TWI787469B - Actinic radiation-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and manufacturing method of electronic component - Google Patents
Actinic radiation-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and manufacturing method of electronic component Download PDFInfo
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- TWI787469B TWI787469B TW108106287A TW108106287A TWI787469B TW I787469 B TWI787469 B TW I787469B TW 108106287 A TW108106287 A TW 108106287A TW 108106287 A TW108106287 A TW 108106287A TW I787469 B TWI787469 B TW I787469B
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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Abstract
本發明提供一種能夠形成縱橫比高且間距窄之圖案之感光化射線性或感放射線性樹脂組成物。並且,提供一種抗蝕劑膜、圖案形成方法及電子元件的製造方法。感光化射線性或感放射線性樹脂組成物包含:醚化合物;樹脂,包含具有酚性極性基之重複單元及具有酸分解性基之重複單元;光酸產生劑;酸擴散控制劑,其為與醚化合物不同之化合物;及溶劑,醚化合物的含量相對於酸擴散控制劑的含量的質量比為0.2以上,醚化合物的含量相對於樹脂B的含量的質量比為0.1以下,固體成分濃度大於20質量%。The present invention provides an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming patterns with high aspect ratio and narrow pitch. Furthermore, there are provided a resist film, a method for forming a pattern, and a method for manufacturing an electronic element. The actinic radiation-sensitive or radiation-sensitive resin composition includes: an ether compound; a resin comprising repeating units having phenolic polar groups and repeating units having acid-decomposable groups; a photoacid generator; an acid diffusion control agent, which is compatible with A compound different from the ether compound; and a solvent, wherein the mass ratio of the content of the ether compound to the content of the acid diffusion control agent is 0.2 or more, the mass ratio of the content of the ether compound to the content of the resin B is 0.1 or less, and the solid content concentration is greater than 20 quality%.
Description
本發明係有關一種感光化射線性或感放射線性樹脂組成物、抗蝕劑膜、圖案形成方法、以及電子元件的製造方法。The present invention relates to an actinic radiation-sensitive or radiation-sensitive resin composition, a resist film, a method for forming a pattern, and a method for manufacturing electronic components.
為了補償在KrF準分子雷射(248 nm)用抗蝕劑以後由光吸收引起之靈敏度的降低,作為抗蝕劑的圖像形成方法使用諸如化學增幅之圖像形成方法。例如,作為正型化學增幅的圖像形成方法,可以舉出如下圖像形成方法:藉由準分子雷射、電子束及極紫外光等的曝光而曝光部的光酸產生劑進行分解而產生酸,並在曝光後的烘烤(PEB:Post Exposure Bake)中將其產生酸用作反應觸媒而使鹼不溶性基團變為鹼可溶性基團,並藉由鹼顯影液去除曝光部。In order to compensate for the decrease in sensitivity caused by light absorption after using a resist for KrF excimer laser (248 nm), an image forming method such as chemical amplification is used as an image forming method of a resist. For example, as an image forming method of positive-type chemical amplification, an image forming method in which a photoacid generator in an exposed portion is decomposed by exposure to excimer laser, electron beam, extreme ultraviolet light, etc. to generate Acid, and in post-exposure baking (PEB: Post Exposure Bake), use it to generate acid as a reaction catalyst to change the alkali-insoluble group into alkali-soluble group, and remove the exposed part by alkali developer.
例如,在專利文獻1中,揭示有具有使用規定的感光化射線性或感放射線性樹脂組成物,並在基板上形成厚度T的膜之步驟之圖案形成方法,作為厚度T,例如,假設為800 nm以上。 [先前技術文獻] [專利文獻]For example, Patent Document 1 discloses a pattern forming method having a step of forming a film with a thickness T on a substrate using a predetermined actinic radiation-sensitive or radiation-sensitive resin composition. As the thickness T, for example, assume Above 800nm. [Prior Art Literature] [Patent Document]
[專利文獻1]國際公開WO2017/057226號[Patent Document 1] International Publication WO2017/057226
目前為止在影像感測器的製造步驟等中,在半導體中實施離子植入。近年來,從該離子植入的高解析化的要求等考慮,即使在藉由使抗蝕劑膜成為厚膜來促進所獲得之圖案的高縱橫比(所形成之線的高度相對於幅度的比大)化之情況下,亦要求能夠使圖案成為窄的間距(間隔)。 本發明人等對專利文獻1中所記載之感光化射線性或感放射線性樹脂組成物進行研究之結果,發現在促進圖案的高縱橫比化時的圖案的間距具有改善空間。Conventionally, in the manufacturing process of image sensors and the like, ion implantation is performed in semiconductors. In recent years, considering the demand for high-resolution ion implantation, etc., even when the high aspect ratio (the height of the formed line with respect to the width) of the obtained pattern is promoted by making the resist film thick, In the case of increasing the ratio), it is also required that the pattern can be made into a narrow pitch (interval). As a result of studying the actinic radiation-sensitive or radiation-sensitive resin composition described in Patent Document 1, the present inventors found that there is room for improvement in the pitch of patterns when increasing the aspect ratio of patterns.
因此,本發明的課題在於,提供一種能夠形成縱橫比高且間距窄之圖案之感光化射線性或感放射線性樹脂組成物。 又,本發明的課題在於提供一種抗蝕劑膜、圖案形成方法及電子元件的製造方法。Therefore, an object of the present invention is to provide an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern with a high aspect ratio and a narrow pitch. Moreover, the subject of this invention is providing the manufacturing method of a resist film, a pattern formation method, and an electronic component.
本發明人等為了實現上述課題而進行了深入研究之結果,發現藉由包含醚化合物之規定的感光化射線性或感放射線性樹脂組成物能夠解決上述課題,以至完成了本發明。 亦即,發現藉由以下構成能夠實現上述目的。As a result of intensive studies to achieve the above-mentioned problems, the present inventors found that the above-mentioned problems can be solved by a predetermined actinic radiation-sensitive or radiation-sensitive resin composition containing an ether compound, and completed the present invention. That is, it discovered that the above object can be achieved by the following constitution.
[1] 一種感光化射線性或感放射線性樹脂組成物,其包含: 醚化合物; 樹脂,包含具有酚性極性基之重複單元及具有酸分解性基之重複單元; 光酸產生劑; 酸擴散控制劑,其為與上述醚化合物不同之化合物;及 溶劑, 所述感光化射線性或感放射線性樹脂組成物中 上述醚化合物的含量相對於上述酸擴散控制劑的含量的質量比為0.2以上, 上述醚化合物的含量相對於上述樹脂的含量的質量比為0.1以下, 固體成分濃度大於20質量%。 [2]如[1]所述之感光化射線性或感放射線性樹脂組成物,其中上述醚化合物包含氮原子。 [3]如[1]或[2]所述之感光化射線性或感放射線性樹脂組成物,其中上述醚化合物為後述之通式(X1)所表示之化合物。 [4]如[3]所述之感光化射線性或感放射線性樹脂組成物,其中後述之通式(X1)中,至少1個Rq1 為苯環基。 [5]如[1]~[4]中任一項所述之感光化射線性或感放射線性樹脂組成物,其中上述樹脂的所有重複單元中,具有苯環基之重複單元的含量小於65莫耳%。 [6]如[1]~[5]中任一項所述之感光化射線性或感放射線性樹脂組成物,其中上述樹脂進一步具有後述之通式(VW)所表示之重複單元。 [7]如[1]~[6]中任一項所述之感光化射線性或感放射線性樹脂組成物,其中上述光酸產生劑為選自包括後述之通式(ZI-3)所表示之化合物及後述之通式(ZI-4)所表示之化合物的組群中的1種以上之化合物。 [8]一種抗蝕劑膜,其使用[1]~[7]中任一項所述之感光化射線性或感放射線性樹脂組成物而形成。 [9]一種圖案形成方法,其包括: 使用[1]~[7]中任一項所述之感光化射線性或感放射線性樹脂組成物而形成抗蝕劑膜之步驟; 對上述抗蝕劑膜進行曝光之步驟;及 使用顯影液對經曝光之上述抗蝕劑膜進行顯影之步驟。 [10]一種電子元件的製造方法,其包括[9]所述之圖案形成方法。 [發明效果][1] An actinic radiation-sensitive or radiation-sensitive resin composition comprising: an ether compound; a resin comprising a repeating unit having a phenolic polar group and a repeating unit having an acid-decomposable group; a photoacid generator; an acid diffusion A control agent, which is a compound different from the above-mentioned ether compound; and a solvent, wherein the mass ratio of the content of the above-mentioned ether compound to the content of the above-mentioned acid diffusion control agent in the actinic radiation-sensitive or radiation-sensitive resin composition is 0.2 or more , the mass ratio of the content of the above-mentioned ether compound to the content of the above-mentioned resin is 0.1 or less, and the solid content concentration is greater than 20% by mass. [2] The actinic radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the ether compound contains a nitrogen atom. [3] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [1] or [2], wherein the ether compound is a compound represented by general formula (X1) described below. [4] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [3], wherein in the general formula (X1) described later, at least one R q1 is a phenyl ring group. [5] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [4], wherein the content of the repeating unit having a benzene ring group in all the repeating units of the resin is less than 65% mole %. [6] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the resin further has a repeating unit represented by the general formula (VW) described below. [7] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [6], wherein the above-mentioned photoacid generator is selected from the group consisting of the following general formula (ZI-3). One or more compounds in the group of the compound represented and the compound represented by the general formula (ZI-4) described later. [8] A resist film formed using the actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [7]. [9] A method for forming a pattern, comprising: a step of forming a resist film using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of [1] to [7]; a step of exposing the resist film; and a step of developing the exposed resist film using a developer. [10] A method of manufacturing an electronic device, including the pattern forming method described in [9]. [Invention effect]
依本發明,能夠提供一種能夠形成縱橫比高且間距窄之圖案之感光化射線性或感放射線性樹脂組成物。 又,依本發明,能夠提供一種抗蝕劑膜、圖案形成方法及電子元件的製造方法。According to the present invention, it is possible to provide an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming a pattern with a high aspect ratio and a narrow pitch. Also, according to the present invention, it is possible to provide a resist film, a method for forming a pattern, and a method for manufacturing an electronic component.
以下,對本發明進行詳細說明。 以下所記載之構成要件的說明有時係基於本發明的代表性實施態樣而進行,但本發明並不限定於該種實施態樣。 本說明書中的“光化射線”或“放射線”係指,例如水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線(EUV光:Extreme Ultraviolet)、X射線及電子束(EB:Electron Beam)等。本說明書中的“光”係指,光化射線或放射線。 只要沒有特別指定,則本說明書中的“曝光”不僅包括使用水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線、X射線及EUV光等進行之曝光,還包含使用電子束及離子束等粒子束進行之描劃。 本說明書中,“~”係以將記載於其前後之數值作為下限值及上限值而包含之含義來使用。Hereinafter, the present invention will be described in detail. The description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. "Actinic ray" or "radiation" in this specification refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams ( EB: Electron Beam), etc. "Light" in this specification refers to actinic rays or radiation. Unless otherwise specified, "exposure" in this manual includes not only exposure using the bright-line spectrum of a mercury lamp, extreme ultraviolet light, extreme ultraviolet light, X-rays, and EUV light represented by excimer lasers, but also exposure using electronic light. Drawing by particle beams such as laser beams and ion beams. In this specification, "-" is used in the meaning which includes the numerical value described before and after it as a lower limit and an upper limit.
本說明書中,(甲基)丙烯酸酯表示丙烯酸酯及甲基丙烯酸酯。又,(甲基)丙烯酸表示丙烯酸及甲基丙烯酸。 本說明書中,樹脂的重量平均分子量(Mw)、數量平均分子量(Mn)及分散度(亦稱為分子量分佈)(Mw/Mn)定義為藉由GPC(凝膠浸透層析術(Gel Permeation Chromatography))裝置(TOSOH CORPORATION製造之HLC-8120GPC)的GPC測量(溶劑:四氫呋喃、流量(樣品注入量):10 μL、管柱:TOSOH CORPORATION製造之TSK gel Multipore HXL-M、管柱溫度:40℃、流速:1.0 mL/分鐘、檢測器:示差折射率檢測器(Refractive Index Detector))的聚苯乙烯換算值。In this specification, (meth)acrylate means acrylate and methacrylate. Moreover, (meth)acrylic acid means acrylic acid and methacrylic acid. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn) and dispersion (also called molecular weight distribution) (Mw/Mn) of the resin are defined by GPC (Gel Permeation Chromatography (Gel Permeation Chromatography) )) GPC measurement of device (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40°C , Flow rate: 1.0 mL/min, Detector: Refractive Index Detector (Refractive Index Detector)) polystyrene conversion value.
本說明書中pKa(酸解離常數pKa)係指,水溶液中的酸解離常數pKa,例如,化學便覽(II)(改訂4版、1993年、日本化學會編、Maruzen Company,Limited)中有定義。酸解離常數pKa的值越低,表示酸強度越大。具體而言,水溶液中的酸解離常數pKa能夠藉由使用無限稀釋水溶液測定在25℃下的酸解離常數來進行實測。或者,亦能夠利用下述軟體套件1,藉由計算來求出基於哈米特取代基常數及公知文獻值的資料庫之值。本說明書中所記載之pKa的值全部表示使用該軟體套件藉由計算而求出之值。The pKa (acid dissociation constant pKa) in this specification refers to the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Chem. The lower the value of the acid dissociation constant pKa, the stronger the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be actually measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can also be used to calculate the value based on the database of Hammett's substituent constants and known literature values. All the values of pKa described in this specification represent values obtained by calculation using this software package.
軟體套件1:Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs)。Software Suite 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
本說明書中的基團(原子團)的標記中,未記述取代及未經取代之標記包含不具有取代基之基團,並且還包含具有取代基之基團。例如,“烷基”係指不僅包含不具有取代基之烷基(未經取代之烷基),還包含具有取代基之烷基(取代烷基)。又,本說明書中的“有機基團”係指包含至少1個碳原子之基團。In the notation of a group (atomic group) in this specification, the notation of substitution and unsubstituted notation includes a group not having a substituent and also a group having a substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Moreover, the "organic group" in this specification means a group containing at least 1 carbon atom.
又,本說明書中,諸如“可以具有取代基”時的取代基的種類、取代基的位置及取代基的數量並沒有特別限制。取代基的數量例如可以為1個、2個、3個或其以上。作為取代基的例子可以舉出除了氫原子以外之1價的非金屬原子團,例如,能夠從以下取代基組群組群T中選擇。 (取代基T) 作為取代基T,可以舉出氟原子、氯原子、溴原子、及碘原子等鹵素原子;甲氧基、乙氧基、及第三丁氧基等的烷氧基;苯氧基及對甲苯氧基等的芳氧基;甲氧羰基、丁氧基羰基、及苯氧基羰基等的烷氧羰基;乙醯氧基、丙醯氧基、及苯甲醯氧基等醯氧基;乙醯基、苯甲醯基、異丁醯基、丙烯醯基、甲基丙烯醯基、及甲氧草醯基等醯基;甲基硫烷基(methyl sulfanyl)及第三丁基硫烷基等的烷基硫烷基(alkyl sulfanyl);苯基硫烷基(phenyl sulfanyl)及對甲苯硫烷基等的芳基硫烷基(aryl sulfanyl);烷基;環烷基;芳基;雜芳基;羥基;羧基;甲醯基;磺基;氰基;烷胺基羰基;芳基胺基羰基;磺醯胺基;甲矽烷基;胺基;單烷胺基;二烷胺基;芳胺基;以及該等組合。In addition, in this specification, the kind of substituent, the position of a substituent, and the number of a substituent, such as "may have a substituent", are not particularly limited. The number of substituents may be, for example, 1, 2, 3 or more. Examples of substituents include monovalent non-metallic atomic groups other than hydrogen atoms, and can be selected from the following substituent group group T, for example. (substituent T) Examples of substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; phenoxy and p-toluene Aryloxy groups such as oxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetyloxy, propionyloxy, and benzoyloxy; Acyl group, benzoyl group, isobutyryl group, acryl group, methacryl group, and acyl group such as acyl group; methylsulfanyl group (methylsulfanyl) and tertiary butylsulfanyl group, etc. Alkyl sulfanyl; aryl sulfanyl such as phenyl sulfanyl and p-toluene sulfanyl; alkyl; cycloalkyl; aryl; heteroaryl ; Hydroxy; Carboxyl; Formyl; Sulfonyl; Cyano; Alkylaminocarbonyl; Arylaminocarbonyl; basis; and such combinations.
[感光化射線性或感放射線性樹脂組成物] 本發明的感光化射線性或感放射線性樹脂組成物(以下,亦簡稱為“抗蝕劑組成物”)包含:醚化合物;樹脂,包含具有酚性極性基之重複單元及具有酸分解性基之重複單元;光酸產生劑;酸擴散控制劑,其為與上述醚化合物不同之化合物;及溶劑。 又,抗蝕劑組成物中,上述醚化合物的含量相對於上述酸擴散控制劑的含量的質量比為0.2以上。 同樣地,抗蝕劑組成物中,上述醚化合物的含量相對於上述樹脂的含量的質量比為0.1以下。 此外,固體成分濃度大於20質量%。[Actinic radiation-sensitive or radiation-sensitive resin composition] The actinic radiation-sensitive or radiation-sensitive resin composition (hereinafter also referred to simply as "resist composition") of the present invention includes: an ether compound; a resin containing repeating units having phenolic polar groups and acid-decomposable groups A repeating unit of ; a photoacid generator; an acid diffusion controller, which is a compound different from the aforementioned ether compound; and a solvent. In addition, in the resist composition, the mass ratio of the content of the ether compound to the content of the acid diffusion controller is 0.2 or more. Likewise, in the resist composition, the mass ratio of the content of the ether compound to the content of the resin is 0.1 or less. In addition, the solid content concentration is greater than 20% by mass.
藉由抗蝕劑組成物採用該種構成而能夠解決本發明的課題之機理尚不明確,但本發明人等認為如下。 認為如下內容有助於解決本發明的課題,亦即,醚化合物在抗蝕劑組成物中以一定比例存在,從而改善抗蝕劑膜對基板等的密合性,即使在形成高縱橫比的圖案時,亦能夠抑制圖案崩塌,進而能夠改善從曝光至顯影過程中所解析之圖案的對比度等。 又,認為本發明的抗蝕劑組成物藉由固體成分濃度大於20質量%,此外樹脂包含具有酚性極性基之重複單元,從而用於形成用於獲得具有高縱橫比之圖案之厚的抗蝕劑膜之適用性得到改善。 又,就藉由使用本發明的抗蝕劑組成物而獲得之圖案而言,圖案的截面形狀(矩形性)亦優異。The mechanism by which the subject of the present invention can be solved by employing such a constitution in the resist composition is not clear, but the inventors of the present invention think as follows. It is considered that the following content contributes to solving the problem of the present invention, that is, the ether compound exists in a certain ratio in the resist composition, thereby improving the adhesion of the resist film to the substrate, etc., even when a high aspect ratio is formed. When forming a pattern, pattern collapse can also be suppressed, thereby improving the contrast of the pattern analyzed in the process from exposure to development. Also, it is considered that the resist composition of the present invention is used to form a thick resist for obtaining a pattern with a high aspect ratio by having a solid content concentration of more than 20% by mass, and the resin contains a repeating unit having a phenolic polar group. The applicability of the etch film is improved. Moreover, the pattern obtained by using the resist composition of this invention is also excellent in the cross-sectional shape (rectangularity) of a pattern.
以下,對本發明的抗蝕劑組成物中所包含之成分進行詳細說明。此外,本發明的抗蝕劑組成物可以為正型抗蝕劑組成物,亦可以為負型抗蝕劑組成物。又,可以為鹼顯影用抗蝕劑組成物,亦可以為有機溶劑顯影用抗蝕劑組成物。其中,正型的抗蝕劑組成物且鹼顯影用抗蝕劑組成物為較佳。 本發明的抗蝕劑組成物典型而言,係化學增幅型抗蝕劑組成物。Hereinafter, components contained in the resist composition of the present invention will be described in detail. In addition, the resist composition of the present invention may be a positive resist composition or a negative resist composition. In addition, it may be a resist composition for alkali development, or may be a resist composition for organic solvent development. Among them, a positive type resist composition and a resist composition for alkali development are preferable. The resist composition of the present invention is typically a chemically amplified resist composition.
<醚化合物> 本發明的抗蝕劑組成物包含醚化合物。 醚化合物的分子量為100~2000為較佳,150~1000為更佳,200~600為進一步較佳。 醚化合物為具有醚基(-O-)之化合物。 醚基在2個鍵結位置分別與碳原子鍵結。 其中,作為醚化合物所具有之醚基,並不表示與羰基碳(形成-C(=O)-之碳原子)直接鍵結而形成酯基之基團。<Ether compound> The resist composition of the present invention contains an ether compound. The molecular weight of the ether compound is preferably from 100 to 2000, more preferably from 150 to 1000, and still more preferably from 200 to 600. The ether compound is a compound having an ether group (-O-). The ether group is bonded to a carbon atom at two bonding positions, respectively. Here, the ether group possessed by the ether compound does not mean a group that is directly bonded to a carbonyl carbon (a carbon atom that forms -C(=O)-) to form an ester group.
