified by a monocyclic alicyclic hydrocarbon group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. a polycyclic alicyclic hydrocarbon group such as a norbornene group, an isobornyl group, an adamantyl group, a tricyclodecanyl group or a tetracyclododecyl group. The above alicyclic hydrocarbon group is preferably a cyclopentyl group, a cyclohexyl group, a norbornyl group, an isobornyl group or an adamantyl group, more preferably a cyclopentyl group or an adamantyl group. The carbon number of the above R 11 and R 12 is preferably from 4 to 15, more preferably from 4 to 12.
上述R11及R12相互結合與該等所鍵結之碳原子一起構成之碳數3~20之脂環構造列舉為例如環丁烷構造、環戊烷構造、環己烷構造、環辛烷構造等單環脂環式烴基;降冰片烷構造、金剛烷構造等之多環脂環式烴基等。上述脂環構造,於該等中,以環戊烷構造、環己烷構造、降冰片烷構造、金剛烷構造較佳,更好為環戊烷構造、金剛烷構造。上述R11及R12之碳數較好為4~15,更好為4~12。 The alicyclic structure having 3 to 20 carbon atoms which is bonded to the above-mentioned R 11 and R 12 together with the bonded carbon atoms is exemplified by, for example, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, and a cyclooctane. A monocyclic alicyclic hydrocarbon group such as a structure; a polycyclic alicyclic hydrocarbon group such as a norbornane structure or an adamantane structure; The alicyclic structure is preferably a cyclopentane structure, a cyclohexane structure, a norbornane structure, or an adamantane structure, and more preferably a cyclopentane structure or an adamantane structure. The carbon number of the above R 11 and R 12 is preferably from 4 to 15, more preferably from 4 to 12.
至於構造單位(I)列舉為例如以下述式(4-1)~(4-4)表示之構造單位。 The structural unit (I) is exemplified by a structural unit represented by the following formulas (4-1) to (4-4).
上述式(4-1)~(4-4)中,R9~R12係與上述式(3)同義。且,r為1~4之整數。 In the above formulae (4-1) to (4-4), R 9 to R 12 are synonymous with the above formula (3). And r is an integer from 1 to 4.
上述式(3)或(4-1)~(4-4)表示之構造單 位列舉為例如以下述式表示之構造單位等。 Construction sheet represented by the above formula (3) or (4-1) to (4-4) The bit number is listed as a structural unit represented by the following formula, for example.
上述式中,R9係與上述式(3)同義。 In the above formula, R 9 is synonymous with the above formula (3).
至於構造單位(I)較好為以上述式(4-1)表示之構造單位、以式(4-2)表示之構造單位,更好為源自(甲基)丙烯酸1-烷基-1-環戊酯之構造單位、源自(甲基)丙烯酸2-烷基-2-金剛烷酯之構造單位。且,源自1-甲基-1-環戊基-(甲基)丙烯酸酯之構造單位,又更 好為源自(甲基)丙烯酸1-乙基-1-環戊酯之構造單位、源自(甲基)丙烯酸2-甲基-2-金剛烷酯之構造單位、源自(甲基)丙烯酸2-異丙基-2-金剛烷酯之構造單位。又,(甲基)丙烯酸酯係指丙烯酸酯或甲基丙烯酸酯。 The structural unit (I) is preferably a structural unit represented by the above formula (4-1) and a structural unit represented by the formula (4-2), more preferably derived from 1-alkyl-1 (meth)acrylate. a structural unit of cyclopentyl ester derived from a structural unit of 2-alkyl-2-adamantyl (meth)acrylate. And, the structural unit derived from 1-methyl-1-cyclopentyl-(meth) acrylate is further It is preferably a structural unit derived from 1-ethyl-1-cyclopentyl (meth)acrylate, a structural unit derived from 2-methyl-2-adamantyl (meth)acrylate, derived from (meth) The structural unit of 2-isopropyl-2-adamantyl acrylate. Further, (meth) acrylate means acrylate or methacrylate.
構造單位(I)之含有比例,相對於構成〔A〕聚合物之全部構造單位,較好為20莫耳%~80莫耳%,更好為40莫耳%~70莫耳%。藉由使含有比例成為上述範圍,而有可使光阻組成物中解離充分量之酸之傾向。構造單位(I)之含有比例未達上述下限時,會有該光阻組成物之圖型形成性下降之情況。構造單位(I)之含有比例超過上述範圍時,會有所形成之阻劑圖型之密著性下降之情況。 The content ratio of the structural unit (I) is preferably from 20 mol% to 80 mol%, more preferably from 40 mol% to 70 mol%, based on the total structural unit of the polymer [A]. By setting the content ratio to the above range, there is a tendency that the photoresist composition can be dissociated in a sufficient amount of acid. When the content ratio of the structural unit (I) is less than the above lower limit, the pattern formation property of the photoresist composition may be lowered. When the content ratio of the structural unit (I) exceeds the above range, the adhesion of the formed resist pattern may be lowered.
構造單位(II)為含由內酯構造、環狀碳酸酯構造及磺內酯構造所組成群組選出之至少1種之構造單位。〔A〕聚合物藉由進一步具有構造單位(II),可調整對顯像液之溶解性。且,可提高由該光阻組成物形成之阻劑圖型與基板之密著性。 The structural unit (II) is a structural unit containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure. [A] The polymer can be adjusted to have solubility in a developing solution by further having a structural unit (II). Moreover, the adhesion between the resist pattern formed by the photoresist composition and the substrate can be improved.
構造單位(II)列舉為例如以下述式表示之構造單位等。 The structural unit (II) is exemplified by a structural unit represented by the following formula, and the like.
上述式中,R13為氫原子、氟原子、甲基或三氟甲基。 In the above formula, R 13 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
上述R13在該等中以甲基較佳。 The above R 13 is preferably a methyl group in the above.
構造單位(II)在該等中以含有內酯構造之構 造單位、含磺內酯構造之構造單位較佳,更好為含內酯構造之構造單位,更好為含降冰片烷內酯構造之構造單位,最好為源自(甲基)丙烯酸降冰片烷內酯基酯之構造單位。 The structural unit (II) in this structure contains a lactone structure The structural unit, the structural unit containing the sultone structure is preferably, more preferably a structural unit containing a lactone structure, more preferably a structural unit containing a norbornene lactone structure, preferably derived from (meth)acrylic acid. The structural unit of borneol lactone.
構造單位(II)之含有比例,相對於構成〔A〕聚合物之全部構造單位,較好為0莫耳%~80莫耳%,更好為20莫耳%~80莫耳%,又更好為30莫耳%~70莫耳%。藉由使構造單位(II)之含有比例成為上述範圍,可進一步提高〔A〕聚合物對顯像液之溶解性。另外,可進一步提高由該光阻組成物形成之阻劑圖型與基板之密著性。構造單位(II)之含有比例超過上述上限時,會有該光阻組成物之圖型形成性下降之情況。 The content ratio of the structural unit (II) is preferably from 0 mol% to 80 mol%, more preferably from 20 mol% to 80 mol%, and more preferably to all structural units constituting the polymer [A]. Good 30% %~70%. By setting the content ratio of the structural unit (II) to the above range, the solubility of the polymer [A] in the developing solution can be further improved. In addition, the adhesion between the resist pattern formed by the photoresist composition and the substrate can be further improved. When the content ratio of the structural unit (II) exceeds the above upper limit, the pattern formation property of the photoresist composition may be lowered.
〔A〕聚合物除了上述構造單位(I)及(II)以外,亦可含有其他構造單位。其他構造單位列舉為例如非酸解離性之含脂環式烴基之構造單位、具有極性基之構造單位等。其他構造單位之含有比例,相對於構成〔A〕聚合物之全部構造單位,通常為30莫耳%以下,較好為20莫耳%以下。 The [A] polymer may contain other structural units in addition to the above structural units (I) and (II). Other structural units are exemplified by, for example, a non-acid dissociable structural unit containing an alicyclic hydrocarbon group, a structural unit having a polar group, and the like. The content ratio of the other structural unit is usually 30 mol% or less, preferably 20 mol% or less, based on the entire structural unit of the polymer [A].
該光阻組成物中之〔A〕聚合物之含量,相對於全部固體成分通常為70質量%以上,較好為75質量%以上。〔A〕聚合物之含量未達上述下限時,會有該光阻組成物之圖型形成性下降之情況。又,該光阻組成物亦可 含有1種或2種以上之〔A〕聚合物。 The content of the [A] polymer in the resist composition is usually 70% by mass or more, preferably 75% by mass or more based on the total solid content. When the content of the polymer [A] is less than the above lower limit, the pattern formation property of the photoresist composition may be lowered. Moreover, the photoresist composition can also One or two or more kinds of [A] polymers are contained.
〔A〕聚合物可例如使用自由基聚合起始劑,在適當溶劑中使獲得各構造單位之單體聚合而合成。 The [A] polymer can be synthesized, for example, by polymerizing a monomer which obtains each structural unit in a suitable solvent using a radical polymerization initiator.
上述自由基起始劑可列舉為例如偶氮雙異丁腈(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)、2,2’-偶氮雙異丁酸二甲酯等偶氮系自由基起始劑;苯甲醯基過氧化物、第三丁基過氧化氫、異丙苯基過氧化氫等過氧化物系自由基起始劑等。作為上述自由基聚合起始劑,於該等中,以AIBN、2,2’-偶氮雙異丁酸二甲酯較佳,更好為AIBN。該等自由基起始劑可單獨使用1種或混合兩種以上使用。 The above radical initiator may, for example, be azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2' -Azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyric acid dimethyl ester, etc. A nitrogen-based radical initiator; a peroxide-based radical initiator such as benzammonium peroxide, tert-butyl hydroperoxide or cumyl hydroperoxide. As the above-mentioned radical polymerization initiator, among these, AIBN, dimethyl 2,2'-azobisisobutyrate is preferred, and AIBN is more preferred. These radical initiators may be used alone or in combination of two or more.
上述聚合中使用之溶劑列舉為例如:正戊烷、正己烷、正庚烷、正辛烷、正壬烷、正癸烷等烷類;環己烷、環庚烷、環辛烷、十氫萘、降冰片烷等環烷類;苯、甲苯、二甲苯、乙基苯、異丙苯等芳香族烴類;氯丁烷類、溴己烷類、二氯乙烷類、六亞甲基二溴、氯苯等鹵化烴類;乙酸乙酯、乙酸正丁酯、乙酸異丁酯、丙酸甲酯等飽和羧酸酯類; 丙酮、2-丁酮、2-戊酮、4-甲基-2-戊酮、2-庚酮等酮類;四氫呋喃、二甲氧基乙烷、二乙氧基乙烷等醚類;甲醇、乙醇、1-丙醇、2-丙醇、4-甲基-2-戊醇等醇類等。上述溶劑以2-丁醇較佳。該等聚合中使用之溶劑可單獨使用或併用2種以上。 The solvent used in the above polymerization is exemplified by, for example, an alkane such as n-pentane, n-hexane, n-heptane, n-octane, n-decane or n-decane; cyclohexane, cycloheptane, cyclooctane, and decahydrogen; Naphthenes such as naphthalene and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; chlorobutanes, bromohexanes, dichloroethanes, hexamethylene Halogenated hydrocarbons such as dibromo and chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate; Ketones such as acetone, 2-butanone, 2-pentanone, 4-methyl-2-pentanone, and 2-heptanone; ethers such as tetrahydrofuran, dimethoxyethane, and diethoxyethane; methanol An alcohol such as ethanol, 1-propanol, 2-propanol or 4-methyl-2-pentanol. The above solvent is preferably 2-butanol. The solvent used in the polymerization may be used singly or in combination of two or more.
上述聚合中之反應溫度通常為40℃~150℃,較好為50℃~120℃。反應時間通常為1小時~48小時,較好為1小時~24小時。 The reaction temperature in the above polymerization is usually from 40 ° C to 150 ° C, preferably from 50 ° C to 120 ° C. The reaction time is usually from 1 hour to 48 hours, preferably from 1 hour to 24 hours.
〔A〕聚合物之利用凝膠滲透層析(GPC)測量之聚苯乙烯換算重量平均分子量(Mw)並無特別限制,通常為1,000以上500,000以下,更好為2,000以上400,000以下,又更好為3,000以上300,000以下。〔A〕聚合物之Mw未達上述下限時,會有所得阻劑膜之耐熱性下降之情況。〔A〕聚合物之Mw超過上述上限時,會有阻劑膜之顯像性下降之情況。 [A] Polymer The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is not particularly limited, and is usually 1,000 or more and 500,000 or less, more preferably 2,000 or more and 400,000 or less, and more preferably It is 3,000 or more and 300,000 or less. When the Mw of the polymer [A] does not reach the above lower limit, the heat resistance of the obtained resist film may be lowered. When the Mw of the polymer [A] exceeds the above upper limit, the developability of the resist film may be lowered.
〔A〕聚合物之Mw相對於藉GPC測定之聚苯乙烯換算數平均分子量(Mn)之比(Mw/Mn)通常為1以上5以下,較好為1以上3以下,更好為1以上2以下。Mw/Mn超過上述上限時,會有所得阻劑膜之耐熱性下降之情況。 The ratio (Mw/Mn) of the Mw of the polymer to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is usually 1 or more and 5 or less, preferably 1 or more and 3 or less, more preferably 1 or more. 2 or less. When Mw/Mn exceeds the above upper limit, the heat resistance of the obtained resist film may be lowered.
本說明書中之聚合物之Mw及Mn係依據以下條件,利用凝膠滲透層析(GPC)測定之值。 The Mw and Mn of the polymer in the present specification are values measured by gel permeation chromatography (GPC) in accordance with the following conditions.
GPC管柱:G2000HXL 2根,G3000HXL 1根, G4000HXL 1根(以上為TOSOH製造),管柱溫度:40℃ GPC column: 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (above manufactured by TOSOH), column temperature: 40 ° C
溶出溶劑:四氫呋喃 Dissolution solvent: tetrahydrofuran
流速:1.0毫升/分鐘 Flow rate: 1.0 ml / min
試料濃度:1.0質量% Sample concentration: 1.0% by mass
試料注入量:100μL Sample injection amount: 100 μL
檢測器:示差折射計 Detector: differential refractometer
標準物質:單分散聚苯乙烯 Reference material: monodisperse polystyrene
〔A〕聚合物所含之低分子量成分係指分子量1,000以下之成分。低分子量成分之含量(質量%)就〔A〕聚合物之玻璃轉移溫度上升之觀點而言,較好未達0.5質量%,更好未達0.2質量%,又更好未達0.1質量%。 [A] The low molecular weight component contained in the polymer means a component having a molecular weight of 1,000 or less. The content (% by mass) of the low molecular weight component is preferably less than 0.5% by mass, more preferably less than 0.2% by mass, even more preferably less than 0.1% by mass, from the viewpoint of the glass transition temperature of the [A] polymer.
