CN106133606B - 添加剂以及包含该添加剂的抗蚀剂下层膜形成用组合物 - Google Patents
添加剂以及包含该添加剂的抗蚀剂下层膜形成用组合物 Download PDFInfo
- Publication number
- CN106133606B CN106133606B CN201580015088.7A CN201580015088A CN106133606B CN 106133606 B CN106133606 B CN 106133606B CN 201580015088 A CN201580015088 A CN 201580015088A CN 106133606 B CN106133606 B CN 106133606B
- Authority
- CN
- China
- Prior art keywords
- formula
- lower membrane
- indicate
- additive
- structural unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
- C08F12/24—Phenols or alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
- C08F212/24—Phenols or alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/385—Esters containing sulfur and containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- 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
-
- 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
- G03F7/094—Multilayer resist systems, e.g. planarising layers
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
- G03F7/2006—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light using coherent light; using polarised light
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
Abstract
本发明的课题是提供用于抗蚀剂下层膜形成用组合物的添加剂、以及包含该添加剂的抗蚀剂下层膜形成用组合物。本发明的解决方法是一种用于抗蚀剂下层膜形成用组合物的添加剂、以及包含前述添加剂的抗蚀剂下层膜形成用组合物,所述添加剂含有具有下述式(1)~式(4)所示的结构单元的共聚物(式中,R1分别独立地表示氢原子或甲基,Ar表示亚芳基,Pr表示保护基或氢原子,X表示直接结合或‑C(=O)O‑R2‑基,构成该‑C(=O)O‑R2‑基的R2表示碳原子数为1~3的亚烷基,该亚烷基与硫原子结合,R3表示氢原子、甲基、甲氧基或卤素,R4表示至少1个氢原子被氟取代了的碳原子数为1~3的烷基,Z表示具有四元环~七元环的内酯骨架、金刚烷骨架或降冰片烷骨架的有机基团。)。
Description
技术领域
本发明涉及添加到抗蚀剂下层膜形成用组合物中的添加剂。特别涉及以在抗蚀剂下层膜上形成期望的形状的抗蚀剂图案为目的的添加剂。进而涉及包含该添加剂的抗蚀剂下层膜形成用组合物。
背景技术
在ArF液浸光刻、极紫外线(EUV)光刻中,要求抗蚀剂线宽度的加工尺寸的微细化。由于在这样微细的抗蚀剂图案的形成中,抗蚀剂图案与底层基板的接触面积变小,因而抗蚀剂图案的纵横比(抗蚀剂图案的高度/抗蚀剂图案的线宽度)变大,担心容易发生抗蚀剂图案的倒塌。因此,在与抗蚀剂图案接触的抗蚀剂下层膜(防反射膜)中,要求与抗蚀剂图案高的密合性,以便不发生前述倒塌。
已经报道了:在抗蚀剂下层膜中,为了表现与抗蚀剂图案的高密合性,通过使用含有内酯结构的抗蚀剂下层膜形成用组合物,从而提高相对于所得的抗蚀剂图案的密合性(专利文献1)。即,通过使用含有内酯结构这样的极性部位的抗蚀剂下层膜形成用组合物,从而对抗蚀剂图案的密合性提高,即使在微细的抗蚀剂图案中也可以期待能够防止抗蚀剂图案的倒塌。
然而,在ArF液浸光刻、极紫外线(EUV)光刻这样要求制作更微细的抗蚀剂图案的光刻工艺中,仅仅依靠含有内酯结构作为抗蚀剂下层膜形成用组合物,对防止抗蚀剂图案的倒塌而言不能说是充分的。
为了实现抗蚀剂下层膜与抗蚀剂图案的高密合性,专利文献2中记载了能够使抗蚀剂下层膜的表面状态改性为碱性状态、抑制抗蚀剂图案的下摆形状变为咬边(undercut)形状的用于抗蚀剂下层膜形成用组合物的添加剂。另一方面,专利文献3中记载了一种用于抗蚀剂下层膜形成用组合物的添加剂,其通过使添加剂成分偏向在抗蚀剂下层膜的表面附近析出,从而能够抑制抗蚀剂图案的下摆形状变为裙形(footing shape)。
专利文献4中记载了一种光刻用抗蚀剂下层膜形成用组合物,含有共聚物、交联剂以及溶剂,所述共聚物具有将磺酸基导入到末端的结构单元。而且,专利文献4记载的发明能够提供一种抗蚀剂下层膜,其能够发挥抑制在形成抗蚀剂下层膜时来源于交联催化剂成分的升华物的产生的效果,能够形成下部几乎不具有裙形的良好的形状的抗蚀剂图案。
现有技术文献
专利文献
专利文献1:国际公开第03/017002号
专利文献2:国际公开第2013/058189号
专利文献3:国际公开第2010/074075号
