WO2005003193A1 - ポジ型レジスト組成物及びそれを用いたレジストパターン形成方法 - Google Patents
ポジ型レジスト組成物及びそれを用いたレジストパターン形成方法 Download PDFInfo
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- WO2005003193A1 WO2005003193A1 PCT/JP2004/009620 JP2004009620W WO2005003193A1 WO 2005003193 A1 WO2005003193 A1 WO 2005003193A1 JP 2004009620 W JP2004009620 W JP 2004009620W WO 2005003193 A1 WO2005003193 A1 WO 2005003193A1
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- positive resist
- structural unit
- acid
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- 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
Definitions
- the present invention relates to a positive resist composition and a method for forming a resist pattern.
- JP-A-2003-113174 proposes a compound having a specific lactone structure.
- Patent Document 1 Japanese Patent No. 2881969
- Patent Document 2 Japanese Patent Application Laid-Open No. 5-346668
- Patent Document 3 JP-A-7-23451-1
- Patent document 4 JP-A-9-73173
- Patent Document 5 JP-A-9-90637
- Patent Document 6 JP-A-10-161313
- Patent Literature 7 Japanese Patent Application Laid-Open No. H10-103195
- Patent Document 8 Japanese Patent Laid-Open No. 11-123
- Patent Document 9 Japanese Unexamined Patent Application Publication No. 2000-111
- this surface roughness appears as a distortion around the hole pattern in a contact hole pattern in a film etched using a resist pattern as a mask, and the line edge roughness in a line and space pattern. It appears as Here, the line edge roughness is uneven unevenness on the line side wall.
- Japanese Patent Application Laid-Open Publication No. 2003-113134 discloses a monomer corresponding to the structural unit (a 1) of the present invention, but a polymer using the monomer is not disclosed. Moreover, it was unknown whether it was suitable for the above purpose.
- the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a resist composition that can suppress the occurrence of surface roughness that occurs in a resist pattern after etching, and preferably after development. . Disclosure of the invention
- a first aspect of the present invention is a compound represented by the following general formula (1): (In the formulas (1) to (4), R is a hydrogen atom or a methyl group, and m is 0 or 1.)
- R is a hydrogen atom or a methyl group, and m is 0 or 1.
- the second aspect is the total of all the structural units, the structural units (a 1) is a polymer of the first aspect contained 30-6 0 mol 0/0.
- the third embodiment is the polymer according to the first or second embodiment, further having an acid dissociable, dissolution inhibiting group, and further comprising a structural unit (a2) derived from a (meth) acrylic acid ester. .
- a fourth embodiment is the polymer according to the third embodiment, wherein the polymer is at least one selected from the following general formulas (I), (II), and (III): .
- R is a hydrogen atom or a methyl group, and R 1 is a lower alkyl group.
- R is a hydrogen atom or a methyl group, and Shaku 2 and 1 ⁇ 3 are each independently a lower alkyl group.
- the structural unit (a 2) is 20 to 100% of the total of all the structural units.
- the polymer according to the third or fourth embodiment which is contained in an amount of 0 mol%.
- the sixth aspect is the polymer according to any one of the first to fifth aspects, further comprising a hydroxyl group, and further comprising a structural unit (a3) derived from a (meth) acrylate.
- a seventh aspect is the polymer according to the sixth aspect, wherein the polymer is one or two of the following general formulas (IV) or (V):
- An eighth aspect is the polymer according to the sixth or seventh aspect, wherein the structural unit (a3) is contained in an amount of 10 to 50 mol% based on the total of all the structural units.
- a ninth aspect is the polymer according to any one of the first to eighth aspects, wherein the polymer has an increased alkali solubility due to the action of an acid, and is used for a positive resist composition.
- a tenth aspect is a positive resist composition
- a resin component (A) an acid generator component (B) that generates an acid upon exposure, and an organic solvent (C)
- B an acid generator component
- C an organic solvent
- the positive resist composition wherein the component (A) comprises the polymer according to the ninth embodiment. 7
- a eleventh aspect is the positive resist composition according to the tenth aspect, wherein the component (B) is an ionic salt having a fluorinated alkylsulfonic acid ion as an arion.
