TW201504766A - Resist underlayer film forming composition - Google Patents
Resist underlayer film forming composition Download PDFInfo
- Publication number
- TW201504766A TW201504766A TW103113545A TW103113545A TW201504766A TW 201504766 A TW201504766 A TW 201504766A TW 103113545 A TW103113545 A TW 103113545A TW 103113545 A TW103113545 A TW 103113545A TW 201504766 A TW201504766 A TW 201504766A
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- underlayer film
- film forming
- forming composition
- photoresist underlayer
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1422—Side-chains containing oxygen containing OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Architecture (AREA)
- Engineering & Computer Science (AREA)
- Materials For Photolithography (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
本發明為關於微影製程用光阻下層膜形成組成物。特以有關用來形成高硬度、且不易因微影製程所形成的光阻圖型而產生彎曲(wiggling)的光阻下層膜的組成物。 The present invention relates to a photoresist underlayer film forming composition for a lithography process. A composition of a photoresist underlayer film which is used to form a high-hardness and which is not easily formed by a photoresist pattern formed by a lithography process.
半導體裝置之製造中係以藉由微影製程來進行微細加工。該微影製程中已知有,對基板上的光阻層以KrF準分子雷射、ArF準分子雷射等紫外線雷射進行曝光時,基板表面上起因於該紫外線雷射反射所產生之駐波所導致之影響而無法形成具有所希望形狀之光阻圖型的問題。為了解決該問題,則採用在基板與光阻層之間設置光阻下層膜(防反射膜)。且,作為用來形成光阻下層膜用的組成物,已知有使用酚醛樹脂。例如,專利文獻1及專利文獻2中揭示一種含有具有下述重複單元的樹脂的光阻下層膜形成材料,該重複單元係使具有雙酚基的化合物酚醛化而得者。更,專利文獻3中揭示一種可旋轉塗布的防 反射膜組成物,其係包含於聚合物之主鏈中具有3個或3個以上經縮合的芳香族環的聚合物。 In the manufacture of semiconductor devices, microfabrication is performed by a lithography process. In the lithography process, when the photoresist layer on the substrate is exposed by an ultraviolet laser such as a KrF excimer laser or an ArF excimer laser, the surface of the substrate is caused by the ultraviolet laser reflection. The problem caused by the wave cannot form a pattern of a photoresist pattern having a desired shape. In order to solve this problem, a photoresist underlayer film (antireflection film) is provided between the substrate and the photoresist layer. Further, as a composition for forming a photoresist underlayer film, a phenol resin is known. For example, Patent Document 1 and Patent Document 2 disclose a photoresist underlayer film forming material containing a resin having a repeating unit obtained by phenolating a compound having a bisphenol group. Further, Patent Document 3 discloses an anti-rotation coating prevention A reflective film composition comprising a polymer having three or more condensed aromatic rings in a main chain of the polymer.
又,由於伴隨光阻圖型之微細化而要求的光阻層的薄膜化,亦已知有至少形成2層光阻下層膜,且將該光阻下層膜使用作為遮罩材料之微影製程。作為前述形成至少2層之材料,可舉出如有機樹脂(例如,丙烯酸樹脂、酚醛樹脂)、矽樹脂(例如,有機聚矽氧烷)、無機矽化合物(例如,SiON、SiO2)。將由上述有機樹脂層所形成之圖型作為遮罩進行乾蝕刻時,該圖型必須具有對蝕刻氣體(例如氟碳)之耐蝕刻性。作為用來形成如此般有機樹脂層之組成物,例如專利文獻4中揭示一種含有下述聚合物的組成物,該聚合物係包含雜環芳香族部分。 Further, it is known that a photoresist film of at least two layers is formed by forming a thin film of a photoresist layer which is required to be miniaturized with a photoresist pattern, and the photoresist film is used as a mask material. . Examples of the material for forming at least two layers include an organic resin (for example, an acrylic resin, a phenol resin), a ruthenium resin (for example, an organic polysiloxane), and an inorganic ruthenium compound (for example, SiON or SiO 2 ). When the pattern formed by the above-described organic resin layer is dry-etched as a mask, the pattern must have etching resistance to an etching gas (for example, fluorocarbon). As a composition for forming such an organic resin layer, for example, Patent Document 4 discloses a composition containing a polymer containing a heterocyclic aromatic moiety.
[專利文獻1]日本特開2006-259249號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-259249
[專利文獻2]日本特開2007-316282號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-316282
[專利文獻3]日本特表2010-528334號公報 [Patent Document 3] Japanese Patent Publication No. 2010-528334
[專利文獻4]日本特開2007-017976號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-017976
然而,將光阻圖型形成於已經由上述微影製程與蝕刻製程的應加工的基板上時,隨著所形成的圖型寬 度之變狹小,而具有所謂容易產生不規則的圖型彎曲之問題。具體而言,此係由於在蝕刻目的之加工基板時,在作為遮罩材料所使用的光阻下層膜中,特以由有機樹脂層所形成的圖型,具有所謂產生左右彎曲之現象。 However, when the photoresist pattern is formed on the substrate to be processed by the above-described lithography process and etching process, the pattern width is formed. The degree is narrow, and there is a problem that the pattern is easily deformed. Specifically, in the case of the underlayer film of the photoresist used as the mask material in the case of processing the substrate for etching purposes, the pattern formed of the organic resin layer has a phenomenon of causing left and right bending.
本發明即為解決上述問題之發明。即,本發明為一種包含聚合物及溶劑的光阻下層膜形成組成物,其中所述聚合物係具有下述式(1)所表示的結構單元,
作為上述及後述的「鹵素基」,列舉例如:氯基、溴基。作為上述及後述的「具有至少1個芳香環的碳原子數6至20的二價有機基」,列舉例如:伸苯基、伸聯苯基、伸聯三苯基、伸茀基、伸萘基、伸蒽基、伸芘 基(下述式(a-1)及下述式(a-2)所表示的基)、伸咔唑基(下述式(b)所表示的基)、及下述式(c)所表示的基(式中,n係表示0或1)。作為上述「具有至少1個芳香環的碳原子數6至20的有機基」,列舉例如:苯基、聯苯基、聯三苯基、茀基、萘基、蒽基、芘基、咔唑基、下述式(d-1)及下述式(d-2)所表示的基(式中,n係表示0或1)。 Examples of the "halogen group" described above and below include a chlorine group and a bromine group. Examples of the "divalent organic group having 6 to 20 carbon atoms having at least one aromatic ring" as described above and below include, for example, a stretching phenyl group, a stretching phenyl group, a stretching triphenyl group, a stretching group, and an anthracene group. Base, stretch base, stretch a group (base represented by the following formula (a-1) and the following formula (a-2)), a carbazole group (base represented by the following formula (b)), and the following formula (c) The base of the expression (where n is 0 or 1). Examples of the above-mentioned "organic group having 6 to 20 carbon atoms having at least one aromatic ring" include, for example, a phenyl group, a biphenyl group, a triphenylene group, a fluorenyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, and an oxazole. The group represented by the following formula (d-1) and the following formula (d-2) (wherein n represents 0 or 1).
前述聚合物亦可進而具有下述式(2)所表示的結構單元,
本發明的光阻下層膜形成組成物,亦可進而含有交聯劑、酸性化合物、熱酸產生劑及界面活性劑中至少1個作為任意成分。 The photoresist underlayer film forming composition of the present invention may further contain at least one of a crosslinking agent, an acidic compound, a thermal acid generator, and a surfactant as an optional component.
使用本發明的光阻下層膜形成組成物所形成的光阻下層膜為高硬度,且藉由應用該光阻下層膜可抑制微影製程中所形成的圖型之彎曲(wiggling)。 The photoresist underlayer film formed by using the photoresist underlayer film forming composition of the present invention has high hardness, and the wiggling of the pattern formed in the lithography process can be suppressed by applying the photoresist underlayer film.