专利文献4:日本特开2010-237491号公报
发明内容
发明所要解决的课题
在形成抗蚀剂图案时,在显影工序中,有时不采用使用碱性显影液除去由正型抗蚀剂溶液形成的抗蚀剂膜的曝光部的方法,而采用使用能够溶解抗蚀剂膜的溶剂、通常为有机溶剂来除去前述抗蚀剂膜的未曝光部分,留下该抗蚀剂膜的曝光部作为抗蚀剂图案的方法。在采用后者的方法的情况下,利用上述的现有技术,难以同时满足防止抗蚀剂图案倒塌的效果和将抗蚀剂图案的截面形状制成挺直形状(straight shape)的效果。因此,本发明的目的在于,提供能够防止抗蚀剂图案的倒塌、且能够将抗蚀剂图案的截面形状制成挺直形状的用于抗蚀剂下层膜形成用组合物的添加剂、以及包含该添加剂的抗蚀剂下层膜形成用组合物。
用于解决课题的方法
本发明的第一方案是一种添加剂,用于抗蚀剂下层膜形成用组合物,含有具有下述式(1)~式(4)所示的结构单元的共聚物,
(式中,R1分别独立地表示氢原子或甲基,Ar表示亚芳基,Pr表示保护基或氢原子,X表示直接结合或-C(=O)O-R2-基,构成该-C(=O)O-R2-基的R2表示碳原子数为1~3的亚烷基,该亚烷基与硫原子结合,R3表示氢原子、甲基、甲氧基或卤素,R4表示至少1个氢原子被氟取代了的碳原子数为1~3的烷基,Z表示具有四元环~七元环的内酯骨架、金刚烷骨架或降冰片烷骨架的有机基团。)
前述保护基是例如,乙酰基、甲氧基甲基、乙氧基乙基、碳原子数为4~8的叔烷基、或三甲基乙酰基。在本发明中,作为前述保护基,优选在酸性条件下受热而脱离的保护基。
前述式(2)所示的结构单元是例如,下述式(2a)或式(2b)所示的结构单元。
(式中,R1分别独立地表示氢原子或甲基,R2表示碳原子数为1~3的亚烷基,R3表示氢原子、甲基、甲氧基或卤素。)
前述式(4)所示的结构单元是例如,下述式(4a)所示的结构单元。
(式中、R1分别独立地氢原子或甲基,R5表示碳原子数为2~5的烃基。)
前述共聚物是使形成前述式(1)所示的结构单元的单体、形成前述式(2)所示的结构单元的单体、形成前述式(3)所示的结构单元的单体、以及形成前述式(4)所示的结构单元的单体共聚而合成的化合物,形成前述式(2)所示的结构单元的单体相对于前述4种单体的合计100摩尔%的比例为例如5~40摩尔%,优选为5~30摩尔%。在形成前述式(2)所示的结构单元的单体的比例超过40摩尔%的情况下,所合成的共聚物有时容易凝胶化。那样的共聚物不易溶解于溶剂中。另一方面,在形成前述式(2)所示的结构单元的单体的比例小于5摩尔%的情况下,有时不能获得本发明的效果。
前述共聚物的重均分子量为例如3000~20000,优选为3000~13000。在前述共聚物的重均分子量在上述范围外的情况下,所形成的抗蚀剂图案的裾形状变为咬边形状或裙形,前述聚合物的重均分子量越大,前述裾形状越容易变为裙形,因此不能获得本发明的效果。
本发明的第一方案涉及的添加剂可以是还含有溶解前述共聚物的溶剂的溶液状,也可以进一步含有在合成前述共聚物时使用的化合物。
本发明的第二方案是含有前述本发明的第一方案的添加剂、与前述共聚物不同的树脂、有机酸、交联剂以及溶剂的抗蚀剂下层膜形成用组合物。
前述树脂是例如,聚酯。相对于前述树脂100质量份含有前述添加剂例如5质量份~20质量份,优选为10质量份~15质量份。
一种抗蚀剂图案的形成方法,包含下述步骤:在基板上形成抗蚀剂下层膜的步骤,在前述抗蚀剂下层膜上形成抗蚀剂膜的步骤,经由光掩模将前述抗蚀剂膜曝光的步骤,在前述曝光后,使用能够溶解前述抗蚀剂膜的未曝光部分的溶剂进行显影并除去前述未曝光部分的步骤,在该方法中,优选使用本发明的第二方案的抗蚀剂下层膜形成用组合物。前述抗蚀剂膜可以使用公知的正型抗蚀剂溶液而形成。能够溶解前述抗蚀剂膜的未曝光部分的溶剂根据形成该抗蚀剂膜时使用的抗蚀剂溶液的种类不同而不同,通常使用公知的有机溶剂。
发明效果
通过将含有本发明涉及的添加剂的抗蚀剂下层膜形成用组合物应用到光刻工艺中,从而能够防止抗蚀剂图案的倒塌、且能够将抗蚀剂图案的截面形状制成挺直形状。此外,能够提高由该抗蚀剂下层膜形成用组合物形成的抗蚀剂下层膜与抗蚀剂图案的密合性。
具体实施方式
[共聚物]
本发明的第一方案涉及的添加剂含有具有前述式(1)~式(4)所示的结构单元的共聚物。
作为形成前述式(1)所示的结构单元的单体,可举出例如,对羟基苯乙烯、对叔丁氧基苯乙烯、间叔丁氧基苯乙烯、对叔戊氧基苯乙烯、对叔辛基氧基苯乙烯、2-叔丁氧基-6-乙烯基萘、对乙酰氧基苯乙烯、2-乙酰氧基-6-乙烯基萘、以及对(1-乙氧基乙氧基)苯乙烯。
作为形成前述式(2)所示的结构单元的单体,可举出例如,2-甲苯磺酰基乙基丙烯酸酯、2-甲苯磺酰基乙基甲基丙烯酸酯、苯基乙烯基砜、以及对甲苯基乙烯基砜。
作为形成前述式(3)所示的结构单元的单体,可举出例如,2,2,2-三氟乙基丙烯酸酯、2,2,2-三氟乙基甲基丙烯酸酯、1,1,1,3,3,3-六氟异丙基丙烯酸酯、1,1,1,3,3,3-六氟异丙基甲基丙烯酸酯、以及甲基丙烯酸(1,2-二氟乙基)酯。
作为形成前述式(4)所示的结构单元的单体,可举出例如,γ-丁内酯丙烯酸酯、γ-丁内酯甲基丙烯酸酯、甲羟戊酸内酯甲基丙烯酸酯、1-金刚烷基丙烯酸酯、1-金刚烷基甲基丙烯酸酯、2-甲基-2-金刚烷基丙烯酸酯、2-甲基-2-金刚烷基甲基丙烯酸酯、2-乙基-2-金刚烷基丙烯酸酯、2-乙基-2-金刚烷基甲基丙烯酸酯、丙烯酸异冰片酯、以及甲基丙烯酸异冰片酯。
作为前述式(1)所示的结构单元,可举出例如,下述式(1-1)~式(1-8)所示的结构单元。作为前述式(1)所示的结构单元的Ar所示的亚芳基,选择亚苯基或亚萘基。前述式(1)所示的结构单元成为酸性部位。