- a twelfth aspect is the posi-type resist composition according to the tenth or i1th aspect, wherein the component (C) is a mixed solvent of propylene glycol monomethyl ether acetate and a polar solvent.
- a thirteenth aspect is the positive resist composition according to the twelfth aspect, wherein the polar solvent is ethyl lactate.
- a fourteenth aspect is the positive resist composition according to any one of the tenth to thirteenth aspects, further comprising a secondary or tertiary lower aliphatic amine (D).
- the positive resist composition according to any one of the tenth to fourteenth aspects is coated on a substrate, pre-betaed, selectively exposed, and then subjected to PEB (post exposure baking).
- PEB post exposure baking
- R is a hydrogen atom, it is an acrylate unit, and when it is a methyl group, it is methacrylate. It is a structural unit.
- the structural unit (a1) is a concept that includes one or both of an acrylate structural unit and a methacrylate structural unit.
- the monomer corresponding to the structural unit (a1) usually exists as a mixture of four isomers from which all of the structural units represented by the general formulas (1) to (4) are obtained.
- the structural unit (a1) may include at least one of the structural units represented by the general formulas (1) to (4).
- m may be either 0 or 1, but 0 is preferable because it is industrially easy to obtain.
- R and m in each structural unit may be different or the same, but usually the same.
- the structural unit (al) is Te opposed to the total structural units constituting the polymer, 3 0-6 0 mole 0/0, it is desirable that preferably contains 3 0-5 0 mol%.
- the lower limit or more when used for a positive resist composition, the effect of suppressing surface roughness is improved.
- the upper limit value is exceeded, when used for a positive resist composition, the amount of other structural units such as a structural unit that imparts the property of increasing alkali solubility to the polymer by the action of an acid is reduced, which is inconvenient. May be caused.
- the rataton functional group is effective for increasing the adhesion between the resist film and the substrate and increasing the hydrophilicity with the developer when the positive resist composition is formed.
- the polymer When used for a positive resist composition, the polymer preferably contains a constituent unit having an acid-dissociable, dissolution-inhibiting group.
- the acid generated from the component (B) acts upon exposure, the polymer dissociates. It is preferred that the soluble dissolution inhibiting group is dissociated and the whole polymer changes from alkali insoluble to alkali soluble. As a result, when light is exposed through a mask pattern in the formation of a resist pattern, the exposed portion is more soluble in the exposed portion, and can be developed in the exposed portion.
- the polymer when used for a positive resist composition, it is preferable that the polymer is a copolymer containing the following other structural units.
- a positive resist composition When used for a positive resist composition, it preferably contains a structural unit having an acid dissociable, dissolution inhibiting group as described above.
- the structural unit having an acid dissociable, dissolution inhibiting group is not particularly limited as long as it is copolymerizable with the structural unit (al) which is essential for the polymer.
- the structural unit (a 2) is preferable in terms of copolymerizability, transparency of the polymer, and the like.
- (Meth) acrylic acid Stell is a general term for acrylate and methacrylate.
- acrylic acid is a general term for methacrylic acid and acrylic acid.
- the acid dissociable, dissolution inhibiting group when used in a positive resist composition, has an alkali dissolution inhibiting property that renders the entire polymer insoluble before exposure, and an acid generated from the component (B) after exposure.
- Any material can be used without particular limitation as long as it is dissociated by the action of and converts the entire polymer to soluble.
- the acid dissociable, dissolution inhibiting group those which form a cyclic or chain tertiary alkyl ester with a carboxyl group of (meth) acrylic acid are widely known.
- an acid dissociable, dissolution inhibiting group containing an aliphatic polycyclic group is preferred.
- polycyclic group examples include a group obtained by removing one hydrogen atom from bicycloalkane, tricycloalkane, tetracycloalkane, and the like.
- Specific examples include groups obtained by removing one hydrogen atom from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
- Such a polycyclic group can be appropriately selected from a large number of proposed polymers (resin components) for a resist composition for an ArF excimer laser.