醚化合物例如為具有下述通式(O1)所表示之基團之化合物為較佳。 *x-(-O-AL-)a -*y (O1)The ether compound is preferably, for example, a compound having a group represented by the following general formula (O1). *x-(-O-AL-) a -*y (O1)
通式(O1)中,*x及*y表示與通式(O1)所表示之基團以外的基團的鍵結位置。In the general formula (O1), *x and *y represent the bonding positions with groups other than the groups represented by the general formula (O1).
AL表示伸烷基。上述伸烷基可以為支鏈狀,亦可以為直鏈狀。又,可以具有環狀結構,亦可以不具有。 上述伸烷基的碳數為1~10為較佳,1~5為更佳,2~3為進一步較佳。 上述伸烷基可以具有之取代基並沒有特別限制,未經取代為較佳。此外,上述的較佳碳數為沒有計入取代基中所包含之碳原子數的數。 其中,作為上述伸烷基,-CH2 -CH2 -或-CH2 -CH2 -CH2 -為較佳。 當AL存在複數個時,存在複數個之AL可以分別相同,亦可以不同。AL represents alkylene. The above-mentioned alkylene group may be branched or linear. Moreover, it may have a ring structure, and may not have it. The number of carbon atoms in the alkylene group is preferably 1-10, more preferably 1-5, and still more preferably 2-3. The substituents that the above-mentioned alkylene group may have are not particularly limited, and are preferably unsubstituted. In addition, the above-mentioned preferable carbon number is a number not including the number of carbon atoms contained in the substituent. Among them, -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 - is preferable as the alkylene group. When there are plural ALs, the plural ALs may be the same or different.
a表示1以上的整數。a為1~10為較佳,1~6為更佳,1~4為進一步較佳。a represents an integer of 1 or more. It is preferable that a is 1-10, it is more preferable that it is 1-6, and it is still more preferable that it is 1-4.
與通式(O1)所表示之基團在*x處鍵結之基團並沒有特別限制,例如,可以舉出氫原子、伸烷基、芳香環基(較佳為碳數6~15。例如,苯環基)或烷基(較佳為碳數1~5)。 又,當a為1時,與通式(O1)所表示之基團在*x處鍵結之原子為羰基碳以外的碳原子。作為上述羰基碳以外的碳原子,例如,為構成芳香環基(較佳為碳數6~15。芳香族烴基為較佳,苯環基為更佳)之碳原子、構成烷基(較佳為碳數1~5)之碳原子或構成伸烷基之碳原子為較佳。The group bonded to the group represented by the general formula (O1) at *x is not particularly limited, for example, a hydrogen atom, an alkylene group, and an aromatic ring group (preferably having 6 to 15 carbon atoms are mentioned. For example, a phenyl ring group) or an alkyl group (preferably having 1 to 5 carbon atoms). Also, when a is 1, the atom bonded to the group represented by the general formula (O1) at *x is a carbon atom other than the carbonyl carbon. As the carbon atom other than the above-mentioned carbonyl carbon, for example, it is a carbon atom constituting an aromatic ring group (preferably having 6 to 15 carbon atoms. An aromatic hydrocarbon group is more preferable, and a benzene ring group is more preferable), constituting an alkyl group (preferably It is preferably a carbon atom having 1 to 5 carbon atoms or a carbon atom constituting an alkylene group.
與通式(O1)所表示之基團在*y處鍵結之基團並沒有特別限制,例如,可以舉出氫原子、羥基、醚基、芳氧基(較佳為碳數6~15。例如,苯氧基)及-NRp Rq 。 Rp 及Rq 分別獨立地表示氫原子或取代基。Rp 與Rq 可以相互鍵結而形成環。Rp 或Rq 可以成為2價的連結基(例如,伸烷基(較佳為碳數1~5))與通式(O1)所表示之基團在*x處鍵結而形成包含通式(O1)所表示之基團之環。 Rp 、Rq 及Rp 與Rq 相互鍵結而形成之環可以分別具有通式(O1)所表示之基團。又,作為上述2價的連結基之Rp 或Rq 可以具有通式(O1)所表示之基團。The group bonded to the group represented by the general formula (O1) at *y is not particularly limited, for example, a hydrogen atom, a hydroxyl group, an ether group, an aryloxy group (preferably having 6 to 15 carbon atoms) .eg, phenoxy) and -NR p R q . R p and R q each independently represent a hydrogen atom or a substituent. R p and R q may be bonded to each other to form a ring. R p or R q can become a divalent linking group (for example, an alkylene group (preferably having 1 to 5 carbons)) and a group represented by the general formula (O1) at *x to form a bond containing the general A ring of the group represented by the formula (O1). R p , R q , and a ring formed by bonding R p and R q to each other may each have a group represented by the general formula (O1). In addition, R p or R q which is the above-mentioned divalent linking group may have a group represented by the general formula (O1).
又,通式(O1)所表示之基團滿足在*x處鍵結之基團為氫原子以外之基團及在*y處鍵結之基團為羥基以外的基團中的至少一方的必要條件為較佳。Also, the group represented by the general formula (O1) satisfies at least one of the group bonded at *x being a group other than a hydrogen atom and the group bonded at *y being a group other than a hydroxyl group Necessary conditions are better.
醚化合物中所具有之通式(O1)所表示之基團的數量為1以上為較佳,1~5為更佳,1~3為進一步較佳。 當醚化合物中存在複數個通式(O1)所表示之基團時,該等可以分別相同,亦可以不同。 此外,醚化合物中所具有之通式(O1)所表示之基團的數係藉由盡量少量計入將各化合物中所存在之通式(O1)所表示之基團的數而獲得之數。例如,“苯基-O-CH2 -CH2 -O-CH2 -CH2 -O-CH2 -CH2 -O-苯基”所表示之醚化合物具有1個a=3的通式(O1)所表示之基團。The number of groups represented by the general formula (O1) contained in the ether compound is preferably 1 or more, more preferably 1-5, and still more preferably 1-3. When a plurality of groups represented by the general formula (O1) exist in the ether compound, these may be respectively the same or different. In addition, the number of groups represented by the general formula (O1) in the ether compound is a number obtained by counting the number of groups represented by the general formula (O1) present in each compound as little as possible. . For example, the ether compound represented by "phenyl-O-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -O-phenyl" has a general formula of a=3 ( The group represented by O1).
醚化合物為含氮化合物為較佳。亦即,醚化合物為包含醚基及氮原子之化合物為較佳。作為含氮化合物之醚化合物所具有之氮原子的數並沒有限制,例如,1~5為較佳。The ether compound is preferably a nitrogen-containing compound. That is, the ether compound is preferably a compound containing an ether group and a nitrogen atom. The number of nitrogen atoms which the ether compound which is a nitrogen-containing compound has is not limited, For example, 1-5 are preferable.
其中,醚化合物為通式(X1)所表示之化合物為較佳。 [Rq1 -(-O-AL-)m ]n -N-Rq2 3-n (X1)Among them, the ether compound is preferably a compound represented by the general formula (X1). [R q1 -(-O-AL-) m ] n -NR q2 3-n (X1)
通式(X1)中,m表示1~10的整數。m為1~6為較佳,1~4為更佳。 當m存在複數個時,亦即當n為2以上的整數時,存在複數個之m可以分別相同,亦可以不同。In general formula (X1), m represents the integer of 1-10. m is preferably 1-6, more preferably 1-4. When there are plural m, that is, when n is an integer of 2 or more, the plural m may be the same or different.
n表示1~3的整數。n represents the integer of 1-3.
AL表示伸烷基。通式(X1)中的AL能夠採取之形態與通式(O1)的AL能夠採取之形態相同。 當AL存在複數個時,存在複數個之AL可以分別相同,亦可以不同。AL represents alkylene. The form that AL in general formula (X1) can take is the same as the form that AL in general formula (O1) can take. When there are plural ALs, the plural ALs may be the same or different.
Rq1 表示氫原子或取代基。作為Rq1 的取代基,例如,有機基團為較佳,芳香環基(較佳為碳數6~15。芳基為較佳,苯環基為更佳)或烷基(較佳為碳數1~5)為更佳。 此外,作為Rq1 中的芳香環基所具有之取代基,例如,烷氧基(較佳為碳數1~5)為較佳。 當Rq1 存在複數個時,存在複數個之Rq1 可以分別相同,亦可以不同。 可以存在複數個之Rq1 中,至少1個Rq1 為苯環基為較佳。R q1 represents a hydrogen atom or a substituent. As a substituent for R q1 , for example, an organic group is preferred, an aromatic ring group (preferably having 6 to 15 carbon atoms. Aryl is preferred, phenyl ring is more preferred) or an alkyl group (preferably carbon Number 1 to 5) is better. Moreover, as a substituent which the aromatic ring group in Rq1 has, for example, an alkoxy group (preferably having 1-5 carbon atoms) is preferable. When there are plural R q1s , the plural R q1s may be the same or different. Among the R q1s that may exist in plural, at least one R q1 is preferably a phenyl ring group.
此外,當藉由可以存在複數個之m中的1個以上為1而通式(X1)中存在[Rq1 -(-O-AL-)]所表示之基團時,該種基團中的Rq1 為有機基團為更佳,芳香環基(較佳為碳數6~15。芳基為較佳,苯環基為更佳)或烷基(較佳為碳數1~5)為進一步較佳。 又,在該種[Rq1 -(-O-AL-)]中,Rq1 中的與(-O-AL-)直接鍵結之原子為選自氫原子及羰基碳之原子以外的原子為較佳,羰基碳以外的碳原子為更佳。作為上述羰基碳以外的碳原子,例如,構成芳香環基(較佳為碳數6~15。芳香族烴環基為較佳,苯環基為更佳)之碳原子或構成烷基(較佳為碳數1~5)之碳原子為較佳。In addition, when a group represented by [R q1 -(-O-AL-)] exists in the general formula (X1) because one or more of the m that may exist in plural is 1, among such groups R q1 is more preferably an organic group, an aromatic ring group (preferably having 6 to 15 carbon atoms. An aryl group is more preferred, and a phenyl ring group is more preferred) or an alkyl group (preferably having 1 to 5 carbon atoms) for further improvement. Also, in this kind of [R q1 -(-O-AL-)], the atom directly bonded to (-O-AL-) in R q1 is an atom other than a hydrogen atom and a carbonyl carbon atom. Preferably, carbon atoms other than carbonyl carbon are more preferred. As a carbon atom other than the above-mentioned carbonyl carbon, for example, a carbon atom constituting an aromatic ring group (preferably having 6 to 15 carbon atoms. An aromatic hydrocarbon ring group is preferred, and a benzene ring group is more preferred) or an alkyl group (more preferably Preferably it is a carbon atom with a carbon number of 1 to 5).
Rq2 表示氫原子或取代基。作為Rq2 的取代基並沒有特別限制,例如,碳數1~20的有機基團為較佳,碳數1~17的烷基酯烷基為更佳。 當Rq2 存在複數個時,存在複數個之Rq2 可以分別相同,亦可以不同。R q2 represents a hydrogen atom or a substituent. The substituent for R q2 is not particularly limited, for example, an organic group having 1 to 20 carbons is preferred, and an alkyl ester alkyl group having 1 to 17 carbons is more preferred. When there are plural R q2s , the plural R q2s may be the same or different.
當n為1或2時,Rq1 與Rq2 可以相互鍵結而形成環。 Rq1 與Rq2 相互鍵結而形成之基團為伸烷基(較佳為碳數1~5)為較佳。 其中,當m中的1個以上為1時,存在於通式(X1)中之[Rq1 -(-O-AL-)]中的Rq1 與Rq2 相互鍵結而形成環為較佳。在該情況下,在Rq1 與Rq2 相互鍵結而形成之基團中,與(-O-AL-)直接鍵結之原子為羰基碳以外的碳原子(例如,構成伸烷基之碳原子)為較佳。When n is 1 or 2, R q1 and R q2 may be bonded to each other to form a ring. The group formed by the mutual bonding of R q1 and R q2 is preferably an alkylene group (preferably having 1 to 5 carbon atoms). Among them, when one or more of m is 1, it is preferable that R q1 and R q2 in [R q1 -(-O-AL-)] present in the general formula (X1) are bonded to each other to form a ring . In this case, in the group formed by bonding R q1 and R q2 to each other, the atom directly bonded to (-O-AL-) is a carbon atom other than the carbonyl carbon (for example, the carbon constituting the alkylene group atom) is preferred.
當通式(X1)中存在複數個[Rq1 -(-O-AL-)m ]時,複數個[Rq1 -(-O-AL-)m ]可以相同,亦可以不同。 通式(X1)中,至少1個Rq1 為芳香環基(較佳為碳數6~15)為較佳,芳基(較佳為碳數6~15)為較佳,苯基為更佳。When there are a plurality of [R q1 -(-O-AL-) m ] in the general formula (X1), the plurality of [R q1 -(-O-AL-) m ] may be the same or different. In the general formula (X1), at least one R q1 is an aromatic ring group (preferably having 6 to 15 carbon atoms), more preferably an aryl group (preferably having 6 to 15 carbon atoms), and more preferably a phenyl group. good.
此外,醚化合物不具有氟原子為較佳。Moreover, it is preferable that an ether compound does not have a fluorine atom.
抗蝕劑組成物中,醚化合物的含量相對於酸擴散控制劑的含量的質量比R1(醚化合物的含量/酸擴散控制劑的含量)為0.2以上,0.2~100為較佳,0.2~20為更佳,0.2~1為進一步較佳。 又,抗蝕劑組成物中,醚化合物的含量相對於樹脂的含量的質量比R2(醚化合物的含量/樹脂的含量)為0.1以下,0.0002~0.05為較佳,0.0002~0.01為更佳,0.0003~0.005為進一步較佳。 在後段中對酸擴散控制劑及樹脂進行詳細說明。 抗蝕劑組成物中,醚化合物的含量只要滿足上述R1及R2的規定,則並沒有特別限制,例如,相對於抗蝕劑組成物的總固體成分為0.006~8質量%為較佳,0.01~1質量%為更佳,0.02~0.5質量%為進一步較佳。 此外,固體成分係指,形成抗蝕劑膜之成分,不包含溶劑。又,只要係形成抗蝕劑膜之成分,則即使其性狀係液體狀亦視為固體成分。 醚化合物可以單獨使用1種,亦可以使用2種以上。當使用2種以上醚化合物時,其合計含量在上述範圍內為較佳。In the resist composition, the mass ratio R1 of the content of the ether compound to the content of the acid diffusion controller (content of the ether compound/content of the acid diffusion controller) is 0.2 or more, preferably 0.2 to 100, and 0.2 to 20 More preferably, 0.2-1 is still more preferable. In addition, in the resist composition, the mass ratio R2 (content of ether compound/content of resin) of the content of the ether compound to the content of the resin is 0.1 or less, preferably 0.0002 to 0.05, more preferably 0.0002 to 0.01, 0.0003 to 0.005 is still more preferable. The acid diffusion controller and the resin will be described in detail in the following paragraphs. In the resist composition, the content of the ether compound is not particularly limited as long as it satisfies the above-mentioned requirements of R1 and R2. For example, it is preferably 0.006 to 8% by mass relative to the total solid content of the resist composition, and 0.01 -1 mass % is more preferable, and 0.02-0.5 mass % is still more preferable. In addition, the solid content means the component which forms a resist film, and does not contain a solvent. In addition, as long as it is a resist film forming component, even if its property is liquid, it is regarded as a solid component. An ether compound may be used individually by 1 type, and may use 2 or more types. When two or more ether compounds are used, the total content thereof is preferably within the above range.
<樹脂> 本發明的抗蝕劑組成物包含樹脂(亦簡稱為“樹脂B”或“樹脂”),該樹脂包含具有酚性極性基之重複單元及具有酸分解性基之重複單元。<Resin> The resist composition of the present invention includes a resin (also simply referred to as "resin B" or "resin") that includes a repeating unit having a phenolic polar group and a repeating unit having an acid-decomposable group.
(具有酚性極性基之重複單元) 樹脂B包含具有酚性極性基之重複單元。酚性極性基係指,極性基鍵結於芳香環基之基團。 上述芳香環基可以為芳香族烴環基,亦可以為芳香族雜環基。又,芳香環基可以為單環,亦可以為多環。又,在芳香環基上可以稠合非芳香環。 作為芳香環基,苯環基、萘環基及蒽環基等碳數6~18的芳香族烴環基、或例如,噻吩環基、呋喃環基、吡咯環基、苯并噻吩環基、苯并呋喃環基、苯并吡咯環基、三口井環基、咪唑環基、苯并咪唑環基、三唑環基、噻二唑環基及噻唑環基等包含雜環之芳香族雜環基為較佳。 其中,上述芳香環基為芳香族烴基為較佳,苯環基為更佳。(Repeating units with phenolic polar groups) Resin B contains repeating units with phenolic polar groups. The phenolic polar group refers to a group in which a polar group is bonded to an aromatic ring group. The aforementioned aromatic ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. In addition, the aromatic ring group may be monocyclic or polycyclic. Also, a non-aromatic ring may be fused to the aromatic ring group. As the aromatic ring group, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a benzene ring group, a naphthalene ring group, and an anthracenyl ring group, or, for example, a thiophene ring group, a furan ring group, a pyrrole ring group, a benzothiophene ring group, Aromatic heterocycles containing heterocycles such as benzofuran ring group, benzopyrrole ring group, sankoujing ring group, imidazole ring group, benzimidazole ring group, triazole ring group, thiadiazole ring group and thiazole ring group base is better. Among them, the above-mentioned aromatic ring group is preferably an aromatic hydrocarbon group, and more preferably a benzene ring group.
作為與芳香環基鍵結之極性基,鹼可溶性基為較佳,例如,可以舉出羥基、羧基、氟化醇基、磺酸基、磺醯胺基、磺醯亞胺基、(烷基磺醯基)(烷基羰基)亞甲基、(烷基磺醯基)(烷基羰基)醯亞胺基、雙(烷基羰基)亞甲基、雙(烷基羰基)醯亞胺基、雙(烷基磺醯基)亞甲基、雙(烷基磺醯基)醯亞胺基、三(烷基羰基)亞甲基及三(烷基磺醯基)亞甲基等酸性基。As the polar group bonded to the aromatic ring group, an alkali-soluble group is preferred, for example, a hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, an (alkyl group) Sulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide , bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene and other acidic groups .
・通式(P01) 具有酚性極性基之重複單元為通式(P01)所表示之重複單元為較佳。・General formula (P01) The repeating unit having a phenolic polar group is preferably a repeating unit represented by the general formula (P01).
[化1] [chemical 1]
R41 、R42 及R43 分別獨立地表示氫原子、烷基、環烷基、鹵素原子、氰基或烷氧羰基。 其中,R41 、R42 及R43 為氫原子為較佳。R 41 , R 42 and R 43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Among them, R 41 , R 42 and R 43 are preferably hydrogen atoms.
作為R41 、R42 及R43 的烷基,甲基、乙基、丙基、異丙基、正丁基、第二丁基、己基、2-乙基己基、辛基及十二烷基等的碳數20以下的烷基為較佳,碳數8以下的烷基為更佳。Alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group as R 41 , R 42 and R 43 An alkyl group having 20 or less carbon atoms is preferred, and an alkyl group having 8 or less carbon atoms is more preferred.
作為烷氧羰基中所包含之烷基,與上述R41 、R42 及R43 中的烷基相同之基團為較佳。The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R 41 , R 42 and R 43 described above.
作為環烷基,可以為單環,亦可以為多環,環丙基、環戊基及環己基等碳數3~8的單環的環烷基為較佳。The cycloalkyl group may be monocyclic or polycyclic, and a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl is preferable.
作為鹵素原子,氟原子為較佳。As the halogen atom, a fluorine atom is preferable.
R42 可以與後述之Ar4 所具有之取代基或L4 鍵結而形成環。R 42 may be bonded to a substituent of Ar 4 described later or L 4 to form a ring.
X4 表示單鍵、-COO-或-CONR44 -。 R44 表示氫原子或烷基。 作為上述烷基,與R41 ~R43 的烷基相同之烷基為較佳。 作為X4 ,單鍵、-COO-或-CONH-為較佳,單鍵或-COO-為更佳,單鍵為進一步較佳。X 4 represents a single bond, -COO- or -CONR 44 -. R 44 represents a hydrogen atom or an alkyl group. As the above-mentioned alkyl group, the same ones as those of R 41 to R 43 are preferred. As X 4 , a single bond, -COO- or -CONH- is preferable, a single bond or -COO- is more preferable, and a single bond is still more preferable.
