Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/40—Imides, e.g. cyclic imides
• • 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
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
  • C08F232/04—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
• • 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
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• • 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

Definitions

• the present invention relates to a resin composition, a pattern forming method, a method for manufacturing an electronic device, and a polymer.
• a resin pattern can be formed on a substrate through a first step of applying the resist composition onto a substrate to form a resin film, a second step of irradiating the resin film with actinic rays or radiation, and a third step of developing the resin film after the second step.
• an etching gas By applying an etching gas to the substrate on which this resin pattern has been formed, only a portion of the substrate can be selectively etched. In other words, the resin pattern functions as an etching mask.
• the resin composition and/or the polymer contained in the resin composition have a suitable degree of alkaline solubility.
• the resin composition and/or the polymer contained in the resin composition have high etching resistance.
• the inventors have now conducted various investigations with the aim of providing a resin composition and polymer that have suitable solubility in alkaline developers and are suitable for use in resist compositions.
• a resin composition comprising:
• R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, provided that at least one of R 1 , R 2 , R 3 and R 4 is a group having a —C(CF 3 ) 2 OH group; a1 is 0, 1 or 2.
• X is a monovalent organic group containing a cyclic skeleton. 2.
• the resin composition wherein the polymer further has a structural unit represented by the following general formula (MI-2): In general formula (MI-2), A is a hydrogen atom or a group containing an alkali-soluble group. 3. 2. The resin composition according to 1. A resin composition, wherein A in the general formula (MI-2) is a group containing a phenolic hydroxy group. 4. 1. The resin composition according to any one of 1. to 3., In the general formula (NB), at least one of R 1 , R 2 , R 3 and R 4 is a group represented by the following general formula (fa): -LC( CF3 ) 2OH (fa) In general formula (fa), L is a single bond or an alkylene group having 1 to 6 carbon atoms. 5. 1.
• a pattern forming method comprising the steps of: 9.
• a method for manufacturing an electronic device comprising: 10.
• R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, provided that at least one of R 1 , R 2 , R 3 and R 4 is a group having a —C(CF 3 ) 2 OH group; a1 is 0, 1 or 2.
• X is a monovalent organic group containing a cyclic skeleton. 11.
• MI-2 a polymer having a structural unit represented by the following general formula (MI-2):
• A is a hydrogen atom or a group containing an alkali-soluble group. 12.
• the present invention provides a resin composition and a polymer that have suitable solubility in an alkaline developer.
• X to Y in the explanation of a numerical range means from X to Y, unless otherwise specified.
• X to Y in the explanation of a numerical range means from X to Y, unless otherwise specified.
• 1 to 5% by mass means "1% by mass to 5% by mass.”
• an "alkyl group” includes not only an alkyl group having no substituents (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• organic group refers to an atomic group obtained by removing one or more hydrogen atoms from an organic compound.
• a "monovalent organic group” refers to an atomic group obtained by removing one hydrogen atom from any organic compound.
• electronic device is used to encompass elements, devices, final products, etc. to which electronic engineering technology is applied, such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuit display devices, information and communication terminals, light-emitting diodes, physical batteries, and chemical batteries.
• the resin composition of the present embodiment is A polymer having a structural unit represented by general formula (NB) below and a structural unit represented by general formula (MI-1) below, A solvent; Includes.
• R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, provided that at least one of R 1 , R 2 , R 3 and R 4 is a group having a —C(CF 3 ) 2 OH group; a1 is 0, 1 or 2.
• X is a monovalent organic group containing a cyclic skeleton.
• the structural unit represented by formula (NB) has a group having a -C(CF 3 ) 2 OH group. Since the -C(CF 3 ) 2 OH group is an alkali-soluble group, the above polymer exhibits alkali-solubility.
• the structural unit represented by formula (MI-1) has a C ⁇ O structure which is a polar group, but contains an atomic group X which is basically hydrophobic, and therefore has a relatively low affinity for an alkaline developer. It is believed that the polymer contains these two structural units, and thus has an appropriate solubility in an alkaline developer. Such moderate solubility is believed to lead to the ability to obtain fine patterns and to suppress swelling of the pattern due to development treatment when the resin composition of this embodiment is used as a photosensitive resin composition to form a pattern.