本發明的光阻下層膜形成組成物中所包含具有上述式(1)所表示的結構單元的聚合物,作為該聚合 物的結構單元,可列舉例如下述式(1-1)至式(1-10)所表示的結構單元。 The polymer having the structural unit represented by the above formula (1) is contained in the photoresist underlayer film forming composition of the present invention as the polymerization. The structural unit of the object is, for example, a structural unit represented by the following formula (1-1) to formula (1-10).
更,作為上述式(2)所表示的結構單元,可列舉例如下述式(2-1)所表示的結構單元。 Further, the structural unit represented by the above formula (2) is, for example, a structural unit represented by the following formula (2-1).
本發明的光阻下層膜形成組成物中所包含的聚合物之重量平均分子量,以標準聚苯乙烯換算值係例如2,000至10,000。 The weight average molecular weight of the polymer contained in the photoresist underlayer film forming composition of the present invention is, for example, 2,000 to 10,000 in terms of a standard polystyrene.
前述聚合物係使具有2個羥基苯基之聯酚(biphenol)化合物與芳香族化合物或雜環式化合物,及因應所需的芳香族醛或芳香族酮,在磺酸化合物等之酸觸媒之存在下進行聚合反應而可合成者。作為使用於前述聚合物之合成的「具有2個羥基苯基之聯酚化合物」,可列舉例如3,3’,5,5’-四甲氧基甲基-4,4’-二羥基聯苯。作為使用於前述聚合物之合成的「芳香族化合物」,可列舉例如:苯、萘、蒽、芘、茀、m-聯三苯。作為使用於前述聚合物之合成的「雜環式化合物」,可列舉例如咔唑。作為使用於前述聚合物之合成的「芳香族醛」,可列舉例如:糠醛、吡啶甲醛(pyridinecarboxaldehyde)、苯甲醛、萘醛、蒽醛、菲醛、柳醛、苯基乙醛、3-苯基丙醛、甲苯醛、(N,N-二甲基胺基)苯甲醛、乙醯氧基苯甲醛、1-芘 甲醛(1-pyrenecarboxaldehyde)、大茴香醛。又,使用於前述聚合物之合成的「芳香族酮」係二芳基酮類,可列舉例如:二苯基酮、苯基萘基酮、二萘基酮、苯基甲苯基酮、二甲苯基酮、9-茀酮。使用於前述聚合物之合成的聯酚化合物並不限定於1種的化合物,亦可使用2種以上,芳香族化合物、雜環式化合物、芳香族醛及芳香族酮亦不限定於1種的化合物,亦可使用2種以上。 The polymer is an acid catalyst such as a sulfonic acid compound, which is a biphenol compound having two hydroxyphenyl groups, an aromatic compound or a heterocyclic compound, and an aromatic aldehyde or an aromatic ketone required for the reaction. It can be synthesized by carrying out a polymerization reaction in the presence of it. As the "biphenol compound having two hydroxyphenyl groups" used for the synthesis of the above polymer, for example, 3,3',5,5'-tetramethoxymethyl-4,4'-dihydroxyl linkage is exemplified. benzene. Examples of the "aromatic compound" used in the synthesis of the above polymer include benzene, naphthalene, anthracene, anthracene, anthracene, and m-biphenylene. Examples of the "heterocyclic compound" used in the synthesis of the above polymer include carbazole. Examples of the "aromatic aldehyde" used for the synthesis of the above polymer include furfural, pyridinecarboxaldehyde, benzaldehyde, naphthaldehyde, furfural, phenanthrene, salicylaldehyde, phenylacetaldehyde, and 3-benzene. Propionaldehyde, tolualdehyde, (N,N-dimethylamino)benzaldehyde, ethoxylated benzaldehyde, 1-oxime Formaldehyde (1-pyrenecarboxaldehyde), anisaldehyde. Further, examples of the "aromatic ketone"-based diaryl ketone used for the synthesis of the polymer include diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyl tolyl ketone, and xylene. Ketone, 9-fluorenone. The phenolic compound to be used in the synthesis of the polymer is not limited to one type of compound, and two or more kinds thereof may be used. The aromatic compound, the heterocyclic compound, the aromatic aldehyde and the aromatic ketone are not limited to one type. Two or more kinds of compounds can also be used.
本發明的光阻下層膜形成組成物中可進而含有交聯劑。前述交聯劑較佳係使用具有至少二個交聯形成取代基之交聯性化合物。例如可舉出,具有羥甲基、甲氧基甲基等之交聯形成取代基之三聚氰胺系化合物、取代脲系化合物及酚系化合物。具體而言係甲氧基甲基化乙炔脲、甲氧基甲基化三聚氰胺等之化合物,可列舉例如:四甲氧基甲基乙炔脲、四丁氧基甲基乙炔脲、六甲氧基甲基三聚氰胺。並且,作為取代脲系化合物,可列舉例如:四甲氧基甲基脲、四丁氧基甲基脲。作為酚系化合物,可列舉例如:四羥基甲基聯酚、四甲氧基甲基聯酚(TMOM-BP)、四甲氧基甲基雙酚。 The photoresist underlayer film forming composition of the present invention may further contain a crosslinking agent. The crosslinking agent is preferably a crosslinkable compound having at least two crosslinks to form a substituent. For example, a melamine-based compound, a substituted urea-based compound, and a phenol-based compound having a substituent such as a methylol group or a methoxymethyl group to form a substituent may be mentioned. Specifically, a compound such as methoxymethylated acetylene urea or methoxymethylated melamine may, for example, be tetramethoxymethylacetylene urea, tetrabutoxymethylacetylene urea or hexamethoxymethyl. Melamine. Further, examples of the substituted urea compound include tetramethoxymethylurea and tetrabutoxymethylurea. Examples of the phenolic compound include tetrahydroxymethylbiphenol, tetramethoxymethylbiphenol (TMOM-BP), and tetramethoxymethylbisphenol.
作為前述交聯劑,又亦可使用具有至少二個環氧基之化合物。作為如此般之化合物,可列舉例如:參(2,3-環氧基丙基)異三聚氰酸酯、1,4-丁二醇二環氧丙基醚、1,2-環氧基-4-(環氧基乙基)環己烷、甘油三環氧丙基醚、二乙二醇二環氧丙基醚、2,6-二環氧丙基苯基環氧丙基醚、1,1,3-參[p-(2,3-環氧基丙氧基)苯基]丙烷、1,2- 環己烷二羧酸二環氧丙基酯、4,4’-亞甲基雙(N,N-二環氧丙基苯胺)、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、三羥甲基乙烷三環氧丙基醚、雙酚-A-二環氧丙基醚、(股)Daicel製的Epolide[註冊商標]GT-401、同GT-403、同GT-301、同GT-302、Ceroxide[註冊商標]2021、同3000、三菱化學(股)製的1001、1002、1003、1004、1007、1009、1010、828、807、152、154、180S75、871、872、日本化藥(股)製的EPPN201、同202、EOCN-102、同103S、同104S、同1020、同1025、同1027、Nagase ChemteX(股)製的Denacol[註冊商標]EX-252、同EX-611、同EX-612、同EX-614、同EX-622、同EX-411、同EX-512、同EX-522、同EX-421、同EX-313、同EX-314、同EX-321、BASF JAPAN(股)製的CY175、CY177、CY179、CY182、CY184、CY192、DIC(股)製的Epiclon 200、同400、同7015、同835LV、同850CRP。作為前述具有至少二個環氧基之化合物,又亦可使用具有胺基之環氧樹脂。作為如此般的環氧樹脂,可列舉例如:YH-434、YH-434L(新日化環氧製造(股)。 As the crosslinking agent, a compound having at least two epoxy groups can also be used. As such a compound, for example, ginseng (2,3-epoxypropyl)isocyanate, 1,4-butanediol diepoxypropyl ether, 1,2-epoxy group -4-(epoxyethyl)cyclohexane, glycerol triepoxypropyl ether, diethylene glycol diepoxypropyl ether, 2,6-diepoxypropyl phenylepoxypropyl ether, 1, 1,3-para [p-(2,3-epoxypropoxy)phenyl]propane, 1,2- Dicyclopropyl propyl cyclohexanedicarboxylate, 4,4'-methylenebis(N,N-diepoxypropylaniline), 3,4-epoxycyclohexylmethyl-3,4 - Epoxycyclohexane carboxylate, trimethylolethane triepoxypropyl ether, bisphenol-A-diglycidyl ether, Epolide [registered trademark] GT-401 manufactured by Daicel Same as GT-403, GT-301, GT-302, Ceroxide [registered trademark] 2021, same 3000, Mitsubishi Chemical Co., Ltd., 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, 807 152, 154, 180S75, 871, 872, EPPN201, 202, EOCN-102, 103S, 104S, 1020, 1025, 1027, Nagase ChemteX (shares) made by Nippon Chemical Co., Ltd. Denacol [registered trademark] EX-252, same as EX-611, with EX-612, with EX-614, with EX-622, with EX-411, with EX-512, with EX-522, with EX-421, with EX-313, with EX-314, with EX-321, BASF JAPAN (share) CY175, CY177, CY179, CY182, CY184, CY192, DIC (share) Epiclon 200, same 400, same 7015, same 835LV Same as 850CRP. As the compound having at least two epoxy groups, an epoxy group having an amine group can also be used. Examples of such an epoxy resin include YH-434 and YH-434L (Nippon Chemical Co., Ltd.).
