WO2023051686A1 - 感光分子及其应用 - Google Patents

感光分子及其应用 Download PDF

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WO2023051686A1
WO2023051686A1 PCT/CN2022/122570 CN2022122570W WO2023051686A1 WO 2023051686 A1 WO2023051686 A1 WO 2023051686A1 CN 2022122570 W CN2022122570 W CN 2022122570W WO 2023051686 A1 WO2023051686 A1 WO 2023051686A1
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group
resin composition
photosensitive
aryl
photosensitive resin
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French (fr)
Inventor
刘付林
赵建章
秦德君
吴琦
许成强
张雪
胡梦雨
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Dalian University of Technology
Huawei Technologies Co Ltd
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Dalian University of Technology
Huawei Technologies Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • 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 embodiments of the present application relate to the technical field of photosensitive materials, in particular to a photosensitive molecule, a photoacid generator, a photosensitive resin composition, a cured film and an electronic device.
  • Chemical Amplification (Chemical Amplification, CA) photosensitive resin composition has high photosensitivity and sensitivity, and can form clear ultra-fine patterns in the photolithography process.
  • the basic principle is that the photoacid generator (Photo acid Generator, PAG) is Light source irradiates to generate acid, and then during the baking process, the generated acid continues to catalyze the cross-linking of the cross-linking agent, or the cross-linking of the cross-linking agent and the polymer resin, resulting in the development of the exposed and unexposed areas of the polymer resin.
  • solubility in the solution that is, the solubility of the exposed area decreases sharply due to crosslinking, while the non-exposed area still maintains good solubility, thus showing the photolithographic pattern.
  • photosensitive dielectric materials In recent years, chemically amplified photoacid generators are gradually used in photosensitive dielectric materials in the field of semiconductor packaging.
  • photosensitive dielectric materials As one of the important components of semiconductor packaging materials, photosensitive dielectric materials not only need to have good photolithography performance, but also need to have good comprehensive properties after curing. Among them, the comprehensive performance of PAG is very important to the influence of lithographic performance.
  • i-line (365nm) photosensitive resin composition the absorption of PAG in i-line determines the sensitivity of lithographic composition.
  • after light exposure The efficiency of photoacid generation and the solubility of molecules will also affect the final pattern fineness.
  • the photosensitive medium material needs to remain in the device as an insulating layer.
  • the formulation of the composition needs to add heterocyclic compounds, solubilizers, coupling agents and other auxiliary agents, making the formulation of the existing photosensitive resin composition very complicated.
  • the embodiment of the present application provides a photosensitive molecule, a photoacid generator containing the photosensitive molecule, and a photosensitive resin composition.
  • the photoacid generator containing the photosensitive molecule can effectively improve the overall photolithographic effect of the photosensitive resin composition and improve pattern resolution. High efficiency, improve the adhesion between the cured resin and the interface of copper, silicon, etc., and reduce the complexity of the formulation of the photosensitive resin composition.
  • the first aspect of the embodiment of the present application provides a photosensitive molecule.
  • the molecular structure of the photosensitive molecule includes a naphthalimide structure, a substituted sulfonic acid group connected to the nitrogen atom in the naphthalimide structure, and a The heterocyclic group X connected to the naphthalene ring in the naphthalimide structure, and R 2 connected to the heterocyclic group;
  • the heterocyclic group X is selected from heterocyclic groups containing O, N or S; the R is selected from halogen, aryl, aralkyl, alkaryl, haloaryl, alkoxyaryl, ring Oxyalkyl, epoxyaryl, hydroxyalkyl, hydroxyaryl, hydroxyalkyl substituted hydroxyaryl, aminoaryl, alkyl ether, aryl ether, epoxyalkoxy, epoxyalkoxy Substituted aryl, or a group containing alkoxysilane.
  • the photosensitive molecules provided in the examples of this application are obtained by derivatization of naphthalimide.
  • the structure of naphthalimide is relatively stable, the synthesis is simple, and the yield is high.
  • By introducing the heterocyclic structure X and Specific R2 group can endow photosensitive molecules with multiple functions. When used as a photoacid generator, it can effectively improve the pattern resolution of the photosensitive resin composition, improve the adhesion between the cured resin and the interface of copper, silicon, etc., simplify the Composition recipe.
  • the heterocyclic group X introduced on the naphthalene ring has a certain ability to resist ion migration and special electronic effects, which can effectively improve the light absorption of the photoacid generator at the i-line (365nm), reduce the light absorption at visible light, and improve Photolithographic effect; at the same time, the heterocyclic group X is easy to derivatize, and the introduction of the heterocyclic group X is conducive to the further introduction of functional groups R 2 of various structures, thereby endowing the photoacid generator with more functions.
  • the substituted sulfonic acid group is represented as -SO 3 R 1 , and the R 1 is selected from an alkyl group, an aryl group, an alkylaryl group, a halogenated alkyl group or a halogenated aryl group.
  • the molecular structure of the photosensitive molecule further includes R 3 connected to the naphthalene ring in the naphthalimide structure, and R 3 includes hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, Aralkyl, alkaryl, alkenaryl, aralkenyl, alkynaryl, aralkynyl, haloalkyl, haloaryl, alkoxyalkyl, alkoxyaryl, epoxyalkyl, hydroxyl Alkyl, hydroxyaryl, hydroxyalkyl-substituted hydroxyaryl, aminoalkyl, aminoaryl, cyanoalkyl, cyanoaryl, carboxyalkyl, carboxyaryl, esteralkyl, esteraryl , alkylcarbonyl, arylcarbonyl, alkyl alcohol, alkyl ether, aryl ether, epoxyalkyloxy, epoxyalkyloxy substituted
  • the molecular structure of the photosensitive molecule can be as shown in formula (I):
  • the heterocyclyl X and R 3 can be at any carbon position on the naphthalene ring, that is, the heterocyclyl X and R 3 can be connected to a carbon atom at any position on the naphthalene ring.
  • the heterocyclyl groups X and R3 are respectively located at any carbon positions of different rings of naphthalene.
  • R 2 can also be located at any carbon position of the heterocyclic group X.
  • the heterocyclic group X refers to an organic cyclic group in which the atoms constituting the ring have other atoms besides carbon atoms.
  • the heterocyclic group can have one heteroatom or two or more heteroatoms. Atoms, heteroatoms can be one kind of atom or two different kinds of atoms; the heterocyclic group can be connected to the carbon atom on the naphthalene ring through a heteroatom, or connected to the carbon atom on the naphthalene ring through a carbon atom .
  • X may be selected from a five-membered heterocyclic group, a six-membered heterocyclic group, or a benzoheterocyclic group containing O, N or S.
  • the five-membered heterocyclic group can specifically be derived from five-membered heterocyclic compounds such as furan, thiophene, pyrrole, thiazole, imidazole, triazole, tetrazole;
  • the six-membered heterocyclic group can be derived from pyridine, pyrazine, pyrimidine , pyridazine and other six-membered heterocyclic compounds.
  • the X is a five-membered or six-membered heterocyclic group containing three nitrogen atoms, and one of the nitrogen atoms is connected to the carbon atom of the naphthalene ring.
  • X is a five-membered heterocyclic group containing three nitrogen atoms, and the molecular structure of the photosensitive molecule is shown in formula (I-a):
  • the X is a five-membered or six-membered heterocyclic group containing four nitrogen atoms, and one of the nitrogen atoms is connected to a carbon atom of the naphthalene ring.
  • X is a five-membered heterocyclic group containing four nitrogen atoms, and the molecular structure of the photosensitive molecule is shown in formula (I-b):
  • R 2 when R 2 is a group containing an aryl group, the aryl group can be phenyl, naphthyl, etc.
  • R 2 is a group containing a terminal hydroxyl group, specifically, R 2 can be a hydroxyalkyl group or a hydroxyaryl group.
  • R 2 is a group containing a terminal hydroxyl group, which can also adjust the alkali solubility of the resin composition, thereby improving the solubility of the resin composition in an alkaline developer, reducing the phenomenon of residual glue in exposed or non-exposed areas, and improving pattern resolution.
  • R 2 is a group containing an epoxy group, specifically a group terminated by an epoxy group, such as an epoxyalkyl group, epoxyaryl group, epoxyalkyloxy group, ring Oxyalkoxy substituted aryl, etc.
  • the epoxy group contained in R 2 can increase the degree of crosslinking of the resin, thereby effectively adjusting the flatness of the pattern and improving the photolithographic effect.
  • epoxyalkyl group can be glycidyl group, epoxybutyl group, epoxypentyl, epoxyhexyl etc.; Oxygen, epoxypentyloxy, epoxyhexyloxy, etc.; epoxyalkyloxy substituted aryl can be glycidoxy substituted phenyl, epoxybutoxy substituted phenyl, epoxypentyloxy substituted Phenyl, epoxyhexyloxy substituted phenyl, etc.
  • R 2 is an alkoxysilane-containing group
  • the alkoxysilane-containing group may include ⁇ -aminopropyltriethoxysilane, ⁇ -ammonia Propyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, ⁇ -Glycidyloxypropyltrimethoxysilane, ⁇ -Methacryloxypropyltrimethoxysilane, ⁇ -Mercaptopropyltrimethoxysilane, Vinyltriethoxysilane, Vinyltrimethoxysilane group of silane, vinyltris( ⁇ -methoxyethoxy)silane.
  • R 2 is an alkoxysilyl-terminated group.
  • R 2 is a group containing alkoxysilane, which can effectively improve the adhesion between the cured film of the photosensitive resin composition and substrates such as silicon wafers and metal layers, and avoid the generation of bleaching phenomenon, and the silicon-oxygen bond has relatively strong Good flexibility and heat resistance, can improve the flexibility and heat resistance of cured film.
  • the carbon-containing groups when the R 1 , R 2 , and R 3 are carbon-containing groups, the carbon-containing groups have a suitable number of carbon atoms so that the photoacid generator has suitable solubility in organic solvents, and at the same time has Good photosensitivity and photoacid generation ability are conducive to improving the photolithographic effect.
  • the number of carbon atoms when R 1 , R 2 , and R 3 are carbon-containing groups, the number of carbon atoms is 1-20. In some embodiments of the present application, when R 1 , R 2 , and R 3 are carbon-containing groups, the number of carbon atoms is 4-20.
  • the molecular structures of the photosensitive molecules are shown in formulas 1-a to 23-a:
  • the second aspect of the embodiment of the present application provides a photosensitive molecule.
  • the molecular structure of the photosensitive molecule includes a naphthalimide structure, the substituted sulfonic acid group connected to the nitrogen atom in the naphthalimide structure, and the The heterocyclic group X connected to the naphthalene ring in the naphthalimide structure, and R 2 connected to the heterocyclic group; the photosensitive molecule is prepared by the following method:
  • the bromine substituent in 4-bromo-1,8-naphthalene dicarboxylic anhydride is grafted to replace the heterocyclic group-XR 2 , and the anhydride group is grafted to replace the sulfonic acid group after amidation to obtain a photosensitive molecule;
  • X includes Heterocyclyl containing O, N or S;
  • R2 includes halogen, aryl, aralkyl, alkaryl, haloaryl, alkoxyaryl, epoxyalkyl, epoxyaryl, hydroxyalkane group, hydroxyaryl group, hydroxyalkyl substituted hydroxyaryl group, aminoaryl group, alkyl ether group, aryl ether group, epoxyalkoxyl group, epoxyalkoxyl substituted aryl group, or alkoxysilane containing of a group.
  • the third aspect of the embodiment of the present application provides a method for preparing photosensitive molecules, including:
  • the bromine substituent in 4-bromo-1,8-naphthalene dicarboxylic anhydride is grafted to replace the heterocyclic group-XR 2 , and after the anhydride group is amidated, the sulfonic acid group is grafted to replace the sulfonic acid group to obtain a photosensitive molecule.
  • the photosensitive molecule includes the naphthalimide structure, the substituted sulfonic acid group connected to the nitrogen atom in the naphthalimide structure, and the heterocyclic group X connected to the naphthalene ring in the naphthalimide structure, and The R 2 connected by the heterocyclic group; wherein, X includes a heterocyclic group containing O, N or S; R 2 includes halogen, aryl, aralkyl, alkaryl, halogenated aryl, alkoxyaryl Epoxyalkyl, epoxyaryl, hydroxyalkyl, hydroxyaryl, hydroxyalkyl substituted hydroxyaryl, aminoaryl, alkyl ether, aryl ether, epoxyalkoxy, epoxy Alkoxy substituted aryl, or a group containing alkoxysilane.
  • the fourth aspect of the embodiment of the present application provides a photoacid generator, the photoacid generator includes the photosensitive molecule described in the first aspect or the second aspect of the embodiment of the present application, or includes the one prepared by the preparation method described in the third aspect Photosensitive molecules.
  • the fifth aspect of the embodiments of the present application provides the application of the photosensitive molecules or photoacid generators mentioned above in the patterning process.
  • the sixth aspect of the embodiment of the present application provides a photosensitive resin composition, which includes a resin or a resin precursor, a crosslinking agent, and the photoacid generator described in the fourth aspect of the embodiment of the present application.
  • the photosensitive resin composition of the present application may be a negative photosensitive resin composition. After the negative photosensitive resin composition is exposed and developed, the unexposed part is washed away, and the exposed part remains.
  • the patterning principle of the negative photosensitive resin composition of the embodiment of the present application is: the photoacid generator is irradiated by the light source to generate acid (substituted or non-substituted sulfonic acid), and in the process of subsequent heat treatment, the generated acid continues to catalyze the generation of crosslinking agent.
  • Cross-linking or cross-linking between the cross-linking agent and the polymer resin, leads to the formation of a significant solubility difference between the exposed area and the unexposed area of the polymer resin in the developer solution, that is, the solubility of the exposed area decreases sharply due to cross-linking, rather than The exposed area still maintains good solubility, and eventually the unexposed area is washed away, and the exposed area remains, thus showing the photolithographic pattern.
  • the photosensitive resin composition of the present application may also be a positive photosensitive resin composition. After the positive photosensitive resin composition is exposed and developed, the exposed part is washed away, and the unexposed part remains.
  • the photoacid generator in the photosensitive resin composition is 0.5-20 parts by mass. In some embodiments, the photoacid generator can be 3-15 parts by mass. In some embodiments, the photoacid generator can be 5-10 parts by mass.
  • the resin or resin precursor in the photosensitive resin composition can be selected according to actual application requirements.
  • the photosensitive resin composition may contain one or more resin components.
  • the resin includes one or more of phenolic resin, epoxy resin, acrylic resin, benzocyclobutene resin, benzoxazole resin, and polyimide resin.
  • the resin precursor includes a phenolic resin precursor, an epoxy resin precursor, an acrylic resin precursor, a benzocyclobutene resin precursor, a benzoxazole resin precursor, a polyimide resin precursor one or more of the body.
  • the weight average molecular weight of the resin may be 5,000-100,000; in some embodiments, the weight average molecular weight of the resin may be 10,000-80,000; in some embodiments, the weight average molecular weight of the resin may be 20,000-50,000.
  • the cross-linking agent includes a polyhydric cross-linking agent
  • the polyhydric cross-linking agent may be a compound monomer containing a benzyl alcohol structure. Under acidic conditions, the monomer can be cross-linked to form polymeric macromolecules, and the solubility is reduced.
  • the compound monomer containing benzyl alcohol structure can be the compound 2,6-bis(hydroxymethyl)-4-cresol shown in formula A, or the compound shown in formula B.
