WO2023051686A1 - Photosensitive molecule and application thereof - Google Patents

Abstract

Embodiments of the present application provide a photosensitive molecule, a photoacid generator containing the photosensitive molecule, and a photosensitive resin composition. The molecular structure of the photosensitive molecule comprises a main structure containing a naphthalene ring, a heterocyclic group X linked with the naphthalene ring in the main structure, and R2 linked with the heterocyclic group. R2 is selected from one of halogen, aryl, aralkyl, alkaryl, haloaryl, alkoxy aryl, epoxy alkyl, epoxy aryl, hydroxyalkyl, hydroxyaryl, hydroxyalkyl-substituted hydroxyaryl, aminoaryl, alkyl ether, aryl ether, epoxy alkoxy, epoxy alkoxy-substituted aryl, or alkoxysilane. According to the photosensitive molecule, the heterocyclic structure and a specific R2 group are introduced into the naphthalene ring, such that the pattern resolution of the photosensitive resin composition and the adhesion to interfaces such as copper and silicon can be effectively improved, the photosensitive molecule is endowed with multiple functions, and the formula of the resin composition is simplified.

Description

Photosensitive molecules and their applications

This application claims the priority of the Chinese patent application with the application number 202111163870.7 and the application title "Photosensitive Molecules and Their Applications" filed with the China Patent Office on September 30, 2021, the entire contents of which are incorporated herein by reference.

technical field

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.

Background technique

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. There is an obvious difference in 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.

In recent years, chemically amplified photoacid generators are gradually used in photosensitive dielectric materials in the field of semiconductor packaging. 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. For i-line (365nm) photosensitive resin composition, the absorption of PAG in i-line determines the sensitivity of lithographic composition. At the same time, after light exposure The efficiency of photoacid generation and the solubility of molecules will also affect the final pattern fineness. In practical application scenarios, the photosensitive medium material needs to remain in the device as an insulating layer. In order to solve the problem of migration of copper ions at the copper interface, the resolution of photolithography patterns, the problem of residual glue in the development process, and the problem of resin and substrate materials Adhesion and other problems, 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.

In view of the above, it is necessary to develop a photoacid generator that can effectively improve the photolithographic effect, improve the performance of the cured resin, and simplify the formulation of the photosensitive resin composition.

Contents of the invention

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.

Specifically, 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. Among them, 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. Under the synergistic effect of the heterocyclic structure X and the specific _R2 group, it can effectively improve the photolithographic effect and the comprehensive performance of the resin composition, improve the adhesion between the cured resin and the interface of copper, silicon, etc., and also simplify the photosensitive resin. The formulation of the composition.

In the embodiment of the present application, 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.

In the embodiment of the present application, 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 aryl, or a group containing alkoxysilane .

In the embodiment of the present application, the molecular structure of the photosensitive molecule can be as shown in formula (I):

In the embodiment of the present application, 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. In some embodiments, 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.

In the embodiment of the present application, 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 . In the embodiment of the present application, X may be selected from a five-membered heterocyclic group, a six-membered heterocyclic group, or a benzoheterocyclic group containing O, N or S. Wherein 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.

In some embodiments of the present application, 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. In one embodiment of the present application, 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):

In some embodiments of the present application, 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. In one embodiment of the present application, 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):

In the embodiment of the present application, when R ₂ is a group containing an aryl group, the aryl group can be phenyl, naphthyl, etc.

In some embodiments of the present application, 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.

In some embodiments of the present application, 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. Wherein, 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.

In some embodiments of the present application, R ₂ is an alkoxysilane-containing group, specifically, the alkoxysilane-containing group may include γ-aminopropyltriethoxysilane, γ-ammonia Propyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-Glycidyloxypropyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane, γ-Mercaptopropyltrimethoxysilane, Vinyltriethoxysilane, Vinyltrimethoxysilane group of silane, vinyltris(β-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.

In the embodiment of the present application, 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. 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 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.

In some embodiments of the present application, 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; wherein, 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 The molecular structure 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.

In the embodiment of the present application, based on 100 parts by mass of the resin, 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.

In the embodiments of the present application, 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. In some embodiments, the resin includes one or more of phenolic resin, epoxy resin, acrylic resin, benzocyclobutene resin, benzoxazole resin, and polyimide resin. In some embodiments, 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. In the embodiment of the present application, 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.

In the embodiment of the present application, the cross-linking agent includes a polyhydric cross-linking agent, specifically, 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. In some embodiments, 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.

In the embodiment of the present application, based on 100 parts by mass of the resin, 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.

In the embodiment of the present application, based on 100 parts by mass of the resin, 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.

In the embodiment of the present application, the photosensitive resin composition further includes an organic solvent.

In the embodiment of the present application, the organic solvent may be one or more of ester, ketone, ether or amide organic solvents.