• the above polymer has a polycyclic aliphatic skeleton in the structural unit represented by general formula (NB), and a monovalent organic group containing a cyclic skeleton is present in the structural unit represented by general formula (MI-1).
• NB polycyclic aliphatic skeleton
• MI monovalent organic group containing a cyclic skeleton
• the presence of these cyclic skeletons provides good etching resistance to the resin composition of this embodiment.
• the resin composition of this embodiment is preferably used as a resist composition.
• examples of the organic group having 1 to 30 carbon atoms for R 1 , R 2 , R 3 , and R 4 include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, an alkoxy group, a heterocyclic group, and a carboxyl group.
• alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
• alkenyl group examples include an allyl group, a pentenyl group, and a vinyl group.
• the alkynyl group includes, for example, an ethynyl group.
• Examples of the alkylidene group include a methylidene group and an ethylidene group.
• Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.
• Examples of the aralkyl group include a benzyl group and a phenethyl group.
• Examples of the alkaryl group include a tolyl group and a xylyl group.
• Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, and an n-hexyloxy group.
• heterocyclic group examples include an epoxy group and an oxetanyl group.
• the organic groups of R 1 , R 2 , R 3 and R 4 are preferably linear alkyl groups having 3 to 30 carbon atoms.
• the organic groups of R 1 , R 2 , R 3 and R 4 are preferably linear alkyl groups having 4 to 20 carbon atoms, more preferably linear alkyl groups having 4 to 10 carbon atoms.
• one to three of R 1 , R 2 , R 3 and R 4 are hydrogen atoms and not hydrophobic atomic groups such as alkyl groups.
• R 1 , R 2 , R 3 and R 4 is a group having a -C(CF 3 ) 2 OH group.
• R 1 , R 2 , R 3 and R 4 are groups having a -C(CF 3 ) 2 OH group, more preferably one of R 1 , R 2 , R 3 and R 4 is a group having a -C(CF 3 ) 2 OH group.
• the group having a —C(CF 3 ) 2 OH group is preferably a group represented by the following general formula (fa). -LC( CF3 ) 2OH (fa)
• L is a single bond or an alkylene group having 1 to 6 carbon atoms. This alkylene group having 1 to 6 carbon atoms may be linear or branched. L is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group.
• X in general formula (MI-1) may be a monovalent organic group containing a cyclic skeleton.
• This cyclic skeleton may be an aromatic group such as a benzene ring, or a cyclic aliphatic group.
• X contains a cyclic aliphatic group.
• the cyclic aliphatic group is preferably saturated and does not contain a carbon-carbon double bond.
• X is preferably a cycloalkyl group or a cyclic aliphatic group, and more specifically, X is preferably a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a norbornyl group, an adamantyl group, or the like. X may or may not have a substituent. From the viewpoint of appropriately controlling the solubility, it is preferable that X has no substituent.
• the polymer further has a structural unit represented by the following general formula (MI-2).
• MI-2 general formula (MI-2)
• swelling of the pattern due to a developer may be easily suppressed when a pattern is formed using the resin composition of this embodiment.
• A is a hydrogen atom or a group containing an alkali-soluble group.
• alkali-soluble group examples include a phenolic hydroxy group, a carboxy group, and a -C( CF3 ) 2OH group.
• A is preferably a group containing a phenolic hydroxy group, and more specifically, A is preferably --C 6 H 4 --OH.
• MI-2 the structural unit represented by general formula (MI-2) has the function of improving the alkali solubility of the polymer, because the two carbonyl groups in the structural unit attract electrons from the N atom, making it easier for the hydrogen atom to dissociate.
• the polymer may or may not have structural units other than the above-listed structural units.
• structural units other than the above-listed structural units include a structural unit in which the maleimide structure in the structural unit represented by general formula (MI-1) is ring-opened, a structural unit in which the maleimide structure in the structural unit represented by general formula (MI-2) is ring-opened, and a structural unit derived from maleic anhydride or a derivative thereof.