本說明書中之低分子量成分之含量(質量%)為由以下條件,使用高速液體層析法(HPLC)測定之值。 The content (% by mass) of the low molecular weight component in the present specification is a value measured by high speed liquid chromatography (HPLC) under the following conditions.
HPLC管柱:Intersil ODS-25μm,4.6mm×250mm(JL Science公司製) HPLC column: Intersil ODS-25μm, 4.6mm ×250mm (made by JL Science Co., Ltd.)
溶出溶劑:丙烯腈/0.1質量%磷酸水溶液 Dissolution solvent: acrylonitrile / 0.1% by mass phosphoric acid aqueous solution
流量:1.0mL/分鐘 Flow rate: 1.0mL/min
試料濃度:1.0質量% Sample concentration: 1.0% by mass
試料注入量:100μL Sample injection amount: 100 μL
檢測器:示差折射計 Detector: differential refractometer
〔B〕酸產生劑係至少含化合物(1)之酸產生劑。酸產生劑係指吸收曝光產生之能量,且產生磺酸等酸之化合物等。藉由使用含有〔A〕聚合物及〔B〕酸產生劑之光阻組成物,可一面發揮優異之MEEF性能,一面形成剖面形狀等圖型形狀及蝕刻耐性優異之阻劑圖型。〔B〕酸產生劑在不損及本發明效果之範圍內,亦可含化合物(1)以外之化合物,亦可作為酸產生劑組成物而使用。該等化合物可單獨使用,亦可併用2種以上。 [B] The acid generator is an acid generator containing at least the compound (1). The acid generator refers to a compound which absorbs energy generated by exposure and which generates an acid such as a sulfonic acid. By using the photoresist composition containing the [A] polymer and the [B] acid generator, it is possible to form a resist pattern having a pattern shape such as a cross-sectional shape and excellent etching resistance while exhibiting excellent MEEF performance. The acid generator (B) may contain a compound other than the compound (1) or may be used as an acid generator composition, within the range not impairing the effects of the present invention. These compounds may be used alone or in combination of two or more.
該光阻組成物藉由具有上述構成而發揮上述效果之理由雖尚不清楚,但例如推測如下。亦即,藉由使R2為上述烷烴二基或上述氟化烷烴二基,可提高〔B〕酸產生劑與〔A〕聚合物等之相溶性,可使〔B〕酸產生劑更均勻地分散於阻劑膜中。結果,阻劑圖型難以如過去者般成為頂端損失形狀,剖面形狀容易成為矩形。且,認為藉由磺酸酯構造與上述R2之適宜極性,而適度控制酸擴散性,故可提高該光阻組成物之MEEF性能。再者,R2內之氟原子數較少,亦即藉由使上述R2之氟數成為上述範圍,可提高對蝕刻之耐性。 Although the reason why the photoresist composition exhibits the above effects by the above configuration is not clear, for example, it is presumed as follows. That is, by making R 2 the alkanediyl group or the above-mentioned fluorinated alkanediyl group, the compatibility of the [B] acid generator with the [A] polymer or the like can be improved, and the [B] acid generator can be made more uniform. Disperse in the resist film. As a result, the resist pattern is difficult to be a tip loss shape as in the past, and the cross-sectional shape is likely to be a rectangle. Further, it is considered that the acid diffusion property is appropriately controlled by the sulfonic acid ester structure and the appropriate polarity of the above R 2 , so that the MEEF performance of the photoresist composition can be improved. Further, the number of fluorine atoms in R 2 is small, that is, by making the fluorine number of the above R 2 into the above range, the resistance to etching can be improved.
化合物(1)係以下述式(1)表示。 The compound (1) is represented by the following formula (1).
【化10】R1-SO2O-R2-SO3 - Q+ (1) R 10 -SO 2 OR 2 -SO 3 - Q + (1)
上述式(1)中,R1為取代或非取代之碳數1~30之1價烴基或取代或非取代之環原子數3~30之1價雜環基。R2為碳數1~30之烷烴二基或氟數小於碳數之碳數2~30之氟化烷烴二基。Q+為1價之光分解性有機陽離子。 In the above formula (1), R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms or a substituted or unsubstituted monovalent heterocyclic group having 3 to 30 ring atoms. R 2 is an alkanediyl group having 1 to 30 carbon atoms or a fluorinated alkanediyl group having a fluorine number of less than 2 to 30 carbon atoms. Q + is a monovalent photodecomposable organic cation.
上述碳數係指烴基中所含之碳數,不含任意取代基中所含之碳數。且,上述環原子數係指雜環基中所含之碳原子及雜原子之個數,不含任意取代基中所含之碳數等。 The above carbon number means the number of carbons contained in the hydrocarbon group, and does not contain the carbon number contained in any substituent. Further, the number of ring atoms refers to the number of carbon atoms and hetero atoms contained in the heterocyclic group, and does not include the number of carbon atoms contained in any substituent.
上述化合物(1)含陰離子與光分解性有機陽離子(Q+)。「光分解性有機陽離子」為可藉曝光而分解,產生質子之含碳原子之陽離子。 The above compound (1) contains an anion and a photodecomposable organic cation (Q + ). The "photodecomposable organic cation" is a cation containing a carbon atom which can be decomposed by exposure to generate a proton.
上述R1由於為上述烴基或上述雜環基,故可確保對〔A〕聚合物或〔E〕溶劑之優異相溶性。烴基之碳數或雜環基之環原子數超過上述上限時,上述相溶性下降。 Since R 1 is the above hydrocarbon group or the above heterocyclic group, excellent compatibility with the [A] polymer or the [E] solvent can be ensured. When the number of carbon atoms of the hydrocarbon group or the number of ring atoms of the heterocyclic group exceeds the above upper limit, the compatibility is lowered.
上述烴基列舉為例如,甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、新戊基、第三戊基、正己基、異己基、正庚基、異庚基、正辛基、異辛基、正壬基、異壬基、正癸基、異癸基等烷基;環丁基、環戊基、環己基、環庚基、環辛基等單環之環烷基;降冰片基、異冰片基、金剛烷基、三環癸基、四環十 二烷基等多環之環烷基;乙烯基、1-丙烯-1-基等烯基;乙炔基、丙炔基等炔基;苯基、萘基、聯苯基、茀基、蒽基、菲基等芳基;苄基、苯乙基、1-萘基甲基、2-萘基甲基、1-萘基乙基、2-萘基乙基等芳烷基等。 The above hydrocarbon group is exemplified by, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, isopentyl, and second pentyl. , neopentyl, third amyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-decyl, isodecyl, n-decyl, isodecyl, etc. a monocyclic cycloalkyl group such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl; norbornyl, isobornyl, adamantyl, tricyclodecyl, tetracycline a polycyclic cycloalkyl group such as a dialkyl group; an alkenyl group such as a vinyl group or a 1-propen-1-yl group; an alkynyl group such as an ethynyl group or a propynyl group; a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group or a fluorenyl group An aryl group such as phenanthryl; an aralkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group or a 2-naphthylethyl group.
烴基之碳數較好為1~20,更好為1~15。 The carbon number of the hydrocarbon group is preferably from 1 to 20, more preferably from 1 to 15.
上述雜環基列舉為例如:呋喃基、吡咯基、噻吩基、噁唑啉基、異噁唑啉基、咪唑基、噻唑基、異噻唑基、吡啶基、嘧啶基、四唑基、吡唑基、嗒嗪基、吡嗪基、噻二唑基、二苯并呋喃基等芳香族雜環基(亦即雜芳基);哌啶基、四氫吡喃基、四氫呋喃基、氧雜環丁基、氮雜環丁基(azetidinyl)、吡咯啶基、嗎啉基、硫嗎啉基、二氧雜環己基、哌嗪基等脂肪族雜環基等。 The above heterocyclic group is exemplified by, for example, furyl, pyrrolyl, thienyl, oxazolinyl, isoxazolinyl, imidazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, tetrazolyl, pyrazole. Aromatic heterocyclic group (ie, heteroaryl) such as pyridyl, pyrazinyl, thiadiazolyl, dibenzofuranyl; piperidinyl, tetrahydropyranyl, tetrahydrofuranyl, oxacyclo An aliphatic heterocyclic group such as a butyl group, an azetidinyl group, a pyrrolidinyl group, a morpholinyl group, a thiomorpholinyl group, a dioxolyl group or a piperazinyl group.
雜環基之環原子數較好為3~20,更好為3~15。 The number of ring atoms of the heterocyclic group is preferably from 3 to 20, more preferably from 3 to 15.
上述烴基及雜環基在不損及本發明效果之範圍內,亦可以任意取代基取代該等之氫原子之一部分或全部。上述取代基只要可獲得期望之物性即無特別限制,列舉為例如烷氧基、羥基、醛基、羧基、羰基、醯胺基、醯亞胺基、胺基、亞胺基、氰基、偶氮基、疊氮基、硫醇基、磺基、硝基、醚基、酯基、具有內酯構造之基、烷基羰基、氧代基、鹵原子等習知之基。上述取代基在該等中 以氧代基較佳。亦即,上述R1較好含羰基。 The above hydrocarbon group and heterocyclic group may be substituted for a part or all of the hydrogen atoms by any substituent, within the range not impairing the effects of the present invention. The above substituent is not particularly limited as long as the desired physical properties are obtained, and examples thereof include an alkoxy group, a hydroxyl group, an aldehyde group, a carboxyl group, a carbonyl group, a decylamino group, a quinone imine group, an amine group, an imido group, a cyano group, and an even group. A conventional group such as a nitrogen group, an azide group, a thiol group, a sulfo group, a nitro group, an ether group, an ester group, a group having a lactone structure, an alkylcarbonyl group, an oxo group or a halogen atom. The above substituent is preferably an oxo group in the above. That is, the above R 1 preferably contains a carbonyl group.
上述R1較好為取代或非取代之烷基、取代或非取代之環烷基、取代或非取代之芳香族雜環基,更好為未經取代之烷基、經取代之環烷基、未經取代之芳香族雜環基,又更好為未經取代之碳數1~4之烷基、經氧代基取代之環烷基、含氧原子作為構成原子之芳香族雜環基,最好為甲基、正丁基、10-樟腦基、二苯并呋喃基。 The above R 1 is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aromatic heterocyclic group, more preferably an unsubstituted alkyl group, a substituted cycloalkyl group. The unsubstituted aromatic heterocyclic group is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, a cycloalkyl group substituted by an oxo group, and an aromatic heterocyclic group having an oxygen atom as a constituent atom. Preferably, it is methyl, n-butyl, 10-camphoryl, dibenzofuranyl.
上述R2為碳數1~30之烷烴二基或氟數小於碳數之碳數2~30之氟化烷烴二基,較好為氟數小於碳數之碳數2~30之氟化烷烴二基。烴基之碳數或雜環基之環原子數超過上述上限時,對溶劑之溶解性下降。 The above R 2 is an alkanediyl group having 1 to 30 carbon atoms or a fluorinated alkanediyl group having a carbon number of 2 to 30 and a carbon number of 2 to 30, preferably a fluorinated alkane having a fluorine number of less than a carbon number of 2 to 30 carbon atoms. Second base. When the number of carbon atoms of the hydrocarbon group or the number of ring atoms of the heterocyclic group exceeds the above upper limit, the solubility in a solvent is lowered.
上述烷烴二基列舉為例如甲烷烴二基、乙烷烴二基、丙烷烴二基、丁烷烴二基、戊烷烴二基、己烷烴二基、庚烷烴二基、辛烷烴二基、壬烷烴二基、癸烷烴二基等。 The above alkanediyl groups are exemplified by, for example, a methane hydrocarbon diyl group, an ethane hydrocarbon diyl group, a propane hydrocarbon diyl group, a butane hydrocarbon diyl group, a pentane hydrocarbon diyl group, a hexane hydrocarbon diyl group, a heptane diyl group, an octane diyl group, a decane hydrocarbon. Dibasic, decane diyl and the like.
上述氟化烷烴二基列舉為例如上述烷烴二基之氫原子之一部分經氟原子取代之基中,氟數小於碳數之基等。藉由使氟數成為上述範圍,推測可使〔B〕酸產生劑具有源自烴部分之親油性、源自氟原子之極性等二者之優異特性。 The fluorinated alkanediyl group is exemplified by a group in which one of the hydrogen atoms of the alkanediyl group is substituted with a fluorine atom, and a fluorine atom is less than a carbon number. When the fluorine number is in the above range, it is presumed that the [B] acid generator has excellent properties of both the lipophilicity derived from the hydrocarbon moiety and the polarity derived from the fluorine atom.
上述烷烴二基之碳數較好為1~20,更好為1~10。且,上述氟化烷烴二基之碳數較好為2~20,更好為2~10。 The carbon number of the above alkanediyl group is preferably from 1 to 20, more preferably from 1 to 10. Further, the carbon number of the fluorinated alkanediyl group is preferably from 2 to 20, more preferably from 2 to 10.
烷烴二基及氟化烷烴二基可為直鏈狀,或可 具有側鏈。 The alkanediyl and fluorinated alkanediyl groups may be linear or may be With side chains.
上述R2較好為氟化烷烴二基,且該氟化烷烴二基之氟數為2以上。該情況下,可提高所產生之酸強度,結果,依據該光阻組成物,可一面發揮更優異之MEEF性能,一面形成圖型形狀及蝕刻耐性更優異之阻劑圖型。 The above R 2 is preferably a fluorinated alkanediyl group, and the fluorine atom of the fluorinated alkanediyl group is 2 or more. In this case, the strength of the acid generated can be increased, and as a result, the resist pattern can be more excellent in pattern shape and etching resistance while exhibiting more excellent MEEF performance.
氟數為2以上之氟化烷烴二基列舉為例如以氟原子取代2個以上之丙烷烴二基、丁烷烴二基、戊烷烴二基、己烷烴二基、庚烷烴二基、辛烷烴二基、壬烷烴二基、癸烷烴二基等之任意氫原子而成者等。 The fluorinated alkanediyl group having a fluorine number of 2 or more is exemplified by, for example, a fluorine atom substituted with two or more propane hydrocarbon diyl groups, a butane hydrocarbon diyl group, a pentane hydrocarbon diyl group, a hexane hydrocarbon diyl group, a heptane diyl group, and an octane hydrocarbon group. Any hydrogen atom such as a base, a decane diyl group or a decane hydrocarbon group is formed.
上述氟數較好為2~10,更好為2~8。又,上述氟數小於上述氟化烷烴二基之碳數。 The above fluorine number is preferably from 2 to 10, more preferably from 2 to 8. Further, the fluorine number is smaller than the carbon number of the fluorinated alkanediyl group.
上述氟化烷烴二基較好以下述式(i)表示。 The above fluorinated alkanediyl group is preferably represented by the following formula (i).
【化11】-R3-CF2- (i) [11]-R 3 -CF 2 - (i)
上述式(i)中,R3為碳數3以上之烷烴二基或碳數3以上之氟化烷烴二基。 In the above formula (i), R 3 is an alkanediyl group having 3 or more carbon atoms or a fluorinated alkanediyl group having 3 or more carbon atoms.