L4 表示單鍵或2價的連結基。 作為2價的連結基,例如,可以舉出醚基、羰基、酯基、硫醚基、-SO2 -、-NR-(R表示氫原子或烷基)、2價的烴基(例如,伸烷基、伸烯基(例:-CH=CH-)、伸炔基(例:-C≡C-)及伸芳基)或將該等組合之基團。 其中,作為2價的連結基,伸烷基為較佳,作為伸烷基,亞甲基、伸乙基、伸丙基、伸丁基、伸己基及伸辛基等的碳數1~8的伸烷基為更佳。 又,當L4 與R42 鍵結而形成環時,L4 表示3價的連結基。在該情況下,在作為L4 的2價的連結基而上述之基團中之能夠進一步具有取代基之基團中,其取代基與R42 相互鍵結而形成單鍵或2價的連結基(例如,上述基團)為較佳,形成單鍵或伸烷基(亞甲基、伸乙基、伸丙基、伸丁基、伸己基及伸辛基等的碳數1~8的伸烷基為較佳)為更佳。 R42 與L4 鍵結時所形成之環為5或6員環為較佳。 其中,L4 為單鍵為較佳。L 4 represents a single bond or a divalent linking group. As a divalent linking group, for example, an ether group, a carbonyl group, an ester group, a thioether group, -SO 2 -, -NR- (R represents a hydrogen atom or an alkyl group), a divalent hydrocarbon group (for example, a Alkyl, alkenylene (eg -CH=CH-), alkynylene (eg -C≡C-) and arylylene) or a combination thereof. Among them, as a divalent linking group, an alkylene group is preferable, and as an alkylene group, a methylene group, an ethylene group, a propylidene group, a butylene group, a hexylene group, and an octylene group have 1 to 8 carbon atoms. The alkylene group is more preferable. Also, when L 4 and R 42 are bonded to form a ring, L 4 represents a trivalent linking group. In this case, among the above-mentioned groups that may further have a substituent as the divalent linking group of L 4 , the substituent and R 42 are bonded to each other to form a single bond or a divalent bond Groups (for example, the above-mentioned groups) are preferred, and form a single bond or an alkylene group (methylene, ethylidene, propylidene, butylene, hexylene, and octyl, etc., with 1 to 8 carbon atoms. alkylene is preferred) is more preferred. The ring formed when R 42 and L 4 are bonded is preferably a 5- or 6-membered ring. Among them, L 4 is preferably a single bond.
Ar4 表示(n+1)價的芳香環基。又,Ar4 除了Y以外,亦可以具有取代基,除了Y以外的取代基不是極性基為較佳。又,當Ar4 所具有之取代基與R42 鍵結而形成環時,Ar4 表示(n+2)價的芳香環基。 作為Ar4 的芳香環基,同樣地例示出上述的芳香環基。 其中,Ar4 為碳數6~18的芳香族烴環基為較佳,苯環基為更佳。 關於Ar4 所具有之取代基與R42 鍵結而形成者,形成單鍵或2價的連結基(例如,上述基團)為較佳,形成單鍵或伸烷基(亞甲基、伸乙基、伸丙基、伸丁基、伸己基及伸辛基等碳數1~8的伸烷基為較佳)為更佳。Ar 4 represents a (n+1)-valent aromatic ring group. In addition, Ar 4 may have a substituent other than Y, and it is preferable that the substituent other than Y is not a polar group. Also, when a substituent of Ar 4 is bonded to R 42 to form a ring, Ar 4 represents an aromatic ring group having a valence of (n+2). As the aromatic ring group of Ar 4 , the above-mentioned aromatic ring groups are similarly exemplified. Among them, Ar 4 is preferably an aromatic hydrocarbon ring group with 6 to 18 carbon atoms, and more preferably a benzene ring group. As for the substituents of Ar 4 that are bonded to R 42 , it is preferable to form a single bond or a divalent linking group (for example, the above-mentioned groups), and to form a single bond or an alkene group (methylene, alkene group) An alkylene group having 1 to 8 carbon atoms such as an ethyl group, a propylidene group, a butylene group, a hexylene group, and an octylene group is more preferable).
Y表示極性基。 作為極性基,同樣地例示出上述極性基。其中,作為極性基,羥基為較佳。 又,當Ar4 為具有苯環基部分之芳香族雜環基時,Y與芳香族雜環基中所包含之苯環基部分進行鍵結為較佳。Y represents a polar group. As the polar group, the above-mentioned polar groups are also exemplified in the same manner. Among them, a hydroxyl group is preferable as a polar group. Also, when Ar 4 is an aromatic heterocyclic group having a benzene ring group, it is preferable that Y is bonded to the benzene ring group included in the aromatic hetero ring group.
n表示1~4的整數。n represents an integer of 1-4.
作為上述烷基、環烷基、烷氧羰基、伸烷基、芳香環基及芳香族烴環基等能夠具有之取代基的例子,可以舉出上述的取代基T。又,關於上述烷基、環烷基、烷氧羰基、伸烷基、芳香環基及芳香族烴環基等進行說明之碳數中不包含取代基所具有之碳原子的數。Examples of substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, aromatic ring group, and aromatic hydrocarbon ring group may have include the above-mentioned substituent T. In addition, the number of carbon atoms in the substituent is not included in the carbon numbers described for the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, aromatic ring group, and aromatic hydrocarbon ring group.
具有酚性極性基之重複單元的含量相對於樹脂B的所有重複單元為20~74莫耳%為較佳,30~64為更佳,45~64莫耳%為進一步較佳。 具有酚性極性基之重複單元可以僅使用1種,亦可以使用2種以上,當使用2種以上時,該等的合計含量在上述範圍內為較佳。The content of the repeating unit having a phenolic polar group is preferably 20 to 74 mol%, more preferably 30 to 64, and still more preferably 45 to 64 mol%, based on all the repeating units of resin B. The repeating unit having a phenolic polar group may be used only by 1 type, or may use 2 or more types, and when using 2 or more types, it is preferable that the total content of these is within the said range.
(具有酸分解性基之重複單元) 樹脂B包含具有酸分解性基之重複單元。 酸分解性基係指,具有極性基被藉由酸的作用而脫離之保護基保護之結構之基團。 保護基係指,藉由酸的作用而脫離之基團。上述保護基為與極性基所具有之氫原子取代而形成酸分解性基為較佳。 樹脂B係一種如下樹脂:由於樹脂B包含具有該種酸分解性基之重複單元,典型而言,樹脂B為鹼不溶性或難溶性的樹脂,並且藉由酸的作用而脫離保護基,從而對鹼的可溶性增大。又,同樣地,典型而言,樹脂B為對有機溶劑為可溶性的樹脂,並且藉由酸的作用而脫離保護基,從而對有機溶劑的可溶性降低。(repeating unit with acid decomposable group) Resin B contains repeating units having acid decomposable groups. The acid-decomposable group refers to a group having a structure in which a polar group is protected by a protecting group detached by the action of an acid. A protecting group refers to a group detached by the action of an acid. It is preferable that the above-mentioned protecting group is an acid-decomposable group formed by substituting a hydrogen atom of a polar group. Resin B is a kind of resin as follows: Since resin B contains repeating units having such acid-decomposable groups, typically, resin B is an alkali-insoluble or poorly soluble resin, and is detached from the protecting group by the action of acid, thereby protecting the Alkali solubility increases. Also, similarly, resin B is typically a resin soluble in organic solvents, and the protecting group is detached by the action of an acid, thereby reducing the solubility in organic solvents.
作為被保護基保護之極性基,鹼可溶性基為較佳,例如,可以舉出羧基、酚性羥基、氟化醇基、磺酸基、磺醯胺基、磺醯亞胺基、(烷基磺醯基)(烷基羰基)亞甲基、(烷基磺醯基)(烷基羰基)醯亞胺基、雙(烷基羰基)亞甲基、雙(烷基羰基)醯亞胺基、雙(烷基磺醯基)亞甲基、雙(烷基磺醯基)醯亞胺基、三(烷基羰基)亞甲基及三(烷基磺醯基)亞甲基等酸性基、以及醇性羥基等。 其中,作為被保護基保護之極性基,羧基、酚性羥基、氟化醇基(較佳為六氟異丙醇基)或磺酸基為較佳,羧基或酚性羥基為更佳,羧基為進一步較佳。As the polar group protected by a protecting group, an alkali-soluble group is preferred, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, an (alkyl group) Sulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide , bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene and other acidic groups , and alcoholic hydroxyl groups. Among them, as the polar group protected by the protecting group, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group (preferably hexafluoroisopropanol group) or sulfonic acid group is preferred, carboxyl group or phenolic hydroxyl group is more preferred, carboxyl group for further improvement.
作為上述保護基,例如,可以舉出式(Y1)~(Y4)所表示之基團。 式(Y1):-C(Rx1 )(Rx2 )(Rx3 ) 式(Y2):-C(=O)OC(Rx1 )(Rx2 )(Rx3 ) 式(Y3):-C(R36 )(R37 )(OR38 ) 式(Y4):-C(Rn)(H)(Ar)As said protecting group, the group represented by formula (Y1)-(Y4) is mentioned, for example. Formula (Y1): -C(Rx 1 )(Rx 2 )(Rx 3 ) Formula (Y2): -C(=O)OC(Rx 1 )(Rx 2 )(Rx 3 ) Formula (Y3): -C (R 36 )(R 37 )(OR 38 ) Formula (Y4): -C(Rn)(H)(Ar)
式(Y1)及式(Y2)中,Rx1 ~Rx3 分別獨立地表示烷基(直鏈狀或支鏈狀)、環烷基(單環或多環)、芳基、芳烷基或烯基。此外,當Rx1 ~Rx3 的全部為烷基(直鏈狀或支鏈狀)時,Rx1 ~Rx3 中的至少2個為甲基為較佳。 其中,Rx1 ~Rx3 分別獨立地表示直鏈狀或支鏈狀的烷基為較佳,Rx1 ~Rx3 分別獨立地表示直鏈狀的烷基為更佳。 Rx1 ~Rx3 中的2個可以鍵結而形成單環或多環。 作為Rx1 ~Rx3 的烷基,甲基、乙基、正丙基、異丙基、正丁基、異丁基或第三丁基等碳數1~4的烷基為較佳。 作為Rx1 ~Rx3 的環烷基,環戊基或環己基等單環的環烷基、或降莰基、四環癸烷基、四環十二烷基、或金剛烷基等多環的環烷基為較佳。 Rx1 ~Rx3 的芳基為碳數6~10的芳基為較佳,例如,可以舉出苯基、萘基及蒽基等。 Rx1 ~Rx3 的芳烷基為碳數7~12的芳烷基為較佳,例如,可以舉出苄基、苯乙基及萘基甲基等。 Rx1 ~Rx3 的烯基為碳數2~8的烯基為較佳,例如,可以舉出乙烯基、烯丙基、丁烯基及環己烯基等。 作為Rx1 ~Rx3 中的2個鍵結而形成之環烷基,環戊基或環己基等單環的環烷基、或降莰基、四環癸烷基、四環十二烷基、或金剛烷基等多環的環烷基為較佳,碳數5~6的單環的環烷基為更佳。 關於Rx1 ~Rx3 中的2個鍵結而形成之環烷基,例如,構成環之亞甲基的1個可以被氧原子等雜原子或羰基等具有雜原子之基團取代。 關於式(Y1)或式(Y2)所表示之基團,例如,Rx1 為甲基或乙基,且Rx2 與Rx3 鍵結而形成上述的環烷基之態樣亦較佳。In formula (Y1) and formula (Y2), Rx 1 to Rx 3 independently represent alkyl (straight chain or branched chain), cycloalkyl (monocyclic or polycyclic), aryl, aralkyl or Alkenyl. Furthermore, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Among them, it is preferable that Rx 1 to Rx 3 each independently represent a linear or branched alkyl group, and it is more preferable that each of Rx 1 to Rx 3 independently represent a linear alkyl group. Two of Rx 1 to Rx 3 may be bonded to form a monocyclic or polycyclic ring. As the alkyl group for Rx 1 to Rx 3 , an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or tert-butyl group is preferable. As the cycloalkyl group of Rx 1 to Rx 3 , a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic group such as norbornyl, tetracyclodecanyl, tetracyclododecyl, or adamantyl Cycloalkyl groups are preferred. The aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, for example, phenyl, naphthyl, anthracenyl, and the like. The aralkyl group of Rx 1 to Rx 3 is preferably an aralkyl group having 7 to 12 carbon atoms, for example, benzyl group, phenethyl group, naphthylmethyl group and the like. The alkenyl group of Rx 1 to Rx 3 is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, butenyl, and cyclohexenyl. Cycloalkyl group formed as two bonds among Rx 1 to Rx 3 , monocyclic cycloalkyl group such as cyclopentyl group or cyclohexyl group, or norbornyl group, tetracyclodecanyl group, tetracyclododecyl group , or a polycyclic cycloalkyl group such as adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. Regarding the cycloalkyl group formed by bonding two of Rx 1 to Rx 3 , for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. Regarding the group represented by formula (Y1) or formula (Y2), for example, Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the aforementioned cycloalkyl group is also preferable.
式(Y3)中,R36 ~R38 分別獨立地表示氫原子或1價的有機基團。R37 與R38 可以相互鍵結而形成環。作為1價的有機基團,可以舉出上述式(Y1)所表示之基團、式(Y1)所表示之基團以外的烷基(可以為直鏈狀,亦可以為支鏈狀,亦可以具有環狀結構。例如,碳數1~10,甲基、乙基、正丙基、異丙基、正丁基、異丁基及1-金剛烷基等)、芳基、芳烷基及烯基等。R36 為氫原子亦較佳。 作為上述芳基、芳烷基及烯基,例如,同樣地可以舉出作為上述Rx1 ~Rx3 中的芳基、芳烷基及烯基而舉出之基團。 又,R38 可以與重複單元中的除了式(Y3)所表示之基團以外的其他基團相互鍵結。例如,R38 可以與重複單元中的主鏈所具有之基團鍵結。當R38 與重複單元中的其他基團相互鍵結時,R38 與其他基團形成單鍵或2價的連結基(伸烷基等)為較佳。又,當R38 與重複單元中的其他基團相互鍵結時,上述重複單元形成包含式(Y3)所表示之基團之環。In formula (Y3), R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group. R 37 and R 38 may be bonded to each other to form a ring. Examples of monovalent organic groups include groups represented by the above-mentioned formula (Y1) and alkyl groups other than groups represented by the formula (Y1) (which may be linear or branched or Can have a ring structure. For example, carbon number 1-10, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and 1-adamantyl, etc.), aryl, aralkyl and alkenyl etc. R 36 is also preferably a hydrogen atom. Examples of the above-mentioned aryl group, aralkyl group and alkenyl group include, for example, the groups mentioned as the aryl group, aralkyl group and alkenyl group in the above-mentioned Rx 1 to Rx 3 in the same manner. In addition, R 38 may be mutually bonded to a group other than the group represented by the formula (Y3) in the repeating unit. For example, R 38 may be bonded to a group included in the main chain of the repeating unit. When R 38 is bonded to other groups in the repeating unit, it is preferred that R 38 and other groups form a single bond or a divalent linking group (alkylene group, etc.). Also, when R 38 is bonded to other groups in the repeating unit, the repeating unit forms a ring including the group represented by formula (Y3).
作為式(Y3),下述式(Y3-1)所表示之基團亦較佳。As formula (Y3), a group represented by the following formula (Y3-1) is also preferable.
[化2] [Chem 2]
其中,L1 及L2 分別獨立地表示氫原子、烷基、環烷基、芳基或將該等組合之基團(例如,將烷基與芳基組合之基團)。 M表示單鍵或2價的連結基。 Q表示可以具有雜原子之烷基、可以具有雜原子之環烷基、可以具有雜原子之芳基、胺基、銨基、巰基、氰基、醛基或將該等組合之基團(例如,將烷基與環烷基組合之基團)。 烷基及環烷基中,例如,亞甲基中的1個可以被氧原子等雜原子、或羰基等具有雜原子之基團取代。 此外,L1 及L2 中的一方為氫原子,另一方為烷基、環烷基、芳基、或將伸烷基與芳基組合之基團為較佳。 Q、M、及L1 中的至少2個可以鍵結而形成環(較佳為、5員環或6員環)。 從圖案的微細化之觀點考慮,L2 為二級或三級烷基為較佳,三級烷基為更佳。作為二級烷基,可以舉出異丙基、環己基或降莰基,作為三級烷基,可以舉出第三丁基或金剛烷基。在該等態樣中,Tg(玻璃轉移溫度)和/或活化能變高,因此能夠確保膜強度,並且能夠抑制模糊。Wherein, L 1 and L 2 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may have a heteroatom, a cycloalkyl group that may have a heteroatom, an aryl group that may have a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group that combines these (such as , a combination of an alkyl group and a cycloalkyl group). Among the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be substituted with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. In addition, it is preferable that one of L 1 and L 2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M, and L may be bonded to form a ring (preferably, a 5-membered ring or a 6-membered ring). From the viewpoint of pattern miniaturization, L 2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl, cyclohexyl, and norbornyl, and examples of the tertiary alkyl group include tert-butyl or adamantyl. In these aspects, Tg (glass transition temperature) and/or activation energy become high, so film strength can be ensured, and fogging can be suppressed.
式(Y4)中,Ar表示芳香環基。Rn表示烷基、環烷基或芳基。Rn與Ar可以相互鍵結而形成非芳香族環。Ar更佳為芳基。 作為上述烷基、環烷基及芳基,例如,同樣地可以舉出作為上述Rx1 ~Rx3 中的烷基、環烷基及芳基而舉出之基團。In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group. As the above-mentioned alkyl group, cycloalkyl group and aryl group, for example, the groups mentioned as the alkyl group, cycloalkyl group and aryl group in the above-mentioned Rx 1 to Rx 3 are similarly exemplified.
・通式(A02) 具有酸分解性基之重複單元可以為通式(A02)所表示之重複單元。・General formula (A02) The repeating unit having an acid-decomposable group may be a repeating unit represented by general formula (A02).
[化3] [Chem 3]
通式(A02)中, Xa1 表示氫原子或可以具有取代基之烷基。 T表示單鍵或2價的連結基。 Rx1 ~Rx3 分別獨立地表示烷基(直鏈狀或支鏈狀)或環烷基(單環或多環)。其中,當Rx1 ~Rx3 的全部為烷基(直鏈狀或支鏈狀)時,Rx1 ~Rx3 中的至少2個為甲基為較佳。 Rx1 ~Rx3 中的2個可以鍵結而形成環烷基(單環或多環)。In the general formula (A02), Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Among them, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Two of Rx 1 to Rx 3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).
作為由Xa1 表示之可以具有取代基之烷基,例如,可以舉出甲基或-CH2 -R11 所表示之基團。R11 表示鹵素原子(氟原子等)、羥基或1價的有機基團,例如,可以舉出碳數5以下的烷基及碳數5以下的醯基,碳數3以下的烷基為較佳,甲基為更佳。作為Xa1 ,氫原子、甲基、三氟甲基或羥基甲基為較佳。Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group or a group represented by -CH 2 -R 11 . R 11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, and an alkyl group having 3 or less carbon atoms is preferred. Preferably, methyl is more preferred. As Xa 1 , a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group is preferable.
作為T的2價的連結基,可以舉出伸烷基、芳香環基、-COO-Rt-基及-O-Rt-基等。式中,Rt表示伸烷基或伸環烷基。 T為單鍵或-COO-Rt-基為較佳。當T表示-COO-Rt-基時,Rt為碳數1~5的伸烷基為較佳,-CH2 -基、-(CH2 )2 -基或-(CH2 )3 -基為更佳。Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene or cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents the -COO-Rt- group, Rt is preferably an alkylene group with 1 to 5 carbons, and the -CH 2 - group, -(CH 2 ) 2 - group or -(CH 2 ) 3 - group is better.
作為Rx1 ~Rx3 的烷基,甲基、乙基、正丙基、異丙基、正丁基、異丁基或第三丁基等碳數1~4的烷基為較佳。 作為Rx1 ~Rx3 的環烷基,環戊基及環己基等單環的環烷基、或降莰基、四環癸烷基、四環十二烷基及金剛烷基等多環的環烷基為較佳。 作為Rx1 ~Rx3 中的2個鍵結而形成之環烷基,環戊基及環己基等單環的環烷基為較佳,除此之外,降莰基、四環癸烷基、四環十二烷基及金剛烷基等多環的環烷基為較佳。其中,碳數5~6的單環的環烷基為較佳。 Rx1 ~Rx3 中的2個鍵結而形成之環烷基,例如,構成環之亞甲基的1個可以被氧原子等雜原子或羰基等具有雜原子之基團取代。 通式(AI)所表示之重複單元中,例如,Rx1 為甲基或乙基,Rx2 與Rx3 鍵結而形成上述的環烷基之態樣為較佳。As the alkyl group for Rx 1 to Rx 3 , an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or tert-butyl group is preferable. Cycloalkyl groups for Rx 1 to Rx 3 , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic ones such as norbornyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl Cycloalkyl is preferred. As the cycloalkyl group formed by bonding two of Rx 1 to Rx 3 , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl are preferred, and in addition, norbornyl, tetracyclodecanyl Polycyclic cycloalkyl groups such as tetracyclododecyl group and adamantyl group are preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. In the cycloalkyl group formed by bonding two of Rx 1 to Rx 3 , for example, one of the methylene groups constituting the ring may be substituted by a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group. Among the repeating units represented by the general formula (AI), for example, Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the aforementioned cycloalkyl group, which is preferable.
當上述各基團具有取代基時,作為取代基,例如,可以舉出烷基(碳數1~4)、鹵素原子、羥基、烷氧基(碳數1~4)、羧基及烷氧羰基(碳數2~6)等。取代基中的碳數為8以下為較佳。When each of the above groups has a substituent, examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (carbon number 2-6), etc. The carbon number in the substituent is preferably 8 or less.