• R 1 , R 2 , R 3 and R 4 in the general formula (NB) are hydrogen atoms or organic groups having 1 to 30 carbon atoms, and are not groups having a -C(CF 3 ) 2 OH group.
• a structural unit in which at least one of R 1 , R 2 , R 3 and R 4 in the general formula (NB) is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and the remaining is a hydrogen atom can be mentioned.
• the alkyl group here may be linear or branched.
• the number of carbon atoms of the alkyl group is, for example, 1 to 20, preferably 1 to 10, and more preferably 3 to 8.
• the number of carbon atoms of the cycloalkyl group is, for example, 5 to 8.
• the number of carbon atoms of the aryl group is, for example, 6 to 20, and more preferably 6 to 12.
• the number of carbon atoms of the aralkyl group is, for example, 7 to 13.
• This structural unit has the function of making the polymer appropriately hydrophobic, thereby adjusting the solubility in an alkaline developer.
• the polymer does not contain an epoxy group-containing structural unit, or if it does contain one, the proportion of such a structural unit in the total structural units of the polymer is preferably 5 mol % or less, more preferably 3 mol % or less, and even more preferably 1 mol % or less.
• the polymer does not contain an oxetanyl group-containing structural unit, or if it does contain one, the proportion of such a structural unit in the total structural units of the polymer is preferably 5 mol % or less, more preferably 3 mol % or less, and even more preferably 1 mol % or less.
• the polymer does not contain any silicon atom-containing structural units, or if it does contain any, the proportion of such units in the total structural units of the polymer is preferably 5 mol % or less, more preferably 3 mol % or less, and even more preferably 1 mol % or less.
• the content of the structural unit represented by formula (NB) in the polymer is preferably 3 to 45 mol %, more preferably 5 to 35 mol %.
• the content of the structural unit represented by formula (MI-1) in the polymer is preferably 20 to 70 mol %, more preferably 30 to 60 mol %.
• the content thereof is preferably from 10 to 65 mol %, more preferably from 20 to 55 mol %, from the viewpoints of optimizing solubility in an alkaline developer and balancing various performance properties.
• the polymer has other structural units, for example, a structural unit in which all of R 1 , R 2 , R 3 and R 4 in general formula (NB) are hydrogen atoms or organic groups having 1 to 30 carbon atoms and are not a group having a -C(CF 3 ) 2 OH group, the content thereof is preferably 1 to 50 mol %, more preferably 10 to 30 mol %, from the viewpoint of obtaining appropriate solubility.
• the solubility of the polymer in an alkaline developer can be optimized.
• the ratio of each structural unit in the polymer the resolution of the pattern can be improved and swelling of the pattern can be suppressed when the resin composition is subjected to an alkaline development treatment to form a pattern.
• the resin composition of this embodiment may contain only one polymer, or may contain two or more polymers.
• all of the polymers may be polymers having a structural unit represented by the general formula (NB) and a structural unit represented by the general formula (MI-1), or some of the polymers may not be polymers having a structural unit represented by the general formula (NB) and a structural unit represented by the general formula (MI-1).
• preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more of all the polymers in the resin composition are polymers having a structural unit represented by the general formula (NB) and a structural unit represented by the general formula (MI-1).
• the weight average molecular weight of the polymer may be appropriately adjusted in consideration of appropriate solubility in an alkaline developer, etc.
• the weight average molecular weight of the polymer is, for example, 3,000 to 100,000, preferably 3,000 to 50,000, more preferably 3,000 to 12,000, and particularly preferably 3,000 to 6,000.
• the polydispersity index (PDI) of the polymer is preferably from 1.1 to 2.0, and more preferably from 1.1 to 1.6.
• the proportion of polymer in the non-volatile components (components other than the solvent) of the resin composition is preferably 1 to 20% by mass, and more preferably 1 to 15% by mass.