- an adamantyl group, a norpolnyl group, and a tetracyclododecanyl group are industrially preferable.
- the structural unit (a 2) is preferably at least one selected from the general formulas (I), (I I), and (I I I).
- the structural unit represented by the general formula (I) is a structural unit in which a hydrocarbon group is ester-bonded to a (meth) acrylic acid structural unit, and an oxygen atom (one) in an ester portion of the (meth) acrylate structural unit.
- a hydrocarbon group is ester-bonded to a (meth) acrylic acid structural unit
- an oxygen atom one in an ester portion of the (meth) acrylate structural unit.
- R 1 is preferably a lower 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, Examples include a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
- an alkyl group having 2 or more carbon atoms, preferably 2 to 5 carbon atoms is preferable, and in this case, the acid dissociation tends to be higher than that of a methyl group.
- a methyl group and an ethyl group are preferred.
- the structural unit represented by the general formula (I I) is a structural unit in which a hydrocarbon group is ester-bonded to a (meth) atalilic acid structural unit as in the general formula (I), and in this case,
- the carbon atom adjacent to the oxygen atom (1 O—) in the ester portion of the (meth) acrylate unit is a tertiary alkyl group, and the alkyl group further has a ring skeleton such as an adamantyl group.
- R 2 and R 3 are each independently preferably a lower alkyl group having 1 to 5 carbon atoms. Such groups tend to be more acid dissociable than the 2-methyl-2-adamantyl group.
- R 2 and R 3 each independently include a lower straight-chain or branched alkyl group similar to R 1 described above. Among them, it is industrially preferable that both R 2 and R 3 are methyl groups.
- the structural unit represented by the general formula (III) is not an ester of a (meth) acrylate constituent unit, but a carbon atom adjacent to an oxygen atom (10_) of another ester is a tertiary alkyl group.
- the (meth) acrylic acid ester structural unit and the ester are linked to a ring skeleton such as a tetracyclododecanyl group.
- R 4 is a tertiary alkyl group such as a tert-butyl group or a tert-amyl group, and a case where R 4 is a tert-butyl group is industrially preferable.
- One COOR 4 may be bonded to the 3 or 4 position of the tetracyclododecanyl group shown in the formula, but it cannot be further specified because it is included as an isomer.
- the carboxyl group residue of the acrylate constituent unit may be bonded at the 8 or 9 position of the tetracyclododecanyl group, but cannot be specified because it is contained as an isomer as described above.
- R 1 is preferably a methyl group or an ethyl group. When both are used, it is preferable that R 1 is a methyl group and R 2 and R 3 are methyl groups because of excellent resolution.
- Structural units (a 2) may be the total of all the structural units of the polymer, the structural unit (a 2) 20 to 60 mole 0/0, contains preferably be 20 to 50 mole 0/0 Desirable.
- the solubility of the polymer changes due to the action of an acid, and the polymer becomes more easily absorbed.
- Exceeding the upper limit may be inconvenient in terms of balance with other structural units.
- the polymer contains the structural unit (a3), since the hydroxyl group is a polar group, the affinity between the entire polymer and an alkali developing solution used for forming a resist pattern is increased. Therefore, when used for a positive resist composition, alkali solubility in the exposed part is improved, which contributes to improvement in resolution, which is preferable.
- the structural unit (a3) for example, a resin for a resist composition for an ArF excimer laser can be appropriately selected from a large number of proposed resins.
- the polycyclic group any of a number of polycyclic groups similar to those exemplified in the description of the structural unit (a1) can be appropriately selected and used. .
- a hydroxyl group-containing adamantyl group (the number of hydroxyl groups is preferably 1 to 3, and more preferably 1.), a carboxyl group-containing tetracyclododecanyl group (of a carboxyl group) The number is preferably from 1 to 2, and more preferably 1.) is preferably used. More specifically, when the structural unit represented by the general formula (IV) is used as (a3), when used for a positive resist composition, the dry etching resistance is increased and the pattern cross-sectional shape is increased. This is preferable because it has the effect of increasing the verticality of the film.
- the polymer when used for a positive resist composition, the polymer increases dry etching resistance and has a perpendicular pattern cross-sectional shape. It is preferred because it has the effect of enhancing the properties.