  • the crosslinking agent in the photosensitive resin composition is 1-30 parts by mass. In some embodiments, the crosslinking agent can be 5-25 parts by mass. In some embodiments, the crosslinking agent can be 10-20 parts by mass.
  • the organic solvent in the photosensitive resin composition is 130-740 parts by mass. In some embodiments, the organic solvent may be 195-520 parts by mass. In some embodiments, the organic solvent may be 240-390 parts by mass.
  • the photosensitive resin composition further includes an organic solvent.
  • the organic solvent may be one or more of ester, ketone, ether or amide organic solvents.
  • the exposure energy required to act on the photosensitive resin composition is 80mJ/cm 2 -170mJ/cm 2 .
  • the seventh aspect of the embodiment of the present application provides a pattern forming method, including:
  • the resin pattern is heat-treated.
  • the eighth aspect of the embodiment of the present application provides a cured film, the cured film is the cured film of the photosensitive resin composition described in the third aspect.
  • the resolution of the pattern on the cured film is less than or equal to 4 ⁇ m.
  • the inclination angle of the pattern on the cured film is greater than 65°.
  • the embodiment of the present application also provides an electronic device, the electronic device includes the cured film described in the eighth aspect of the embodiment of the present application; or the electronic device includes a cured film formed by curing the composition containing the photosensitive molecule described in the first aspect Cured film.
  • the electronic device includes a silicon chip or a metal layer, the cured film is arranged on the silicon chip or the metal layer, and the adhesion between the cured film and the silicon chip reaches the national standard "GBT9286-1998 ⁇ Reliability test 3B or 4B standard; the adhesion between the cured film and the metal layer meets the national standard reliability test 4B or 5B standard.
  • the cured film is used as a protective layer, a passivation layer, an interlayer insulation layer, a buffer layer, a planarization layer, an ⁇ -ray shielding layer or a rewiring layer in the electronic device.
  • FIG. 1 is a schematic diagram of a packaging structure of an electronic device 100 provided in an embodiment of the present application
  • Fig. 2 and Fig. 3 are the lithographic effect diagrams of the photosensitive resin composition of the embodiment 3 of the present application;
  • Fig. 4 is the lithography effect figure of the photosensitive resin composition of the embodiment 4 of the present application.
  • Fig. 5 is the lithography effect diagram of the photosensitive resin composition of comparative example 1 of the present application.
  • FIG. 6 and FIG. 7 are photolithography effect diagrams of the photosensitive resin composition of Comparative Example 2 of the present application.
  • Negative adhesives are widely used in the field of chip packaging due to their excellent heat resistance and mechanical properties.
  • the current mainstream route of negative adhesives is to introduce photocrosslinkable groups (such as acrylics) into the molecular structure of the resin. Upon exposure to light, photoinitiators generate free radicals that initiate crosslinking of the exposed polymers, resulting in solubility differences.
  • photocrosslinkable groups such as acrylics
  • photoinitiators Upon exposure to light, photoinitiators generate free radicals that initiate crosslinking of the exposed polymers, resulting in solubility differences.
  • the principle of chemical amplification has been gradually introduced from fine photoresist to photosensitive medium materials.
  • NI photoacid generator As an example, as shown in formula C, it is the NI photoacid generator Mechanism of photoacid generation, NI type photoacid generator undergoes Norrish I type cleavage under light to generate sulfonic acid, and the generated sulfonic acid can trigger the crosslinking reaction of polyhydroxy crosslinking agent at the exposure place, because the acid only acts A catalytic effect rather than participating in the reaction, so only a small amount of photoacid generator is needed to continuously catalyze the crosslinking reaction at the exposed place.
  • NI type photoacid generator undergoes Norrish I type cleavage under light to generate sulfonic acid, and the generated sulfonic acid can trigger the crosslinking reaction of polyhydroxy crosslinking agent at the exposure place, because the acid only acts A catalytic effect rather than participating in the reaction, so only a small amount of photoacid generator is needed to continuously catalyze the crosslinking reaction at the exposed place.
  • the embodiment of the present application provides a photosensitive molecule, a photoacid generator comprising the photosensitive molecule, and a photosensitive resin composition comprising the photoacid generator.
  • the photosensitive molecule is a naphthalimide derivative.
  • the photosensitive molecule can obtain the performance advantages of the two structures of the naphthalimide and the heterocyclic structure, and improve the light absorption characteristics of the photosensitive molecule, and the heterocyclic structure
  • the introduction of the derivatization increases the range of derivatization.
  • the photosensitive molecule By introducing various functional groups on the heterocycle or naphthalene ring, it can endow the photosensitive molecule with multifunctionality, so that the main structure of naphthalimide, which has no effect after illumination, has adhesion, cross-linking Linkability, etc., to further increase the solubility difference between the exposed area and the non-exposed area, and finally effectively improve the overall photolithographic effect of the photosensitive resin composition, improve the pattern resolution, and improve the adhesion of the cured resin on the interface of silicon, copper, etc., and at the same time Reduce the complexity of the formulation of the photosensitive resin composition.
  • the embodiment of the present application provides a photosensitive molecule.
  • the molecular structure of the photosensitive molecule includes a naphthalimide structure, a substituted sulfonic acid group connected to the nitrogen atom in the naphthalimide structure, and a substituted sulfonic acid group connected to the naphthalene ring in the naphthalimide structure.
  • the photosensitive molecules in the embodiments of the present application can be used as photoacid generators, or used in other application scenarios that require photosensitization.
  • the photosensitive molecules used as photoacid generators will be introduced in detail below.
  • the photoacid generators provided in the examples of the present application are obtained by derivatization of naphthalimide.
  • the structure of naphthalimide is relatively stable, the synthesis is simple, and the yield is high.
  • the introduced heterocyclyl X and R groups have certain resistance Ion mobility and special electronic effects can well control the light absorption range and absorbance of photoacid generators, effectively improve the light absorption of photoacid generators at the i-line, reduce light absorption at visible light, and improve photolithographic effects; And can improve the resin composition cured film that comprises this photoacid generator to have good silicon interface, copper interface adhesion performance;
  • functional group R 2 can also give photoacid generator more functions, improve photolithography effect and The comprehensive performance of the resin composition simplifies the formulation of the photosensitive resin composition.
  • the substituted sulfonic acid group is represented as -SO 3 R 1 , and R 1 may include an alkyl group, an aryl group, an alkylaryl group, a halogenated alkyl group or a halogenated aryl group.
  • the alkyl group can be a C 1 -C 20 alkyl group, such as methyl group, ethyl group and the like.
  • Aryl can be phenyl.
  • the alkylaryl group may be a C 7 -C 20 alkylaryl group, such as methylphenyl, ethylphenyl, etc.
  • the haloalkyl group can be a C 1 -C 20 haloalkyl group, such as trifluoromethyl, trifluoroethyl, etc.
  • the halogenated aryl group can be a C 6 -C 20 halogenated aryl group, such as fluorophenyl, bromophenyl, etc.
  • the molecular structure of the photoacid generator also includes R3 connected to the naphthalene ring in the naphthalimide structure, and R3 is selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, aromatic Alkyl, alkaryl, alkenaryl, aralkenyl, alkynaryl, aralkynyl, haloalkyl, haloaryl, alkoxyalkyl, alkoxyaryl, epoxyalkyl, hydroxyalkane hydroxyaryl, hydroxyalkyl-substituted hydroxyaryl, aminoalkyl, aminoaryl, cyanoalkyl, cyanoaryl, carboxyalkyl, carboxyaryl, esteralkyl, esteraryl, An alkylcarbonyl group, an arylcarbonyl group, an alkyl alcohol group, an alkyl ether group, an aryl ether group, an epoxyalkyl
  • the molecular structure of the photoacid generator can be as shown in formula (I):
  • the heterocyclyl X, R 3 can be at any carbon position on the naphthalene ring, that is, the heterocyclyl X, R 3 can be connected to any carbon position on the naphthalene ring.
  • the heterocyclyl groups X and R3 are respectively located at any carbon positions of different rings of naphthalene.
  • R 2 can also be located at any carbon position of the heterocyclic group X.
  • the halogen may include fluorine, chlorine, bromine, and iodine.
  • the specific selection ranges of various groups of R3 may be the same as the selection ranges of R2 .
  • the aryl group can be phenyl (such as formula 1-a and 2-a); the aralkyl group can be benzyl, phenethyl, etc.; the alkaryl group can be Methyl substituted phenyl (such as formula 9-a), ethyl substituted phenyl, etc.; halogenated aryl can be fluorophenyl (such as formula 4-a), bromophenyl, chlorophenyl, etc.; Oxyaryl can be methoxyphenyl (such as formula 8-a), ethoxyphenyl, etc.; epoxyalkyl can be epoxypropyl, epoxybutyl, epoxypentyl, epoxyhexyl etc.; Epoxy aryl can be epoxy ethyl phenyl, epoxy propyl phenyl; Hydroxyalkyl can include hydroxy n-butyl, hydroxy isopropyl (such as formula 7
  • the carbon-containing groups when R 1 , R 2 , and R 3 are carbon-containing groups, the carbon-containing groups have a suitable number of carbon atoms so that the photoacid generator has suitable solubility in organic solvents, and at the same time has better Excellent photosensitivity and photoacid generation ability, which is beneficial to improve the photolithography effect.
  • the number of carbon atoms when R 1 , R 2 , and R 3 are carbon-containing groups, the number of carbon atoms is 1-20.
  • the number of carbon atoms can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 , 15, 16, 17, 18, 19, 20.
  • R 2 is a group containing a terminal hydroxyl group, specifically, R 2 can be a hydroxyalkyl group or a hydroxyaryl group.
  • R2 is a group containing a terminal hydroxyl group, which can also adjust the alkali solubility of the resin composition, thereby improving the solubility of the resin composition in alkaline developer, reducing the residual glue phenomenon in exposed or non-exposed areas, and improving pattern resolution and Regularity of graphic appearance.
  • R 2 is a group containing an epoxy group, specifically a group terminated by an epoxy group, such as an epoxyalkyl group, epoxyaryl group, epoxyalkyloxy group, ring Oxyalkoxy substituted aryl, etc.
  • the epoxy group contained in R 2 can increase the degree of crosslinking of the resin, thereby effectively adjusting the flatness of the pattern and improving the photolithography effect.
  • epoxyalkyl group can be epoxypropyl group, epoxybutyl group, epoxypentyl, epoxyhexyl etc.; Oxygen, epoxyhexyloxy, etc.; epoxyalkyloxy substituted aryl can be glycidoxy substituted phenyl, epoxybutoxy substituted phenyl, epoxypentyloxy substituted phenyl, epoxyhexyl Oxygen substituted phenyl, etc.
  • R 2 is an alkoxysilane-containing group
  • an alkoxysilane-containing group may include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyl Trimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, ⁇ - Glycidyloxypropyltrimethoxysilane, ⁇ -Methacryloxypropyltrimethoxysilane, ⁇ -Mercaptopropyltrimethoxysilane, Vinyltriethoxysilane, Vinyltrimethoxysilane , Groups of vinyl tris( ⁇ -methoxyethoxy)silane.
  • the alkoxysilane part in R2 is derived from the above-mentioned alkoxysilane.
  • R 2 is an alkoxysilyl-terminated group, that is, the end of R 2 is an alkoxysilyl group.
  • R 2 is a group containing alkoxysilane, which can effectively improve the adhesion between the cured film of the photosensitive resin composition and substrates such as silicon wafers and metal layers, and avoid the generation of bleaching phenomenon, and the silicon-oxygen bond has relatively strong Good flexibility can improve the flexibility of the cured film, and the alkoxysilane has a large steric hindrance effect, which is conducive to maintaining the heat resistance of the cured resin film and can improve the stability of the device retaining the cured film.
  • a heterocyclic group refers to an organic ring group in which the atoms constituting the ring have other atoms besides carbon atoms.
  • the heterocyclic group can have one heteroatom or two or more heteroatoms , the heteroatom can be one kind of atom or two different kinds of atoms; the heterocyclic group can be connected to the carbon atom on the naphthalene ring through a heteroatom, or can be connected to the carbon atom on the naphthalene ring through a carbon atom.
  • X may be selected from a five-membered heterocyclic group, a six-membered heterocyclic group, or a benzoheterocyclic group containing O, N or S.
  • the five-membered heterocyclic group can specifically be derived from five-membered heterocyclic compounds such as furan, thiophene, pyrrole, thiazole, imidazole, triazole, tetrazole;
  • the six-membered heterocyclic group can be derived from pyridine, pyrazine, pyrimidine , pyridazine and other six-membered heterocyclic compounds.
  • the heterocyclic group X is a five-membered or six-membered heterocyclic group containing three nitrogen atoms, and one of the nitrogen atoms is connected to a carbon atom of the naphthalene ring.
  • X is a five-membered heterocyclic group containing three nitrogen atoms, and the molecular structure of the photoacid generator is shown in formula (I-a):
  • the heterocyclic group X is a five-membered or six-membered heterocyclic group containing four nitrogen atoms, and one of the nitrogen atoms is connected to a carbon atom of the naphthalene ring.
  • X is a five-membered heterocyclic group containing four nitrogen atoms, and the molecular structure of the photoacid generator is shown in formula (I-b):
  • the heterocyclic group X is a five-membered or six-membered heterocyclic group containing three nitrogen atoms or four nitrogen atoms, which can be synthesized by reacting -N3 on the naphthalene ring with ethynyl or formyl It can be realized without purification, and the electric absorption of this structure can better control the light absorption wavelength of the photoacid generator.
  • nitrogen azoles are easy to form complexes with metal ions (such as copper ions), which can effectively reduce the absorption of copper ions and other metal ions.
  • the migration and diffusion in the cured film of the resin composition is also conducive to improving the ability of the resin composition itself to interact with the copper interface and the silicon interface.
  • the molecular structure of the photoacid generator is shown in formulas 1-a to 23-a:
  • the embodiment of the present application provides a preparation method of a photoacid generator, comprising:
  • the bromine substituent in 4-bromo-1,8-naphthalene dicarboxylic anhydride is grafted to replace the heterocyclic group-XR 2 , and after the anhydride group is amidated, the sulfonic acid group is grafted to replace the sulfonic acid group to obtain a photoacid generator, wherein, X includes heterocyclic groups containing O, N or S; R includes halogen, aryl, aralkyl, alkaryl, haloaryl, alkoxyaryl, epoxyalkyl, epoxyaryl, Hydroxyalkyl, hydroxyaryl, hydroxyalkyl-substituted hydroxyaryl, aminoaryl, alkyl ether, aryl ether, epoxyalkyloxy, epoxyalkyloxy-substituted aryl, or alkoxy-containing groups of silanes.
  • the bromine substituent in 4-bromo-1,8-naphthalene dicarboxylic anhydride may be azide, and then the substituted heterocyclic group -Grafting of XR 2 .
  • the azidation process may be using sodium azide.
  • the process of amidation of anhydride groups may be by adding an amidation agent, specifically including hydroxylamine hydrochloride, sodium bicarbonate may also be added during the amidation process, and the process of grafting substituted sulfonic acid groups may be by adding substituted sulfonic anhydride.
  • an amidation agent specifically including hydroxylamine hydrochloride, sodium bicarbonate may also be added during the amidation process
  • the process of grafting substituted sulfonic acid groups may be by adding substituted sulfonic anhydride.
  • photoacid generator 1-a its preparation method may specifically include:
  • the embodiment of the present application also provides a photosensitive resin composition, which includes a resin or a resin precursor, a crosslinking agent, the photoacid generator mentioned in the embodiment of the present application, and an organic solvent.