• Polymers can usually be synthesized (produced) by radical polymerization. That is, a monomer (having a radically polymerizable carbon-carbon double bond) corresponding to the structural unit of each of the general formulas above can be polymerized in an appropriate organic solvent by the action of a radical initiator to synthesize (produce) the polymer.
• a radical initiator to synthesize (produce) the polymer.
• publicly known information can be appropriately referred to.
• known information can be appropriately referred to regarding the purification method of the synthesized polymer (method of reducing impurities).
• the resin composition of the present embodiment is used as a resist composition, it is preferable to reduce impurities as much as possible.
• Preferred solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, mixtures thereof, and the like.
• PGME propylene glycol monomethyl ether
• PMEA propylene glycol monomethyl ether acetate
• MIBC methyl isobutyl carbinol
• GBL gamma butyrolactone
• NMP N-methylpyrrolidone
• MAK methyl-n-amyl ketone
• the solvent may be a single solvent or a mixed solvent.
• the amount of the solvent used is appropriately adjusted so that the concentration of non-volatile components in the composition becomes usually about 1 to 20% by mass, preferably about 1 to 15% by mass.
• the resin composition is preferably photosensitive.
• Photosensitive means that the solubility in an alkaline developer changes due to the action of actinic rays or radiation.
• the resin composition preferably contains a compound that generates an acid under the action of actinic rays or radiation (acid generator), and a compound that causes a crosslinking reaction under the action of acid (crosslinking agent).
• a resin film formed from a resin composition containing an acid generator and a crosslinking agent is irradiated with actinic rays or radiation, and then the resin film is developed, thereby forming a negative resin pattern.
• the resin composition preferably contains a compound containing two or more diazirine structures in one molecule (hereinafter referred to as a diazirine compound).
• a resin film formed from a resin composition containing a diazirine compound is irradiated with actinic rays or radiation, and then the resin film is developed to form a negative resin pattern.
• N2 is eliminated from the diazirine structure, and carbene (a dicoordinated carbon atom having only six valence electrons and no charge) is generated. The generated carbene reacts with a polymer to form a bond.
• the diazirine compound can form a bond with various polymers.
• a diazirine compound that "contains two or more diazirine structures in one molecule" is used, so that the polymer is "crosslinked” by the diazirine compound. Therefore, the part of the resin film that is irradiated with actinic rays or radiation becomes insoluble or hardly soluble in the developer. Therefore, a pattern can be formed by selectively irradiating the resin film with actinic rays or radiation and then performing a development process.
• the di-arylidine compound preferably contains a structure represented by the following general formula (b). Specifically, the di-arylidine compound preferably contains two or more structures represented by the following general formula (b) in one molecule.
• the structures represented by general formula (b) present in one molecule of the di-diazine compound may be the same structure or different structures.
• An example of the latter is compound (B) having, in one molecule, a structure represented by general formula (b) where n is 0 and a structure represented by general formula (b) where n is 1.
• R EWG can be any group generally recognized as an electron-withdrawing group in the field of organic chemistry.
• R EWG include fluorinated alkyl groups, chlorinated alkyl groups, -NO 2 , -CN, -CHO, -COR, -COOR, -COOH, -SO 2 R, and -SO 3 H.
• R is a monovalent organic group, and specific examples thereof include the same as the organic group having 1 to 30 carbon atoms in general formula (NB).
• R EWG is preferably a fluorinated alkyl group, more preferably a perfluoroalkyl group, and even more preferably a trifluoromethyl group.
• R include organic groups having 1 to 30 carbon atoms, halogen atoms, and hydroxy groups, which are R 1 , R 2 , R 3 and R 4 in general formula (NB). From the viewpoint of ease of synthesis/availability of the di-azirine compound, n is preferably 0.
• the di-aryl amine compound more preferably contains a structure represented by the following general formula (b1):
• R EWG , R, n and * are the same as those in general formula (b).
• the preferred embodiments of R EWG , R and n are the same as those mentioned in formula (b).
• the electron donating property of the oxygen atom increases the reactivity of the di-diazine structure portion, and carbene tends to be more easily generated by irradiation with an electron beam or EUV light.