作為前述交聯劑,又亦可使用具有至少2個嵌段異氰酸酯基之化合物。作為如此般的化合物,可列舉例如:三井化學(股)製之Takenate[註冊商標]B-830、同B-870N、Evonik Degussa公司製之VESTANAT[註冊商標]B1358/100。 As the crosslinking agent, a compound having at least two blocked isocyanate groups can also be used. Examples of such a compound include Takenate [registered trademark] B-830 manufactured by Mitsui Chemicals Co., Ltd., and B-870N, and VESTANAT [registered trademark] B1358/100 manufactured by Evonik Degussa Co., Ltd.
作為前述交聯劑,又亦可使用具有至少2個乙烯基醚基之化合物。作為如此般的化合物,可列舉例如:雙(4-(乙烯基氧基甲基)環己基甲基)戊二梭酯、三(乙二醇)二乙烯基醚、己二酸二乙烯基酯、二乙二醇二乙烯基醚、1,2,4-參(4-乙烯基氧基丁基)偏苯三甲酸酯、1,3,5-參(4-乙烯基氧基丁基)偏苯三甲酸酯、雙(4-(乙烯基氧基)丁基)對酞酸酯、雙(4-(乙烯基氧基)丁基)異酞酸酯、乙二醇二乙烯基醚、1,4-丁二醇二乙烯基醚、伸丁二醇二乙烯基醚、四乙二醇二乙烯基醚、新戊二醇二乙烯基醚、三羥甲基丙烷三乙烯基醚、三羥甲基乙烷三乙烯基醚、己二醇二乙烯基醚、1,4-環己烷二醇二乙烯基醚、四乙二醇二乙烯基醚、季戊四醇二乙烯基醚、季戊四醇三乙烯基醚及環己烷二甲醇二乙烯基醚。 As the crosslinking agent, a compound having at least two vinyl ether groups can also be used. Examples of such a compound include bis(4-(vinyloxymethyl)cyclohexylmethyl)pentanesuccinate, tris(ethylene glycol) divinyl ether, and divinyl adipate. , diethylene glycol divinyl ether, 1,2,4- cis (4-vinyloxybutyl) trimellitate, 1,3,5-gin (4-vinyloxybutyl) Pyromellitate, bis(4-(vinyloxy)butyl)paraphthalate, bis(4-(vinyloxy)butyl)isodecanoate, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, butanediol divinyl ether, tetraethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, three Hydroxymethylethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol triethylene Ethyl ether and cyclohexane dimethanol divinyl ether.
可添加選自此等各種交聯劑之1種類,亦可組合2種以上添加。前述交聯劑之含有比例係相對於從本發明的光阻下層膜形成組成物去除後述溶劑之固形分而言,例如為2質量%至60質量%。 One type of various crosslinking agents selected from these may be added, and two or more types may be added in combination. The content ratio of the crosslinking agent is, for example, 2% by mass to 60% by mass based on the solid content of the solvent to be described later from the photoresist underlayer film forming composition of the present invention.
本發明的光阻下層膜形成組成物可進而含有酸性化合物。前述酸性化合物係作用為促進交聯反應之觸媒,可列舉例如:p-甲苯磺酸、三氟甲烷磺酸、吡啶鎓-p-甲苯磺酸酯、水楊酸、樟腦磺酸、5-磺基水楊酸、4-氯苯磺酸、4-羥基苯磺酸、苯二磺酸、1-萘磺酸、檸檬酸、安息香酸、羥基安息香酸等之磺酸化合物及羧酸化合物、鹽酸、硫酸、硝酸、磷酸等之無機酸。可取代上述酸性化合 物或與上述酸性化合物一同含有熱酸產生劑。前述熱酸產生劑亦係作用為促進交聯反應之觸媒,可列舉例如三氟甲烷磺酸之第4級銨鹽。可添加選自此等酸性化合物及熱酸產生劑之1種類,亦可組合2種以上添加。前述酸性化合物或熱酸產生劑之含有比例係相對於從本發明的光阻下層膜形成組成物去除後述溶劑之固形分而言,例如為0.1質量%至20質量%。 The photoresist underlayer film forming composition of the present invention may further contain an acidic compound. The acidic compound functions as a catalyst for promoting a crosslinking reaction, and examples thereof include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, camphorsulfonic acid, 5- Sulfonic acid compounds and carboxylic acid compounds of sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, etc. A mineral acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid. Can replace the above acid compound Or a thermal acid generator together with the above acidic compound. The thermal acid generator also functions as a catalyst for promoting the crosslinking reaction, and examples thereof include a fourth-order ammonium salt of trifluoromethanesulfonic acid. One type of the acidic compound and the thermal acid generator may be added, and two or more types may be added in combination. The content ratio of the acidic compound or the thermal acid generator is, for example, 0.1% by mass to 20% by mass based on the solid content of the solvent to be described later from the photoresist underlayer film forming composition of the present invention.
本發明的光阻下層膜形成組成物可進而含有界面活性劑。作為前述界面活性劑,可列舉例如:聚氧乙烯月桂基醚、聚氧乙烯硬脂醯基醚、聚氧乙烯十六基醚、聚氧乙烯油烯基醚等之聚氧乙烯烷基醚類、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等之聚氧乙烯烷基芳基醚類、聚氧乙烯‧聚氧丙烯嵌段共聚物類、山梨醇酐單月桂酸酯、山梨醇酐單棕櫚酸酯、山梨醇酐單硬脂酸酯、山梨醇酐單油酸酯、山梨醇酐三油酸酯、山梨醇酐三硬脂酸酯等之山梨醇酐脂肪酸酯類、聚氧乙烯山梨醇酐單月桂酸酯、聚氧乙烯山梨醇酐單棕櫚酸酯、聚氧乙烯山梨醇酐單硬脂酸酯、聚氧乙烯山梨醇酐三油酸酯、聚氧乙烯山梨醇酐三硬脂酸酯等之聚氧乙烯山梨醇酐脂肪酸酯類等之非離子系界面活性劑、Eftop[註冊商標]EF301、同EF303、同EF352(三菱材料電子化成(股)製)、Megafac[註冊商標]F171、同F173、同R-30、同R-30-N、同R-40、同R-40-LM(DIC(股)製)、Fluorad FC430、同FC431(住友3M(股)製)、Asahiguide[註冊商標]AG710、 Surflon[註冊商標]S-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106(旭硝子(股)製)等之氟系界面活性劑、有機聚矽氧烷聚合物KP341(信越化學工業(股)製)。可添加選自此等界面活性劑之1種類,亦可組合2種以上添加。前述界面活性劑之含有比例係相對於從本發明的光阻下層膜形成組成物去除後述溶劑之固形分而言,例如為0.01質量%至5質量%。 The photoresist underlayer film forming composition of the present invention may further contain a surfactant. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl sulfonyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oleyl ether. Polyoxyethylene alkyl aryl ether, polyoxyethylene ‧ polyoxypropylene block copolymer, sorbitan monolaurate Sorbitol fatty acid esters such as sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate , polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol A nonionic surfactant such as a polyoxyethylene sorbitan fatty acid ester such as an alcoholic anhydride tristearate, Eftop [registered trademark] EF301, EF303, and EF352 (manufactured by Mitsubishi Materials Corporation) Megafac [registered trademark] F171, with F173, with R-30, with R-30-N, with R-40, with R-40-LM (DIC) ), Fluorad FC430, FC431 (Sumitomo 3M (share) system), Asahiguide [registered trademark] AG710, Surflon [registered trademark] S-382, same as SC101, with SC102, with SC103, with SC104, with SC105, with SC106 (asahi (product)), fluorine-based surfactant, organic polyoxyalkylene polymer KP341 ( Shin-Etsu Chemical Industry Co., Ltd.). One type of the surfactant selected from these may be added, or two or more types may be added in combination. The content ratio of the surfactant is, for example, 0.01% by mass to 5% by mass based on the solid content of the solvent to be described later from the photoresist underlayer film forming composition of the present invention.