In the embodiment of the present application, when the photosensitive resin composition is used for patterning, 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:

Coating the photosensitive resin composition described in the sixth aspect of the embodiment of the present application on the substrate to form a coating film;

exposing the coating film according to a preset pattern;

using a developing solution to develop the exposed coating film to obtain a resin pattern;

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.

In the embodiment of the present application, the resolution of the pattern on the cured film is less than or equal to 4 μm.

In the embodiment of the present application, 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.

In the embodiment of the present application, 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.

In the embodiments of the present application, the cured film is used as a protective layer, a passivation layer, an interlayer insulation layer, a buffer layer, a planarization layer, an α-ray shielding layer or a rewiring layer in the electronic device.

Description of drawings

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.

Detailed ways

The embodiments of the present application will be described below with reference to the drawings in the embodiments 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. In recent years, the principle of chemical amplification has been gradually introduced from fine photoresist to photosensitive medium materials. Taking naphthalimide (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.

Considering the balance between the photosensitive performance of the photosensitive medium material and the physical and chemical properties of the cured film after curing, 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. By introducing a heterocyclic structure on the naphthalene ring, 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. 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 heterocyclic group X, R ₂ connected to the heterocyclic group; wherein, the heterocyclic group X is selected from heterocyclic groups containing O, N or S; the R ₂ group is selected from halogen, aryl, aralkyl, alkane Aryl, haloaryl, alkoxyaryl, epoxyalkyl, epoxyaryl, hydroxyalkyl, hydroxyaryl, hydroxyalkylsubstituted hydroxyaryl, aminoaryl, alkylether, aryl Ether group, epoxy alkoxy group, epoxy alkoxy substituted aryl group, or a group in alkoxy silane.

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; In addition, 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.

In the embodiment of the present application, 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.

In the embodiment of the present application, 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 epoxyalkyloxy group, an epoxyalkyloxy-substituted aryl group, or one of alkoxysilane-containing groups. _R3 can improve the light absorption wavelength and absorbance of the photoacid generator and the overall performance of the resin composition to a certain extent by selecting different groups.

In the embodiment of the present application, the molecular structure of the photoacid generator can be as shown in formula (I):

In the embodiment of the present application, 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. In some embodiments, 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.

In the embodiments of the present application, when R ₁ , R ₂ , and R ₃ contain halogen, the halogen may include fluorine, chlorine, bromine, and iodine.

In the embodiments of the present application, the specific selection ranges of various groups of _R3 may be the same as the selection ranges of _R2 .

In the embodiment of the present application, in R ₂ and R ₃ , 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-a); Hydroxy aryl includes hydroxybenzene Base (such as formula 5-a), dihydroxyphenyl; hydroxyalkyl substituted hydroxyaryl includes hydroxyalkyl substituted hydroxyphenyl, such as hydroxymethyl substituted hydroxyphenyl (such as formula 6-a); aminoaryl can It is an amino-substituted phenyl group (such as formula 16-a); the alkyl ether group can include ether group, etc.; the aryl ether group can include benzyl ether group, phenethyl ether group, etc.; the epoxy alkoxy group can be ring Oxypropyloxy, epoxybutoxy, epoxypentyloxy, epoxyhexyloxy, etc.; epoxyalkyloxy substituted aryl can be glycidyloxy substituted phenyl (such as formula 10-a and formula 11-a), epoxybutoxy substituted phenyl, epoxypentyloxy substituted phenyl, epoxyhexyloxy substituted phenyl, etc.; alkoxysilane-containing groups (such as formula 12-a and formula 13 -a) may contain γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ - radicals of mercaptopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane.

In the embodiment of the present application, 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. 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 1-20. Specifically, when R ₁ , R ₂ , and R ₃ are carbon-containing groups, 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.

In some embodiments of the present application, 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.

In some embodiments of the present application, 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. Wherein, 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.

In some embodiments of the present application, R ₂ is an alkoxysilane-containing group, specifically, an alkoxysilane-containing group may include γ-aminopropyltriethoxysilane, γ-aminopropyl Trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ- Glycidyloxypropyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane, γ-Mercaptopropyltrimethoxysilane, Vinyltriethoxysilane, Vinyltrimethoxysilane , Groups of vinyl tris(β-methoxyethoxy)silane. Specifically, 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.

In the embodiment of the present application, 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. In the embodiment of the present application, X may be selected from a five-membered heterocyclic group, a six-membered heterocyclic group, or a benzoheterocyclic group containing O, N or S. Wherein 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.

In some embodiments of the present application, 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. In one embodiment of the present application, 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):

In some embodiments of the present application, 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. In one embodiment of the present application, 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):

In the examples of this application, 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. At the same time, 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.

In some embodiments of the present application, 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.