• the use of a di-diazine compound containing the structure represented by general formula (b1) tends to further increase sensitivity.
• the di-aryl amine compound can specifically have a structure represented by the following general formula (BB):
• multiple A's may be present.
• the multiple A's may have the same structure or different structures.
• k is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3.
• L can specifically be a linear or branched alkylene group, a group in which two hydrogen atoms have been removed from an alicyclic group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -NR- (R is a monovalent organic group), -S-, -SO 2 -, a group in which two or more of these groups are linked together, etc.
• L is preferably a linear or branched alkylene group, an arylene group, -O-, or a group in which two or more of these groups are linked together.
• L is typically a k-valent organic group.
• the "length" of the L portion is appropriate.
• the "length" of the L moiety here is defined as the number of atoms present in the shortest path from an atom to which a certain A is directly covalently bonded in L in the di-allylidine compound represented by general formula (BB) as the starting point, to an atom to which another A is directly covalently bonded (end point), by tracing only the covalent bonds in L.
• the "length" of the L moiety is determined by including the oxygen atom linked to the benzene ring in general formula (b1) in L.
• the oxygen atom in general formula (b1) is used as the starting point or end point.
• the di-allylidine compound has 3 or more A, the shortest length among the lengths that can be defined is adopted as the "length".
• the “length” of the L moiety in this compound (B) is 10.
• the "length” of the L portion in BondLynx GEN-I used in the Examples below is 1, the "length” of the L portion in BondLynx GEN-IIIa is 10, and the "length” of the L portion in BondLynx GEN-IIIe is 14.
• the "length" of the L portion is, for example, 1 to 20, preferably 1 to 16. As another example, the “length” of the L portion is preferably 6 to 20, more preferably 8 to 20.
• the L portion is “appropriately long"
• the diazirine compound (or the carbene generated from the diazirine compound) in the film formed from the composition into a film is more likely to react with the polymer, which may further improve the sensitivity.
• the L portion is "not too long", contact between the diazirine compound (or the carbene generated from the diazirine compound) and the polymer is suppressed, which may improve the stability of the composition over time.
• the composition tends to have improved stability over time.
• the composition tends to have improved stability over time by using a di-allylidine compound in which L has a fluorine atom in general formula (BB), a di-allylidine compound in which L is an organic group substituted with a fluorine atom in general formula (BB), a di-allylidine compound in which L is a fluorinated alkylene group in general formula (BB), etc.
• L is electron-withdrawing or L is substituted with an electron-withdrawing group, so that the generation of carbene by N2 elimination is thermodynamically slightly unfavorable, that is, carbene is slightly difficult to generate.
• the unintended decomposition of the di-azirine compound is suppressed, and the sensitivity is improved.
• the sensitivity may be slightly worsened, when the stability over time of the composition is important, it is preferable to select a di-azirine compound in which L is electron-withdrawing or L is substituted with an electron-withdrawing group.
• the molecular weight of the di-arylidine compound is typically 100 to 2000, preferably 100 to 1000.
• the di-arylidine compound is typically a low molecular weight compound and is not a polymer.
• Diazine compounds can be purchased, for example, from XlynX Materials Inc., based in Canada. Specific examples of the di-diazine compound include compounds having a di-diazine structure exemplified in Patent Document 2. Furthermore, a di-azine compound having the structure shown below is also preferably used.
• a di-diazine compound When a di-diazine compound is used, only one di-diazine compound may be used, or two or more di-diazine compounds may be used in combination. From the viewpoint of the balance of various performances, when a di-azine compound is used, the amount thereof is usually 5 to 50 parts by mass, preferably 8 to 40 parts by mass, and more preferably 10 to 30 parts by mass, based on 100 parts by mass of the polymer.
• the resin composition of the present embodiment may contain optional components other than those described above.
• the optional components include a developing aid, a plasticizer, an antioxidant, a leveling agent, a surfactant, and the like.