本發明的光阻下層膜形成組成物係可藉由使上述各成分溶解於適當溶劑中而調製,且係在均勻溶液狀態下使用。作為如此般溶劑,可列舉例如:乙二醇單甲基醚、乙二醇單乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇、丙二醇單甲基醚、丙二醇單丙基醚、丙二醇單甲基醚乙酸酯、丙二醇丙基醚乙酸酯、甲基賽璐蘇乙酸酯、乙基賽璐蘇乙酸酯、甲苯、二甲苯、甲基乙基酮、環戊酮、環己酮、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸甲酯、丙酮酸甲酯、丙酮酸乙酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮。此等有機溶劑可使用1種,或可將2種以上組合使用。從前述組成物去除有機溶劑之固形分之比例係例如為0.5質量%至30質量%,較佳為0.8質量%至15質量%。 The photoresist underlayer film forming composition of the present invention can be prepared by dissolving the above components in a suitable solvent, and is used in a uniform solution state. Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, and propylene glycol monomethyl ether. , propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, methyl cyproterone acetate, ethyl cyproterone acetate, toluene, xylene, methyl ethyl Ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3- Methyl methyl butyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, acetone Ester, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrole Pyridone. These organic solvents may be used alone or in combination of two or more. The ratio of the solid content of the organic solvent removed from the above composition is, for example, 0.5% by mass to 30% by mass, preferably 0.8% by mass to 15% by mass.
將本發明的光阻下層膜形成組成物塗布並烘 烤之步驟,係於基材(例如矽晶圓,而該矽晶圓亦可被氧化矽膜、氮化矽膜、氧化氮化矽膜、或鋁、鎢等之金屬膜所被覆)上,藉由旋轉塗布器、塗布器等之適當塗布方法塗布該組成物,之後,使用加熱板等之加熱手段並藉由烘烤而進行者。烘烤條件方面,可適宜選自烘烤溫度100℃至400℃、烘烤時間0.3分至10分鐘之中。 Coating and baking the photoresist underlayer film forming composition of the present invention The baking step is performed on a substrate (for example, a germanium wafer, and the germanium wafer may be coated with a tantalum oxide film, a tantalum nitride film, a tantalum oxide film, or a metal film of aluminum or tungsten). The composition is applied by a suitable coating method such as a spin coater or an applicator, and then it is carried out by baking using a heating means such as a hot plate. In terms of baking conditions, it may be suitably selected from a baking temperature of from 100 ° C to 400 ° C and a baking time of from 0.3 minutes to 10 minutes.
於藉由前述步驟所形成的第1光阻下層膜上形成有機聚矽氧烷膜作為第2光阻下層膜,且於其上形成光阻圖型。此第2光阻下層膜可為藉由CVD、PVD等蒸鍍法所形成的SiON膜或SiN膜。更,於此第2光阻下層膜上亦可形成防反射膜(BARC)作為第3光阻下層膜,該第3光阻下層膜亦可為不具有防反射能的光阻形狀補正膜。形成前述光阻圖型之步驟中,曝光藉由通過形成指定的圖型用之遮罩(Reticle)或以直接描繪而進行者。曝光源係可使用例如:g線、i線、KrF準分子雷射、ArF準分子雷射、EUV、電子線。曝光後,因應所需可施行曝光後加熱(Post Exposure Bake)。之後,藉由顯影液(例如2.38質量%氫氧化四甲基銨水溶液)來進行顯影,並再注入潤洗液或純水,去除已使用的顯影液。之後,施行光阻圖型之乾燥及提高與基底之密著性之後烘烤。 An organic polysiloxane film is formed on the first photoresist underlayer film formed by the above steps as a second photoresist underlayer film, and a photoresist pattern is formed thereon. The second photoresist underlayer film may be an SiON film or a SiN film formed by a vapor deposition method such as CVD or PVD. Further, an antireflection film (BARC) may be formed on the second photoresist underlayer film as the third photoresist underlayer film, and the third photoresist underlayer film may be a photoresist shape correction film having no antireflection energy. In the step of forming the aforementioned photoresist pattern, exposure is performed by forming a mask for a specified pattern or by direct drawing. As the exposure source, for example, a g line, an i line, a KrF excimer laser, an ArF excimer laser, an EUV, an electron line can be used. After exposure, Post Exposure Bake can be performed as needed. Thereafter, development is carried out by a developing solution (for example, 2.38 mass% aqueous solution of tetramethylammonium hydroxide), and a rinse liquid or pure water is further injected to remove the used developer. Thereafter, the photoresist pattern is dried and the adhesion to the substrate is improved, followed by baking.
前述光阻圖型形成後所進行的蝕刻步驟,其係藉由乾蝕刻來進行。作為乾蝕刻所使用的蝕刻氣體,在對於第2光阻下層膜(有機聚矽氧烷膜)而言,可列舉例如CHF3、CF4、C2F6,在對於由本發明的光阻下層膜形成 組成物所形成的第1光阻下層膜而言,可列舉例如O2、N2O、NO2,在對於具有段差或凹部及/或凸部的表面而言,可列舉例如CHF3、CF4、C2F6。更,此等氣體亦可混合氬、氮或二氧化碳後使用。 The etching step performed after the formation of the photoresist pattern is performed by dry etching. The etching gas used for the dry etching is, for example, CHF 3 , CF 4 , or C 2 F 6 for the second photoresist lower layer film (organic polyoxyalkylene film), and the lower layer for the photoresist of the present invention. The first photoresist underlayer film formed of the film formation composition may, for example, be O 2 , N 2 O or NO 2 , and for the surface having a step or a concave portion and/or a convex portion, for example, CHF 3 may be mentioned. , CF 4 , C 2 F 6 . Further, these gases may be used after mixing argon, nitrogen or carbon dioxide.
以下,列舉合成例及實施例說明關於本發明,但本發明並不受到下述記載所限定。 Hereinafter, the present invention will be described by way of Synthesis Examples and Examples, but the present invention is not limited by the following description.
下述合成例1至合成例3、比較合成例1及比較合成例2中表示之重量平均分子量及多分散度,係根據藉由凝膠滲透層析法(以下,本說明書中略稱GPC)所得之測量結果。測量係使用東曹(股)製GPC系統,且測量條件係如下述所示。 The weight average molecular weight and polydispersity shown in the following Synthesis Example 1 to Synthesis Example 3, Comparative Synthesis Example 1 and Comparative Synthesis Example 2 are obtained by gel permeation chromatography (hereinafter, abbreviated as GPC in the present specification). The measurement results. The measurement system used a GPC system manufactured by Tosoh Co., Ltd., and the measurement conditions were as follows.
