Photosensitive molecules and their applications

Abstract

The embodiment of the present application provides a photosensitive molecule and a photoacid generator and a photosensitive resin composition containing the photosensitive molecule, wherein the molecular structure includes a main structure containing a naphthalene ring, a heterocyclic group X connected to the naphthalene ring in the main structure, and R2 connected to the heterocyclic group; R2 is selected from a group selected from halogen, aryl, aralkyl, alkaryl, halogenated aryl, alkoxyaryl, epoxyalkyl, epoxyaryl, hydroxyalkyl, hydroxyaryl, hydroxyalkyl substituted hydroxyaryl, aminoaryl, alkyl ether, aryl ether, epoxyalkoxy, epoxyalkoxy substituted aryl, or alkoxysilane. The photosensitive molecule can effectively improve the pattern resolution of the photosensitive resin composition and the adhesion to the interface of copper, silicon, etc. by introducing a heterocyclic structure and a specific R2 group on the naphthalene ring, giving the photosensitive molecule multifunctionality and simplifying the resin composition formula.

Description

Technical Field

[0001] The embodiments of the present application relate to the technical field of photosensitive materials, and in particular, to a photosensitive molecule, a photoacid generator, a photosensitive resin composition, a cured film, and an electronic device. Background Art

[0002] Chemical amplification (CA) type photosensitive resin compositions have high photosensitivity and sensitivity, and can form clear ultra-fine patterns in the photolithography process. The basic principle is that the photoacid generator (PAG) generates acid when exposed to a light source, and then during the baking process, the generated acid continuously catalyzes the cross-linking of the cross-linking agent, or the cross-linking agent and the polymer resin cross-link, resulting in an obvious solubility difference between the exposed area and the unexposed area of ​​the polymer resin in the developer, that is, the solubility of the exposed area drops sharply due to cross-linking, while the unexposed area still maintains good solubility, thereby displaying the photolithography pattern.

[0003] In recent years, photosensitive medium materials in the field of semiconductor packaging have gradually used chemically amplified photoacid generators. As one of the important components of semiconductor packaging materials, photosensitive medium materials not only need to have good lithography performance, but also require the cured resin to have good comprehensive performance. Among them, the comprehensive performance of PAG is crucial to the lithography performance. For i-line (365nm) photosensitive resin compositions, the absorption of PAG at i-line determines the sensitivity of the photolithography composition. At the same time, the photoacid generation efficiency after illumination and the solubility of molecules will also affect the final pattern fineness. In actual application scenarios, the photosensitive medium material ultimately needs to remain in the device as an insulating layer. In order to solve the migration problems of copper ions at the copper interface, the resolution problems of the photolithography pattern, the residual glue problems during the development process, and the adhesion problems between the resin and the substrate material, the composition formula also needs to add heterocyclic compounds, solubilizers, coupling agents and other additives, making the existing photosensitive resin composition formula very complicated.

[0004] In view of the above, it is necessary to develop a photoacid generator that can effectively enhance the photolithography effect, improve the performance of the cured resin, and simplify the formulation of the photosensitive resin composition. Summary of the invention

[0005] The embodiments of the present application provide 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 photolithography effect of the photosensitive resin composition, improve the pattern resolution, improve the adhesion between the resin and the interface of copper, silicon, etc. after curing, and reduce the complexity of the formulation of the photosensitive resin composition.

[0006] Specifically, the first aspect of the embodiment of the present application provides a photosensitive molecule, the molecular structure of the photosensitive molecule includes a naphthalene imide structure, a substituted sulfonic acid group connected to the nitrogen atom in the naphthalene imide structure, and a heterocyclic group X connected to the naphthalene ring in the naphthalene imide structure, and R2 connected to the heterocyclic group;

[0007] The heterocyclic group X is selected from a heterocyclic group containing O, N or S; and R2 is selected from a group selected from halogen, aryl, aralkyl, alkaryl, halogenated aryl, alkoxyaryl, epoxyalkyl, epoxyaryl, hydroxyalkyl, hydroxyaryl, hydroxyalkyl substituted hydroxyaryl, aminoaryl, alkyl ether, aryl ether, epoxyalkoxy, epoxyalkoxy substituted aryl, or alkoxy-containing silane.