• surfactant is not particularly limited. Any surfactant that can be appropriately dissolved or dispersed in a solvent can be used. Examples of the surfactant include those described in U.S. Patent Application Publication No. 2008/0248425, paragraph [0276]. Other examples include the "F-TOP" series from Shin-Akita Chemical Industry Co., Ltd., the "Florard” series from 3M Company, the “Megafac” series from DIC Corporation, and the "Surflon” series from AGC Sei Chemical Co., Ltd.
• a fluorine-based surfactant or a silicon-based surfactant can be preferably used, and in particular, a nonionic surfactant containing a fluorine atom is preferably used.
• the amount used can be, for example, 0.01 to 3 parts by mass, specifically 0.1 to 1 part by mass, per 100 parts by mass of the polymer.
• a pattern can be formed by using a resin composition whose solubility in an alkaline developer changes due to the action of actinic rays or radiation, that is, a photosensitive resin composition, through the following steps.
• a resin pattern can be formed on a substrate by the following three steps: a first step of applying a resin composition onto a substrate to form a resin film; a second step of irradiating the resin film formed in the first step with an electron beam or with EUV light; and a third step of developing the resin film after the second step to obtain a substrate on which a resin pattern has been formed.
• the substrate on which the resin film is formed is not particularly limited, and examples thereof include a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, a copper substrate, and a copper-plated substrate.
• the substrate may be an unprocessed substrate, or a substrate having electrodes or elements formed on its surface.
• An anti-reflection film may be provided on the substrate in advance.
• the anti-reflection film either an inorganic film type made of titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, or an organic film type made of a light absorbent and a polymer material can be used.
• the organic anti-reflection film commercially available organic anti-reflection films such as the DUV30 series and DUV-40 series manufactured by Brewer Science, and the AR-2, AR-3, and AR-5 manufactured by Shipley can also be used.
• the method for forming the resin film is not particularly limited.
• spin coating using a spinner is common, but other methods are also acceptable.
• spray coating using a spray coater, dipping, printing, roll coating, inkjet methods, etc. are also acceptable.
• the composition applied to the substrate is typically dried by a heat treatment.
• the heating temperature is usually 50 to 140°C, preferably 60 to 120°C.
• An appropriate drying temperature can be set from the viewpoints of rapid and sufficient drying of the solvent and suppression of carbene generation from the di-azirine compound.
• the heating time varies depending on the heating device, but when a hot plate is used, it is usually 30 to 300 seconds, preferably about 60 to 180 seconds, and when a hot air oven is used, it is usually 5 to 60 minutes, preferably about 10 to 30 minutes.
• the thickness (dry thickness) of the resin film is not particularly limited and may be adjusted as appropriate depending on the size and aspect ratio of the final pattern to be obtained.
• the film thickness can be adjusted by adjusting the concentration of non-volatile components in the composition or by changing the application method.
• the film thickness is, for example, 10 to 1000 nm, specifically 20 to 500 nm.
• the exposure step is usually carried out by irradiating the resin film with actinic rays or radiation.
• Preferred examples of the actinic ray or radiation include far ultraviolet ray, extreme ultraviolet ray (EUV light), and electron beam.
• EUV light extreme ultraviolet ray
• the dose can be, for example, 10 to 1000 ⁇ C/cm 2 , specifically 20 to 500 ⁇ C/cm 2.
• the acceleration voltage of the electron beam can be, for example, 10 to 200 keV, specifically 30 to 150 keV.
• the amount of irradiation can be, for example, 0.1 to 500 mJ/cm 2 , specifically 1 to 250 mJ/cm 2 .
• the far-ultraviolet or EUV light is usually irradiated through a photomask.
• the alkali solubility of the resin composition of this embodiment is appropriately adjusted. Therefore, the resin composition of this embodiment is preferably used for forming fine patterns using electron beams or EUV light.
• the resin film may be heated (Post Exposure Bake).
• the temperature is, for example, 70 to 150°C, preferably 70 to 120°C.
• the time is usually 30 to 300 seconds, preferably 50 to 180 seconds, when using a hot plate, for example.