藉由使〔B〕酸產生劑具有以上述式(i)表示之基,可進一步提高所產生之酸強度,結果可進一步提高該光阻組成物之上述特性。又,上述式(i)之-CF2-基與上述式(1)之-SO3 -基鍵結。 By having the [B] acid generator having the group represented by the above formula (i), the acid strength generated can be further increased, and as a result, the above characteristics of the photoresist composition can be further improved. Further, the -CF 2 - group of the above formula (i) is bonded to the -SO 3 - group of the above formula (1).
上述R3列舉為例如1個氫原子經氟原子取代或未經取代之丙烷烴二基、1個或2個氫原子經氟原子取 代或未經取代之丁烷烴二基、1個~3個氫原子經氟原子取代或未經取代之戊烷烴二基、1個~4個氫原子經氟原子取代或未經取代之己烷烴二基、1個~5個氫原子經氟原子取代或未經取代之庚烷烴二基、1個~6個氫原子經氟原子取代或未經取代之辛烷烴二基、1個~7個氫原子經氟原子取代或未經取代之壬烷烴二基、1個~8個氫原子經氟原子取代或未經取代之癸烷烴二基。且,在不損及本發明效果之範圍內,任一氫原子均可經氟原子取代。 The above R 3 is exemplified by, for example, a propane hydrocarbon diyl group in which one hydrogen atom is substituted or unsubstituted with a fluorine atom, a butane hydrocarbon diyl group in which one or two hydrogen atoms are substituted or unsubstituted by a fluorine atom, and one to three a pentane hydrocarbon diyl group in which a hydrogen atom is substituted or unsubstituted with a fluorine atom, a hexane hydrocarbon diyl group in which one to four hydrogen atoms are substituted or unsubstituted by a fluorine atom, and one to five hydrogen atoms are substituted by a fluorine atom or not a substituted heptane diyl group, a 1-6 alkyl group substituted with a fluorine atom or a fluorine atom substituted by a fluorine atom, or a decane diyl group having 1 to 7 hydrogen atoms substituted or unsubstituted by a fluorine atom, A decane diyl group in which one to eight hydrogen atoms are substituted or unsubstituted with a fluorine atom. Further, any hydrogen atom may be substituted with a fluorine atom within a range not impairing the effects of the present invention.
上述R3之碳數在烷烴二基及氟化烷烴二基之任一情況下,均較好為3~29,更好為3~19,又更好為3~9。碳數在上述範圍內時,而有化合物(1)對〔A〕聚合物顯示更優異相溶性之傾向。 The carbon number of the above R 3 is preferably from 3 to 29, more preferably from 3 to 19, still more preferably from 3 to 9, in any of the alkanediyl group and the fluorinated alkanediyl group. When the carbon number is in the above range, the compound (1) tends to exhibit more excellent compatibility with the [A] polymer.
上述R3較好為1個氫原子經氟原子取代或未經取代之丙烷烴二基、1個或2個氫原子經氟原子取代或未經取代之丁烷烴二基、1個~3個氫原子經氟原子取代或未經取代之戊烷烴二基、1個~4個氫原子經氟原子取代或未經取代之己烷烴二基、1個~5個氫原子經氟原子取代或未經取代之庚烷烴二基、1個~6個氫原子經氟原子取代或未經取代之辛烷烴二基、更好為丙烷烴二基、二氟丙烷烴二基、二氟辛烷烴二基、六氟辛烷烴二基。 The above R 3 is preferably a propane hydrocarbon diyl group in which one hydrogen atom is substituted or unsubstituted by a fluorine atom, a butane hydrocarbon diyl group in which one or two hydrogen atoms are substituted or unsubstituted by a fluorine atom, and one to three a pentane hydrocarbon diyl group in which a hydrogen atom is substituted or unsubstituted with a fluorine atom, a hexane hydrocarbon diyl group in which one to four hydrogen atoms are substituted or unsubstituted by a fluorine atom, and one to five hydrogen atoms are substituted by a fluorine atom or not Substituted heptane diyl, one to six hydrogen atoms substituted or unsubstituted octane diyl, more preferably propane dienyl, difluoropropane diyl, difluorooctane diyl , hexafluorooctane diyl.
上述化合物(1)之陰離子列舉為例如以下述式(5-1)~(5-14)表示之陰離子等。該等陰離子可單獨使用,亦可併用2種以上。 The anion of the compound (1) is exemplified by an anion represented by the following formulas (5-1) to (5-14). These anions may be used singly or in combination of two or more.
上述化合物(1)之陰離子較好為以上述式(5-1)、(5-4)、(5-5)、(5-6)’(5-7)、(5-8)及(5-11)表示之陰離子,更好為以上述式(5-1)表示之陰離子。 The anion of the above compound (1) is preferably the above formulas (5-1), (5-4), (5-5), (5-6)' (5-7), (5-8) and The anion represented by 5-11) is more preferably an anion represented by the above formula (5-1).
上述Q+只要為1價光分解性有機陽離子即無特別限制,列舉為例如習知之光分解性有機陽離子。 The Q + is not particularly limited as long as it is a monovalent photodecomposable organic cation, and is exemplified by a conventional photodecomposable organic cation.
光分解性有機陽離子列舉為例如鋶離子、錪離子、咪唑鎓離子、吡啶鎓離子、銨離子、吡咯啶鎓離子、鏻離子等。至於光分解性有機陽離子,在該等中,以鋶離子、錪離子較佳。光分解性有機陽離子為鋶離子及錪離子之任一種時,會有提高該光阻組成物之MEEF性能等上述特性之傾向。該等光分解性有機陽離子可單獨使用,亦可併用2種以上。 The photodecomposable organic cation is exemplified by, for example, a cerium ion, a cerium ion, an imidazolium ion, a pyridinium ion, an ammonium ion, a pyrrolidinium ion, a cerium ion, or the like. As for the photodecomposable organic cation, among these, ruthenium ions and ruthenium ions are preferred. When the photodegradable organic cation is any of cerium ions and cerium ions, the above characteristics of the MEEF performance of the photoresist composition tend to be improved. These photodecomposable organic cations may be used singly or in combination of two or more.
上述Q+更好為由以下述式(2-1)表示之鋶陽離子及以下述式(2-2)表示之錪陽離子所組成群組選出之至少一種。可提高阻劑圖型之感度。 The Q + is more preferably at least one selected from the group consisting of a phosphonium cation represented by the following formula (2-1) and a phosphonium cation represented by the following formula (2-2). It can improve the sensitivity of the resist pattern.
上述式(2-1)中,R4、R5及R6各獨立為取代或非取代之碳數1~20之烷基或取代或非取代之碳數6~30之芳基,或表示此等基中之任2個以上相互結合與 該等所鍵結之硫原子一起構成之環構造。 In the above formula (2-1), R 4 , R 5 and R 6 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or Any two or more of these groups are bonded to each other to form a ring structure together with the bonded sulfur atoms.
上述式(2-2)中,R7及R8各獨立為取代或非取代之碳數1~20之烷基或取代或非取代之碳數6~30之芳基,或表示此等基相互結合與該等所鍵結之碘原子一起構成之環構造。 In the above formula (2-2), R 7 and R 8 are each independently a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted sum of carbon atoms of an aryl group having 6 to 30, or represents a group such A ring structure formed by bonding together with the iodine atoms bonded thereto.
上述碳數係指各官能基中所含之碳數,不含任意取代基中所含之碳數。 The above carbon number means the number of carbons contained in each functional group, and does not contain the carbon number contained in any substituent.
上述烷基或芳基之碳數超過上述上限時,會有降低該化合物與〔A〕聚合物之間之相溶性或對〔E〕溶劑之溶解性之情況。 When the carbon number of the alkyl group or the aryl group exceeds the above upper limit, the compatibility between the compound and the [A] polymer or the solubility in the [E] solvent may be lowered.
上述R4~R8可具有之任意取代基列舉為例如R1中所例示之習知官能基。 Any of the substituents which R 4 to R 8 may have are exemplified by, for example, a conventional functional group exemplified in R 1 .
上述R4、R5及R6中所含之烷基列舉為例如R1中所例示者等。上述烷基之碳數較好為1~15,更好為1~10。 The alkyl group contained in the above R 4 , R 5 and R 6 is exemplified by, for example, those exemplified as R 1 . The carbon number of the above alkyl group is preferably from 1 to 15, more preferably from 1 to 10.
上述R4、R5及R6中所含之芳基列舉為例如R1中所例示者等。至於上述芳基,於該等中,較好為苯基。上述芳基之碳數較好為6~25,更好為6~20。 The aryl group contained in the above R 4 , R 5 and R 6 is exemplified by, for example, those exemplified as R 1 . As the above aryl group, among these, a phenyl group is preferred. The carbon number of the above aryl group is preferably from 6 to 25, more preferably from 6 to 20.
上述R4、R5及R6亦可表示此等基中之任2個以上相互結合與該等所鍵結之硫原子一起構成之環構造。環構造列舉為例如脂環構造內之1個碳原子經硫原子取代之構造等。環原子數較好為3~20,更好為3~15。環原子數為上述範圍時,會有提高阻劑圖型感度之傾向。 The above R 4 , R 5 and R 6 may also represent a ring structure in which any two or more of these groups are bonded to each other and to the sulfur atom to which they are bonded. The ring structure is exemplified by a structure in which one carbon atom in the alicyclic structure is substituted with a sulfur atom. The number of ring atoms is preferably from 3 to 20, more preferably from 3 to 15. When the number of ring atoms is in the above range, there is a tendency to increase the sensitivity of the resist pattern.
上述鋶陽離子列舉為例如三苯基鋶陽離子、 環己基2-氧代環己基甲基鋶陽離子、二環己基2-氧代環己基鋶陽離子、2-氧代環己基二甲基鋶陽離子、4-羥基-1-萘基二甲基鋶陽離子、二苯基-4-羥基苯基鋶陽離子、4-第三丁氧基苯基二苯基鋶陽離子等習知之陽離子。上述鋶陽離子於該等中較好為三苯基鋶陽離子。 The above phosphonium cation is exemplified by, for example, a triphenylphosphonium cation Cyclohexyl 2-oxocyclohexylmethylphosphonium cation, dicyclohexyl 2-oxocyclohexylphosphonium cation, 2-oxocyclohexyldimethylphosphonium cation, 4-hydroxy-1-naphthyldimethylsulfonium cation A conventional cation such as a diphenyl-4-hydroxyphenylphosphonium cation or a 4-tert-butoxyphenyldiphenylphosphonium cation. The above phosphonium cation is preferably a triphenylphosphonium cation in the above.
上述R7及R8所含之烷基列舉為例如R1中所例示者等。上述烷基之碳數較好為1~15,更好為1~10。 The alkyl group contained in the above R 7 and R 8 is exemplified by, for example, those exemplified as R 1 . The carbon number of the above alkyl group is preferably from 1 to 15, more preferably from 1 to 10.
上述R7及R8中所含之芳基列舉為例如R1中所例示者等。上述芳基於該等中較好為苯基。上述芳基之碳數較好為6~25,更好為6~20。 The aryl group contained in the above R 7 and R 8 is exemplified by, for example, those exemplified as R 1 . The above aryl is preferably a phenyl group based on the above. The carbon number of the above aryl group is preferably from 6 to 25, more preferably from 6 to 20.
上述R7及R8亦可表示此等基相互結合與該等所鍵結之碘原子一起構成之環構造。環構造列舉為例如脂環構造內之1個碳原子經碘原子取代之構造等。環原子數較好為3~20,更好為3~15。環原子數為上述範圍時,會有提高阻劑圖型感度之傾向。 The above R 7 and R 8 may also represent a ring structure in which these groups are bonded to each other and the iodine atoms bonded thereto. The ring structure is exemplified by a structure in which one carbon atom in the alicyclic structure is substituted with an iodine atom. The number of ring atoms is preferably from 3 to 20, more preferably from 3 to 15. When the number of ring atoms is in the above range, there is a tendency to increase the sensitivity of the resist pattern.
上述錪陽離子列舉為例如二苯基錪陽離子、雙(4-第三丁基苯基)錪全氟正辛烷磺酸鹽、雙(4-第三丁基苯基)錪等習知之陽離子。上述錪陽離子於該等中以二苯基錪陽離子較佳。 The above ruthenium cation is exemplified by a conventional cation such as a diphenylphosphonium cation, a bis(4-t-butylphenyl)phosphonium perfluorooctane sulfonate or a bis(4-t-butylphenyl)fluorene. The above phosphonium cation is preferably a diphenylphosphonium cation in the above.
上述化合物(1)列舉為例如上述陰離子與光分解性有機陽離子之組合等。 The compound (1) is exemplified by, for example, a combination of the above anion and a photodecomposable organic cation.
上述化合物(1)較好為以下述式表示之化合物。 The above compound (1) is preferably a compound represented by the following formula.
〔B〕酸產生劑中所含之化合物(1)之含有率並無特別限制,通常為10質量%以上,較好為20質量%以上100%以下。含有率未達上述下限時,會有阻劑圖型之剖面形狀降低之情況。 The content of the compound (1) contained in the acid generator is not particularly limited, but is usually 10% by mass or more, preferably 20% by mass or more and 100% or less. When the content rate is less than the above lower limit, the cross-sectional shape of the resist pattern may be lowered.
〔B〕酸產生劑中所含之化合物(1)以外之其他酸產生劑列舉為例如化合物(1)以外之鎓鹽化合物、含鹵素化合物、重氮酮化合物、碸化合物、磺酸化合物、重氮甲烷系化合物、硝基苄基磺酸鹽系化合物、亞胺基磺酸鹽系化合物等。 The acid generator other than the compound (1) contained in the acid generator is exemplified by, for example, an onium salt compound other than the compound (1), a halogen-containing compound, a diazoketone compound, an anthraquinone compound, a sulfonic acid compound, and a heavy A nitrogen-methane-based compound, a nitrobenzylsulfonate-based compound, an imidosulfonate-based compound, or the like.