具有酸分解性基之重複單元的含量相對於樹脂B的所有重複單元為10~80莫耳%為較佳,15~60莫耳%為更佳,20~45莫耳%為進一步較佳。 具有酸分解性基之重複單元可以僅使用1種,亦可以使用2種以上,當使用2種以上時,該等的合計含量在上述範圍內為較佳。The content of the repeating unit having an acid-decomposable group is preferably 10 to 80 mol%, more preferably 15 to 60 mol%, and still more preferably 20 to 45 mol%, based on all the repeating units of resin B. The repeating unit having an acid-decomposable group may be used alone or in two or more kinds. When two or more kinds are used, the total content thereof is preferably within the above-mentioned range.
(通式(VW)所表示之重複單元) 樹脂B具有通式(VW)所表示之重複單元亦較佳。(repeating unit represented by general formula (VW)) It is also preferable that the resin B has a repeating unit represented by the general formula (VW).
[化4] [chemical 4]
通式(VW)中,Rv表示氫原子、烷基或-CH2 -O-Rv2。Rv2表示氫原子、烷基或醯基。 Rv為氫原子、甲基、羥基甲基或三氟甲基為較佳,氫原子或甲基為更佳。In the general formula (VW), Rv represents a hydrogen atom, an alkyl group or -CH 2 -O-Rv2. Rv2 represents a hydrogen atom, an alkyl group or an acyl group. Rv is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.
Rw表示具有脂環基之烴基。關於Rw,Rw可以為脂環基其本身,Rw可以為在局部包含脂環基之基團。 上述烴基可以具有取代基,作為可以具有之取代基,極性基(作為更具體的例子,目前為止作為極性基而例示之基團)以外的基團為較佳。 Rw所具有之脂環基可以為單環(單環式烴環基),亦可以為多環(多環式烴環基)。Rw represents a hydrocarbon group having an alicyclic group. Regarding Rw, Rw may be an alicyclic group itself, and Rw may be a group partially containing an alicyclic group. The above-mentioned hydrocarbon group may have a substituent, and the optional substituent is preferably a group other than a polar group (as a more specific example, a group exemplified so far as a polar group). The alicyclic group that Rw has may be monocyclic (monocyclic hydrocarbon ring group) or polycyclic (polycyclic hydrocarbon ring group).
作為單環式烴環基,單環的脂環基為較佳,環戊烷環基或環己烷環基為更佳。 多環式烴環基中包含環集合烴環基及交聯環式烴環基。 作為上述環集合烴環基,例如,可以舉出雙環己烷環基及全氫萘環基。 作為上述交聯環式烴環基,例如,可以舉出蒎烷環基、莰烷(bornane)環基、降蒎烷環基、降莰烷環基及雙環辛烷環基(雙環[2.2.2]辛烷環基、雙環[3.2.1]辛烷環基等)等2環式烴環基;高不雷烷(homobledane)環基、金剛烷環基、三環[5.2.1.02,6 ]癸烷環基及三環[4.3.1.12,5 ]十一烷環基等3環式烴環基;以及四環[4.4.0.12,5 .17,10 ]十二烷環基及全氫-1,4-亞甲基-5,8-亞甲基萘環基等4環式烴環基等。又,交聯環式烴環基中還包含縮合環式烴環基(例如,全氫萘(十氫萘)環基、全氫蒽環基、全氫菲環基、全氫苊環基、全氫茀環基、全氫茚環基及全氫萉環基等複數個5~8員環烷環基稠合之縮合環基)。As the monocyclic hydrocarbon ring group, a monocyclic alicyclic group is preferable, and a cyclopentane ring group or a cyclohexane ring group is more preferable. The polycyclic hydrocarbon ring group includes a ring-assembled hydrocarbon ring group and a cross-linked ring hydrocarbon ring group. Examples of the ring-aggregating hydrocarbon ring group include a bicyclohexane ring group and a perhydronaphthalene ring group. As the above-mentioned crosslinked cyclic hydrocarbon ring group, for example, pinane ring group, bornane (bornane) ring group, norpinane ring group, norbornane ring group and bicyclooctane ring group (bicyclo[2.2. 2] octane ring group, bicyclo [3.2.1] octane ring group, etc.) and other 2-ring hydrocarbon ring groups; homobledane (homobledane) ring group, adamantane ring group, tricyclic [5.2.1.0 2, 6 ] decane ring group and tricyclic [4.3.1.1 2,5 ] undecane ring group and other 3-ring hydrocarbon ring groups; and tetracyclo [4.4.0.1 2,5 .1 7,10 ] dodecane ring 4-ring hydrocarbon ring groups such as perhydro-1,4-methylene-5,8-methylenenaphthalene ring groups, etc. Also, the crosslinked cyclic hydrocarbon ring group also includes condensed ring hydrocarbon ring group (for example, perhydronaphthalene (decalin) ring group, perhydroanthracyclyl, perhydrophenanthrene ring group, perhydroacenaphthyl ring group, A condensed ring group in which multiple 5- to 8-membered cycloalkane ring groups such as perhydroindenyl ring group, perhydroindene ring group, and perhydroindene ring group are condensed).
作為交聯環式烴環基,降莰烷環基、金剛烷環基、雙環辛烷環基或三環[5、2、1、02,6 ]癸烷環基為較佳,降莰烷環基或金剛烷環基為更佳。As a cross-linked cyclic hydrocarbon ring group, norbornane ring group, adamantane ring group, bicyclooctane ring group or tricyclic [5, 2, 1, 0 2,6 ] decane ring group is preferred, norbornane ring group Alkyl ring group or adamantyl ring group is more preferable.
作為該等脂環基可以具有之取代基,例如,鹵素原子或烷基為較佳。As the substituent which these alicyclic groups may have, for example, a halogen atom or an alkyl group is preferable.
此外,通式(VW)所表示之重複單元不具有酸分解性基。亦即,例如,Rw不表示如上所述之藉由酸的作用而脫離之保護基(例如,式(Y1)所表示之基團)。In addition, the repeating unit represented by the general formula (VW) does not have an acid decomposable group. That is, for example, Rw does not represent a protecting group detached by the action of an acid as described above (for example, a group represented by formula (Y1)).
以下,例示出通式(VW)所表示之重複單元。 式中,Ra表示H、CH3 、CH2 OH或CF3 。Hereinafter, the repeating unit represented by general formula (VW) is illustrated. In the formula, Ra represents H, CH 3 , CH 2 OH or CF 3 .
[化5] [chemical 5]
當樹脂B具有通式(VW)所表示之重複單元時,其含量相對於樹脂B的所有重複單元為1~40莫耳%為較佳,3~25莫耳%為更佳,5~15莫耳%為進一步較佳。 通式(VW)所表示之重複單元可以僅使用1種,亦可以使用2種以上,當使用2種以上時,該等的合計含量在上述範圍內為較佳。When resin B has a repeating unit represented by the general formula (VW), its content relative to all repeating units of resin B is preferably 1-40 mol%, 3-25 mol% is more preferable, 5-15 Mole% is further preferred. The repeating unit represented by the general formula (VW) may be used alone or in two or more kinds. When two or more kinds are used, the total content thereof is preferably within the above-mentioned range.
樹脂B可以具有上述重複單元以外的重複單元。作為這種重複單元,例如,可以舉出在通式(P01)所表示之重複單元中,諸如n為0的重複單元(基於(甲基)丙烯酸芐酯之重複單元等)。Resin B may have repeating units other than the above-mentioned repeating units. As such a repeating unit, for example, among the repeating units represented by the general formula (P01), such as repeating units in which n is 0 (benzyl (meth)acrylate-based repeating units, etc.).
樹脂B的所有重複單元中,具有苯環基之重複單元的含量為80莫耳%以下為較佳,小於65莫耳%為更佳,60莫耳%以下為進一步較佳。下限並沒有特別限制,例如,20莫耳%以上為較佳,30莫耳%以上為更佳,45莫耳%以上為進一步較佳。 此外,當樹脂B的具有酚性極性基之重複單元的芳香環基為苯環基時,該具有酚性極性基之重複單元相當於具有苯環基之重複單元。Among all the repeating units of resin B, the content of the repeating unit having a phenyl ring group is preferably 80 mol % or less, more preferably less than 65 mol %, and even more preferably 60 mol % or less. The lower limit is not particularly limited. For example, 20 mol% or more is preferable, 30 mol% or more is more preferable, and 45 mol% or more is still more preferable. In addition, when the aromatic ring group of the repeating unit having a phenolic polar group in the resin B is a benzene ring group, the repeating unit having a phenolic polar group corresponds to a repeating unit having a benzene ring group.
樹脂B能夠按照常規方法(例如,利用自由基聚合)進行合成。 作為基於GPC法之聚苯乙烯換算值,樹脂B的重量平均分子量為1,000~200,000為較佳,3,000~25,000為更佳,10,000~25,000為進一步較佳。藉由將樹脂B的重量平均分子量設為1,000~200,000,能夠防止耐熱性及耐乾蝕刻性的劣化,進而,能夠防止顯影性之劣化及因黏度變高而引起之製膜性之劣化。 樹脂B的分散度(分子量分佈)通常為1~5,1~3為較佳,1.2~3.0為更佳,1.2~2.0為進一步較佳。分散度越小者,解析度及光阻形狀越優異,進而,光阻圖案的側壁光滑,粗糙度優異。Resin B can be synthesized by a conventional method (for example, by radical polymerization). The weight average molecular weight of the resin B is preferably from 1,000 to 200,000, more preferably from 3,000 to 25,000, and still more preferably from 10,000 to 25,000 as a polystyrene conversion value based on the GPC method. By setting the weight average molecular weight of the resin B to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance and dry etching resistance, and further, deterioration of developability and deterioration of film forming properties due to increase in viscosity. The dispersion degree (molecular weight distribution) of resin B is 1-5 normally, Preferably it is 1-3, More preferably, it is 1.2-3.0, More preferably, it is 1.2-2.0. The smaller the degree of dispersion, the better the resolution and the shape of the photoresist, and the smoother the sidewall of the photoresist pattern, the better the roughness.
本發明的抗蝕劑組成物中,只要樹脂B的含量滿足上述質量比R2的規定,則並沒有限定,例如,相對於總固體成分為70~99.9質量%為較佳,80~99.0質量%為更佳,95~98.5質量%為進一步較佳。 又,樹脂B可以僅使用1種,亦可以使用2種以上,當使用2種以上時,該等的合計含量在上述範圍內為較佳。In the resist composition of the present invention, the content of the resin B is not limited as long as it satisfies the aforementioned mass ratio R2, for example, it is preferably 70 to 99.9% by mass, 80 to 99.0% by mass relative to the total solid content It is more preferable, and 95-98.5 mass % is still more preferable. Moreover, resin B may use only 1 type, and may use 2 or more types, When using 2 or more types, it is preferable that these total content exists in the said range.
<光酸產生劑> 本發明的抗蝕劑組成物進一步包含光酸產生劑。 光酸產生劑為藉由光化射線或放射線的照射而產生酸之化合物。 作為光酸產生劑,藉由光化射線或放射線的照射而產生有機酸之化合物為較佳。例如,可以舉出鋶鹽化合物、錪鹽化合物、重氮鹽化合物、鏻鹽化合物、醯亞胺磺酸鹽化合物、肟磺酸鹽化合物、重氮二碸化合物、二碸化合物及鄰硝基苄基磺酸鹽化合物。<Photoacid generator> The resist composition of the present invention further contains a photoacid generator. A photoacid generator is a compound that generates acid upon irradiation with actinic rays or radiation. As the photoacid generator, a compound that generates an organic acid by irradiation with actinic rays or radiation is preferable. For example, percite salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazonium disulfide compounds, disulfide compounds, and o-nitrobenzyl Sulfonate compounds.
作為光酸產生劑,能夠單獨使用藉由光化射線或放射線的照射而產生酸之公知的化合物,或作為該等的混合物而適當選擇使用。例如,能夠將美國專利申請公開2016/0070167A1號說明書的<0125>~<0319>段、美國專利申請公開2015/0004544A1號說明書的<0086>~<0094>段及美國專利申請公開2016/0237190A1號說明書的<0323>~<0402>段中所揭示之公知的化合物作為光酸產生劑(C)而較佳地使用。As the photoacid generator, a known compound that generates an acid upon irradiation with actinic rays or radiation can be used alone, or a mixture thereof can be appropriately selected and used. For example, paragraphs <0125> to <0319> of US Patent Application Publication 2016/0070167A1, paragraphs <0086> to <0094> of US Patent Application Publication 2015/0004544A1, and US Patent Application Publication 2016/0237190A1 Known compounds disclosed in paragraphs <0323> to <0402> of the specification are preferably used as the photoacid generator (C).
作為光酸產生劑,例如,下述通式(ZI)、通式(ZII)或通式(ZIII)所表示之化合物為較佳。As the photoacid generator, for example, a compound represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) is preferable.
[化6] [chemical 6]
上述通式(ZI)中, R201 、R202 及R203 分別獨立地表示有機基團。 作為R201 、R202 及R203 的有機基團的碳數為1~30為較佳,1~20為更佳。In the above general formula (ZI), R 201 , R 202 and R 203 each independently represent an organic group. The carbon number of the organic groups as R 201 , R 202 and R 203 is preferably 1-30, more preferably 1-20.
作為R201 、R202 及R203 的有機基團,可以分別獨立地舉出芳基(碳數6~15為較佳)、直鏈狀或支鏈狀的烷基(碳數1~10為較佳)及環烷基(碳數3~15為較佳)等。 此外,該等芳基、烷基及環烷基的較佳碳數中未計入該等基團所具有之取代基中所包含之碳原子的數。The organic groups of R 201 , R 202 and R 203 include independently aryl groups (preferably having 6 to 15 carbons), linear or branched alkyl groups (with 1 to 10 carbons being preferably) and cycloalkyl (preferably with 3 to 15 carbons), etc. In addition, the preferable carbon number of these aryl groups, alkyl groups and cycloalkyl groups does not include the number of carbon atoms included in the substituents these groups have.
又,R201 ~R203 中的2個可以鍵結而形成環結構,環內可以具有氧原子、硫原子、酯基、醯胺基或羰基。作為R201 ~R203 中的2個鍵結而形成之基團,可以舉出伸烷基(例如,伸丁基、伸戊基)及-CH2 -CH2 -O-CH2 -CH2 -等。 Z- 表示陰離子(非親核性陰離子為較佳。)。In addition, two of R 201 to R 203 may be bonded to form a ring structure, and the ring may have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of groups formed by bonding two of R 201 to R 203 include alkylene (for example, butylene, pentylene) and -CH 2 -CH 2 -O-CH 2 -CH 2 -Wait. Z - represents anion (non-nucleophilic anion is preferred.).
作為通式(ZI)中的陽離子的較佳態樣,可以舉出後述之化合物(ZI-1)、化合物(ZI-2)、化合物(ZI-3)及化合物(ZI-4)中的對應之基團。 此外,光酸產生劑可以為具有複數個通式(ZI)所表示之結構之化合物。例如,可以為具有通式(ZI)所表示之化合物的R201 ~R203 中的至少1個和通式(ZI)所表示之另一化合物的R201 ~R203 中的至少1個藉由單鍵或連結基而鍵結之結構之化合物。As a preferred aspect of the cation in the general formula (ZI), the corresponding ones in the compound (ZI-1), compound (ZI-2), compound (ZI-3) and compound (ZI-4) described later can be mentioned. group. In addition, the photoacid generator may be a compound having a plurality of structures represented by general formula (ZI). For example, at least one of R 201 to R 203 of the compound represented by general formula (ZI) and at least one of R 201 to R 203 of another compound represented by general formula (ZI) may be obtained by A compound with a structure linked by a single bond or a linking group.
首先,對化合物(ZI-1)進行說明。 化合物(ZI-1)為上述通式(ZI)的R201 ~R203 中的至少1個為芳基之芳基鋶化合物,亦即,將芳基鋶設為陽離子之化合物。 關於芳基鋶化合物,R201 ~R203 的全部可以為芳基,亦可以為R201 ~R203 的一部分為芳基,而剩餘部分為烷基或環烷基。 作為芳基鋶化合物,例如,可以舉出三芳基鋶化合物、二芳基烷基鋶化合物、芳基二烷基鋶化合物、二芳基環烷基鋶化合物及芳基二環烷基鋶化合物。First, compound (ZI-1) will be described. The compound (ZI-1) is an aryl permeicum compound in which at least one of R 201 to R 203 of the general formula (ZI) is an aryl group, that is, a compound in which aryl permeicium is used as a cation. Regarding the aryl permeicium compound, all of R 201 to R 203 may be aryl groups, or a part of R 201 to R 203 may be aryl groups, and the rest may be alkyl groups or cycloalkyl groups. Examples of the aryl permeium compounds include triaryl permedium compounds, diarylalkyl permeable compounds, aryl dialkyl permeable compounds, diarylcycloalkyl permeable compounds and aryl dicycloalkyl permeable compounds.
作為芳基鋶化合物中所包含之芳基,苯基或萘基為較佳,苯基為更佳。芳基可以為包含具有氧原子、氮原子或硫原子等之雜環結構之芳基。作為雜環結構,可以舉出吡咯殘基、呋喃殘基、噻吩殘基、吲哚殘基、苯并呋喃殘基及苯并噻吩殘基等。當芳基鋶化合物具有2個以上的芳基時,存在2個以上之芳基可以相同,亦可以不同。 芳基鋶化合物可以具有之烷基或環烷基為碳數1~15的直鏈狀烷基、碳數3~15的支鏈狀烷基、或碳數3~15的環烷基為較佳,例如,可以舉出甲基、乙基、丙基、正丁基、第二丁基、第三丁基、環丙基、環丁基及環己基等。As the aryl group contained in the aryl permeicium compound, phenyl or naphthyl is preferable, and phenyl is more preferable. The aryl group may be an aryl group including a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl permeate compound has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the aryl permeate compound can have is a linear alkyl group with 1 to 15 carbons, a branched chain alkyl group with 3 to 15 carbons, or a cycloalkyl group with 3 to 15 carbons. Preferable examples include methyl, ethyl, propyl, n-butyl, second-butyl, third-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.
R201 ~R203 的芳基、烷基及環烷基可以分別獨立地具有烷基(例如,碳數1~15)、環烷基(例如,碳數3~15)、芳基(例如,碳數6~14)、烷氧基(例如,碳數1~15)、鹵素原子、羥基或苯硫基作為取代基。The aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 may each independently have an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, carbon number 6-14), an alkoxy group (eg, carbon number 1-15), a halogen atom, a hydroxyl group or a phenylthio group as a substituent.
接著,對化合物(ZI-2)進行說明。 化合物(ZI-2)中,式(ZI)中的R201 ~R203 分別獨立地為表示不具有芳香環之有機基團之化合物。在此芳香環還包含包括雜原子之芳香族環。 作為R201 ~R203 的不具有芳香環之有機基團,碳數1~30為較佳,碳數1~20為更佳。 R201 ~R203 分別獨立地為烷基、環烷基、烯丙基或乙烯基為較佳,直鏈狀或支鏈狀的2-氧代烷基、2-氧代環烷基或烷氧羰基甲基為更佳,直鏈狀或支鏈狀的2-氧代烷基為進一步較佳。Next, compound (ZI-2) will be described. In the compound (ZI-2), R 201 to R 203 in the formula (ZI) are each independently a compound representing an organic group not having an aromatic ring. Aromatic rings here also include aromatic rings which include heteroatoms. The organic groups having no aromatic ring as R 201 to R 203 preferably have 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. R 201 to R 203 are independently alkyl, cycloalkyl, allyl or vinyl, preferably linear or branched 2-oxoalkyl, 2-oxocycloalkyl or alkane Oxycarbonylmethyl is more preferred, and linear or branched 2-oxoalkyl is still more preferred.
作為R201 ~R203 的烷基及環烷基,可以較佳地舉出碳數1~10的直鏈狀烷基或碳數3~10的支鏈狀烷基(例如,甲基、乙基、丙基、丁基及戊基)及碳數3~10的環烷基(例如,環戊基、環己基及降莰基)。 R201 ~R203 可以進一步被鹵素原子、烷氧基(例如,碳數1~5)、羥基、氰基或硝基取代。As the alkyl group and cycloalkyl group for R 201 to R 203 , preferably straight chain alkyl groups with 1 to 10 carbons or branched chain alkyl groups with 3 to 10 carbons (for example, methyl, ethyl, etc.) group, propyl group, butyl group and pentyl group) and cycloalkyl group with 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group and norbornyl group). R 201 to R 203 may be further substituted by a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.
接著,對化合物(ZI-3)進行說明。化合物(ZI-3)為通式(ZI-3)所表示之化合物。Next, compound (ZI-3) will be described. Compound (ZI-3) is a compound represented by general formula (ZI-3).