[0008] The photosensitive molecules provided by the embodiments of the present application are obtained by derivatization of naphthalene imide, and the naphthalene imide structure is relatively stable, simple to synthesize, and has a high yield. By introducing heterocyclic structure X and specific R2 groups on the naphthalene ring of the naphthalene imide structure, the photosensitive molecules can be given multifunctionality. When used as a photoacid generator, the pattern resolution of the photosensitive resin composition can be effectively improved, and the adhesion of the resin to the interface of copper, silicon, etc. after curing can be improved, and the composition formula can be simplified. Among them, the heterocyclic group X introduced on the naphthalene ring has a certain anti-ion migration ability and a special electronic effect, which can effectively improve the light absorption of the photoacid generator at i-line (365nm), reduce the light absorption at the visible light, and improve the photolithography effect; at the same time, the heterocyclic group X is easy to derivatize, and the introduction of the heterocyclic group X is conducive to further introducing the functional group R2 of various structures, thereby giving the photoacid generator more functions. Under the synergistic effect of the heterocyclic structure X and the specific R2 group, the comprehensive performance of the photolithography effect and the resin composition can be effectively improved, the adhesion of the resin to the interface of copper, silicon, etc. after curing can be improved, and the formula of the photosensitive resin composition can also be simplified.

[0009] In the embodiment of the present application, the substituted sulfonic acid group is represented by -SO3R1, and R1 is selected from an alkyl group, an aryl group, an alkylaryl group, a halogenated alkyl group or a halogenated aryl group.

[0010] In the embodiment of the present application, the molecular structure of the photosensitive molecule also includes R3 connected to the naphthalene ring in the naphthaleneimide structure, and R3 includes hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, alkenylaryl, aralkylene, alkynyl aryl, aralkynyl, halogenated alkyl, halogenated aryl, alkoxyalkyl, alkoxyaryl, epoxyalkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkyl substituted hydroxyaryl, aminoalkyl, aminoaryl, cyanoalkyl, cyanoaryl, carboxylalkyl, carboxylaryl, ester alkyl, ester aryl, alkylcarbonyl, arylcarbonyl, alkyl alcohol, alkyl ether, aryl ether, epoxy alkyloxy, epoxy alkyloxy substituted aryl, or a group containing alkoxy silane.

[0011] In the embodiment of the present application, the molecular structure of the photosensitive molecule may be as shown in formula (I):

[0012]

[0013] In the embodiments of the present application, heterocyclic group X and R3 can be at any carbon position on the naphthalene ring, that is, heterocyclic group X and R3 can be connected to carbon atoms at any position on the naphthalene ring. In some embodiments, heterocyclic group X and R3 are respectively located at any carbon position of different rings of naphthalene. R2 can also be located at any carbon position of heterocyclic group X.

[0014] 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 in addition to carbon atoms. The heterocyclic group may have one heteroatom or two or more heteroatoms, and the heteroatom may be one atom or two different atoms; the heterocyclic group may be connected to the carbon atom on the naphthalene ring through a heteroatom, or may be connected to the carbon atom on the naphthalene ring through a carbon atom. In the embodiment of the present application, X may be a five-membered heterocyclic group, a six-membered heterocyclic group, or a benzoheterocyclic group selected from O, N or S. The five-membered heterocyclic group may specifically be a five-membered heterocyclic compound derived from furan, thiophene, pyrrole, thiazole, imidazole, triazole, tetrazole, etc.; the six-membered heterocyclic group may be a six-membered heterocyclic compound derived from pyridine, pyrazine, pyrimidine, pyridazine, etc.

[0015] In some embodiments of the present application, 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 a 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 (Ia):

[0016]

[0017] In some embodiments of the present application, 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 a 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 (Ib):

[0018]

[0019] In the embodiment of the present application, when R2 is a group containing an aryl group, the aryl group may be a phenyl group, a naphthyl group, or the like.