  • the photosensitive resin composition of the present application may be a negative photosensitive resin composition. After the negative photosensitive resin composition is exposed and developed, the unexposed part is washed away, and the exposed part remains.
  • the patterning principle of the negative photosensitive resin composition of the embodiment of the present application is: the photoacid generator is irradiated by the light source to generate acid (substituted or non-substituted sulfonic acid), and in the process of subsequent heat treatment, the generated acid continues to catalyze the generation of crosslinking agent.
  • Cross-linking or cross-linking between the cross-linking agent and the polymer resin, leads to the formation of a significant solubility difference between the exposed area and the unexposed area of the polymer resin in the developer solution, that is, the solubility of the exposed area decreases sharply due to cross-linking, rather than The exposed area still maintains good solubility, and eventually the unexposed area is washed away, and the exposed area remains, thus showing the photolithographic pattern.
  • the photosensitive resin composition of the present application may also be a positive photosensitive resin composition. After the positive photosensitive resin composition is exposed and developed, the exposed part is washed away, and the unexposed part remains.
  • the patterning principle of the positive-type photosensitive resin composition of the embodiment of the present application is: during the pre-baking process, the vinyl ether in the composition reacts with the hydroxyl groups on the resin molecular chain, and is insoluble in alkaline developing solution. After exposure, PAG generates H + , catalyzing the removal of vinyl ether in the exposed area, exposing the original hydroxyl group, and becoming soluble in alkaline developer, while the non-exposed area is still insoluble.
  • the photoacid generator in the photosensitive resin composition may be 0.5-20 parts by mass. In some embodiments, the photoacid generator in the photosensitive resin composition is 3-15 parts by mass. In some embodiments, the photoacid generator in the photosensitive resin composition is 7-12 parts by mass. In a specific embodiment, the mass parts of the photoacid generator in the photosensitive resin composition are 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 copies.
  • the photoacid generator of the embodiment of the present application has a high absorbance at the i-line, and the photoacid generator has high photosensitivity and photoacid generating ability, so that it can better form acid and catalyze the occurrence of crosslinking reaction. Improve the solubility difference between the exposed area and the non-exposed area, and improve the resolution of the pattern.
  • the photoacid generators in the embodiments of the present application are universally applicable to resins and have no special requirements.
  • the resin or resin precursor in the photosensitive resin composition can be selected according to actual application requirements, and the resin or resin precursor can be prepared by itself or purchased from the market.
  • the photosensitive resin composition may contain one or more resin components.
  • the resin includes one or more of phenolic resin, epoxy resin, acrylic resin, benzocyclobutene resin, benzoxazole resin, and polyimide resin.
  • the resin precursor includes phenolic resin precursor, epoxy resin precursor, acrylic resin precursor, benzocyclobutene resin precursor, benzoxazole resin precursor, polyimide resin precursor one or more of .
  • the weight average molecular weight of the resin may be 5,000-100,000; in some embodiments, the weight average molecular weight of the resin may be 10,000-80,000; in some embodiments, the weight average molecular weight of the resin may be 20,000-50,000.
  • the cross-linking agent includes a polyhydroxy cross-linking agent
  • the cross-linking agent may be a compound monomer containing a benzyl alcohol structure.
  • the monomer can be cross-linked to form polymeric macromolecules, and the solubility is reduced.
  • the compound monomer containing benzyl alcohol structure can be the compound 2,6-bis(hydroxymethyl)-4-cresol shown in formula A, or the compound (MBHP) shown in formula B .
  • the crosslinking agent in the photosensitive resin composition is 1-30 parts by mass. In some embodiments, the crosslinking agent in the photosensitive resin composition is 5-25 parts by mass. In some embodiments, the crosslinking agent in the photosensitive resin composition is 10-20 parts by mass.
  • the organic solvent in the photosensitive resin composition is 130-740 parts by mass. In some embodiments, the organic solvent in the photosensitive resin composition is 195-520 parts by mass. In some embodiments, the organic solvent in the photosensitive resin composition is 240-390 parts by mass.
  • the organic solvent may be one or more of ester, ketone, ether or amide organic solvents.
  • the ester organic solvent can be ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyrate butyrate Esters, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkoxyacetate, alkyl 3-alkoxypropionate, 2- Alkoxy propionate alkyl esters, 2-alkoxy-2-methyl propionate methyl ester and 2-alkoxy-2-methyl propionate ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl
  • the ketone organic solvent can be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
  • Ether organic solvents can be diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.
  • the amide organic solvent can be N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide,
  • the above photosensitive resin composition may be prepared by uniformly mixing a resin or a resin precursor, a crosslinking agent, a photoacid generator, and an organic solvent.
  • the exposure energy required to act on the photosensitive resin composition is 80mJ/cm 2 -170mJ/cm 2 .
  • the exposure energy can be 80mJ/cm 2 , 90mJ/cm 2 , 100mJ/cm 2 , 110mJ/cm 2 , 120mJ/cm 2 , 130mJ/cm 2 , 150mJ/cm 2 , 160mJ/cm 2 , 170mJ /cm 2 .
  • the embodiment of the present application also provides a pattern forming method, including:
  • the substrate can be silicon-based or metal (such as copper), and the thickness of the coating film can be adjusted according to actual needs. After the coating film is formed, the coating film can be dried by heating to evaporate part of the solvent.
  • a 365nm mercury lamp light source can be used for exposure, and the exposure energy can be 80mJ/cm 2 -170mJ/cm 2 . Drying can be done after exposure.
  • the developer may be determined according to the solubility of the photosensitive resin composition, for example, it may be an alkaline developer.
  • the exposed areas remain, while the non-exposed areas are washed away, thereby forming a resin pattern.
  • Heat treatment can cure the resin to form a cured film.
  • the temperature of heat treatment can be 100-350°C.
  • the specific temperature can be determined according to the curing performance of the resin. (1h) ⁇ 200°C (1h) ⁇ 300°C (1h) temperature programmed curing. Degree of temperature curing is conducive to complete curing, forming a uniform, stable and high-quality cured film.
  • the embodiment of the present application also provides a cured film, which is the cured film of the above-mentioned photosensitive resin composition, and is obtained by curing the above-mentioned photosensitive resin composition.
  • the cured film is a patterned cured film obtained by photolithographic curing of the above photosensitive resin composition.
  • the resolution of the pattern on the cured film is less than or equal to 4 ⁇ m.
  • the resolution of the pattern may be 4 ⁇ m, 3 ⁇ m, 2 ⁇ m, 1 ⁇ m, 0.5 ⁇ m.
  • the inclination angle of the pattern on the cured film is >65°.
  • the inclination angle of the pattern on the cured film may be 70°, 75°, 80°, 85°, 90°.
  • the inclination angle is the inclination angle of the pattern relative to the plane of the base film layer, and the closer the inclination angle is to 90°, the better the patterning effect is.
  • the embodiment of the present application also provides an electronic device 100, and the electronic device 100 includes the above-mentioned cured film in the embodiment of the present application.
  • the cured film can be used as a protective layer, a passivation layer, an interlayer insulation layer, a buffer layer, a planarization layer, an ⁇ -ray shielding layer, or a rewiring layer in the electronic device 100 .
  • 1 is a schematic diagram of a partial packaging structure of an electronic device 100.
  • the electronic device 100 includes a semiconductor chip 10, a pad 20 disposed on one surface of the semiconductor chip 10, a passivation layer 30 disposed on the chip 10 and the pad 20, and a passivation layer 30 disposed on the chip 10 and the pad 20.
  • a rewiring layer 40 is formed on the layer 30 , and the rewiring layer 40 includes a first dielectric layer 401 , a second dielectric layer 402 , a rewiring seed layer 403 and a rewiring metal layer 404 .
  • the first dielectric layer 401 is disposed on the passivation layer 30, and a via hole exposing the pad 20 is formed on the first dielectric layer 401, and a rewiring seed layer 403 and a rewiring metal layer 404 are sequentially formed in the via hole,
  • the second dielectric layer 402 is disposed on the first dielectric layer 401 and covers the rewiring metal layer 404.
  • a via hole exposing the rewiring metal layer 404 is formed on the second dielectric layer 402, and a metal layer is sequentially formed in the via hole.
  • the semiconductor chip 10 can be any form of chip, for example, it can be an integrated circuit (IC) in a bare state, the pad 20 can include conductive materials such as aluminum, and the passivation layer 30 can include oxide, nitride, etc.
  • the first dielectric layer 401 and the second dielectric layer 402 may be patterned cured films formed by curing the photosensitive resin composition of the embodiment of the present application.
  • the redistribution metal layer 404 is a copper layer.
  • the metal connection layer 501 may be a Ti/Cu sputtered layer, and the UBM layer 502 may be a Ni layer.
  • the packaging structure of semiconductor chips there is usually a bonding interface between the cured film and silicon and copper.
  • the embodiment of the present application forms a cured film by using the photosensitive resin composition of the embodiment of the present application, which can effectively improve the bonding interface between the cured film and silicon and copper. , to improve the stability of the package structure.
  • the cured film is arranged on the silicon wafer or the metal layer, and the adhesion between the cured film and the silicon wafer reaches the national standard reliability hundred grid test 3B or 4B standard; the adhesion between the cured film and the metal layer reaches National standard reliability hundred grid test 4B or 5B standard.
  • the metal layer can be, for example, a copper layer.
  • the photoacid generator provided in the embodiments of the present application can also be used in various photosensitive materials, such as coatings, inks, resists, negative photosensitive materials, photolithographic materials, and the like.
  • the prepared photosensitive resin composition was spin-coated on a silicon wafer to form a film, and baked on a hot plate at 110° C. for 3 minutes to evaporate part of the solvent to obtain a dried composition coating film.
  • the film was placed under a mask, and exposed using a contact exposure machine with a mercury lamp light source of 365 nm, and the exposure energy range was 100-150 mJ/cm 2 .
  • After the exposed film is baked on a hot plate at 130°C for 2 minutes; after spray development in the developing machine, it is rinsed with deionized water, the film layer in the exposed area is retained, and the film layer in the non-exposed area is removed, and the silicon is blown away by nitrogen gas.
  • the remaining liquid on the sheet is then cured according to the temperature program of 100°C (1h) ⁇ 200°C (1h) ⁇ 300°C (1h) to form a patterned cured film.
  • the prepared photosensitive resin composition was spin-coated on a copper sheet to form a film, and baked on a hot plate at 110° C. for 3 minutes to evaporate part of the solvent to obtain a dried composition coating film.
  • the film was placed under a mask and exposed using a 365 nm mercury lamp light source with an exposure energy of 100-150 mJ/cm 2 . After exposure, the film was baked on a hot plate at 130°C for 2 minutes; after spray development in the developing machine, it was rinsed with deionized water, and the residual liquid on the copper sheet was blown off with nitrogen, and then according to 100°C (1h) ⁇ 200°C (1h) ) ⁇ 300°C (1h) temperature-programmed curing to form a patterned cured film.
  • the photoacid generator prepared in Example 1 was tested with an ultraviolet-visible spectrometer, and it was known that the photoacid generator prepared in Example 1 had good absorbance at the i-line, had better absorption of 365nm light, and had high photosensitivity.
  • the results show that the photolithographic pattern stripes under the mask plate with a line width of 4 ⁇ m are clear and flat without residual adhesive adhesion, and the pattern resolution obtainable by the photosensitive resin composition is 4 ⁇ m.
  • the adhesion between the embodiment 1 cured film and the silicon chip and the cured film and the copper sheet is tested by the hundred-grid test method, and the results show that the adhesion between the embodiment 1 cured film and the silicon chip and the cured film and the copper sheet Efforts are made to reach the 3B and 4B standards of the national standard reliability test.
  • the 100-grid test is carried out with reference to the standard "GBT9286-1998".
  • the national standard 100-grid test includes the following 6 grades: 5B standard: the edge of the cut is completely smooth, and there is no peeling at the edge of the grid; 4B standard: there are small pieces of peeling at the intersection of the cut, and the actual damage of the cross-cut area does not exceed 5%; 3B standard: the incision There is peeling at the edge or intersection, and the damaged area is greater than 5% but less than 15%; 2B standard: partial peeling or large pieces of peeling off at the edge of the incision, or part of the grid is completely peeled off, and the damaged area is greater than 15% but less than 35%; 1B standard: incision The edge is peeled off in large pieces, or part of the grid is completely peeled off, and the damaged area is greater than 35% but less than 65%; 0B standard: the damaged area is greater than 65%.
  • the photoacid generator of the embodiment of the present application introduces an azole ring into the naphthalene ring of naphthalene imide, and introduces a phenyl group on the azole ring, and uses the special electronic effect of the phenyl and the azole ring to regulate photoacid generation
  • the best light-absorbing wavelength of the agent falls at 345-355nm, and at the same time, it can make the adhesion between the cured film and silicon and copper have a high level.
  • the photosensitive resin composition is formed by vacuum defoaming after stirring and mixing uniformly.
  • the prepared photosensitive resin composition was spin-coated on a silicon wafer to obtain a patterned cured film.
  • the method was the same as in Example 1, wherein the exposure energy during the exposure process was 80-150 mJ/cm 2 .
  • the prepared photosensitive resin composition was spin-coated on a copper sheet to obtain a patterned cured film, the method was the same as in Example 1, wherein the exposure energy during the exposure process was 80-150mJ/cm 2 .
  • the photoacid generator prepared in Example 2 was tested with an ultraviolet-visible spectrometer, and it was known that the photoacid generator prepared in Example 2 had good absorbance at the i-line, had better absorption of 365nm light, and had high photosensitivity.
  • the photosensitive resin composition of Example 2 of the present application is used for patterning, and the results show that the photolithographic pattern stripes under the mask plate with a line width of 2 ⁇ m are clear and flat without residual adhesive adhesion, and the pattern resolution obtainable by the photosensitive resin composition is 2 ⁇ m.
  • the adhesion between the embodiment 2 cured film and the silicon chip and the cured film and the copper sheet is tested by the hundred-grid test method, and the results show that the adhesion between the embodiment 2 cured film and the silicon chip and the cured film and the copper sheet Efforts are made to reach the 3B and 4B standards of the national standard reliability test.
  • the photoacid generator of the embodiment of the present application introduces the nitrogen azole ring on the naphthalene ring of the naphthalene imide, and introduces the polyhydroxy phenyl group on the nitrogen azole ring.
  • the electrons of the polyhydroxy phenyl group and the nitrogen azole ring can
  • the best light-absorbing wavelength of the photoacid generator is controlled by the effect of 350-360nm; at the same time, it can make the adhesion between the cured film and silicon and copper have a high level; in addition, the polyhydroxyphenyl can improve the alkalinity of the resin composition. Solubility in the developer, which can finally improve the resolution of the pattern and reduce the phenomenon of residual glue in the non-exposed area.
  • the prepared photosensitive resin composition was spin-coated on a silicon wafer to obtain a patterned cured film.
  • the method was the same as in Example 1, wherein the exposure energy during the exposure process was 100-150 mJ/cm 2 .
  • the prepared photosensitive resin composition was spin-coated on a copper sheet to obtain a patterned cured film.
  • the method was the same as in Example 1, wherein the exposure energy during the exposure process was 100-150 mJ/cm 2 .
  • the photoacid generator prepared in Example 3 was tested with an ultraviolet-visible spectrometer, and it was known that the photoacid generator prepared in Example 3 had good absorbance at the i-line, had better absorption of 365nm light, and had high photosensitivity.
