Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
  • C08F212/36—Divinylbenzene
• • 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
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • 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
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
  • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
  • C08K5/3417—Five-membered rings condensed with carbocyclic rings
• • 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
  • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

• the present disclosure relates to a photocurable composition, particularly to a photocurable composition adapted for inkjet adaptive planarization.
• IAP Inkjet Adaptive Planarization
• a substrate e.g., a wafer containing an electronic circuit
• jetting liquid drops of a curable composition on the surface of the substrate and bringing a flat superstrate in direct contact with the added liquid to form a flat liquid layer.
• the flat liquid layer is typically solidified under UV light exposure, and after removal of the superstrate a planar surface is obtained which can be subjected to subsequent processing steps, for example baking, etching, and/or further deposition steps.
• a photocurable composition can comprise a polymerizable material and at least one photoinitiator, wherein the polymerizable material comprises at least one multifunctional vinylbenzene monomer in an amount of at least 30 wt% based on the total weight of the polymerizable material; the at least one photoinitiator including an oxime ester compound; and the photocurable composition is adapted that a UV shrinkage after forming a photo-cured layer at 23°C is not greater than 4.0 %.
• the photocurable composition can be adapted that a photocured layer formed from the photocurable composition can have a thermal shrinkage after a baking treatment at 350°C of not greater than 3.5%, the baking treatment including 2 minutes baking of the photo-cured layer on a stainless steel plate having a temperature of 350°C under N2 environment.
• the oxime ester compound of the photocurable composition can have a structure of formula (1):
• R I (1) with Ri being an aromatic ring system or a heteroaromatic ring system, R2 being H or Ci-Cs alkyl, R3 being H or Ci-Cs alkyl.
• the oxime ester compound can include a structure of formula (2):
• the oxime ester compound of the photocurable composition can include a structure of formula (3):
• the photocurable composition can further comprise at least 0.05 wt% 4-tert-butyl catechol (TBC).
• TBC 4-tert-butyl catechol
• an amount of the oxime ester compound can be at least 1 wt% and not greater than 7 wt% based on a total weight of the photocurable composition.
• the at least one photoinitiator can further include a photoinitiator not being an oxime ester compound.
• an amount of the polymerizable material can be at least 85 wt% based on the total weight of the photocurable composition.
• the multi-functional vinylbenzene monomer of the polymerizable material can include at least three vinyl groups.
• the multi-functional vinylbenzene monomer can be a biphenyl compound including three vinyl groups.
• the polymerizable material can further include at least one multi-functional acrylate monomer.
• the multi-functional acrylate monomer can include at least one acrylate group and at least one vinyl group.
• a total amount of the multifunctional vinylbenzene monomer and of the multi-functional acrylate monomer can be at least 85 wt% based on the total weight of the polymerizable material.
• the polymerizable material of the photocurable composition can have a weight% ratio of the multi-functional vinylbenzene monomer to the multi-functional acrylate monomer can range from 2: 1 to 1:2.
• the viscosity of the photocurable composition can be not greater than 50 mPa s.
• a method of forming a photo-cured layer on a substrate can comprise: applying a layer of a photocurable composition on the substrate, wherein the photocurable composition comprises a polymerizable material and at least one photoinitiator, the polymerizable material comprising at least one multi-functional vinylbenzene monomer in an amount of at least 30 wt% based on the total weight of the polymerizable material; and the at least one photoinitiator including an oxime ester compound; bringing the photocurable composition into contact with a template or a superstrate; irradiating the photocurable composition with light to form a photo-cured layer; and removing the template or the superstrate from the photo-cured layer.
• the photocurable composition comprises a polymerizable material and at least one photoinitiator, the polymerizable material comprising at least one multi-functional vinylbenzene monomer in an amount of at least 30 wt% based on the total weight of the polymerizable material; and
• irradiating the photocurable composition can be conducted with UV light, and a UV shrinkage after forming the photo-cured layer may be not greater than 4.0 %.