In some embodiments, when X is a triazole or tetrazole group, 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.

In the embodiment of the present application, 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.

Taking photoacid generator 1-a as an example, its preparation method may specifically include:

(1) Dissolve 4-bromo-1,8-naphthalene dicarboxylic anhydride (compound 1a) in DMF (N,N-dimethylformamide), add sodium azide at room temperature, and react at 50°C-80°C . After the reaction, the reaction solution was precipitated by ice water, and the yellow precipitate was collected by filtration and dried to obtain compound 1b.

(2) Dissolve compound 1b and phenylacetylene in a mixed solution of tetrahydrofuran THF and water (THF:H ₂ O volume ratio can be 4:1), add copper sulfate pentahydrate and sodium ascorbate successively under nitrogen atmosphere, and heat to reflux for reaction . After the reaction, the reaction solution was poured into ice water to precipitate, and the yellow-green precipitate was collected by filtration, and compound 1c was obtained after drying.

(3) Compound 1c, hydroxylamine hydrochloride and sodium bicarbonate were added to ethanol, and heated to reflux for reaction. After the reaction was completed, the mixture was filtered under reduced pressure, washed with ethanol and deionized water, and dried to obtain compound 1d as an orange powder.

(4) Dissolve the above compound 1d in acetonitrile, add pyridine and trifluoromethanesulfonic anhydride dropwise under an ice bath under nitrogen atmosphere, and then heat to 50-80°C for reaction. After the reaction, cool the reaction solution to room temperature , suction filtration, the filter residue was rinsed with acetonitrile and then dried with an oil pump to obtain a white powder compound, namely photoacid generator 1-a.

The above reaction process is as follows:

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.

In the embodiment of the present application, based on 100 parts by mass of the polymer resin, 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. In the embodiments of the present application, 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. In some embodiments, the resin includes one or more of phenolic resin, epoxy resin, acrylic resin, benzocyclobutene resin, benzoxazole resin, and polyimide resin. In some embodiments, 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 . In the embodiment of the present application, 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.

In the embodiment of the present application, the cross-linking agent includes a polyhydroxy cross-linking agent, specifically, the 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. In some embodiments, 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 .

In the embodiment of the present application, based on 100 parts by mass of the polymer resin, 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.

In the embodiment of the present application, based on 100 parts by mass of the polymer resin, 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.

In the embodiment of the present application, the organic solvent may be one or more of ester, ketone, ether or amide organic solvents. Wherein, 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, γ-butyrolactone, ε-caprolactone, δ-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 acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. 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, N,N-dimethylformamide, etc.

In the embodiment of the present application, 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.

In the embodiment of the present application, when the photosensitive resin composition is used for patterning, the exposure energy required to act on the photosensitive resin composition is 80mJ/cm ² -170mJ/cm ² . In a specific embodiment, 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:

S01, coating the photosensitive resin composition mentioned above in the embodiment of the present application on the substrate to form a coating film;

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.

S02, exposing the coating film according to a preset pattern;

In the embodiment of the present application, when exposing the coating film, 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.

S03, using a developing solution to develop the exposed coating film to obtain a resin pattern;

In the embodiments of the present application, the developer may be determined according to the solubility of the photosensitive resin composition, for example, it may be an alkaline developer. For a negative photosensitive resin composition, the exposed areas remain, while the non-exposed areas are washed away, thereby forming a resin pattern.

S04, performing heat treatment on the 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.

In the embodiment of the present application, the resolution of the pattern on the cured film is less than or equal to 4 μm. The smaller the resolution value of the pattern, the higher the resolution of the pattern. The resolution of the pattern may be 4 μm, 3 μm, 2 μm, 1 μm, 0.5 μm.

In the embodiment of the present application, the inclination angle of the pattern on the cured film is >65°. Specifically, 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 α-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. A connection layer 501 , an UBM layer 502 , and a solder bump 503 . 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. In 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.

In the embodiment of the present application, 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 embodiments of the present application will be further described below in terms of multiple embodiments.

Example 1

(1) Synthesis of photoacid generator 1-a

(1) Compound 1a was dissolved in DMF, and an aqueous solution of sodium azide in equimolar ratio was added dropwise at room temperature, and reacted at high temperature for 2 h. After the reaction, the reaction solution was cooled to room temperature and then poured into ice water to precipitate. The yellow precipitate was collected by filtration and dried by air for 7 hours to obtain compound 1b.

(2) Dissolving compound 1b and excess phenylacetylene (about 4 times the molar amount) in a mixed solution of tetrahydrofuran THF and water, adding copper sulfate pentahydrate in equimolar amounts and sodium ascorbate in 5 times the molar amount successively under a nitrogen atmosphere, High temperature reflux reaction for 5h. The reaction solution was poured into ice water to precipitate, the yellow-green precipitate was collected by filtration, and dried by air for 4 hours to obtain compound 1c.