[0020] In some embodiments of the present application, R2 is a group containing a terminal hydroxyl group, specifically, R2 can be a hydroxyalkyl group or a hydroxyaryl group. R2 is a group containing a terminal hydroxyl group, and can also adjust the alkali solubility of the resin composition, thereby improving the solubility of the resin composition in the alkaline developer, reducing the residual adhesive phenomenon in the exposed or non-exposed area, and improving the pattern resolution.

[0021] In some embodiments of the present application, R2 is a group containing an epoxy group, specifically a group terminated with an epoxy group, for example, an alkylene oxide, an arylene oxide, an alkylene oxide substituted aryl group, etc. R2 containing an epoxy group can increase the degree of crosslinking of the resin, thereby effectively adjusting the pattern flatness and improving the photolithography effect. Among them, the alkylene oxide can be a glycidyl group, a butylene oxide, a glycidyl group, a hexylene oxide, etc.; the alkylene oxide, i.e., an alkylene oxide, can be a glycidyl group, a glycidyl group, a glycidyl group, a glycidyl group, a hexylene oxide, etc.; the alkylene oxide substituted aryl group can be a glycidyl group substituted phenyl group, a glycidyl group substituted phenyl group, a glycidyl group substituted phenyl group, a glycidyl group substituted phenyl group, a hexylene oxide substituted phenyl group, etc.

[0022] In some embodiments of the present application, R2 is a group containing alkoxysilane, specifically, the group containing alkoxysilane can be a group including γ-aminopropyl triethoxysilane, γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidyl ether oxypropyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri(β-methoxyethoxy) silane. R2 is an alkoxysilane-terminated group. R2 is an alkoxysilane-containing group, which can effectively improve the adhesion between the cured film of the photosensitive resin composition and the substrates such as silicon wafers and metal layers, avoid the occurrence of the drifting glue phenomenon, and the silicon oxygen bond has good flexibility and heat resistance, which can improve the flexibility and heat resistance of the cured film.

[0023] In the embodiments of the present application, when R1, R2, and R3 are carbon-containing groups, the carbon-containing groups have a suitable number of carbon atoms so that the photoacid generator has a suitable solubility in the organic solvent, and at the same time have good photosensitivity and photoacid generation ability, which is beneficial to improving the photolithography effect. In some embodiments of the present application, when R1, R2, and R3 are carbon-containing groups, the number of carbon atoms is 1-20. In some embodiments of the present application, when R1, R2, and R3 are carbon-containing groups, the number of carbon atoms is 4-20.

[0024] In some embodiments of the present application, the molecular structure of the photosensitive molecule is as shown in Formulas 1-a to 23-a:

[0025]

[0026]

[0027]

[0028] 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 a heterocyclic group X connected to the naphthalene ring in the naphthalimide structure, and R2 connected to the heterocyclic group; the photosensitive molecule is prepared by the following method:

[0029] The bromine substitution position in 4-bromo-1,8-naphthalene dicarboxylic anhydride is grafted with a heterocyclic group -X-R2, and the sulfonic acid group is grafted after the anhydride group is amidated to obtain a photosensitive molecule; wherein X includes a heterocyclic group containing O, N or S; and R2 includes a halogen, an aryl, an aralkyl, an alkylaryl, a halogenated aryl, an alkoxyaryl, an epoxyalkyl, an epoxyaryl, a hydroxyalkyl, a hydroxyaryl, a hydroxyalkyl substituted hydroxyaryl, an aminoaryl, an alkyl ether group, an aryl ether group, an epoxyalkyloxy group, an epoxyalkyloxy substituted aryl group, or a group in an alkoxy-containing silane.

[0030] A third aspect of the present application provides a method for preparing a photosensitive molecule, comprising:

[0031] The bromine substitution position in 4-bromo-1,8-naphthalene dicarboxylic anhydride is grafted with a substituted heterocyclic group -X-R2, and the sulfonic acid group is grafted with a substituted sulfonic acid group after the anhydride group is amidated to obtain a photosensitive molecule, wherein the molecular structure of the photosensitive molecule includes a naphthalene imide structure, the substituted sulfonic acid group connected to the nitrogen atom in the naphthalene imide structure, and a heterocyclic group X connected to the naphthalene ring in the naphthalene imide structure, and R2 connected to the heterocyclic group; wherein X includes a heterocyclic group containing O, N or S; and R2 includes a halogen, an aryl, an aralkyl, an alkylaryl, a halogenated aryl, an alkoxyaryl, an epoxyalkyl, an epoxyaryl, a hydroxyalkyl, a hydroxyaryl, a hydroxyalkyl substituted hydroxyaryl, an aminoaryl, an alkyl ether group, an aryl ether group, an epoxyalkyloxy group, an epoxyalkyloxy substituted aryl group, or a group in an alkoxy-containing silane.