• the photo-cured layer can have a thermal shrinkage after a baking treatment at 350°C of not greater than 3.5%, the baking treatment including 2 minutes baking under N2 of the photo-cured layer on a stainless steel plate having a temperature of 350°C.
• a method of manufacturing an article can comprise: applying a layer of a photocurable composition on the substrate, wherein the photocurable composition comprises a polymerizable material and at least one photoinitiator, the polymerizable material comprising at least one multi-functional vinyl benzene monomer in an amount of at least 30 wt% based on the total weight of the polymerizable material; and the at least one photoinitiator including an oxime ester compound; bringing the photocurable composition into contact with a template or a superstate; irradiating the photocurable composition with light to form a photocured layer; removing the template or the superstate from the photo-cured layer; forming a pattern on the substrate; processing the substrate on which the pattern has been formed in the forming; and manufacturing an article from the substrate processed in the processing.
• the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
• a process, method, article, or apparatus that comprises a list of features is not necessarily limited only to those features but may include other features not expressly listed or inherent to such process, method, article, or apparatus.
• the present disclosure is directed to a photocurable composition
• a photocurable composition comprising a polymerizable material and a photoinitiator, wherein the photoinitiator may include an oxime ester compound and the polymerizable material can comprise a multi-functional vinylbenzene monomer in an amount of at least 30 wt%.
• the photocurable composition of the present disclosure can have the advantage of being usable in inkjet adaptive planarization (LAP) processing by having a low viscosity, low shrinkage during curing and an exceptional high thermal stability.
• LAP inkjet adaptive planarization
• the photocurable composition of the present disclosure can be adapted that a UV shrinkage after forming a photo-cured layer at 23°C may be not greater than 4.0 %, or not greater than 3.5%, or not greater than 3.0%.
• a photo-cured layer formed from the photocurable composition can have a shrinkage after a baking treatment at 350°C of not greater than 3.5%, the baking treatment including 2 minutes baking of the photo-cured layer on a stainless steel plate having a temperature of 350°C.
• the linear shrinkage after the baking treatment at 350°C may be not greater than 3.0%, not greater than 2.5%, not greater than 2.0%, not greater than 1.5%, or not greater than 1.0%, or not greater than 0.5%.
• the oxime ester compound of the photoinitiator can have a structure of formula (1): R i (1), with Ri being an aromatic ring system or a heteroaromatic ring system, R2 being H or Ci-Cs alkyl, R3 being H or Ci-Cs alkyl.
• the oxime ester compound can have a structure of formula (2):
• the oxime ester compound may have a structure of formula (3):
• the oxime ester can have a structure of formula (4):
• the amount of the oxime ester compound of the photoinitiator can be at least 1.0 wt% based on the total weight of the photocurable composition, or at least 1 .5 wt%, or at least 2.0 wt%, or at least 2.5 wt%, or at least 3.0 wt%, or at least 3.5 wt%, or at least 4.0 wt%.
• the amount of the oxime ester compound may be not greater than 10 wt% based on the total weight of the photocurable composition, or not greater than 8 wt%, or not greater than 7 wt%, or not greater than 6 wt%, or not greater than 5 wt%, or not greater than 4 wt%.
• the amount of the oxime ester compound of the photoinitiator can be a value between any of the minimum and maximum numbers noted above.
• the photoinitiator of the photocurable composition can further include at least one photoinitiator which is not an oxime ester compound.
• the polymerizable material of the photocurable composition can be a major amount of the composition. In one embodiment, the amount of the polymerizable material can be at least 60 wt% based on the total weight of the photocurable composition, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or at least 92 wt%, or at least 95 wt%.
• the term multi-functional vinylbenzene of the polymerizable material relates to a polymerizable monomer containing one or more benzene rings and at least two vinyl groups directly attached to the one or more benzene rings.
• the multifunctional vinylbenzene can comprise at least three vinyl groups or at least four vinyl groups.
• the multi-functional vinylbenzene monomer can comprise two benzene rings and three vinyl groups attached to the benzene rings.