(3) Compound 1c, hydroxylamine hydrochloride and sodium bicarbonate were dissolved in ethanol at a molar ratio of 5:6:6. Reflux at high temperature for 8 hours, filter under reduced pressure, wash repeatedly with ethanol and deionized water, and blow dry to obtain compound 1d as an orange-yellow powder.

(4) Dissolve compound 1d in acetonitrile, add dropwise 2 times the molar amount of pyridine and 2 times the molar amount of trifluoromethanesulfonic anhydride under a nitrogen atmosphere and an ice bath, and react at high temperature for 3 hours. After the reaction is completed, the reaction solution is Cool to room temperature, filter directly with suction, rinse the filter residue with acetonitrile and dry it with an oil pump to obtain a white powder compound, photoacid generator 1-a. Characterization results of photoacid generator 1-a: 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). Mass Spectrum [M+H] ⁺ : Calculated 489.0, found 489.1.

The synthetic reaction process of above-mentioned steps (1) to step (4) is as follows:

(2) Preparation of photosensitive resin composition

Add 6FAP (36.6g, 100mmol) and p-aminophenol (0.655g, 6mmol) into N-methylpyrrolidone (NMP) and stir to dissolve completely, then add 6FDA (45.6g, 103mmol) under nitrogen atmosphere and adjust the solid content to 25wt .%, stirred at room temperature for 14h to obtain viscous liquid PAA. Then 40 mL of toluene and 6 drops of isoquinoline were added, the temperature was raised to 180° C., and the reaction was refluxed for 14 h. Evaporate all the toluene in the system, cool to room temperature, precipitate in a mixed solvent with a volume ratio of ethanol:water of 1:1, and dry in vacuum at 120°C for 12 hours to obtain off-white solid polyimide resin PHI, the molecular weight of which is about 30,000 . The reaction formula of the preparation process of polyimide resin PHI is as follows, where n represents the degree of polymerization.

Get the PHI resin of the molecular weight of 100 mass parts about 30000, the photoacid generator prepared by 10 mass parts embodiment 1 and the crosslinking agent MBHP of 20 mass parts, be dissolved in the N-methylpyrrolidone (NMP) of 303 mass parts, The total solid content of the composition (the total amount of the three solids of resin, acid generator, and crosslinking agent in the mass fraction of the solvent) was 30wt.%. Stir and mix evenly and vacuum defoam to form a photosensitive resin composition.

(3) Preparation of patterned cured film

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.

Using the photosensitive resin composition of Example 1 of the present application for patterning, the results show that the photolithographic pattern stripes under the mask plate with a line width of 4 μm are clear and flat without residual adhesive adhesion, and the pattern resolution obtainable by the photosensitive resin composition is 4 μm.

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.

Example 2

(1) Synthesis of photoacid generator 6-a

(1) Dissolve 4-bromophenol and potassium hydroxide in 2-propanol at a molar ratio of 3:4, add 0.3 mL of formaldehyde solution dropwise, and heat and stir at 40°C for 48 hours. After cooling to room temperature, pour 1mL of hydrochloric acid and let stand for 6h to form a red precipitate. After the red precipitate was removed by suction filtration and then stood for two days, a white precipitate was precipitated, and compound 4a was obtained as a white solid after drying.

(2) 95 mg of compound 4a was dissolved in pyridine, and 0.2 mL of acetic anhydride was added dropwise in an ice-water bath. After stirring at room temperature for 1.5 h, 10 mL of ethyl acetate was added. The pyridine was removed by washing with copper sulfate pentahydrate solution, the organic layer was dried and concentrated by rotary evaporation, and the white solid compound 4b was obtained after column chromatography with ethyl acetate and n-hexane.

(3) Dissolve 128mg of compound 4b and 0.07mL of trimethylsilylacetylene in triethylamine, add 6.7mg of triphenylphosphine, 8.3mg of cuprous iodide and 5.2mg of bis(triphenylphosphine) di palladium chloride. Heated to reflux for 24h. After filtration, the solvent was removed by rotary evaporation, and brown liquid compound 4c was obtained after column chromatography with ethyl acetate and n-hexane.

(4) Under the condition of ice-water bath, the THF solution of compound 4c was added dropwise to the THF solution of lithium aluminum hydride, stirred at room temperature for 2 h, and 1 mL of deionized water was added dropwise under the condition of ice-water bath. The reaction solution was stirred at room temperature for 12 h. 10 mL of aqueous HCl solution was added to precipitate the aluminum salt. Filtration, after vacuum rotary evaporation, dissolved in ethyl acetate and then washed with saturated brine, the organic layer was dried over anhydrous magnesium sulfate, filtered, rotary evaporation to remove the solvent, to obtain white solid compound 4d (i.e. hydroxymethyl substituted hydroxybenzene acetylene).