[0032] A fourth aspect of the embodiments of the present application provides a photoacid generator, which includes the photosensitive molecule described in the first aspect or the second aspect of the embodiments of the present application, or includes the photosensitive molecule prepared by the preparation method described in the third aspect.

[0033] A fifth aspect of the embodiments of the present application provides the application of the above-mentioned photosensitive molecules or photoacid generators in patterning processing.

[0034] A sixth aspect of the embodiments of the present application provides a photosensitive resin composition, which includes a resin or a resin precursor, a cross-linking agent, and the photoacid generator described in the fourth aspect of the embodiments of the present application.

[0035] 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 portion is washed away, and the exposed portion is retained. The patterning principle of the negative photosensitive resin composition of the present application embodiment is: the photoacid generator is irradiated by a light source to generate acid (substituted or unsubstituted sulfonic acid), and during the subsequent heat treatment process, the generated acid continuously catalyzes the cross-linking agent to cross-link, or the cross-linking agent and the polymer resin to cross-link, resulting in an obvious solubility difference between the exposed area and the unexposed area of ​​the polymer resin in the developer, that is, the solubility of the exposed area drops sharply due to cross-linking, while the unexposed area still maintains good solubility, and finally the unexposed area is washed away, and the exposed area is retained, thereby displaying a photolithographic pattern.

[0036] 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 is retained.

[0037] 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 may be 3-15 parts by mass. In some embodiments, the photoacid generator may be 5-10 parts by mass.

[0038] In the embodiment of the present application, the resin or resin precursor in the photosensitive resin composition can be selected according to the 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 one or more of phenolic resin precursor, epoxy resin precursor, acrylic resin precursor, benzocyclobutene resin precursor, benzoxazole resin precursor, and polyimide resin precursor. In the embodiment of the present application, the weight average molecular weight of the resin may be 5000-100000; in some embodiments, the weight average molecular weight of the resin may be 10000-80000; in some embodiments, the weight average molecular weight of the resin may be 20000-50000.

[0039] In the embodiment of the present application, the cross-linking agent includes a polyhydroxy cross-linking agent, and specifically the polyhydroxy cross-linking agent can be a compound monomer containing a benzyl alcohol structure. The monomer can be cross-linked under acidic conditions to form a polymerized macromolecule with reduced solubility. In some embodiments, the compound monomer containing a benzyl alcohol structure can be a compound 2,6-bis(hydroxymethyl)-4-methylphenol as shown in formula A, or a compound as shown in formula B.

[0040]

[0041] 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 may be 5-25 parts by mass. In some embodiments, the crosslinking agent may be 10-20 parts by mass.

[0042] 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.

[0043] In the embodiment of the present application, the photosensitive resin composition further includes an organic solvent.

[0044] In the embodiment of the present application, the organic solvent may be one or more organic solvents including esters, ketones, ethers or amides.

[0045] 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 80 mJ / cm 2 -170 mJ / cm 2 .

[0046] A seventh aspect of the present application provides a pattern forming method, comprising:

[0047] Applying the photosensitive resin composition described in the sixth aspect of the embodiment of the present application on a substrate to form a coating film;

[0048] exposing the coating film according to a preset pattern;

[0049] Developing the exposed coating film with a developer to obtain a resin pattern;

[0050] The resin pattern is heat-treated.

[0051] An eighth aspect of the embodiment of the present application provides a cured film, which is a cured film of the photosensitive resin composition described in the third aspect.

[0052] In an embodiment of the present application, a resolution of the pattern on the cured film is less than or equal to 4 μm.

