Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/135—Nozzles
  • B41J2/16—Production of nozzles
  • B41J2/162—Manufacturing of the nozzle plates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/135—Nozzles
  • B41J2/16—Production of nozzles
  • B41J2/1621—Manufacturing processes
  • B41J2/1631—Manufacturing processes photolithography
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
  • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
• • 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Definitions

• the present invention relates to a photosensitive resin composition capable of forming a fine resin by forming a resin pattern using a photolithographic technique and a pattern forming method, and more specifically, a fine resin pattern of the order of 10 ⁇ m.
• the present invention relates to a photosensitive resin composition having high sensitivity and high resolution that enables the formation of a resin, and a pattern forming method using the resin composition.
• Photocurable composition that cures and does not peel easily (Patent Document 1), multifunctional biphenyl A formaldehyde aldehyde novolac resin and acid generator Triphenylsulfonium hexafluoroantimonate
• Patent Document 2 A thick film formable photocurable composition consisting of a nitrate and a solvent cyclopentanone has been reported.
• an acid generator in addition to the diazonaphthoquinone type acid generator, it can be used for optical shaping.
• Various acid generators have been developed to provide high sensitivity resin compositions.
• aromatic sulfone cation polymerization initiators can be mentioned.
• a photosensitive resin composition using such an acid generator as an improvement factor a resin composition containing a cationically polymerizable organic compound and an energy ray sensitive cationic polymerization initiator (Patent Document 3 ) Etc. have been proposed.
• Patent Document 1 Japanese Patent Publication No. 7-78628
• Patent Document 2 US Pat. No. 6,391,523
• Patent Document 3 Japanese Patent Application Laid-Open No. 9-268205
• the present invention has been made in view of the above-described conventional circumstances, and the object of the present invention is to provide a pattern having a high resolution, that is, a high aspect ratio profile with which volumetric shrinkage during heat curing becomes small. It is an object of the present invention to provide a photosensitive resin composition capable of forming a photosensitive resin and having high sensitivity, and a pattern forming method using the resin composition. Means to solve the problem
• a photosensitive resin composition is prepared by combining a polyfunctional epoxy resin and a specific acid generator, and this photosensitive resin composition is used. It has been found that, by forming a resin pattern, it is possible to form a resin pattern of a profile having a high aspect ratio and a high sensitivity, which reduces the volumetric shrinkage during heat curing.
• a photosensitive resin composition according to the present invention comprises a polyfunctional epoxy resin and a cationic polymerization initiator represented by the following general formula (1): It is characterized by [Formula 1]
• X and X each represent a hydrogen atom, a halogen atom, an oxygen atom or a halogen
• Y represents a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom, a hydrocarbon group, or a substituent, or an alkoxy group.
• the polyfunctional epoxy resin is preferably a polyfunctional bisphenol A novolac epoxy resin, and the cationic polymerization initiator is preferably a compound represented by the following chemical formula (2).
• a high molecular weight linear bifunctional epoxy resin may be further contained.
• it may contain a naphthol type sensitizer.
• a solvent it may contain ⁇ -petite lataton or may contain oxetane derivatives and epoxy derivatives.
• the photosensitive resin composition laminate of the present invention is characterized in that at least one surface, preferably both surfaces of the photosensitive resin composition layer obtained from the photosensitive resin composition is protected with a protective film. It features.
• the photosensitive resin composition laminate can be stored, for example, in a roll shape. That is, as the use form of the photosensitive resin composition of the present invention, a film in which one side or both sides of the photosensitive resin composition layer obtained from the photosensitive resin composition is protected with a resin film (protective film) It can be made into a shape (photosensitive resin composition laminate). Then, the resin film (protective film) is peeled off and attached to a portion where a pattern is to be formed, and thereafter, it is possible to form a cured resin pattern through pattern exposure, development, and heat treatment. .