The synthetic reaction process of above-mentioned steps (1) to step (4) is as follows:

(5) Compound 1b, hydroxylamine hydrochloride and sodium bicarbonate were dissolved in ethanol at a molar ratio of 5:6:6. Reflux at high temperature for 8 hours, filter under reduced pressure, wash repeatedly with ethanol and deionized water, and blow dry to obtain compound 4e as an orange-yellow powder.

(6) Dissolve compound 4e in acetonitrile, add 2 times the molar amount of pyridine and 2 times the molar amount of trifluoromethanesulfonic anhydride dropwise under a nitrogen atmosphere and an ice bath, and react at high temperature for 3 hours. After the reaction is completed, the reaction solution is cooled After reaching room temperature, suction filtration was performed directly, and the filter residue was washed with acetonitrile and then dried with an oil pump to obtain compound 4f as a yellow powder. (7) Dissolve equimolar ratio of compound 4f and compound 4d in THF solution, add equimolar amount of copper sulfate pentahydrate and 5 times molar amount of sodium ascorbate successively under nitrogen atmosphere, and react under high temperature reflux for 5 h. The reaction solution was poured into ice water to precipitate, and the yellow-green precipitate was collected by filtration, and air-dried for 4 hours to obtain photoacid generator 6-a. Mass spectrum [M+H]+: Calculated 564.0, found 564.1.

The synthetic reaction process of above-mentioned steps (5) to step (7) is as follows:

(2) Preparation of photosensitive resin composition

Get the PHI resin of the molecular weight of 100 mass parts about 30000, the photoacid generator prepared by 8 mass parts embodiment 2 and the crosslinking agent MBHP of 20 mass parts, be dissolved in 298 mass parts N-methylpyrrolidone (NMP), make The total solid content of the composition is 30wt.%. The photosensitive resin composition is formed by vacuum defoaming after stirring and mixing uniformly.

(3) Preparation of patterned cured film

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 μm are clear and flat without residual adhesive adhesion, and the pattern resolution obtainable by the photosensitive resin composition is 2 μm.

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. On the one hand, 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.

Example 3

(1) Synthesis of photoacid generator 10-a

(1) Compound 1a was dissolved in DMF (N,N-dimethylformamide), and an equimolar aqueous solution of sodium azide was added dropwise to the reaction system for 2 hours at room temperature. After the reaction was completed, the reaction solution was cooled to room temperature and then poured into ice water to precipitate. The yellow precipitate was collected by filtration, and dried at 50° C. for 7 hours to obtain compound 1b. (2) Dissolving compound 1b and 4-ethynylphenol in an equimolar ratio in DMF, adding an equimolar quantity of copper sulfate pentahydrate and 5 times the molar quantity of sodium ascorbate. The reaction mixture was stirred at high temperature for 14 h, poured into ice water, and filtered with suction to obtain a solid precipitate. The precipitate was washed with cold water and dried to obtain compound 6a.

(3) Compound 6a and NaH were added into anhydrous tetrahydrofuran at a molar ratio of 1:3. After stirring at room temperature for 1 hour under a nitrogen atmosphere, a tetrahydrofuran solution of 5 times the molar amount of epichlorohydrin was added dropwise to the reaction mixture. It was heated to reflux for 8 hours, and after cooling to room temperature, the solution mixture was poured into water and extracted with ether. The organic layers were combined, dried with anhydrous Na ₂ SO ₄ , the solvent was removed by rotary evaporation, and purified by column chromatography to obtain compound 6b.

(4) Compound 6b, hydroxylamine hydrochloride, and sodium bicarbonate were dissolved in ethanol at a molar ratio of 5:6:6. Reflux for 3 hours, cool to room temperature, filter with suction, wash repeatedly with ethanol and deionized water, and dry at 70° C. to obtain compound 6c as an orange-yellow powder.

(5) Compound 6c was dissolved in acetonitrile, and 2 times the molar amount of pyridine and 2 times the molar amount of trifluoromethanesulfonyl chloride were added dropwise. React at high temperature for 15 hours, remove the solvent by rotary evaporation, and purify by silica gel column chromatography to obtain photoacid generator 10-a. Mass Spectrum [M+H]+: Calculated 560.1, found 560.2.

The synthetic reaction process of above-mentioned steps (1) to step (5) is as follows:

(2) Preparation of photosensitive resin composition

Get the PHI resin of the molecular weight of 100 mass parts about 30000, the photoacid generator synthesized in 8 mass parts embodiment 3 and the crosslinking agent MBHP of 20 mass parts, be dissolved in the N-methylpyrrolidone (NMP) of 298 mass parts , so that the total solid content of the composition is 30wt.%. Stir and mix evenly, then vacuum defoam to form a photosensitive resin composition.