[0053] In an embodiment of the present application, the inclination angle of the pattern on the cured film is greater than 65°.

[0054] The embodiment of the present application also provides an electronic device, which 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 molecules described in the first aspect.

[0055] In the embodiment of the present application, the electronic device includes a silicon wafer or a metal layer, and the cured film is arranged on the silicon wafer or the metal layer. The adhesion between the cured film and the silicon wafer meets 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.

[0056] In the embodiment of the present application, the cured film is used as a protective layer, a passivation layer, an interlayer insulating layer, a buffer layer, a planarization layer, an α-ray shielding layer or a rewiring layer in the electronic device. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 A schematic diagram of the packaging structure of an electronic device 100 provided in an embodiment of the present application;

[0058] Figure 2 and Figure 3 This is a photolithography effect diagram of the photosensitive resin composition of Example 3 of the present application;

[0059] Figure 4 This is a photolithography effect diagram of the photosensitive resin composition of Example 4 of the present application;

[0060] Figure 5 This is a photolithography effect diagram of the photosensitive resin composition of Comparative Example 1 of the present application;

[0061] Figure 6 and Figure 7 This is a photolithography effect diagram of the photosensitive resin composition of Comparative Example 2 of the present application. DETAILED DESCRIPTION

[0062] The embodiments of the present application will be described below in conjunction with the drawings in the embodiments of the present application.

[0063] Negative photoresists are widely used in the field of chip packaging due to their excellent heat resistance and mechanical properties. The mainstream route currently used for negative photoresists is to introduce photo-crosslinkable groups (such as acrylic acid) into the resin molecular structure. Under light, the photoinitiator generates free radicals to initiate polymer crosslinking at the exposed location, forming a solubility difference. In recent years, the principle of chemical amplification has gradually been introduced from fine photoresists to photosensitive medium materials. Taking naphthylimide (NI) type photoacid generator as an example, as shown in Formula C, it is the photo-induced acid generation mechanism of NI type photoacid generator. NI type photoacid generator undergoes Norrish I type cleavage under light to produce sulfonic acid. The produced sulfonic acid can induce the crosslinking reaction of polyhydroxy crosslinkers at the exposed location. Because the acid only plays a catalytic role and does not participate in the reaction, only a small amount of photoacid generator is needed to continuously catalyze the crosslinking reaction at the exposed location.

[0064]

[0065] Considering the balance between the photosensitivity 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 including the photosensitive molecule, and a photosensitive resin composition including the photoacid generator. The photosensitive molecule is a naphthalene imide derivative. By introducing a heterocyclic structure on the naphthalene ring, the photosensitive molecule can obtain the performance advantages of both naphthalene imide and heterocyclic structures, improve the light absorption characteristics of the photosensitive molecule, and the introduction of the heterocyclic structure increases the scope of derivatization. By introducing various functional groups on the heterocyclic or naphthalene ring, the photosensitive molecule can be given multifunctionality, so that the naphthalene imide main structure that originally had no effect after illumination has adhesion, cross-linking, etc., further improving the solubility difference between the exposed area and the non-exposed area, and finally effectively improving the overall lithography effect of the photosensitive resin composition, improving the pattern resolution, and improving the adhesion of the resin at the interface of silicon, copper, etc. after curing, while reducing the complexity of the formulation of the photosensitive resin composition.

[0066] An embodiment of the present application provides a photosensitive molecule, the molecular structure of which includes a naphthaleneimide structure, a substituted sulfonic acid group connected to the nitrogen atom in the naphthaleneimide structure, a heterocyclic group X connected to the naphthalene ring in the naphthaleneimide structure, and R2 connected to the heterocyclic group; wherein the heterocyclic group X is selected from a heterocyclic group containing O, N or S; and the R2 group is selected from a halogen, an aryl, an aralkyl, an alkylaryl, a halogenated aryl, an alkoxyaryl, an epoxyalkyl, an epoxyaryl, a hydroxyalkyl, a hydroxyaryl, a hydroxyalkyl substituted hydroxyaryl, an aminoaryl, an alkyl ether group, an aryl ether group, an epoxyalkyloxy group, an epoxyalkyloxy substituted aryl group, or a group containing an alkoxysilane.