- —COOH may be bonded to the '3 or 4 position of the tetracyclododecanyl group shown in the formula, but it cannot be further specified because it is included as an isomer.
- the carboxyl group residue of the (meth) atalylate constituent unit may be bonded to position 8 or 9 of the tetracyclododecalyl group, but cannot be specified because it is contained as an isomer as described above.
- This polymer may contain other structural units in addition to the structural units (a1) to (a3).
- structural units containing rataton (a4) other than structural unit (a1), or structural units (a5) other than structural units (a1) to (a4), etc. Is mentioned.
- the lactone functional group is effective for increasing the adhesion between the resist film and the substrate and increasing the hydrophilicity with the developer when used as a positive resist composition.
- a structural unit (a4) containing a lactone other than the structural unit (a1) can be used to enhance these effects.
- (a4) is preferably, for example, a structural unit containing a ratatone-containing monocyclic or polycyclic group and derived from a (meth) acrylic acid ester.
- examples of the lactone-containing monocyclic group include groups obtained by removing one hydrogen atom from ⁇ -butyrolactone.
- lactone-containing polycyclic group examples include groups obtained by removing one hydrogen atom from a rataton-containing bicycloalkane having the following structural formula. '
- the ratatone-containing monocyclic or polycyclic group is one or more selected from the following general formulas.
- a structural unit derived from a (meth) acrylate ester containing a lactone-containing monocycloalkyl group or a bicycloalkyl group represented by the following structural formula is preferable.
- a styrolactone ester or a norbornane ratatone ester of (meth) acrylic acid having an ester bond at carbon is particularly preferable because it is easily available on an industrial scale.
- the structural unit ( a5 ) is not particularly limited as long as it is another structural unit that is not classified into the structural units (a1) to (a4) described above. In other words, it may be any as long as it does not contain an acid dissociable, dissolution inhibiting group, lactone, or hydroxyl group.
- a structural unit containing an aliphatic polycyclic group and derived from a (meth) acrylate ester is preferred.
- a structural unit when it is used for a positive resist composition, it changes from an isolated pattern to a semi-dense pattern (a line-and-space pattern having a line width of 1 to 2 and a space width of 1.2 to 2). Excellent in resolution and preferred.
- Examples of the aliphatic polycyclic group include the same as those exemplified in the case of the structural unit (a 1), and are conventionally known as Ar F positive resist materials. Many are available. In particular, at least one selected from the group consisting of a tricyclodecanyl group, an adamantyl group and a tetracyclododecanyl group is preferred in view of industrial availability. Examples of these structural units (a5) are shown in the following general formulas (IX) to (XI).
- R is a hydrogen atom or a methyl group
- R is a hydrogen atom or a methyl group
- the structural unit other than the structural unit (a1) can be appropriately selected depending on the application, etc., but a polymer containing the structural unit (a1) and the structural unit (a2) is preferable, A ternary system containing the unit (a 3) is preferred.
- Structural units (a 1) the case of binary polymers (a 2), the structural units (a 1) is 30 in all the structural units 60 mole 0/0, preferably with 20 to 50 mol%, construction units (a 2) 20 to 60 mole 0/0, preferably when 20 to 50 mole 0/0, the pattern shape, preferable from the viewpoint of excellent resistance to dry Etsu quenching property.
- the structural units (a 1) is 30 in all the structural units 60 mole 0/0, preferably a 30 to 50 mole 0/0
- the structural unit ( a 2) is all the structural units in 20 to 60 mole 0/0, preferably from 20 to 50 mole 0/0
- (a 3) is 10 in all the structural units 50 mole 0/0, preferably 10 to 40 mol 0
- the value of / 0 is preferable in terms of excellent resolution.
- the heating temperature should be higher when there are more methacrylate structural units. Therefore, the sensitivity of the positive resist composition tends to be improved.
- the weight average molecular weight of the polymer is not particularly limited, but is preferably 5,000 to 30,000, more preferably 8,000 to 20,000. If it is larger than this range, the solubility in a resist solvent will be poor when used for a positive resist composition, and if it is small, the cross-sectional shape of the resist pattern may be poor.