作为前述式(2)所示的结构单元,可举出例如,下述式(2-1)~式(2-4)所示的结构单元。下述式中只示出前述式(2)所示的结构单元的R3表示氢原子或甲基的例子,在R3表示卤素的情况下,选自氟、氯、溴以及碘。前述式(2)所示的结构单元成为光产酸部位。
作为前述式(3)所示的结构单元,可举出例如,下述式(3-1)~式(3-5)所示的结构单元。前述式(3)所示的结构单元是使共聚物向膜表面转移的部位。
作为前述式(4)所示的结构单元,可举出例如,下述式(4-1)~式(4-16)所示的结构单元。作为前述式(4)所示的结构单元的Z,选择具有导入到抗蚀剂溶液中的聚合物的骨架(环状结构)的有机基团。
本发明涉及的添加剂的共聚物通过具有所有前述式(1)~式(4)所示的结构单元,从而由包含该添加剂的抗蚀剂下层膜形成用组合物形成的抗蚀剂下层膜的表面附近的酸度被调节,该抗蚀剂下层膜与抗蚀剂图案的密合性提高,其结果是该抗蚀剂图案的倒塌能够得到抑制、且能够使在该抗蚀剂下层膜上形成的抗蚀剂图案的截面形状呈挺直形状。
[树脂]
本发明的第二方案涉及的抗蚀剂下层膜形成用组合物含有与前述添加剂的共聚物不同的树脂。前述树脂只要是在抗蚀剂下层膜形成用组合物中使用的聚合物就不特别限定。可举出例如,具有下述式(5)所示的结构单元的聚合物、以及具有下述式(6)所示的结构单元的聚合物。
[交联剂]
前述抗蚀剂下层膜形成用组合物还含有交联剂。作为前述交联剂,可举出例如,六甲氧基甲基三聚氰胺、四甲氧基甲基苯胍胺、1,3,4,6-四(甲氧基甲基)甘脲(POWDERLINK〔注册商标〕1174)、1,3,4,6-四(丁氧基甲基)甘脲、1,3,4,6-四(羟甲基)甘脲、1,3-双(羟甲基)脲、1,1,3,3-四(丁氧基甲基)脲以及1,1,3,3-四(甲氧基甲基)脲。前述交联剂的含有比例相对于前述树脂为例如1~30质量%。
[有机酸]
前述抗蚀剂下层膜形成用组合物还含有有机酸。前述有机酸是促进交联反应的催化剂成分,可举出例如,对甲苯磺酸、三氟甲烷磺酸、对甲苯磺酸吡啶水杨酸、樟脑磺酸、5-磺基水杨酸、4-氯苯磺酸、4-羟基苯磺酸、4-羟基苯磺酸甲酯、苯二磺酸、1-萘磺酸、柠檬酸、苯甲酸、羟基苯甲酸等磺酸化合物以及羧酸化合物。这些有机酸可以以单独形式含有,也可以以两种以上的组合的形式含有。前述有机酸的含有比例相对于前述交联剂为例如0.1~20质量%。
[溶剂]
前述抗蚀剂下层膜形成用组合物还含有溶剂。作为前述溶剂,可举出例如,丙二醇单甲基醚(PGME)、丙二醇单甲基醚乙酸酯(PGMEA)、丙二醇单乙基醚、丙二醇单丙基醚、甲基乙基甲酮、乳酸乙酯、环己酮、γ-丁内酯、N-甲基吡咯烷酮、以及选自这些溶剂中的两种以上的混合物。前述溶剂的比例相对于前述抗蚀剂下层膜形成用组合物为例如50~99.5质量%。
[其它添加物]
前述抗蚀剂下层膜形成用组合物还可以根据需要含有表面活性剂。表面活性剂是用于提高前述抗蚀剂下层膜形成用组合物对基板的涂布性的添加物,可以使用非离子系表面活性剂、氟系表面活性剂这样的公知的表面活性剂。作为前述表面活性剂的具体例,可举出例如,聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯十六烷基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚类,聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等聚氧乙烯烷基芳基醚类,聚氧乙烯-聚氧丙烯嵌段共聚物类,失水山梨糖醇单月桂酸酯、失水山梨糖醇单棕榈酸酯、失水山梨糖醇单硬脂酸酯、失水山梨糖醇单油酸酯、失水山梨糖醇三油酸酯、失水山梨糖醇三硬脂酸酯等失水山梨糖醇脂肪酸酯类,聚氧乙烯失水山梨糖醇单月桂酸酯、聚氧乙烯失水山梨糖醇单棕榈酸酯、聚氧乙烯失水山梨糖醇单硬脂酸酯、聚氧乙烯失水山梨糖醇三油酸酯、聚氧乙烯失水山梨糖醇三硬脂酸酯等聚氧乙烯失水山梨糖醇脂肪酸酯类等非离子系表面活性剂,エフトップ〔注册商标〕EF301、エフトップEF303、エフトップEF352(三菱マテリアル电子化成(株)制)、メガファック〔注册商标〕F171、メガファックF173、メガファックR-30、メガファックR-40、メガファックR-40-LM(DIC(株)制)、フロラードFC430、フロラードFC431(住友スリーエム(株)制)、アサヒガード〔注册商标〕AG710、サーフロン〔注册商标〕S-382、サーフロンSC101、サーフロンSC102、サーフロンSC103、サーフロンSC104、サーフロンSC105、サーフロンSC106(旭硝子(株)制)等氟系表面活性剂、有机硅氧烷聚合物KP341(信越化学工业(株)制)。这些表面活性剂可以以单独形式含有,也可以以两种以上组合的形式含有。在前述抗蚀剂下层膜形成用组合物含有表面活性剂的情况下,前述表面活性剂的比例相对于前述树脂为例如0.1~5质量%,优选为0.2~3质量%。
实施例
本说明书的下述合成例1~合成例15所示的聚合物的平均分子量是利用凝胶渗透色谱法(以下简称为GPC。)的测定结果。测定中使用東ソー(株)制GPC装置,测定条件等如下。
GPC柱:Shodex〔注册商标〕·Asahipak〔注册商标〕(昭和电工(株))
柱温:40℃
溶剂:N,N-二甲基甲酰胺(DMF)
流量:0.6ml/分钟
标准试样:聚苯乙烯(東ソー(株)制)
<合成例1>
使单烯丙基二缩水甘油基异氰脲酸酯10.00g、3,3’-二硫代二丙酸7.48g、以及乙基三苯基溴化膦0.66g溶解于丙二醇单甲基醚72.94g中,然后在125℃下反应4小时,获得含有聚合物(树脂)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为4800。
<合成例2>