[0067] The photosensitive molecules in the embodiments of the present application can be used as photoacid generators, and can also be used in other application scenarios with photosensitivity requirements. The following mainly introduces the use of photosensitive molecules as photoacid generators in detail.

[0068] The photoacid generator provided in the embodiment of the present application is obtained by derivatization of naphthaleneimide. The naphthaleneimide structure is relatively stable, the synthesis is simple, and the yield is high. The introduced heterocyclic group X and R2 group have certain resistance to ion migration and special electronic effects, and can well regulate the light absorption range and absorbance of the photoacid generator, effectively improve the light absorption of the photoacid generator at the i-line, reduce the light absorption at the visible light, and improve the photolithography effect; and can improve the resin composition containing the photoacid generator. The cured film has good silicon interface and copper interface adhesion performance; in addition, the functional group R2 can also give the photoacid generator more functions, improve the photolithography effect and the comprehensive performance of the resin composition, and simplify the formula of the photosensitive resin composition.

[0069] In the embodiment of the present application, the substituted sulfonic acid group is represented by -SO3R1, and R1 may include an alkyl group, an aryl group, an alkylaryl group, a halogenated alkyl group or a halogenated aryl group. The alkyl group may be C1-C 20The alkyl group may be, for example, methyl, ethyl, etc. The aryl group may be phenyl. The alkylaryl group may be C7-C 20 The alkylaryl group may be, for example, methylphenyl, ethylphenyl, etc. The halogenated alkyl group may be C1-C 20 The halogenated alkyl group may be, for example, trifluoromethyl, trifluoroethyl, etc. The halogenated aryl group may be C6-C 20 The halogenated aryl group may be, for example, fluorophenyl, bromophenyl, etc.

[0070] In the embodiment of the present application, the molecular structure of the photoacid generator also includes R3 connected to the naphthalene ring in the naphthalene imide structure, and R3 is selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, alkenyl aryl, aralkenyl, alkynyl aryl, aralkynyl, haloalkyl, haloaryl, alkoxyalkyl, alkoxyaryl, epoxyalkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkyl substituted hydroxyaryl, aminoalkyl, aminoaryl, cyanoalkyl, cyanoaryl, carboxylalkyl, carboxylaryl, ester alkyl, ester aryl, alkylcarbonyl, arylcarbonyl, alkyl alcohol, alkyl ether, aryl ether, epoxy alkoxy, epoxy alkoxy substituted aryl, or a group containing alkoxysilane. R3 can improve the absorption wavelength and absorbance of the photoacid generator and the comprehensive performance of the resin composition to a certain extent by selecting different groups.

[0071] In the embodiment of the present application, the molecular structure of the photoacid generator can be as shown in formula (I):

[0072]

[0073] In the embodiments of the present application, heterocyclic groups X and R3 can be at any carbon position on the naphthalene ring, that is, heterocyclic groups X and R3 can be connected to carbons at any position on the naphthalene ring. In some embodiments, heterocyclic groups X and R3 are respectively located at any carbon position of different rings of naphthalene. R2 can also be located at any carbon position of heterocyclic group X.

[0074] In the embodiment of the present application, when R1, R2, and R3 contain halogen, the halogen may include fluorine, chlorine, bromine, and iodine.

[0075] In the embodiment of the present application, the specific selection range of various groups of R3 may be the same as the selection range of R2.