- this polymer is obtained by using a monomer [(meth) atalylate] corresponding to each of the structural units (a1) to (a5) and a radical polymerization initiator such as azobisisobutyronitrile (AIBN). It can be easily produced by known radical polymerization or the like.
- a radical polymerization initiator such as azobisisobutyronitrile (AIBN). It can be easily produced by known radical polymerization or the like.
- the monomer corresponding to the structural unit (a1) is obtained, for example, by subjecting (meth) acrylic acid to an addition reaction of a spirolatatone derivative having a double bond by a known method described in Patent Document 9.
- a spirolatatone derivative has a double bond between a carbon atom at the position where the carboxyl group of the (meth) acrylic acid is bonded and a carbon atom adjacent to the carbon atom. That is, the monomer is obtained by an addition reaction of (meth) acrylic acid to a double bond of the spirolatatone derivative.
- Monomers corresponding to the structural units (a2) to (a5) are on the market and can be obtained.
- component (A) Ingredient
- the component (A) there is no particular limitation as long as it is a polymer having the above-mentioned constitutional unit (a1) as an essential component and has a property of increasing the solubility of an acid by the action of an acid. Can be.
- component (B) an arbitrary one can be appropriately selected from those conventionally known as an acid generator in a chemically amplified resist.
- this acid generator examples include diphenyl odonium trifluoromethanesulfonate, (4-methoxyphenyphenyphenyl // odonium trifluoronoroleromethane snolephonate, bis (p-tert-butynolef ⁇ ne) -Nore-no-de-no-mo-tri-no-reno-no-methanole-honate, tri-pheno-ino-res-no-reno-no-me-tri-no-re-no-re-no-re-no-meth-no-reno-no-re-no-meth, Nolehonate, (4-methinoreflenole) dipheninolenesore- ⁇ mnonafnoreleptane snorrehonate, (p-tert-peptinolelefinore) dihue-norresn
- This component (B) may be used alone or in combination of two or more.
- the compounding amount is 0.5 to 30 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the component (A).
- amount is 0.5 parts by mass or more, pattern formation is sufficiently performed.
- amount is 30 parts by mass or less, a uniform solution is obtained, and storage stability tends to be improved.
- the positive resist composition can be produced by dissolving the component (A), the component (B), and an optional component (D) described later, preferably the component (C). Po
- the amount of the component (c) in the di-type resist composition is not particularly limited, and may be, for example, a concentration at which a positive-type resist composition that can be coated on a substrate or the like is obtained.
- the component (C) is not particularly limited as long as it can dissolve the component (A) and the component (B) to form a uniform solution. Any one or two or more of them can be appropriately selected and used.
- ketones such as acetone, methyl ethyl ketone, hexahexanone, methyl isoamyl ketone and 2-heptanone
- ethylene glycol ethylene glycol monoacetate, diethylene glycolone, diethylene glycolone monoacetate, propylene glycol, propylene Polyhydric alcohols such as glycol monoacetate, zipper pyrendal cornole, or dipropylene dalicon oleate monoacetate monomethinole ether, monoethy / leetenole, monopropynoleatenole, monobutynoleatenole or monophenyl ether And its derivatives, cyclic ethers such as dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, Kishipuropion acid methylation, esters
- organic solvents may be used alone or as a mixed solvent of two or more.
- the amount of the solvent used is not particularly limited, but is set to a concentration that can be applied to a substrate or the like.
- the solid content (a component remaining as a solid when the solvent (C) is removed) constituting the positive resist composition of the present invention is contained in the range of 2 to 20% by mass, and more preferably 3 to 15% by mass. The amount is preferred.
- propylene daricol monomethyl ether acetate (PGME A) and a polar solvent having a hydroxyl group ⁇ lactone such as propylene glycol monomethyl ether (PGME), ethyl lactate (EL), and ⁇ -butyrolactone are used.
- the mixed solvent is preferable because the storage stability of the positive resist composition is improved.
- the mass ratio of PGMEA: EL is preferably from 6: 4 to 4: 6. .