  • Fig. 2 and Fig. 3 are the lithography effect figure of the photosensitive resin composition of the embodiment 3 of the present application
  • concrete map 2 is the lithography pattern (after curing) under the mask plate of line width 8 ⁇ m
  • Fig. 3 is the mask of line width 4 ⁇ m
  • the photoacid generator of the embodiment of the present application introduces an oxazole ring on the naphthalene ring of the naphthalene imide, and introduces an epoxy alkoxy group on the oxazole ring to replace the phenyl group.
  • the electronic effect of the phenyl group and the azole ring regulates the optimal light absorption wavelength of the photoacid generator to fall at 355-380nm; at the same time, it can make the adhesion between the cured film and silicon and copper have a high level; in addition, through the epoxy group Cross-linking reaction can occur under acid catalysis and high temperature, which can increase the degree of cross-linking of the resin during the development and curing process, improve the flatness of the pattern, and increase the inclination angle from the ordinary 60°-70° to around 90°.
  • the prepared photosensitive resin composition was spin-coated on a silicon wafer to obtain a patterned cured film.
  • the method was the same as in Example 1, wherein the exposure energy during the exposure process was 120-170 mJ/cm 2 .
  • the prepared photosensitive resin composition was spin-coated on a copper sheet to obtain a patterned cured film.
  • the method was the same as in Example 1, wherein the exposure energy during the exposure process was 120-170 mJ/cm 2 .
  • the photoacid generator prepared in Example 4 was tested with an ultraviolet-visible spectrometer, and it was known that the photoacid generator prepared in Example 4 had good absorbance at the i-line, had better absorption of 365nm light, and had high photosensitivity.
  • Fig. 4 is the lithography effect diagram of the photosensitive resin composition of Example 4 of the present application, specifically the lithography pattern (after curing) under masks with different line widths. It can be seen from FIG. 4 that the photolithographic pattern under the mask plate with a line width of 2 ⁇ m is clear and flat without adhesive residue, and the pattern resolution obtainable by the photosensitive resin composition is 2 ⁇ m.
  • the adhesion between the embodiment 4 cured film and the silicon chip and the cured film and the copper sheet is tested by the hundred-grid test method, and the results show that the adhesion between the embodiment 4 cured film and the silicon chip and the cured film and the copper sheet Efforts are made to meet the 4B and 5B standards of the national standard reliability test.
  • the photoacid generator of the embodiment of the present application introduces an azole ring on the naphthalene ring of naphthalene imide, and introduces a substituted phenyl group containing alkoxysilane at the end on the azole ring.
  • the substituted phenyl group and The electronic effect of the azole ring regulates the optimal light absorption wavelength of the photoacid generator to fall around 380nm, which improves the photosensitivity of the i-line; at the same time, the alkoxysilane group at the end can further improve the adhesion between the cured film and silicon wafer, copper, etc.
  • the adhesion between the sheets eliminates the bleaching phenomenon, and at the same time improves the structural stability of the cured film layer.
  • the prepared photosensitive resin composition was spin-coated on a silicon wafer to obtain a patterned cured film.
  • the method was the same as in Example 1, wherein the exposure energy during the exposure process was 100-150 mJ/cm 2 .
  • the prepared photosensitive resin composition was spin-coated on a copper sheet to obtain a patterned cured film.
  • the method was the same as in Example 1, wherein the exposure energy during the exposure process was 100-150 mJ/cm 2 .
  • the photoacid generator prepared in Example 5 is tested by an ultraviolet-visible spectrometer, and it is known that the photoacid generator prepared in Example 5 has good absorbance at the i-line, has good absorption to the light of 365nm, and has high photosensitivity.
  • the results show that the photolithographic pattern under the mask plate with a line width of 4 ⁇ m is clear and smooth, without adhesion, and the best pattern resolution obtainable by the photosensitive resin composition is about 4 ⁇ m .
  • the photoacid generator of the embodiment of the present application introduces a tetrazole ring on the naphthalene ring of the naphthalene imide, and introduces a substituted phenyl group on the tetrazolium ring, and can utilize the electronic effect of the phenyl group and the tetrazolium ring to control
  • the optimum light absorption wavelength of the photoacid generator falls around 345-360nm, which improves the photosensitivity of the i-line; at the same time, it can make the adhesion between the cured film and silicon and copper have a high level.
  • the preparation of photosensitive resin composition get the PHI-30000 resin of 100 mass parts that embodiment 1 synthesizes, the photoacid generator PTMA ((5-propylsulfonyloxyimino-5H-thiophene-2- subunit)-(2-methylphenyl)acetonitrile) and 20 mass parts of crosslinking agent MBHP, dissolved in 298 mass parts of N-methylpyrrolidone (NMP), so that the total solid content of the composition is 30w. t.%, stirring and mixing evenly, vacuum defoaming to form a photosensitive resin composition.
  • PTMA ((5-propylsulfonyloxyimino-5H-thiophene-2- subunit)-(2-methylphenyl)acetonitrile)
  • NMP N-methylpyrrolidone
  • the prepared photosensitive resin composition was spin-coated on a silicon wafer to prepare a patterned cured film.
  • the method was the same as in Example 1, wherein the exposure energy during the exposure process was 150-200 mJ/cm 2 .
  • the prepared photosensitive resin composition was spin-coated on a copper sheet to obtain a patterned cured film, the method was the same as in Example 1, wherein the exposure energy during the exposure process was 150-200mJ/cm 2 .
  • the optimum light absorption wavelength of the photoacid generator PTMA is 415nm, and the light absorbance at the i-line is not good.
  • FIG. 5 is a lithography effect diagram of the photosensitive resin composition of Comparative Example 1 of the present application, specifically, lithography patterns (after curing) under masks with different line widths. It can be seen from FIG. 5 that the photosensitive resin composition of Comparative Example 1 of the present application was used for severe bleaching after photolithography and development, and the adhesion between the base film and the silicon wafer was insufficient, and stripes with a resolution of 10 ⁇ m could barely be obtained.
  • the photosensitive resin composition is formed by vacuum defoaming after stirring and mixing evenly.
  • the prepared photosensitive resin composition was spin-coated on a silicon wafer to prepare a patterned cured film.
  • the method was the same as in Example 1, wherein the exposure energy during the exposure process was 150-200 mJ/cm 2 .
  • the prepared photosensitive resin composition was spin-coated on a copper sheet to obtain a patterned cured film, the method was the same as in Example 1, wherein the exposure energy during the exposure process was 150-200mJ/cm 2 .