(3) Preparation of patterned cured film

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 μm; Fig. 3 is the mask of line width 4 μm The photolithographic pattern under the plate (after curing). It can be seen from Figure 2 that the photolithographic pattern under the mask plate with a line width of 8 μm is straight without collapse, and the pattern is clear and flat. It can be seen from FIG. 3 that the photolithographic pattern under the mask plate with a line width of 4 μm can be basically developed, and the optimal pattern resolution obtained by the photosensitive resin composition is about 4 μm.

The adhesion between the embodiment 3 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 3 cured film and the silicon chip and the cured film and the copper sheet Efforts are made to meet the 4B standard of the national standard reliability test.

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. On the one hand, it can be replaced by an epoxy alkoxy 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°.

Example 4

(1) Preparation of photoacid generator 13-a

(1) Dissolve copper chloride and N,N-diisopropylethylamine of catalytic amount in ether, under the condition of ice-water bath, slowly add the mixture of 3-chloropropyne and trichlorosilane in equimolar amount Mix ether solution, rise to room temperature and stir for 2h. After the solid in the reaction solution was filtered, it was distilled under reduced pressure at 80° C. to obtain compound 3a.

(2) Compound 1b and excess compound 3a (about 4 times the molar amount) were dissolved in THF, and an equimolar amount of copper sulfate pentahydrate and 5 times the molar amount of sodium ascorbate were successively added under a nitrogen atmosphere, and the reaction was refluxed at high temperature for 5 hours. The reaction solution was poured into ice water to precipitate, and the yellow-green precipitate was collected by filtration, and dried by air for 4 hours to obtain compound 3b.

(3) Compound 3b, hydroxylamine hydrochloride, and sodium bicarbonate were dissolved in ethanol at a molar ratio of 5:6:6, refluxed at high temperature for 8 hours, filtered under reduced pressure, washed repeatedly with ethanol and deionized water, and drummed at 70°C. Air-dried to obtain compound 3c as an orange-yellow powder.

(4) Dissolve compound 3c in acetonitrile, add 2 times the molar amount of pyridine and 2 times the molar amount of trifluoromethanesulfonic anhydride dropwise under nitrogen atmosphere and ice bath, react at 60°C for 3 hours, cool to room temperature, and filter directly , the filter residue was washed with acetonitrile and then dried with an oil pump to obtain photoacid generator 13-a as white powder. Mass spectrum [M+H] ⁺ : Calculated value is 588.1, found value is 588.2.

The synthetic reaction process of above-mentioned steps (1) to step (4) is as follows:

(2) Preparation of photosensitive resin composition

Get the PHI resin of the molecular weight of 100 mass parts about 30000, the photoacid generator synthesized in 12 mass parts embodiment 4 and the crosslinking agent MBHP of 20 mass parts, be dissolved in the N-methylpyrrolidone (NMP) of 308 mass parts , so that the total solid content of the composition is 30wt.%. Stir and mix evenly, then vacuum defoam to form a photosensitive resin composition.

(3) Preparation of patterned cured film

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 μm is clear and flat without adhesive residue, and the pattern resolution obtainable by the photosensitive resin composition is 2 μm.

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. On the one hand, 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.

Example 5

(1) Preparation of photoacid generator 2-a

(1) Compound 1b and excess benzonitrile (about 4 times the molar amount) were dissolved in THF, and an equimolar amount of copper sulfate pentahydrate and 5 times the molar amount of sodium ascorbate were successively added under a nitrogen atmosphere, and the reaction was refluxed at high temperature for 5 hours. The reaction solution was poured into ice water to precipitate, and the yellow-green precipitate was collected by filtration, and dried by air for 4 hours to obtain compound 2a.

(2) Compound 2a, hydroxylamine hydrochloride and sodium bicarbonate were dissolved in ethanol at a molar ratio of 5:6:6. Reflux at high temperature for 8 hours, filter under reduced pressure, wash repeatedly with ethanol and deionized water, and blow dry to obtain compound 2b as an orange-yellow powder.

(3) Dissolve compound 2b in acetonitrile, add 2 times the molar amount of pyridine and 2 times the molar amount of trifluoromethanesulfonic anhydride dropwise under nitrogen atmosphere and ice bath, react at 60°C for 3 hours, cool to room temperature, and filter directly , the filter residue was washed with acetonitrile and then dried with an oil pump to obtain photoacid generator 2-a as white powder. Mass Spectrum [M+H]+: Calculated 489.0, Found 489.1.

The synthetic reaction process of above-mentioned steps (1) to step (3) is as follows:

(2) Preparation of photosensitive resin composition

Get the PHI resin of the molecular weight of 100 mass parts about 30000, the photoacid generator synthesized in 10 mass parts embodiment 5 and the crosslinking agent MBHP of 20 mass parts, be dissolved in the N-methylpyrrolidone (NMP) of 303 mass parts , so that the total solid content of the composition is 30wt.%. Stir and mix evenly, then vacuum defoam to form a photosensitive resin composition.