- the mass ratio of PGME A: PGME is preferably 8: 2 to 2: 8, preferably 8: 2 to 5: 5.
- the organic solvent (C) a mixed solvent of at least one selected from PGMEA and ethyl lactate with y-butyrolactone is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
- the positive resist composition further includes an optional component (D) for improving the resist pattern shape, post exposure stability of the latent image formed, by the pattern wise exposure oi the resist layer, and the like.
- an optional component (D) for improving the resist pattern shape, post exposure stability of the latent image formed, by the pattern wise exposure oi the resist layer, and the like.
- a secondary lower aliphatic amine refers to an alkyl or alkyl alcohol amine having 5 or less carbon atoms.
- Examples of the secondary and tertiary amines include trimethylamine, getinoleamine, triethylamine, di-n-propylamine, and the like.
- Tri_n-propylamine, tripentylamine, diethanolamine, triethanolamine, triisopropanolamine, and the like are included, and alkanolamines such as triethanolamine are particularly preferred.
- amines are usually used in the range of 0.01 to 2% by mass relative to 100% by mass of the component (A).
- the positive resist composition may further contain an organic carboxylic acid or phosphorus oxo acid as an optional component (E).
- an acid or a derivative thereof can be contained.
- the component (D) and the component (E) can be used in combination, or any one of them can be used.
- organic carboxylic acid for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
- Phosphorus oxo acids or derivatives thereof include phosphoric acids such as phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester, and esters thereof. Derivatives, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid-di-n-butynoleestenole, feninolephosphonic acid, phosphonic acid dipheninoleestenole, phosphonic acid dibenzyl ester, etc. And phosphinic acids such as phosphinic acid and phenylphosphinic acid and derivatives thereof such as esters thereof. Among them, phosphonic acid is particularly preferable.
- the component (E) is used in an amount of 0.01 to 5.0 parts by mass per 100 parts by mass of the component (A).
- Positive resist compositions may further include additives that are miscible as desired, such as additional resins to improve resist film performance, surfactants to improve coatability, dissolution inhibitors, and plasticizers. Agents, stabilizers, coloring agents, anti-halation agents and the like can be added.
- this positive resist composition has high transparency at wavelengths of 200 nm or less, it is particularly useful as a positive resist composition for ArF excimer lasers.
- F 2 excimer laser extreme ultraviolet
- V UV vacuum ultraviolet
- electron beams X-rays
- it is also effective to radiation such as soft X-ray.
- the positive resist composition can suppress the occurrence of surface roughness such as line and roughness generated in the resist pattern on one or preferably after the etching and after the development. In particular, the effect of suppressing surface roughness after etching is high.
- This positive resist composition has good resolution.
- the design rules required in semiconductor device manufacturing have become ever narrower, and a resolution of 150 nm or less or around 100 nm is required. However, it can also be used for such applications.
- This positive resist composition gives a wide depth of focus and is preferable in view of manufacturability and the like.
- the method of forming a resist pattern according to the present invention can be performed, for example, as follows. That is, first, the above positive resist composition is applied on a substrate such as silicon wafer with a spinner or the like, and then 80 to 150 is applied. Under the temperature condition of C, a pre-beta (PAB treatment) is applied for 40 to 120 seconds, preferably 60 to 90 seconds, and for example, A After selectively exposing Ar F excimer laser light through a desired mask pattern using an rF exposure device, PEB (post-exposure bake) treatment is performed for 40 to 120 seconds at a temperature of 80 to 150 ° C. Preferably, it is applied for 60 to 90 seconds.
- PAB treatment pre-beta
- PEB treatment post-exposure bake
- An organic or inorganic antireflection film may be provided between the substrate and the coating layer of the resist composition.
- Example 1 Example 1
- Component (A) The following monomer 2-methyl-2- ⁇ Dammann chill meth Tari rate 4 0 mole 0/0 (- R 1 is a methyl group general formula (I), R is a methyl group, structural unit (a corresponds to 2)), the following general formula (1) 'to (4), in indicated by, R is a mixture of methyl der Ru methacrylate four 40 mole 0/0,
- R is a methyl group or a hydrogen atom.