GPC管柱:TSKgel SuperMultipore[註冊商標]Hz-N(東曹(股)) GPC pipe column: TSKgel SuperMultipore [registered trademark] Hz-N (Dongcao (share))
管柱溫度:40℃ Column temperature: 40 ° C
溶媒:四氫呋喃(THF) Solvent: tetrahydrofuran (THF)
流量:0.35ml/分 Flow rate: 0.35ml/min
標準試料:聚苯乙烯(東曹(股)) Standard sample: polystyrene (Dongcao (share))
於200mL四頸燒瓶中添加3,3’,5,5’-四甲氧基甲基-4,4’-二羥基聯苯(以下,本說明書中略稱為TMOM-BP)(23.83g、0.066mol、本州化學工業(股)製)、芘 (27.00g、0.134mol、東京化成工業(股)製)、對甲苯磺酸一水合物(0.53g、0.003mol、東京化成工業(股)製),再置入1,4-噁烷(119.84g、關東化學(股)製),進行攪拌,昇溫至確認到回流為止,使其溶解並開始聚合。6小時後放冷至60℃,之後,使再沈澱於甲醇(1000g、關東化學(股)製)中。過濾所得到的沈澱物,使用減壓乾燥機以60℃、12小時使其乾燥,而得到具有下述式(3)所表示的結構單元的目的之聚合物(以下,本說明書中略稱為TMOM-Py)28.6g。所得到的TMOM-Py之藉由GPC所測量之以聚苯乙烯換算的重量平均分子量為2600。 3,3',5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl (hereinafter, abbreviated as TMOM-BP in the present specification) (23.83 g, 0.066) was added to a 200 mL four-necked flask. Mol, Honshu Chemical Industry Co., Ltd.) (27.00g, 0.134mol, manufactured by Tokyo Chemical Industry Co., Ltd.), p-toluenesulfonic acid monohydrate (0.53g, 0.003mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and then placed with 1,4-oxane (119.84) g. Kanto Chemical Co., Ltd.), stirred, and heated until the reflux was confirmed, dissolved and started to polymerize. After 6 hours, it was allowed to cool to 60 ° C, and then reprecipitated in methanol (1000 g, manufactured by Kanto Chemical Co., Ltd.). The obtained precipitate was filtered and dried using a vacuum dryer at 60 ° C for 12 hours to obtain a polymer having the objective of the following formula (3) (hereinafter, abbreviated as TMOM in the present specification) -Py) 28.6g. The obtained TMOM-Py had a weight average molecular weight of 2,600 in terms of polystyrene measured by GPC.
於100mL四頸燒瓶中添加TMOM-BP(2.21g、0.006mol、本州化學工業(股)製)、咔唑(5.00g、0.030mol 、東京化成工業(股)製)、1-芘甲醛(1-pyrenecarboxaldehyde)(5.76g、0.025mol、Sigma-Aldrich公司製)、對甲苯磺酸一水合物(0.89g、0.006mol、東京化成工業(股)製),再置入1,4-噁烷(25.75g、關東化學(股)製),進行攪拌,昇溫至確認到回流為止,使其溶解並開始聚合。7小時後放冷至60℃,之後,使再沈澱於甲醇(1000g、關東化學(股)製)中。過濾所得到的沈澱物,使用減壓乾燥機以60℃、12小時使其乾燥,而得到具有下述式(4)所表示的2種結構單元的目的之聚合物(以下,本說明書中略稱為TMOM-Cz-PCA)6.3g。所得到的TMOM-Cz-PCA之藉由GPC所測量之以聚苯乙烯換算的重量平均分子量為8900。 TMOM-BP (2.21g, 0.006mol, manufactured by Honshu Chemical Industry Co., Ltd.), carbazole (5.00g, 0.030mol) was added to a 100 mL four-necked flask. , Tokyo Chemical Industry Co., Ltd.), 1-pyrenecarboxaldehyde (5.76 g, 0.025 mol, manufactured by Sigma-Aldrich Co., Ltd.), p-toluenesulfonic acid monohydrate (0.89 g, 0.006 mol, Tokyo Chemical Industry Co., Ltd.) (manufactured by the company), 1,4-oxane (25.75 g, manufactured by Kanto Chemical Co., Ltd.) was placed, stirred, and the temperature was raised until the reflux was confirmed, and the polymerization was started. After 7 hours, it was allowed to cool to 60 ° C, and then reprecipitated in methanol (1000 g, manufactured by Kanto Chemical Co., Ltd.). The obtained precipitate was filtered, and dried at 60 ° C for 12 hours using a vacuum dryer to obtain a polymer having the following two structural units represented by the following formula (4) (hereinafter, abbreviated in the present specification) For TMOM-Cz-PCA) 6.3g. The weight average molecular weight of the obtained TMOM-Cz-PCA measured by GPC in terms of polystyrene was 8,900.
於200mL四頸燒瓶中添加TMOM-BP(13.93g、0.038mol、本州化學工業(股)製)、萘(10.00g、0.078mol、東京化成工業(股)製)、對甲苯磺酸一水合物(0.31g、0.002mol、東京化成工業(股)製),再置入1,4-噁烷(56.56g、關東化學(股)製),進行攪拌,昇溫至確認到回流為止,使其溶解並開始聚合。5小時後放冷至60℃,之後,使再沈澱於甲醇(1000g、關東化學(股)製)中。過濾所得到的沈澱物,使用減壓乾燥機以60℃、12小時使其乾燥,而得到具有下述式(5)所表示的結構單元的目的之聚合物(以下,本說明書中略稱為TMOM-Na)5.9g。所得到的TMOM-Na之藉由GPC所測量之以聚苯乙烯換算的重量平均分子量為5000。 To a 200 mL four-necked flask, TMOM-BP (13.93 g, 0.038 mol, manufactured by Honshu Chemical Industry Co., Ltd.), naphthalene (10.00 g, 0.078 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), p-toluenesulfonic acid monohydrate was added. (0.31 g, 0.002 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and then placed 1,4-oxane (56.56 g, manufactured by Kanto Chemical Co., Ltd.), stirred, and heated until the reflux was confirmed to dissolve. And start to aggregate. After 5 hours, it was allowed to cool to 60 ° C, and then reprecipitated in methanol (1000 g, manufactured by Kanto Chemical Co., Ltd.). The obtained precipitate was filtered, and dried at 60 ° C for 12 hours using a vacuum dryer to obtain a polymer having the objective of the following formula (5) (hereinafter, abbreviated as TMOM in the present specification) -Na) 5.9 g. The obtained TMOM-Na had a weight average molecular weight of 5,000 in terms of polystyrene measured by GPC.
在氮氣下,於100mL四頸燒瓶中添加咔唑(6.69g、 0.040mol、東京化成工業(股)製)、9-茀酮(7.28g、0.040mol、東京化成工業(股)製)、對甲苯磺酸一水合物(0.76g、0.0040mol、東京化成工業(股)製),再置入1,4-噁烷(6.69g、關東化學(股)製),進行攪拌,昇溫至100℃為止,使其溶解並開始聚合。24小時後放冷至60℃,之後添加氯仿(34g、關東化學(股)製)使稀釋,並使再沈澱於甲醇(168g、關東化學(股)製)中。過濾所得到的沈澱物,使用減壓乾燥機以80℃、24小時使其乾燥,而得到具有下述式(6)所表示的結構單元的目的之聚合物9.37g。所得到的聚合物之藉由GPC所測量之以聚苯乙烯換算的重量平均分子量為2800。 Add carbazole (6.69 g, in a 100 mL four-necked flask under nitrogen) 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd., 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, Tokyo Chemical Industry Co., Ltd.) In the system), 1,4-oxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was placed, stirred, and heated to 100 ° C to dissolve and start polymerization. After 24 hours, it was allowed to cool to 60 ° C, and then chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.) was added to dilute it, and it was reprecipitated in methanol (168 g, manufactured by Kanto Chemical Co., Ltd.). The obtained precipitate was filtered, and dried at 80 ° C for 24 hours using a vacuum dryer to obtain 9.37 g of a polymer having a structural unit represented by the following formula (6). The obtained polymer had a weight average molecular weight of 2,800 in terms of polystyrene as measured by GPC.