上述鎓鹽化合物列舉為例如化合物(1)以外之錪鹽及鋶鹽,以及鏻鹽、重氮鎓鹽、吡啶鎓鹽等、具體而言列舉為二苯基錪三氟甲烷磺酸鹽、二苯基錪九氟正丁烷磺酸鹽、二苯基錪全氟正辛烷磺酸鹽、二苯基錪2-雙環〔2.2.1〕庚-2-基-1,1,2,2-四氟乙烷磺酸鹽、雙(4-第三丁基苯基)錪三氟甲烷磺酸鹽、雙(4-第三丁基苯基)錪九氟正丁烷磺酸鹽、雙(4-第三丁基苯基)錪全氟正辛烷磺酸鹽、雙(4-第三丁基苯基)錪2-雙環〔2.2.1〕庚-2-基-1,1,2,2-四氟乙烷磺酸鹽、環己基2-氧代環己基甲基鋶三氟甲烷磺酸鹽、二環己基2-氧代環己基鋶三氟甲烷磺酸鹽、2-氧代環己基二甲基鋶三氟甲烷磺酸鹽等。 The onium salt compound is exemplified by, for example, a phosphonium salt and a phosphonium salt other than the compound (1), and a phosphonium salt, a diazonium salt, a pyridinium salt or the like, specifically, diphenylsulfonium trifluoromethanesulfonate, and Phenyl quinone nonafluorobutane sulfonate, diphenyl fluorene perfluoro-n-octane sulfonate, diphenyl hydrazine 2-bicyclo[2.2.1]heptan-2-yl-1,1,2,2 -tetrafluoroethane sulfonate, bis(4-tert-butylphenyl)phosphonium trifluoromethanesulfonate, bis(4-t-butylphenyl)phosphonium nonafluorobutane sulfonate, double (4-tert-butylphenyl)phosphonium perfluorooctane sulfonate, bis(4-t-butylphenyl)phosphonium 2-bicyclo[2.2.1]hept-2-yl-1,1, 2,2-tetrafluoroethane sulfonate, cyclohexyl 2-oxocyclohexylmethyl fluorene trifluoromethanesulfonate, dicyclohexyl 2-oxocyclohexyl fluorene trifluoromethane sulfonate, 2-oxygen Cyclohexyldimethylsulfonium trifluoromethanesulfonate and the like.
含鹵素化合物列舉為例如含鹵烷基之烴化合物、含鹵烷基之雜環式化合物等。具體而言列舉為例如苯基雙(三氯甲基)-s-三嗪、4-甲氧基苯基雙(三氯甲基)-s-三嗪、1-萘基雙(三氯甲基)-s-三嗪等(三氯甲 基)-s-三嗪衍生物;1,1-雙(4-氯苯基)-2,2,2-三氯乙烷等。 The halogen-containing compound is exemplified by, for example, a halogenated alkyl group-containing hydrocarbon compound, a halogenated alkyl group-containing heterocyclic compound, and the like. Specifically, for example, phenylbis(trichloromethyl)-s-triazine, 4-methoxyphenylbis(trichloromethyl)-s-triazine, 1-naphthylbis(trichloromethane) Base)-s-triazine, etc. a s-triazine derivative; 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, and the like.
重氮酮化合物列舉為例如1,3-二酮-2-重氮化合物、重氮苯醌化合物、重氮萘醌化合物等。具體而言列舉為例如1,2-萘醌重氮-4-磺醯氯、1,2-萘醌重氮-5-磺醯氯、2,3,4,4’-四羥基二苯甲酮之1,2-萘醌重氮-4-磺酸酯、1,2-萘醌重氮-5-磺酸酯、1,1,1-參(4-羥基苯基)乙烷之1,2-萘醌重氮-4-磺酸酯、1,2-萘醌重氮-5-磺酸酯等。 The diazoketone compound is exemplified by, for example, a 1,3-diketone-2-diazo compound, a diazonium quinone compound, a diazonaphthoquinone compound, or the like. Specifically, for example, 1,2-naphthoquinonediazide-4-sulfonium chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 2,3,4,4'-tetrahydroxydiphenyl Ketone 1,2-naphthoquinonediazide-4-sulfonate, 1,2-naphthoquinonediazide-5-sulfonate, 1,1,1-cis (4-hydroxyphenyl)ethane 1 2-naphthoquinonediazide-4-sulfonate, 1,2-naphthoquinonediazide-5-sulfonate, and the like.
碸化合物列舉為例如β-酮碸、β-磺醯基碸、或該等化合物之α-重氮化合物等。具體而言列舉為例如4-參苯乙醯基碸、均三甲苯基苯乙醯基碸、雙(苯基磺醯基)甲烷等。 The ruthenium compound is exemplified by, for example, β-ketooxime, β-sulfonylhydrazine, or an α-diazonium compound of the compounds. Specifically, for example, 4-paraphenylethylhydrazine, mesitylene phenethyl hydrazine, bis(phenylsulfonyl)methane, and the like are exemplified.
磺酸化合物列舉為例如烷基磺酸酯、烷基磺酸醯亞胺、鹵烷基磺酸酯、芳基磺酸酯、亞胺基磺酸酯等。 The sulfonic acid compound is exemplified by, for example, an alkylsulfonate, an alkylsulfonium iminoamine, a haloalkylsulfonate, an arylsulfonate, an imidosulfonate or the like.
具體而言列舉為苯偶因甲烷磺酸酯、連苯三酚之參(三氟甲烷磺酸酯)、硝基苄基-9,10-二乙氧基蒽-2-磺酸酯、三氟甲烷磺醯基雙環〔2.2.1〕庚-5-烯-2,3-二羰二醯亞胺、九氟正丁烷磺醯基雙環〔2.2.1〕庚-5-烯-2,3-二碳二醯亞胺、全氟正辛烷磺醯基雙環〔2.2.1〕庚-5-烯-2,3-二碳二醯亞胺、2-雙環〔2.2.1〕庚-2-基-1,1,2,2-四氟乙烷磺醯基雙環〔2.2.1〕庚-5-烯-2,3-二碳二醯亞胺、N-(三氟甲烷磺醯氧基)琥珀醯亞胺、N-(九氟正丁烷磺醯氧基)琥珀醯亞胺、N-(全氟正辛烷磺醯基氧基)琥珀 醯亞胺、N-(2-雙環〔2.2.1〕庚-2-基-1,1,2,2-四氟乙烷磺醯氧基)琥珀醯亞胺、1,8-萘二羧酸醯亞胺三氟甲烷磺酸酯、1,8-萘二羧酸醯亞胺九氟正丁烷磺酸酯、1,8-萘二羧酸醯亞胺全氟正辛烷磺酸酯等。 Specifically, it is exemplified by benzoin methanesulfonate, pyrogallol (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyindole-2-sulfonate, and three Fluoromethanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo[2.2.1]hept-5-ene-2, 3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, 2-bicyclo[2.2.1]heptane- 2-yl-1,1,2,2-tetrafluoroethanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, N-(trifluoromethanesulfonate) Oxy) succinimide, N-(nonafluoro-n-butane sulfonyloxy) succinimide, N-(perfluoro-n-octane sulfonyloxy) amber Yttrium, N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, 1,8-naphthalene dicarboxylate Barium imide trifluoromethanesulfonate, octadecyl n-butane sulfonate 1,8-naphthalene dicarboxylate, perfluoro-n-octane sulfonate of 1,8-naphthalene dicarboxylate Wait.
該等化合物可單獨使用,亦可併用2種以上。〔B〕酸產生劑之調配量,相對於〔A〕聚合物100質量份通常為0.1質量份~20質量份,較好為0.5質量份~15質量份。調配量在上述範圍內時,有可確保〔A〕聚合物與〔B〕酸產生劑之間之優異相溶性之傾向。調配量超過上述上限時,該光阻組成物對曝光之光的透明性降低,而難以獲得具有期望之上述特性的阻劑圖型。調配量未達上述下限時,該光阻組成物之感度或顯像性降低。 These compounds may be used alone or in combination of two or more. The amount of the acid generator to be added is usually 0.1 parts by mass to 20 parts by mass, preferably 0.5 parts by mass to 15 parts by mass, per 100 parts by mass of the [A] polymer. When the amount is within the above range, there is a tendency to ensure excellent compatibility between the [A] polymer and the [B] acid generator. When the compounding amount exceeds the above upper limit, the transparency of the photoresist composition to the exposed light is lowered, and it is difficult to obtain a resist pattern having the desired characteristics described above. When the amount of the compound does not reach the above lower limit, the sensitivity or developability of the photoresist composition is lowered.
含化合物(1)之酸產生劑並無特別限制,可根據習知方法製造。 The acid generator containing the compound (1) is not particularly limited and can be produced according to a conventional method.
列舉化合物(1)之製造方法之一例時,係使用Br-R2-OH(R2與上述式(1)同義)作為起始原料所得之上述化合物可藉由具有下述步驟之製造方法獲得:在連二亞硫酸鈉及碳酸氫鈉存在下,使上述起始原料在乙腈水溶液中加熱之步驟,在過氧化氫水及鎢酸二鈉存在下加熱前一步驟所得之水層的步驟,於前一步驟中所得之水層中添加光分解性有機陽離子 (Q+)之氯化物(Q+與上述式(1)同義)、二氯甲烷及水,在室溫下攪拌之步驟,及於前一步驟所得之二氯甲烷溶液中添加三乙胺及4-二甲胺基吡啶,經冷卻,接著滴加R1-SO2Cl(R1與上述式(1)同義)之二氯甲烷溶液,並經攪拌之步驟。各步驟中之如溫度、壓力、時間或設備之其他步驟條件並無特別限制,係依據使用原料等適當設定。各步驟之階段數並無特別限制,可藉1階段進行,亦可藉多階段進行。 When an example of the production method of the compound (1) is exemplified, the above compound obtained by using Br-R 2 -OH (R 2 is synonymous with the above formula (1)) as a starting material can be obtained by a production method having the following steps. The step of heating the above starting material in an aqueous solution of acetonitrile in the presence of sodium dithionite and sodium hydrogencarbonate, heating the aqueous layer obtained in the previous step in the presence of hydrogen peroxide water and disodium tungstate, before a step of adding a photodegradable organic cation (Q + ) chloride (Q + synonymous with the above formula (1)), dichloromethane and water to the aqueous layer obtained in the first step, stirring at room temperature, and before Adding triethylamine and 4-dimethylaminopyridine to the dichloromethane solution obtained in one step, cooling, and then dropwise adding a solution of R 1 -SO 2 Cl (R 1 is synonymous with the above formula (1)) And the step of stirring. The conditions such as temperature, pressure, time, or other steps of the apparatus in each step are not particularly limited, and are appropriately set depending on the materials used. The number of stages in each step is not particularly limited and can be carried out in one stage or in multiple stages.
該光阻組成物亦可含有〔C〕酸擴散控制體、〔D〕含氟原子之聚合物及〔E〕溶劑作為適宜成分,且,在不損及本發明效果之範圍內,亦可含〔F〕偏在化促進劑、界面活性劑、脂環式骨架化合物、增感劑、交聯劑、界面活性劑、溶解抑制劑、可塑劑、安定劑、著色劑、防光暈劑、染料、顏料、接著助劑、鹼可溶性樹脂、具有酸解離性之保護基的低分子鹼溶解性控制劑、鹼性化合物、溶解阻止劑、儲存安定化劑、消泡劑等其他任意成分。其他成分之調配量可依據其目的適當決定。針對該等成分說明於下。 The resist composition may further contain a [C] acid diffusion controlling agent, [D] a fluorine atom-containing polymer, and [E] a solvent as suitable components, and may also contain a range which does not impair the effects of the present invention. [F] partialization accelerator, surfactant, alicyclic skeleton compound, sensitizer, crosslinking agent, surfactant, dissolution inhibitor, plasticizer, stabilizer, colorant, antihalation agent, dye, A pigment, a secondary auxiliary agent, an alkali-soluble resin, a low molecular alkali solubility control agent having an acid dissociable protecting group, a basic compound, a dissolution inhibitor, a storage stabilizer, an antifoaming agent, and the like. The amount of other ingredients may be appropriately determined depending on the purpose. These components are described below.
〔C〕酸擴散控制體為控制因曝光產生之酸在阻劑膜中之擴散現象,發揮抑制未曝光區域中不佳化學反應之效 果,進一步提高所得光阻組成物之儲存安定性,且進一步提高作為阻劑之解像度,並且可抑制因自曝光至顯像處理之擱置時間變動造成之阻劑圖型之線寬變化,獲得製程安定性極優異之光阻組成物。〔C〕酸擴散控制體在該光阻組成物中之含有形態可為游離化合物形態(以下適當稱為「〔C〕酸擴散控制劑」),亦可為作為聚合物之一部份納入之形態,亦可為該二者之形態。 [C] The acid diffusion control body controls the diffusion of acid generated by exposure in the resist film, and exerts the effect of suppressing poor chemical reaction in the unexposed area. Further, the storage stability of the obtained photoresist composition is further improved, and the resolution as a resist is further improved, and the line width variation of the resist pattern due to the change in the leaving time from the exposure to the development treatment can be suppressed, and the process can be obtained. A photoresist composition with excellent stability. [C] The acid diffusion control body may be in the form of a free compound in the form of a free compound (hereinafter referred to as "[C] acid diffusion controlling agent"), or may be incorporated as part of the polymer. The form can also be the form of the two.
〔C〕酸擴散控制劑列舉為例如胺化合物、含有醯胺基之化合物、脲化合物、含氮雜環化合物等。 The [C] acid diffusion controlling agent is exemplified by, for example, an amine compound, a guanamine group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, and the like.
胺化合物列舉為例如單(環)烷基胺類;二(環)烷基胺類;三(環)烷基胺類;經取代之烷基苯胺或其衍生物;乙二胺、N,N,N',N’-四甲基乙二胺、四亞甲基二胺、六亞甲基二胺、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、4,4’-二胺基二苯甲酮、4,4’-二胺基二苯基胺、2,2-雙(4-胺基苯基)丙烷、2-(3-胺基苯基)-2-(4-胺基苯基)丙烷、2-(4-胺基苯基)-2-(3-羥基苯基)丙烷、2-(4-胺基苯基)-2-(4-羥基苯基)丙烷、1,4-雙(1-(4-胺基苯基)-1-甲基乙基)苯、1,3-雙(1-(4-胺基苯基)-1-甲基乙基)苯、雙(2-二甲胺基乙基)醚、雙(2-二乙胺基乙基)醚、1-(2-羥基乙基)-2-咪唑啶酮、2-喹噁啉醇、N,N,N’,N’-肆(2-羥基丙基)乙二胺、N,N,N’,N”,N”-五甲基二乙三胺等。 The amine compounds are exemplified by, for example, mono(cyclo)alkylamines; di(cyclo)alkylamines; tri(cyclo)alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N, N , N', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodi Phenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3- Aminophenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl) -2-(4-hydroxyphenyl)propane, 1,4-bis(1-(4-aminophenyl)-1-methylethyl)benzene, 1,3-bis(1-(4-amine) Phenyl)-1-methylethyl)benzene, bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether, 1-(2-hydroxyethyl)- 2-imidazolidinone, 2-quinoxaline alcohol, N,N,N',N'-indole (2-hydroxypropyl)ethylenediamine, N,N,N',N",N"-penta Base diethylene triamine and the like.
至於含醯胺基之化合物舉例有例如含有N-第三丁氧基羰基之胺基化合物、甲醯胺、N-甲基甲醯胺、 N,N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、丙醯胺、苯甲醯胺、吡咯烷酮、N-甲基吡咯烷酮、N-乙醯基-1-金剛烷胺、異氰尿酸三(2-羥基乙基)酯等。 As the compound containing a guanamine group, for example, an amine compound containing N-tert-butoxycarbonyl group, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N-methylpyrrolidone , N-ethinyl-1-adamantanamine, tris(2-hydroxyethyl) isocyanurate, and the like.