  • the optimal absorption wavelength of the photoacid generator in Comparative Example 2 is at 340nm, and the absorbance at the i-line is average.
  • Fig. 6 and Fig. 7 are the lithography effect figure of the photosensitive resin composition of comparative example 2 of the present application, wherein, Fig. 6 is the lithography pattern (after curing) under the mask plate of line width 8 ⁇ m; Fig. 7 is the line width 4 ⁇ m mask Photolithographic pattern under the stencil (after curing). It can be seen from Figure 6 that the dissolution and shrinkage of the photolithographic pattern stripes under the mask with a line width of 8 ⁇ m leads to poor flatness. Adhesions are severe. The pattern resolution of the photosensitive resin composition of Comparative Example 2 was 8 ⁇ m.
  • the optimum light absorption wavelength of the photoacid generators of Examples 1-5 of the present application is closer to 365nm, and the absorbance at the i-line is higher, so the photolithographic pattern The resolution is improved, and Examples 1-5 show that at least a resolution of 4 ⁇ m can be obtained.
  • the adhesion between the cured film of the photosensitive resin composition of Examples 1-5 of the present application and the silicon and copper interfaces is improved.
  • the use of the photoacid generator of the embodiment of the present application can also reduce the exposure dose required in the exposure process to a certain extent.

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Abstract

本申请实施例提供一种感光分子和包含该感光分子的光产酸剂和感光树脂组合物，其分子结构包括含萘环的主结构、与主结构中萘环连接的杂环基X，与杂环基连接的R 2；R 2选自卤素、芳基、芳烷基、烷芳基、卤代芳基、烷氧基芳基、环氧烷基、环氧芳基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基芳基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。该感光分子通过在萘环上引入杂环结构和特定的R 2基团，可有效改善感光树脂组合物的图案分辨率，及与铜、硅等界面的粘附性，赋予感光分子多功能，简化树脂组合物配方。

Description

感光分子及其应用
本申请要求于2021年9月30日提交中国专利局、申请号为202111163870.7、申请名称为“感光分子及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请实施例涉及感光材料技术领域，特别是涉及一种感光分子、光产酸剂、感光树脂组合物、固化膜和电子器件。
背景技术
化学增幅(Chemical Amplification，CA)型感光树脂组合物具有高的感光性和灵敏度，可以在光刻工艺中形成清晰的超精细图案，其基本原理为光产酸剂(Photo acid Generator，PAG)受到光源照射产酸，而后在烘烤的过程中，产生的酸持续催化交联剂发生交联、或交联剂和聚合物树脂发生交联，导致聚合物树脂的曝光区域和未曝光区域在显影液中形成明显的溶解度差异，即曝光区域由于发生交联溶解性急剧下降，而非曝光区域依然保持较好的溶解性，从而显示出光刻图案。
近年来半导体封装领域的感光介质材料也逐渐使用化学增幅型的光产酸剂。感光介质材料作为半导体封装材料的重要组成部分之一，不仅需要具有良好的光刻性能，还需要固化后的树脂具有良好的综合性能。其中，PAG的综合性能对光刻性能的影响至关重要，针对i-line(365nm)感光树脂组合物而言，PAG在i-line的吸收决定了光刻组合物的灵敏度，同时，光照后的光产酸效率、分子的溶解性等也会影响最终的图案精细程度。在实际应用场景中，感光介质材料最终需要作为绝缘层留在器件中，为解决铜界面处铜离子的迁移问题、光刻图案的分辨率问题、显影过程中的残胶问题以及树脂与基底材料粘附性等问题，组合物配方中还需加入杂环类化合物、增溶剂、偶联剂等助剂，使得现有感光树脂组合物的配方非常复杂。
鉴于上述，有必要开发一种能够有效提升光刻效果、改善固化后树脂性能、简化感光树脂组合物的配方的光产酸剂。
发明内容
本申请实施例提供一种感光分子和包含该感光分子的光产酸剂和感光树脂组合物，包含该感光分子的光产酸剂可有效改善感光树脂组合物的整体光刻效果，提高图案分辨率，改善固化后树脂与铜、硅等界面的粘附性，降低感光树脂组合物的配方复杂程度。
具体地，本申请实施例第一方面提供一种感光分子，所述感光分子的分子结构包括萘酰亚胺结构、与所述萘酰亚胺结构中氮原子连接的取代磺酸基、以及与所述萘酰亚胺结构中萘环连接的杂环基X，与所述杂环基连接的R 2；
所述杂环基X选自含有O、N或S的杂环基；所述R 2选自卤素、芳基、芳烷基、烷芳基、卤代芳基、烷氧基芳基、环氧烷基、环氧芳基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基芳基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。
本申请实施例提供的感光分子，通过萘酰亚胺衍生化得到，萘酰亚胺结构较稳定、合成简便、产率高，通过在萘酰亚胺结构的萘环上引入杂环结构X和特定的R 2基团，可赋予感光 分子多功能，作为光产酸剂使用时，可有效改善感光树脂组合物的图案分辨率，改善固化后树脂与铜、硅等界面的粘附性，简化组合物配方。其中，萘环上引入的杂环基X具有一定的抗离子迁移能力和特殊的电子效应，能够有效提升光产酸剂在i-line(365nm)处的吸光，减少在可见光处的吸光，改善光刻效果；同时杂环基X易衍生化，杂环基X的引入有利于进一步引入各种结构的功能基团R 2，从而赋予光产酸剂更多功能。在杂环结构X和特定的R 2基团的协同作用下可以有效改善光刻效果以及树脂组合物的综合性能，改善固化后树脂与铜、硅等界面的粘附性，也可简化感光树脂组合物的配方。
本申请实施方式中，所述取代磺酸基表示为-SO 3R 1，所述R 1选自烷基、芳基、烷基芳基、卤代烷基或卤代芳基。
本申请实施方式中，所述感光分子的分子结构还包括与所述萘酰亚胺结构中萘环连接的R 3，R 3包括氢、卤素、烷基、烯基、炔基、芳基、芳烷基、烷芳基、烯芳基、芳烯基、炔芳基、芳炔基、卤代烷基、卤代芳基、烷氧基烷基、烷氧基芳基、环氧烷基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基烷基、氨基芳基、氰基烷基、氰基芳基、羧基烷基、羧基芳基、酯基烷基、酯基芳基、烷基羰基、芳基羰基、烷基醇基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。
本申请实施方式中，感光分子的分子结构可以是如式(I)所示：
Figure PCTCN2022122570-appb-000001
本申请实施方式中，杂环基X、以及R 3可以是在萘环上的任意碳位上，即杂环基X、以及R 3可以是与萘环上的任意位置的碳原子相连接。一些实施方式中，杂环基X、R 3分别位于萘的不同环的任意碳位上。R 2也可以是位于杂环基X的任意碳位上。
本申请实施方式中，杂环基X是指构成环的原子除碳原子外还有其他原子的有机环状基团，杂环基可以有一个杂原子，也可以有两个或更多个杂原子，杂原子可以是一种原子，也可以是两种不同的原子；杂环基可以是通过杂原子与萘环上的碳原子连接，也可以是通过碳原子与萘环上的碳原子连接。本申请实施方式中，X可以是选自含有O、N或S的五元杂环基、六元杂环基、或苯并杂环基。其中五元杂环基具体可以是源自呋喃、噻吩、吡咯、噻唑、咪唑、三氮唑、四氮唑等五元杂环化合物；六元杂环基可以是源自吡啶、吡嗪、嘧啶、哒嗪等六元杂环化合物。
本申请一些实施方式中，所述X为含有三个氮原子的五元或六元杂环基，且其中的一个氮原子与萘环的碳原子连接。本申请一实施方式中，X为含有三个氮原子的五元杂环基，感光分子的分子结构如式(I-a)所示：
Figure PCTCN2022122570-appb-000002
本申请一些实施方式中，所述X为含有四个氮原子的五元或六元杂环基，且其中的一个氮原子与萘环的碳原子连接。本申请一实施方式中，X为含有四个氮原子的五元杂环基，感光分子的分子结构如式(I-b)所示：
Figure PCTCN2022122570-appb-000003
本申请实施方式中，R 2为包含芳基的基团时，芳基可以是苯基、萘基等。
本申请一些实施方式中，R 2为含有端羟基的基团，具体地，R 2可以是羟基烷基、羟基芳基。R 2为含有端羟基的基团，还可以调节树脂组合物的碱溶性，从而提升树脂组合物在碱性显影液中的溶解度，减少曝光或非曝光区域的残胶现象，提升图案分辨率。
本申请一些实施方式中，R 2为含有环氧基的基团，具体地是以环氧基封端的基团，例如可以是环氧烷基、环氧芳基、环氧烷氧基、环氧烷氧基取代芳基等。R 2含有环氧基能够提高树脂的交联程度，从而可以有效调节图案平整度，提升光刻效果。其中，环氧烷基可以是环氧丙基、环氧丁基、环氧戊基、环氧己基等；环氧烷氧基即环氧烷氧基可以是环氧丙氧基、环氧丁氧基、环氧戊氧基、环氧己氧基等；环氧烷氧基取代芳基可以是环氧丙氧基取代苯基、环氧丁氧基取代苯基、环氧戊氧基取代苯基、环氧己氧基取代苯基等。
本申请一些实施方式中，R 2为含烷氧基硅烷的基团，具体地，所述含烷氧基硅烷的基团可以是包括含γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷的基团。R 2为烷氧基硅烷基封端的基团。R 2为含烷氧基硅烷的基团，可有效提高感光树脂组合物的固化膜与硅片、金属层等基底之间的粘附力，避免漂胶现象的产生，而且硅氧键具有较好的柔韧性和耐热性，可以提高固化膜的柔韧性和耐热性。
本申请实施方式中，所述R 1、R 2、R 3为含碳基团时，含碳基团具有适合的碳原子数能够使得光产酸剂在有机溶剂中具有适合的溶解度，同时具有较好的感光性和光产酸能力，有利于提升光刻效果。本申请一些实施方式中，R 1、R 2、R 3为含碳基团时，碳原子数为1-20。本申请一些实施方式中，R 1、R 2、R 3为含碳基团时，碳原子数为4-20。
本申请一些实施方式中，所述感光分子的分子结构如式1-a至23-a所示：
Figure PCTCN2022122570-appb-000004
Figure PCTCN2022122570-appb-000005
Figure PCTCN2022122570-appb-000006
本申请实施例第二方面提供一种感光分子，所述感光分子的分子结构包括萘酰亚胺结构、与所述萘酰亚胺结构中氮原子连接的所述取代磺酸基、以及与所述萘酰亚胺结构中萘环连接的杂环基X，与所述杂环基连接的R 2；所述感光分子采用如下方法制备得到：
将4-溴-1,8-萘二甲酸酐中的溴取代位接枝取代杂环基-X-R 2，并在酐基酰胺化后接枝取代磺酸基，得到感光分子；其中，X包括含有O、N或S的杂环基；R 2包括卤素、芳基、芳烷基、烷芳基、卤代芳基、烷氧基芳基、环氧烷基、环氧芳基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基芳基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。
本申请实施例第三方面提供一种感光分子的制备方法，包括：
将4-溴-1,8-萘二甲酸酐中的溴取代位接枝取代杂环基-X-R 2，并在酐基酰胺化后接枝取代磺酸基，得到感光分子，所述感光分子的分子结构包括萘酰亚胺结构、与所述萘酰亚胺结构中氮原子连接的所述取代磺酸基、以及与所述萘酰亚胺结构中萘环连接的杂环基X，与所述杂环基连接的R 2；其中，X包括含有O、N或S的杂环基；R 2包括卤素、芳基、芳烷基、烷芳基、卤代芳基、烷氧基芳基、环氧烷基、环氧芳基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基芳基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。
本申请实施例第四方面提供一种光产酸剂，该光产酸剂包括本申请实施例第一方面或第二方面所述的感光分子，或者包括第三方面所述制备方法制备得到的感光分子。
本申请实施例第五方面提供上述的感光分子或光产酸剂在图案化处理中的应用。
本申请实施例第六方面提供一种感光树脂组合物，所述感光树脂组合物包括树脂或树脂前驱体、交联剂、本申请实施例第四方面所述的光产酸剂。
本申请的感光树脂组合物可以是负型感光树脂组合物。负型感光树脂组合物经曝光显影后，未曝光部分被洗掉，曝光部分保留。本申请实施例负型感光树脂组合物的图案化原理为：光产酸剂受到光源照射产酸(取代或非取代磺酸)，在后续热处理的过程中，产生的酸持续催化交联剂发生交联、或交联剂和聚合物树脂发生交联，导致聚合物树脂的曝光区域和未曝光区域在显影液中形成明显的溶解度差异，即曝光区域由于发生交联溶解性急剧下降，而非曝光区域依然保持较好的溶解性，最终未曝光区域被洗掉，曝光区域保留，从而显示出光刻图案。
本申请的感光树脂组合物也可以是正型感光树脂组合物。正型感光树脂组合物经曝光显影后，曝光部分被洗掉，未曝光部分保留。
本申请实施方式中，以树脂为100质量份计，所述感光树脂组合物中光产酸剂为0.5-20质量份。一些实施例中，光产酸剂可为3-15质量份。一些实施例中，光产酸剂可为5-10质量份。
本申请实施方式中，感光树脂组合物中的树脂或树脂前驱体可以根据实际应用需求进行选择。感光树脂组合物中可以是包含一种或多种树脂组分。一些实施方式中，所述树脂包括酚醛树脂、环氧树脂、丙烯酸树脂、苯并环丁烯树脂、苯并噁唑树脂、聚酰亚胺树脂中的一种或多种。一些实施方式中，所述树脂前驱体包括酚醛树脂前驱体、环氧树脂前驱体、丙烯酸树脂前驱体、苯并环丁烯树脂前驱体、苯并噁唑树脂前驱体、聚酰亚胺树脂前驱体中的一种或多种。本申请实施方式中，树脂的重均分子量可为5000-100000；一些实施例中，树脂的重均分子量可为10000-80000；一些实施例中，树脂的重均分子量可为20000-50000。
本申请实施方式中，所述交联剂包括多羟基交联剂，具体地多羟基交联剂可以是含有苄基醇结构的化合物单体。该单体在酸性条件下，可以发生交联，形成聚合型大分子，溶解度降低。一些实施方式中，含有苄基醇结构的化合物单体可以是如式A所示的化合物2,6-双(羟甲基)-4-甲酚，或如式B所示的化合物。
Figure PCTCN2022122570-appb-000007
本申请实施方式中，以树脂为100质量份计，所述感光树脂组合物中所述交联剂为1-30质量份。一些实施例中，交联剂可为5-25质量份。一些实施例中，交联剂可为10-20质量份。
本申请实施方式中，以树脂为100质量份计，所述感光树脂组合物中所述有机溶剂为130-740质量份。一些实施例中，有机溶剂可为195-520质量份。一些实施例中，有机溶剂可为240-390质量份。
本申请实施方式中，所述感光树脂组合物还包括有机溶剂。
本申请实施方式中，所述有机溶剂可以是包括酯类、酮类、醚类或酰胺类有机溶剂中的一种或多种。
本申请实施方式中，采用所述感光树脂组合物进行图案化时所需作用在所述感光树脂组合物上的曝光能量为80mJ/cm 2-170mJ/cm 2。