對合成例1中取得之聚合物20g混合界面活性劑之Megafac R-30(DIC(股)製)0.06g,使其溶解於環己酮80g而作成溶液。之後,使用孔徑0.10μm之聚乙烯製微濾器進行過濾,再更使用孔徑0.05μm之聚乙烯製微濾器 進行過濾,而調製成藉由多層膜所構成的微影製程用光阻下層膜形成組成物。 To a solution of 20 g of the polymer obtained in Synthesis Example 1, a mixed surfactant of 0.06 g of Megafac R-30 (manufactured by DIC Co., Ltd.) was dissolved in 80 g of cyclohexanone to prepare a solution. Thereafter, filtration was carried out using a polyethylene microfilter having a pore size of 0.10 μm, and a polyethylene microfilter having a pore diameter of 0.05 μm was further used. Filtration was carried out to prepare a composition for forming a photoresist film for a lithography process composed of a multilayer film.
對合成例2中取得之聚合物20g混合界面活性劑之Megafac R-30(DIC(股)製)0.06g,使其溶解於環己酮80g而作成溶液。之後,使用孔徑0.10μm之聚乙烯製微濾器進行過濾,再更使用孔徑0.05μm之聚乙烯製微濾器進行過濾,而調製成藉由多層膜所構成的微影製程用光阻下層膜形成組成物。 To 20 g of a polymer obtained in Synthesis Example 2, 0.06 g of Megafac R-30 (manufactured by DIC Co., Ltd.) was mixed with a surfactant, and dissolved in 80 g of cyclohexanone to prepare a solution. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a photoreceptor underlayer film formed by a multilayer film. Things.
對合成例3中取得之聚合物20g混合界面活性劑之Megafac R-30(DIC(股)製)0.06g,使其溶解於環己酮80g而作成溶液。之後,使用孔徑0.10μm之聚乙烯製微濾器進行過濾,再更使用孔徑0.05μm之聚乙烯製微濾器進行過濾,而調製成藉由多層膜所構成的微影製程用光阻下層膜形成組成物。 To 20 g of a polymer obtained in Synthesis Example 3, 0.06 g of Megafac R-30 (manufactured by DIC Co., Ltd.) was mixed with a surfactant, and dissolved in 80 g of cyclohexanone to prepare a solution. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a photoreceptor underlayer film formed by a multilayer film. Things.
對比較合成例1中取得之聚合物20g混合界面活性劑之Megafac R-30(DIC(股)製)0.06g,使其溶解於環己酮80g而作成溶液。之後,使用孔徑0.10μm之聚乙烯製微濾器進行過濾,再更使用孔徑0.05μm之聚乙烯製微濾 器進行過濾,而調製成藉由多層膜所構成的微影製程用光阻下層膜形成組成物。 To a mixture of 20 g of a polymer obtained in Synthesis Example 1 and 0.06 g of Megafac R-30 (manufactured by DIC Co., Ltd.), which was mixed with a surfactant, was dissolved in 80 g of cyclohexanone to prepare a solution. Thereafter, filtration was carried out using a polyethylene microfilter having a pore size of 0.10 μm, and further, a microfiltration of polyethylene having a pore diameter of 0.05 μm was further used. The device is filtered to form a composition for forming a photoresist film for a lithography process composed of a multilayer film.
對比較合成例1中取得之聚合物20g混合作為交聯劑的TMOM-BP(本州化學工業(股)製)3.0g、作為觸媒的吡啶鎓對甲苯磺酸酯0.6g、作為界面活性劑的Megafac R-30(DIC(股)製)0.06g,使其溶解於環己酮80g而作成溶液。之後,使用孔徑0.10μm之聚乙烯製微濾器進行過濾,再更使用孔徑0.05μm之聚乙烯製微濾器進行過濾,而調製成藉由多層膜所構成的微影製程用光阻下層膜形成組成物。 For the comparison of 20 g of the polymer obtained in Synthesis Example 1, 3.0 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.) and 0.6 g of pyridinium p-toluenesulfonate as a catalyst were mixed as a crosslinking agent. 0.06 g of Megafac R-30 (manufactured by DIC Co., Ltd.) was dissolved in 80 g of cyclohexanone to prepare a solution. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a photoreceptor underlayer film formed by a multilayer film. Things.
使用旋轉塗布器分別將實施例1至實施例3、比較例1及比較例2中調製的光阻下層膜形成組成物塗布於矽晶圓上。將已塗布的晶圓在加熱板上以240℃烘烤1分鐘、或以400℃烘烤2分鐘,而形成光阻下層膜(膜厚0.25μm)。將此等光阻下層膜使用奈米壓痕儀裝置G200(Agilent Technologies公司製)來測量膜之硬度。將其結果表示於表1中。 The photoresist underlayer film forming compositions prepared in Examples 1 to 3, Comparative Example 1, and Comparative Example 2 were applied onto a tantalum wafer using a spin coater. The coated wafer was baked on a hot plate at 240 ° C for 1 minute or at 400 ° C for 2 minutes to form a photoresist underlayer film (film thickness 0.25 μm). These photoresist underlayer films were measured for hardness by using a nanoindenter apparatus G200 (manufactured by Agilent Technologies). The results are shown in Table 1.
由上述表1之結果可得知,使用關於本發明的實施例1至實施例3的光阻下層膜形成組成物,並以400℃、2分鐘烘烤而形成的光阻下層膜,相較於使用比較例1及比較例2的光阻下層膜形成組成物並以相同條件烘烤而形成的光阻下層膜,本發明的光阻下層膜(實施例1~實施例3)具有高硬度。 From the results of Table 1 above, it was found that the photoresist underlayer film formed by baking the film under the photoresist of Examples 1 to 3 of the present invention and baked at 400 ° C for 2 minutes was compared. The photoresist underlayer film (Examples 1 to 3) of the present invention has high hardness after the photoresist underlayer film formed by using the photoresist underlayer film of Comparative Example 1 and Comparative Example 2 and baked under the same conditions. .
使用旋轉塗布器分別將實施例1至實施例3、比較例1中調製的光阻下層膜形成組成物塗布於矽晶圓上。將已塗布的晶圓在加熱板上以400℃烘烤2分鐘,而形成光阻下層膜(膜厚0.25μm)。將此光阻下層膜浸漬於光阻劑所使用的溶劑(乳酸乙酯、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、環己酮)中,並確認不溶於此等溶劑。 The photoresist underlayer film forming compositions prepared in Examples 1 to 3 and Comparative Example 1 were applied onto a tantalum wafer, respectively, using a spin coater. The coated wafer was baked on a hot plate at 400 ° C for 2 minutes to form a photoresist underlayer film (film thickness 0.25 μm). This photoresist underlayer film was immersed in a solvent (ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or cyclohexanone) used for the photoresist, and it was confirmed that it was insoluble in these solvents.
使用旋轉塗布器分別將實施例1至實施例3中調製的光阻下層膜形成組成物塗布於矽晶圓上。將已塗布的晶圓在加熱板上以240℃烘烤1分鐘、或以400℃烘烤2分鐘,而形成光阻下層膜(膜厚0.05μm)。將此等光阻下層膜使用分光橢圓測厚儀來測量在波長193nm的折射率(n值)及光學吸光係數(k值,亦稱為衰減係數)。將其結果表示於表2中。 The photoresist underlayer film forming compositions prepared in Examples 1 to 3 were respectively applied onto a tantalum wafer using a spin coater. The coated wafer was baked on a hot plate at 240 ° C for 1 minute or at 400 ° C for 2 minutes to form a photoresist underlayer film (film thickness 0.05 μm). These resistive underlayer films were measured using a spectroscopic elliptical thickness gauge to measure the refractive index (n value) at a wavelength of 193 nm and the optical absorptivity (k value, also referred to as an attenuation coefficient). The results are shown in Table 2.