[0076] In the embodiment of the present application, in R2 and R3, the aryl group can be a phenyl group (such as formula 1-a and 2-a); the aralkyl group can be a benzyl group, a phenethyl group, etc.; the alkaryl group can be a methyl substituted phenyl group (such as formula 9-a), an ethyl substituted phenyl group, etc.; the halogenated aryl group can be a fluorophenyl group (such as formula 4-a), a bromophenyl group, a chlorophenyl group, etc.; the alkoxyaryl group can be a methoxyphenyl group (such as formula 8-a), an ethoxyphenyl group, etc.; the epoxyalkyl group can be a glycidyl group, a butyl group, a epoxypentyl group, a hexyl group, etc.; the epoxyaryl group can be an epoxyethyl phenyl group, an epoxypropyl phenyl group; the hydroxyalkyl group can include a hydroxybutyl group, a hydroxyisopropyl group (such as formula 7-a); the hydroxyaryl group includes a hydroxyphenyl group (such as formula 5-a), a dihydroxyphenyl group; the hydroxyalkyl substituted hydroxyaryl group includes a hydroxyalkyl substituted hydroxyphenyl group, for example, a hydroxymethyl substituted hydroxyphenyl group (such as formula 6-a); the aminoaryl group can be an amino substituted phenyl group (such as formula 16-a); the alkyl ether group can include an ethyl ether group, etc.; the aryl ether group may include benzyl ether group, phenethyl ether group, etc.; the epoxyalkoxy group may be glycidoxy, glycidoxy, glycidoxy, glycidoxy, glycidoxy, etc.; the epoxyalkoxy substituted aryl group may be glycidoxy substituted phenyl (such as formula 10-a and formula 11-a), glycidoxy substituted phenyl, glycidoxy substituted phenyl, glycidoxy substituted phenyl, etc.; the group containing alkoxysilane (such as formula 12-a and formula 13-a) may be a group containing γ- Groups of aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltri(β-methoxyethoxy)silane.

[0077] In the embodiments of the present application, when R1, R2, and R3 are carbon-containing groups, the carbon-containing groups have a suitable number of carbon atoms so that the photoacid generator has a suitable solubility in the organic solvent, and at the same time have good photosensitivity and photoacid generation ability, which is beneficial to improving the photolithography effect. In some embodiments of the present application, when R1, R2, and R3 are carbon-containing groups, the number of carbon atoms is 1-20. Specifically, when R1, R2, and R3 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.

[0078] In some embodiments of the present application, R2 is a group containing a terminal hydroxyl group, specifically, R2 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 the alkaline developer, reducing the residual adhesive phenomenon in the exposed or non-exposed area, and improving the pattern resolution and the regularity of the graphic morphology.

[0079] In some embodiments of the present application, R2 is a group containing an epoxy group, specifically a group terminated with an epoxy group, for example, an alkylene oxide, an arylene oxide, an alkylene oxide substituted aryl group, etc. R2 containing an epoxy group can increase the crosslinking degree of the resin, thereby effectively adjusting the pattern flatness and improving the photolithography effect. Among them, the alkylene oxide can be a glycidyl group, a butylene oxide, a glycidyl group, a glycidyl group, a hexyl oxide group, etc.; the alkylene oxide can be a glycidyl group, a glycidyl group, a glycidyl group, a glycidyl group, a hexyl oxide group, etc.; the alkylene oxide substituted aryl group can be a glycidyl group substituted phenyl group, a glycidyl group substituted phenyl group, a glycidyl group substituted phenyl group, a glycidyl group substituted phenyl group, etc.

[0080] In some embodiments of the present application, R2 is a group containing an alkoxysilane, specifically, the group containing an alkoxysilane can be a group including γ-aminopropyl triethoxysilane, γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-mercaptopropyl trimethoxy silane, vinyl triethoxy silane, vinyl trimethoxy silane, vinyl tri(β-methoxyethoxy) silane. Specifically, the alkoxysilane moiety in R2 is derived from the above-mentioned alkoxysilane. R2 is an alkoxysilane-terminated group, that is, the end of R2 is an alkoxysilane group. R2 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 to avoid the occurrence of adhesive drift. In addition, the silicon-oxygen bond has good flexibility, which can improve the flexibility of the cured film. The alkoxysilane has a large steric hindrance effect, which is beneficial to maintaining the heat resistance of the resin cured film and can improve the stability of the device retaining the cured film.