脲化合物列舉為例如尿素、甲基脲、1,1-二甲基脲、1,3-二甲基脲、1,1,3,3-四甲基脲、1,3-二苯基脲、三正丁基硫脲等。 Urea compounds are exemplified by, for example, urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea , tri-n-butyl thiourea, and the like.
含氮雜環化合物列舉為例如咪唑類;吡啶類;哌嗪類;吡嗪、吡唑、嗒嗪、喹唑啉、嘌呤、吡咯啶、哌啶、哌啶乙醇、3-哌啶基-1,2-丙二醇、嗎啉、4-甲基嗎啉、1-(4-嗎啉基)乙醇、4-乙醯基嗎啉、3-(N-嗎啉基)-1,2-丙二醇、1,4-二甲基哌嗪、1,4-二氮雜雙環〔2.2.2〕辛烷、N-第三丁氧基羰基4-羥基哌啶等。 The nitrogen-containing heterocyclic compound is exemplified by, for example, imidazoles; pyridines; piperazines; pyrazine, pyrazole, pyridazine, quinazoline, anthracene, pyrrolidine, piperidine, piperidine ethanol, 3-piperidinyl-1 , 2-propanediol, morpholine, 4-methylmorpholine, 1-(4-morpholinyl)ethanol, 4-ethylmercaptomorpholine, 3-(N-morpholinyl)-1,2-propanediol, 1,4-Dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, N-t-butoxycarbonyl 4-hydroxypiperidine, and the like.
〔C〕酸擴散控制體於該等中較好為N-第三丁氧基羰基4-羥基哌啶。 The [C] acid diffusion controlling agent is preferably N-tert-butoxycarbonyl 4-hydroxypiperidine in the above.
該等〔C〕酸擴散控制體可單獨使用,亦可併用2種以上。〔C〕酸擴散控制體之含量在〔C〕酸擴散控制體為〔C〕酸擴散控制劑時,相對於〔A〕聚合物100質量份較好未達15質量份,更好未達10質量份。〔C〕酸擴散控制體之含量為上述以上時,會有作為阻劑之感度下降之情況。 These [C] acid diffusion control bodies may be used singly or in combination of two or more. When the [C] acid diffusion controlling agent is the [C] acid diffusion controlling agent, it is preferably less than 15 parts by mass, more preferably less than 10 parts by mass based on 100 parts by mass of the [A] polymer. Parts by mass. When the content of the [C] acid diffusion controlling agent is at least the above, the sensitivity as a resist may be lowered.
該光阻組成物可進而含有氟原子之含有率高於〔A〕 聚合物之聚合物(以下亦稱為「〔D〕含氟原子之聚合物」)。藉由使該光阻組成物含有〔D〕含氟原子之聚合物,即使提高阻劑膜之疏水性進行液浸曝光時,物質溶出抑制性亦優異,且充分提高阻劑膜與液浸液之後退接觸角,以高速進行掃描曝光時發揮不使水滴殘留等之效果,故作為該光阻組成物之液浸曝光用之利用性高。 The photoresist composition may further contain a fluorine atom in a higher content than [A] A polymer of a polymer (hereinafter also referred to as "[D] a polymer of a fluorine atom"). When the photoresist composition contains the polymer of [D] fluorine atom, the liquid elution exposure is improved even when the hydrophobicity of the resist film is increased, and the substance elution inhibition property is excellent, and the resist film and the liquid immersion liquid are sufficiently improved. When the contact angle is retracted and the effect of not allowing water droplets to remain during scanning exposure at a high speed, the use of the photoresist composition for immersion exposure is high.
〔D〕含氟原子之聚合物樣態只要具有氟原子即無特別限制,列舉為例如主鏈上鍵結氟化烷基之構造;側鏈上鍵結氟化烷基之構造;主鏈與側鏈上均鍵結氟化烷基之構造等。 [D] The polymer form of the fluorine atom is not particularly limited as long as it has a fluorine atom, and is, for example, a structure in which a fluorinated alkyl group is bonded to the main chain; a structure in which a fluorinated alkyl group is bonded to a side chain; The structure of the fluorinated alkyl group is bonded to the side chain.
獲得主鏈上鍵結有氟化烷基之構造的單體列舉為例如丙烯酸α-三氟甲酯化合物、丙烯酸β-三氟甲酯化合物、丙烯酸α,β-三氟甲酯化合物、1種以上之乙烯部位之氫原子經三氟甲基等之氟化烷基取代之化合物等。 The monomer having a structure in which a fluorinated alkyl group is bonded to the main chain is exemplified by, for example, an α-trifluoromethyl acrylate compound, a β-trifluoromethyl acrylate compound, an α,β-trifluoromethyl acrylate compound, and a compound. A compound in which a hydrogen atom of the above ethylene moiety is substituted with a fluorinated alkyl group such as a trifluoromethyl group.
獲得側鏈上鍵結有氟化烷基之構造的單體列舉為例如降冰片烯等脂環式烯烴化合物之側鏈為氟化烷基或其衍生物者,列舉為丙烯酸或甲基丙烯酸之側鏈為氟化烷基或其衍生基之酯化合物、1種以上之烯烴之側鏈(不含雙鍵之部位)為氟化烷基或其衍生基者等。 The monomer having a structure in which a fluorinated alkyl group is bonded to a side chain is exemplified by a fluorinated alkyl group or a derivative thereof, for example, an alicyclic olefin compound such as norbornene, which is exemplified by acrylic acid or methacrylic acid. The side chain is an ester compound of a fluorinated alkyl group or a derivative thereof, and a side chain (a site containing no double bond) of one or more kinds of olefins is a fluorinated alkyl group or a derivative thereof.
獲得於主鏈與側鏈上鍵結有氟化烷基之構造的單體列舉為例如α-三氟甲基丙烯酸、β-三氟甲基丙烯酸、α,β-三氟甲基丙烯酸等側鏈為氟化烷基或其衍生基之酯化合物、1種以上之乙烯部位之氫原子經三氟甲基等氟 化烷基取代之化合物的側鏈經氟化烷基或其衍生基取代者、1種以上之脂環式烯烴化合物之鍵結於雙鍵上之氫原子經三氟甲基等氟化烷基取代,且側鏈為氟化烷基或其衍生基者等。又,所謂脂環式烯烴化合物係表示環之一部分為雙鍵之化合物。 The monomer having a structure in which a fluorinated alkyl group is bonded to the main chain and the side chain is exemplified by, for example, α-trifluoromethacrylic acid, β-trifluoromethacrylic acid, α,β-trifluoromethacrylic acid, or the like. The chain is a fluorinated alkyl group or an ester compound thereof, and one or more hydrogen atoms of an ethylene moiety are subjected to fluorine such as a trifluoromethyl group. The side chain of the alkyl-substituted compound is substituted by a fluorinated alkyl group or a derivative thereof, and a hydrogen atom bonded to a double bond of one or more alicyclic olefin compounds is a fluorinated alkyl group such as a trifluoromethyl group. Substituted, and the side chain is a fluorinated alkyl group or a derivative thereof or the like. Further, the alicyclic olefin compound is a compound in which a part of the ring is a double bond.
至於上述構造,較好為以下述式表示之構造單位。 As for the above structure, the structural unit represented by the following formula is preferable.
上述式中,R14及R15各獨立為氫原子、氟原子或具有至少1個氟原子之碳數1~20之1價烴基。 In the above formula, R 14 and R 15 each independently represent a hydrogen atom, a fluorine atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms and having at least one fluorine atom.
且,〔D〕含氟原子之聚合物在不損及本發明效果之範圍內,亦可具有由具有酸解離性基之構造單位、內酯構造、環狀碳酸酯構造及磺內酯構造所組成群組選出之至少1種之構造單位作為含氟構造單位以外之構造單位。該構造單位列舉為例如〔A〕聚合物中之構造單位(I)、(II)中所例示者等。 Further, the polymer of the [D] fluorine atom may have a structural unit having an acid dissociable group, a lactone structure, a cyclic carbonate structure, and a sultone structure, within a range not impairing the effects of the present invention. At least one structural unit selected from the group is selected as a structural unit other than the fluorine-containing structural unit. The structural unit is exemplified by, for example, those exemplified in the structural units (I) and (II) in the [A] polymer.
〔D〕含氟原子之聚合物較好為含有含氟構造單位及含酸解離性基之構造單位之共聚物。 [D] The fluorine atom-containing polymer is preferably a copolymer containing a fluorine-containing structural unit and a structural unit containing an acid-dissociable group.
〔D〕含氟原子之聚合物中,含氟構造單位之含有比例,相對於構成〔D〕含氟原子之聚合物之全部構造單位,較好為5莫耳%~100莫耳%,更好為10莫耳%~80莫耳%,又更好為20莫耳%~70莫耳%。含有比例超過上述上限時有引起圖型崩塌或圖型剝離之情況。含有比例未達上述下限時,有物質溶出抑制性降低之情況。〔D〕聚合物可為無規共聚物,亦可為嵌段共聚物。 In the polymer of the fluorine atom-containing polymer, the content ratio of the fluorine-containing structural unit is preferably from 5 mol% to 100 mol% based on the total structural unit of the polymer constituting the fluorine atom-containing [D]. It is preferably 10% by mole to 80% by mole, and more preferably 20% by mole to 70% by mole. When the content exceeds the above upper limit, it may cause pattern collapse or pattern peeling. When the content ratio is less than the above lower limit, the substance dissolution inhibiting property may be lowered. [D] The polymer may be a random copolymer or a block copolymer.
另外,〔D〕含氟原子之聚合物中,氟原子含有率較好為1質量%~60質量%,更好為2質量%~25質量%。氟原子含有率超過上述上限時有引起所形成之阻劑圖型圖型崩塌或圖型剝離之情況。氟原子含有率未達上述上限時,有物質溶出抑制性降低之情況。聚合物中之氟原子含有率可利用13C-NMR自聚合物之構造算出。 Further, in the polymer of the fluorine atom-containing unit [D], the fluorine atom content is preferably from 1% by mass to 60% by mass, more preferably from 2% by mass to 25% by mass. When the fluorine atom content exceeds the above upper limit, there is a case where the formed resist pattern pattern collapses or the pattern is peeled off. When the fluorine atom content rate is less than the above upper limit, the substance elution inhibiting property may be lowered. The fluorine atom content in the polymer can be calculated from the structure of the polymer by 13 C-NMR.
該等〔D〕含氟原子之聚合物可單獨使用,亦 可併用2種以上。〔D〕含氟原子之聚合物之含量,相對於〔A〕聚合物100質量份,較好未達15質量份,更好未達10質量份。〔D〕含氟原子之聚合物含量為其以上時,會有無法獲得期望阻劑特性之情況。 These [D] fluorine atom-containing polymers can be used alone, Two or more types can be used in combination. The content of the polymer of the fluorine atom is preferably less than 15 parts by mass, more preferably less than 10 parts by mass, per 100 parts by mass of the [A] polymer. When the polymer content of the fluorine atom is at least the above, the desired resist properties may not be obtained.
上述〔D〕含氟原子之聚合物與〔A〕聚合物之情況相同,可例如藉由使用自由基聚合起始劑,在適當溶劑中使對應於特定之各構造單位之單體聚合而合成。 The polymer of the above [D] fluorine atom is the same as the case of the polymer [A], and can be synthesized, for example, by polymerizing a monomer corresponding to each specific structural unit in a suitable solvent by using a radical polymerization initiator. .
該光阻組成物通常含有〔E〕溶劑。所用之〔E〕溶劑只要至少可溶解〔A〕聚合物及〔B〕酸產生劑之溶劑即無特別限制。至於該等溶劑,可使用例如醇類、醚類、二乙二醇烷基醚類、乙二醇烷基醚乙酸酯類、烷二醇單烷基醚類、丙二醇單烷基醚乙酸酯類、丙二醇單烷基醚丙酸酯類、芳香族烴類、酮類、酯類、醯胺類、腈類及其混合溶劑等。 The photoresist composition usually contains [E] a solvent. The solvent of the [E] to be used is not particularly limited as long as it dissolves at least the solvent of the [A] polymer and the [B] acid generator. As such solvents, for example, alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, alkylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates can be used. And propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, esters, guanamines, nitriles and mixed solvents thereof.
上述〔E〕溶劑列舉為:醇類為例如苄基醇、二丙酮醇等;醚類為例如四氫呋喃、二異丙醚、二正丁醚、二正戊醚、二異戊基醚、二正己醚等二烷基醚等;二乙二醇烷基醚類為例如二乙二醇單甲醚、二乙二醇單***、二乙二醇二甲醚、二乙二醇二***、二乙二醇乙基甲醚等;乙二醇烷基醚乙酸酯類為例如甲基溶纖素乙酸酯、乙 基溶纖素乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單***乙酸酯等;丙二醇單烷基醚類為例如丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚等;丙二醇單烷基醚乙酸酯類為例如丙二醇單甲醚乙酸酯(乙酸丙二醇單甲醚)、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯等;丙二醇單烷基醚丙酸酯類為例如丙二醇單甲醚丙酸酯、丙二醇單***丙酸酯、丙二醇單丙醚丙酸酯、丙二醇單丁醚丙酸酯等;芳香族烴類為例如甲苯、二甲苯等;酮類為例如甲基乙基酮、甲基異丁基酮、環己酮、2-庚酮、4-羥基-4-甲基-2-戊酮等;酯類列舉為例如乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸異丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基 丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯等;醯胺類為例如甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮等;腈類為例如乙腈、丙腈等。 The solvent of the above [E] is exemplified by an alcohol such as benzyl alcohol or diacetone alcohol; and ethers such as tetrahydrofuran, diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, diisoamyl ether, and di-n-hexane. Dialkyl ethers such as ethers; diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol ethyl methyl ether or the like; ethylene glycol alkyl ether acetate is, for example, methyl cellosolve acetate, B a base of cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; propylene glycol monoalkyl ethers are, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Propylene glycol monobutyl ether or the like; propylene glycol monoalkyl ether acetate is, for example, propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether Acetate or the like; propylene glycol monoalkyl ether propionate such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc.; aromatic The hydrocarbons are, for example, toluene, xylene, etc.; the ketones are, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, etc. The esters are exemplified by, for example, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2- Ethyl hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, Butyl acrylate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutyric acid Methyl ester, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, acetoxyacetate Ester, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxide , butyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.; guanamines such as formamidine, N-methyl group Indoleamine, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; nitriles such as acetonitrile, C Nitrile and the like.
至於上述〔E〕溶劑,於該等中,以丙二醇單烷基醚乙酸酯類、酮類較佳,更好為乙酸丙二醇單甲醚、環己酮。 The solvent of the above [E] is preferably propylene glycol monoalkyl ether acetate or ketone, more preferably propylene glycol monomethyl ether or cyclohexanone.