- Component (B) triphenylsulfonimnononafluorobutanesulfonate 2.5 parts by mass
- the positive resist and the composition are applied on a silicon wafer using a spinner, pre-beta (PAB treatment) at 130 ° C for 60 seconds on a hot plate, and dried to obtain a film thickness of 350 ⁇ m.
- a nm resist layer was formed.
- a 30 nm line and space pattern (1: 1) has a depth of focus of 500 nm.
- 3 ⁇ is the standard deviation calculated by measuring the width of the resist pattern of the sample at 32 locations using the side length S ⁇ (manufactured by Hitachi, Ltd., product name “S-9220”).
- an unpatterned resist film (a substrate coated with a positive resist composition and exposed without passing through a mask pattern) was prepared and etched under the following conditions. . • Etching conditions: Gas mixture of 30 sccm of tetrafluoromethane, 30 sccm of trifluoromethane, and 100 sccm of helium; pressure: 0.3 To rr; RF (Ratio Frequency): frequency 400 kHz—output 600 W; temperature: 20 ° C time: 2 minutes; Etching equipment: TCE-76 1 2X (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.)
- the etched surface was quantified by an AFM (Atomic Force Microscope), and the root mean square roughness (Rms), which is a measure of surface roughness, was found to be 6. O nm.
- AFM Anamic Force Microscope
- Example 1 As the component (A), 2-methyl-12-adamantyl methacrylate was converted to 2-ethyl-12-adamantyl methacrylate (R 1 in the general formula (I) is an ethyl group, and R is methyl.
- Terpolymer where the mass average molecular weight is 10,000
- the mixture of monomers represented by the general formulas (1) 'to (4)' where R is a mixture of acrylates of hydrogen atoms
- a positive resist composition was prepared and evaluated in the same manner as in Example 1 except that) was used, except that the conditions of PAB treatment and PEB treatment were 110 ° C for 60 seconds, 100 ° C for 60 seconds, and 60 ° C for 60 seconds. Seconds.
- Example 2 the component (A) was replaced by 2-ethyl-2-adamantyl methacrylate with 2-ethyl-2-adamantyl acrylate (wherein R 1 in the general formula (I) is an ethyl group, Is hydrogen) and the PAB treatment and PEB treatment conditions are 105 ° C, 60 seconds Z95 ° C, A positive resist composition was produced and evaluated in the same manner as in Example 2 except that the time was set to 60 seconds.
- R 1 in the general formula (I) is an ethyl group, Is hydrogen
- a positive resist was prepared in the same manner as in Example 1 except that the components were changed as follows, and the conditions of the PAB treatment and the PEB treatment were changed to 130 ° C for 60 seconds, 130 ° C for 60 seconds, and 60 seconds, respectively.
- the composition was manufactured and patterned.
- Component (A) an acrylate monomer represented by the following general formula ( ⁇ ) (corresponding to the constituent unit (a2)): 50 moles 0 /. ,
- R is a hydrogen atom ⁇ chestnut rate monomer one four mixtures 40 mole 0/0, And an acrylate monomer represented by the following general formula (xm) (constituent unit (equivalent to): 10 mol%,
- the monomers represented by the general formulas (1) and (4) ' are converted into a mono-gamma mabutyrolataton methacrylate (in the general formula (VDI), R is a monomer unit of a methyl group). Evaluation was performed in the same manner as in Example 1 except that the same ternary polymer was used except for the change.
- the 130 nm line-and-space pattern (1: 1) was slightly tapered but resolved with a generally good shape.
- the 130 nm L / S was 1: 1 with a depth of focus of 300 nm and a sensitivity of 15 mjZcm 2 . 3 ⁇ was found to be 5.0 nm.
- Rms measured in the same manner as in Example 1 was 11.5 nm. Comparative Example 2
- the monomers represented by the general formulas (1) ′ to (4) ′ are converted into ⁇ -gamma mbutyrolataton methacrylate (where R is a monomer unit of a methyl group in the general formula ( ⁇ )).