使用旋轉塗布器分別將實施例1至實施例3中調製的光阻下層膜形成組成物塗布於矽晶圓上。將已塗布的晶圓在加熱板上以400℃烘烤2分鐘,而形成光阻下層膜(膜厚0.2μm)。將此等光阻下層膜從矽晶圓上刮取,而得到粉末體。使用TG/DTA(BRUKER公司製TG-DTA2010SR)來測量所得到的粉末體在400℃的熱重量減少。將其結果表示於表3中。 The photoresist underlayer film forming compositions prepared in Examples 1 to 3 were respectively applied onto a tantalum wafer using a spin coater. The coated wafer was baked on a hot plate at 400 ° C for 2 minutes to form a photoresist underlayer film (film thickness 0.2 μm). These photoresist underlayer films were scraped from the tantalum wafer to obtain a powder. The thermal weight reduction of the obtained powder body at 400 ° C was measured using TG/DTA (TG-DTA2010SR manufactured by BRUKER Co., Ltd.). The results are shown in Table 3.
乾蝕刻速度之測量所用的蝕刻器及蝕刻氣體為以下者。 The etcher and etching gas used for the measurement of the dry etching rate are as follows.
蝕刻器:RIE-10NR(Samco(股)製) Etch: RIE-10NR (made by Samco)
蝕刻氣體:CF4 Etching gas: CF 4
使用旋轉塗布器分別將實施例1至實施例3中調製的光阻下層膜形成組成物塗布於矽晶圓上。將已塗布的晶圓在加熱板上以240℃烘烤1分鐘、或以400℃烘烤2分鐘,而形成光阻下層膜(膜厚0.25μm)。接著,使用作為蝕刻氣體的CF4氣體,測量此等光阻下層膜之乾蝕刻速度。又,使用旋轉塗布器將苯酚酚醛樹脂(市售品,GPC所得之以聚苯乙烯換算所測量之重量平均分子量Mw為2000、多分散度Mw/Mn為2.5)溶液塗布於矽晶圓上,在加熱板上以205℃烘烤1分鐘而形成苯酚酚醛樹脂膜(膜厚0.25μm)。接著,使用作為蝕刻氣體的CF4氣體,並測量該苯酚酚醛樹脂膜之乾蝕刻速度。將此苯酚酚醛樹脂膜之乾蝕刻速度設成1.00時之由實施例1至實施例3中調製之光阻下層膜形成組成物所形成之光阻下層膜之乾蝕刻速度算出作為乾蝕刻速度比,其結果係如表4所示。乾 蝕刻速度比越小則表示對CF4氣體之耐蝕刻性越高。 The photoresist underlayer film forming compositions prepared in Examples 1 to 3 were respectively applied onto a tantalum wafer using a spin coater. The coated wafer was baked on a hot plate at 240 ° C for 1 minute or at 400 ° C for 2 minutes to form a photoresist underlayer film (film thickness 0.25 μm). Next, the dry etching rate of the underlying film of these photoresists was measured using CF 4 gas as an etching gas. Further, a solution of a phenol novolac resin (a commercially available product, a weight average molecular weight Mw measured by polystyrene in terms of polystyrene of 2000 and a polydispersity Mw/Mn of 2.5) obtained by a GPC was applied onto a tantalum wafer using a spin coater. The phenol phenol resin film (film thickness: 0.25 μm) was formed by baking at 205 ° C for 1 minute on a hot plate. Next, CF 4 gas as an etching gas was used, and the dry etching rate of the phenol phenol resin film was measured. When the dry etching rate of the phenol phenol resin film was set to 1.00, the dry etching rate of the photoresist underlayer film formed by the photoresist underlayer film forming compositions prepared in Examples 1 to 3 was calculated as the dry etching rate ratio. The results are shown in Table 4. The smaller the dry etching rate ratio, the higher the etching resistance to CF 4 gas.
乾蝕刻速度比=(光阻下層膜之乾蝕刻速度)/(苯酚酚醛樹脂膜之乾蝕刻速度) Dry etching rate ratio = (dry etching rate of photoresist underlayer film) / (dry etching rate of phenol novolak film)
使用旋轉塗布器分別將實施例1至實施例3及比較例2中調製的光阻下層膜形成組成物塗布於附有氧化矽膜的矽晶圓上。將已塗布的晶圓在加熱板上以400℃烘烤2分鐘,而形成光阻下層膜(膜厚200nm)。於該光阻下層膜上塗布含有聚矽氧烷的習知矽硬遮罩形成組成物,將其以240℃烘烤1分鐘後而形成矽硬遮罩層(膜厚45nm)。更,於其上塗布光阻溶液(PAR855 S90(住友化學(股)製)),將其以100℃烘烤1分鐘後而形成光阻層(膜厚120nm)。使用遮罩將此光阻層以波長193nm進行曝光,並進行曝光後加熱(PEB,以105℃、1分鐘),之後顯影而得到光阻圖型。之後,以氟系氣體(成分為CF4)來進行乾蝕刻,而將光阻圖型轉印至硬遮罩層。接下來,以氧系氣體(成分為O2)來進行乾蝕刻,而將光阻圖型轉印至上述光阻下層膜。之後,更以氟系氣體(成分為 C4F8)來進行乾蝕刻,來進行矽晶圓上的氧化矽膜之去除。最終,使用電子顯微鏡來觀察分別所得到的圖型形狀。 The photoresist underlayer film forming compositions prepared in Examples 1 to 3 and Comparative Example 2 were applied onto a tantalum wafer with a hafnium oxide film, respectively, using a spin coater. The coated wafer was baked on a hot plate at 400 ° C for 2 minutes to form a photoresist underlayer film (film thickness: 200 nm). A conventional hard mask forming composition containing polyoxyalkylene was applied onto the underlayer film of the photoresist, and baked at 240 ° C for 1 minute to form a hard mask layer (film thickness: 45 nm). Further, a photoresist solution (PAR855 S90 (manufactured by Sumitomo Chemical Co., Ltd.)) was applied thereon, and baked at 100 ° C for 1 minute to form a photoresist layer (film thickness: 120 nm). This photoresist layer was exposed to light at a wavelength of 193 nm using a mask, and subjected to post-exposure heating (PEB at 105 ° C for 1 minute), followed by development to obtain a photoresist pattern. Thereafter, dry etching is performed using a fluorine-based gas (component is CF 4 ), and the photoresist pattern is transferred to the hard mask layer. Next, dry etching is performed using an oxygen-based gas (component is O 2 ), and the photoresist pattern is transferred to the photoresist underlayer film. Thereafter, dry etching is performed using a fluorine-based gas (component is C 4 F 8 ) to remove the cerium oxide film on the germanium wafer. Finally, an electron microscope was used to observe the shape of the pattern obtained separately.
伴隨著圖型寬度變窄易產生被稱為彎曲(wiggling)之不規則的圖型之彎曲,因而,使用上述實施例1至實施例3中調製的光阻下層膜形成組成物來進行上述圖型形成步驟時,以電子顯微鏡可觀測到所得到的圖型已開始出現彎曲(wiggling)。發生圖型之彎曲(wiggling)時,將無法基於忠實的圖型來加工基板,因此,需藉由在產生圖型之彎曲(波浪狀)之前的圖型寬度(界限圖型寬度)來進行基板加工。開始產生圖型之彎曲(wiggling)的界限圖型寬度,當該值愈窄愈可進行微細的基板加工。解析度之測量係使用測長掃描型電子顯微鏡((股)Hitachi High-Technologies製)。將測量結果表示於表5中。 As the width of the pattern is narrowed, it is easy to produce a curvature of an irregular pattern called wiggling. Therefore, the above-described pattern is formed by using the photoresist underlayer film forming composition prepared in the above-described Embodiments 1 to 3. In the type forming step, it was observed by an electron microscope that the resulting pattern had begun to appear to be wigling. When a pattern wagling occurs, the substrate cannot be processed based on a faithful pattern. Therefore, the substrate width (bound pattern width) before the curvature (wavy) of the pattern is generated machining. The boundary pattern width of the wiggling of the pattern is started to be generated, and the narrower the value, the finer substrate processing can be performed. The measurement of the resolution was performed using a length-measuring scanning electron microscope (manufactured by Hitachi High-Technologies). The measurement results are shown in Table 5.