使单甲基二缩水甘油基异氰脲酸酯10.00g、3,3’-二硫代二丙酸7.85g、以及乙基三苯基溴化膦0.66g溶解于丙二醇单甲基醚72.94g中,然后在105℃下反应24小时,获得含有聚合物(树脂)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为3400。
<合成例3>
向500ml四颈烧瓶中添加2-甲苯磺酰基乙醇60.00g、三乙胺45.48g、氢醌0.007g、以及丙酮180g,在5℃下进行搅拌。向该搅拌物中滴加甲基丙烯酰氯46.98g,然后升温至25℃,再进行1小时搅拌。将所得的盐过滤,然后利用丙酮60g洗涤该盐,回收滤液。通过将回收的滤液滴加到水300g中来使固体析出,利用水120g洗涤该固体,然后进行减压干燥,从而获得粗产物。向所得的粗产物中添加庚烷300g和乙酸乙酯90g,在70℃下使其加热溶解,通过过滤除去不溶物。通过向滤液中滴加庚烷60g并慢慢冷却来进行重结晶,利用庚烷60g洗涤所得的固体,进行减压干燥,从而获得作为目的物的2-甲苯磺酰基乙基甲基丙烯酸酯。
<合成例4>
使对叔丁氧基苯乙烯2.70g(45mol%)、由合成例3获得的2-甲苯磺酰基乙基甲基丙烯酸酯0.30g(5mol%)、2,2,2-三氟乙基甲基丙烯酸酯1.20g(20mol%)、γ-丁内酯甲基丙烯酸酯1.80g(30mol%)、以及偶氮二异丁腈0.30g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为9800。
<合成例5>
使对叔丁氧基苯乙烯2.40g(40mol%)、由合成例3获得的2-甲苯磺酰基乙基甲基丙烯酸酯1.50g(10mol%)、2,2,2-三氟乙基甲基丙烯酸酯0.60g(20mol%)、γ-丁内酯甲基丙烯酸酯1.80g(30mol%)、以及偶氮二异丁腈0.30g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为5600。
<合成例6>
使对叔丁氧基苯乙烯1.80g(30mol%)、由合成例3获得的2-甲苯磺酰基乙基甲基丙烯酸酯1.20g(20mol%)、2,2,2-三氟乙基甲基丙烯酸酯1.20g(20mol%)、γ-丁内酯甲基丙烯酸酯1.80g(30mol%)、以及偶氮二异丁腈0.30g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为7800。
<合成例7>
使对叔丁氧基苯乙烯1.50g(25mol%)、由合成例3获得的2-甲苯磺酰基乙基甲基丙烯酸酯1.50g(25mol%)、2,2,2-三氟乙基甲基丙烯酸酯1.20g(20mol%)、γ-丁内酯甲基丙烯酸酯1.80g(30mol%)、以及偶氮二异丁腈0.30g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为7400。
<合成例8>
使对叔丁氧基苯乙烯1.20g(20mol%)、由合成例3获得的2-甲苯磺酰基乙基甲基丙烯酸酯1.80g(30mol%)、2,2,2-三氟乙基甲基丙烯酸酯1.20g(20mol%)、γ-丁内酯甲基丙烯酸酯1.80g(30mol%)、以及偶氮二异丁腈0.30g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为7300。
<合成例9>
使对叔丁氧基苯乙烯1.50g(25mol%)、由合成例3获得的2-甲苯磺酰基乙基甲基丙烯酸酯1.50g(25mol%)、2,2,2-三氟乙基甲基丙烯酸酯2.40g(40mol%)、γ-丁内酯甲基丙烯酸酯0.60g(10mol%)、以及偶氮二异丁腈0.30g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为6300。
<合成例10>
使对叔丁氧基苯乙烯1.50g(25mol%)、由合成例3获得的2-甲苯磺酰基乙基甲基丙烯酸酯1.50g(25mol%)、2,2,2-三氟乙基甲基丙烯酸酯1.80g(30mol%)、γ-丁内酯甲基丙烯酸酯1.20g(20mol%)、以及偶氮二异丁腈0.30g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为5500。
<合成例11>
使对叔丁氧基苯乙烯1.50g(25mol%)、由合成例3获得的2-甲苯磺酰基乙基甲基丙烯酸酯1.50g(25mol%)、2,2,2-三氟乙基甲基丙烯酸酯0.60g(10mol%)、γ-丁内酯甲基丙烯酸酯2.40g(40mol%)、以及偶氮二异丁腈0.30g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为5900。
<合成例12>
使对叔丁氧基苯乙烯1.50g(25mol%)、由合成例3获得的2-甲苯磺酰基乙基甲基丙烯酸酯1.50g(25mol%)、2,2,2-三氟乙基甲基丙烯酸酯1.20g(20mol%)、γ-丁内酯甲基丙烯酸酯1.80g(30mol%)、以及偶氮二异丁腈0.45g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为4700。
<合成例13>
使对叔丁氧基苯乙烯1.50g(25mol%)、由合成例3获得的2-甲苯磺酰基乙基甲基丙烯酸酯1.50g(25mol%)、2,2,2-三氟乙基甲基丙烯酸酯1.20g(20mol%)、γ-丁内酯甲基丙烯酸酯1.80g(30mol%)、以及偶氮二异丁腈0.23g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为9700。
<合成例14>