(3) Preparation of patterned cured film

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.

Using the photosensitive resin composition of Example 4 of the present application for patterning, the results show that the photolithographic pattern under the mask plate with a line width of 4 μm is clear and smooth, without adhesion, and the best pattern resolution obtainable by the photosensitive resin composition is about 4 μm .

The adhesion between the embodiment 4 cured film and the silicon chip and the cured film and the copper sheet was tested by the hundred grid test method, and the results showed that the adhesion between the embodiment 5 cured film and the silicon chip and the cured film and the copper sheet was tested. 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 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.

Comparative example 1

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.

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 .

In comparative example 1, 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 μm could barely be obtained.

The adhesion between the comparative example 1 cured film and the silicon chip, and the cured film and the copper sheet was tested by the hundred-grid test method, and the results showed that the adhesion between the comparative example 1 cured film and the silicon chip, and the cured film and the copper sheet Efforts are made to meet the 2B standard of the national standard reliability test.

Comparative example 2

(1) Synthesis of unsubstituted naphthalimide-type photoacid generators

(1) Dissolve 1,8-naphthalene dianhydride, hydroxylamine hydrochloride and sodium bicarbonate in ethanol at a ratio of 5:6:6, and reflux at high temperature for 3 hours. The reaction mixture was suction-filtered under reduced pressure, washed repeatedly with ethanol and water, and dried at 80°C to obtain dark yellow powder NI-OH.

(2) Dissolve NI-OH and pyridine in acetonitrile at a molar ratio of 2:3, and slowly add trifluoromethanesulfonic anhydride in an equimolar amount to pyridine dropwise under ice bath. After stirring and reacting at high temperature for 12 hours (the reaction was monitored by TLC, the product point no longer increased), rotary evaporation under reduced pressure gave a brownish-yellow solid. The crude product was subjected to silica gel column chromatography to obtain a white solid, that is, unsubstituted naphthalimide-type photoacid generator NI-Tf. 1H NMR (400MHz, DMSO-d6, ppm) δ: 8.65-8.62 (m, 4H), 7.96-8.00 (m, 2H). Mass Spectrum [M+H]+: Calculated 346.0, found 346.0.

(2) Preparation of photosensitive resin composition

Get 100 mass parts of PHI-30000 resin, 10 mass parts of PAG synthesized in Comparative Example 2 and 20 mass parts of crosslinking agent MBHP, dissolve in 303 mass parts of N-methylpyrrolidone (NMP), so that the composition The total solid content is 30w.t.%. 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 μm; Fig. 7 is the line width 4 μm 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 μm leads to poor flatness. Adhesions are severe. The pattern resolution of the photosensitive resin composition of Comparative Example 2 was 8 μm.

The adhesion between the comparative example 2 cured film and the silicon chip and the cured film and the copper sheet was tested by the hundred grid test method, and the results showed that the adhesion between the comparative example 2 cured film and the silicon chip and the cured film and the copper sheet was tested. Efforts are made to meet the 3B standard of the national standard reliability test.

The best light-absorbing wavelength of photoacid generator in embodiment 1-5 and comparative example 1-2, the lithography performance of photosensitive resin composition and the adhesion result of cured film of photosensitive resin composition and silicon, copper interface are summarized as follows Table 1 shows.

Table 1. Embodiment and comparative example test result

As can be seen from the results in Table 1, compared with Comparative Examples 1-2, 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 μm can be obtained. Compared with Comparative Examples 1-2, 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. In some embodiments, 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.

Claims (26)

1. A photosensitive molecule, characterized in that 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, R ₂ connected to the heterocyclic group;