本申请实施例第七方面提供一种图案形成方法，包括：
将本申请实施例第六方面所述的感光树脂组合物涂覆在基体上，形成涂膜；
根据预设图案曝光所述涂膜；
采用显影液显影曝光后的所述涂膜获得树脂图案；
对所述树脂图案进行热处理。
本申请实施例第八方面提供一种固化膜，所述固化膜为第三方面所述感光树脂组合物的固化膜。
本申请实施方式中，所述固化膜上的图案的分辨率小于或等于4μm。
本申请实施方式中，所述固化膜上的图案的倾角大于65°。
本申请实施例还提供一种电子器件，所述电子器件包括本申请实施例第八方面所述的固化膜；或者所述电子器件包括由包含第一方面所述感光分子的组合物固化形成的固化膜。
本申请实施方式中，所述电子器件包括硅片或金属层，所述固化膜设置在硅片或金属层上，所述固化膜与所述硅片之间的附着力达到国标《GBT9286-1998》可靠性百格测试3B或4B标准；所述固化膜与所述金属层之间的附着力达到国标可靠性百格测试4B或5B标准。
本申请实施方式中，所述固化膜在所述电子器件中作为保护层、钝化层、层间绝缘层、缓冲层、平坦化层、α射线屏蔽层或再布线层。
附图说明
图1为本申请实施例提供的电子器件100的封装结构示意图；
图2和图3为本申请实施例3的感光树脂组合物的光刻效果图；
图4为本申请实施例4的感光树脂组合物的光刻效果图；
图5为本申请对比例1的感光树脂组合物的光刻效果图；
图6和图7为本申请对比例2的感光树脂组合物的光刻效果图。
具体实施方式
下面将结合本申请实施例中的附图，对本申请实施例进行说明。
负性胶凭借自身优异的耐热性能与机械性能，广泛用于芯片封装领域，当前的负性胶采用的主流路线为在树脂分子结构中引入可光交联的基团(如丙烯酸类)，在光照下，光引发剂产生自由基引发曝光处的聚合物交联，形成溶解度差异。近年来，化学增幅的原理逐渐从精细的光刻胶引入到感光介质材料，以萘酰亚胺(NI)型光产酸剂为例，如式C所示，为NI型光产酸剂的光致产酸机理，NI型光产酸剂在光照下发生Norrish I型裂解，产生磺酸，产生的磺酸在曝光处可以引发多羟基类交联剂的交联反应，因为酸仅仅起到一个催化作用而并非参与反应，因此仅需少量的光产酸剂即可持续催化曝光处的交联反应。
Figure PCTCN2022122570-appb-000008
考虑到感光介质材料光敏性能与固化后固化膜物化性能的平衡，本申请实施例提供一种感光分子，及包括该感光分子的光产酸剂和包含光产酸剂的感光树脂组合物，该感光分子为萘酰亚胺衍生物，通过在萘环上引入杂环结构，感光分子可以获得萘酰亚胺和杂环结构两种结构的性能优势，改善感光分子的吸光特性，而且杂环结构的引入增大了衍生化的范围，通过在杂环或萘环上引入各种官能团，可以赋予感光分子多功能性，使得光照后原本没有作用的萘酰亚胺主体结构具有粘附性、交联性等，进一步提升曝光区与非曝光区的溶解度差异，最终有效改善感光树脂组合物的整体光刻效果，提高图案分辨率，改善固化后树脂在硅、铜等界面的粘附性，同时降低感光树脂组合物的配方复杂程度。
本申请实施例提供一种感光分子，该感光分子的分子结构包括萘酰亚胺结构、与萘酰亚胺结构中氮原子连接的取代磺酸基、以及与萘酰亚胺结构中萘环连接的杂环基X，与杂环基连接的R 2；其中，杂环基X选自含有O、N或S的杂环基；R 2基团选自卤素、芳基、芳烷基、烷芳基、卤代芳基、烷氧基芳基、环氧烷基、环氧芳基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基芳基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。
本申请实施例的感光分子可以用作为光产酸剂，也可以是用于其他有感光需求的应用场景，下面主要以感光分子作为光产酸剂使用进行详细介绍。
本申请实施例提供的光产酸剂，通过萘酰亚胺衍生化得到，萘酰亚胺结构较稳定、合成简便、产率高，引入的杂环基X和R 2基团具有一定的抗离子迁移能力和特殊的电子效应，能够很好地调控光产酸剂的吸光范围与吸光度，有效提升光产酸剂在i-line处的吸光，减少在可见光处的吸光，改善光刻效果；而且能够提高包含该光产酸剂的树脂组合物固化膜具有良好的硅界面、铜界面粘附性能；另外，功能基团R 2还可赋予光产酸剂更多功能，改善光刻效果和树脂组合物的综合性能，简化感光树脂组合物的配方。
本申请实施方式中，取代磺酸基表示为-SO 3R 1，R 1可包括烷基、芳基、烷基芳基、卤代烷基或卤代芳基。烷基可以是C 1-C 20的烷基，例如可以是甲基、乙基等。芳基可以是苯基。烷基芳基可以是C 7-C 20的烷基芳基，例如可以是甲基苯基、乙基苯基等。卤代烷基可以是C 1-C 20的卤代烷基，例如可以是三氟甲基、三氟乙基等。卤代芳基可以是C 6-C 20的卤代芳基，例如可以是氟代苯基、溴代苯基等。
本申请实施方式中，光产酸剂的分子结构还包括与萘酰亚胺结构中萘环连接的R 3，R 3选自氢、卤素、烷基、烯基、炔基、芳基、芳烷基、烷芳基、烯芳基、芳烯基、炔芳基、芳 炔基、卤代烷基、卤代芳基、烷氧基烷基、烷氧基芳基、环氧烷基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基烷基、氨基芳基、氰基烷基、氰基芳基、羧基烷基、羧基芳基、酯基烷基、酯基芳基、烷基羰基、芳基羰基、烷基醇基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。R 3通过选择不同的基团可以一定程度改善光产酸剂的吸光波长和吸光度以及树脂组合物的综合性能。
本申请实施方式中，光产酸剂的分子结构可以是如式(I)所示：
Figure PCTCN2022122570-appb-000009
本申请实施方式中，杂环基X、R 3可以是在萘环上的任意碳位上，即杂环基X、R 3可以是与萘环上的任意位置的碳相连接。一些实施方式中，杂环基X、R 3分别位于萘的不同环的任意碳位上。R 2也可以是位于杂环基X的任意碳位上。
本申请实施方式中，R 1、R 2、R 3包含卤素时，卤素可以是包括氟、氯、溴、碘。
本申请实施方式中，R 3各种基团的具体选择范围可以是与R 2的选择范围相同。
本申请实施方式中，R 2、R 3中，芳基可以是苯基(如式1-a和2-a)；芳烷基可以是苯甲基、苯乙基等；烷芳基可以是甲基取代苯基(如式9-a)、乙基取代苯基等；卤代芳基可以是氟代苯基(如式4-a)、溴代苯基、氯代苯基等；烷氧基芳基可以是甲氧基苯基(如式8-a)、乙氧基苯基等；环氧烷基可以是环氧丙基、环氧丁基、环氧戊基、环氧己基等；环氧芳基可以是环氧乙基苯基、环氧丙基苯基；羟基烷基可以包括羟基正丁基、羟基异丙基(如式7-a)；羟基芳基包括羟基苯基(如式5-a)、二羟基苯基；羟基烷基取代羟基芳基包括羟基烷基取代羟基苯基，例如羟基甲基取代羟基苯基(如式6-a)；氨基芳基可以是氨基取代苯基(如式16-a)；烷基醚基可包括乙醚基等；芳基醚基可包括苯甲基醚基、苯乙基醚基等；环氧烷氧基可以是环氧丙氧基、环氧丁氧基、环氧戊氧基、环氧己氧基等；环氧烷氧基取代芳基可以是环氧丙氧基取代苯基(如式10-a和式11-a)、环氧丁氧基取代苯基、环氧戊氧基取代苯基、环氧己氧基取代苯基等；含烷氧基硅烷的基团(如式12-a和式13-a)可以是包括含γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷的基团。
本申请实施方式中，R 1、R 2、R 3为含碳基团时，含碳基团具有适合的碳原子数能够使得光产酸剂在有机溶剂中具有适合的溶解度，同时具有较好的感光性和光产酸能力，有利于提升光刻效果。本申请一些实施方式中，R 1、R 2、R 3为含碳基团时，碳原子数为1-20。具体地，R 1、R 2、R 3为含碳基团时，碳原子数可为1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20。
本申请一些实施方式中，R 2为含有端羟基的基团，具体地，R 2可以是羟基烷基、羟基芳基。R 2为含有端羟基的基团，还可以调节树脂组合物的碱溶性，从而提升树脂组合物在碱性显影液中的溶解度，减少曝光或非曝光区域的残胶现象，提升图案分辨率和图形形貌规整度。
本申请一些实施方式中，R 2为含有环氧基的基团，具体地是以环氧基封端的基团，例如 可以是环氧烷基、环氧芳基、环氧烷氧基、环氧烷氧基取代芳基等。R 2含有环氧基能够提高树脂的交联程度，从而可以有效调节图案平整度，提升光刻效果。其中，环氧烷基可以是环氧丙基、环氧丁基、环氧戊基、环氧己基等；环氧烷氧基可以是环氧丙氧基、环氧丁氧基、环氧戊氧基、环氧己氧基等；环氧烷氧基取代芳基可以是环氧丙氧基取代苯基、环氧丁氧基取代苯基、环氧戊氧基取代苯基、环氧己氧基取代苯基等。
本申请一些实施方式中，R 2为含烷氧基硅烷的基团，具体地，含烷氧基硅烷的基团可以是包括含γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷的基团。具体地，R 2中烷氧基硅烷部分源自上述烷氧基硅烷。R 2为烷氧基硅烷基封端的基团，即R 2的末端为烷氧基硅烷基。R 2为含烷氧基硅烷的基团，可有效提高感光树脂组合物的固化膜与硅片、金属层等基底之间的粘附力，避免漂胶现象的产生，而且硅氧键具有较好的柔韧性，可以提高固化膜的柔韧性，烷氧基硅烷位阻效应大，有利于维持树脂固化膜的耐热性，可提高保留该固化膜的器件的稳定性。
本申请实施方式中，杂环基是指构成环的原子除碳原子外还有其他原子的有机环状基团，杂环基可以有一个杂原子，也可以有两个或更多个杂原子，杂原子可以是一种原子，也可以是两种不同的原子；杂环基可以是通过杂原子与萘环上的碳原子连接，也可以是通过碳原子与萘环上的碳原子连接。本申请实施方式中，X可以是选自含有O、N或S的五元杂环基、六元杂环基、或苯并杂环基。其中五元杂环基具体可以是源自呋喃、噻吩、吡咯、噻唑、咪唑、三氮唑、四氮唑等五元杂环化合物；六元杂环基可以是源自吡啶、吡嗪、嘧啶、哒嗪等六元杂环化合物。
本申请一些实施方式中，杂环基X为含有三个氮原子的五元或六元杂环基，且其中的一个氮原子与萘环的碳原子连接。本申请一实施方式中，X为含有三个氮原子的五元杂环基，光产酸剂的分子结构如式(I-a)所示：
Figure PCTCN2022122570-appb-000010
本申请一些实施方式中，杂环基X为含有四个氮原子的五元或六元杂环基，且其中的一个氮原子与萘环的碳原子连接。本申请一实施方式中，X为含有四个氮原子的五元杂环基，光产酸剂的分子结构如式(I-b)所示：
Figure PCTCN2022122570-appb-000011
本申请实施例中，杂环基X为含有三个氮原子或四个氮原子的五元或六元杂环基，在合 成上可以通过萘环上的-N 3与乙炔基或甲腈反应实现，无需提纯，且该结构吸电性可较好地调控光产酸剂的吸光波长，同时氮唑类易与金属离子(如铜离子)形成配合物，能有效减少铜离子等金属离子向树脂组合物固化膜中迁移扩散，还有利于提升树脂组合物自身与铜界面、硅界面作用的能力。
本申请一些实施方式中，所述光产酸剂的分子结构如式1-a至23-a所示：
Figure PCTCN2022122570-appb-000012
Figure PCTCN2022122570-appb-000013
本申请实施例提供一种光产酸剂的制备方法，包括：
将4-溴-1,8-萘二甲酸酐中的溴取代位接枝取代杂环基-X-R 2，并在酐基酰胺化后接枝取代磺酸基，得到光产酸剂，其中，X包括含有O、N或S的杂环基；R 2包括卤素、芳基、芳烷基、烷芳基、卤代芳基、烷氧基芳基、环氧烷基、环氧芳基、羟基烷基、羟基芳基、羟基烷 基取代羟基芳基、氨基芳基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷的基团。
一些实施方式中，当X为三氮唑或四氮唑基团时，可以是将4-溴-1,8-萘二甲酸酐中的溴取代位叠氮化后，再实现取代杂环基-X-R 2的接枝。叠氮化过程可以是采用叠氮化钠。
本申请实施方式中，酐基酰胺化过程可以是加入酰胺化试剂，具体可以是包括盐酸羟胺，酰胺化过程还可以加入碳酸氢钠，接枝取代磺酸基的过程可以是加入取代磺酸酐。
以光产酸剂1-a为例，其制备方法具体可以是包括：
(1)将4-溴-1,8-萘二甲酸酐(化合物1a)溶解在DMF(N,N-二甲基甲酰胺)中，室温下加入叠氮化钠，50℃-80℃反应。反应结束后，反应液通过冰水析出，过滤收集黄色沉淀，干燥后得到化合物1b。
(2)将化合物1b和苯乙炔溶解在四氢呋喃THF和水的混合溶液中(THF:H 2O体积比可以是4:1)，氮气气氛下先后加入五水硫酸铜和抗坏血酸钠，加热回流反应。反应结束后，将反应液倒入冰水中析出，过滤收集黄绿色沉淀，干燥后得到化合物1c。
(3)将化合物1c、盐酸羟胺和碳酸氢钠加入乙醇中，加热回流反应，反应结束后减压抽滤，用乙醇、去离子水洗涤，干燥得到橙黄色粉末化合物1d。
(4)将上述化合物1d溶于乙腈中，在氮气氛围下，冰浴下滴加吡啶和三氟甲磺酸酐，再加热至50-80℃进行反应，反应结束后，待反应液冷却到室温，抽滤，滤渣用乙腈冲洗后用油泵抽干，得到白色粉末化合物，即为光产酸剂1-a。
上述反应过程如下所示：
Figure PCTCN2022122570-appb-000014
本申请实施例还提供一种感光树脂组合物，感光树脂组合物包括树脂或树脂前驱体、交联剂、本申请实施例上述的光产酸剂、以及有机溶剂。
本申请的感光树脂组合物可以是负型感光树脂组合物。负型感光树脂组合物经曝光显影后，未曝光部分被洗掉，曝光部分保留。本申请实施例负型感光树脂组合物的图案化原理为：光产酸剂受到光源照射产酸(取代或非取代磺酸)，在后续热处理的过程中，产生的酸持续催化交联剂发生交联、或交联剂和聚合物树脂发生交联，导致聚合物树脂的曝光区域和未曝光区域在显影液中形成明显的溶解度差异，即曝光区域由于发生交联溶解性急剧下降，而非曝光区域依然保持较好的溶解性，最终未曝光区域被洗掉，曝光区域保留，从而显示出光刻图案。
本申请的感光树脂组合物也可以是正型感光树脂组合物。正型感光树脂组合物经曝光显影后，曝光部分被洗掉，未曝光部分保留。本申请实施例正型感光树脂组合物的图案化原理为：在前烘过程中，组合物中的乙烯基醚与树脂分子链上的羟基反应，不溶于碱性显影液，曝光后PAG产生H +，催化曝光区的乙烯基醚脱除，露出原有的羟基，变为可溶于碱性显影 液，而非曝光区依然不溶。
本申请实施方式中，以高分子树脂为100质量份计，感光树脂组合物中光产酸剂可为0.5-20质量份。一些实施例中，感光树脂组合物中光产酸剂为3-15质量份。一些实施例中，感光树脂组合物中光产酸剂为7-12质量份。具体实施例中，感光树脂组合物中光产酸剂的质量份为0.5、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20份。本申请实施例的光产酸剂在i-line处的吸光度高，则光产酸剂的光敏感性高、光产酸能力强，从而可以更好地形成酸，催化交联反应的发生，提升曝光区和非曝光区的溶解度差异，提升图案的分辨率。
本申请实施例的光产酸剂对树脂具有普适性，没有特殊要求。本申请实施方式中，感光树脂组合物中的树脂或树脂前驱体可以根据实际应用需求进行选择，树脂或树脂前驱体可以是自行制备得到，也可以是通过市售购得。感光树脂组合物中可以是包含一种或多种树脂组分。一些实施方式中，树脂包括酚醛树脂、环氧树脂、丙烯酸树脂、苯并环丁烯树脂、苯并噁唑树脂、聚酰亚胺树脂中的一种或多种。一些实施方式中，树脂前驱体包括酚醛树脂前驱体、环氧树脂前驱体、丙烯酸树脂前驱体、苯并环丁烯树脂前驱体、苯并噁唑树脂前驱体、聚酰亚胺树脂前驱体中的一种或多种。本申请实施方式中，树脂的重均分子量可为5000-100000；一些实施例中，树脂的重均分子量可为10000-80000；一些实施例中，树脂的重均分子量可为20000-50000。
本申请实施方式中，交联剂包括多羟基交联剂，具体地交联剂可以是含有苄基醇结构的化合物单体。该单体在酸性条件下，可以发生交联，形成聚合型大分子，溶解度降低。一些实施方式中，含有苄基醇结构的化合物单体可以是如式A所示的化合物2,6-双(羟甲基)-4-甲酚，或如式B所示的化合物(MBHP)。
Figure PCTCN2022122570-appb-000015
本申请实施方式中，以高分子树脂为100质量份计，感光树脂组合物中交联剂为1-30质量份。一些实施例中，感光树脂组合物中交联剂为5-25质量份。一些实施例中，感光树脂组合物中交联剂为10-20质量份。
本申请实施方式中，以高分子树脂为100质量份计，感光树脂组合物中有机溶剂为130-740质量份。一些实施例中，感光树脂组合物中有机溶剂为195-520质量份。一些实施例中，感光树脂组合物中有机溶剂为240-390质量份。