使对叔丁氧基苯乙烯1.50g(25mol%)、苯基乙烯基砜1.50g(25mol%)、2,2,2-三氟乙基甲基丙烯酸酯1.20g(20mol%)、γ-丁内酯甲基丙烯酸酯1.80g(30mol%)、以及偶氮二异丁腈0.30g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为4300。
<合成例15>
使对叔丁氧基苯乙烯3.00g(50mol%)、2,2,2-三氟乙基甲基丙烯酸酯1.20g(20mol%)、γ-丁内酯甲基丙烯酸酯1.80g(30mol%)、以及偶氮二异丁腈0.30g溶解于丙二醇单甲基醚12.60g中。将该溶液缓慢滴加到已经升温至100℃的丙二醇单甲基醚12.60g中,滴加后在100℃下使其反应2小时,获得含有聚合物(共聚物)的溶液。对所得的溶液中包含的聚合物进行GPC分析,结果利用标准聚苯乙烯换算的重均分子量为19800。由本合成例获得的聚合物是不具有前述式(2)所示的结构单元的共聚物。
使由上述合成例1或合成例2获得的树脂、作为添加剂的想要通过合成例4~合成例15获得的任一种共聚物、交联剂、有机酸、表面活性剂以及溶剂以下述表1所示的比例进行混合,分别调制实施例1~实施例13以及比较例1~比较例4的抗蚀剂下层膜形成用组合物。表1所示的添加剂的添加量不表示聚合物溶液的添加量,而表示聚合物(共聚物)自身的添加量。在表1中,将四甲氧基甲基甘脲(日本サイテックインダストリーズ(株)制、商品名:POWDERLINK〔注册商标〕1174)简称为“PL-LI”,4-羟基苯磺酸简称为“PSA”,5-磺基水杨酸简称为“5-SSA”,4-羟基苯磺酸甲酯简称为“MSP”,メガファック〔注册商标〕R-40(DIC(株)制)简称为“R-40”,丙二醇单甲基醚乙酸酯简称为“PGMEA”,丙二醇单甲基醚简称为“PGME”。在表1中,实施例1~实施例13以及比较例1~比较例4的抗蚀剂下层膜形成用组合物中的各成分以质量份表示,将溶剂作为100质量份。
表1
(光学常数测定)
使用旋涂器将实施例1~实施例13以及比较例1~比较例4所调制的抗蚀剂下层膜形成用组合物分别涂布在硅晶片上。将该硅晶片在加热板上、在205℃下进行1分钟加热,形成抗蚀剂下层膜(膜厚28nm)。然后,使用光谱椭偏仪(J.A.Woollam社制、VUV-VASE VU-302)测定这些抗蚀剂下层膜在波长193nm、248nm下的折射率(n值)和光学吸光系数(k值,也称为衰减系数)。在下述表2中,n1、k1分别表示波长193nm的折射率和吸光系数,n2、k2分别表示波长248nm的折射率和吸光系数。
表2
(利用ArF曝光的抗蚀剂图案的形成)
使用旋涂器将实施例1~实施例13以及比较例1~比较例4所调制的抗蚀剂下层膜形成用组合物分别涂布在硅晶片上。将该硅晶片在加热板上、在205℃下进行60秒烘烤,获得膜厚为28nm的抗蚀剂下层膜。在该抗蚀剂下层膜上旋转涂布ArF准分子激光用正型抗蚀剂溶液,在80℃下进行60秒加热,形成ArF抗蚀剂膜。对于该抗蚀剂膜,使用ArF准分子激光用曝光装置((株)ニコン制、NSR S307R),在规定的条件下进行曝光。曝光后,在95℃下进行60秒烘烤(PEB),在冷却板上冷却至室温,利用乙酸丁酯进行显影,然后利用乙酸丁酯进行冲洗处理,形成线与间隙的抗蚀剂图案。在这里,由于使用乙酸丁酯作为显影液而不是碱性水溶液,所以冲洗处理使用水是不合适的。使用扫描型电子显微镜((株)日立ハイテクフィールディング制、S-4800)评价可否形成62nm和45nm各自的线与间隙(以下简称为L/S。)、以及通过图案截面观察的62nm的L/S的图案形状,将该结果示于下述表3和图1中。
表3
使用由实施例1~实施例13调制的抗蚀剂下层膜形成用组合物所形成的62nm的L/S的图案形状都不是咬边、裙形中的任一种,而是挺直形状,也未观察到图案倒塌。另一方面,使用由比较例1~比较例4调制的抗蚀剂下层膜形成用组合物所形成的62nm的L/S的图案形状为咬边或裙形。此外,只有在使用由比较例1和比较例2调制的抗蚀剂下层膜形成用组合物的情况下,不能形成45nm的L/S。
附图说明
图1是显示的是,使用实施例1~实施例13以及比较例1~比较例4所调制的抗蚀剂下层膜形成用组合物,在形成于硅晶片上的抗蚀剂下层膜上形成62nm的L/S的抗蚀剂图案,利用扫描型电子显微镜(SEM)观察截面,结果所得的SEM像。
Claims (10)
1.一种添加剂,用于抗蚀剂下层膜形成用组合物,含有具有下述式(1)~式(4)所示的结构单元的共聚物,
式中,R1分别独立地表示氢原子或甲基,Ar表示亚芳基,Pr表示保护基或氢原子,X表示直接结合或-C(=O)O-R2-基,构成该-C(=O)O-R2-基的R2表示碳原子数为1~3的亚烷基,该亚烷基与硫原子结合,R3表示氢原子、甲基、甲氧基或卤素,R4表示至少1个氢原子被氟取代了的碳原子数为1~3的烷基,Z表示具有四元环~七元环的内酯骨架、金刚烷骨架或降冰片烷骨架的有机基团。
2.根据权利要求1所述的添加剂,所述保护基是乙酰基、甲氧基甲基、乙氧基乙基、碳原子数为4~8的叔烷基、或三甲基乙酰基。
3.根据权利要求1或2所述的添加剂,所述式(2)所示的结构单元是下述式(2a)或式(2b)所示的结构单元,
式中,R1、R2和R3与权利要求1中的R1、R2和R3的含义相同。
4.根据权利要求1或2所述的添加剂,所述式(4)所示的结构单元是下述式(4a)所示的结构单元,
式中,R1分别独立地表示氢原子或甲基,R5表示碳原子数为2~5的烃基。
5.根据权利要求1或2所述的添加剂,所述共聚物是使形成所述式(1)所示的结构单元的单体、形成所述式(2)所示的结构单元的单体、形成所述式(3)所示的结构单元的单体、以及形成所述式(4)所示的结构单元的单体共聚而合成的化合物,形成所述式(2)所示的结构单元的单体相对于所述4种单体的合计100摩尔%的比例为5~40摩尔%。