[化7] [chemical 7]
通式(ZI-3)中,R1 表示烷基、環烷基、芳基或苄基。當R1 具有環結構時,上述環結構可以具有氧原子、硫原子、酯基、醯胺基或碳-碳雙鍵。 R2 及R3 分別獨立地表示氫原子、烷基、環烷基、鹵素原子、氰基或芳基。 Rx 及Ry 分別獨立地表示烷基、環烷基、2-氧代烷基、烷氧羰基烷基、烯丙基或乙烯基。 此外,R2 與R3 可以相互鍵結而形成環。又,R1 與R2 可以相互鍵結而形成環,所形成之環具有碳-碳雙鍵亦較佳。又,Rx 與Ry 可以相互鍵結而形成環,所形成之環具有氧原子、硫原子、酯基、醯胺基或碳-碳雙鍵亦較佳。 Z- 表示陰離子。In the general formula (ZI-3), R 1 represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group. When R 1 has a ring structure, the above-mentioned ring structure may have an oxygen atom, a sulfur atom, an ester group, an amido group or a carbon-carbon double bond. R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group. In addition, R 2 and R 3 may be bonded to each other to form a ring. In addition, R 1 and R 2 may be bonded to each other to form a ring, and the formed ring preferably has a carbon-carbon double bond. In addition, R x and R y may be bonded to each other to form a ring, and the formed ring preferably has an oxygen atom, a sulfur atom, an ester group, an amido group or a carbon-carbon double bond. Z - represents anion.
通式(ZI-3)中,作為R1 所表示之烷基及環烷基,碳數1~15(較佳為碳數1~10)的直鏈狀烷基、碳數3~15(較佳為碳數3~10)的支鏈狀烷基或碳數3~15(較佳為碳數1~10)的環烷基為較佳,具體而言,可以舉出甲基、乙基、丙基、正丁基、第二丁基、第三丁基、環丙基、環丁基、環己基及降莰基等。 作為R1 所表示之芳基,苯基或萘基為較佳,苯基為更佳。芳基可以為包含具有氧原子或硫原子等之雜環結構之芳基。作為雜環結構,可以舉出呋喃環、噻吩環、苯并呋喃環及苯并噻吩環等。In the general formula (ZI-3), as the alkyl group and cycloalkyl group represented by R 1 , straight-chain alkyl groups having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), straight-chain alkyl groups having 3 to 15 carbon atoms ( Preferably a branched chain alkyl group with 3 to 10 carbons) or a cycloalkyl group with 3 to 15 carbons (preferably 1 to 10 carbons), specifically, methyl, ethyl Base, propyl, n-butyl, second butyl, third butyl, cyclopropyl, cyclobutyl, cyclohexyl and norbornyl, etc. As the aryl group represented by R1, phenyl or naphthyl is preferable, and phenyl is more preferable. The aryl group may be an aryl group including a heterocyclic structure having an oxygen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.
上述R1 進一步具有取代基(例如,取代基組群組群T)亦較佳。 此外,當R1 具有環結構時,上述環結構可以具有氧原子、硫原子、酯基、醯胺基或碳-碳雙鍵。It is also preferable that the above-mentioned R 1 further has a substituent (for example, substituent group T). In addition, when R 1 has a ring structure, the above-mentioned ring structure may have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbon-carbon double bond.
作為R2 及R3 所表示之烷基、環烷基及芳基,可以舉出與上述R1 相同者,其較佳態樣亦相同。又,R2 與R3 可以鍵結而形成環。 作為R2 及R3 所表示之鹵素原子,例如,可以舉出氟原子、氯原子、溴原子及碘原子。Examples of the alkyl group, cycloalkyl group and aryl group represented by R 2 and R 3 include the same ones as those described above for R 1 , and their preferred aspects are also the same. Also, R 2 and R 3 may be bonded to form a ring. Examples of the halogen atom represented by R 2 and R 3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
作為Rx 及Ry 所表示之烷基及環烷基,可以舉出與上述R1 相同者,其較佳態樣亦相同。 作為Rx 及Ry 所表示之2-氧代烷基,例如,可以舉出碳數1~15(較佳為碳數1~10)者,具體而言,可以舉出2-氧代丙基、及2-氧代丁基等。 作為Rx 及Ry 所表示之烷氧羰基烷基,例如,可以舉出碳數1~15(較佳為碳數1~10)者。又,Rx 與Ry 可以鍵結而形成環。 又,Rx 與Ry 可以相互鍵結而形成環,Rx 與Ry 相互鍵結而形成之環可以具有氧原子、硫原子、酯基、醯胺基或碳-碳雙鍵。 此外,所形成之環具有氧原子等係指,例如,能夠相互鍵結之2個基團(例如,Rx 與Ry )相互鍵結而形成伸烷基,且該種伸烷基中的亞甲基被氧原子等取代之形態等。 作為Rx 與Ry 相互鍵結而形成之環,3~10員環為較佳,4~8員環為更佳,5或6員環為進一步較佳。Examples of the alkyl and cycloalkyl groups represented by R x and R y include the same ones as those described above for R 1 , and their preferred embodiments are also the same. Examples of the 2-oxoalkyl group represented by R x and R y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), specifically, 2-oxopropane base, and 2-oxobutyl, etc. Examples of the alkoxycarbonylalkyl group represented by R x and R y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). In addition, R x and R y may be bonded to form a ring. In addition, R x and R y may be bonded to each other to form a ring, and the ring formed by R x and R y bonded to each other may have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbon-carbon double bond. In addition, the formed ring has an oxygen atom, etc. means, for example, two groups that can be bonded to each other (for example, R x and R y ) are bonded to each other to form an alkylene group, and the alkylene group in this A form in which a methylene group is substituted by an oxygen atom, etc. The ring formed by bonding R x and R y to each other is preferably a 3-10-membered ring, more preferably a 4-8-membered ring, and still more preferably a 5- or 6-membered ring.
通式(ZI-3)中,R1 與R2 可以鍵結而形成環結構,所形成之環結構可以具有碳-碳雙鍵。In the general formula (ZI-3), R 1 and R 2 may be bonded to form a ring structure, and the formed ring structure may have a carbon-carbon double bond.
關於上述化合物(ZI-3),其中,化合物(ZI-3A)為較佳。 化合物(ZI-3A)為下述通式(ZI-3A)所表示之化合物,並且為具有苯甲醯甲基鋶鹽結構之化合物。Among the above compounds (ZI-3), compound (ZI-3A) is preferred. The compound (ZI-3A) is a compound represented by the following general formula (ZI-3A), and is a compound having a benzoylmethyl percite salt structure.
[化8] [chemical 8]
通式(ZI-3A)中, R1c ~R5c 分別獨立地表示氫原子、烷基、環烷基、芳基、烷氧基、芳氧基、烷氧羰基、烷基羰氧基、環烷基羰氧基、鹵素原子、羥基、硝基、烷硫基或芳硫基。 作為R6c 及R7c ,與上述通式(ZI-3)中的R2 及R3 的含義相同,其較佳態樣亦相同。 作為Rx 及Ry ,與上述通式(ZI-3)中的Rx 及Ry 的含義相同,其較佳態樣亦相同。In the general formula (ZI-3A), R 1c to R 5c independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a ring An alkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group. R 6c and R 7c have the same meaning as R 2 and R 3 in the above general formula (ZI-3), and their preferred embodiments are also the same. R x and R y have the same meanings as R x and R y in the above general formula (ZI-3), and their preferred embodiments are also the same.
R1c ~R5c 中的任意2個以上、Rx 與Ry 可以分別鍵結而形成環,該環可以分別獨立地具有氧原子、硫原子、酯基、醯胺基或碳-碳雙鍵。又,R5c 與R6c 、R5c 與Rx 可以分別鍵結而形成環,該環分別獨立地具有碳-碳雙鍵亦較佳。又,R6c 與R7c 可以分別鍵結而形成環。 此外,所形成之環具有氧原子等係指,例如,能夠鍵結之2個基團(例如,Rx 與Ry )相互鍵結而形成伸烷基,且該種伸烷基中的亞甲基被氧原子等取代之形態。 又,作為上述環,可以舉出芳香族或非芳香族的烴環、芳香族或非芳香族的雜環及組合2個以上該等環而得之多環縮合環。作為環,3~10員環為較佳,4~8員環為更佳,5或6員環為進一步較佳。Any two or more of R 1c to R 5c , R x and R y may be bonded to form a ring, and the ring may independently have an oxygen atom, a sulfur atom, an ester group, an amido group, or a carbon-carbon double bond . In addition, R 5c and R 6c , and R 5c and R x may be bonded to form a ring, and it is also preferable that the rings each independently have a carbon-carbon double bond. Also, R 6c and R 7c may be bonded to each other to form a ring. In addition, the formed ring has an oxygen atom, etc. means, for example, two groups that can be bonded (for example, R x and R y ) are bonded to each other to form an alkylene group, and the alkylene group in such an alkylene group A form in which a methyl group is substituted by an oxygen atom, etc. In addition, examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring obtained by combining two or more of these rings. As the ring, a 3- to 10-membered ring is preferable, a 4- to 8-membered ring is more preferable, and a 5- or 6-membered ring is further preferable.
作為R1c ~R5c 中的任意2個以上、R6c 與R7c 、及Rx 與Ry 鍵結而形成之基團,可以舉出伸丁基、伸戊基及-CH2 -CH2 -O-CH2 -CH2 -等。 作為R5c 與R6c 及R5c 與Rx 鍵結而形成之基團,單鍵或伸烷基為較佳。作為伸烷基,可以舉出亞甲基及伸乙基等。 Zc- 表示陰離子。Examples of groups formed by bonding any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include butyl, pentylene, and -CH 2 -CH 2 -O- CH2 - CH2 -etc. As the group formed by bonding R 5c and R 6c and R 5c and R x , a single bond or an alkylene group is preferable. Examples of the alkylene group include a methylene group, an ethylene group, and the like. Zc - represents an anion.
接著,對化合物(ZI-4)進行說明。 化合物(ZI-4)為下述通式(ZI-4)所表示之化合物。Next, compound (ZI-4) will be described. Compound (ZI-4) is a compound represented by the following general formula (ZI-4).
[化9] [chemical 9]
通式(ZI-4)中, l表示0~2的整數。 r表示0~8的整數。 R13 表示氫原子、氟原子、羥基、烷基、烷氧基、烷氧羰基、或具有環烷基之基團(可以為環烷基其本身,亦可以為在局部包含環烷基之基團。環烷基部分可以為單環,亦可以為多環)。該等基團可以具有取代基。 R14 表示羥基、烷基、烷氧基、烷氧羰基、烷基羰基、烷基磺醯基、或具有環烷基之基團(可以為環烷基其本身,亦可以為在局部包含環烷基之基團。環烷基部分可以為單環,亦可以為多環。例如,環烷基磺醯基、或環烷氧基等)。該等基團可以具有取代基。當R14 存在複數個時,存在複數個之R14 可以分別相同,亦可以不同。 R15 分別獨立地表示烷基、環烷基或萘基。該等基團可以具有取代基。2個R15 可以相互鍵結而形成環。2個R15 相互鍵結而形成環時,可以在環骨架內包含氧原子或氮原子等雜原子。在一態樣中,2個R15 為伸烷基,相互鍵結而形成環結構為較佳。In general formula (ZI-4), l represents the integer of 0-2. r represents an integer of 0-8. R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (it may be a cycloalkyl group itself, or a group partially containing a cycloalkyl group) group. The cycloalkyl part can be monocyclic or polycyclic). These groups may have substituents. R 14 represents a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a group having a cycloalkyl group (it may be a cycloalkyl group itself, or it may be a group containing a ring in part. An alkyl group. The cycloalkyl part can be monocyclic or polycyclic. For example, cycloalkylsulfonyl, cycloalkoxy, etc.). These groups may have substituents. When there are plural R14s , the plural R14s may be the same or different. R 15 each independently represent an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have substituents. Two R 15 may be bonded to each other to form a ring. When two R 15 are bonded to each other to form a ring, a heteroatom such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. In one aspect, two R 15 are alkylene groups, and it is preferable to bond with each other to form a ring structure.
通式(ZI-4)中,R13 、R14 及R15 的烷基為直鏈狀或支鏈狀。烷基的碳數為1~10為較佳。作為烷基,甲基、乙基、正丁基或第三丁基等為更佳。In the general formula (ZI-4), the alkyl groups of R 13 , R 14 and R 15 are linear or branched. The carbon number of the alkyl group is preferably 1-10. As the alkyl group, methyl group, ethyl group, n-butyl group or t-butyl group are more preferable.
接著,對通式(ZII)及(ZIII)進行說明。 通式(ZII)及(ZIII)中,R204 ~R207 分別獨立地表示芳基、烷基或環烷基。 作為R204 ~R207 的芳基,苯基或萘基為較佳,苯基為更佳。R204 ~R207 的芳基可以為包含具有氧原子、氮原子或硫原子等之雜環結構之芳基。作為具有雜環結構之芳基的骨架,例如,可以舉出吡咯、呋喃、噻吩、吲哚、苯并呋喃及苯并噻吩等。 作為R204 ~R207 的烷基及環烷基,碳數1~10的直鏈狀烷基或碳數3~10的支鏈狀烷基(例如,甲基、乙基、丙基、丁基及戊基)、或碳數3~10的環烷基(例如,環戊基、環己基及降莰基)為較佳。Next, general formulas (ZII) and (ZIII) will be described. In general formulas (ZII) and (ZIII), R 204 to R 207 each independently represent an aryl group, an alkyl group or a cycloalkyl group. As the aryl group for R 204 to R 207 , phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl groups of R 204 to R 207 may be aryl groups including a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. As the alkyl group and cycloalkyl group of R 204 ~ R 207 , a straight chain alkyl group with 1 ~ 10 carbons or a branched chain alkyl group with 3 ~ 10 carbons (for example, methyl, ethyl, propyl, butyl, etc.) and pentyl), or cycloalkyl groups with 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl) are preferred.
R204 ~R207 的芳基、烷基、及環烷基可以分別獨立地具有取代基。作為R204 ~R207 的芳基、烷基、及環烷基可以具有之取代基,例如,可以舉出烷基(例如,碳數1~15)、環烷基(例如,碳數3~15)、芳基(例如,碳數6~15)、烷氧基(例如,碳數1~15)、鹵素原子、羥基及苯硫基等。 Z- 表示陰離子。The aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may each independently have a substituent. As substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have, for example, an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), 15), aryl group (eg, carbon number 6-15), alkoxy group (eg, carbon number 1-15), halogen atom, hydroxyl group and thiophenyl group, etc. Z - represents anion.
作為通式(ZI)中的Z- 、通式(ZII)中的Z- 、通式(ZI-3)中的Zc- 及通式(ZI-4)中的Z- ,下述通式(3)所表示之陰離子為較佳。As Z - in the general formula (ZI), Z - in the general formula (ZII), Zc - in the general formula (ZI-3) and Z - in the general formula (ZI - 4), the following general formula ( 3) The anions indicated are preferred.
[化10] [chemical 10]
通式(3)中, o表示1~3的整數。p表示0~10的整數。q表示0~10的整數。In general formula (3), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.
Xf表示氟原子或被至少1個氟原子取代之烷基。該烷基的碳數為1~10為較佳,1~4為更佳。又,作為被至少1個氟原子取代之烷基,全氟烷基為較佳。 Xf為氟原子或碳數1~4的全氟烷基為較佳,氟原子或CF3 為更佳。尤其,兩者的Xf為氟原子為進一步較佳。Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The carbon number of the alkyl group is preferably 1-10, more preferably 1-4. Also, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 . In particular, it is still more preferable that Xf of both is a fluorine atom.
R4 及R5 分別獨立地表示氫原子、氟原子、烷基或被至少1個氟原子取代之烷基。當R4 及R5 存在複數個時,R4 及R5 可以分別相同,亦可以不同。 R4 及R5 所表示之烷基可以具有取代基,碳數1~4為較佳。R4 及R5 較佳為氫原子。 被至少一個氟原子取代之烷基的具體例及較佳態樣與通式(3)中的Xf的具體例及較佳態樣相同。R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When R 4 and R 5 exist in plural, R 4 and R 5 may be the same or different. The alkyl groups represented by R 4 and R 5 may have substituents, preferably having 1 to 4 carbon atoms. R 4 and R 5 are preferably hydrogen atoms. Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in the general formula (3).
L表示2價的連結基。當L存在複數個時,L可以分別相同,亦可以不同。 作為2價的連結基,例如,可以舉出-COO-(-C(=O)-O-)、-OCO-、-CONH-、-NHCO-、-CO-、-O-、-S-、-SO-、-SO2 -、伸烷基(較佳為碳數1~6)、伸環烷基(較佳為碳數3~15)、伸烯基(較佳為碳數2~6)及將複數個該等組合而成之2價的連結基等。在該等中,-COO-、-OCO-、-CONH-、-NHCO-、-CO-、-O-、-SO2 -、-COO-伸烷基-、-OCO-伸烷基-、-CONH-伸烷基-或-NHCO-伸烷基-為較佳,-COO-、-OCO-、-CONH-、-SO2 -、-COO-伸烷基-或-OCO-伸烷基-為更佳。L represents a divalent linking group. When there are plural Ls, L may be respectively the same or different. Examples of divalent linking groups include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S- , -SO-, -SO 2 -, alkylene (preferably 1 to 6 carbons), cycloalkylene (preferably 3 to 15 carbons), alkenylene (preferably 2 to 15 carbons 6) and a divalent linking group formed by combining a plurality of them. Among them, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO 2 -, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene- or -NHCO-alkylene- is preferred, -COO-, -OCO-, -CONH-, -SO 2 -, -COO-alkylene- or -OCO-alkylene - for better.
W表示包含環狀結構之有機基團。在該等中,環狀的有機基團為較佳。 作為環狀的有機基團,例如,可以舉出脂環基、芳基及雜環基。 脂環基可以為單環式脂環基,亦可以為多環式脂環基。作為單環式的脂環基,例如,可以舉出環戊基、環己基及環辛基等單環的環烷基。作為多環式的脂環基,例如,可以舉出降莰基、三環癸烷基、四環癸烷基、四環十二烷基及金剛烷基等多環的環烷基。其中,降莰基、三環癸烷基、四環癸烷基、四環十二烷基、及金剛烷基等具有碳數7以上的大體積結構之脂環基為較佳。W represents an organic group including a ring structure. Among these, a cyclic organic group is preferable. As a cyclic organic group, an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example. The alicyclic group may be a monocyclic alicyclic group or a polycyclic alicyclic group. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl. Among them, norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, adamantyl and other alicyclic groups having a bulky structure with 7 or more carbon atoms are preferred.
芳基可以為單環式芳基,亦可以為多環式芳基。作為該芳基,例如,可以舉出苯基、萘基、菲基及蒽基。 雜環基可以為單環,亦可以為多環。多環能夠更加抑制酸的擴散。又,雜環基可以具有芳香族性,亦可以不具有芳香族性。作為具有芳香族性之雜環,例如,可以舉出呋喃環、噻吩環、苯并呋喃環、苯并噻吩環、二苯并呋喃環、二苯并噻吩環及吡啶環。作為不具有芳香族性之雜環,例如,可以舉出四氫吡喃環、內酯環、磺內酯環及十氫異喹啉環。作為雜環基中的雜環,呋喃環、噻吩環、吡啶環或十氫異喹啉環為特佳。The aryl group may be a monocyclic aryl group or a polycyclic aryl group. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl and anthracenyl. The heterocyclic group may be monocyclic or polycyclic. Polycyclic rings are more resistant to acid diffusion. Moreover, a heterocyclic group may or may not have aromaticity. As an aromatic heterocycle, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring are mentioned, for example. As a non-aromatic heterocycle, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring are mentioned, for example. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferable.
上述環狀的有機基團可以具有取代基。作為該取代基,例如,可以舉出烷基(可以為直鏈狀及支鏈狀中的任一種、碳數1~12為較佳)、環烷基(可以為單環、多環(包含螺環)中的任一種,碳數3~20為較佳)、芳基(碳數6~14為較佳)、羥基、烷氧基、酯基、醯胺基、聚胺酯基、脲基、硫醚基、磺醯胺基及磺酸酯基。此外,構成環狀的有機基團之碳(有助於形成環之碳)可以為羰基碳。The above-mentioned cyclic organic group may have a substituent. As the substituent, for example, an alkyl group (which may be any of straight chain and branched chain, preferably having 1 to 12 carbon atoms), cycloalkyl group (which may be monocyclic, polycyclic (including any one of spiro ring), carbon number 3-20 is better), aryl group (carbon number 6-14 is better), hydroxyl group, alkoxyl group, ester group, amido group, polyurethane group, urea group, Thioether group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (the carbon contributing to the formation of the ring) may be carbonyl carbon.
作為通式(3)所表示之陰離子,SO3 - -CF2 -CH2 -OCO-(L)q’-W、SO3 - -CF2 -CHF-CH2 -OCO-(L)q’-W、SO3 - -CF2 -COO-(L)q’-W、SO3 - -CF2 -CF2 -CH2 -CH2 -(L)q-W、SO3 - -CF2 -CH(CF3 )-OCO-(L)q’-W為較佳。其中,L、q及W與通式(3)相同。q’表示0~10的整數。As anions represented by general formula (3), SO 3 - -CF 2 -CH 2 -OCO-(L)q'-W, SO 3 - -CF 2 -CHF-CH 2 -OCO-(L)q' -W, SO 3 - -CF 2 -COO-(L)q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 -(L)qW, SO 3 - -CF 2 -CH( CF 3 )-OCO-(L)q'-W is preferred. Among them, L, q and W are the same as the general formula (3). q' represents the integer of 0-10.