- Example 2 was repeated except that the conditions of ⁇ treatment and ⁇ ⁇ treatment were changed to 120 ° C, 60 seconds / 110 ° (:, 60 seconds, respectively) using the same modified terpolymer. Evaluation was performed in the same manner.
- the 130 nm line-and-space pattern (1: 1) was slightly tapered but resolved with a generally good shape.
- the depth of focus of 200 nm L / S of 1: 1 was 200 nm, and the sensitivity was 15 mj / cm 2 . When 3 ⁇ was determined, it was 7.0 nm.
- Rms measured in the same manner as in Example 1 was 13.5 nm. From these results, it was confirmed that in all of the examples according to the present invention, the value of Rms was small, and the occurrence of surface roughness after etching could be suppressed. The LER value also tends to be relatively small, and it has been found that the surface roughness of the resist pattern after alkali development tends to be suppressed.
- the resist pattern shape was also good, the sensitivity tended to be high, and the resolution was also good.
- the depth of focus (DOF) was also found to be large.
- the component (A) is a copolymer composed of an acrylate constituent unit and a methacrylate constituent unit, and has a high glass transition point. : 6 processing? The temperature of the £ 8 process could be increased, resulting in higher sensitivity.
- Example 3 the component (A) is a copolymer composed of an acrylate constituent unit and a methacrylate constituent unit, and has a high glass transition point. : 6 processing? The temperature of the £ 8 process could be increased, resulting in higher sensitivity.
- the component (A) was composed of only the acrylate constituent unit, the glass transition point was lower and the sensitivity was slightly lower than in Example 2, but the effect of suppressing surface roughness after etching was particularly good.
- the present invention is extremely useful industrially.
Description
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US10/563,501 US20060194141A1 (en) | 2003-07-07 | 2004-06-30 | Positive resist composition and method for forming resist pattern using same |
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US7960087B2 (en) | 2005-03-11 | 2011-06-14 | Fujifilm Corporation | Positive photosensitive composition and pattern-forming method using the same |
JP4472586B2 (ja) * | 2005-06-20 | 2010-06-02 | 東京応化工業株式会社 | ポジ型レジスト組成物およびレジストパターン形成方法 |
JP5678963B2 (ja) * | 2010-09-30 | 2015-03-04 | Jsr株式会社 | 感放射線性樹脂組成物、重合体及び化合物 |
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JPH09325496A (ja) * | 1996-06-04 | 1997-12-16 | Sony Corp | 感光性組成物 |
JP2002371114A (ja) * | 2001-06-14 | 2002-12-26 | Shin Etsu Chem Co Ltd | ラクトン構造を有する新規(メタ)アクリレート化合物、重合体、フォトレジスト材料、及びパターン形成法 |
JP2003113174A (ja) * | 2001-07-30 | 2003-04-18 | Mitsubishi Chemicals Corp | ラクトン構造を有する多環式化合物 |
JP2003146979A (ja) * | 2001-11-14 | 2003-05-21 | Mitsubishi Chemicals Corp | ラクトン類の製造方法 |
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TW573225B (en) * | 2000-02-28 | 2004-01-21 | Sumitomo Chemical Co | Chemically amplified positive resist composition |
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- 2004-06-30 WO PCT/JP2004/009620 patent/WO2005003193A1/ja active Application Filing
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Publication number | Priority date | Publication date | Assignee | Title |
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JPH09325496A (ja) * | 1996-06-04 | 1997-12-16 | Sony Corp | 感光性組成物 |
JP2002371114A (ja) * | 2001-06-14 | 2002-12-26 | Shin Etsu Chem Co Ltd | ラクトン構造を有する新規(メタ)アクリレート化合物、重合体、フォトレジスト材料、及びパターン形成法 |
JP2003113174A (ja) * | 2001-07-30 | 2003-04-18 | Mitsubishi Chemicals Corp | ラクトン構造を有する多環式化合物 |
JP2003146979A (ja) * | 2001-11-14 | 2003-05-21 | Mitsubishi Chemicals Corp | ラクトン類の製造方法 |
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TWI282038B (en) | 2007-06-01 |
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