6.根据权利要求1或2所述的添加剂,所述共聚物的重均分子量为3000~20000。
7.一种抗蚀剂下层膜形成用组合物,含有权利要求1~6中任一项所述的添加剂、与所述共聚物不同的树脂、有机酸、交联剂以及溶剂。
8.根据权利要求7所述的抗蚀剂下层膜形成用组合物,所述树脂是聚酯。
9.根据权利要求7或8所述的抗蚀剂下层膜形成用组合物,相对于所述树脂100质量份含有所述添加剂5~20质量份。
10.一种抗蚀剂图案的形成方法,包含下述步骤:使用权利要求7~9中任一项所述的抗蚀剂下层膜形成用组合物在基板上形成抗蚀剂下层膜的步骤,使用正型抗蚀剂溶液在所述抗蚀剂下层膜上形成抗蚀剂膜的步骤,经由光掩模将所述抗蚀剂膜曝光的步骤,在所述曝光后,使用能够溶解所述抗蚀剂膜的未曝光部分的溶剂进行显影并除去所述未曝光部分的步骤。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-064376 | 2014-03-26 | ||
JP2014064376 | 2014-03-26 | ||
PCT/JP2015/055445 WO2015146443A1 (ja) | 2014-03-26 | 2015-02-25 | 添加剤及び該添加剤を含むレジスト下層膜形成組成物 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106133606A CN106133606A (zh) | 2016-11-16 |
CN106133606B true CN106133606B (zh) | 2019-06-28 |
Family
ID=54194976
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201580015088.7A Active CN106133606B (zh) | 2014-03-26 | 2015-02-25 | 添加剂以及包含该添加剂的抗蚀剂下层膜形成用组合物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10067423B2 (zh) |
JP (1) | JP6394926B2 (zh) |
KR (1) | KR102100268B1 (zh) |
CN (1) | CN106133606B (zh) |
TW (1) | TWI653247B (zh) |
WO (1) | WO2015146443A1 (zh) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9927705B2 (en) * | 2013-07-23 | 2018-03-27 | Nissan Chemical Industries, Ltd. | Additive for resist underlayer film-forming composition and resist underlayer film-forming composition containing the same |
JP6816983B2 (ja) * | 2015-08-27 | 2021-01-20 | 住友化学株式会社 | レジスト組成物及びレジストパターン製造方法 |
CN108351593B (zh) * | 2015-11-17 | 2021-10-26 | 日产化学工业株式会社 | 抗蚀剂下层膜形成用组合物用添加剂及包含该添加剂的抗蚀剂下层膜形成用组合物 |
KR102374269B1 (ko) * | 2016-03-09 | 2022-03-15 | 닛산 가가쿠 가부시키가이샤 | 레지스트 하층막 형성 조성물 및 이것을 이용한 레지스트 패턴의 형성방법 |
CN109313389B (zh) * | 2016-03-30 | 2020-07-14 | 日产化学株式会社 | 包含具有甘脲骨架的化合物作为添加剂的抗蚀剂下层膜形成组合物 |
KR102446546B1 (ko) | 2016-09-15 | 2022-09-23 | 닛산 가가쿠 가부시키가이샤 | 레지스트 하층막 형성 조성물 |
KR102557875B1 (ko) | 2017-02-03 | 2023-07-20 | 닛산 가가쿠 가부시키가이샤 | 우레아결합을 갖는 구조단위를 갖는 폴리머를 포함하는 레지스트 하층막 형성 조성물 |
JP7092132B2 (ja) * | 2017-07-27 | 2022-06-28 | 日産化学株式会社 | 剥離層形成用組成物及び剥離層 |
EP3704547B1 (en) * | 2017-11-03 | 2022-07-13 | Basf Se | Use of compositions comprising a siloxane-type additive for avoiding pattern collapse when treating patterned materials with line-space dimensions of 50 nm or below |
JPWO2020111068A1 (ja) * | 2018-11-29 | 2021-10-28 | Jsr株式会社 | レジスト下層膜形成用組成物、レジスト下層膜及びレジストパターン形成方法 |
KR102348675B1 (ko) | 2019-03-06 | 2022-01-06 | 삼성에스디아이 주식회사 | 레지스트 하층막용 조성물 및 이를 이용한 패턴 형성 방법 |