• a non-limiting example of such monomer can be 3,4’,5-trivinyl-l,rbiphenyl (3VPH).
• the amount of the multi-functional vinylbenzene monomer can be at least 30 wt% based on the total weight of the polymerizable material, such at least 35 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, or at least 95 wt%.
• the amount of the multi-functional vinylbenzene monomer may be not greater than 98 wt% based on the total weight of the polymerizable material, or not greater than 95 wt%, or not greater than 90 wt%, or not greater than 80 wt%, or not greater than 70 wt%, or not greater than 60 wt%, or not greater than 50 wt%.
• the amount of the multifunctional vinylbenzene monomer can be a value between any of the minimum and maximum numbers noted above.
• the polymerizable material can further comprise a multifunctional acrylate monomer.
• the multi-functional acrylate monomer can include at least two acrylate groups, or at least three acrylate groups, or at least four acrylate groups.
• the multi-functional acrylate monomer can include at least one acrylate group and at least one vinyl group.
• the term acrylate monomer relates to substituted and non- substituted acrylate monomers.
• Non-limiting examples of substituted acrylate monomers can be Ci-Cs alkylacrylate, for example, methacrylate or ethyl acrylate.
• the term “vinyl group” does not relate to a vinyl group which is part of an acrylate group and is a functional group by itself.
• the multi-functional acrylate monomer can include one acrylate group and two vinyl groups and an aromatic ring structure, for example, one or more benzene rings.
• the amount of the multi-functional acrylate monomer can be at least 20 wt% based on the total weight of the polymerizable material, or at least 30 wt%, or at least 40 wt%, or at least 50 wt%, or at least 60 wt%. In another aspect, the amount of the multi-functional acrylate monomer may be not greater than 70 wt% based on the total weight of the polymerizable material, or not greater than 60 wt%, or not greater than 50 wt%. The amount of the multifunctional acrylate monomer can be a value between any of the minimum and maximum numbers noted above.
• the polymerizable material can consist essentially of the multi-functional vinylbenzene monomer and the multi-functional acrylate monomer.
• a weight% ratio of the multi-functional vinylbenzene monomer to the multi-functional acrylate monomer can range from 2:1 to 1 :2, or from 1.5: 1 to 1 :1.5.
• consisting essentially of the multi-functional vinylbenzene monomer and the multi-functional acrylate monomer means that not more than 1 wt% of the polymerizable material include other types of polymerizable monomers, oligomers, or polymers.
• the polymerizable material can include next to the multi-functional vinylbenzene monomer and the multi-functional acrylate monomer other types of polymerizable compounds, for example, mono-functional monomers, or polymerizable oligomers, or polymerizable polymers.
• An amount of the other polymerizable compounds can be at least 1 wt% based on the total weight of the polymerizable material, or at least 5 wt%, or at least 10 wt%.
• the amount of other polymerizable compounds may not be greater than 30 wt%, or not greater than 20 wt%, or not greater than 15 wt%, or not greater than 10 wt%.
• the photocurable composition can be essentially free of a maleimide monomer.
• Essentially free of a maleimide monomer means herein that not more than 0.5 wt% of the polymerizable material may be a maleimide monomer.
• the photocurable composition can be free of a maleimide monomer.
• the photocurable composition can include 4-tert- butylcatechol (TBC) as a stabilizer in an amount of at least 0.05 wt% based on the total weight of the photocurable composition.
• TBC 4-tert- butylcatechol
• the amount of TBC can be at least 0.1 wt% based on the total weight of the photocurable composition, or at least 0.2 wt%, or at least 0.3 wt%.
• the amount of TBC may be not greater than 1 wt% based on the total weight of the photocurable composition, or not greater than 0.5 wt%, or not greater than 0.3 wt%, or not greater than 0.2 wt%.
• the photocurable composition of the present disclosure can be essentially free of a solvent.
• solvent relates to a compound which can dissolve or disperse the polymerizable monomers but does not itself polymerize during the photo-curing of the photocurable composition.