該等〔E〕溶劑可單獨使用,亦可併用2種以上。〔E〕溶劑之含量相對於〔A〕聚合物100質量份,較好為500質量份~8,000質量份,更好為600質量份~7,000質量份。含量超過上述上限時,有製造成本變高之情況。含量未達上述下限時,無法使〔A〕聚合物等充分溶解。 These [E] solvents may be used singly or in combination of two or more. The content of the solvent of [E] is preferably from 500 parts by mass to 8,000 parts by mass, more preferably from 600 parts by mass to 7,000 parts by mass, per 100 parts by mass of the [A] polymer. When the content exceeds the above upper limit, the manufacturing cost may become high. When the content is less than the above lower limit, the [A] polymer or the like cannot be sufficiently dissolved.
該光阻組成物可含有具有使上述〔D〕含氟原子之聚合物更有效率地偏析在阻劑膜表面之效果的〔F〕偏在化促進劑。藉由使該光阻組成物含有該添加劑,可使含氟原子之聚合物之添加量比以往更少。據此,可一面維持MEEF性能、LWR性能、圖型崩塌耐性等阻劑基本特性,一面進一步抑制成分自阻劑膜溶出於液浸液中,可利用高速掃描以更高速進行液浸曝光,該等添加劑列舉為例如γ- 丁內酯等內酯化合物、碳酸伸丙酯等環狀碳酸酯化合物、丁二腈等腈化合物、丙三醇等多元醇等。上述添加劑於該等中以γ-丁內酯較佳。 The photoresist composition may contain a [F] biasing accelerator having an effect of segregating the polymer of the above-mentioned [D] fluorine atom more efficiently on the surface of the resist film. By including the additive in the photoresist composition, the amount of the fluorine atom-containing polymer can be made smaller than in the related art. According to this, it is possible to further suppress the component self-resistance film from being dissolved in the liquid immersion liquid while maintaining the basic characteristics of the resist such as MEEF performance, LWR performance, and pattern collapse resistance, and to perform immersion exposure at a higher speed by high-speed scanning. Such additives are listed as, for example, γ- A lactone compound such as butyrolactone, a cyclic carbonate compound such as propylene carbonate, a nitrile compound such as succinonitrile or a polyhydric alcohol such as glycerin. The above additives are preferably γ-butyrolactone in these.
該等〔F〕偏在化促進劑可單獨使用,亦可併用2種以上。〔F〕偏在化促進劑之含量,相對於〔A〕聚合物100質量份,較好為1質量份~100質量份,更好為2質量份~80質量份。含量超過上述上限時,有製造成本變高之情況。含量未達上述下限時,有必要增多〔D〕含氟原子之聚合物。 These [F] partialization accelerators may be used singly or in combination of two or more. The content of the [F] biasing accelerator is preferably from 1 part by mass to 100 parts by mass, more preferably from 2 parts by mass to 80 parts by mass, per 100 parts by mass of the [A] polymer. When the content exceeds the above upper limit, the manufacturing cost may become high. When the content is less than the above lower limit, it is necessary to increase the polymer of the [D] fluorine atom.
界面活性劑係發揮改良塗佈性、條紋性、顯像性等之效果。至於界面活性劑列舉為例如聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯正辛基苯基醚、聚氧乙烯正壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯等非離子系界面活性劑,以及以下之商品名KP341(信越化學工業製造)、POLYFLOW No.75、POLYFLOW No.95(以上為共榮社化學製造)、EF TOP EF301、EF TOP EF303、EF TOP EF352(以上為TOHCHEM PRODUCTS製造)、MEGAFAC F171、MEGAFAC F173(以上為DIC製造)、FLORARD FC430、FLORARD FC431(以上為住友3M製造)、ASAHI GUARD AG710、SURFLON S-382、SURFLON SC-101、SURFLON SC-102、SURFLON SC-103、SURFLON SC-104、SURFLON SC-105、SURFLON SC-106(以上為旭硝子製造)等。該等界面活性劑可單獨使用,亦可併用2種以上。 The surfactant has an effect of improving coatability, streaking property, developing property, and the like. As the surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-decyl phenyl ether, poly A nonionic surfactant such as ethylene glycol dilaurate or polyethylene glycol distearate, and the following trade names KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75, and POLYFLOW No. 95 (above Kyoeisha Chemical Manufacturing Co., Ltd., EF TOP EF301, EF TOP EF303, EF TOP EF352 (above manufactured by TOHCHEM PRODUCTS), MEGAFAC F171, MEGAFAC F173 (above DIC), FLORARD FC430, FLORARD FC431 (above Sumitomo 3M) , ASAHI GUARD AG710, SURFLON S-382, SURFLON SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (above, manufactured by Asahi Glass). These surfactants may be used singly or in combination of two or more.
含有脂環式骨架之化合物可發揮改善乾蝕刻耐性、圖型形狀、與基板之接著性等之效果。 The compound containing an alicyclic skeleton exhibits effects of improving dry etching resistance, pattern shape, adhesion to a substrate, and the like.
至於含有脂環式骨架之化合物列舉為例如1-金剛烷羧酸、2-金剛烷酮、1-金剛烷羧酸第三丁酯等金剛烷衍生物類;脫氧膽酸第三丁酯、脫氧膽酸第三丁氧羰基甲酯、脫氧膽酸2-乙氧基乙酯等脫氧膽酸酯類;石膽酸第三丁酯、石膽酸第三丁氧羰基甲酯、石膽酸2-乙氧基乙酯等石膽酸酯類;3-〔2-羥基-2,2-雙(三氟甲基)乙基〕四環〔4.4.0.12,5.17,10〕十二烷、2-羥基-9-甲氧基羰基-5-氧代-4-氧雜-三環〔4.2.1.03,7〕壬烷等。該等含脂環式骨架之化合物可單獨使用,亦可併用2種以上。 The compound containing an alicyclic skeleton is exemplified by adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid tert-butyl ester; tert-butyl deoxycholate, deoxygenated Deoxycholate esters such as tert-butoxycarbonyl methyl cholate and 2-ethoxyethyl deoxycholate; tert-butyl lithochate, third butoxycarbonyl methyl lithate, lithocholic acid 2 -lithocholate such as ethoxyethyl ester; 3-[2-hydroxy-2,2-bis(trifluoromethyl)ethyl]tetracycline [4.4.0.1 2,5 .1 7,10 ] Dioxane, 2-hydroxy-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo[4.2.1.0 3,7 ]decane, and the like. These alicyclic skeleton-containing compounds may be used singly or in combination of two or more.
增感劑為表示增加由〔B〕酸產生劑產生之酸之生成量的作用者,且發揮提高該光阻組成物之「表觀感度」之效果。 The sensitizer is an effect indicating an increase in the amount of acid generated by the [B] acid generator, and exhibits an effect of improving the "apparent sensitivity" of the resist composition.
增感劑列舉為例如咔唑類、苯乙酮類、二苯 甲酮類、萘類、酚類、雙乙醯、伊紅(eosin)、玫瑰紅、芘(pyrenes)類、蒽類、菲噻嗪類等。該等增感劑可單獨使用,亦可併用2種以上。 Sensitizers are listed, for example, as oxazoles, acetophenones, diphenyls Ketones, naphthalenes, phenols, diacetyl, eosin, rose red, pyrenes, anthraquinones, phenothiazines, and the like. These sensitizers may be used alone or in combination of two or more.
光阻組成物之調製方法並無特別限制,可依據習知方法進行。光阻組成物可藉由例如於有機溶劑中以特定比例混合〔A〕聚合物、〔B〕酸產生劑及任意成分而調製。且,該光阻組成物可調製成溶解或分散於適當有機溶劑中之狀態而使用。 The method of preparing the photoresist composition is not particularly limited and can be carried out according to a conventional method. The photoresist composition can be prepared by, for example, mixing the [A] polymer, the [B] acid generator, and an optional component in a specific ratio in an organic solvent. Further, the photoresist composition can be used in a state of being dissolved or dispersed in a suitable organic solvent.
該阻劑圖型之形成方法具有下列步驟:形成阻劑膜之步驟(以下亦稱為「阻劑膜形成步驟」),使上述阻劑膜曝光之步驟(以下亦稱為「曝光步驟」),及使上述經曝光之阻劑膜顯像之步驟(以下亦稱為「顯像步驟」),且上述阻劑膜係由上述光阻組成物所形成。 The method for forming the resist pattern has the following steps: a step of forming a resist film (hereinafter also referred to as "resist film forming step"), and a step of exposing the resist film (hereinafter also referred to as "exposure step") And a step of developing the exposed resist film (hereinafter also referred to as "development step"), and the resist film is formed of the photoresist composition.
依據該阻劑圖型形成方法,由於使用上述該光阻組成物,故可一面發揮優異之MEEF性能,一面形成剖面形狀之矩形性及蝕刻耐性優異之阻劑圖型。以下,針對各步驟加以說明。 According to the resist pattern forming method, since the photoresist composition described above is used, it is possible to form a resist pattern having excellent cross-sectional shape rectangularness and etching resistance while exhibiting excellent MEEF performance. Hereinafter, each step will be described.
阻劑膜形成步驟係使用該光阻組成物形成阻劑膜。至於形成阻劑膜之基板可使用例如矽晶圓、二氧化矽、以抗反射膜被覆之晶圓等。光阻組成物之塗佈方法列舉為例如旋轉塗佈、澆鑄塗佈、輥塗佈等方法。以上述塗佈形成之塗膜較好藉由預烘烤(PB)蒸發去除塗膜中之溶劑。PB溫度通常為60℃~140℃,較好為80℃~120℃。PB時間通常為5秒~600秒,較好為10秒~300秒。 The resist film forming step uses the photoresist composition to form a resist film. As the substrate on which the resist film is formed, for example, a germanium wafer, a germanium dioxide, a wafer coated with an antireflection film, or the like can be used. The coating method of the photoresist composition is exemplified by methods such as spin coating, casting coating, and roll coating. The coating film formed by the above coating is preferably subjected to pre-baking (PB) evaporation to remove the solvent in the coating film. The PB temperature is usually from 60 ° C to 140 ° C, preferably from 80 ° C to 120 ° C. The PB time is usually 5 seconds to 600 seconds, preferably 10 seconds to 300 seconds.
曝光步驟係使阻劑膜形成步驟中形成之阻劑膜曝光。該曝光係透過光罩等(視情況透過水等液浸介質)照射曝光之光而進行。曝光之光係依據成為目的之圖型線寬而定,列舉為例如可見光、紫外線、遠紫外線、極紫外線、X射線、γ射線等之電磁波;電子束、α射線等之帶電粒子射線。且作為曝光之光,該等中,較好為遠紫外線、極紫外線、電子束等,更好為ArF準分子雷射光(波長193nm)、KrF準分子雷射光(波長248nm)、EUV(13.5nm)、電子束,又更好為ArF準分子雷射光、電子束。 The exposure step exposes the resist film formed in the resist film formation step. This exposure is performed by irradiating the exposed light through a photomask or the like (as the case may be, a liquid immersion medium such as water). The light to be exposed is determined by, for example, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, gamma ray, or the like, and charged particle rays such as an electron beam or an alpha ray. Further, as the light to be exposed, it is preferably far ultraviolet rays, extreme ultraviolet rays, electron beams, etc., more preferably ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), EUV (13.5 nm). ), electron beam, and better ArF excimer laser light, electron beam.
上述曝光後較好進行曝光後烘烤(PEB),而在阻劑膜之經曝光部分中,促進因曝光而自〔B〕酸產生劑產生之酸進行之〔A〕聚合物之酸解離性基的解離。藉 由該PEB,可確實地產生經曝光部分(曝光部)與未曝光部分(未曝光部)對顯像液之溶解性差。PEB溫度通常為50℃~180℃,較好為80℃~130℃。PEB時間通常為5秒~600秒,較好為10秒~300秒。 After the above exposure, post-exposure bake (PEB) is preferably carried out, and in the exposed portion of the resist film, the acid dissociation of the [A] polymer which promotes the acid generated from the [B] acid generator by exposure is promoted. The dissociation of the base. borrow From the PEB, it is possible to surely produce poor solubility of the exposed portion (exposed portion) and the unexposed portion (unexposed portion) with respect to the developing liquid. The PEB temperature is usually from 50 ° C to 180 ° C, preferably from 80 ° C to 130 ° C. The PEB time is usually 5 seconds to 600 seconds, preferably 10 seconds to 300 seconds.
進行液浸曝光時,在曝光步驟前,為了保護液浸液與阻劑膜之直接接觸,亦可在阻劑膜上設置於液浸液中不溶性之液浸用保護膜。液浸用保護膜可使用於顯像步驟前利用溶劑剝離之溶劑剝離型保護膜(參照例如特開2006-227632號公報)、與顯像步驟之顯像同時剝離之顯像液剝離型保護膜(參照例如國際公開第2005/069076號、國際公開第2006/035790號等)之任一種。但,就處理量之觀點而言,較好使用顯像液剝離型液浸用保護膜。 In the immersion exposure, in order to protect the liquid immersion liquid from direct contact with the resist film before the exposure step, a protective film for liquid immersion which is insoluble in the liquid immersion liquid may be provided on the resist film. The protective film for liquid immersion can be used as a solvent-peelable protective film which is peeled off by a solvent before the development step (see, for example, JP-A-2006-227632), and a developing liquid peeling type protective film which is simultaneously peeled off from the development of the developing step. (See, for example, International Publication No. 2005/069076, International Publication No. 2006/035790, etc.). However, from the viewpoint of the amount of treatment, a protective liquid for liquid immersion liquid immersion is preferably used.
顯像步驟係使曝光步驟中曝光之阻劑膜顯像。藉此,形成特定之阻劑圖型。上述顯像方法可為鹼顯像,亦可為有機溶劑顯像。通常,利用鹼顯像係形成正型阻劑圖型,利用有機溶劑顯像係形成負型阻劑圖型。上述顯像後,一般以水或醇等洗滌液洗淨,並乾燥。 The developing step is to develop the exposed resist film in the exposure step. Thereby, a specific resist pattern is formed. The above development method may be alkali imaging or organic solvent imaging. Generally, a positive resist pattern is formed by an alkali developing system, and a negative resist pattern is formed by using an organic solvent developing system. After the above development, it is usually washed with a washing liquid such as water or alcohol, and dried.