• the resin film (protective film) on one side of the photosensitive resin composition layer is a polyethylene terephthalate film as the resin film (protective film)
• the resin film (protective film) on the other side The medium force of polyethylene terephthalate film, polypropylene film, and polyethylene film is selected.
• the photosensitive resin composition is laminated on a desired support, and after drying, the photosensitive resin composition layer is exposed to a predetermined pattern and exposed.
• the resin composition of the present invention is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern of a predetermined shape.
• the photosensitive resin composition laminate in the form of a film may be stuck.
• the photosensitive resin composition solution may be applied and dried.
• the photosensitive resin composition and the pattern formation method according to the present invention it is possible to form a resin pattern having a high aspect ratio, a high aspect ratio profile and a small volume shrinkage at the time of heat curing. As a result, a force S can be obtained that enables fine resin molding with good dimensional stability to be possible.
• the present invention is a photosensitive resin composition
• a photosensitive resin composition comprising a polyfunctional epoxy resin and a cationic polymerization initiator represented by the general formula (1).
• the combination of the multifunctional epoxy resin and the cationic polymerization initiator provides high sensitivity, small volume shrinkage during heat curing, A resin pattern having a profile of spectral ratio can be formed.
• the cationic polymerization initiator may be contained in a relatively small amount because the generation efficiency of the cation by irradiation of radiation is high.
• the sensitivity of the photosensitive resin composition can be significantly enhanced by the combination of the cationic polymerization initiator and the polyfunctional epoxy resin.
• the cationic polymerization initiator has a unique affinity that it can efficiently attack the epoxy group in the molecule of the polyfunctional epoxy resin, in particular the polyfunctional bisphenol A novolac epoxy resin, to promote polymerization. Since it has, it is presumed to have the above-mentioned excellent effect. Furthermore, this combination has the effect of reducing the volume shrinkage during heat curing of the photosensitive resin composition layer.
• the photosensitive resin composition of the present invention when used, it is possible to form a resin pattern having a high aspect ratio profile and having a high volumetric sensitivity and a low volumetric shrinkage at the time of heat curing. As a result, desired resin molding can be realized with high dimensional stability.
• the multifunctional epoxy resin in the present invention is not particularly limited as long as it is an epoxy resin containing an epoxy group sufficient to form a thick film pattern in one molecule.
• the multifunctional epoxy resin used in the present invention include phenol 'novolak epoxy resin, ortho cresol novolac epoxy resin, triphenyl-type nopolac epoxy resin, bisphenol A novolac epoxy resin and the like. be able to.
• polyfunctional bisphenol A novolac type epoxy resin is preferred, and its functionality is preferably pentafunctional or higher.
• the polyfunctional bisphenol A novolac epoxy resin is preferably a resin represented by the following general formula (3).
• the epoxy group of the bisphenol A novolac epoxy resin represented by the general formula (3) may be a polymer polymerized with a bisphenol A epoxy resin or a bisphenol A novolac epoxy resin.
• R—R in the general formula (3) is independently H
• n is an integer of 0 or more that represents a repeating unit.
• the softening point of the polyfunctional epoxy resin is not particularly limited as long as it is solid at normal temperature.
• the softening point of the multifunctional epoxy resin is preferably 50 to 100 ° C. force S, more preferably 60 to 80 ° C. force S.
• the composition ratio of the polyfunctional epoxy resin in the photosensitive resin composition is preferably 80-99.9%, more preferably 92-99.4%.
• the cationic polymerization initiator in the present invention is irradiated with radiation such as ultraviolet light, deep ultraviolet light, excimer laser such as KrF and ArF, X-ray and electron beam to generate a cation, and the cation is polymerized. It is a compound that can be an initiator.
• the cationic polymerization initiator is preferably a compound represented by the following general formula (1).
• X and X each represent a hydrogen atom, a halogen atom, an oxygen atom or a halo
• a hydrocarbon group which may contain a gen atom, or an alkoxy group which may have a substituent attached thereto, which may be the same as or different from one another.
• X and X are halo among them.