• the term “essentially free of a solvent” means herein an amount of solvent being not greater than 5 wt% based on the total weight of the photocurable composition.
• the amount of a solvent can be not greater than 3 wt%, not greater than 2 wt%, not greater than 1 wt%, or the photocurable composition can be free of a solvent, except for unavoidable impurities.
• the photocurable composition and the present disclosure can comprise a solvent in an amount higher than 5 wt% based on the total weight of the photocurable composition.
• the amount of solvent can be at least 7 wt% based on the total weight of the photocurable composition, or at least 10 wt%, or at least 15 wt%, at least 20 wt%, or at least 25 wt%.
• the amount of solvent may be not greater than 40 wt%, or not greater than 30 wt%, or not greater than 20 wt%, or not greater than 10 wt% based on the total weight of the photocurable composition.
• the curable composition of the present disclosure can have a low viscosity which may allow the use of these compositions in IAP applications.
• the viscosity of the curable composition at a temperature of 23°C can be not greater than 50 mPa s, such as not greater than 40 mPa s, or not greater than 30 mPa s, not greater than 20 mPa s, not greater than 15 mPa s, or not greater than 10 mPa- s.
• the viscosity may be at least 5 mPa s, or at least 7 mPa s.
• the photocurable composition can contain at least one optional additive.
• optional additives can be surfactants, dispersants, stabilizer, co-solvents, initiators, inhibitors, dyes, or any combination thereof.
• the present disclosure is directed to a laminate comprising a substrate and a photo-cured layer overlying the substrate, wherein the photo-cured layer can be formed from the photocurable composition described above.
• the laminate can further include one or more layers between the substrate and the cured layer, for example an adhesion layer.
• the present disclosure is further directed to a method of forming a photo-cured layer.
• the method can comprise applying the photocurable composition described above on a substrate, bringing the photocurable composition into contact with a template or superstate; irradiating the photocurable composition with light to form the photo-cured layer; and removing the template or superstate from the photo-cured layer.
• the light irradiation can be conducted with light having a wavelength between 250 nm to 760 nm. In a preferred aspect, the light irradiation may be conducted with light having a wavelength between 300 nm and 450 nm.
• the substrate and the solidified (photo-cured) layer may be subjected to additional processing to form a desired article, for example, by including an etching process to transfer an image into the substrate that corresponds to the pattern in one or both of the solidified layer and/or patterned layers that are underneath the solidified layer.
• the substrate can be further subjected to known steps and processes for device (article) fabrication, including, for example, curing, oxidation, layer formation, deposition, doping, planarization, etching, formable material removal, dicing, bonding, and packaging, and the like.
• the substrate may be processed to produce a plurality of articles (devices).
• the cured layer may be further used as an interlayer insulating film of a semiconductor device, such as LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM, or as a resist film used in a semiconductor manufacturing process.
• a semiconductor device such as LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM, or as a resist film used in a semiconductor manufacturing process.
• photocurable compositions including certain combinations of an oxime ester compound as photoinitiator and multi-functional vinylbenzene as part of the polymerizable material can be very suitable for IAP processing. It was possible to balance parameters important for IAP processing, such as a low viscosity, UV curing speed, low shrinkage during UV curing to obtain a flat surface, and high heat stability in order to make downstream processes possible at temperatures, such as 35O°C, or 400°C, or even 450°C.
• a first set of photocurable compositions was prepared comprising 50 parts by weight 3,3’-divinylbiphenyl (DVBP), 50 parts by weight m-xylene diacrylate (MXDA), 1 part by weight of nonionic fluorosurfactant FS 3100 (from Dupont), 0.3 parts by weight 4-tert-butylcatechol (TBC) and 1 part or 2 parts by weight photoinitiator.
• the compositions were varied by using different types and amounts of oxime ester photoinitiators.
• Comparative compositions Cl and C2 contained typical photoinitiators well known for photocurable compositions adapted for IAP processing, and which are not oxime esters: Irgacure 819 and 907.