本發明的藉由多層膜所構成的微影製程用光阻下層膜形成組成物,可提供亦能兼具作為防反射膜效果的光阻下層膜。又,得知本發明的光阻下層膜形成組成物 係具有可於其上層以CVD法來形成硬遮罩的耐熱性。又,即使是縮小圖型寬度之情形,亦不易產生圖型之彎曲(wiggling)並可得到良好圖型,可得到在至少50nm附近的圖型寬度為未產生彎曲的良好圖型。 In the lithographic process photoresist underlayer film formed of a multilayer film of the present invention, a photoresist underlayer film which can also serve as an antireflection film can be provided. Further, the photoresist underlayer film forming composition of the present invention is known It has heat resistance in which a hard mask can be formed by a CVD method on its upper layer. Further, even in the case where the width of the pattern is reduced, it is less likely to cause wiggling of the pattern and a good pattern can be obtained, and a pattern having a pattern width of at least about 50 nm is obtained as a good pattern in which no bending occurs.
Claims (6)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013086861 | 2013-04-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
TW201504766A true TW201504766A (en) | 2015-02-01 |
Family
ID=51731278
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103113545A TW201504766A (en) | 2013-04-17 | 2014-04-14 | Resist underlayer film forming composition |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP6327481B2 (en) |
KR (1) | KR102004697B1 (en) |
CN (1) | CN105143979B (en) |
TW (1) | TW201504766A (en) |
WO (1) | WO2014171326A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI748087B (en) * | 2017-04-25 | 2021-12-01 | 日商日產化學工業股份有限公司 | Resistor underlayer film forming composition using stilbene compound |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102552910B1 (en) * | 2015-03-06 | 2023-07-10 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Compound, resin, material for forming lower layer film for lithography, lower layer film for lithography, pattern formation method, and purification method of compound or resin |
CN107340688B (en) * | 2016-04-29 | 2022-05-06 | 东友精细化工有限公司 | Composition for hard mask |
CN117539127A (en) * | 2017-01-13 | 2024-02-09 | 日产化学株式会社 | Composition for forming resist underlayer film containing amide solvent |
KR102349937B1 (en) * | 2017-03-27 | 2022-01-10 | 동우 화인켐 주식회사 | Composition for hard mask |
KR102383692B1 (en) * | 2017-06-30 | 2022-04-05 | 동우 화인켐 주식회사 | Composition for hard mask |
US11248086B2 (en) | 2018-05-01 | 2022-02-15 | Tokyo Ohka Kogyo Co., Ltd. | Hard-mask forming composition and method for manufacturing electronic component |
KR20210113990A (en) * | 2019-01-11 | 2021-09-17 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Film formation composition, resist composition, radiation-sensitive composition, amorphous film production method, resist pattern formation method, lithography underlayer film formation composition, lithography underlayer film production method and circuit pattern formation method |
JPWO2021112194A1 (en) * | 2019-12-04 | 2021-06-10 | ||
JPWO2021172296A1 (en) | 2020-02-28 | 2021-09-02 | ||
WO2021172295A1 (en) | 2020-02-28 | 2021-09-02 | 日産化学株式会社 | Composition for forming resist underlayer film |
CN116419937A (en) | 2020-11-19 | 2023-07-11 | 日产化学株式会社 | Composition for forming resist underlayer film |
WO2022244710A1 (en) | 2021-05-18 | 2022-11-24 | 日産化学株式会社 | Composition for forming resist underlayer film |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4570485B2 (en) * | 2005-03-04 | 2010-10-27 | 株式会社ニデック | Ophthalmic equipment |
JP4539845B2 (en) * | 2005-03-17 | 2010-09-08 | 信越化学工業株式会社 | Photoresist underlayer film forming material and pattern forming method |
JP4592463B2 (en) * | 2005-03-24 | 2010-12-01 | 三菱電線工業株式会社 | Electrical connector |
US7375172B2 (en) | 2005-07-06 | 2008-05-20 | International Business Machines Corporation | Underlayer compositions containing heterocyclic aromatic structures |
JP4662063B2 (en) | 2006-05-25 | 2011-03-30 | 信越化学工業株式会社 | Photoresist underlayer film forming material and pattern forming method |
US8017296B2 (en) | 2007-05-22 | 2011-09-13 | Az Electronic Materials Usa Corp. | Antireflective coating composition comprising fused aromatic rings |
KR101579266B1 (en) * | 2008-01-11 | 2016-01-04 | 닛산 가가쿠 고교 가부시키 가이샤 | Composition Having Urea Group For Forming Silicon-Containing Resist Underlying Film |
WO2012067040A1 (en) * | 2010-11-17 | 2012-05-24 | 日産化学工業株式会社 | Resist underlayer film forming composition, and method for forming resist pattern using same |
US8906592B2 (en) * | 2012-08-01 | 2014-12-09 | Az Electronic Materials (Luxembourg) S.A.R.L. | Antireflective coating composition and process thereof |
-
2014
- 2014-04-01 WO PCT/JP2014/059633 patent/WO2014171326A1/en active Application Filing
- 2014-04-01 JP JP2015512438A patent/JP6327481B2/en active Active
- 2014-04-01 CN CN201480021117.6A patent/CN105143979B/en active Active
- 2014-04-01 KR KR1020157027401A patent/KR102004697B1/en active IP Right Grant
- 2014-04-14 TW TW103113545A patent/TW201504766A/en unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI748087B (en) * | 2017-04-25 | 2021-12-01 | 日商日產化學工業股份有限公司 | Resistor underlayer film forming composition using stilbene compound |
Also Published As
Publication number | Publication date |
---|---|
KR20160002741A (en) | 2016-01-08 |
JP6327481B2 (en) | 2018-05-23 |
CN105143979A (en) | 2015-12-09 |
KR102004697B1 (en) | 2019-07-29 |
CN105143979B (en) | 2019-07-05 |
JPWO2014171326A1 (en) | 2017-02-23 |
WO2014171326A1 (en) | 2014-10-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI595322B (en) | Resist underlayer film forming composition | |
TW201504766A (en) | Resist underlayer film forming composition | |
CN107077071B (en) | Resist underlayer film forming composition containing polymer having arylene group | |
JP7287389B2 (en) | Composition for forming resist underlayer film using carbon-oxygen double bond | |
TWI783812B (en) | Resist underlayer film-forming composition | |
US10191374B2 (en) | Resist underlayer film-forming composition | |
TWI602026B (en) | Resist underlayer film forming composition | |
CN108713164B (en) | Composition for forming resist underlayer film and method for forming resist pattern using same | |
KR102508058B1 (en) | Resist underlayer film forming composition using fluorene compound | |
JP2023062060A (en) | Resist underlayer film-forming composition | |
WO2020255984A1 (en) | Composition for forming resist underlayer film capable of wet etching, containing heterocyclic compound having dicyanostyryl group | |
TWI727044B (en) | Resist underlayer film forming composition | |
TWI834886B (en) | Wet-etchable resist underlayer film-forming composition containing dicyanostyrene group, method for manufacturing patterned substrate, and method for manufacturing semiconductor device | |
WO2022107759A1 (en) | Resist underlayer film-forming composition | |
CN114174926A (en) | Composition for forming resist underlayer film |