• the fluorine atom is more preferred.
• Y contains a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom, Y represents a hydrocarbon group, or a substituent, or an alkoxy group. .
• Y is more preferably a chlorine atom.
• Examples of the cationic polymerization initiator include: 4- (4-benzophenylthio) phenyldisulfenylsulfanium hexafluoroantimonate, 4- (4-benzoylphenyl 2-noretio) phenylbis (4) -Hydroxyethylphenoxene-Hexahydroxy oral antimonate, 4-(4-Benzylphenylthio) phenyl bis (4-fluorophenynore) sulfonium hexafluoroantimonate, 4- (4-benzoicyl phenothioate) ) Phenylbis (4-chlorophenol) sulfonium to hexafluoroantimonate, 4 ⁇ 4 to 1 (2-croports benzole) phenylthio ⁇ phenylbis (4-fluoropheninole) sulfonium to Xafluro antimonate, 4_ ⁇ 4
• Uoropheninole) sulfonium oxa aphoro anmonate 4 _ ⁇ 4_ (4-Methoxy benzyl) phenylthio ⁇ phenyl bis (4-fluoropheninole) sulfodinium hexafluoroantimonate, 4_ ⁇ 4_ (4_fluorobenzonole) phenylthio ⁇ Phenylbis (4-fluorophenyl) sulfonium hexyl hexaantimonate, 4- ⁇ 4- (2-methoxycarbonylbenzenole) phenylthio ⁇ phenyl bis (4-fluorophenyl) sulfodium Hexafluoroantimonate can be mentioned.
• the composition ratio of the cationic polymerization initiator in the photosensitive resin composition is preferably 0.1-5%, more preferably 0.1-10%.
• the photosensitive resin composition may further contain a high molecular weight linear bifunctional epoxy resin to improve film formability.
• the above-mentioned high molecular weight linear bifunctional epoxy resin is preferably a resin represented by the following general formula (4):
• R—R in the general formula (4) is each independently H or CH. m is repeated
• the polymer linear bifunctional epoxy resin is not particularly limited, but is preferably a polymer of bisphenone A-type epoxy or bis-phenol F-type epoxy, and preferably has a weight average molecular weight of 2000-7000. , Weight average molecular weight 3000-5000 preferred later. If the weight average molecular weight is less than 2000, the film formability is not improved, and if the weight average molecular weight is greater than 700, it is not compatible with the multifunctional epoxy resin.
• Bisphenol A type epoxy resin manufactured by Japan Epoxy Resins Co., Ltd., trade name: “epi coat 1009”, weight average
• Molecular weights of 3750 are particularly preferred.
• the weight average molecular weight can be measured by gel permeation chromatography.
• the photosensitive resin composition may further contain a naphthol type sensitizer.
• a naphthol type sensitizer In the case where the sensitivity is high, if there is a gap between the mask and the resist surface, as a result of exposure, a phenomenon occurs in which the size of the resin pattern obtained becomes thicker than the mask size. This fattening phenomenon can be suppressed without lowering the sensitivity by containing a naphthol type sensitizer. It is preferable to add a naphthol-type sensitizer in this way, because it is possible to suppress the error of the resist pattern dimension with respect to the mask pattern dimension.
• Examples of the naphthol type sensitizer include 1-naphthol, 1 / 3-naphthol, naphthomethyl methyl ether, and 1-naphtholethyl ether. Of these, 1_naphthol is the most preferable in consideration of the effect of suppressing the thickness of the resist without reducing the sensitivity.
• the composition ratio of the naphthol-type sensitizer in the photosensitive resin composition is too high, it is not preferable because it has a reverse tapered shape and the line width is too narrow.
• the composition ratio is preferably 0.1-13%, which is preferably 0-10%.
• the photosensitive resin composition can further contain a solvent.
• a solvent for example, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA”), methyl isobutyl ketone (hereinafter referred to as "MIBK:”), butyl acetate, methyl amyl ketone (2-heptanone) And ethyl acetate, and methyl ethyl ketone (hereinafter referred to as "MEK”).