   The heterocyclic group X includes a heterocyclic group containing O, N or S; the _R includes halogen, aryl, aralkyl, alkaryl, haloaryl, alkoxyaryl, alkylene oxide group, epoxy aryl group, hydroxyalkyl group, hydroxyaryl group, hydroxyalkyl substituted hydroxyaryl group, aminoaryl group, alkyl ether group, aryl ether group, epoxy alkoxy group, epoxy alkoxy substituted aryl group group, or a group containing alkoxysilane.
2. The photosensitive molecule according to claim 1, wherein the substituted sulfonic acid group is represented as -SO ₃ R ₁ , and the R ₁ includes alkyl, aryl, alkylaryl, halogenated alkyl or halogenated aryl A group of groups.
3. The photosensitive molecule according to claim 1 or 2, wherein 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 the carbon atom of the naphthalene ring connect.
4. The photosensitive molecule according to claim 1 or 2, wherein 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 the carbon atom of the naphthalene ring connect.
5. The photosensitive molecule according to any one of claims 1-4, wherein the alkoxysilane-containing group includes γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxy Silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidyl ether Oxypropyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane, γ-Mercaptopropyltrimethoxysilane, Vinyltriethoxysilane, Vinyltrimethoxysilane, Vinyl A group in tris(β-methoxyethoxy)silane.
6. The photosensitive molecule according to any one of claims 1-5, wherein the molecular structure of the photosensitive molecule also 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, Alkylaryl, Aralkynyl, Haloalkyl, Haloaryl, Alkoxyalkyl , alkoxyaryl, epoxyalkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkyl-substituted hydroxyaryl, aminoalkyl, aminoaryl, cyanoalkyl, cyanoaryl, carboxyalkyl, Carboxyl aryl, ester alkyl, ester aryl, alkyl carbonyl, aryl carbonyl, alkyl alcohol, alkyl ether, aryl ether, epoxy alkoxy, epoxy alkoxy substituted aryl group, or a group containing alkoxysilane.
7. The photosensitive molecule according to claim 6, wherein when said R ₁ , R ₂ , and R ₃ are carbon-containing groups, the number of carbon atoms is 1-20.
8. A photosensitive molecule, characterized in that 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 amine structure, and the 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; wherein, 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.
9. A method for preparing a photosensitive molecule, characterized in that it comprises:

   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 The molecular structure 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.
10. A photoacid generator, characterized in that the photoacid generator comprises the photosensitive molecule according to any one of claims 1-8 or the photosensitive molecule prepared by the preparation method according to claim 9.
11. The photosensitive molecule according to any one of claims 1-8, or the photosensitive molecule prepared by the preparation method according to claim 9, or the application of the photoacid generator according to claim 10 in patterning treatment.
12. A photosensitive resin composition, characterized in that the photosensitive resin composition comprises a resin or a resin precursor, a crosslinking agent and the photoacid generator according to claim 10.
13. The photosensitive resin composition according to claim 12, characterized in that, based on 100 parts by mass of the resin, the photoacid generator in the photosensitive resin composition is 0.5-20 parts by mass.
14. The photosensitive resin composition according to claim 12 or 13, wherein the resin comprises phenolic resin, epoxy resin, acrylic resin, benzocyclobutene resin, benzoxazole resin, polyimide resin one or more of.
15. The photosensitive resin composition according to any one of claims 12-14, wherein the crosslinking agent comprises a polyhydroxyl crosslinking agent, and the polyhydroxyl crosslinking agent comprises a compound monomer containing a benzyl alcohol structure .
16. The photosensitive resin composition according to any one of claims 12-15, characterized in that, based on 100 parts by mass of the resin, the crosslinking agent in the photosensitive resin composition is 1-30 parts by mass.
17. The photosensitive resin composition according to any one of claims 12-16, characterized in that, the photosensitive resin composition further comprises an organic solvent.
18. The photosensitive resin composition according to claim 17, wherein the organic solvent in the photosensitive resin composition is 130-740 parts by mass based on 100 parts by mass of the resin.
19. The photosensitive resin composition according to claim 17 or 18, wherein the organic solvent comprises one or more of ester, ketone, ether or amide organic solvents.
20. The photosensitive resin composition according to any one of claims 12-19, characterized in that, when the photosensitive resin composition is used for patterning, the exposure energy required to act on the photosensitive resin composition is 80-170mJ /cm ² .
21. A method for forming a pattern, comprising:

    Coating the photosensitive resin composition described in any one of claims 12-20 on the substrate to form a coating film;

    exposing the coating film according to a preset pattern;

    using a developing solution to develop the exposed coating film to obtain a resin pattern;

    The resin pattern is heat-treated.
22. A cured film, characterized in that the cured film is the cured film of the photosensitive resin composition according to any one of claims 12-20.
23. The cured film according to claim 22, wherein the cured film is a patterned cured film, and the resolution of the pattern on the cured film is less than or equal to 4 μm.
24. An electronic device, characterized in that the electronic device comprises the cured film according to claim 22 or 23, or the electronic device comprises a cured film comprising the photosensitive molecule according to any one of claims 1-8. formed cured film.
25. The electronic device according to claim 24, characterized in that, the electronic device comprises a silicon chip or a metal layer, and the cured film is arranged on the silicon chip or the metal layer; between the cured film and the silicon chip The adhesion between them reaches the national standard reliability test 3B or 4B; the adhesion between the cured film and the metal layer meets the national standard reliability test 4B or 5B.
26. The electronic device according to claim 24 or 25, wherein the cured film is used as a protective layer, a passivation layer, an interlayer insulating layer, a buffer layer, a planarization layer, and an alpha ray shielding layer in the electronic device or redistribution layer.

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