US20230103242A1 (en) * | 2019-12-04 | 2023-03-30 | Nissan Chemical Corporation | Method for producing polymer |
KR20230045952A (ko) | 2021-09-29 | 2023-04-05 | 주식회사 동진쎄미켐 | 포토레지스트 하층막 형성용 고분자 화합물, 이를 포함하는 euv용 포토레지스트 하층막 조성물, euv용 포토레지스트 하층막의 제조방법 및 포토레지스트 막 패턴의 형성 방법 |
WO2023204287A1 (ja) * | 2022-04-22 | 2023-10-26 | 日産化学株式会社 | レジスト下層膜形成用組成物 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4940760A (en) * | 1988-02-16 | 1990-07-10 | E. I. Du Pont De Nemours And Company | Group Transfer Polymerization process employing supported initiators |
TW201039067A (en) * | 2008-12-26 | 2010-11-01 | Nissan Chemical Ind Ltd | Additive for resist underlayer coating forming composition and resist underlayer coating forming containing the additive |
JP2011164345A (ja) * | 2010-02-09 | 2011-08-25 | Shin-Etsu Chemical Co Ltd | レジスト下層膜材料、パターン形成方法 |
WO2012081619A1 (ja) * | 2010-12-17 | 2012-06-21 | 日産化学工業株式会社 | レジスト下層膜形成組成物及びそれを用いたレジストパターンの形成方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3196361B2 (ja) * | 1991-12-25 | 2001-08-06 | 日立化成工業株式会社 | 塗料用樹脂組成物及び海中構造物用防汚塗料 |
JPH06130706A (ja) * | 1992-10-15 | 1994-05-13 | Fuji Photo Film Co Ltd | 平版印刷用原版 |
EP1426822B1 (en) | 2001-08-20 | 2009-04-08 | Nissan Chemical Industries, Ltd. | Composition for forming antireflective film for use in lithography |
JP3914490B2 (ja) * | 2002-11-27 | 2007-05-16 | 東京応化工業株式会社 | リソグラフィー用下層膜形成材料およびこれを用いた配線形成方法 |
JP3759526B2 (ja) * | 2003-10-30 | 2006-03-29 | 丸善石油化学株式会社 | 半導体リソグラフィー用共重合体の製造方法 |
JP5382321B2 (ja) | 2009-03-31 | 2014-01-08 | 日産化学工業株式会社 | レジスト下層膜形成組成物及びそれを用いたレジストパターンの形成方法 |
KR101779884B1 (ko) | 2011-10-20 | 2017-09-19 | 닛산 가가쿠 고교 가부시키 가이샤 | 레지스트 하층막 형성조성물용 첨가제 및 이를 포함하는 레지스트 하층막 형성조성물 |
US9927705B2 (en) * | 2013-07-23 | 2018-03-27 | Nissan Chemical Industries, Ltd. | Additive for resist underlayer film-forming composition and resist underlayer film-forming composition containing the same |
US9761449B2 (en) * | 2013-12-30 | 2017-09-12 | Taiwan Semiconductor Manufacturing Company, Ltd. | Gap filling materials and methods |
JP6258830B2 (ja) * | 2014-09-25 | 2018-01-10 | Hoya株式会社 | マスクブランク、マスクブランクの製造方法及び転写用マスクの製造方法 |
-
2015
- 2015-02-25 US US15/128,392 patent/US10067423B2/en active Active
- 2015-02-25 WO PCT/JP2015/055445 patent/WO2015146443A1/ja active Application Filing
- 2015-02-25 CN CN201580015088.7A patent/CN106133606B/zh active Active
- 2015-02-25 KR KR1020167024603A patent/KR102100268B1/ko active IP Right Grant
- 2015-02-25 JP JP2016510150A patent/JP6394926B2/ja active Active