• PGMEA propylene glycol monomethyl ether acetate
• MIBK methyl isobutyl ketone
• MEK methyl amyl ketone
• a ⁇ -peptidic lataton is preferable because it reacts and is incorporated into the resist.
• PGMEA, MIBK, butyl acetate and MEK are preferred in view of the wettability with the substrate film and the surface tension.
• the photosensitive resin composition may further contain an oxetane derivative and an epoxy derivative.
• an oxetane derivative or an epoxy derivative In the case of forming a dry film resist, by containing an oxetane derivative or an epoxy derivative, the flexibility of the photosensitive resin composition before curing is increased without reducing the physical properties of the photosensitive resin composition after curing. Can.
• oxetane induction Although the body is not particularly limited, specifically, for example, 3-ethyl 3-hydroxymethyl nore oxetane, 1,4-bis [[[([3-ethinole 3-oxetaninol) methoxy] methinole] benzene, di [bis] 1-Ethyl (3-oxetanyl)] methyl ether etc. can be mentioned.
• epoxy derivatives examples include bisphenol A-type epoxy resin and bisphenol F-type epoxy resin having a weight average molecular weight of 7000 or less, preferably 2000 or less, more preferably 1000 or less.
• S-bisphenol A type epoxy resin manufactured by Japan Epoxy Resins Co., Ltd., trade name: “epicoat 828”, weight average molecular weight 380.
• the weight average molecular weight can be measured by one method of gel permeation chromatography.
• the photosensitive resin composition of the present invention may further contain, if desired, miscible additives, for example, an additional resin for improving the performance of the pattern, a plasticizer, a stabilizer, a colorant, and a surfactant. Etc. can be added and contained.
• a solution may be applied to be used as a cured film, or a photosensitive film obtained from the photosensitive resin composition with a resin film (protective film) may be used.
• a dry film (photosensitive resin composition laminate) in which at least one side, preferably both sides, of the resin composition layer is protected may be formed and pasted on a desired support before pattern exposure.
• a polyethylene terephthalate film is used on one side of the photosensitive resin composition layer obtained from the photosensitive resin composition as the resin film (protective film)
• a polyethylene terephthalate film is used as the protective film used on the other side.
• Preferred is a polymeric film of polypropylene fino rem and polyethylene film.
• the photosensitive resin composition is supplied as a film (photosensitive resin composition laminate), the steps of coating on a support and drying can be omitted, and the process can be further simplified. Pattern formation using the photosensitive resin composition of the present invention can be conveniently performed.
• the photosensitive resin composition of the present invention is dissolved in a solvent, and the solution is applied onto a desired support, for example, a substrate such as a silicon wafer, using a spin coater or the like, and dried. Then, the resin composition layer is pattern-exposed to radiation, exposed, and developed with a developer. By doing so, a good resin pattern faithful to the mask pattern can be formed without depending on the support used. Resin putter obtained The heat treatment can be performed to obtain a cured resin pattern of a predetermined shape.
• the photosensitive resin composition of the present invention is formed into a dry film (photosensitive resin composition laminate), and the protective film is removed from the dry film (photosensitive resin composition laminate), and desired.
• the resulting photosensitive resin composition layer is applied to a pattern by radiation, and developed with a developer, so that a good resin pattern faithful to the mask pattern depends on the support used. It is capable of forming power S. As a result, for example, it becomes possible to realize micro resin molding necessary for molding of an electronic device such as an ink jet recording head with excellent dimensional stability.
• the resulting resin pattern can be heat treated to obtain a cured resin pattern of a predetermined shape.
• the photosensitive composition which mixed the polyfunctional epoxy resin, the initiator, and the other component according to the composition (a unit is a mass part) of following Table 1 was obtained.
• A-1) Multifunctional bisphenol A novolac type epoxy resin (trade name: “epi coat 15 7S70", manufactured by Japan Epoxy Resins Co., Ltd.)