• Post-exposure baking is usually carried out in chemically amplified compositions in order to promote a chain reaction caused by the action of an acid generated by irradiation with actinic rays or radiation.
• the resin composition of the present embodiment is not necessarily a chemically amplified type.
• the resin composition containing the above-mentioned di-diazine compound is not necessarily a chemically amplified type. Therefore, in principle, patterning is possible without performing post-exposure heating.
• it may be effective to perform post-exposure heating.
• a pattern can be obtained by developing the resin film irradiated with actinic rays or radiation. Usually, development is carried out using a developer by a method such as immersion method, paddle method, or rotary spray method. Usually, the unexposed part of the photosensitive resin film is dissolved and removed by development, and a negative pattern is obtained.
• an alkaline aqueous solution is usually used, and specific examples of the alkaline aqueous solution include (i) inorganic alkaline aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, (ii) organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine, and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.
• an aqueous solution of tetramethylammonium hydroxide is particularly preferred.
• the concentration of tetramethylammonium hydroxide is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.
• the developer may contain an organic solvent, specifically a developer whose main component is an organic solvent (50% by mass or more of the developer is an organic solvent). Ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, etc. may be used as the developer containing an organic solvent.
• an organic solvent specifically a developer whose main component is an organic solvent (50% by mass or more of the developer is an organic solvent).
• Ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, etc. may be used as the developer containing an organic solvent.
• the description in paragraphs 0299 to 0305 of Patent Document 1 may be referred to.
• a resin pattern can be obtained on the substrate.
• Ultrapure water or alcohol is suitable as the rinsing liquid.
• the substrate on which the resin pattern obtained by the above-mentioned first to third steps is formed can be etched to process the substrate. Specifically, by applying an etching gas to the substrate on which the resin pattern is formed, a pattern can be formed in the portion of the substrate on which the resin pattern is not formed. In other words, the resin pattern functions as a "resist pattern" that prevents the substrate from being processed during etching.
• the etching may be wet etching, but is usually dry etching in terms of ease of fine processing.
• the specific etching conditions and usable etching gases may be appropriately changed and optimized according to the structure and specifications of the electronic device to be manufactured.
• the pattern formed with the resin composition of this embodiment functions as a resist pattern during etching.
• the resin composition of this embodiment is preferably "for forming a resist pattern during an etching process.”
• the resin composition of this embodiment is preferably not used for forming a permanent film such as an insulating film (a film that remains in the final electronic device).
• the resin pattern remaining after the fourth step (etching) is usually removed with a resist remover. Residues generated by etching can be removed by an etching residue removing solution. As the resist stripping liquid and etching residue removing liquid, known liquids can be appropriately used.
• ⁇ Polymer> So far, the embodiments have been described mainly with reference to a "resin composition” that contains a polymer having a specific structural unit and a solvent.
• the polymers described in the section ⁇ Resin composition> are useful because they have alkali solubility and other favorable properties.
• the polymers described in the section ⁇ Resin composition> are applicable to various uses by themselves and can be used for various purposes other than photosensitive resin compositions. Specific embodiments of the polymer have been described in the section [Polymer] of ⁇ Resin composition>, and therefore will not be described again.
• HFANB 9.2 g, 33 mmol
• CyMI 6.0 g, 33 mmol
• H-MI 3.2 g, 33.3 mmol
• a polymerization initiator VR-110 (0.51 g, 2 mmol) manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. was added to a solvent (anisole, 7.5 g). This polymerization initiator solution was added to the monomer polymerization solution heated to 150° C. under a nitrogen atmosphere. The amount of the polymerization initiator was 0.02 mol per 1 mol of monomer.
• the amount of the monomer added and the amount of the polymerization solvent were adjusted so that the non-volatile components of the monomer and polymerization initiator were about 20 mass %.
• the polymerization solvent containing the monomers and the polymerization initiator (2) was stirred at 150° C. under a nitrogen atmosphere for 1.5 hours.
• the mixture was allowed to cool to room temperature.
• the cooled polymerization solvent was added dropwise to heptane in an amount four times the mass of the polymerization solvent, to precipitate a white to yellow powder.