至於上述顯像液,在鹼顯像時,列舉為例如使氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨水、乙胺、正丙胺、二乙胺、二正丙胺、三乙胺、甲基二乙胺、乙基二甲胺、三乙醇胺、氫氧化四甲基銨(TMAH)、吡咯、哌啶、膽鹼、1,8-二氮雜雙環 〔5.4.0〕-7-十一碳烯、1,5-二氮雜雙環-〔4.3.0〕-5-壬烯等鹼性化合物之至少一種溶解而成之鹼性水溶液等。至於上述顯像液,於該等中,以TMAH水溶液較佳,更好為2.38質量%之TMAH水溶液。 As for the above-mentioned developing solution, in the case of alkali development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, and di-n-butyl are exemplified. Propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] An aqueous alkaline solution obtained by dissolving at least one of a basic compound such as 7-undecene and 1,5-diazabicyclo-[4.3.0]-5-decene. As the above developing solution, in the above, a TMAH aqueous solution is preferred, and a 2.38 mass% TMAH aqueous solution is more preferred.
另外,有機溶劑顯像時,列舉為烴系溶劑、醚系溶劑、酯系溶劑、酮系溶劑、醇系溶劑等有機溶劑,或含有機溶劑之溶劑等。上述有機溶劑列舉為例如作為上述光阻組成物之〔E〕溶劑而列舉之溶劑的1種或2種以上等。上述有機溶劑,於該等中,較好為酯系溶劑、酮系溶劑。至於酯系溶劑較好為乙酸酯系溶劑,更好為乙酸正丁酯。至於酮系溶劑較好為鏈狀酮,更好為2-庚酮。 Further, in the case of developing an organic solvent, an organic solvent such as a hydrocarbon solvent, an ether solvent, an ester solvent, a ketone solvent or an alcohol solvent, or a solvent containing an organic solvent may be mentioned. The above-mentioned organic solvent is exemplified by one or two or more kinds of solvents exemplified as the solvent (E) of the above-mentioned photoresist composition. Among these, the organic solvent is preferably an ester solvent or a ketone solvent. The ester solvent is preferably an acetate solvent, more preferably n-butyl acetate. The ketone solvent is preferably a chain ketone, more preferably 2-heptanone.
本發明之光阻組成物可使用作為化學增幅性阻劑。化學增幅型阻劑中,利用藉由曝光產生之酸之作用,使〔A〕聚合物等之酸解離性基解離而產生以羧基為代表之極性基。結果,提高阻劑之曝光部對鹼顯像液之溶解性,使該曝光部利用鹼顯像液而溶解,去除,獲得正型阻劑圖型。另外,藉由使用含有機溶劑等之較低極性者作為顯像液,使因上述曝光產生之極性基之部分難溶化於顯像液中,而獲得負型之阻劑圖型。 The photoresist composition of the present invention can be used as a chemical amplification resist. In the chemically amplified resist, the acid dissociable group such as [A] polymer is dissociated by the action of an acid generated by exposure to generate a polar group represented by a carboxyl group. As a result, the solubility of the exposed portion of the resist to the alkali developing solution is increased, and the exposed portion is dissolved and removed by the alkali developing solution to obtain a positive resist pattern. Further, by using a lower polarity containing an organic solvent or the like as a developing liquid, a portion of the polar group generated by the above exposure is hardly dissolved in the developing liquid to obtain a negative resist pattern.
該光阻組成物由於相溶性優異,故可使自該光阻組成物獲得之阻劑圖型具有優異之上述特性。具體而言,可一面發揮4.7以下,更好4.4以下之MEEF性能,一面形成圖型形狀良好、蝕刻耐性亦優異之阻劑圖型。 Since the photoresist composition is excellent in compatibility, the resist pattern obtained from the photoresist composition can be excellent in the above characteristics. Specifically, it is possible to form a resist pattern which is excellent in pattern shape and excellent in etching resistance while exhibiting MEEF performance of 4.7 or less and more preferably 4.4 or less.
依據本發明之光阻組成物、阻劑圖型形成方 法及酸產生劑,可一面發揮優異之MEEF性能,一面形成剖面形狀之矩形性及蝕刻耐性優異之阻劑圖型。據此,可適用於半導體裝置、液晶裝置等各種電子裝置之微影步驟之圖型形成中。 Photoresist composition and resist pattern forming party according to the present invention The method and the acid generator can form a resist pattern having excellent cross-sectional shape and excellent etching resistance while exhibiting excellent MEEF performance. Accordingly, the present invention can be applied to pattern formation of lithography steps of various electronic devices such as semiconductor devices and liquid crystal devices.
以下,以本發明之實施例更具體說明,但本發明並不受該等實施例之限制。 Hereinafter, the embodiments of the present invention will be more specifically described, but the present invention is not limited by the examples.
使用日本電子製JNM-EX400,使用氘化氯仿作為測定溶劑進行分析。 The analysis was carried out using JNM-EX400 manufactured by JEOL Ltd. using deuterated chloroform as a measuring solvent.
使用TOSOH製造之GPC管柱(G2000HXL:2根,G3000HXL:1根,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,以單分散聚苯乙烯作為標準利用凝膠滲透層析法(GPC)測定。又,分散度(Mw/Mn)係由Mw及Mn之測定結果算出。 GPC column manufactured by TOSOH (G2000HXL: 2, G3000HXL: 1 , G4000HXL: 1), at a flow rate: 1.0 ml/min, solvent: tetrahydrofuran, column temperature: 40 ° C analysis conditions, monodisperse Polystyrene was measured as a standard by gel permeation chromatography (GPC). Further, the degree of dispersion (Mw/Mn) was calculated from the measurement results of Mw and Mn.
低分子量成分之含量(質量%)為藉以下條件使用高速液體層析法(HPLC)測定之值。 The content (% by mass) of the low molecular weight component is a value measured by high speed liquid chromatography (HPLC) under the following conditions.
HPLC管柱:Intersil ODS-25μm,4.6mm×250mm(JL Science公司製) HPLC column: Intersil ODS-25μm, 4.6mm ×250mm (made by JL Science Co., Ltd.)
溶出溶劑:丙烯腈/0.1質量%磷酸水溶液 Dissolution solvent: acrylonitrile / 0.1% by mass phosphoric acid aqueous solution
流量:1.0mL/分鐘 Flow rate: 1.0mL/min
試料濃度:1.0質量% Sample concentration: 1.0% by mass
試料注入量:100μL Sample injection amount: 100 μL
檢測器:示差折射計 Detector: differential refractometer
將化合物(1)55.0g(230mmol)添加於溶解有連二亞硫酸鈉60.1g(345mmol)與碳酸氫鈉32.8g (391mmol)而成之乙腈水溶液100g(乙腈:水之質量比4:3)中,加熱至65℃,攪拌7小時。分液純化上述反應溶液且回收水層。 55.0 g (230 mmol) of the compound (1) was added to dissolve 60.1 g (345 mmol) of sodium dithionite and 32.8 g of sodium hydrogencarbonate. (391 mmol) of 100 g of an acetonitrile aqueous solution (acetonitrile: water mass ratio of 4:3) was heated to 65 ° C and stirred for 7 hours. The above reaction solution was fractionated and the aqueous layer was recovered.
於所得水層中添加乙腈100g、31質量%之過氧化氫9.79g(288mmol)之含過氧化氫之水溶液29.2g、鎢酸二鈉7.59g(23 mmol),加熱至40℃,且攪拌8小時。分液純化上述反應溶液且回收水層。 To the obtained aqueous layer, 100 g of acetonitrile, 19.9 g (288 mmol) of hydrogen peroxide (31.9%), 29.2 g of an aqueous solution containing hydrogen peroxide, and 7.59 g (23 mmol) of disodium tungstate were added, and the mixture was heated to 40 ° C, and stirred. hour. The above reaction solution was fractionated and the aqueous layer was recovered.
於該水層(固體成分36.2g;138mmol)中添加氯化三苯基鋶41.2g(138mmol)、二氯甲烷120g及水60g,且在室溫攪拌2小時。分液純化上述反應溶液,回收有機層後予以濃縮,獲得62.3g之上述化合物(2)。 41.2 g (138 mmol) of triphenylsulfonium chloride, 120 g of dichloromethane and 60 g of water were added to the aqueous layer (solid content: 36.2 g; 138 mmol), and the mixture was stirred at room temperature for 2 hours. The reaction solution was purified by liquid separation, and the organic layer was collected and concentrated to give 62.3 g of the above compound (2).
於將所得化合物(2)62.3g(124mmol)溶解於二氯甲烷310g中而成之溶液中添加三乙胺18.8g(186mmol)、4-二甲胺基吡啶0.303g(2.48mmol),冷卻至0℃。接著,滴加D-樟腦-10-磺醯氯37.4g(149mmol)之二氯甲烷溶液30mL,攪拌6小時。接著,使用二氯甲烷、水進行分液純化,獲得化合物(B-1)(收量79.1g,總收率48%)。 To a solution obtained by dissolving 62.3 g (124 mmol) of the obtained compound (2) in 310 g of dichloromethane, 18.8 g (186 mmol) of triethylamine and 0.303 g (2.48 mmol) of 4-dimethylaminopyridine were added and cooled. 0 ° C. Then, 30 mL of a 37.4 g (149 mmol) dichloromethane solution of D-camphor-10-sulfonium chloride was added dropwise thereto, and the mixture was stirred for 6 hours. Subsequently, it was subjected to liquid separation purification using dichloromethane and water to obtain Compound (B-1) (yield: 79.1 g, total yield: 48%).
1H-NMR分析(測定溶劑:氘化氯仿,基準物質:四甲基矽烷);δ=7.69-7.78(m,15H),4.26-4.36(m,2H),3.58(d,1H),3.00(d,1H),2.34-2.48(m,4H),1.93-2.12(m,5H),1.65-1.69(m,1H),1.41-1.48(m,1H),1.10(s,3H),0.87(s,3H)。 1 H-NMR analysis (measurement solvent: deuterated chloroform, reference material: tetramethyl decane); δ=7.69-7.78 (m, 15H), 4.26-4.36 (m, 2H), 3.58 (d, 1H), 3.00 (d, 1H), 2.34 - 2.48 (m, 4H), 1.93 - 2.12 (m, 5H), 1.65-1.69 (m, 1H), 1.41-1.48 (m, 1H), 1.10 (s, 3H), 0.87 (s, 3H).
與合成例1同樣操作,獲得以下述式(B-2)~(B-7)表示之化合物。 In the same manner as in Synthesis Example 1, a compound represented by the following formula (B-2) to (B-7) was obtained.
1H-NMR分析(測定溶劑:氘化氯仿,基準物質:四甲基矽烷);δ=7.69-7.78(m,15H),4.26-4.36(m,2H),3.01(s,3H),2.43-2.56(m,2H),2.04-2.11 (m,2H)。 1 H-NMR analysis (measurement solvent: deuterated chloroform, reference material: tetramethyl decane); δ=7.69-7.78 (m, 15H), 4.26-4.36 (m, 2H), 3.01 (s, 3H), 2.43 -2.56 (m, 2H), 2.04-2.11 (m, 2H).
1H-NMR分析(測定溶劑:氘化氯仿,基準物質:四甲基矽烷);δ=7.69-7.78(m,15H),4.23-4.27(m,2H),3.07-3.11(m,2H),2.41-2.56(m,2H),2.03-2.11(m,2H),1.79-1.87(m,2H),1.42-1.51(m,2H),0.95(t,3H)。 1 H-NMR analysis (measurement solvent: deuterated chloroform, reference material: tetramethyl decane); δ = 7.69-7.78 (m, 15H), 4.23-4.27 (m, 2H), 3.07-3.11 (m, 2H) , 2.41-2.56 (m, 2H), 2.03-2.11 (m, 2H), 1.79-1.87 (m, 2H), 1.42-1.51 (m, 2H), 0.95 (t, 3H).
1H-NMR分析(測定溶劑:氘化氯仿,基準物質:四甲基矽烷);δ=8.97(s,1H),8.47(d,1H),8.06(d,1H),7.98(d,1H),7.69-7.82(m,18H),4.26-4.36(m,2H),2.43-2.56(m,2H),2.04-2.11(m,2H)。 1 H-NMR analysis (measurement solvent: deuterated chloroform, reference material: tetramethyl decane); δ=8.97 (s, 1H), 8.47 (d, 1H), 8.06 (d, 1H), 7.98 (d, 1H) ), 7.69-7.82 (m, 18H), 4.26-4.36 (m, 2H), 2.43-2.56 (m, 2H), 2.04-2.11 (m, 2H).
1H-NMR分析(測定溶劑:氘化氯仿,基準物質:四甲基矽烷);δ=7.69-7.78(m,15H),4.26-4.36(m,2H),3.58(d,1H),3.00(d,1H),2.34-2.48(m,4H),1.93-2.12(m,3H),1.65-1.69(m,5H),1.41-1.48(m,7H),1.10(s,3H),0.87(s,3H)。 1 H-NMR analysis (measurement solvent: deuterated chloroform, reference material: tetramethyl decane); δ=7.69-7.78 (m, 15H), 4.26-4.36 (m, 2H), 3.58 (d, 1H), 3.00 (d, 1H), 2.34 - 2.48 (m, 4H), 1.93 - 2.12 (m, 3H), 1.65-1.69 (m, 5H), 1.41-1.48 (m, 7H), 1.10 (s, 3H), 0.87 (s, 3H).
1H-NMR分析(測定溶劑:氘化氯仿,基準物質:四 甲基矽烷);δ=7.69-7.78(m,15H),4.26-4.36(m,2H),3.58(d,1H),3.00(d,1H),2.34-2.48(m,4H),1.93-2.12(m,3H),1.65-1.69(m,5H),1.41-1.48(m,3H),1.10(s,3H),0.87(s,3H)。 1 H-NMR analysis (measurement solvent: deuterated chloroform, reference material: tetramethyl decane); δ=7.69-7.78 (m, 15H), 4.26-4.36 (m, 2H), 3.58 (d, 1H), 3.00 (d, 1H), 2.34 - 2.48 (m, 4H), 1.93 - 2.12 (m, 3H), 1.65-1.69 (m, 5H), 1.41-1.48 (m, 3H), 1.10 (s, 3H), 0.87 (s, 3H).
1H-NMR分析(測定溶劑:氘化氯仿,基準物質:四甲基矽烷);δ=7.69-7.78(m,15H),4.26-4.36(m,2H),3.58(d,1H),3.00(d,1H),2.74-2.88(m,4H),1.93-2.12(m,5H),1.65-1.69(m,1H),1.41-1.48(m,1H),1.10(s,3H),0.87(s,3H)。 1 H-NMR analysis (measurement solvent: deuterated chloroform, reference material: tetramethyl decane); δ=7.69-7.78 (m, 15H), 4.26-4.36 (m, 2H), 3.58 (d, 1H), 3.00 (d, 1H), 2.74-2.88 (m, 4H), 1.93-2.12 (m, 5H), 1.65-1.69 (m, 1H), 1.41-1.48 (m, 1H), 1.10 (s, 3H), 0.87 (s, 3H).
合成中使用之化合物(單體)示於下。 The compound (monomer) used in the synthesis is shown below.