• a second set of photocurable compositions was prepared by combining the following ingredients: 40 parts by weight 3,4’,5-trivinyl-l,l’-biphenyl (3VPH), 60 parts by weight 3,5- divinylbenzyl acrylate (DVB A), 1 part by weight of nonionic fluorosurfactant FS 3100 (from Dupont), 0.5 parts by weight TBC, and photoinitiator of varying type and amounts.
• the types of photoinitiator were the same as in the first set of photocurable compositions, except that as comparative examples was further used Irgacure 907.
• the amount of the photoinitiator varied by using 2-, 4-, and 6 parts by weight photoinitiator based on the total weight of the photocurable compositions.
• a further set of comparative photocurable compositions was prepared by using as polymerizable monomers the combination of 60 wt% MXDA and 35 wt% trimethylolpropane triacrylate, and 1 wt% surfactant FS2000M1.
• As photoinitiators were varied OXE02 and Irgacure 907 in amounts of 2 wt% and 4 wt%.
• Table 3 A summary of the compositions and test results can be seen in Table 3.
• the photocurable compositions were cured using an Anton Paar MCR-301 rheometer coupled to a UV curing system and heater.
• the sample was radiated with a mercury UV lamp with a 365 nm band filter.
• the light intensity was set to 38 mW/cm 2 and the UV radiation was conducted at room temperature (23°C).
• the distance between glass plate and measuring unit was reduced to a gap of 0.1mm.
• radicals generated by the photoinitiators were consumed by the inhibitor present in the resist, wherefore the storage modulus did not increase until all inhibitor was gone. This time period was recorded as induction time.
• the UV radiation exposure was continued until a storage modulus of IxlO 7 Pa was obtained.
• the thickness of the layers of the photocurable composition before curing was 35 microns, and the shrinkage was observed by tracking the change in the thickness of the layers during the UV curing.
• compositions made with photoinitiators OXE01, OXE02, and OXE03 all had a lower shrinkage during UV curing than comparative compositions (C1-C8) using photoinitiators Irgacure 819 or Irgacure 907 at all photoinitiator concentrations.
• a UV-cured layer was prepared by depositing a 500 nm thick liquid film of the photocurable composition unto a blank fused silica template.
• the Anton Paar MCR-301 rheometer coupled with a Hamamatsu Lightningcure LC8 UV source described above was used.
• the liquid film was radiated with a light intensity of 38 mW/cm2 at 365 nm for 263 seconds, which corresponds to a curing energy dosage of 10 J/cm 2 .
• the photo-cured film was subj ected to a high temperature baking treatment by placing the UV-cured film for two minutes on a hot plate having a temperature of 350°C under nitrogen.
• the thickness of the film before and after the baking was measured with a JA Woollam Spectroscopic Ellipsometer M-2000 X-210.
• the measured thermal shrinkage values are summarized in Tables 1, 2, and 3. It can be seen that especially the second set of photocurable compositions summarized in Table 2, had a very low thermal shrinkage of below 3 percent if photoinitiators OXE02 or OXE03 were used. However, photoinitiator OXE02 could not achieve a thermal shrinkage of below 4.5 percent if the monomer combination did not include the tri-functional vinyl monomer but instead a trifunctional acrylate monomer, see C9, CIO, and Cl 1 of Table 3. However, the thermal shrinkage when using photoinitiator OXE02 in this set of experiments was also lower in comparison to the use of photoinitiator Irgacure 907.
• the viscosities of the photocurable compositions were measured using a Brookfield Viscometer LVDV-II + Pro at 200 rpm, with a spindle size #18 and a spin speed of 135 rpm.
• LVDV-II + Pro Brookfield Viscometer LVDV-II + Pro at 200 rpm, with a spindle size #18 and a spin speed of 135 rpm.
• For the viscosity testing about 6-7 mL of sample liquid was added into the sample chamber, enough to cover the spindle head. The sample contained in the chamber was about 20 minutes equilibrated to reach the desired measuring temperature of 23 °C before the actual measurement was started. For all viscosity testing, at least three measurements were conducted and an average value was calculated.

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