• A-2) Multifunctional bisphenol A novolac type epoxy resin (trade name: “Epiclon N-885, manufactured by Dainippon Ink and Chemicals, Inc.)
• (B-1) cationic polymerization initiator (trade name: "Adeca Obtommer SP-172", manufactured by Asahi Denka Kogyo Co., Ltd.)
• the resulting photosensitive resin composition was coated on a silicon wafer by a spin coater and dried to obtain a photosensitive resin composition layer having a thickness of 30 / m.
• the photosensitive resin composition layer was prebetared by a hot plate at 60 ° C. for 5 minutes and at 90 ° C. for 5 minutes.
• pattern exposure Proximity, GHI line
• PAB post exposure bake
• Development was performed for 4 minutes by immersion using PGMEA.
• the resin pattern after development was subjected to post-beta for 1 hour at 200 ° C. using an oven together with the substrate to obtain a cured resin pattern on the substrate.
• the obtained photosensitive resin composition is uniformly coated on a polyethylene terephthalate (PET) film (support film, manufactured by Teijin Ltd.) with a thickness of 38 ⁇ m, and it is heated at 65 ° C. by a hot air convection dryer. It was dried for 5 minutes and at 80 ° C. for 5 minutes. Thereafter, a PET (protective film) with a release agent having a film thickness of 25 zm is laminated on the exposed surface to form a dry film resist (hereinafter referred to as "DFR”) having a photosensitive resin composition layer having a film thickness of 30 ⁇ m. Formed).
• PET polyethylene terephthalate
• support film manufactured by Teijin Ltd.
• DFR dry film resist
• the protective film of this DFR was peeled off and laminated on a silicon wafer at a roll temperature of 80 ° C., an air pressure of 2 kg / cm 2 , and a velocity of 0.5 m / min to laminate a photosensitive resin composition layer.
• This photosensitive resin composition layer was subjected to pattern exposure (proximity, GHI line) using Parallel light aligner (Mask liner: manufactured by Canon Co., Ltd.). Thereafter, PEB was rowed for 5 minutes at 90 ° C. on a hot plate, and development was performed for 4 minutes by an immersion method using PGMEA. Next, an oven was used for 1 hour post beta at 200 ° C. to obtain a cured resin pattern on the substrate.
• the exposure dose represents the required exposure dose
• fine line adhesion refers to the fine pattern width line width in close contact in the formed resist pattern (exposure through a mask with a line width of 6 ⁇ m). Average line width).
• the thin line adhesion was evaluated only in Example 1-12.
• the heat shrinkage due to post-beta (%) is the percentage of heat shrinkage due to post-beta after pattern formation.
• Example 2 From Table 1, in each of Examples 1 to 6, good results were obtained. Further, in Example 2, it was found that by adding 1-naphthol, the thickness of the resist can be suppressed without decreasing the sensitivity. On the other hand, in the comparative example, at least two values of the necessary exposure amount, fine line adhesion, and thermal contraction were larger than those in the example.
• the photosensitive resin composition according to the present invention is useful for forming a resin pattern having a high aspect ratio profile, and in particular, it is possible to obtain dimensional stability in fine size electronic devices and the like. High Re, suitable for resin molding.

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• 2004
  • 2004-12-15 CN CN2004800262121A patent/CN1849560B/zh not_active Expired - Lifetime
  • 2004-12-15 EP EP04807118A patent/EP1729175B1/en not_active Expired - Lifetime
  • 2004-12-15 US US10/565,104 patent/US20060188820A1/en not_active Abandoned
  • 2004-12-15 KR KR1020067005036A patent/KR100795252B1/ko not_active Expired - Lifetime
  • 2004-12-15 WO PCT/JP2004/018759 patent/WO2005093514A1/ja not_active Ceased
  • 2004-12-22 TW TW093140070A patent/TW200532376A/zh not_active IP Right Cessation

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