- 2015-03-16 TW TW104108322A patent/TWI653247B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4940760A (en) * | 1988-02-16 | 1990-07-10 | E. I. Du Pont De Nemours And Company | Group Transfer Polymerization process employing supported initiators |
TW201039067A (en) * | 2008-12-26 | 2010-11-01 | Nissan Chemical Ind Ltd | Additive for resist underlayer coating forming composition and resist underlayer coating forming containing the additive |
JP2011164345A (ja) * | 2010-02-09 | 2011-08-25 | Shin-Etsu Chemical Co Ltd | レジスト下層膜材料、パターン形成方法 |
WO2012081619A1 (ja) * | 2010-12-17 | 2012-06-21 | 日産化学工業株式会社 | レジスト下層膜形成組成物及びそれを用いたレジストパターンの形成方法 |
TW201241016A (en) * | 2010-12-17 | 2012-10-16 | Nissan Chemical Ind Ltd | Resist underlayer film forming composition and method for forming resist pattern by use of the composition |
Also Published As
Publication number | Publication date |
---|---|
US10067423B2 (en) | 2018-09-04 |
TWI653247B (zh) | 2019-03-11 |
TW201602140A (zh) | 2016-01-16 |
KR20160138397A (ko) | 2016-12-05 |
WO2015146443A1 (ja) | 2015-10-01 |
CN106133606A (zh) | 2016-11-16 |
JPWO2015146443A1 (ja) | 2017-04-13 |
US20170108777A1 (en) | 2017-04-20 |
KR102100268B1 (ko) | 2020-04-13 |
JP6394926B2 (ja) | 2018-09-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106133606B (zh) | 添加剂以及包含该添加剂的抗蚀剂下层膜形成用组合物 | |
CN104185816B (zh) | 含有含苯基吲哚的酚醛清漆树脂的抗蚀剂下层膜形成用组合物 | |
CN1981240B (zh) | 使用乙烯基醚交联剂的减反射涂层 | |
CN101659615B (zh) | 含有开环邻苯二甲酸酐的有机防反射层组合物及其制备方法 | |
CN1977220B (zh) | 含有具有卤原子的萘环的形成光刻用下层膜的组合物 | |
JP6497535B2 (ja) | レジスト下層膜形成組成物用添加剤及び該添加剤を含むレジスト下層膜形成組成物 | |
CN109991811A (zh) | 一种酸扩散抑制剂及其制备方法与光刻胶组合物 | |
TWI750225B (zh) | 光阻下層膜形成組成物 | |
TWI489217B (zh) | 電子線微影用光阻底層膜形成組成物 | |
TWI746785B (zh) | 包含具有含有脲鍵的結構單元的聚合物之阻劑下層膜形成組成物 | |
JP4831324B2 (ja) | スルホンを含有するレジスト下層膜形成組成物 | |
TW200907581A (en) | Coating compositions | |
JP5737526B2 (ja) | レジスト下層膜形成組成物及びそれを用いたレジストパターンの形成方法 | |
JP2010237491A (ja) | レジスト下層膜形成組成物及びそれを用いたレジストパターンの形成方法 | |
CN103339532B (zh) | 微透镜形成用感光性树脂组合物 | |
TW201248331A (en) | Non-photosensitive resist underlayer film forming composition | |
TW201241016A (en) | Resist underlayer film forming composition and method for forming resist pattern by use of the composition | |
CN105579909B (zh) | 抗蚀剂下层膜形成用组合物和使用其的抗蚀剂图案的形成方法 | |
JP5794228B2 (ja) | レジスト下層膜形成用組成物 | |
JP2008152203A (ja) | 下層レジスト組成物、該組成物に有用な新規化合物、及び該組成物を用いたパターン形成方法 | |
TWI422562B (zh) | 光敏化合物和包含該光敏化合物的光敏組合物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |