WO2006061975A1 - Procede de formation d'un modele d’enduit de protection - Google Patents

Procede de formation d'un modele d’enduit de protection Download PDF

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Publication number
WO2006061975A1
WO2006061975A1 PCT/JP2005/020949 JP2005020949W WO2006061975A1 WO 2006061975 A1 WO2006061975 A1 WO 2006061975A1 JP 2005020949 W JP2005020949 W JP 2005020949W WO 2006061975 A1 WO2006061975 A1 WO 2006061975A1
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WIPO (PCT)
Prior art keywords
group
resist
structural unit
pattern
resist composition
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Application number
PCT/JP2005/020949
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English (en)
Japanese (ja)
Inventor
Takeshi Iwai
Jun Iwashita
Original Assignee
Tokyo Ohka Kogyo Co., Ltd.
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Publication date
Application filed by Tokyo Ohka Kogyo Co., Ltd. filed Critical Tokyo Ohka Kogyo Co., Ltd.
Publication of WO2006061975A1 publication Critical patent/WO2006061975A1/fr

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    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

Definitions

  • the present invention relates to a resist pattern forming method.
  • the resist materials that satisfy the high-resolution conditions that can reproduce patterns with fine dimensions, it contains a base resin whose alkali solubility changes due to the action of acid and an acid generator that generates acid upon exposure.
  • a chemically amplified resist composition is known!
  • the chemically amplified resist composition includes a negative type containing an alkali-soluble resin, an acid generator and a cross-linking agent, and a positive type containing a resin and an acid generator whose alkali solubility is increased by the action of an acid. There is.
  • the resist layer is selectively used. Exposure step, post-exposure heat treatment (PEB treatment), resist The layer is developed to form a resist pattern.
  • PEB treatment post-exposure heat treatment
  • a dense pattern with a narrow interval between adjacent patterns and a sparse pattern with a wide interval between adjacent patterns are used. And may form.
  • the conventional resist pattern formation has a problem that it tends to be narrower than the DOF when forming a dense depth of focus (DOF) dense pattern when forming a sparse pattern.
  • DOF dense depth of focus
  • Patent Document 2 for example, a second resist layer (upper layer) is stacked on a first resist layer (lower layer) on which a dense pattern is formed, and the dense pattern is embedded.
  • a technique is disclosed in which a pattern different from the dense pattern is formed in the upper layer, a part of the dense pattern in the lower layer is exposed, and the remaining dense pattern is embedded.
  • the upper layer pattern is formed so as to embed a part of the pattern formed in the lower layer.
  • the upper layer pattern is formed in a larger size than the pattern formed in the lower layer. More specifically, for example, when forming a hole pattern in the upper and lower layers, the upper layer is formed with a pattern that is larger than the diameter of the hole formed in the lower dense pattern, and the upper and lower hole patterns are connected. To form. Then, in the range where the upper hole pattern is formed, the lower dense pattern can be exposed. As long as the upper layer is not removed, a part of the dense pattern in the lower layer is embedded.
  • a sparse pattern composed of a pattern formed in the lower layer and a pattern formed in the upper layer continuous with the pattern is formed on a part of the substrate.
  • this pattern uses a dense pattern formed in the lower layer, the lower layer pattern in contact with the substrate is formed in a desired size, and a sparse pattern satisfying the DOF characteristics can be obtained.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-167347
  • Patent Document 2 US Publication US 2003— 0104319A1
  • the present invention has been made in view of the above circumstances, and in a resist pattern forming method in which a dense pattern is formed in a lower layer and a pattern different from the lower layer is formed in an upper layer, the resist pattern forming method capable of suppressing mixing It is an issue to provide.
  • the present invention adopts the following configuration.
  • the following steps (i) to (ii) selectiveively using the first negative resist composition on the substrate to form a first resist layer and form a dense pattern) (Ii) forming a second resist layer on the first resist layer using a second negative resist composition or a positive resist composition, and selectively exposing the first resist layer;
  • a resist pattern and a second resist layer are simultaneously developed to expose a part of the unexposed portion of the first resist layer, comprising:
  • a negative resist composition or a positive resist composition dissolved in an organic solvent is used without dissolving the first resist layer. This is a method of forming a resist pattern.
  • a first resist layer is formed on a substrate using a negative resist composition, selectively exposed, and then developed.
  • 2 resist layer is formed and selectively exposed
  • a resist pattern forming method including a step of developing after light development and embedding part of the dense pattern,
  • a negative resist composition or a positive resist composition dissolved in an organic solvent is used without dissolving the first resist layer. This is a method of forming a resist pattern.
  • Exposure is a concept that encompasses not only light irradiation but also entire irradiation of radiation such as electron beam irradiation.
  • a resist pattern forming method capable of suppressing mixing can be provided by a resist pattern forming method in which a dense pattern is formed in a lower layer and a pattern is formed in an upper layer. .
  • FIG. 1A is an explanatory diagram showing a flow of an example of the procedure of the first mode (process 1).
  • FIG. 1B is an explanatory diagram showing a flow of an example of the procedure of the second mode (process 2).
  • FIG. 2A is an explanatory diagram (cross-sectional view) of process 1.
  • FIG. 2B is an explanatory view (cross-sectional view) of Process 1.
  • FIG. 2C is an explanatory diagram (cross-sectional view) of Process 1.
  • FIG. 3A is an explanatory view (cross-sectional view) of Process 2.
  • FIG. 3B is an explanatory diagram (sectional view) of process 2.
  • FIG. 3C is an explanatory diagram (cross-sectional view) of Process 2.
  • FIG. 3D is an explanatory diagram (cross-sectional view) of Process 2.
  • FIG. 4 is a plan view showing a state after forming dense patterns and sparse patterns through process 1 or 2.
  • the following steps (i) to (ii) selectiveively using the first negative resist composition on the substrate to form a first resist layer and form a dense pattern) (Ii) forming a second resist layer on the first resist layer using a second negative resist composition or a positive resist composition, and selectively exposing the first resist layer;
  • a resist pattern and a second resist layer are simultaneously developed to expose a part of the unexposed portion of the first resist layer, comprising:
  • a negative resist composition or a positive resist composition dissolved in an organic solvent is used without dissolving the first resist layer. This is a method of forming a resist pattern.
  • the dense pattern indicates that the interval between adjacent patterns is narrow when a pattern such as a line shape or a hole shape is formed.
  • the ratio of the distance to the adjacent pattern with respect to the width of the pattern is preferably 1 or less, particularly preferably 0.9 or less, and even 0.8 or less. is there.
  • the lower limit is substantially 0.5 or more.
  • the width of the pattern in the hole-shaped pattern indicates the range in which the resist layer is removed, for example, the diameter of the hole in the hole pattern.
  • the pattern width in the line pattern indicates the line width.
  • the sparse pattern has a larger interval between adjacent patterns than the dense pattern.
  • the ratio of the interval between adjacent patterns to the width of the pattern is preferably 2 or more, particularly preferably 3 or more, and even 5 or more.
  • the upper limit is practically 10 or less.
  • the width and interval of the pattern indicate the size near the interface between the substrate and the resist layer.
  • FIG. 1A shows a flow of an example of the procedure of the first aspect (hereinafter referred to as process 1).
  • 2A to 2C are explanatory views (cross-sectional views) of process 1.
  • FIG. Fig. 4 is a plan view showing a state after forming a dense pattern and a sparse pattern through a process.
  • a chemically amplified negative resist composition (hereinafter referred to as “acid generator”) that contains an acid generator component that generates acid upon exposure on a substrate 1 using a coating apparatus (hereinafter referred to as “acid generator”). 1) (see Fig. 2A).
  • the applied resist film is heat-treated to form the first resist layer 2 (see FIG. 2A).
  • Karo heat conditions are 80-150, for example. C, about 40 to 120 seconds (preferably 60 to 90 seconds).
  • the thickness of the first resist layer 2 is, for example, about 0.05 to about L 0 m, preferably 0.1 to 0.5 ⁇ m.
  • the first resist layer 2 is selectively exposed to form a dense pattern. (See Figure 2A).
  • the “exposure portion” refers to an exposed range.
  • “Unexposed area” refers to the area that is exposed and V ⁇ .
  • the exposed portion 2a ′ and the unexposed portion 2b are formed by selectively exposing the first resist layer 2 using a mask (reticle) 3 for a dense pattern.
  • FIG. 2A is an example in which exposure is performed to form a dense pattern in which the hole pattern force pattern width D 1 and interval L 1 are formed in a size of about 1: 1.
  • the first resist layer 2 densely plurality of holes 2a unexposed portion 2 b of the width D 1 of the pattern is formed by developing (dissolving) is at a spacing L 1 Selective exposure is performed so as to form a dense pattern.
  • the wavelength used for the exposure is not particularly limited.
  • ArF excimer laser is preferred Appropriate (same for the following exposure process).
  • the first resist layer 2 subjected to the selective exposure is heat-treated to appropriately diffuse the acid component generated from the acid generator in the first resist layer 2 and to negatively expose the exposed portion 2a ′.
  • Karo heat conditions are 80-150, for example. C, about 40 to 120 seconds (preferably 60 to 90 seconds).
  • a chemically amplified negative resist composition or a positive resist composition containing an acid generator is applied onto the first resist layer 2 (see FIG. 2B).
  • a negative resist composition is applied.
  • the first negative resist composition and the second negative resist composition are a negative resist composition that forms the first resist layer 2 and a negative resist composition that forms the second resist layer 12. It is a term used to distinguish the resist composition from the convenience.
  • the applied resist film is heat-treated to form the second resist layer 12 (see FIG. 2B).
  • Karo heat conditions are 80-150, for example. C, about 40 to 120 seconds (preferably 60 to 90 seconds).
  • the thickness of the second resist layer 12 is, for example, about 0.05 to about L 0 m, preferably 0.1 to 0.5 ⁇ m.
  • the second resist layer 12 is exposed.
  • FIG. 2B is an example in which the hole pattern is exposed to form a sparse pattern in which the pattern width D 2 and the interval L 2 are formed with a size of about 1: 2.
  • the second resist layer 12 has a pattern width D 2.
  • hole 12a unexposed portion 12b of is formed by developing (dissolving) is subjected to selective exposure Te use ⁇ a mask 13 such as are arranged at intervals L 2.
  • the diameter of the sparse pattern hole 12a (pattern The width (D 2 ) is designed to be larger than the diameter (pattern width) D 1 of the hole 2 a formed in the first resist layer 2.
  • the hole 12a is formed in a range including the hole 2a formed immediately below.
  • the second resist layer 12 subjected to the selective exposure is heat-treated to appropriately diffuse the acid component generated from the acid generator in the second resist layer 12, thereby negating the exposed portion 12a ′ (FIG. 2 See B).
  • Karo heat conditions are 80-150, for example. C, about 40 to 120 seconds (preferably 60 to 90 seconds).
  • TMHA aqueous solution tetramethylammonium hydroxide aqueous solution having a concentration of 0.1 to LO mass% (preferably 0.5 to 5 mass%) is used for the development processing.
  • the unexposed portion 12b of the second resist layer 12 is removed to form a sparsely patterned hole 12a. Then, the developer entering from the hole 12a comes into contact with the first resist layer 2 constituting the bottom surface of the hole 12a, whereby the unexposed portion 2b of the first resist layer 2 is developed and removed. To be exposed. As a result, a hole 2a immediately below the hole 12a is formed. As a result, a sparse hole pattern in which the holes 2a and 12a are continuous is formed.
  • the second resist layer 12 is developed with a developer, and the dense pattern unexposed portion 2b formed on the first resist layer 2 As a result, hole 2a is formed.
  • the hole 2 a is formed in a dense pattern that can ensure a wide DOF characteristic, and thus can be accurately formed in a desired size.
  • the sparse holes 12a are formed on a part of the holes 2a of the dense pattern formed in the first resist layer 2.
  • the DOF characteristics of the upper second resist layer 12 are not required to be as high as those of the pattern formed in the lower layer (first resist layer 2).
  • the force that is the hole 2a in the lower layer 2 is important. This is because when the substrate is etched, the lower layer 2 pattern is transferred (when it is transferred to the substrate, it depends on the lower layer 2 pattern).
  • the second resist layer 12 is different from the case where the positive resist composition is used and the second negative resist composition described above.
  • the light transmission part (exposed part) and the light blocking part (unexposed part) of the mask used when exposing 12 are reversed, and the exposed part is removed by the developer. .
  • the method of the present invention is characterized in that a specific negative resist composition or a positive resist composition is used as the resist composition used for forming the second resist layer 12. Since these materials are the same as those in the second embodiment, they will be described together after explaining the process example of the second embodiment.
  • a first resist layer is formed on a substrate using a negative resist composition, selectively exposed, and then developed.
  • Forming a dense pattern on the first resist layer (ii) using a second negative resist composition or a positive resist composition on the dense pattern of the first resist layer.
  • a negative resist composition or positive resist composition dissolved in an organic solvent without dissolving the first resist layer.
  • FIG. 1B shows a flow of an example of the procedure of the second aspect (hereinafter referred to as process 2).
  • 3A to 3D are explanatory views (cross-sectional views) of process 2.
  • FIG. Fig. 4 is a plan view showing a state after forming a dense pattern and a sparse pattern through a process.
  • the first resist layer 2 is developed.
  • the development processing for example, 0.. 1 to: LO wt% (preferred properly is 0.5 to 5 mass 0/0) concentration of TMHA solution (tetramethylammonium - Umuhidorokishido solution) is used.
  • the unexposed portion 2b is removed as shown in FIG. 3B, and the first resist layer 2 is designed with a pattern width D 1 and a distance L 1 of about 1: 1.
  • a dense pattern having a plurality of holes 2a is obtained.
  • the first resist layer 2 entirely, hole 2a of the width D 1 of the pattern is dense patterns are densely arranged at intervals L 1 is formed.
  • a chemically amplified second negative resist composition or positive resist containing an acid generator is formed on the first resist layer 2 on which a dense pattern is formed using a coating apparatus. Apply the composition.
  • a negative resist composition is applied.
  • the first negative resist composition and the second negative resist composition are the first resist. This term is used to distinguish the negative resist composition forming the second resist layer 2 from the negative resist composition forming the second resist layer 12 for convenience.
  • the negative resist composition is filled in the hole 2a, the hole 2a is buried, a resist film is formed thereon, and the resist pattern formed on the first resist pattern layer 2 is covered with the resist film. Is done.
  • the applied resist film is heated to form the second resist layer 12 (see FIG. 3C).
  • the heating temperature is, for example, about 80 to 150 ° C. and 40 to 120 seconds (preferably 60 to 90 seconds).
  • the thickness of the second resist layer 12 (the length from the surface of the first resist layer 2 to the surface of the second resist layer 12) is, for example, about 0.05-1.0.0 m, preferably It is about 1 to 0.5 m.
  • the second resist layer 12 is exposed.
  • the second resist layer 12 is selectively exposed using a desired mask (reticle) 13.
  • FIG. 3C shows an example in which exposure is performed to form a sparse pattern in which the hole pattern force pattern width D 2 and interval L 2 are formed with a size of about 1: 2.
  • the same area is exposed using the same mask as in the first aspect, and as shown in FIG. 4, the region 21 is not exposed, and the second resist layer 12 is not exposed in the region 22. If hole 12a of the width D 2 of the turns is selectively exposed so as to be arranged at intervals L 2, the exposure unit 1 2a ', the unexposed portion 12b is formed.
  • the sparse diameter of the pattern of holes 12a (width of the pattern) D 2 is than the diameter (pattern width) D 1 of the hole 2a formed in the first resist layer 2 Largely designed.
  • the hole 12a is formed in a range including the hole 2a formed immediately below.
  • the second resist layer 12 subjected to the selective exposure is subjected to a heat treatment to be in the second resist layer 12.
  • the acid component generated from the acid generator is appropriately diffused while being appropriately diffused (see FIG. 3C).
  • the heating temperature is, for example, about 80 to 150 ° C. and about 40 to 120 seconds (preferably 60 to 90 seconds).
  • a sparse hole pattern in which the holes 12a and the holes 2a immediately below are continuous is formed.
  • the second resist layer 12 is developed with a developing solution, and the second negative film in which the dense pattern of the first resist layer 2 is embedded.
  • the mold resist composition is also removed at the same time to form holes 2a. That is, in this method, a wide DOF dense pattern formed in the first resist layer 2 is embedded in the second resist layer 12, selectively exposed and developed, and a part of the second resist layer 12 is removed. Then, by exposing a part of the dense pattern, this dense pattern is used as a sparse pattern. In the dense pattern, the portion V and the second resist layer 12 that are not removed is buried with the second resist layer 12.
  • the DOF characteristics of the upper second resist layer 12 are not required to be as high as those of the pattern formed in the first resist layer (lower layer) 2.
  • the force that is the hole 2a in the lower layer 2 is important. This is because when the substrate is etched, the lower layer 2 pattern is transferred (when transferred to the substrate, it depends on the lower layer pattern).
  • the second resist layer is formed after the first resist layer is developed and developed, the second resist layer is not affected by the acid generator in the first resist layer, and has a higher level. Precision flutter There is also an advantage in forming a pattern.
  • the second resist layer 12 is formed, the second resist layer 12 is exposed when a positive resist yarn composition is used, which is different from the above example.
  • the light transmitting part (exposed part) and the light blocking part (unexposed part) of the mask used at the time are reversed, and the exposed part is removed by the developer, and the others are the same.
  • the method of the present invention is characterized in that a specific second negative resist composition or positive resist composition is used as the resist composition for forming the second resist layer 12. Since these materials are the same as those in the first aspect, they will be described together below.
  • the second negative resist composition used in the present invention is characterized by dissolving materials such as a base material component and an acid generator component that generates acid upon exposure in a specific organic solvent.
  • an organic solvent that does not dissolve the first resist layer is used. Thereby, mixing can be suppressed.
  • any solvent that is not compatible with the first resist layer can be used.
  • the fact that the first resist layer is not dissolved preferably means, for example, that after forming a first resist layer having a thickness of 0.2 m under a condition of 23 ° C and immersing it in an organic solvent, after 60 minutes. This also indicates that no change in film thickness occurs.
  • solvents examples include alcohol solvents and fluorine solvents. These can be used alone or in combination.
  • the organic solvent preferably contains an alcohol solvent.
  • monohydric alcohol is more preferred, and depending on the number of carbons, primary or secondary monohydric alcohol is preferred, but primary monohydric alcohol is most preferred. .
  • the boiling point is preferably 80 to 160 ° C, more preferably 90 to 150 ° C 1
  • the temperature is most preferably from 00 to 135 ° C, from the viewpoint of coating properties, stability of the composition during storage, and heating temperature of the PAB process or PEB process.
  • the monohydric alcohol means that the number of hydroxy groups contained in the alcohol molecule is one, and does not include dihydric alcohols, trihydric alcohols or derivatives thereof.
  • the alcohol solvent include n-amyl alcohol (boiling point 138.0 ° C), s-amyl alcohol (boiling point 119.3 ° C), t-amyl alcohol (101.8 ° C).
  • isobutanol (2-methyl-1-propanol), 4-methyl-2-pentanol, n-butanol and the like are preferable. Of these, isobutanol and n-butanol are preferred.
  • fluorine-based solvent examples include perfanololeo 2 butinoletetrahydrofuran.
  • One or more organic solvents can be used in combination.
  • an organic solvent other than an alcohol solvent or a fluorine solvent may be used, but an alcohol solvent or a fluorine solvent is preferable. It is preferable to use 80% by mass or more, preferably 100% by mass of the solvent.
  • any one or more of conventionally known solvents for chemically amplified resists can be appropriately selected and used.
  • latatones such as ⁇ -butyrolatatatone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol
  • Polyhydric alcohols such as monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of dipropylene glycol monoacetate and derivatives thereof
  • Cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxypropionate
  • the amount of the organic solvent used is not particularly limited, but is a concentration that can be applied to a substrate and the like, and is appropriately set according to the coating film thickness.
  • the second negative resist composition is a chemically amplified type containing (AO-0) alkali-soluble resin, (B) an acid generator component that generates acid upon exposure, and (C) a crosslinker component. Is preferred.
  • AO-0 Alkali-soluble resin
  • B Acid generator component that generates acid upon exposure
  • C Crosslinker component
  • other optional components that can be added are not particularly limited. Any material proposed as a material for a negative resist composition can be used as appropriate.
  • the second negative resist composition has high sensitivity.
  • Preferred examples include the following.
  • Constuent unit refers to a monomer unit constituting a polymer (resin).
  • “Acrylic acid-derived structural unit” means a structural unit formed by cleavage of an ethylenic double bond of acrylic acid.
  • a structural unit derived from an acrylate ester means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
  • “Acrylic ester force-derived structural unit” includes a concept in which the ⁇ -position hydrogen atom is substituted with another substituent such as a halogen atom, an alkyl group, or a halogenialkyl group.
  • structural unit that also induces acrylic acid power and “structural unit that also induces acrylic ester power”, the term “hi-position (carbon atom at the ⁇ -position)” is used unless otherwise specified. This is the carbon atom to which the group is bonded.
  • the “structural unit that also induces acrylic acid power” is a structural unit in which a hydrogen atom bonded to a carbon atom at the ⁇ -position is substituted with another substituent such as a halogen atom, an alkyl group, a halogenated alkyl group,
  • the concept includes a structural unit derived from an acrylate ester in which a hydrogen atom is bonded to a carbon atom at the ⁇ - position.
  • alkyl group includes a linear, cyclic or branched alkyl group unless otherwise specified.
  • halogen includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and is preferably a fluorine atom.
  • (AO-0) resin component As the (AO-0) component, a resin component containing (AO) at least a fluorinated hydroxyalkyl group and an alicyclic group is preferable.
  • (AO) component (A) a structural unit (al) containing an alicyclic group having a fluorinated hydroxyalkyl group, and a structural unit derived from an acrylate ester, A rosin component having a structural unit (a2) containing a hydroxyl group-containing alicyclic group is preferred.
  • constitutional unit (al) containing alicyclic group having fluorinated hydroxyalkyl group (al) Having constitutional unit (al) is likely to cause problems in negative resist compositions. An effect is obtained.
  • the alicyclic group has a fluorinated hydroxyalkyl group.
  • the fluorinated hydroxyalkyl group has a hydroxyl group that is part of a hydrogen atom of the alkyl group. Or all substituted by fluorine It is. In the group, the hydrogen atom of the hydroxyl group is easily released by fluorination.
  • the alkyl group is linear or branched, and the carbon number is not particularly limited, but is, for example, 1 to 20, preferably 4 to 16.
  • the number of hydroxyl groups is not particularly limited, but is usually one.
  • a fluorinated alkyl group and a ⁇ or fluorine atom are bonded to the ⁇ -position carbon atom to which the hydroxy group is bonded (here, the ⁇ -position carbon atom of the hydroxyalkyl group).
  • the fluorinated alkyl group bonded to the ⁇ -position it is preferable that all of the hydrogen atoms of the alkyl group are substituted with fluorine! /.
  • the alicyclic group may be monocyclic or polycyclic! /, But is preferably a polycyclic group.
  • An alicyclic hydrocarbon group is preferred. Moreover, it is preferable that it is saturated.
  • the alicyclic group preferably has 5 to 15 carbon atoms!
  • examples of the monocyclic group include groups in which one hydrogen atom has been removed from a cycloalkane.
  • examples of the polycyclic group include groups in which one or two hydrogen atoms have been removed from a bicycloalkane, tricycloalkane, tetracycloalkane or the like.
  • examples of the monocyclic group include groups obtained by removing one or two hydrogen atoms from cyclopentane or cyclohexane, and removing two hydrogen atoms from cyclohexane. Is preferred.
  • polycyclic group examples include groups in which one or two hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
  • groups obtained by removing two hydrogen atoms from cyclohexane, adamantane, norbornane, and tetracyclododecane are preferred because they are easily available on the industry.
  • groups in which two hydrogen atoms have been removed from norbornane are particularly preferred.
  • the alicyclic group is bonded to the ester group [— c (o) o—] of the attalic acid ester, in which the structural unit (al) is preferably a structural unit derived from acrylic acid force.
  • the structural unit (al) is preferably a structural unit derived from acrylic acid force.
  • a structure (a structure in which a hydrogen atom of a carboxyl group is substituted with the above alicyclic group) is preferred.
  • R is a hydrogen atom, an alkyl group, a fluorinated alkyl group or a fluorine atom, and m, n and p are each independently an integer of 1 to 5.
  • R is a hydrogen atom, an alkyl group, a fluorinated alkyl group or a fluorine atom.
  • alkyl group a lower alkyl group having 5 or less carbon atoms is preferred, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group.
  • a methyl group is preferred.
  • the fluorinated alkyl group is preferably a group in which one or more hydrogen atoms of a lower alkyl group having 5 or less carbon atoms are substituted with fluorine atoms. Specific examples of the alkyl group are the same as described above.
  • the hydrogen atoms substituted with fluorine atoms may be part or all of the hydrogen atoms constituting the alkyl group.
  • a hydrogen atom or an alkyl group is preferable, a hydrogen atom or a methyl group is particularly preferable, and a hydrogen atom is most preferable.
  • N, m, and p are each preferably 1.
  • ⁇ , ⁇ 'bis (trifluoromethyl) bisulfite [2. 2. 1] hepta 5 hen 1 2 configuration derived from ethanol acrylate The unit is also preferred from the standpoint of effect and easy synthesis and high etching resistance.
  • one type or a mixture of two or more types can be used as the structural unit (al).
  • the effect of suppressing swelling is improved. Moreover, the effect of improving etching resistance can be obtained.
  • the hydroxyl group (alcohol hydroxyl group) of the structural unit (a2) is converted into (C) a crosslinking agent by the action of the acid generated from the acid generator (B).
  • the property of the component (A) that is soluble in the alkali developer is changed to an insoluble property and is negative.
  • the hydroxyl group-containing alicyclic group is preferably bonded to the ester group (—C (O) 2 O 3) of the acrylate ester.
  • another substituent may be bonded to the ⁇ -position ( ⁇ -position carbon atom) instead of a hydrogen atom.
  • Preferred examples of the substituent include an alkyl group, a fluorinated alkyl group, and a fluorine atom.
  • the hydroxyl group-containing alicyclic group is a group in which a hydroxyl group is bonded to the alicyclic group.
  • 1 to 3 hydroxyl groups are preferably bonded, and more preferably one.
  • an alicyclic group may be bonded with an alkyl group having 1 to 4 carbon atoms.
  • the alicyclic group may be monocyclic or polycyclic! /, But is preferably a polycyclic group. Also
  • An alicyclic hydrocarbon group is preferred. Moreover, it is preferable that it is saturated.
  • the alicyclic group preferably has 5 to 15 carbon atoms.
  • examples of the monocyclic group include groups in which one hydrogen atom has been removed from a cycloalkane.
  • examples of the polycyclic group include groups in which one hydrogen atom has been removed from a bicycloalkane, tricycloalkane, tetracycloalkane or the like.
  • monocyclic groups include cyclopentane and cyclohexane.
  • a group such as a cyclohexyl group is preferred.
  • polycyclic group examples include groups in which one hydrogen atom has been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
  • a cyclohexyl group, adamantyl group, norbornyl group, and tetracyclodole group are readily available from the industrial viewpoint.
  • a cyclohexyl group and an adamantyl group are preferred, and an adamantyl group is particularly preferred.
  • R is a hydrogen atom, an alkyl group, a fluorinated alkyl group or a fluorine atom, and q is an integer of 1 to 3.
  • R is a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a fluorine atom bonded to the ⁇ -position, and is the same as described in the general formula (1).
  • R is most preferably a hydrogen atom!
  • q is preferably a force 1 which is an integer of 1 to 3.
  • the bonding position of the hydroxyl group is not particularly limited, but it is preferably bonded to the position 3 of the adamantyl group.
  • one type or a mixture of two or more types can be used as the structural unit (a2).
  • the component (A) preferably has a structural unit (a3) in addition to the structural unit (al) and the structural unit (a2).
  • the structural unit (a3) By having the structural unit (a3), the effect of improving the resolution can be obtained. Also, film loss can be suppressed. In addition, the controllability of the crosslinking reaction during pattern formation is improved. Furthermore, the film density tends to improve. Thereby, there exists a tendency for heat resistance to improve. Furthermore, etching resistance is improved.
  • the structural unit (a3) is clearly distinguished from the structural unit (a2) by not having a cyclic structure.
  • the component (A) having the structural unit (a3) is added to the negative resist composition, the hydroxyl group of the structural unit (a3) and the hydroxyl group hydroxy group of the structural unit (a3) are combined.
  • the group reacts with the crosslinking agent (C) by the action of the acid generated from the acid generator (B), so that the component (A) is soluble in an alkali developer but is insoluble. Change and become negative.
  • Having an alcoholic hydroxyl group in the side chain includes, for example, a structural unit having a hydroxyalkyl group bonded thereto.
  • the hydroxyalkyl group may be bonded to the ⁇ -position carbon atom of the main chain (the portion where the ethylenic double bond of acrylic acid is cleaved), or substituted with a hydrogen atom of the carboxy group of acrylic acid to form an ester.
  • the structural unit (a3) which may constitute, at least one of these is preferably both present.
  • an alkyl group, a fluorinated alkyl group, or a fluorine atom may be bonded to the ⁇ -position carbon atom instead of a hydrogen atom.
  • the structural unit (a3) is preferably represented by the following general formula (3).
  • R 1 is a hydrogen atom, an alkyl group, a fluorinated alkyl group, a fluorine atom or a hydroxyalkyl group
  • R 2 is a hydrogen atom, an alkyl group or a hydroxyalkyl group
  • R 2 At least one is a hydroxyalkyl group.
  • the hydroxyalkyl group is preferably a lower hydroxyalkyl group having 10 or less carbon atoms, more preferably a lower hydroxyalkyl group having 2 to 8 carbon atoms, most preferably a hydroxymethyl group or Hydroxyethyl group.
  • the number of hydroxyl groups and the bonding position are not particularly limited, but are usually one and preferably bonded to the terminal of the alkyl group.
  • the alkyl group is preferably a lower alkyl group having 10 or less carbon atoms, more preferably a lower alkyl group having 2 to 8 carbon atoms, and most preferably an ethyl group or a methyl group.
  • the fluorinated alkyl group is preferably a group in which part or all of the hydrogen atoms in a lower alkyl group having 5 or less carbon atoms (preferably an ethyl group or a methyl group) are substituted with fluorine.
  • R 2 the alkyl group and hydroxyalkyl group are the same as R 1 .
  • the structural unit (a3) includes a structural unit derived from (hydroxyalkyl) acrylic acid alkyl ester from the viewpoint of improving the effect and improving the film density. And is preferred.
  • (a-hydroxymethyl) acrylic acid ethyl ester or ⁇ (hydroxymethyl) -acrylic acid methyl ester is also preferred.
  • a structural unit derived from a structural unit (a3) force (a alkyl) acrylic acid hydroxyalkyl ester is included.
  • a structural unit derived from a-methyl monoacrylic acid hydroxychetyl ester or ⁇ -methyl-acrylic acid hydroxymethyl ester is preferable.
  • one type or a mixture of two or more types can be used as the structural unit (a3).
  • the component (A) further has a structural unit (a4) derived from an acrylate ester containing a latathone-containing monocyclic or polycyclic group. Is preferred.
  • the structural unit (a3) may be used in combination.
  • the ratatone-containing monocyclic or polycyclic group of the structural unit (a4) is used for forming a resist film, the adhesion of the resist film to the substrate is increased or the hydrophilicity with the developer is increased. It is effective for raising. In addition, the effect of suppressing swelling is improved.
  • the rataton here refers to one ring containing the -O-C (O) -structure, and this is counted as the ring of one eye. Therefore, in the case of only a rataton ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure.
  • any structural unit can be used without particular limitation as long as it has a rataton ring having both the ester structure (—O—C (O) —) and a ring structure. Is available
  • examples of the ratatone-containing monocyclic group include groups in which one ⁇ -peptidyl rataton force hydrogen atom is removed.
  • examples of the latatatone-containing polycyclic group include groups in which a bicycloalkane, tricycloalkane, or tetracycloalkane having a latathone ring has one hydrogen atom removed.
  • a latatone-containing polycyclic group having a norbornane latathone is preferable, among which a latathone-containing polycyclic group is preferable.
  • substituents may be bonded to the ⁇ -position (the carbon atom at the ⁇ -position) instead of a hydrogen atom.
  • substituents include an alkyl group, a fluorinated alkyl group, and a fluorine atom.
  • examples of the structural unit (a4) include structural units represented by the following general formulas (a4-l) to (a4-5).
  • R is the same as described above.
  • R ′ is independently a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 5 carbon atoms, and m is an integer of 0 or 1.
  • R ′ is preferably a hydrogen atom in view of industrial availability.
  • one type may be used alone, or two or more types may be used in combination. May be.
  • the structural unit (al) is a structural unit represented by the general formula (1), and R in the general formula (1) is a hydrogen atom.
  • R in the general formula (1) is a hydrogen atom.
  • a hydrogen atom is bonded to the ⁇ position (carbon atom to which the carboxy group is bonded) of the structural unit (a2). The reason is that the dissolution contrast becomes good.
  • the structural unit (al) is a structural unit represented by the general formula (1), and R in the general formula (1) is a hydrogen atom.
  • a hydrogen atom is preferably bonded to the ⁇ -position of the structural unit (a2). This is because the dissolution contrast is good.
  • the structural unit (al) is a structural unit represented by the general formula (1), and R in the general formula (1) is a hydrogen atom.
  • a hydrogen atom is preferably bonded to the ⁇ -position of the structural unit (a2), and a hydrogen atom is preferably bonded to the a-position of the structural unit (a4).
  • the structural unit (al) is a structural unit represented by the general formula (1), and R in the general formula (1) is a hydrogen atom.
  • a hydrogen atom is preferably bonded to the ⁇ -position of the structural unit (a2), and a hydrogen atom is preferably bonded to the a-position of the structural unit (a4). The reason is that the dissolution contrast becomes good.
  • each structural unit in the resin is within the following numerical range. Is preferably satisfied.
  • the proportion of the structural unit (al) is preferably 20 to 80 mol%, more preferably 30 to 70 mole 0/0, and most preferably 35 to 55 mole 0/0.
  • the proportion of the structural unit (a2) is preferably 20 to 80 mole 0/0, more preferably 30 to 70 mol%, and most preferably 45 to 65 mole 0/0.
  • the proportion of each structural unit in the resin Preferably satisfies the following numerical range.
  • the proportion of the structural unit (al) is preferably 20 to 80 mol%, more preferably from 3 0 to 70 mole 0/0, and most preferably 35 to 55 mole 0/0.
  • the proportion of the structural unit (a2) is preferably 10 to 70 mole 0/0, more preferably 10 to 50 mol%, more preferably from 20 to 40 mole 0/0.
  • the proportion of the structural unit (a3) is preferably 10 to 70 mole 0/0, more preferably 10 to 40 mol%, and most preferably 15 to 35 mole 0/0.
  • the effect of suppressing swelling is improved.
  • the structural unit (a2) and the structural unit (a3) are blended in a balanced manner, an appropriate contrast can be obtained and the resolution can be improved.
  • etching resistance is improved. Better exposure A margin can be obtained.
  • the proportion of the structural unit (al) is preferably 20 to 85 mol%, more preferably 3 0-70 mole 0/0, and most preferably 35 to 50 mole 0/0.
  • the proportion of the structural unit (a2) is preferably 14 to 70 mole 0/0, more preferably 15 to 50 mol%, and most preferably from 30 to 50 mole 0/0.
  • the proportion of the structural unit (a4) is preferably 1 to 70 mol 0/0, more preferably 3 to 50 mol%, and most preferably 5 to 20 mol%.
  • the proportion of each structural unit in the resin is within the following numerical range. It is preferable to satisfy
  • the proportion of the structural unit (al) is preferably 10 to 85 mol%, more preferably from 2 0 to 70 mole 0/0, and most preferably 25 to 50 mole 0/0.
  • the proportion of the structural unit (a2) is preferably 10 to 80 mole 0/0, more preferably 20 to 70 mol%, and most preferably from 30 to 50 mole 0/0.
  • the proportion of the structural unit (a3) is preferably 4 to 70 mol%, more preferably 7 to 50 mol%, and most preferably 10 to 30 mole 0/0.
  • the proportion of the structural unit (a4) is preferably 1 to 70 mol 0/0, more preferably 3 to 50 mol% And most preferably 5 to 20 mol%.
  • the component (A) may have a copolymerizable structural unit other than the structural units (al) to (a4) selected, but may be a structural unit (al ) To structural unit (a4) is preferred.
  • the main component is preferably a total of 70 mol% or more of the structural units in which these forces are also selected.
  • it is 80 mol% or more, and among them, 100% is preferable.
  • component (A) particularly preferred is a resin comprising the structural unit (al) and the structural unit (a2), or the structural unit (al), the structural unit (a2) and the structural unit (a3).
  • coconut oil particularly preferred is a resin comprising the structural unit (al) and the structural unit (a2), or the structural unit (al), the structural unit (a2) and the structural unit (a3).
  • a structural unit (al), a structural unit (a2) and a structural unit (a4), or a structural unit (al) to a structural unit (a4) is a resin that also has unit (al), structural unit (a2) and structural unit (a3) forces.
  • the weight average molecular weight of component (A) (Mw; weight average molecular weight in terms of polystyrene by gel permeation chromatography) is preferably 2000 to 30000, more preferably 200
  • LOOOO most preferably 3000 to 8000. Is it swollen by making this range? It is preferable from the viewpoint of suppression of wrinkles and thereby suppression of microbridges. Also preferred from the point of high resolution.
  • the molecular weight is low, and better properties tend to be obtained.
  • the component (A) can be obtained, for example, by subjecting a monomer for deriving each structural unit to radical polymerization by a conventional method.
  • Component (A) can be used alone or in combination.
  • the preferred mass average molecular weight of the component (AO-0) and the component (AO) is the same as that of the component (A).
  • the (AO 0) component and the (AO) component can be used alone or in combination.
  • As the (AO-0) component and the (AO) component it is possible to use a resin other than the (A) component. If the content of the (AO 0) component is adjusted according to the resist film thickness to be formed,
  • the component (B) can be used without particular limitation from known acid generators used in conventional chemically amplified resist compositions.
  • acid generators examples include onium salt-based acid generators such as iodine salts and sulfo-um salts, oxime sulfonate-based acid generators, bisalkyl or bis-aryl sulfo-diazomethanes,
  • acid generators such as diazomethane acid generators such as poly (bissulfol) diazomethanes, iminosulfonate acid generators and disulfone acid generators are known.
  • sodium salt-based acid generators include trifluoromethane sulfonate or nonafluorobutane sulfonate of diphenylodium, trifluoromethanesulfonate or nona of bis (4-tertbutylbutyl) ododonium.
  • oxime sulfonate-based acid generators include ⁇ (methylsulfo-luoxyimino) -phenolacetonitrile, OC- (methylsulfo-luoxyimino) - ⁇ -methoxyphenylacetonitrile, ⁇ - (trifluoromethyl) Sulfo-luoxyimino) -phenylaceto-tolyl, ⁇ - (trifluoromethylsulfo-ruximino) -p-methoxyphenylacetonitrile, at- (ethylsulfonyloxyximino) -p-methoxyphenylacetonitryl, ⁇ - (Propylsulfo-luoxyimino) p-methylphenolacetonitrile, ⁇ (methylsulfo-luoxyimino) ⁇ -bromophenolacetonitrile, and the like. Of these, ⁇ (methylsulfo-luoxyi
  • bisalkyl or bisarylsulfol diazomethanes include bis (isopropylsulfol) diazomethane, bis ( ⁇ toluenesulfol) diazomethane, bis (1 , 1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (2,4 dimethylphenylsulfol) diazomethane, and the like.
  • Poly (bissulfonyl) diazomethanes include, for example, 1,3 bis (phenolsulfodiazomethylsulfo) propane (compound ⁇ ), 1, 4-having the structure shown below.
  • X represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; ⁇ and ⁇ are each independently at least one hydrogen atom is a fluorine atom.
  • X is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has, for example, 2 carbon atoms. -6, preferably 3-5, most preferably 3 carbon atoms.
  • ⁇ and ⁇ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has, for example, 1 to: LO, preferably Is 1-7, more preferably 1-3.
  • the carbon number of the alkylene group of X or ⁇ , the carbon number of the alkyl group of ⁇ is smaller! /, And the solubility in the resist solvent is better.
  • the proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to: LOO%, and most preferably all hydrogen atoms are fluorine.
  • R "to R" each independently represents an aryl group or an alkyl group.
  • At least one of R U to R 13 represents an aryl group. Of R U to R 13 , two or more are preferably aryl groups. Most preferably, R U to R 13 are all aryl groups.
  • the aryl group of R U to R 13 is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, which may or may not be substituted with an alkyl group, an alkoxy group, a halogen atom, or the like. Examples thereof include a good phenyl group and naphthyl group. An aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at a low cost.
  • the alkyl group of R U to R 13 is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, A decanyl group and the like can be mentioned, and a methyl group can be mentioned as a preferable one because it is excellent in resolution and can be synthesized at low cost.
  • R U to R 13 are most preferably all phenyl groups.
  • the (B) component should be an ohmic salt containing a fluorinated alkyl sulfonate ion as a ion. Is preferred.
  • an ohmic salt having a fluorinated alkyl sulfonic acid ion as the ion.
  • one type of acid generator may be used alone, or two or more types may be used in combination.
  • the content of component (B) is 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of component (AO-0). By setting it within the above range, the pattern can be sufficiently formed. Moreover, since a uniform resist solution is obtained and storage stability becomes favorable, it is preferable.
  • Component (C) is not particularly limited, and is a chemically amplified negative resist known so far. It can be used by arbitrarily selecting from the crosslinking agent components used in the composition.
  • amino group-containing compounds such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, glycoluril, etc. are reacted with formaldehyde or formaldehyde and lower alcohol, and the hydrogen atom of the amino group is replaced with hydroxymethyl group or lower alkoxymethyl group. Substituted compounds are listed.
  • those using melamine are melamine crosslinking agents
  • those using urea are urea crosslinking agents
  • those using ethylene urea are ethylene urea crosslinking agents
  • those using glycoluril are glycols.
  • hexamethoxymethylmelamine bismethoxymethylurea, bismethoxymethylbismethoxyethyleneurea, tetramethoxymethyldaricoluril, tetrabutoxymethylglycoluril and the like.
  • the component (C) is particularly preferably at least one selected from melamine crosslinking agents, urea crosslinking agents, ethylene urea crosslinking agents, propylene urea crosslinking agents, and glycoluril crosslinking agents. is there. Particularly preferred is a glycoluril-based crosslinking agent.
  • glycoluril-based crosslinking agent glycoluril substituted at the N-position with a hydroxyalkyl group which is a crosslinking group and Z or a lower alkoxyalkyl group is preferred.
  • glycoluril-based cross-linking agent examples include mono-, di-, tri- and tetra-hydroxymethyl glycol glycol, mono-, di-, tri- and / or tetramethoxymethyl glycoluril, mono-, di-, Examples include tri- and / or tetraethoxymethylated glycoluril, mono-, di-, tri- and / or tetrapropoxymethylethyl glycoluril, mono-, di-, tri- and / or tetrabutoxymethylethylglycoluril.
  • “mono, di, tri and / Or “tetra” indicates that one or more of mono-, di-, tri-, and tetra-forms may be contained, and tri-tetra is particularly preferable.
  • This cross-linking agent can be obtained, for example, as a commercial product “Mx270” (product name, manufactured by Sanwa Chemical Co., Ltd.). These are mostly tri- and tetra-isomers, and are a mixture of monomers, dimers and trimers.
  • the amount of component (C) is 315 parts by mass, preferably 5 to: LO parts by mass with respect to 100 parts by mass of component (AO-0).
  • the (AO-0) component can be made insoluble in alkali.
  • the upper limit value or less it is possible to prevent a decrease in resolution. There is a tendency that the resolution is improved when the addition amount of the crosslinking agent is small.
  • a nitrogen-containing organic compound (D) (hereinafter referred to as component (D)) is further added as an optional component. Can be combined.
  • any known one may be used, but aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines are preferred. .
  • Aliphatic amines contain at least one hydrogen atom of ammonia NH and have 12 or more carbon atoms.
  • Examples include amines substituted with the lower alkyl group or hydroxyalkyl group (alkylamines or alkylalcoholamines). Specific examples thereof include mono-alkylamines such as n-hexylamine, n-ptylamine, n-octylamine, n-norlamin, n-decylamine; jetylamine, di-n-propylamine, di-n-ptylamine, di-n-octylamine.
  • Dialkylamines such as dicyclohexylamine; trimethylamine, triethylamine, tri- n -propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-ptyluamine, tri-n-octylamine, Tri-n-noramine, tri-n-de-ramine, tri-n-dodecylamine, etc.
  • Alkylamines; alkylethanolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di- n- octanolamine, tri-n-octanolamine and the like.
  • Component (D) is usually used in the range of 0.01 to 5.0 parts by mass per 100 parts by mass of component (AO-0).
  • alkyl alcoholamines are preferred, with alkyl alcoholamines and trialkylamines being preferred.
  • alkyl alcoholamines triethanolamine is most preferably an alkyl alcoholamine such as triisopropanolamine.
  • an organic carboxylic acid or oxalic acid of phosphorus or a derivative thereof ( E) (hereinafter referred to as component (E)) can be contained.
  • the (D) component and the (E) component can be used together, or V or one of them can be used.
  • the organic carboxylic acid for example, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
  • Phosphoric acid or its derivatives include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenol ester and other phosphoric acid or derivatives such as those esters, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid Phosphonic acid such as n-butyl ester, phenol phosphonic acid, diphosphoric phosphonic acid ester, dibenzyl phosphonic acid ester and derivatives thereof, phosphinic acid such as phosphinic acid, phenol phosphinic acid and the like And derivatives such as esters, of which phosphonic acid is particularly preferred.
  • Component (E) is used at a ratio of 0.01 to 5.0 parts by mass per 100 parts by mass of (AO-0) component.
  • Negative resist compositions further contain miscible additives as desired, such as additional grease to improve resist film performance, surfactants to improve coatability, solvents.
  • additional grease to improve resist film performance such as additional grease to improve resist film performance, surfactants to improve coatability, solvents.
  • An anti-decompressant, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like can be added as appropriate.
  • an organic solvent that does not dissolve the first resist layer 2 is used as in the case of the second negative resist composition.
  • the explanation of the organic solvent is the same as that of the second negative resist composition.
  • ( ⁇ -Lower alkyl) acrylic acid ester means one or both of a low-grade alkyl acrylic acid ester such as a methacrylic acid ester and an acrylic acid ester.
  • a lower alkyl acrylate ester means a hydrogen atom bonded to a carbon atom of an acrylate ester substituted with a lower alkyl group.
  • Constuent unit means a monomer unit constituting a polymer.
  • a structural unit derived from an acrylate ester means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
  • the “structural unit that can also induce ⁇ -lower alkyl acrylate ester force” means a structural unit that is formed by cleavage of an ethylenic double bond of an ⁇ -lower alkyl acrylate ester.
  • (a-lower alkyl) acrylic ester force-derived structural unit means a structural unit formed by cleavage of an ethylenic double bond of (a-lower alkyl) acrylic ester.
  • the positive resist yarn composition comprises (AO ') a resin component whose alkali solubility is increased by the action of an acid, and (B) an acid generator component that generates an acid upon exposure. Because
  • the (AO ′) component is preferably a rosin component that contains a structural unit that also induces ( ⁇ ′) (lower alkyl) acrylate power and that increases alkali solubility by the action of an acid.
  • ( ⁇ ,) component is a lower alkyl) acrylic containing an acid dissociable, dissolution inhibiting group It is preferable to have a structural unit (a3,) derived from an acid ester force-derived structural unit ( & 1,) and a polar group-containing polycyclic group — a lower alkyl) acrylate ester. .
  • a hydrogen atom or a lower alkyl group is bonded to the ⁇ carbon atom.
  • the lower alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a ⁇ butyl group, an isobutyl group, a tert-butyl group, and a pentyl group. , Isopentyl group, neopentyl group and the like. Industrially, methyl groups are preferred!
  • a hydrogen atom or a methyl group is preferred.
  • the acid dissociable, dissolution inhibiting group of the structural unit (al ') has an alkali dissolution inhibiting property that makes the entire ( ⁇ ') component before exposure insoluble in alkali, and at the same time from the acid generator ( ⁇ ) after exposure. It is a group that dissociates by the action of the generated acid and changes the entire ( ⁇ ′) component to alkali-soluble.
  • various resins proposed for ArF excimer laser resist compositions can be appropriately selected and used.
  • a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group of acrylic acid and a group that forms a cyclic or chain alkoxyalkyl are widely known.
  • a cyclic or chain alkoxyalkyl ester is an ester formed by replacing a hydrogen atom of a carboxy group with an alkoxyalkyl group, and the carboxy group (one C (O)
  • the alkoxyalkyl group is bonded to the oxygen atom at the terminal of —O—), and this alkoxyalkyl ester group is cleaved between the oxygen atom and the alkoxyalkyl group when an acid acts.
  • Examples of such cyclic or chain alkoxyalkyl groups include 1-methoxymethyl group, 1 ethoxyethyl group, 1 isopropoxycetyl, 1-cyclohexyloxychetyl group, 2-adamantoxymethyl group, 1 methyladamantoxymethyl Group, 4-oxo-2 adamantoxymethyl group, etc.
  • Examples of the acid dissociable, dissolution inhibiting group that forms a chain-like tertiary alkyl ester include a t-butyl group and a tert-amyl group.
  • a cyclic unit particularly a structural unit containing an “acid dissociable, dissolution inhibiting group containing an alicyclic group” is preferable.
  • the alicyclic group may be either monocyclic or polycyclic.
  • a number of proposed intermediate forces can be selected and used from the viewpoint of etching resistance.
  • Polycyclic alicyclic groups are preferred.
  • the alicyclic group is preferably saturated with a hydrocarbon group being preferred.
  • Examples of monocyclic alicyclic groups include groups in which one hydrogen atom has been removed from a cycloalkane.
  • Examples of the polycyclic alicyclic group include groups obtained by removing one hydrogen atom from bicycloalkane, tricycloalkane, tetracycloalkane and the like.
  • examples of the monocyclic group include a cyclopentyl group and a cyclohexyl group.
  • examples of the polycyclic group include groups in which one hydrogen atom is removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
  • adamantyl group obtained by removing one hydrogen atom from adamantane is industrially preferred.
  • norbornyl group obtained by removing one hydrogen atom from norbornane is industrially preferred.
  • tricyclodecanyl obtained by removing one hydrogen atom from tricyclodecane is industrially preferred.
  • the structural unit (al ') is preferably at least one selected from the following general formulas ( ⁇ ) to ( ⁇ ).
  • R represents a hydrogen atom or a lower alkyl group
  • R 21 represents a lower alkyl group
  • R 24 is a tertiary alkyl group.
  • R represents a hydrogen atom or a lower alkyl group.
  • the lower alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n -butyl group, an isobutyl group, a tert-butyl group, or a pentyl group.
  • a methyl group is preferable. Of these, a hydrogen atom or a methyl group is preferred.
  • R 21 is preferably a lower linear or branched alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, An isopentyl group, a neopentyl group, etc. are mentioned. Among them, methyl group, A til group is preferred because it is easily available industrially.
  • R 22 and R 23 are each independently preferably a linear or branched lower alkyl group having 1 to 5 carbon atoms.
  • R 22 and R 23 are methyl groups is industrially preferred, and examples thereof include a structural unit derived from 2- (1-adamantyl) -2-propyl acrylate. .
  • the R 24 is preferably a chain-like tertiary alkyl group or a cyclic tertiary alkyl group.
  • Examples of the chain-like tertiary alkyl group include a tert butyl group and a tert amyl group, and a tert butyl group is industrially preferable.
  • the tertiary alkyl group is an alkyl group having a tertiary carbon atom.
  • Examples of the cyclic tertiary alkyl group are the same as those exemplified in the above-mentioned “acid dissociable, dissolution inhibiting group containing an alicyclic group”, and include 2-methyl-2-adamantyl group and 2-ethyl-2-adamantyl group. Groups, 2- (1-adamantyl) 2-propyl group, 1-ethylcyclohexyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-methylcyclopentyl group and the like.
  • group 1 COOR 24 may be bonded to the 3 or 4 position of the tetracyclodode group shown in the formula, but the bonding position cannot be specified.
  • carboxy group residue of the attalylate constituent unit is also bonded to the 8 or 9 position shown in the formula, but the bonding position cannot be specified.
  • the structural unit (al ') can be used alone or in combination of two or more.
  • the structural unit (al ') is, (Alpha' to the total of) all the structural units within the component, 20 to 60 mol%, preferably 30 to 50 mole 0/0, at 35 to 45 mole 0/0 Most preferably it is.
  • a pattern can be obtained by setting it to the lower limit value or more, and a balance with other structural units can be achieved by setting the upper limit value or less.
  • composition unit (a3) [0144], composition unit (a3,)
  • the structural unit (a3 ′) increases the hydrophilicity of the entire component ( ⁇ ′), increases the affinity with the developer, improves the alkali solubility in the exposed area, and contributes to improved resolution. .
  • any of a lower alkyl group and a hydrogen atom may be bonded to the ⁇ carbon atom.
  • the lower alkyl group is the same as described above.
  • the polar group include a hydroxyl group, a cyano group, a carboxy group, and an amino group, and a hydroxyl group is particularly preferable.
  • polycyclic group examples include a polycyclic alicyclic hydrocarbon group (polycyclic group).
  • the polycyclic group can be appropriately selected from a large number of polycyclic groups similar to those exemplified in the structural unit (al ′).
  • the structural unit (a3) is preferably at least one selected from the following general formulas ( ⁇ ′) to (IX ′).
  • R is a hydrogen atom or a lower alkyl group, and n is an integer of 1 to 3.
  • R ° is the same as above.
  • n ′ is 1 and the hydroxyl group is bonded to the 3-position of the adamantyl group.
  • R is a hydrogen atom or a lower alkyl group, and k is an integer of 1 to 3.
  • R ° is the same as above.
  • k 1
  • the cyan group is bonded to the 5th or 6th position of the norbornyl group.
  • the structural unit (al) represented by the “alicyclic group having a fluorinated hydroxyalkyl group” of the second negative resist composition can also be used.
  • the structural unit (a3 ') can be used singly or in combination of two or more.
  • the structural unit (a3 ') is, (Alpha') with respect to the sum of all structural units constituting the component, 10-50 mol 0/0, preferably the preferably contains 15 to 40 mole 0/0 device the most successful Masui 20 to 30 mole 0/0.
  • Lithographic properties are improved by setting it to the lower limit value or more, and balancing with other structural units can be achieved by setting the upper limit value or less.
  • the component ( ⁇ ′) may contain a structural unit other than the structural units (al ′) and (a3 ′).
  • the force is preferably 70 mol% or more, preferably a total of these structural units, Is 8
  • the description of the structural unit (a2,) is the same as the description of the structural unit (a4).
  • the structural unit (a2,) can be used alone or in combination.
  • the structural unit (a2,) is, (A,) with respect to the total of all the structural units within the component, 20 to 60 mole 0/0, preferably the preferably contains 20 to 50 mole 0/0 device 30 it is most favorable preferable is 45 mol 0/0. Lithographic properties are improved by setting the value to the lower limit or higher, and balance with other structural units can be achieved by setting the lower limit or lower.
  • a structural unit that contains a polycyclic alicyclic hydrocarbon group and is derived from an (ex lower alkyl) acrylate ester force is preferred.
  • the polycyclic alicyclic hydrocarbon group include those similar to those exemplified in the case of the structural unit (al ′), and in particular, a tricyclohexane group, an adamantyl group, a tetracyclodode group, and the like.
  • At least one selected from the group consisting of a force group, a norbol group and an isobol group force is preferred from the viewpoint of industrial availability.
  • structural unit (a4 ′) include the following structures ( ⁇ ) to ( ⁇ ).
  • This building block is usually obtained as a mixture of isomers at the 5- or 6-position.
  • R is a hydrogen atom or a lower alkyl group
  • R ° is the same as above.
  • a structural unit (a4 structural unit (a4)') is, (Alpha ') component, 1 to 25 mole 0/0 for total of all the structural units, preferably 5 to 20 mol 0 / Included in the range of 0 ! /, Preferred! / ⁇
  • the component ( ⁇ ') can be composed of one or more types of rosin.
  • the component ( ⁇ ′) is obtained, for example, by polymerizing a monomer related to each structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisobutyl-tolyl ( ⁇ ). be able to.
  • a radical polymerization initiator such as azobisisobutyl-tolyl ( ⁇ ).
  • the weight average molecular weight of the component ( ⁇ ') (polystyrene equivalent weight average molecular weight by gel permeation chromatography, the same shall apply hereinafter) is, for example, 30000 or less, preferably 20000 or less, preferably 12000 or less. It is even more preferable that there is more preferably 10000 or less.
  • the lower limit value is not particularly limited, but is preferably 4000 or more, and more preferably 5000 or more, from the viewpoints of suppressing turnover and improving resolution.
  • the preferred mass average molecular weight of the (AO ') component is the same as that of the ()') component.
  • the (AO ′) component can be used alone or in combination.
  • As the ( ⁇ ′) component it is also possible to use a rosin other than the ( ⁇ ′) component.
  • the content of the (AO ′) component may be adjusted according to the resist film thickness to be formed.
  • the same one as the second negative resist composition can be used.
  • the first negative resist composition there is no restriction that an organic solvent that does not dissolve the first resist layer 2 is used unlike the second negative resist composition. Therefore, it is also possible to use an organic solvent other than the alcohol solvent, the fluorine organic solvent, etc. described in the second negative resist composition.
  • the organic solvent used in the second negative resist composition is preferably used in the same manner as the organic solvent in the second negative resist composition, and an alcohol-based organic solvent is particularly preferably used. More preferably, isobutanol and Z or n-butanol are used.
  • organic solvent other than the alcohol-based solvent and the fluorine-based organic solvent described in the second negative resist composition examples include those that can dissolve each component to be used to form a uniform solution. Any one of conventionally known solvents for chemically amplified resists can be selected and used as appropriate.
  • ketones such as ⁇ -butyrolatatone, acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene Polyols and their derivatives such as glycol, propylene glycolol monoacetate, dipropylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of dipropylene glycol monoacetate, and dioxane Cyclic ethers, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, Methyl Tokishipuropion acid, and ethoxy propionic acid Echiru
  • a mixed solvent obtained by mixing propylene glycol monomethyl ether acetate (PGME IV) and a polar solvent is preferable.
  • the mixing ratio may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Preferably within the range.
  • the mass ratio of PGMEA: EL is preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3! / ,.
  • a mixed solvent of at least one selected from among PGMEA and EL and ⁇ -petit-mouth rataton is also preferable.
  • the mixing ratio of the former and the latter is preferably 70: 30-95: 5.
  • a second negative resist composition or a positive resist composition dissolved in a specific organic solvent is used as the second resist layer as described above.
  • resin component 100 parts by mass of resin 1 represented by the following chemical formula, 5.0 parts by mass of triphenylsulfo-munonafluorobutane sulfonate as an acid generator, nitrogen-containing organic compound
  • resin 1 represented by the following chemical formula
  • triphenylsulfo-munonafluorobutane sulfonate as an acid generator
  • nitrogen-containing organic compound As a product, 0.45 parts by mass of triethanolamine was dissolved in isobutanol as an organic solvent to obtain a positive resist composition having a solid content concentration of 6% by mass.
  • An organic anti-reflective coating composition “ARC-29” (trade name, manufactured by Brew Science Co., Ltd.) is applied onto an 8-inch silicon wafer using a spinner, and then 215 ° C. for 60 seconds on a hot plate. By baking and drying, an organic antireflection film having a thickness of 77 nm was formed. Then, after applying the negative resist composition prepared in the reference example using a spinner, pre-beta (PAB) on a hot plate at 80 ° C for 60 seconds and drying to form a 2 OOnm resist layer. Formed.
  • PAB pre-beta
  • the positive resist composition prepared in the above reference example is applied using a spinner, and pre-beta (PAB) is performed on a hot plate at 115 ° C. for 60 seconds. Then, a 200 nm-thick resist layer was formed by drying. At that time, there was no mixing with the underlying resist layer.
  • PEB treatment was performed at 100 ° C for 60 seconds, followed by paddle development with an aqueous 2.38 mass% tetramethyl ammonium hydroxide solution at 23 ° C for 60 seconds, followed by washing with water for 20 seconds and drying.
  • a dense / dense mixed pattern with a dense contact hole pattern of 1 and a sparse pattern with a hole width of 140 nm could be formed.
  • An organic anti-reflective coating composition “ARC-29” (trade name, manufactured by Brew Science Co., Ltd.) is applied onto an 8-inch silicon wafer using a spinner, and then 215 ° C. for 60 seconds on a hot plate. By baking and drying, an organic antireflection film having a thickness of 77 nm was formed. Then, after applying the negative resist composition prepared in the reference example using a spinner, pre-beta (PAB) at 80 ° C for 60 seconds on a hot plate and drying to form a 2 OOnm resist layer. Formed.
  • PAB pre-beta
  • the present invention can be applied to formation of a resist pattern in the manufacture of semiconductor elements, liquid crystal display elements, and the like.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

La présente invention concerne la formation d’un modèle d’enduit de protection qui comprend : (i) un procédé de formation d’une première couche d’enduit de protection sur un substrat en utilisant une première composition négative d’enduit de protection et en procédant à une exposition sélective, et (ii) un procédé de formation d’une deuxième couche d’enduit de protection sur un substrat en utilisant une composition négative d’enduit de protection ou une composition positive d’enduit de protection et en procédant à une exposition sélective, puis en développant simultanément la première couche d'enduit de protection et la deuxième et en exposant une partie d’une région non exposée de la première couche d’enduit de protection. Le procédé de formation du modèle d’enduit de protection est caractérisé en ce qu'un matériau dissous dans un solvant organique ne dissolvant pas la première couche d’enduit de protection est utilisé en tant que seconde composition d’enduit de protection, négative ou positive.
PCT/JP2005/020949 2004-12-08 2005-11-15 Procede de formation d'un modele d’enduit de protection WO2006061975A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8263322B2 (en) 2008-10-01 2012-09-11 Tokyo Ohka Kogyo Co., Ltd. Method of forming resist pattern
US8859187B2 (en) 2006-10-20 2014-10-14 Tokyo Ohka Kogyo Co., Ltd. Method of forming resist pattern and negative resist composition

Families Citing this family (2)

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KR100876783B1 (ko) * 2007-01-05 2009-01-09 주식회사 하이닉스반도체 반도체 소자의 미세 패턴 형성 방법
JP6136811B2 (ja) * 2012-10-22 2017-05-31 Jsr株式会社 フォトレジスト組成物及びネガ型レジストパターン形成方法

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JPH0844070A (ja) * 1994-07-28 1996-02-16 Toshiba Corp 半導体装置の製造方法
JP2004199084A (ja) * 1996-09-13 2004-07-15 Toshiba Corp レジストパターン形成方法
JP2000147783A (ja) * 1998-11-17 2000-05-26 Mitsubishi Electric Corp 微細パターン形成方法を用いた半導体装置の製造方法および当該方法により製造した半導体装置
JP2001066782A (ja) * 1999-08-26 2001-03-16 Mitsubishi Electric Corp 半導体装置の製造方法並びに半導体装置
JP2002305135A (ja) * 2001-04-05 2002-10-18 Fujitsu Ltd レジストパターンの形成方法
US20030104319A1 (en) * 2001-11-30 2003-06-05 Taiwan Semiconductor Manufacturing Company Contact hole printing by packing and unpacking

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8859187B2 (en) 2006-10-20 2014-10-14 Tokyo Ohka Kogyo Co., Ltd. Method of forming resist pattern and negative resist composition
US8263322B2 (en) 2008-10-01 2012-09-11 Tokyo Ohka Kogyo Co., Ltd. Method of forming resist pattern

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