本申请实施方式中，有机溶剂可以是包括酯类、酮类、醚类或酰胺类有机溶剂中的一种或多种。其中，酯类有机溶剂可以是乙酸乙酯、乙酸正丁酯、乙酸异丁酯、甲酸戊酯、乙酸异戊酯、丙酸丁酯、丁酸异丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁内酯、ε-己内酯、δ-戊内酯、烷氧基乙酸烷基酯、3-烷氧基丙酸烷基酯类、2-烷氧基丙酸烷基酯类、2-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙酰乙酸甲酯、乙酰乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯等。酮类有机溶剂可以是甲基乙基酮、环己酮、环戊酮、2-庚酮、3-庚酮等。醚类有机溶剂可以是二乙二醇二甲醚、四氢呋喃、乙二醇单甲醚、乙二醇单乙醚、甲基溶纤剂乙酸酯、乙基溶纤剂乙酸酯、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、丙二醇单甲醚、丙二醇单甲醚乙酸酯、丙二 醇单乙醚乙酸酯、丙二醇单丙醚乙酸酯等。酰胺类有机溶剂可以是N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N,N-二甲基乙酰氨、N,N-二甲基甲酰氨等。
本申请实施方式中，上述感光树脂组合物可以是将树脂或树脂前驱体、交联剂、光产酸剂、以及有机溶剂混合均匀后制备得到。
本申请实施方式中，采用感光树脂组合物进行图案化时所需作用在感光树脂组合物上的曝光能量为80mJ/cm 2-170mJ/cm 2。具体实施例中，曝光能量可以是80mJ/cm 2、90mJ/cm 2、100mJ/cm 2、110mJ/cm 2、120mJ/cm 2、130mJ/cm 2、150mJ/cm 2、160mJ/cm 2、170mJ/cm 2。
本申请实施例还提供一种图案形成方法，包括：
S01、将本申请实施例上述的感光树脂组合物涂覆在基体上，形成涂膜；
基体可以硅基材质或金属材质(例如铜)，涂膜的厚度可以根据实际需要进行调整。涂膜形成后可通过加热干燥涂膜，使部分溶剂挥发。
S02、根据预设图案曝光涂膜；
本申请实施方式中，曝光涂膜时可使用365nm汞灯光源进行曝光，曝光能量可以是80mJ/cm 2-170mJ/cm 2。曝光后可进行干燥处理。
S03、采用显影液显影曝光后的涂膜获得树脂图案；
本申请实施方式中，显影液可以是根据感光树脂组合物的溶解性能确定，例如可以是碱性显影液。对于负型感光树脂组合物，曝光区域保留，而非曝光区域被洗掉，从而形成树脂图案。
S04、对树脂图案进行热处理。热处理可以使树脂实现固化形成固化膜，热处理的温度可以是100-350℃，具体温度可根据树脂的固化性能而定，一些实施方式中，热处理可以是采用程序升温固化，例如可以是按照100℃(1h)→200℃(1h)→300℃(1h)的程序升温固化。程度升温固化有利于固化完全，形成膜层均匀、稳定、质量高的固化膜。
本申请实施例还提供一种固化膜，固化膜为上述感光树脂组合物的固化膜，由上述感光树脂组合物经固化得到。该固化膜为图案化的固化膜，由上述感光树脂组合物经光刻固化得到。
本申请实施方式中，固化膜上的图案的分辨率为小于或等于4μm。图案的分辨率值越小，表示图案的分辨率越高。图案的分辨率可以是为4μm、3μm、2μm、1μm、0.5μm。
本申请实施方式中，固化膜上的图案的倾角为>65°。具体地，固化膜上的图案的倾角可以是为70°、75°、80°、85°、90°。倾角是图案相对基底膜层平面的倾斜角度，倾角越接近90°表明图案化的效果越好。
本申请实施例还提供一种电子器件100，电子器件100包括本申请实施例上述的固化膜。固化膜在电子器件100中可作为保护层、钝化层、层间绝缘层、缓冲层、平坦化层、α射线屏蔽层或再布线层等。图1为电子器件100的局部封装结构示意图，电子器件100包括半导体芯片10，设置在半导体芯片10的一个表面上的焊盘20，设置在芯片10和焊盘20上的钝化层30，钝化层30上形成有再布线层40，再布线层40包括第一介电层401、第二介电层402、再布线种子层403和再布线金属层404。第一介电层401设置在钝化层30上，第一介电层401上形成有使焊盘20露出的过孔，再布线种子层403和再布线金属层404依次形成在过孔中，第二介电层402设置在第一介电层401上并覆盖再布线金属层404，第二介电层402上形成有使再布线金属层404露出的过孔，过孔内依次形成有金属连接层501、凸块下金属层502、焊锡凸块503。半导体芯片10可以是任意形式的芯片，例如可以是处于裸态的集成电路(IC)，焊盘20可包括铝等导电材料，钝化层30可以是包括氧化物、氮化物等。第一介电层401和 第二介电层402可为本申请实施例的感光树脂组合物固化形成的图案化的固化膜。再布线金属层404为铜层。金属连接层501可以是Ti/Cu溅射层，凸块下金属层502可以是Ni层。在半导体芯片的封装结构中，通常存在固化膜与硅、铜的结合界面，本申请实施例通过采用本申请实施例感光树脂组合物形成固化膜，可以有效改善固化膜与硅、铜的结合界面，提升封装结构的稳定性。
本申请实施方式中，固化膜设置在硅片或金属层上，固化膜与硅片之间的附着力达到国标可靠性百格测试3B或4B标准；固化膜与金属层之间的附着力达到国标可靠性百格测试4B或5B标准。金属层例如可为铜层。
本申请实施例提供的光产酸剂还可以用于各类感光材料中，例如涂料、油墨、抗蚀剂、负型感光材料、光刻材料等。
下面分多个实施例对本申请实施例进行进一步的说明。
实施例1
(一)光产酸剂1-a的合成
(1)将化合物1a溶解在DMF中，室温下滴加等摩尔比的叠氮化钠的水溶液，高温下反应2h。反应结束后，待反应液冷却到室温后倒入冰水中析出，过滤收集黄色沉淀，鼓风干燥7h得到化合物1b。
(2)将化合物1b和过量苯乙炔(约4倍摩尔量)溶解在四氢呋喃THF和水的混合溶液中，氮气气氛下先后加入等摩尔量的五水硫酸铜和5倍摩尔量的抗坏血酸钠，高温回流反应5h。将反应液倒入冰水中析出，过滤收集黄绿色沉淀，鼓风干燥4h得到化合物1c。
(3)将化合物1c、盐酸羟胺和碳酸氢钠按照摩尔比5:6:6的比例溶解于乙醇中。在高温下回流8小时，减压抽滤，用乙醇、去离子水反复洗涤，鼓风干燥得到橙黄色粉末化合物1d。
(4)将化合物1d溶于乙腈中，在氮气氛围和冰浴下滴加2倍摩尔量的吡啶和2倍摩尔量的三氟甲磺酸酐，高温下反应3h，反应结束后，待反应液冷却到室温，直接抽滤，滤渣用乙腈冲洗后用油泵抽干，得到白色粉末化合物即光产酸剂1-a。光产酸剂1-a表征结果：1H NMR(400MHz,CDCl 3,ppm)δ:8.87-8.84(m,2H),8.57-8.55(d,1H),8.31(s,1H),8.02-7.99(m,4H),7.56-7.52(m,2H),7.48-7.44(m,1H)。质谱[M+H] +:计算值为489.0，实验值为489.1。
上述步骤(1)至步骤(4)的合成反应过程如下所示：
Figure PCTCN2022122570-appb-000016
(二)感光树脂组合物的制备
将6FAP(36.6g，100mmol)和对氨基苯酚(0.655g，6mmol)加入N-甲基吡咯烷酮(NMP)中搅拌溶解完全后，氮气环境下加入6FDA(45.6g，103mmol)并调节固含量至25wt.％，室温搅拌14h，得到粘稠液体PAA。然后加入甲苯40mL，异喹啉6滴，升温至180℃，回流反应14h。将体系中甲苯全部蒸出，冷却至室温，在乙醇：水体积比为1:1的混合溶剂中 析出，120℃真空干燥12h，得到灰白色固体聚酰亚胺树脂PHI，树脂的分子量为30000左右。聚酰亚胺树脂PHI的制备过程反应式如下所示，式中n表示聚合度。
Figure PCTCN2022122570-appb-000017
取100质量份的分子量30000左右的PHI树脂、10质量份实施例1制备的光产酸剂以及20质量份的交联剂MBHP，溶解于303质量份的N-甲基吡咯烷酮(NMP)中，使得组合物的总固含量(树脂、产酸剂、交联剂三种固体的总量占溶剂的质量分数)为30wt.％，搅拌混合均匀后真空脱泡，形成感光树脂组合物。
(三)图案化的固化膜的制备
将配制好的感光树脂组合物旋涂在硅片上成膜，在110℃的热板上加热前烘3min使部分溶剂挥发，得到干燥后的组合物涂膜。将该膜置于掩膜下，使用365nm汞灯光源的接触式曝光机进行曝光，曝光能量范围为100-150mJ/cm 2。曝光后的膜在热板上130℃烘2min后；在显影机中进行喷淋显影后用去离子水漂洗，曝光区域的膜层被保留，非曝光区域的膜层被去除，氮气吹去硅片上残留的液体，然后按照100℃(1h)→200℃(1h)→300℃(1h)的程序升温固化，形成图案化的固化膜。
将配制好的感光树脂组合物旋涂在铜片上成膜，在110℃的热板上加热前烘3min使部分溶剂挥发，得到干燥后的组合物涂膜。将该膜置于掩膜下，使用365nm汞灯光源进行曝光，曝光能量为100-150mJ/cm 2。曝光后的膜在热板上130℃烘2min后；在显影机中进行喷淋显影后用去离子水漂洗，氮气吹去铜片上残留的液体，然后按照100℃(1h)→200℃(1h)→300℃(1h)的程序升温固化，形成图案化的固化膜。
将实施例1制备的光产酸剂采用紫外可见光谱仪进行测试，获知实施例1制备的光产酸剂在i-line处吸光度好，对365nm的光具有较好吸收，光敏感度高。
采用本申请实施例1的感光树脂组合物的进行图案化，结果显示线宽4μm掩膜版下的光刻图案条纹清晰平整无残胶粘连，该感光树脂组合物可获得的图案分辨率为4μm。
采用百格测试法对实施例1固化膜与硅片、以及固化膜与铜片之间的附着力进行测试，结果显示实施例1固化膜与硅片、以及固化膜与铜片之间的附着力分别达到国标可靠性百格测试3B与4B标准。
百格测试参照标准《GBT9286-1998》进行。国标百格测试包括以下6个等级：5B标准：切口的边缘完全光滑、格子边缘没有任何剥落；4B标准：切口相交处有小片剥落，划格区实际破损不超过5％；3B标准：切口的边缘或相交处有剥落，破损面积大于5％，小于15％；2B标准：切口边缘有部分剥落或大片剥落，或部分格子整片剥落，破损面积大于15％，小于35％；1B标准：切口边缘大片剥落，或部分格子整片剥落，破损面积大于35％，小于65％；0B标准：破损面积大于65％。
本申请实施例的光产酸剂通过在萘酰亚胺的萘环上引入氮唑环，并在氮唑环上引入基苯基，利用苯基与氮唑环的特殊电子效应调控光产酸剂的最佳吸光波长落在345～355nm，同时 可以使固化膜与硅、铜之间的附着力具有较高水平。
实施例2
(一)光产酸剂6-a的合成
(1)将4-溴苯酚和氢氧化钾按摩尔比3:4溶解在2-丙醇中，滴加0.3mL甲醛水溶液后，在40℃下加热搅拌48小时。冷却到室温后，倒入1mL盐酸后静置6h形成红色沉淀。抽滤去除红色沉淀后再静置两天，析出白色沉淀，干燥后得到白色固体的化合物4a。
(2)将95mg化合物4a溶解在吡啶中，冰水浴的条件下滴加0.2mL的乙酸酐。在室温下搅拌1.5h后，加入10mL的乙酸乙酯。用五水硫酸铜溶液洗涤以除去吡啶，有机层干燥后旋蒸浓缩，用乙酸乙酯和正己烷柱层析后得到白色的固体化合物4b。
(3)将128mg化合物4b及0.07mL三甲基硅乙炔溶解在三乙胺中，氮气气氛下加入6.7mg三苯基磷、8.3mg碘化亚铜及5.2mg双(三苯基磷)二氯化钯。加热回流24h。过滤，旋蒸除去溶剂，用乙酸乙酯和正己烷柱层析后得到棕色液体化合物4c。
(4)在冰水浴的条件下，向氢化铝锂的THF溶液中滴加化合物4c的THF溶液，室温下搅拌2h，冰水浴条件下滴加1mL的去离子水。将反应液在室温下继续搅拌12h。加入10mLHCl水溶液反应液以沉淀出铝盐。过滤，减压旋蒸后，用乙酸乙酯溶解后再用饱和食盐水洗涤，有机层用无水硫酸镁干燥，过滤，旋蒸除去溶剂，得到白色固体化合物4d(即羟甲基取代羟基苯乙炔)。
上述步骤(1)至步骤(4)的合成反应过程如下所示：
Figure PCTCN2022122570-appb-000018
(5)将化合物1b、盐酸羟胺和碳酸氢钠按摩尔比5:6:6的比例溶解于乙醇中。高温下回流8小时，减压抽滤，用乙醇、去离子水反复洗涤，鼓风干燥得到橙黄色粉末化合物4e。
(6)将化合物4e溶于乙腈中，在氮气氛围和冰浴下滴加2倍摩尔量的吡啶和2倍摩尔量的三氟甲磺酸酐，高温反应3h，反应结束后，待反应液冷却到室温，直接抽滤，滤渣用乙腈冲洗后用油泵抽干，得到为黄色粉末的化合物4f。(7)将等摩尔比的化合物4f和化合物4d溶解在THF溶液中，氮气气氛下先后加入等摩尔量的五水硫酸铜和5倍摩尔量的抗坏血酸钠，高温回流反应5h。将反应液倒入冰水中析出，过滤收集黄绿色沉淀，鼓风干燥4h得到光产酸剂6-a。质谱[M+H]+:计算值为564.0，实验值为564.1。
上述步骤(5)至步骤(7)的合成反应过程如下所示：
Figure PCTCN2022122570-appb-000019
(二)感光树脂组合物的制备
取100质量份的分子量30000左右的PHI树脂、8质量份实施例2制备的光产酸剂以及20质量份的交联剂MBHP，溶解于298质量份N-甲基吡咯烷酮(NMP)中，使得组合物的总固含量为30wt.％，搅拌混合均匀后真空脱泡，形成感光树脂组合物。
(三)图案化的固化膜的制备
将配制好的感光树脂组合物旋涂在硅片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为80-150mJ/cm 2。
将配制好的感光树脂组合物旋涂在铜片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为80-150mJ/cm 2。
将实施例2制备的光产酸剂采用紫外可见光谱仪进行测试，获知实施例2制备的光产酸剂在i-line处吸光度好，对365nm的光具有较好吸收，光敏感度高。
采用本申请实施例2的感光树脂组合物进行图案化，结果显示，线宽2μm掩膜版下的光刻图案条纹清晰平整无残胶粘连，该感光树脂组合物可获得的图案分辨率为2μm。
采用百格测试法对实施例2固化膜与硅片、以及固化膜与铜片之间的附着力进行测试，结果显示实施例2固化膜与硅片、以及固化膜与铜片之间的附着力分别达到国标可靠性百格测试3B与4B标准。
本申请实施例的光产酸剂通过在萘酰亚胺的萘环上引入氮唑环，并在氮唑环上引入多羟基苯基，一方面可以利用多羟基苯基与氮唑环的电子效应调控光产酸剂的最佳吸光波长落在350～360nm；同时可以使固化膜与硅、铜之间的附着力具有较高水平；另外通过多羟基苯基可以提高树脂组合物在碱性显影液中的溶解性，从而最终可提高图案的分辨率，减少非曝光区的残胶现象。
实施例3
(一)光产酸剂10-a的合成
(1)将化合物1a溶解在DMF(N,N-二甲基甲酰胺)中，室温下将滴加等摩尔量的叠氮化钠的水溶液到反应体系中高温反应2h。反应结束后，待反应液冷却到室温后倒入冰水中析出，过滤收集黄色沉淀，50℃鼓风干燥7h得到化合物1b。(2)将等摩尔比的化合物1b和4-乙炔基苯酚溶解于DMF中，加入等摩尔量的五水硫酸铜5倍摩尔量的抗坏血酸钠。反应混合物在高温下搅拌反应14h，倒入冰水中，抽滤得到固体沉淀。用冷水洗涤沉淀后，烘干，得到化合物6a。
(3)将化合物6a和NaH按摩尔比为1:3的比例加入无水四氢呋喃中。氮气氛下室温搅拌1小时后，将5倍摩尔量环氧氯丙烷的四氢呋喃溶液逐滴加入反应混合物。加热回流8小时，冷却至室温后，将溶液混合物倒入水中，并用乙醚萃取。合并有机层，用无水Na 2SO 4干燥，旋蒸除去溶剂，通过柱色谱法提纯即可得到化合物6b。
(4)将化合物6b、盐酸羟胺、碳酸氢钠按摩尔比5:6:6的比例溶解于乙醇中。回流反应3h，冷却到室温后抽滤，用乙醇、去离子水反复洗涤，70℃下鼓风干燥得到橙黄色粉末化合物6c。
(5)将化合物6c溶于乙腈，滴加2倍摩尔量的吡啶与2倍摩尔量的三氟甲烷磺酰氯。高温反应15h，旋蒸除去溶剂，经硅胶柱层析提纯得到光产酸剂10-a。质谱[M+H]+:计算值为560.1，实验值为560.2。
上述步骤(1)至步骤(5)的合成反应过程如下所示：
Figure PCTCN2022122570-appb-000020
(二)感光树脂组合物的制备
取100质量份的分子量30000左右的PHI树脂、8质量份实施例3中合成的光产酸剂以及20质量份的交联剂MBHP，溶解于298质量份的N-甲基吡咯烷酮(NMP)中，使得组合物的总固含量为30wt.％，搅拌混合均匀后真空脱泡，形成感光树脂组合物。
(三)图案化的固化膜的制备
将配制好的感光树脂组合物旋涂在硅片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为100-150mJ/cm 2。
将配制好的感光树脂组合物旋涂在铜片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为100-150mJ/cm 2。
将实施例3制备的光产酸剂采用紫外可见光谱仪进行测试，获知实施例3制备的光产酸剂在i-line处吸光度好，对365nm的光具有较好吸收，光敏感度高。
图2和图3为本申请实施例3的感光树脂组合物的光刻效果图，具体地图2为线宽8μm掩膜版下的光刻图案(固化后)；图3为线宽4μm掩膜版下的光刻图案(固化后)。由图2可知，线宽8μm掩膜版下的光刻图案陡直无塌陷，图案清晰平整。由图3可知，线宽4μm掩膜版下的光刻图案可基本显影开出，该感光树脂组合物可获得的最佳图案分辨率约为4μm。
采用百格测试法对实施例3固化膜与硅片、以及固化膜与铜片之间的附着力进行测试，结果显示实施例3固化膜与硅片、以及固化膜与铜片之间的附着力均达到国标可靠性百格测试4B标准。