在一態樣中,作為通式(ZI)中的Z- 、通式(ZII)中的Z- 、通式(ZI-3)中的Zc- 及通式(ZI-4)中的Z- ,氟烷基磺酸陰離子(更佳為全氟烷基磺酸陰離子)亦較佳。上述氟烷基磺酸陰離子(包含全氟烷基磺酸陰離子)的碳數為2~10為較佳3~5為更佳。In one aspect, as Z - in the general formula (ZI), Z - in the general formula (ZII), Zc - in the general formula (ZI-3), and Z - in the general formula (ZI - 4) , Fluoroalkylsulfonic acid anion (more preferably perfluoroalkylsulfonic acid anion) is also preferred. The carbon number of the above-mentioned fluoroalkylsulfonic acid anion (including perfluoroalkylsulfonic acid anion) is 2-10, preferably 3-5.
以下,分別例示出光酸產生劑的陰離子及陽離子。The anions and cations of the photoacid generator are exemplified below, respectively.
[化11] [chemical 11]
[化12] [chemical 12]
[化13] [chemical 13]
能夠任意組合上述陽離子及陰離子來用作光酸產生劑。Any combination of the above-mentioned cations and anions can be used as a photoacid generator.
光酸產生劑可以為低分子化合物的形態,亦可以為摻入於聚合物的局部之形態。又,亦可以併用低分子化合物的形態和摻入於聚合物的局部中之形態。 光酸產生劑為低分子化合物的形態為較佳。 當光酸產生劑為低分子化合物的形態時,其分子量為3,000以下為較佳,2,000以下為更佳,1,000以下為進一步較佳。 本發明的抗蝕劑組成物中,光酸產生劑的含量相對於組成物的總固體成分為0.1~35質量%為較佳,0.5~20質量%為更佳,1~10質量%為進一步較佳,1~5質量%為特佳。 又,樹脂B可以僅使用1種,亦可以使用2種以上,當使用2種以上時,該等的合計含量在上述範圍內為較佳。The photoacid generator may be in the form of a low-molecular compound, or may be partially incorporated into a polymer. Moreover, the form of a low-molecular-weight compound and the form mixed with the part of a polymer can also be used together. The photoacid generator is preferably in the form of a low-molecular compound. When the photoacid generator is in the form of a low molecular weight compound, its molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. In the resist composition of the present invention, the content of the photoacid generator is preferably 0.1 to 35% by mass, more preferably 0.5 to 20% by mass, further preferably 1 to 10% by mass, based on the total solid content of the composition. More preferably, 1 to 5% by mass is particularly preferred. Moreover, resin B may use only 1 type, and may use 2 or more types, When using 2 or more types, it is preferable that these total content exists in the said range.
<酸擴散控制劑> 本發明的抗蝕劑組成物進一步包含作為與上述醚化合物不同之化合物之酸擴散控制劑。 酸擴散控制劑捕獲曝光時從光酸產生劑等中產生之酸,並且作為抑制因多餘的產生酸引起之未曝光部中的樹脂B的反應之猝滅劑發揮作用為較佳。 例如,能夠將鹼性化合物(DA)、藉由光化射線或放射線的照射而鹼性降低或消失之鹼性化合物(DB)(具有質子受體性官能基,並且藉由光化射線或放射線的照射進行分解而質子受體性降低、消失、或從質子受體性變成酸性之化合物)、相對於光酸產生劑成為相對弱之酸之鎓鹽(DC)、具有氮原子且具有藉由酸的作用而脫離之基團之低分子化合物(DD)、或在陽離子部具有氮原子之鎓鹽化合物(DE)等用作酸擴散控制劑。 其中,酸擴散控制劑為鹼性化合物(DA)及具有氮原子且具有藉由酸的作用而脫離之基團之低分子化合物(DD)為較佳。<Acid diffusion control agent> The resist composition of the present invention further includes an acid diffusion control agent as a compound different from the aforementioned ether compound. The acid diffusion control agent preferably captures acid generated from a photoacid generator or the like during exposure and functions as a quencher that suppresses the reaction of the resin B in the unexposed portion due to excess generated acid. For example, a basic compound (DA), a basic compound (DB) that can reduce or disappear alkalinity by irradiation of actinic rays or radiation (having a proton-accepting functional group, and irradiated to decompose and the proton-accepting property decreases, disappears, or becomes acidic from the proton-accepting property), an onium salt (DC) that becomes a relatively weak acid relative to the photoacid generator, has a nitrogen atom and has a A low-molecular compound (DD) of a group detached by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in a cationic portion is used as an acid diffusion control agent. Among them, the acid diffusion control agent is preferably a basic compound (DA) and a low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid.
(鹼性化合物(DA)) 作為鹼性化合物(DA),具有下述式(A)~(E)所表示之結構之化合物為較佳。(basic compound (DA)) As the basic compound (DA), compounds having structures represented by the following formulas (A) to (E) are preferred.
[化14] [chemical 14]
通式(A)及(E)中, R200 、R201 及R202 可以相同,亦可以不同,分別獨立地表示氫原子、烷基(較佳為碳數1~20)、環烷基(較佳為碳數3~20)或芳基(碳數6~20)。R201 與R202 可以相互鍵結而形成環。 R203 、R204 、R205 及R206 可以相同,亦可以不同,分別獨立地表示碳數1~20的烷基。In the general formulas (A) and (E), R 200 , R 201 and R 202 may be the same or different, and each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group ( Preferably, it is an aryl group (with 3 to 20 carbon atoms) or an aryl group (with 6 to 20 carbon atoms). R 201 and R 202 may be bonded to each other to form a ring. R 203 , R 204 , R 205 and R 206 may be the same or different, and each independently represents an alkyl group having 1 to 20 carbons.
通式(A)及(E)中的烷基可以具有取代基,亦可以未經取代。 關於上述烷基,作為具有取代基之烷基,碳數1~20的胺基烷基、碳數1~20的羥基烷基或碳數1~20的氰基烷基為較佳。 通式(A)及(E)中的烷基為未經取代為更佳。The alkyl groups in the general formulas (A) and (E) may have a substituent or may be unsubstituted. Regarding the above-mentioned alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbons, a hydroxyalkyl group having 1 to 20 carbons, or a cyanoalkyl group having 1 to 20 carbons are preferable. The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
作為鹼性化合物(DA),胍、胺基吡咯啶、吡唑、吡唑啉、哌口井、胺基口末啉、胺基烷基口末啉、或哌啶等為較佳,具有咪唑結構、二氮雜雙環結構、鎓氫氧化物結構、羧酸鎓結構、三烷基胺結構、苯胺結構或吡啶結構之化合物、具有羥基之烷基胺衍生物、或具有羥基之苯胺衍生物等為更佳。As the basic compound (DA), guanidine, aminopyrrolidinium, pyrazole, pyrazoline, piperidine, aminoindoline, aminoalkylinoridine, or piperidine are preferred, with imidazole structure, diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives with hydroxyl, or aniline derivatives with hydroxyl, etc. for better.
(具有氮原子且具有藉由酸的作用而脫離之基團之低分子化合物(DD)) 又,酸擴散控制劑為具有氮原子且具有藉由酸的作用而脫離之基團之低分子化合物(DD)(以下,亦稱為“化合物(DD)”)亦較佳。化合物(DD)為在氮原子上具有藉由酸的作用而脫離之基團之胺衍生物為較佳。 作為藉由酸的作用而脫離之基團,縮醛基、碳酸酯基、胺甲酸酯基、三級酯基、三級羥基或半縮醛胺醚為較佳,胺甲酸酯基或半縮醛胺醚為更佳。 化合物(DD)的分子量為100~1000為較佳,100~700為更佳,100~500為進一步較佳。 化合物(DD)可以具有在氮原子上具有保護基之胺甲酸酯基。作為構成胺甲酸酯基之保護基,由下述通式(d-1)表示。(A low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid) Moreover, it is also preferable that the acid diffusion control agent is a low-molecular compound (DD) (hereinafter also referred to as "compound (DD)") having a nitrogen atom and a group detached by the action of an acid. Compound (DD) is preferably an amine derivative having a group detached by the action of an acid on the nitrogen atom. As the group detached by the action of acid, acetal group, carbonate group, carbamate group, tertiary ester group, tertiary hydroxyl group or hemiaminal ether are preferred, carbamate group or Hemiaminal ethers are more preferred. The molecular weight of the compound (DD) is preferably from 100 to 1,000, more preferably from 100 to 700, and still more preferably from 100 to 500. Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the urethane group is represented by the following general formula (d-1).
[化15] [chemical 15]
通式(d-1)中, Rb分別獨立地表示氫原子、烷基(較佳為碳數1~10)、環烷基(較佳為碳數3~30)、芳基(較佳為碳數3~30)、芳烷基(較佳為碳數1~10)或烷氧基烷基(較佳為碳數1~10)。Rb彼此可以相互鍵結而形成環。 作為Rb所表示之烷基、環烷基、芳基、芳烷基、及烷氧基烷基可以具有之取代基,分別獨立地為羥基、氰基、胺基、吡咯烷基、哌啶基、口末啉基、橋氧基等官能基、烷氧基、或鹵素原子為較佳。In general formula (d-1), Rb independently represent a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an arane group (preferably having 1 to 10 carbon atoms) or alkoxyalkyl group (preferably having 1 to 10 carbon atoms). Rb may be bonded to each other to form a ring. The substituents that the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkoxyalkyl group represented by Rb may have are independently hydroxyl, cyano, amino, pyrrolidinyl, and piperidinyl Functional groups such as , perolyl, and bridged oxy groups, alkoxy groups, or halogen atoms are preferred.
作為Rb,直鏈狀或支鏈狀的烷基、環烷基、或芳基為較佳,直鏈狀或支鏈狀的烷基、或環烷基為更佳。 作為2個Rb相互鍵結而形成之環,可以舉出脂環式烴環、芳香族烴環、雜環式烴環及其衍生物等。 作為通式(d-1)所表示之基團的具體結構,可以舉出美國專利公報US2012/0135348A1號說明書的<0466>段中所揭示之結構,但並不限定於此。Rb is preferably a straight-chain or branched alkyl group, cycloalkyl group, or aryl group, and more preferably a straight-chain or branched alkyl group or cycloalkyl group. Examples of the ring in which two Rb are bonded to each other include an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring, a heterocyclic hydrocarbon ring, derivatives thereof, and the like. Specific structures of the group represented by the general formula (d-1) include structures disclosed in paragraph <0466> of US Patent Publication No. US2012/0135348A1, but are not limited thereto.
化合物(DD)具有下述通式(6)所表示之結構為較佳。Compound (DD) preferably has a structure represented by the following general formula (6).
[化16] [chemical 16]
通式(6)中, l表示0~2的整數,m表示1~3的整數,且滿足l+m=3。 Ra表示氫原子、烷基、環烷基、芳基或芳烷基。當l為2時,2個Ra可以相同,亦可以不同,2個Ra亦可以相互鍵結而與式中的氮原子一同形成雜環。該雜環中可以具有除了式中的氮原子以外的雜原子。又,作為該雜環的取代基,羥基為較佳。 Rb與上述通式(d-1)中的Rb的含義相同,較佳例亦相同。 通式(6)中,作為Ra的烷基、環烷基、芳基及芳烷基分別獨立地具有作為Rb的烷基、環烷基、芳基、及芳烷基可以具有之取代基而例示之取代基亦較佳。In general formula (6), l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l+m=3 is satisfied. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may be bonded to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may have heteroatoms other than the nitrogen atom in the formula. Also, as the substituent of the heterocyclic ring, a hydroxyl group is preferable. Rb has the same meaning as Rb in the above general formula (d-1), and preferred examples are also the same. In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb each independently have substituents that the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb may have. The exemplified substituents are also preferable.
作為上述Ra的烷基、環烷基、芳基及芳烷基(該等基團可以被上述基團取代)的具體例,可以舉出與關於Rb而前述的例相同之基團。 作為本發明中的特佳之化合物(DD)的具體例,可以舉出美國專利申請公開2012/0135348A1號說明書的<0475>段中所揭示之化合物,但並不限定於此。Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted by the above-mentioned groups) of the aforementioned Ra include the same groups as those described above for Rb. Specific examples of particularly preferable compound (DD) in the present invention include compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012/0135348A1, but are not limited thereto.
以下,示出酸擴散控制劑的較佳例。Preferred examples of the acid diffusion control agent are shown below.
[化17] [chemical 17]
[化18] [chemical 18]
本發明的抗蝕劑組成物中,只要酸擴散控制劑的含量滿足上述質量比R1的規定,則並沒有限制,但例如,相對於總固體成分為0.006~8質量%為較佳,0.01~1質量%為更佳,0.02~0.1質量%為進一步較佳。In the resist composition of the present invention, the content of the acid diffusion control agent is not limited as long as it satisfies the above-mentioned mass ratio R1, but for example, it is preferably 0.006 to 8% by mass relative to the total solid content, and 0.01 to 8% by mass. 1 mass % is more preferable, and 0.02-0.1 mass % is further more preferable.
<溶劑> 本發明的抗蝕劑組成物包含溶劑。 在本發明的抗蝕劑組成物中,能夠適當使用公知的抗蝕劑溶劑。例如,能夠較佳地使用美國專利申請公開2016/0070167A1號說明書的<0665>~<0670>段、美國專利申請公開2015/0004544A1號說明書的<0210>~<0235>段、美國專利申請公開2016/0237190A1號說明書的<0424>~<0426>段、及美國專利申請公開2016/0274458A1號說明書的<0357>~<0366>段中所揭示之公知的溶劑。 作為能夠在製備組成物時使用之溶劑,例如,可以舉出伸烷基二醇單烷基醚羧酸酯、伸烷基二醇單烷基醚、乳酸烷基酯、烷氧基丙酸烷基酯、環狀內酯(較佳為碳數4~10)、可以具有環之單酮化合物(較佳為碳數4~10)、伸烷基碳酸酯、烷氧基乙酸烷基酯及丙酮酸烷基酯等有機溶劑。<Solvent> The resist composition of the present invention contains a solvent. In the resist composition of the present invention, known resist solvents can be appropriately used. For example, paragraphs <0665> to <0670> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication 2015/0004544A1, US Patent Application Publication 2016 Known solvents disclosed in paragraphs <0424> to <0426> of specification No. /0237190A1 and paragraphs <0357> to <0366> of specification US Patent Application Publication No. 2016/0274458A1. Examples of solvents that can be used in the preparation of the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkylene alkoxy propionate, etc. base esters, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have rings (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxy acetates and Organic solvents such as alkyl pyruvate.
作為有機溶劑,可以使用混合了結構中具有羥基之溶劑和不具有羥基之溶劑之混合溶劑。 作為具有羥基之溶劑及不具有羥基之溶劑,能夠適當選擇前述的例示化合物,作為包含羥基之溶劑,伸烷基二醇單烷基醚或乳酸烷基等為較佳,丙二醇單甲醚(PGME)、丙二醇單乙醚(PGEE)、2-羥基異丁酸甲酯或乳酸乙酯為更佳。 又,作為不具有羥基之溶劑,伸烷基二醇單烷基醚乙酸酯、烷基烷氧基丙酸酯、可以具有環之單酮化合物、環狀內酯或乙酸烷基酯等為較佳,在該等中,丙二醇單甲醚乙酸酯(PGMEA)、乙基乙氧基丙酸酯、2-庚酮、γ-丁內酯、環己酮、環戊酮或乙酸丁酯為更佳,丙二醇單甲醚乙酸酯、γ-丁內酯、乙基乙氧基丙酸酯、環己酮、環戊酮或2-庚酮為進一步較佳。作為不具有羥基之溶劑,伸丙基碳酸酯亦較佳。 具有羥基之溶劑與不具有羥基之溶劑的混合比(質量比)為1/99~99/1,10/90~90/10為較佳,20/80~60/40為更佳。從塗佈均勻性的觀點考慮,包含50質量%以上的不具有羥基之溶劑之混合溶劑為較佳。 溶劑包含丙二醇單甲醚乙酸酯為較佳,可以為丙二醇單甲醚乙酸酯單獨溶劑,亦可以為包含丙二醇單甲醚乙酸酯之2種以上的混合溶劑。As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent not having a hydroxyl group can be used. As a solvent with a hydroxyl group and a solvent without a hydroxyl group, the aforementioned exemplary compounds can be appropriately selected. As a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or lactic acid alkyl group is preferred, and propylene glycol monomethyl ether (PGME ), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate are more preferred. Also, as a solvent not having a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound which may have a ring, cyclic lactone or alkyl acetate, etc. Preferably, among these, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, gamma-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate More preferably, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, cyclohexanone, cyclopentanone or 2-heptanone are further more preferable. Propylene carbonate is also preferable as a solvent having no hydroxyl group. The mixing ratio (mass ratio) of the solvent having a hydroxyl group to the solvent not having a hydroxyl group is 1/99-99/1, preferably 10/90-90/10, more preferably 20/80-60/40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent not having a hydroxyl group is preferable. It is preferable that the solvent contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate, or may be a mixed solvent of two or more types of propylene glycol monomethyl ether acetate.
<界面活性劑> 本發明的抗蝕劑組成物可以進一步包含界面活性劑。作為界面活性劑,氟系和/或矽系界面活性劑(具體而言,氟系界面活性劑、矽系界面活性劑、或具有氟原子和矽原子兩者之界面活性劑)為較佳。<Surfactant> The resist composition of the present invention may further contain a surfactant. As the surfactant, fluorine-based and/or silicon-based surfactants (specifically, fluorine-based surfactants, silicon-based surfactants, or surfactants having both fluorine atoms and silicon atoms) are preferred.
作為氟系和/或矽系界面活性劑,可以舉出美國專利申請公開第2008/0248425號說明書的<0276>段中所記載之界面活性劑。 又,亦能夠使用除了美國專利申請公開第2008/0248425號說明書的<0280>段中所記載之、氟系和/或矽系界面活性劑以外的其他界面活性劑。Examples of the fluorine-based and/or silicon-based surfactant include those described in paragraph <0276> of US Patent Application Publication No. 2008/0248425. In addition, other surfactants than the fluorine-based and/or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008/0248425 can also be used.
界面活性劑可以單獨使用1種,亦可以併用2種以上。 當本發明的抗蝕劑組成物包含界面活性劑時,界面活性劑的含量相對於組成物的總固體成分為0.0001~2質量%為較佳,0.0005~1質量%為更佳。 界面活性劑可以單獨使用1種,亦可以使用2種以上。當使用2種以上界面活性劑時,其合計含量在上述範圍內為較佳。Surfactants may be used alone or in combination of two or more. When the resist composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. Surfactants may be used alone or in combination of two or more. When two or more surfactants are used, the total content thereof is preferably within the above range.
(其他添加劑) 本發明的抗蝕劑組成物可以進一步包含不同的成分,例如,可以含有選自包括疏水性樹脂、酸增殖劑、染料、塑化劑、光敏劑、光吸收劑、鹼可溶性樹脂、溶解抑制劑及溶解促進劑等的組群中的1種以上的成分。(other additives) The resist composition of the present invention may further contain various components, for example, may contain a group selected from the group consisting of hydrophobic resins, acid proliferators, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors and one or more components in the group of a dissolution accelerator and the like.
<製備方法> 本發明的抗蝕劑組成物的固體成分濃度大於20質量%,21~50質量%為更佳,22~40質量%為更佳,23~35質量%為進一步較佳。 此外,固體成分濃度係指,相對於組成物的總質量的固體成分的合計含量(除了溶劑以外的其他抗蝕劑成分的質量的合計)的質量百分率。<Preparation method> The solid content concentration of the resist composition of the present invention is more than 20% by mass, more preferably 21 to 50% by mass, more preferably 22 to 40% by mass, and still more preferably 23 to 35% by mass. In addition, the solid content concentration refers to the percentage by mass of the total solid content (total mass of resist components other than the solvent) relative to the total mass of the composition.
本發明的抗蝕劑組成物藉由如下方式使用,亦即,將上述成分溶解於規定的有機溶劑中,較佳為溶解於上述混合溶劑中,並對其進行過濾器過濾之後,塗佈於規定的支撐體(基板)上。過濾器過濾中所使用之過濾器的細孔尺寸為0.1 μm以下為較佳,0.05 μm以下為更佳,0.03 μm以下為進一步較佳。又,組成物的固體成分濃度高時(例如,25質量%以上),過濾器過濾中所使用之過濾器的細孔尺寸為3 μm以下為較佳,0.5 μm以下為更佳,0.3 μm以下為進一步較佳。該過濾器為聚四氟乙烯製、聚乙烯製或尼龍製者為較佳。在過濾器過濾中,例如,在日本專利申請公開第2002-062667號說明書(日本特開2002-062667)中所揭示那樣,可以進行循環過濾,亦可以串聯或並聯連接複數種過濾器來進行過濾。又,組成物可以過濾複數次。進而,在過濾器過濾的前後,可以對組成物進行脫氣處理等。The resist composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably in the above-mentioned mixed solvent, filtering it with a filter, and applying it on on the specified support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. Also, when the solid content concentration of the composition is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and 0.3 μm or less for further improvement. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-062667 (Japanese Patent Application Laid-Open No. 2002-062667 ), it is possible to perform cyclic filtration, or to perform filtration by connecting multiple types of filters in series or in parallel. . Also, the composition can be filtered multiple times. Furthermore, the composition may be degassed before and after filtering through the filter.
本發明的抗蝕劑組成物的黏度為20~500 mPa・s為較佳。從塗佈性更加優異之觀點考慮,本發明的抗蝕劑組成物的黏度為20~300 mPa・s為更佳。 此外,在室溫(23℃)下,能夠使用E型黏度計來測量黏度。The viscosity of the resist composition of the present invention is preferably 20 to 500 mPa·s. The viscosity of the resist composition of the present invention is more preferably 20 to 300 mPa·s from the viewpoint of better coatability. In addition, at room temperature (23° C.), the viscosity can be measured using an E-type viscometer.
<用途> 本發明的抗蝕劑組成物有關一種藉由光化射線或放射線的照射進行反應而性質發生變化之感光化射線性或感放射線性樹脂組成物。更詳細而言,本發明的抗蝕劑組成物有關一種使用於IC(積體電路(Integrated Circuit))等半導體製造步驟、液晶或熱能頭等的電路基板的製造、壓印用模具結構體的製作、其他感光蝕刻加工步驟或平版印刷板、或酸硬化性組成物的製造中之感光化射線性或感放射線性樹脂組成物。本發明中所形成之圖案能夠使用於蝕刻步驟、離子植入步驟、凸塊電極形成步驟、再配線形成步驟及MEMS(Micro Electro Mechanical Systems:微機電系統)等中。<Use> The resist composition of the present invention relates to an actinic radiation-sensitive or radiation-sensitive resin composition whose properties are changed by reacting with irradiation of actinic rays or radiation. More specifically, the resist composition of the present invention relates to a mold structure used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing circuit boards such as liquid crystals and thermal heads, and imprinting. Actinic radiation-sensitive or radiation-sensitive resin compositions in fabrication, other photoetching processing steps or lithographic printing plates, or the manufacture of acid-hardening compositions. The pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode formation step, a rewiring formation step, MEMS (Micro Electro Mechanical Systems: Micro Electro Mechanical Systems) and the like.
[抗蝕劑膜、圖案形成方法] 本發明亦有關一種使用上述感光化射線性或感放射線性樹脂組成物之圖案形成方法。以下,對本發明的圖案形成方法進行說明。又,與圖案形成方法的說明一同對本發明的抗蝕劑膜(感光化射線性或感放射線性膜)進行說明。[Resist film, pattern forming method] The present invention also relates to a pattern forming method using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. In addition, the resist film (actinic radiation-sensitive or radiation-sensitive film) of the present invention will be described together with the description of the pattern forming method.
本發明的圖案形成方法具有: (i)使用上述抗蝕劑組成物(感光化射線性或感放射線性樹脂組成物)在支撐體上形成抗蝕劑膜(感光化射線性或感放射線性膜)之步驟(抗蝕劑膜形成步驟); (ii)對上述抗蝕劑膜進行曝光(照射光化射線或放射線)之步驟(曝光步驟);及 (iii)使用顯影液對上述經曝光之抗蝕劑膜進行顯影之步驟(顯影步驟)。The pattern forming method of the present invention has: (i) A step of forming a resist film (actinic radiation-sensitive or radiation-sensitive film) on a support using the above-mentioned resist composition (actinic radiation-sensitive or radiation-sensitive resin composition) (resist film formation step); (ii) A step of exposing (irradiating actinic rays or radiation) to the above resist film (exposure step); and (iii) A step of developing the above-mentioned exposed resist film using a developer (developing step).
本發明的圖案形成方法只要包括上述(i)~(iii)的步驟,則並沒有特別限定,可以進一步具有下述步驟。 本發明的圖案形成方法中,(ii)曝光步驟中的曝光方法可以為液浸曝光。 本發明的圖案形成方法中,在(ii)曝光步驟之前包括(iv)預加熱(PB:PreBake)步驟為較佳。 本發明的圖案形成方法中,在(ii)曝光步驟之後且(iii)顯影步驟之前包括(v)曝光後加熱(PEB:Post Exposure Bake)步驟為較佳。 本發明的圖案形成方法中,可以包括複數次(ii)曝光步驟。 本發明的圖案形成方法中,可以包括複數次(iv)預加熱步驟。 本發明的圖案形成方法中,可以包括複數次(v)曝光後加熱步驟。The pattern forming method of the present invention is not particularly limited as long as it includes the above steps (i) to (iii), and may further include the following steps. In the pattern forming method of the present invention, the exposure method in (ii) the exposure step may be liquid immersion exposure. In the pattern forming method of the present invention, it is preferable to include (iv) a preheating (PB: PreBake) step before the (ii) exposure step. In the pattern forming method of the present invention, it is preferable to include (v) a post-exposure heating (PEB: Post Exposure Bake) step after the (ii) exposure step and before the (iii) image development step. In the pattern forming method of the present invention, the (ii) exposure step may be included a plurality of times. In the pattern forming method of the present invention, a plurality of (iv) preheating steps may be included. In the pattern forming method of the present invention, a plurality of (v) post-exposure heating steps may be included.
在本發明的圖案形成方法中,上述(i)成膜步驟、(ii)曝光步驟及(iii)顯影步驟能夠藉由通常習知之方法進行。In the pattern forming method of the present invention, the above-mentioned (i) film-forming step, (ii) exposing step, and (iii) developing step can be performed by commonly known methods.
(i)在抗蝕劑膜形成步驟中所形成之抗蝕劑膜的膜厚為500~11000 nm為較佳,1000~9000 nm為更佳,3000~7000 nm為進一步較佳。(i) The film thickness of the resist film formed in the resist film forming step is preferably 500 to 11000 nm, more preferably 1000 to 9000 nm, and still more preferably 3000 to 7000 nm.
又,根據需要,可以在抗蝕劑膜與支撐體之間形成抗蝕劑下層膜(例如,SOG(Spin On Glass:旋塗玻璃)、SOC(Spin On Carbon:旋塗碳)及防反射膜)。作為構成抗蝕劑下層膜之材料,能夠適當使用公知的有機系或無機系的材料。 可以在抗蝕劑膜的上層形成保護膜(頂塗層)。作為保護膜,能夠適當使用公知的材料。例如,能夠較佳地使用美國專利申請公開第2007/0178407號說明書、美國專利申請公開第2008/0085466號說明書、美國專利申請公開第2007/0275326號說明書、美國專利申請公開第2016/0299432號說明書、美國專利申請公開第2013/0244438號說明書、國際專利申請公開第2016/157988A號說明書中所揭示之保護膜形成用組成物。作為保護膜形成用組成物,包含上述酸擴散控制劑者為較佳。 可以在包含上述疏水性樹脂之抗蝕劑膜的上層形成保護膜。Also, if necessary, a resist underlayer film (for example, SOG (Spin On Glass: Spin On Glass), SOC (Spin On Carbon: Spin On Carbon) and an antireflection film can be formed between the resist film and the support. ). As the material constituting the resist underlayer film, known organic or inorganic materials can be used as appropriate. A protective film (top coat layer) may be formed on the upper layer of the resist film. As a protective film, a well-known material can be used suitably. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, and U.S. Patent Application Publication No. 2016/0299432 . The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016/157988A. As a composition for protective film formation, what contains the said acid diffusion control agent is preferable. A protective film can be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.
支撐體並沒有特別限定,能夠使用除了在IC等半導體的製造步驟或者液晶或熱能頭等電路基板的製造步驟以外,在其他感光蝕刻加工的微影步驟等中一般使用之基板。作為支撐體的具體例,可以舉出矽、SiO2 及SiN等無機基板等。The support is not particularly limited, and substrates generally used in the lithography process of other photosensitive etching processes, etc., can be used in addition to the manufacturing steps of semiconductors such as ICs or the manufacturing steps of circuit substrates such as liquid crystals and thermal heads. Specific examples of the support include inorganic substrates such as silicon, SiO 2 , and SiN.
關於加熱溫度,在(iv)預加熱步驟及(v)曝光後加熱步驟中的任一步驟中,均為70~160℃為較佳,70~155℃為更佳,80~150℃為進一步較佳。 關於加熱時間,在(iv)預加熱步驟及(v)曝光後加熱步驟中的任一步驟中均為30~300秒鐘為較佳,30~180秒鐘為更佳,30~90秒鐘為進一步較佳。 加熱能夠利用曝光裝置及顯影裝置所具備之機構進行,亦可以使用加熱板等進行。Regarding the heating temperature, in any one of the (iv) preheating step and (v) post-exposure heating step, 70 to 160°C is preferable, 70 to 155°C is more preferable, and 80 to 150°C is further preferable. better. Regarding the heating time, it is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and 30 to 90 seconds in either of the (iv) preheating step and (v) post-exposure heating step for further improvement. Heating can be performed using the mechanisms provided in the exposure device and the developing device, or can be performed using a hot plate or the like.
曝光步驟中所使用之光源波長並沒有特別限制,例如,可以舉出紅外光、可見光、紫外光、遠紫外光、極紫外光(EUV光)、X射線及電子束等。在該等中,遠紫外光為較佳,其波長為250 nm以下為較佳。具體而言,為KrF準分子雷射(248 nm)、ArF準分子雷射(193 nm)、F2 準分子雷射(157 nm)、X射線、EUV光(13 nm)及電子束等,KrF準分子雷射、ArF準分子雷射、EUV光或電子束為較佳,KrF準分子雷射為更佳。The wavelength of the light source used in the exposure step is not particularly limited, and examples include infrared light, visible light, ultraviolet light, deep ultraviolet light, extreme ultraviolet light (EUV light), X-rays, and electron beams. Among them, far-ultraviolet light is preferred, and its wavelength is preferably below 250 nm. Specifically, KrF excimer laser ( 248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV light (13 nm) and electron beams, etc. KrF excimer laser, ArF excimer laser, EUV light or electron beam are preferred, and KrF excimer laser is more preferred.
(iii)顯影步驟中使用之顯影液可以為鹼顯影液,亦可為包含有機溶劑之顯影液(以下,亦稱為有機系顯影液)。(iii) The developer used in the image development step may be an alkali developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).
作為鹼顯影液,通常使用以四甲基氫氧化銨為代表之四級銨鹽,除此以外,還能夠使用無機鹼、一~三級胺、醇胺及環狀胺等鹼水溶液。 進而,上述鹼顯影液可以包含適當量的醇類和/或界面活性劑。鹼顯影液的鹼濃度通常為0.1~20質量%。鹼顯影液的pH通常為10~15。 使用鹼顯影液進行顯影之時間通常為10~300秒鐘。 鹼顯影液的鹼濃度、pH及顯影時間能夠根據所形成之圖案而適當進行調整。Quaternary ammonium salts typified by tetramethylammonium hydroxide are generally used as alkaline developing solutions, and aqueous alkaline solutions such as inorganic alkalis, primary to tertiary amines, alcohol amines, and cyclic amines can also be used. Furthermore, the above-mentioned alkali developing solution may contain alcohols and/or surfactants in an appropriate amount. The alkali concentration of an alkali developing solution is 0.1-20 mass % normally. The pH of the alkaline developing solution is usually 10-15. The development time using an alkaline developing solution is usually 10 to 300 seconds. The alkali concentration, pH, and developing time of an alkali developing solution can be adjusted suitably according to the pattern to be formed.
有機系顯影液為包含選自包括酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑、醚系溶劑及烴系溶劑的組群中的至少1種有機溶劑之顯影液為較佳。The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
作為酮系溶劑,例如,可以舉出1-辛酮、2-辛酮、1-壬酮、2-壬酮、丙酮、2-庚酮(甲基戊基酮)、4-庚酮、1-己酮、2-己酮、二異丁酮、環己酮、甲基環己酮、苯基丙酮、甲基乙基酮、甲基異丁基酮、乙醯丙酮、丙酮基丙酮、紫羅蘭酮、二丙酮醇、乙醯甲醇、苯乙酮、甲基萘基酮、異佛爾酮及伸丙基碳酸酯等。Examples of ketone-based solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1 -hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, violet Ketone, Diacetone Alcohol, Acetyl Methanol, Acetophenone, Methyl Naphthyl Ketone, Isophorone and Propylene Carbonate, etc.
作為酯系溶劑,例如,可以舉出乙酸甲酯、乙酸丁酯、乙酸乙酯、乙酸異丙酯、乙酸戊酯、乙酸異戊酯、乙酸戊酯、丙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯、乙基-3-乙氧基丙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯、丁酸丁酯、2-羥基異丁酸甲酯、乙酸異戊酯、異丁酸異丁酯及丙酸丁酯等。Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, Alcohol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, Methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, butyl propionate, etc.
作為醇系溶劑、醯胺系溶劑、醚系溶劑及烴系溶劑,能夠使用美國專利申請公開2016/0070167A1號說明書的<0715>~<0718>段中所揭示之溶劑。As the alcohol-based solvent, amide-based solvent, ether-based solvent, and hydrocarbon-based solvent, solvents disclosed in paragraphs <0715> to <0718> of US Patent Application Publication No. 2016/0070167A1 can be used.
上述溶劑可以混合複數種,亦可以與除了上述以外的溶劑或水混合。作為顯影液整體的含水率,小於50質量%為較佳,小於20質量%為更佳,小於10質量%為進一步較佳,實質上不含水分為特佳。 The above-mentioned solvents may be mixed in plural, and may be mixed with solvents other than the above-mentioned ones or water. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably not substantially containing water.
相對於有機系顯影液之有機溶劑的含量相對於顯影液的總量為50~100質量%為較佳,80~100質量%為更佳,90~100質量%為進一步較佳,95~100質量%為特佳。 The content of the organic solvent relative to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and 95 to 100% by mass relative to the total amount of the developer. Quality % is especially good.
有機系顯影液可以根據需要含有適當量的公知的界面活性劑。 The organic developer may contain an appropriate amount of a known surfactant as needed.
界面活性劑的含量相對於顯影液的總量通常為0.001~5質量%,0.005~2質量%為較佳,0.01~0.5質量%為更佳。 The content of the surfactant is usually 0.001 to 5% by mass relative to the total amount of the developer, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass.
有機系顯影液可以包含上述酸擴散控制劑。 The organic developer may contain the above-mentioned acid diffusion control agent.
作為顯影方法,例如,可以舉出:將基板在裝滿顯影液之槽中浸漬一定時間之方法(浸漬法);在基板表面藉由表面張力將顯影液隆起並靜置一定時間之方法(浸置法);對基板表面噴塗顯影液之方法(噴射法);及在以一定速度旋轉之基板上一邊以一定速度掃描顯影液噴出噴嘴一邊持續噴出顯影液之方法(動態分配法)等。 As the developing method, for example, a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dipping method); The method of spraying the developer on the surface of the substrate (spray method); and the method of continuously spraying the developer while scanning the nozzle of the developer at a certain speed on the substrate rotating at a certain speed (dynamic distribution method), etc.
可以組合使用鹼水溶液進行顯影之步驟(鹼顯影步驟)及使用包含有機溶劑之顯影液進行顯影之步驟(有機溶劑顯影步驟)。藉此,能夠僅使中間水平的曝光強度的區域不溶解而形成圖案,因此能夠形成更加微細的圖案。 A step of developing using an aqueous alkali solution (alkali developing step) and a step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined. Thereby, since it is possible to form a pattern without dissolving only a region of an intermediate level of exposure intensity, it is possible to form a finer pattern.
在(iii)顯影步驟之後,包括使用沖洗液清洗之步驟(沖洗步驟)為較佳。 After the (iii) developing step, it is preferable to include a step of washing with a rinse solution (rinsing step).
使用鹼顯影液之顯影步驟之後的沖洗步驟中所使用之沖洗液,例如能夠使用純水。純水可以包含適當量的界面活性劑。在該情況下,可以在顯影步驟或沖洗步驟之後,追加藉由超臨界流體去除附著於圖案上之顯影液或沖洗液之處理。進而,為了去除殘留於圖案中的水分,可以在沖洗處理或藉由超臨界流體之處理之後進行加熱處理。As the rinse solution used in the rinse step after the development step using an alkaline developing solution, for example, pure water can be used. Pure water may contain a suitable amount of surfactant. In this case, after the developing step or the rinsing step, a process of removing a developing solution or a rinsing solution adhering to the pattern with a supercritical fluid may be added. Furthermore, in order to remove moisture remaining in the pattern, heat treatment may be performed after rinsing treatment or treatment with a supercritical fluid.
在使用包含有機溶劑之顯影液之顯影步驟之後的沖洗步驟中所使用之沖洗液只要不溶解圖案,則並沒有特別限制,能夠使用包含通常的有機溶劑之溶液。作為沖洗液,使用包含選自包括烴系溶劑、酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑及醚系溶劑之組群組群中的至少1種有機溶劑之沖洗液為較佳。 作為烴系溶劑、酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑、及醚系溶劑的具體例,可以舉出與在包含有機溶劑之顯影液中說明者相同者。 作為用於此時之沖洗步驟之沖洗液,包含1元醇之沖洗液為更佳。The rinse solution used in the rinse step after the developing step using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common organic solvent can be used. As the rinsing liquid, it is better to use a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. good. Specific examples of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents include the same ones described in the developer containing an organic solvent. As the rinsing liquid used in the rinsing step at this time, a rinsing liquid containing monohydric alcohol is more preferable.
作為沖洗步驟中所使用之1元醇,可以舉出直鏈狀、支鏈狀或環狀的1元醇。具體而言,可以舉出1-丁醇、2-丁醇、3-甲基-1-丁醇、三級丁醇、1-戊醇、2-戊醇、1-己醇、4-甲基-2-戊醇、1-庚醇、1-辛醇、2-己醇、環戊醇、2-庚醇、2-辛醇、3-己醇、3-庚醇、3-辛醇、4-辛醇及甲基異丁基甲醇。作為碳數5以上的1元醇,可以舉出1-己醇、2-己醇、4-甲基-2-戊醇、1-戊醇、3-甲基-1-丁醇及甲基異丁基甲醇等。Examples of the monohydric alcohol used in the rinsing step include linear, branched or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methanol 2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol , 4-octanol and methyl isobutyl carbinol. Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl alcohol. Isobutyl Methanol etc.
各成分可以混合複數種,亦可以與除了上述以外的有機溶劑混合來使用。 沖洗液中的含水率為10質量%以下為較佳,5質量%以下為更佳,3質量%以下為進一步較佳。藉由將含水率設為10質量%以下,可以獲得良好的顯影特性。Each component may mix plural types, and may mix and use it with the organic solvent other than the above. The water content in the rinse liquid is preferably at most 10% by mass, more preferably at most 5% by mass, and still more preferably at most 3% by mass. Favorable image development characteristics can be acquired by making water content into 10 mass % or less.
沖洗液可以包含適當量的界面活性劑。 在沖洗步驟中,使用沖洗液對進行顯影之基板進行清洗處理。清洗處理的方法並沒有特別限定,例如,可以舉出在以一定速度旋轉之基板上持續噴出沖洗液之方法(旋轉塗佈法)、將基板在裝滿沖洗液之槽中浸漬一定時間之方法(浸漬法)、或對基板表面噴塗顯影液之方法(噴射法)等。其中,以旋轉塗佈法進行清洗處理,清洗後使基板以2,000~4,000 rpm(revolution per minute:每分鐘轉數)的轉速旋轉,藉此將沖洗液從基板上去除為較佳。又,在沖洗步驟之後包括加熱步驟(Post Bake:後烘烤)亦較佳。藉由該加熱步驟去除殘留於圖案之間及圖案內部之顯影液及沖洗液。在沖洗步驟之後的加熱步驟中,加熱溫度通常為40~160℃,70~120℃為較佳,70~115℃為更佳。加熱時間通常為10秒鐘~3分鐘,30秒鐘~90秒鐘為較佳。The rinse solution may contain a suitable amount of surfactant. In the rinsing step, the substrate to be developed is cleaned with a rinsing solution. The method of cleaning treatment is not particularly limited, and examples include a method of continuously spraying a rinse solution on a substrate rotating at a constant speed (spin coating method), and a method of immersing the substrate in a tank filled with a rinse solution for a certain period of time. (dipping method), or the method of spraying the developer on the surface of the substrate (spray method), etc. Among them, it is preferable to perform cleaning treatment by a spin coating method, and to remove the rinse solution from the substrate by rotating the substrate at a rotation speed of 2,000 to 4,000 rpm (revolution per minute) after cleaning. In addition, it is also preferable to include a heating step (Post Bake: post-baking) after the rinsing step. The developing solution and rinse solution remaining between the patterns and inside the patterns are removed by this heating step. In the heating step after the rinsing step, the heating temperature is usually 40 to 160°C, preferably 70 to 120°C, more preferably 70 to 115°C. The heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
本發明的圖案形成方法中所獲得之圖案的膜厚(圖案的高度)為500~11000 nm為較佳,1000~9000 nm為更佳,3000~7000 nm為進一步較佳。 當所形成之圖案為線狀時,藉由圖案高度除以線寬之值而求出之縱橫比為0.3~20為較佳,0.5~15為更佳,1~10為進一步較佳。 當所形成之圖案為溝槽(槽)圖案狀或接觸孔圖案狀時,藉由圖案高度除以溝槽寬度或孔徑之值而求出之縱橫比為0.3~20為較佳,0.5~15為更佳,1~10為進一步較佳。The film thickness (height of the pattern) of the pattern obtained in the pattern forming method of the present invention is preferably 500 to 11000 nm, more preferably 1000 to 9000 nm, and still more preferably 3000 to 7000 nm. When the formed pattern is linear, the aspect ratio obtained by dividing the pattern height by the line width is preferably 0.3-20, more preferably 0.5-15, and more preferably 1-10. When the formed pattern is a groove (groove) pattern or a contact hole pattern, the aspect ratio obtained by dividing the pattern height by the value of the groove width or aperture is preferably 0.3-20, 0.5-15 1-10 is more preferable.