將化合物(M-1)21.12g(55莫耳%)、化合物(M-3)3.84g(10莫耳%)及化合物(M-5)13.44g(35莫耳%)溶解於80g之2-丁酮中,再添加AIBN 3.54g,調製單體溶液。接著,使饋入有40g之2-丁酮之200mL三頸燒瓶進行氮氣吹拂30分鐘後,邊攪拌邊加熱至80℃,以滴加漏斗,於3小時內滴加所調製之單體溶液。以滴加開始作為聚合反應之開始時間,實施聚合反應6小時。接著於聚合反應結束後,以水冷使聚合溶液冷卻至30℃以下。將冷卻之聚合溶液投入800g甲醇中,過濾所析出之白色粉末。以160g甲醇洗淨經過濾之白色粉末兩次後,再經過 濾,於50℃乾燥17小時,合成白色粉末狀之聚合物(A-1)。 Compound (M-1) 21.12 g (55 mol%), compound (M-3) 3.84 g (10 mol%), and compound (M-5) 13.44 g (35 mol%) were dissolved in 80 g of 2 In the butanone, 3.54 g of AIBN was further added to prepare a monomer solution. Next, a 200 mL three-necked flask to which 40 g of 2-butanone was fed was subjected to nitrogen blowing for 30 minutes, and then heated to 80 ° C with stirring to drip the funnel, and the prepared monomer solution was added dropwise over 3 hours. The polymerization reaction was carried out for 6 hours starting from the start of the dropwise addition as the start time of the polymerization reaction. Then, after completion of the polymerization reaction, the polymerization solution was cooled to 30 ° C or lower by water cooling. The cooled polymerization solution was poured into 800 g of methanol, and the precipitated white powder was filtered. After washing the filtered white powder twice with 160 g of methanol, The mixture was filtered and dried at 50 ° C for 17 hours to synthesize a white powdery polymer (A-1).
(A-1)之Mw為4,500,Mw/Mn為1.4。(A-1)之低分子量成分含量為0.04質量%。經13C-NMR分析之結果,源自(M-1)、(M-3)及(M-5)之各構造單位之含有比例分別為54莫耳%、11莫耳%及35莫耳%。 (A-1) had Mw of 4,500 and Mw/Mn of 1.4. The content of the low molecular weight component of (A-1) was 0.04% by mass. As a result of 13 C-NMR analysis, the content ratios of the structural units derived from (M-1), (M-3), and (M-5) were 54 mol%, 11 mol%, and 35 mol, respectively. %.
除使用下述表1所示之種類及使用量之單體以外,餘與聚合例1同樣操作,合成成為〔A〕聚合物之(A-2)。單體之合計質量與聚合例1相同。所得各聚合物之低分子量成分之含量、Mw及(Mw/Mn)示於表1。 (A-2) was synthesized in the same manner as in Polymerization Example 1 except that the monomer of the type and the amount of use shown in the following Table 1 was used. The total mass of the monomers was the same as in Polymerization Example 1. The content, Mw and (Mw/Mn) of the low molecular weight component of each of the obtained polymers are shown in Table 1.
將化合物(M-4)14.3g(30莫耳%)及化合物(M-6)45.7g(70莫耳%)溶解於2-丁酮60g中,投入AIBN 3g,調整單體溶液。使投入有30g之2-丁酮之300mL三 頸燒瓶進行氮氣吹拂30分鐘後,邊攪拌反應器邊加熱至80℃,使用滴加漏斗,於3小時內滴加上述單體溶液。以滴加開始作為聚合開始時間,實施聚合反應6小時。聚合反應結束後,以水冷使聚合溶液冷卻至30℃以下,投入600g之甲醇:水=8:2(質量比)之溶液中使聚合物沉澱。去除上澄液後,將甲醇120g添加於沉澱之聚合物中,洗淨聚合物。去除上澄液後,在50℃乾燥17小時,合成含氟原子之聚合物(D-1)。(D-1)之Mw為4,200,(Mw/Mn)為1.3。且,經13C-NMR分析之結果,氟原子含有率為5質量%,源自(M-4)及(M-6)之構造單位之含有比例分別為32.0莫耳%及68.0莫耳%。 14.3 g (30 mol%) of the compound (M-4) and 45.7 g (70 mol%) of the compound (M-6) were dissolved in 60 g of 2-butanone, and 3 g of AIBN was added thereto to adjust the monomer solution. The 300 mL three-necked flask to which 30 g of 2-butanone was charged was subjected to nitrogen blowing for 30 minutes, and then heated to 80 ° C while stirring the reactor, and the above monomer solution was added dropwise over 3 hours using a dropping funnel. The polymerization reaction was carried out for 6 hours starting from the start of the dropwise addition as the polymerization start time. After completion of the polymerization reaction, the polymerization solution was cooled to 30 ° C or lower by water cooling, and 600 g of a solution of methanol:water = 8:2 (mass ratio) was added to precipitate a polymer. After removing the supernatant, 120 g of methanol was added to the precipitated polymer to wash the polymer. After removing the supernatant liquid, it was dried at 50 ° C for 17 hours to synthesize a fluorine atom-containing polymer (D-1). (D-1) has Mw of 4,200 and (Mw/Mn) of 1.3. Further, as a result of 13 C-NMR analysis, the fluorine atom content was 5% by mass, and the content ratios of the structural units derived from (M-4) and (M-6) were 32.0 mol% and 68.0 mol%, respectively. .
光阻組成物之調製中使用之〔B〕酸產生劑、〔C〕酸擴散控制體、〔E〕溶劑及〔F〕偏在化促進劑示於下。 The [B] acid generator, the [C] acid diffusion controller, the [E] solvent, and the [F] biasing accelerator used in the preparation of the photoresist composition are shown below.
E-1:乙酸丙二醇單甲醚 E-1: propylene glycol monomethyl ether acetate
E-2:烷己酮 E-2: alkenyl ketone
F-1:γ-丁內酯 F-1: γ-butyrolactone
混合作為〔A〕聚合物之(A-1)100質量份、作為〔B〕酸產生劑之(B-1)15質量份、作為〔C〕酸擴散控制體之(C-1)1.1質量份、作為〔D〕含氟原子之聚合物之(D-1)7質量份、作為〔E〕溶劑之(E-1)2,590質量份及(E-2)1,110質量份、以及作為〔F〕偏在化促進劑之(F-1)15質量份,以孔徑0.20μm之過濾器過濾所得混合液,調製光阻組成物。 100 parts by mass of (A-1) of the polymer [A], 15 parts by mass of (B-1) as the acid generator (B), and (C-1) 1.1 mass of the [C] acid diffusion control body. And (7) parts by mass of (D-1) as a polymer of [D] fluorine atom, (E-1) 2,590 parts by mass of (E) solvent, and (110) parts by mass of (E-2), and as [F] The (F-1) 15 parts by mass of the partialization accelerator was filtered through a filter having a pore diameter of 0.20 μm to prepare a photoresist composition.
除使用下述表2所示之種類及調配量之各成分以外,餘與實施例1同樣操作,調製各光阻組成物。 Each of the photoresist compositions was prepared in the same manner as in Example 1 except that each of the components shown in Table 2 below and the blending amount were used.
使用抗反射膜形成用組成物(ARC66,日產化學製),於12吋矽晶圓表面上形成膜厚105nm之抗反射膜。使用上述調製之各光阻組成物於該抗反射膜上形成膜厚95nm之阻劑膜,在115℃進行45秒之SB。接著,使用ArF準分子雷射液浸曝光裝置(NSR S610C,NIKON製),以NA=1.3,比率=0.800,環形(Annular)條件,透過50nm線與100nm間隔形成用之遮罩圖型曝光此阻劑膜。曝光後,在100℃進行45秒之PEB。隨後,使用2.38質量%之TMAH水溶液進行顯像,以水洗淨並進行乾燥,形成線與間隔之正型阻劑圖型。該阻劑圖型形成時,將透過目標尺寸為50nm之1對1之線與間隔之遮罩形成之線寬係形成為線寬50nm之1對1之線與間隔的曝光量作為最適曝光量。又,阻劑圖型之測量係使用掃描型電子顯微鏡(CG4000,日立高科技製)進行。 An antireflection film having a film thickness of 105 nm was formed on the surface of the 12 Å wafer using a composition for forming an antireflection film (ARC66, manufactured by Nissan Chemical Co., Ltd.). A resist film having a film thickness of 95 nm was formed on the antireflection film by using each of the photoresist compositions prepared above, and SB was performed at 115 ° C for 45 seconds. Next, an ArF excimer laser immersion exposure apparatus (NSR S610C, manufactured by NIKON) was used to expose the mask pattern by 50 nm line and 100 nm interval by NA=1.3, ratio=0.800, and Annular conditions. Resist film. After exposure, PEB was performed at 100 ° C for 45 seconds. Subsequently, development was carried out using a 2.38 mass% aqueous solution of TMAH, washed with water and dried to form a positive resist pattern of line and space. When the resist pattern is formed, a line width formed by a 1 to 1 line and a spacer mask having a target size of 50 nm is formed as a line-width of 50 nm with a line-to-space exposure amount as an optimum exposure amount. . Further, the measurement of the resist pattern was carried out using a scanning electron microscope (CG4000, manufactured by Hitachi High-Tech Co., Ltd.).
針對上述調製之各光阻組成物,根據下述方法評價感度、以及MEEF性能及剖面形狀之矩形性、蝕刻耐性。其評價結果示於表3。 With respect to each of the photoresist compositions prepared as described above, the sensitivity, the squareness of the MEEF performance and the cross-sectional shape, and the etching resistance were evaluated by the following methods. The evaluation results are shown in Table 3.
將上述最適曝光量作為感度。此時,感度為50mJ/cm2以下時,感度評價為「良好」,超過50mJ/cm2時評價為「不良」。 The above optimum exposure amount is taken as the sensitivity. At this time, when the sensitivity was 50 mJ/cm 2 or less, the sensitivity was evaluated as "good", and when it was more than 50 mJ/cm 2 , the evaluation was "poor".
使用掃描型電子顯微鏡(CG4000,日立高科技製),在上述最適曝光量下,以5種遮罩尺寸(48.0nm線/100nm間隔、49.0nm線/100nm間隔、50.0nm線/100nm間隔、51.0nm線/100nm間隔、52.0nm線/100nm間隔)解像,測定阻劑圖型尺寸。使用該測定值,以橫軸設為遮罩尺寸,縱軸設為以各遮罩尺寸所形成之線寬進行作圖,以最小平方法算出近似直線之斜率,以該斜率作為MEEF性能。MEEF性能係其值愈接近1顯示愈良好。MEEF性能為4.7以下時評價為「良好」,超過4.7時評價為「不良」。 Using a scanning electron microscope (CG4000, manufactured by Hitachi High-Technology), at the above optimum exposure amount, five mask sizes (48.0 nm line/100 nm interval, 49.0 nm line/100 nm interval, 50.0 nm line/100 nm interval, 51.0) The nm line/100 nm interval, 52.0 nm line/100 nm interval) resolution, and the size of the resist pattern was measured. Using this measured value, the horizontal axis is set as the mask size, and the vertical axis is plotted as the line width formed by each mask size, and the slope of the approximate straight line is calculated by the least square method, and this slope is used as the MEEF performance. The MEEF performance is such that the closer the value is to 1, the better the display. When the MEEF performance was 4.7 or less, the evaluation was "good", and when it was more than 4.7, the evaluation was "poor".
使用上述掃描型電子顯微鏡,觀察阻劑圖型,以任意點測定圖型上部之線寬x與圖型下部之線寬y合計10點。算出各比例x/y,求出該等之相加平均值。該值(x/y)若在0.9≦(x/y)≦1.1之範圍內,則剖面形狀之矩形性評價為「良好」,(x/y)<0.9或1.1<(x/y)時評價為「不良」。 Using the scanning electron microscope described above, the resist pattern was observed, and the line width x of the upper portion of the pattern and the line width y of the lower portion of the pattern were measured at 10 points at any point. Each ratio x/y is calculated, and the sum average of these is obtained. When the value (x/y) is in the range of 0.9 ≦ (x/y) ≦ 1.1, the squareness of the cross-sectional shape is evaluated as "good", and (x/y) is <0.9 or 1.1 < (x/y). The evaluation was "bad".
可評價蝕刻耐性時,針對以下述式之實線包圍之部分算出一般已知之大西參數。該數值為正值且愈小,則蝕刻 耐性評價為「良好」,該數值愈大則可評價為「不良」 When the etching resistance can be evaluated, a generally known Western parameter is calculated for a portion surrounded by a solid line of the following formula. The value is positive and the smaller the etch The evaluation of patience is "good". The larger the value, the lower the rating.
大西參數=(下述部分中之總原子數)/{(下述部分中之碳原子數)一(下述部分中之氧原子數)一(下述部分中之氟原子數)} Daxi parameter = (total number of atoms in the following section) / { (number of carbon atoms in the following section) - (number of oxygen atoms in the following section) - (number of fluorine atoms in the following section)}
實施例之化合物之大西參數,化合物(B-1)~(B-4)為15.00,化合物(B-5)為5.40,化合物(B-6)為27.00,化合物(B-7)為6.00。另外,比較例之化合物之大西參數係,化合物(CB-1)~(CB-4)為-9.00。且關於化合物(CB-5),係針對鍵結於陰離子部中之-SO3 -之部分算出大西參數後,為-2.60。此係因該部分中之氟數比碳數多所致。 The Daxi parameter of the compound of the Example, the compound (B-1) to (B-4) was 15.00, the compound (B-5) was 5.40, the compound (B-6) was 27.00, and the compound (B-7) was 6.00. Further, in the Daxi parameter system of the compound of the comparative example, the compound (CB-1) to (CB-4) was -9.00. Further, the compound (CB-5) was -2.60 after the calculation of the Western parameter for the portion of -SO 3 - bonded to the anion portion. This is because the fluorine number in this part is more than the carbon number.
如由表3之結果所了解,依據實施例之光阻組成物,MEEF小,圖型形狀及蝕刻耐性均良好,依據比較例之光阻組成物,則MEEF較大,圖型形狀及蝕刻耐性 均不良。 As understood from the results of Table 3, according to the photoresist composition of the examples, the MEEF is small, the pattern shape and the etching resistance are good, and according to the photoresist composition of the comparative example, the MEEF is large, the pattern shape and the etching resistance are good. Both are bad.
依據本發明之光阻組成物及阻劑圖型形成方法,可一面發揮優異之MEEF性能,一面形成剖面形狀之矩形性及蝕刻耐性優異之阻劑圖型。本發明之酸產生劑可較好地使用作為該光阻組成物之成分。據此,該等可較好地使用於半導體裝置、液晶裝置等各種電子裝置之微影步驟之圖型形成中。 According to the photoresist composition and the resist pattern forming method of the present invention, it is possible to form a resist pattern having excellent cross-sectional shape rectangularness and etching resistance while exhibiting excellent MEEF performance. The acid generator of the present invention can be preferably used as a component of the photoresist composition. Accordingly, these can be preferably used in pattern formation of lithography steps of various electronic devices such as semiconductor devices and liquid crystal devices.
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