本申请实施例的光产酸剂通过在萘酰亚胺的萘环上引入氮唑环，并在氮唑环上引入环氧烷氧基取代苯基，一方面可以利用环氧烷氧基取代苯基与氮唑环的电子效应调控光产酸剂的最佳吸光波长落在355～380nm；同时可以使固化膜与硅、铜之间的附着力具有较高水平；另 外通过环氧基团在酸催化与高温下能够发生交联反应，可以提高树脂在显影与固化过程中的交联程度，提升图案的平整度，倾角由普通的60°-70°提高到90°附近。
实施例4
(一)光产酸剂13-a的制备
(1)将催化量的氯化铜和N,N-二异丙基乙胺溶解在乙醚中，在冰水浴的条件下，缓慢滴加等摩尔量的3-氯丙炔和三氯硅烷的混合乙醚溶液，升到室温后搅拌2h。将反应液中的固体过滤后，80℃的条件下减压蒸馏，得到化合物3a。
(2)将化合物1b和过量化合物3a(约4倍摩尔量)溶解在THF中，氮气气氛下先后加入等摩尔量的五水硫酸铜和5倍摩尔量的抗坏血酸钠，高温回流反应5h。将反应液倒入冰水中析出，过滤收集黄绿色沉淀，鼓风干燥4h得到化合物3b。
(3)将化合物3b、盐酸羟胺和碳酸氢钠按摩尔比5:6:6的比例溶于乙醇中，高温回流8小时，减压抽滤，用乙醇、去离子水反复洗涤，70℃鼓风干燥得到橙黄色粉末化合物3c。
(4)将化合物3c溶于乙腈中，在氮气氛围和冰浴下滴加2倍摩尔量的吡啶和2倍摩尔量的三氟甲磺酸酐，60℃反应3h后冷却到室温，直接抽滤，滤渣用乙腈冲洗后用油泵抽干，得到为白色粉末的光产酸剂13-a。质谱[M+H] +:计算值为588.1，实验值为588.2。
上述步骤(1)至步骤(4)的合成反应过程如下所示：
Figure PCTCN2022122570-appb-000021
(二)感光树脂组合物的制备
取100质量份的分子量30000左右的PHI树脂、12质量份实施例4中合成的光产酸剂以及20质量份的交联剂MBHP，溶解于308质量份的N-甲基吡咯烷酮(NMP)中，使得组合物的总固含量为30wt.％，搅拌混合均匀后真空脱泡，形成感光树脂组合物。
(三)图案化的固化膜的制备
将配制好的感光树脂组合物旋涂在硅片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为120-170mJ/cm 2。
将配制好的感光树脂组合物旋涂在铜片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为120-170mJ/cm 2。
将实施例4制备的光产酸剂采用紫外可见光谱仪进行测试，获知实施例4制备的光产酸剂在i-line处吸光度好，对365nm的光具有较好吸收，光敏感度高。
图4为本申请实施例4的感光树脂组合物的光刻效果图，具体地为不同线宽掩膜版下的 光刻图案(固化后)。由图4可知，线宽2μm掩膜版下的光刻图案清晰平整无残胶粘连，该感光树脂组合物可获得的图案分辨率为2μm。
采用百格测试法对实施例4固化膜与硅片、以及固化膜与铜片之间的附着力进行测试，结果显示实施例4固化膜与硅片、以及固化膜与铜片之间的附着力分别达到国标可靠性百格测试4B与5B标准。
本申请实施例的光产酸剂通过在萘酰亚胺的萘环上引入氮唑环，并在氮唑环上引入末端含烷氧基硅烷的取代苯基，一方面可以利用取代苯基与氮唑环的电子效应调控光产酸剂的最佳吸光波长落在380nm附近，提高i-line光敏感性；同时通过末端的烷氧基硅烷基团可以更进一步提高固化膜与硅片、铜片之间的附着力，消除了漂胶现象，同时可提高固化膜层结构稳定性。
实施例5
(一)光产酸剂2-a的制备
(1)将化合物1b和过量苯甲腈(约4倍摩尔量)溶解在THF中，氮气气氛下先后加入等摩尔量的五水硫酸铜和5倍摩尔量的抗坏血酸钠，高温回流反应5h。将反应液倒入冰水中析出，过滤收集黄绿色沉淀，鼓风干燥4h得到化合物2a。
(2)将化合物2a、盐酸羟胺和碳酸氢钠按照摩尔比5:6:6的比例溶解于乙醇中。高温回流8小时，减压抽滤，用乙醇、去离子水反复洗涤，鼓风干燥得到橙黄色粉末化合物2b。
(3)将化合物2b溶于乙腈中，在氮气氛围和冰浴下滴加2倍摩尔量的吡啶和2倍摩尔量的三氟甲磺酸酐，60℃反应3h后冷却到室温，直接抽滤，滤渣用乙腈冲洗后用油泵抽干，得到为白色粉末的光产酸剂2-a。质谱[M+H]+:计算值为489.0，实验值为489.1。
上述步骤(1)至步骤(3)的合成反应过程如下所示：
Figure PCTCN2022122570-appb-000022
(二)感光树脂组合物的制备
取100质量份的分子量30000左右的PHI树脂、10质量份实施例5中合成的光产酸剂以及20质量份的交联剂MBHP，溶解于303质量份的N-甲基吡咯烷酮(NMP)中，使得组合物的总固含量为30wt.％，搅拌混合均匀后真空脱泡，形成感光树脂组合物。
(三)图案化的固化膜的制备
将配制好的感光树脂组合物旋涂在硅片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为100-150mJ/cm 2。
将配制好的感光树脂组合物旋涂在铜片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为100-150mJ/cm 2。
将实施例5制备的光产酸剂采用紫外可见光谱仪进行测试，获知实施例5制备的光产酸 剂在i-line处吸光度好，对365nm的光具有较好吸收，光敏感度高。
采用本申请实施例4的感光树脂组合物进行图案化，结果显示线宽4μm掩膜版下的光刻图案清晰平整，无粘连，该感光树脂组合物可获得的最佳图案分辨率约为4μm。
采用百格测试法对实施例4固化膜与硅片、以及固化膜与铜片之间的附着力进行测试，结果显示实施例5固化膜与硅片、以及固化膜与铜片之间的附着力分别达到国标可靠性百格测试3B与4B标准。
本申请实施例的光产酸剂通过在萘酰亚胺的萘环上引入四氮唑环，并在四氮唑环上引入取代苯基，可以利用苯基与四氮唑环的电子效应调控光产酸剂的最佳吸光波长落在345-360nm附近，提高i-line光敏感性；同时可以使固化膜与硅、铜之间的附着力具有较高水平。
对比例1
感光树脂组合物的制备：取实施例1合成的100质量份的PHI-30000树脂、12质量份的光产酸剂PTMA((5-丙基磺酰氧基亚氨基-5H-噻吩-2-亚基)-(2-甲基苯基)乙腈)以及20质量份的交联剂MBHP，溶解于298质量份的N-甲基吡咯烷酮(NMP)中，使得组合物的总固含量为30w.t.％，搅拌混合均匀后真空脱泡，形成感光树脂组合物。
将配制好的感光树脂组合物旋涂在硅片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为150-200mJ/cm 2。
将配制好的感光树脂组合物旋涂在铜片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为150-200mJ/cm 2。
对比例1中光产酸剂PTMA的最佳吸光波长在415nm，i-line处吸光度不佳。
图5为本申请对比例1的感光树脂组合物的光刻效果图，具体地为不同线宽掩膜版下的光刻图案(固化后)。从图5可以看出，采用本申请对比例1的感光树脂组合物光刻显影后漂胶严重，底膜与硅片的粘附力不足，勉强可以得到10μm分辨率的条纹。
采用百格测试法对对比例1固化膜与硅片、以及固化膜与铜片之间的附着力进行测试，结果显示对比例1固化膜与硅片、以及固化膜与铜片之间的附着力均达到国标可靠性百格测试2B标准。
对比例2
(一)无取代的萘酰亚胺型光产酸剂的合成
(1)将1,8-萘二酐、盐酸羟胺和碳酸氢钠按照比5:6:6的比例溶解于乙醇，高温下回流3h。将反应混合物减压抽滤，用乙醇和水反复洗涤，80℃干燥得到深黄色粉末NI-OH。
(2)将NI-OH和吡啶按照摩尔比2:3的比例溶解于乙腈，冰浴下缓慢滴加与吡啶等摩尔量的三氟甲磺酸酐。高温搅拌反应12小时后(TLC监测反应，产物点不再增加)，减压旋蒸得到棕黄色固体。粗产物经硅胶柱层析得到白色固体，即无取代的萘酰亚胺型光产酸剂NI-Tf。1H NMR(400MHz,DMSO-d6,ppm)δ:8.65-8.62(m,4H),7.96-8.00(m,2H)。质谱[M+H]+：计算值为346.0，实验值为346.0。
Figure PCTCN2022122570-appb-000023
(二)感光树脂组合物的制备
取100质量份的PHI-30000树脂、10质量份对比例2中合成的PAG以及20质量份的交联剂MBHP，溶解于303质量份的N-甲基吡咯烷酮(NMP)中，使得组合物的总固含量为30w.t.％，搅拌混合均匀后真空脱泡，形成感光树脂组合物。
将配制好的感光树脂组合物旋涂在硅片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为150-200mJ/cm 2。
将配制好的感光树脂组合物旋涂在铜片上制得图案化的固化膜，方法同实施例1，其中曝光过程中的曝光能量为150-200mJ/cm 2。
对比例2的光产酸剂的最佳吸收波长在340nm，在i-line处吸光度一般。
图6和图7为本申请对比例2的感光树脂组合物的光刻效果图，其中，图6为线宽8μm掩膜版下的光刻图案(固化后)；图7为线宽4μm掩膜版下的光刻图案(固化后)。从图6可以看出，线宽8μm掩膜版下的光刻图案条纹溶解收缩导致平整度差，从图7可以看出，线宽4μm掩膜版下的光刻图案条纹间显影不净导致粘连严重。对比例2的感光树脂组合物的图案分辨率为8μm。
采用百格测试法对对比例2固化膜与硅片、以及固化膜与铜片之间的附着力进行测试，结果显示对比例2固化膜与硅片、以及固化膜与铜片之间的附着力均达到国标可靠性百格测试3B标准。
将实施例1-5与对比例1-2中光产酸剂的最佳吸光波长、感光树脂组合物的光刻性能以及感光树脂组合物固化膜与硅、铜界面的粘附性结果汇总如表1所示。
表1.实施例与对比例试验结果
Figure PCTCN2022122570-appb-000024
由表1的结果可知，相比对比例1-2，本申请实施例1-5的光产酸剂的最佳吸光波长向365nm靠近，且i-line处的吸光度较高，因此光刻图案的分辨率提升，实施例1-5显示至少可以获得4μm的分辨率。相比对比例1-2，本申请实施例1-5的感光树脂组合物固化膜与硅、铜界面的粘附性提升。一些实施例中，采用本申请实施例的光产酸剂还可以一定程度使曝光过程中所需曝光剂量降低。

Claims (26)

  1. 一种感光分子，其特征在于，所述感光分子的分子结构包括萘酰亚胺结构、与所述萘酰亚胺结构中氮原子连接的取代磺酸基、以及与所述萘酰亚胺结构中萘环连接的杂环基X，与所述杂环基连接的R 2；
    所述杂环基X包括含有O、N或S的杂环基；所述R 2包括卤素、芳基、芳烷基、烷芳基、卤代芳基、烷氧基芳基、环氧烷基、环氧芳基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基芳基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。
  2. 如权利要求1所述的感光分子，其特征在于，所述取代磺酸基表示为-SO 3R 1，所述R 1包括烷基、芳基、烷基芳基、卤代烷基或卤代芳基中的一个基团。
  3. 如权利要求1或2所述的感光分子，其特征在于，所述杂环基X为含有三个氮原子的五元或六元杂环基，且其中的一个氮原子与萘环的碳原子连接。
  4. 如权利要求1或2所述的感光分子，其特征在于，所述杂环基X为含有四个氮原子的五元或六元杂环基，且其中的一个氮原子与萘环的碳原子连接。
  5. 如权利要求1-4任一项所述的感光分子，其特征在于，所述含烷氧基硅烷的基团包括含γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷中的一个基团。
  6. 如权利要求1-5任一项所述的感光分子，其特征在于，所述感光分子的分子结构还包括与所述萘酰亚胺结构中萘环连接的R 3，R 3包括氢、卤素、烷基、烯基、炔基、芳基、芳烷基、烷芳基、烯芳基、芳烯基、炔芳基、芳炔基、卤代烷基、卤代芳基、烷氧基烷基、烷氧基芳基、环氧烷基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基烷基、氨基芳基、氰基烷基、氰基芳基、羧基烷基、羧基芳基、酯基烷基、酯基芳基、烷基羰基、芳基羰基、烷基醇基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。
  7. 如权利要求6所述的感光分子，其特征在于，所述R 1、R 2、R 3为含碳基团时，碳原子数为1-20。
  8. 一种感光分子，其特征在于，所述感光分子的分子结构包括萘酰亚胺结构、与所述萘酰亚胺结构中氮原子连接的所述取代磺酸基、以及与所述萘酰亚胺结构中萘环连接的杂环基X，与所述杂环基连接的R 2；所述感光分子采用如下方法制备得到：
    将4-溴-1,8-萘二甲酸酐中的溴取代位接枝取代杂环基-X-R 2，并在酐基酰胺化后接枝取代磺酸基，得到感光分子；其中，X包括含有O、N或S的杂环基；R 2包括卤素、芳基、芳烷基、烷芳基、卤代芳基、烷氧基芳基、环氧烷基、环氧芳基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基芳基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。
  9. 一种感光分子的制备方法，其特征在于，包括：
    将4-溴-1,8-萘二甲酸酐中的溴取代位接枝取代杂环基-X-R 2，并在酐基酰胺化后接枝取代磺酸基，得到感光分子，所述感光分子的分子结构包括萘酰亚胺结构、与所述萘酰亚胺结构中氮原子连接的所述取代磺酸基、以及与所述萘酰亚胺结构中萘环连接的杂环基X，与所述杂环基连接的R 2；其中，X包括含有O、N或S的杂环基；R 2包括卤素、芳基、芳烷基、烷 芳基、卤代芳基、烷氧基芳基、环氧烷基、环氧芳基、羟基烷基、羟基芳基、羟基烷基取代羟基芳基、氨基芳基、烷基醚基、芳基醚基、环氧烷氧基、环氧烷氧基取代芳基、或含烷氧基硅烷中的一个基团。
  10. 一种光产酸剂，其特征在于，所述光产酸剂包括权利要求1-8任一项所述的感光分子或权利要求9所述的制备方法制备得到的感光分子。
  11. 如权利要求1-8任一项所述的感光分子，或权利要求9所述的制备方法制备得到的感光分子，或如权利要求10所述的光产酸剂在图案化处理中的应用。
  12. 一种感光树脂组合物，其特征在于，所述感光树脂组合物包括树脂或树脂前驱体、交联剂和如权利要求10所述的光产酸剂。
  13. 如权利要求12所述的感光树脂组合物，其特征在于，以树脂为100质量份计，所述感光树脂组合物中光产酸剂为0.5-20质量份。
  14. 如权利要求12或13所述的感光树脂组合物，其特征在于，所述树脂包括酚醛树脂、环氧树脂、丙烯酸树脂、苯并环丁烯树脂、苯并噁唑树脂、聚酰亚胺树脂中的一种或多种。
  15. 如权利要求12-14任一项所述的感光树脂组合物，其特征在于，所述交联剂包括多羟基交联剂，所述多羟基交联剂包括含有苄基醇结构的化合物单体。
  16. 如权利要求12-15任一项所述的感光树脂组合物，其特征在于，以树脂为100质量份计，所述感光树脂组合物中所述交联剂为1-30质量份。
  17. 如权利要求12-16任一项所述的感光树脂组合物，其特征在于，所述感光树脂组合物还包括有机溶剂。
  18. 如权利要求17所述的感光树脂组合物，其特征在于，以树脂为100质量份计，所述感光树脂组合物中所述有机溶剂为130-740质量份。
  19. 如权利要求17或18所述的感光树脂组合物，其特征在于，所述有机溶剂包括酯类、酮类、醚类或酰胺类有机溶剂中的一种或多种。
  20. 如权利要求12-19任一项所述的感光树脂组合物，其特征在于，采用所述感光树脂组合物进行图案化时所需作用在所述感光树脂组合物上的曝光能量为80-170mJ/cm 2。
  21. 一种图案形成方法，其特征在于，包括：
    将权利要求12-20任一项所述的感光树脂组合物涂覆在基体上，形成涂膜；
    根据预设图案曝光所述涂膜；
    采用显影液显影曝光后的所述涂膜获得树脂图案；
    对所述树脂图案进行热处理。
  22. 一种固化膜，其特征在于，所述固化膜为权利要求12-20任一项所述感光树脂组合物的固化膜。
  23. 如权利要求22所述的固化膜，其特征在于，所述固化膜为图案化的固化膜，所述固化膜上的图案的分辨率小于或等于4μm。
  24. 一种电子器件，其特征在于，所述电子器件包括权利要求22或23所述的固化膜，或者所述电子器件包括由包含权利要求1-8任一项所述的感光分子的组合物固化形成的固化膜。
  25. 如权利要求24所述的电子器件，其特征在于，所述电子器件包括硅片或金属层，所述固化膜设置在所述硅片或金属层上；所述固化膜与所述硅片之间的附着力达到国标可靠性百格测试3B或4B标准；所述固化膜与所述金属层之间的附着力达到国标可靠性百格测试4B或5B标准。
  26. 如权利要求24或25所述的电子器件，其特征在于，所述固化膜在所述电子器件中作为保护层、钝化层、层间绝缘层、缓冲层、平坦化层、α射线屏蔽层或再布线层。
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