在本發明的抗蝕劑組成物及本發明的圖案形成方法中所使用之各種材料(例如,抗蝕劑溶劑、顯影液、沖洗液、防反射膜形成用組成物或頂塗層形成用組成物等)不包含金屬成分、異構物及殘留單體等雜質為較佳。作為上述的各種材料中所包含之該等雜質的含量,1 ppm以下為較佳,100 ppt以下為更佳,10 ppt以下為進一步較佳,實質上不包含(測定裝置的檢測極限以下)為特佳。Various materials used in the resist composition of the present invention and the pattern forming method of the present invention (for example, resist solvent, developer, rinse solution, composition for forming an antireflection film, or composition for forming a top coat layer) It is better not to contain impurities such as metal components, isomers and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably not more than 1 ppm, more preferably not more than 100 ppt, and still more preferably not more than 10 ppt, and substantially not contained (below the detection limit of the measuring device) is Excellent.
作為從上述各種材料中去除金屬等雜質之方法,例如,可以舉出使用過濾器的過濾。作為過濾器孔徑,細孔尺寸10 nm以下為較佳,5 nm以下為更佳,3 nm以下為進一步較佳。作為過濾器的材質,聚四氟乙烯製造、聚乙烯製造或尼龍製過濾器為較佳。過濾器可以使用預先用有機溶劑清洗者。在過濾器過濾步驟中,可以串聯或並聯連接複數種過濾器來使用。使用複數種過濾器時,可以組合使用孔徑和/或材質不同之過濾器。又,可以對各種材料進行複數次過濾,進行複數次過濾之步驟可以為循環過濾步驟。作為過濾器,如日本專利申請公開第2016-201426號說明書(日本特開2016-201426)中所揭示之溶出物減少者為較佳。 除了過濾器過濾以外,可以進行基於吸附材料之雜質的去除,亦可以組合使用過濾器過濾和吸附材料。作為吸附材料,能夠使用公知的吸附材料,例如,能夠使用矽膠或沸石等的無機系吸附材料或活性碳等有機系吸附材料。作為金屬吸附劑,例如,可以舉出日本專利申請公開第2016-206500號說明書(日本特開2016-206500)中揭示者。 又,作為降低上述各種材料中所包含之金屬等雜質之方法,可以舉出選擇金屬含量少之原料作為構成各種材料之原料,對構成各種材料之原料進行過濾器過濾、或藉由Teflon(註冊商標)對裝置內進行襯覆等而盡可能抑制污染之條件下進行蒸餾等方法。對構成各種材料之原料進行之過濾器過濾中之較佳條件與上述條件相同。 為了使抗蝕劑組成物的金屬雜質的含量成為少量(例如,質量ppt等級),在抗蝕劑組成物的材料(樹脂及光酸產生劑等)的製造步驟(合成原料之步驟等)中所使用之裝置的裝置內進行部分或整體的搪玻璃(glasslining)處理亦較佳。該種方法例如記載於2017年12月21日的化學工業日報中。As a method of removing impurities such as metals from the above-mentioned various materials, for example, filtration using a filter is mentioned. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. Filters can be used pre-cleaned with organic solvents. In the filter filtration step, a plurality of types of filters can be connected in series or in parallel and used. When using multiple types of filters, filters with different pore diameters and/or materials can be used in combination. In addition, various materials may be filtered multiple times, and the step of performing multiple times of filtration may be a circulating filtration step. As a filter, a filter with reduced extractables as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426) is preferable. In addition to filter filtration, removal of impurities by adsorption materials can be performed, and filter filtration and adsorption materials can also be used in combination. As the adsorbent, a known adsorbent can be used, for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Laid-Open No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500). Also, as a method of reducing impurities such as metals contained in the above-mentioned various materials, it is possible to select raw materials with a small metal content as raw materials constituting various materials, filter the raw materials constituting various materials, or use Teflon (registered Trademark) to line the inside of the device, etc., to conduct distillation under the conditions of suppressing pollution as much as possible. Preferable conditions in filter filtration of raw materials constituting various materials are the same as those described above. In order to reduce the content of metal impurities in the resist composition to a small amount (for example, ppt level by mass), in the production steps (steps of synthesizing raw materials, etc.) of the materials (resin, photoacid generator, etc.) of the resist composition It is also preferable to perform partial or whole glasslining treatment in the device of the device used. Such a method is described, for example, in Chemical Industry Daily on December 21, 2017.
為了防止雜質的混入,將上述各種材料保存於美國專利申請公開第2015/0227049號說明書、日本專利申請公開第2015-123351號說明書(日本特開2015-123351)等中所記載之容器中為較佳。In order to prevent the mixing of impurities, it is better to store the above-mentioned various materials in the containers described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351), etc. good.
可以對藉由本發明的圖案形成方法形成之圖案應用改善圖案的表面粗糙之方法。作為改善圖案的表面粗糙之方法,例如,可以舉出美國專利申請公開第2015/0104957號說明書中所揭示之藉由含氫氣體的電漿來處理圖案之方法。除此以外,可以應用日本專利申請公開第2004-235468號說明書(日本特開2004-235468)、美國專利申請公開第2010/0020297號說明書及Proc. of SPIE Vol.8328 83280N-1“EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement”中所記載之公知的方法。 又,藉由上述方法形成之圖案能夠用作例如日本專利申請公開第1991-270227號說明書(日本特開平3-270227)及美國專利申請公開第2013/0209941號說明書中所揭示之間隔物製程的芯材(Core)。A method of improving the surface roughness of the pattern can be applied to the pattern formed by the pattern forming method of the present invention. As a method for improving the surface roughness of a pattern, for example, a method of treating a pattern with a hydrogen-containing gas plasma disclosed in US Patent Application Publication No. 2015/0104957 can be mentioned. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297 and Proc. of SPIE Vol.8328 83280N-1 "EUV Resist Curing Known methods described in "Technique for LWR Reduction and Etch Selectivity Enhancement". In addition, the pattern formed by the above method can be used, for example, as a spacer manufacturing process disclosed in Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and U.S. Patent Application Publication No. 2013/0209941. Core material (Core).
[電子元件的製造方法] 又,本發明還有關一種包括上述圖案形成方法之電子元件的製造方法。藉由本發明的電子元件的製造方法製造之電子元件較佳地搭載於電氣電子設備(例如,家電、OA(辦公自動化:Office Automation)關連設備、媒體相關設備、光學用設備及通訊設備等)。 [實施例][Manufacturing method of electronic components] Moreover, the present invention also relates to a method of manufacturing an electronic component including the above pattern forming method. The electronic component produced by the method for producing an electronic component of the present invention is preferably mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation: Office Automation)-related equipment, media-related equipment, optical equipment, communication equipment, etc.). [Example]
以下,基於實施例對本發明進行進一步詳細的說明。以下實施例中所示之材料、使用量、比例、處理內容及處理步驟等只要不脫離本發明的主旨,則能夠適當進行變更。因此,本發明的範圍並不藉由以下所示之實施例而被限定性解釋。Hereinafter, the present invention will be described in more detail based on examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the Examples shown below.
[抗蝕劑組成物(感光化射線性或感放射線性樹脂組成物)的製備] 使用以下所示之成分製備了抗蝕劑組成物(感光化射線性或感放射線性樹脂組成物)。[Preparation of resist composition (actinic radiation-sensitive or radiation-sensitive resin composition)] A resist composition (actinic radiation-sensitive or radiation-sensitive resin composition) was prepared using the components shown below.
<醚化合物> 作為醚化合物,使用了以下所示之化合物。<Ether compound> As ether compounds, the compounds shown below were used.
[化19] [chemical 19]
<樹脂> 作為樹脂,使用了以下示出之樹脂。<Resin> As the resin, the resins shown below were used.
[化20] [chemical 20]
在下述表中示出各樹脂中的、各重複單元的組成比(莫耳比率、從左依次對應)、重量平均分子量及分散度(重量平均分子量/數量平均分子量)。The following table shows the composition ratio (molar ratio, corresponding from left) of each repeating unit, weight average molecular weight, and degree of dispersion (weight average molecular weight/number average molecular weight) in each resin.
[表1]
<光酸產生劑> 作為光酸產生劑,使用了以下示出之光酸產生劑。<Photoacid generator> As the photoacid generator, the photoacid generator shown below was used.
[化21] <酸擴散控制劑> 作為酸擴散控制劑,使用了以下化合物。[chem 21] <Acid diffusion control agent> As the acid diffusion control agent, the following compounds were used.
[化22] [chem 22]
<界面活性劑> 作為界面活性劑,使用了以下化合物。<Surfactant> As surfactants, the following compounds were used.
G1:下述示出之化合物 G2:MEGAFACE-R4(氟系界面活性劑、DIC Corporation製造)G1: Compounds shown below G2: MEGAFACE-R4 (fluorine-based surfactant, manufactured by DIC Corporation)
[化23] [chem 23]
<溶劑> 作為溶劑,使用了PGMEA(丙二醇單甲醚乙酸酯)與PGME(丙二醇單甲醚)的混合溶劑(混合比:PGMEA/PGME=80/20(質量比))。 <抗蝕劑組成物的製備><Solvent> As a solvent, a mixed solvent of PGMEA (propylene glycol monomethyl ether acetate) and PGME (propylene glycol monomethyl ether) (mixing ratio: PGMEA/PGME=80/20 (mass ratio)) was used. <Preparation of resist composition>
以滿足下述表中所記載之固體成分的配合之方式將醚化合物、樹脂、光酸產生劑、酸擴散控制劑及界面活性劑溶解於溶劑中,並將溶液製備成表中所記載之固體成分濃度。使用口徑為0.3 μm的膜濾器對所獲得之溶液進行精密過濾而獲得了抗蝕劑組成物。 將各實施例或比較例中所使用之抗蝕劑組成物的配合示於下述表中。 表中的含量的標記表示各自的成分相對於總固體成分之含量(質量%)。Dissolve the ether compound, resin, photoacid generator, acid diffusion controller, and surfactant in a solvent so that the solid content described in the following table is satisfied, and the solution is prepared as a solid described in the table Ingredient concentration. The obtained solution was micro-filtered using a membrane filter with a diameter of 0.3 μm to obtain a resist composition. The composition of the resist composition used in each Example or Comparative Example is shown in the following table. The notation of the content in the table shows the content (mass %) of each component with respect to the total solid content.
[表2]
[評價] <圖案的形成> 在使用Tokyo Electron Limited.製造之旋塗機“ACT-8”實施了六甲基二矽氮烷處理之8英吋Si基板(Advanced Materials Technology,Inc.製造(以下,亦稱為“基板”。))上,旋轉塗佈了抗蝕劑組成物。 在140℃下將該基板加熱(PB:PreBake)60秒鐘並進行乾燥,形成了膜厚4.2 μm的抗蝕劑膜。然後,使用KrF準分子雷射掃描儀(ASML製造、PAS5500/850C波長248 nm),經由線寬500 nm、空間寬度300 nm的遮罩並以各種曝光量進行了曝光。 在115℃下,進一步對曝光後的抗蝕劑膜進行了60秒鐘的加熱,然後使用2.38質量%氫氧化四甲基銨(TMAH)水溶液,浸漬60秒鐘並進行顯影而獲得了線與空間圖案。 利用純水將所獲得之圖案沖洗了30秒鐘之後,在110℃下進行了60秒鐘的加熱。[Evaluation] <Formation of patterns> An 8-inch Si substrate (manufactured by Advanced Materials Technology, Inc.) subjected to hexamethyldisilazane treatment using a spin coater "ACT-8" manufactured by Tokyo Electron Limited. (hereinafter also referred to as "substrate". )) on which the resist composition was spin-coated. This substrate was heated (PB: PreBake) at 140° C. for 60 seconds and dried to form a resist film with a film thickness of 4.2 μm. Then, using a KrF excimer laser scanner (manufactured by ASML, PAS5500/850C wavelength 248 nm), exposure was performed at various exposure amounts through a mask with a line width of 500 nm and a space width of 300 nm. At 115°C, the exposed resist film was further heated for 60 seconds, then immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and developed to obtain a line and Space pattern. After the obtained pattern was rinsed with pure water for 30 seconds, it heated at 110 degreeC for 60 seconds.
<間距的評價(空間的測量)> 使用Hitachi,Ltd.製造之側長SEM S-9380觀察了所製作之圖案。將能夠確認到抗蝕劑膜之被曝光之部分完全顯影(去除)以至基板的表面露出之最小曝光量作為最佳曝光量Eopt。測量了以該Eopt形成圖案時之相鄰的線間的幅度(空間(nm))。能夠評價為該值越小越能夠形成解析性優異,並且間距更窄之圖案。 此外,上述“相鄰的線間的幅度”係指,在將圖案的厚度設為d時,連接彼此相鄰之線中的d/2的高度的位置彼此之距離。<Evaluation of spacing (measurement of space)> The produced pattern was observed using a side length SEM S-9380 manufactured by Hitachi, Ltd. The minimum exposure dose at which it can be confirmed that the exposed portion of the resist film is completely developed (removed) so that the surface of the substrate is exposed is taken as the optimum exposure dose Eopt. The amplitude (space (nm)) between adjacent lines when the pattern was formed by this Eopt was measured. It can be evaluated that the smaller this value is, the more excellent the resolution can be and form a pattern with a narrower pitch. In addition, the above-mentioned "width between adjacent lines" refers to the distance between positions connecting adjacent lines having a height of d/2 when the thickness of the pattern is defined as d.
<截面形狀(矩形性)的評價> 用掃描式電子顯微鏡觀察以最佳曝光量Eopt形成之圖案的截面,並對照下述基準對所觀察之線的形狀評價了截面形狀(矩形性)。<Evaluation of cross-sectional shape (rectangularity)> The cross-section of the pattern formed at the optimum exposure amount Eopt was observed with a scanning electron microscope, and the cross-sectional shape (rectangularity) was evaluated for the shape of the observed line with reference to the following references.
A:線的形狀為矩形。 B:線的形狀為錐形。 C:線的形狀為錐形,進而,在顯影時部分非曝光部被去除而發生了薄膜化。 -:發生圖案崩塌而未能夠形成圖案。 此外,當溝槽(藉由曝光而抗蝕劑去除之區域)的上邊的幅度比底邊的幅度大1.5倍以上時,將線的形狀評價為錐形。A: The shape of the line is a rectangle. B: The shape of the wire is tapered. C: The shape of the line is tapered, and a part of the non-exposed portion was removed during image development, resulting in thinning. -: Pattern collapse occurs without being able to form a pattern. In addition, when the width of the upper side of the groove (the region where the resist was removed by exposure) was greater than the width of the bottom side by 1.5 times or more, the shape of the line was evaluated as tapered.
[結果] 下述表中示出,各實施例或比較例中的評價結果、及各實施例或比較例中所使用之抗蝕劑組成物的特徵。 表中,“R1”的欄中示出,抗蝕劑組成物中的、醚化合物的含量相對於酸擴散控制劑的含量的質量比(醚化合物的含量/酸擴散控制劑的含量)。 “R2”的欄中示出,抗蝕劑組成物中的、醚化合物的含量相對於樹脂B的含量的質量比(醚化合物的含量/樹脂B的含量)。 “含氮”的欄中示出,抗蝕劑組成物中的醚化合物是否為含氮化合物。當滿足本必要條件時作為A,不滿足時作為B。 “式(X1)”的欄中示出,抗蝕劑組成物中的醚化合物是否為通式(X1)所表示之化合物。當滿足本必要條件時作為A,不滿足時作為B。 “Rq1 :苯環基”的欄中示出,當抗蝕劑組成物中的醚化合物為式(X1)所表示之化合物時,Rq1 是否為苯環基。當滿足本必要條件時作為A,不滿足時作為B。 “酚性極性單元”的欄中示出,抗蝕劑組成物中的樹脂是否包含具有酚性極性基之重複單元。當滿足本必要條件時作為A,不滿足時作為B。 “苯單元含量”的欄中示出,抗蝕劑組成物中的樹脂中的、具有苯環基之重複單元相對於樹脂的總質量的含量(質量%)。 “式(Z1-3)”的欄中示出,抗蝕劑組成物中的光酸產生劑是否為通式(Z1-3)所表示之化合物。當滿足本必要條件時作為A,不滿足時作為B。[Results] The evaluation results in each Example or Comparative Example and the characteristics of the resist composition used in each Example or Comparative Example are shown in the following table. In the table, the column "R1" shows the mass ratio of the content of the ether compound to the content of the acid diffusion controller in the resist composition (content of ether compound/content of acid diffusion controller). The column of "R2" shows the mass ratio of the content of the ether compound to the content of the resin B in the resist composition (content of the ether compound/content of the resin B). In the column of "nitrogen-containing", whether or not the ether compound in the resist composition is a nitrogen-containing compound is shown. When this necessary condition is satisfied, it is regarded as A, and when it is not satisfied, it is regarded as B. In the column of "Formula (X1)", whether or not the ether compound in the resist composition is represented by the general formula (X1) is shown. When this necessary condition is satisfied, it is regarded as A, and when it is not satisfied, it is regarded as B. The column "R q1 : phenyl ring group" indicates whether R q1 is a benzene ring group when the ether compound in the resist composition is a compound represented by formula (X1). When this necessary condition is satisfied, it is regarded as A, and when it is not satisfied, it is regarded as B. The column of "phenolic polar unit" shows whether or not the resin in the resist composition contains a repeating unit having a phenolic polar group. When this necessary condition is satisfied, it is regarded as A, and when it is not satisfied, it is regarded as B. The column of "benzene unit content" shows the content (mass %) of the repeating unit having a benzene ring group in the resin in the resist composition with respect to the total mass of the resin. In the column of "formula (Z1-3)", whether the photoacid generator in a resist composition is a compound represented by general formula (Z1-3) is shown. When this necessary condition is satisfied, it is regarded as A, and when it is not satisfied, it is regarded as B.
[表3]
如上述表所示,確認到藉由使用本發明的抗蝕劑組成物能夠形成縱橫比高且間距窄之圖案。又,所形成之圖案的截面形狀亦比藉由使用比較例的抗蝕劑組成物而獲得之圖案的截面形狀良好。 另一方面,藉由比較例的抗蝕劑組成物未能夠獲得所期望的圖案。此外,在比較例4中,在PB之後抗蝕劑膜中發生破裂,而未能夠形成圖案。 又,進行使用將固體成分濃度設為10質量%之抗蝕劑組成物之試驗之結果,未能夠形成作為評價標準之膜厚(4.2 μm)的抗蝕劑膜。As shown in the above table, it was confirmed that a pattern with a high aspect ratio and a narrow pitch can be formed by using the resist composition of the present invention. Also, the cross-sectional shape of the formed pattern was better than that of the pattern obtained by using the resist composition of the comparative example. On the other hand, the desired pattern could not be obtained with the resist composition of the comparative example. Furthermore, in Comparative Example 4, cracks occurred in the resist film after PB, and pattern formation was not possible. Also, as a result of a test using a resist composition having a solid content concentration of 10% by mass, it was not possible to form a resist film having a film thickness (4.2 μm) as an evaluation standard.
根據表中所示之結果,確認到當醚化合物為含氮化合物時,能夠形成間距更窄之圖案(實施例1~4的比較)。 確認到,當醚化合物為通式(X1)所表示之化合物,進而相當於Rq1 的基團為苯環基時,能夠形成間距更窄之圖案,並且所獲得之圖案的截面形狀亦更加優異(實施例1~3的比較)。 確認到,當具有苯環基之重複單元的含量相對於樹脂的總質量為小於65莫耳%時,能夠形成間距更窄之圖案,並且所獲得之圖案的截面形狀亦更加優異(實施例1、5及6的比較)。 確認到,當光酸產生劑為式(ZI-3)所表示之化合物時,能夠形成間距更窄之圖案(實施例1、7及10的比較)。From the results shown in the table, it was confirmed that when the ether compound is a nitrogen-containing compound, a pattern with a narrower pitch can be formed (comparison of Examples 1 to 4). It was confirmed that when the ether compound is a compound represented by the general formula (X1) and the group corresponding to R q1 is a phenyl ring group, a pattern with a narrower pitch can be formed, and the cross-sectional shape of the obtained pattern is also more excellent (Comparison of Examples 1 to 3). It was confirmed that when the content of the repeating unit having a benzene ring group was less than 65 mol% relative to the total mass of the resin, a pattern with a narrower pitch could be formed, and the cross-sectional shape of the obtained pattern was also more excellent (Example 1 , 5 and 6 comparison). It was confirmed that when the photoacid generator is a compound represented by the formula (ZI-3), a pattern with a narrower pitch can be formed (comparison of Examples 1, 7, and 10).
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