• the powder was filtered, washed with heptane, and then dried overnight in a vacuum dryer at 80°C, to obtain a white to yellow polymer powder.
• the ratio of each structural unit in the obtained polymer was determined by measuring the amount of each remaining monomer in the polymerization solvent after completion of the above (3) by gas chromatography. In other words, the amount of monomer introduced into the polymer was considered to be the amount of monomer charged minus the amount of remaining monomer.
• the number average molecular weight Mn and weight average molecular weight Mw of the obtained polymer were determined by gel permeation chromatography (GPC) using polystyrene as the standard substance.
• incorporation rates of each monomer were 28 mol%, 47 mol%, and 25 mol%. These incorporation rates were almost consistent with the monomer consumption rates measured by gas chromatography.
• ⁇ Measurement of polymer dissolution rate The synthesized polymer was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a concentration of 10% by mass. Each of these solutions was spin-coated onto a silicon wafer, and the solvent was dried to obtain a resin film having a thickness T of about 300 nm. This resin film was immersed together with the silicon wafer in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide at 25° C., and the time t until the film thickness became zero was measured. The dissolution rate was then calculated by T/t.
• PMEA propylene glycol monomethyl ether acetate
• a polymer shown in Table 2 below and any one of the following di-azine compounds were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a photosensitive resin composition.
• the amount of the di-azine compound was 20 parts by mass based on 100 parts by mass of the polymer.
• the non-volatile component concentration was adjusted to 10% by mass for the evaluation of [Alkaline solubility] (Table 2) and [Electron beam irradiation dose and film remaining rate] (Table 3) described later.
• the amount of PGMEA was adjusted to obtain a non-volatile component concentration of 3% by mass for the evaluation of [Line and space (L/S) pattern formation] (Table 4).
• the composition was applied onto a silicon wafer by spin coating, and the solvent was dried to form a resin film.
• the thickness of the resin film was as shown in Table 3.
• the resin film was irradiated with an electron beam at an acceleration voltage of 130 keV.
• the electron beam was irradiated with different doses between 20 and 300 ⁇ C/ cm2 .
• the resin film was immersed together with the silicon wafer in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.
• the development time (the time during which the resin film was immersed in the developer) was as shown in Table 3.
• Example 1 200nm L/S: 150 ⁇ C/cm 2 , 100nm L/S: 150 ⁇ C/cm 2 , 50nm L/S: 150 ⁇ C/cm 2
• Example 2 200 nm L/S: 150 ⁇ C/cm 2 (100 nm L/S or less is not resolved satisfactorily)
• Example 3 200nm L/S: 150 ⁇ C/cm 2 , 100nm L/S: 200 ⁇ C/cm 2 , 50nm L/S: 250 ⁇ C/cm 2
• the resin film was immersed together with the silicon wafer in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide or an aqueous solution diluted with pure water so that the tetramethylammonium hydroxide concentration was 1.19% by mass.
• the development time (the time during which the resin film was immersed in the developer) was as shown in Table 4.
• the surface of the silicon wafer after development was observed under an electron microscope to evaluate the resolution of the L/S pattern. If the pattern was resolved, the degree of swelling of the pattern was also observed.
• Information mainly relating to the polymer is summarized in Table 1.
• Information mainly relating to the composition and evaluation results of the photosensitive resin composition is summarized in Tables 2 to 4.
• the solvent "GBL” means gamma-butyrolactone.
• the mixing ratio of the polymerization solvents is a mass ratio.
• the "%" for the ratio of structural units derived from each monomer in the polymer means mol %.
• the resin film became insoluble in an alkaline developer. Specifically, the residual film rate increased with an increase in the amount of electron beam irradiation.
• the resin composition shown in Table 3 can be preferably used as a photosensitive resin composition.
• fine patterns could be formed by irradiating the resin films formed from the resin compositions shown in Table 4 with electron beams.
• very fine patterns of 50 nm L/S could be formed.
• swelling of the L/S patterns obtained in Examples 1 to 3 due to the developer was sufficiently suppressed.

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