[0081] In the embodiment of the present application, a heterocyclic group refers to an organic cyclic group in which the atoms constituting the ring have other atoms in addition to carbon atoms. The heterocyclic group may have one heteroatom, or two or more heteroatoms, and the heteroatom may be one atom or two different atoms; the heterocyclic group may be connected to a carbon atom on a naphthalene ring through a heteroatom, or may be connected to a carbon atom on a naphthalene ring through a carbon atom. In the embodiment of the present application, X may be a five-membered heterocyclic group, a six-membered heterocyclic group, or a benzoheterocyclic group selected from O, N, or S. The five-membered heterocyclic group may specifically be a five-membered heterocyclic compound derived from furan, thiophene, pyrrole, thiazole, imidazole, triazole, tetrazole, etc.; the six-membered heterocyclic group may be a six-membered heterocyclic compound derived from pyridine, pyrazine, pyrimidine, pyridazine, etc.

[0082] 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 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 photoacid generator is shown in formula (Ia):

[0083]

[0084] 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 the 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 (Ib):

[0085]

[0086] In the embodiment of the present 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 an acetylene group or a carbonitrile without purification, and the electron absorption of the structure can better regulate the 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 migration and diffusion of metal ions such as copper ions into the cured film of the resin composition, and are also beneficial to enhance the ability of the resin composition itself to interact with the copper interface and the silicon interface.

[0087] In some embodiments of the present application, the molecular structure of the photoacid generator is as shown in Formulas 1-a to 23-a:

[0088]

[0089]

[0090] The present invention provides a method for preparing a photoacid generator, comprising:

[0091] The bromine substitution position in 4-bromo-1,8-naphthalene dicarboxylic anhydride is grafted with a heterocyclic group -X-R2, and the sulfonic acid group is grafted with the anhydride group after amidation to obtain a photoacid generator, wherein X includes a heterocyclic group containing O, N or S; and R2 includes a halogen, an aryl, an aralkyl, an alkylaryl, a halogenated aryl, an alkoxyaryl, an epoxyalkyl, an epoxyaryl, a hydroxyalkyl, a hydroxyaryl, a hydroxyalkyl substituted hydroxyaryl, an aminoaryl, an alkyl ether group, an aryl ether group, an epoxyalkyloxy group, an epoxyalkyloxy substituted aryl group, or a group containing an alkoxysilane.

[0092] In some embodiments, when X is a triazole or tetrazole group, the bromine substitution position in 4-bromo-1,8-naphthalenedicarboxylic anhydride may be azidated before grafting the substituted heterocyclic group -X-R2. The azidation process may be performed using sodium azide.

[0093] In the embodiment of the present application, the amidation process of the anhydride group may be performed by adding an amidation reagent, which may specifically include hydroxylamine hydrochloride. Sodium bicarbonate may also be added during the amidation process. The process of grafting and replacing the sulfonic acid group may be performed by adding a substituted sulfonic anhydride.

[0094] Taking the photoacid generator 1-a as an example, its preparation method may specifically include:

[0095] (1) 4-bromo-1,8-naphthalene dicarboxylic anhydride (compound 1a) was dissolved in DMF (N,N-dimethylformamide), and sodium azide was added at room temperature and reacted at 50°C-80°C. After the reaction was completed, the reaction solution was precipitated with ice water, and the yellow precipitate was collected by filtration and dried to obtain compound 1b.

[0096] (2) Compound 1b and phenylacetylene are dissolved in a mixed solution of tetrahydrofuran (THF) and water (the volume ratio of THF:H2O may be 4:1), copper sulfate pentahydrate and sodium ascorbate are added successively under a nitrogen atmosphere, and the mixture is heated under reflux for reaction. After the reaction is completed, the reaction solution is poured into ice water for precipitation, and the yellow-green precipitate is collected by filtration and dried to obtain compound 1c.

[0097] (3) Compound 1c, hydroxylamine hydrochloride and sodium bicarbonate were added to ethanol and heated under 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 an orange-yellow powder compound 1d.

[0098] (4) The compound 1d is dissolved in acetonitrile, and pyridine and trifluoromethanesulfonic anhydride are added dropwise in an ice bath under a nitrogen atmosphere, and then heated to 50-80°C for reaction. After the reaction is completed, the reaction solution is cooled to room temperature and filtered. The filter residue is rinsed with acetonitrile and then pumped dry with an oil pump to obtain a white powder compound, which is the photoacid generator 1-a.

[0099] The above reaction process is as follows:

[0100]

[0101] The embodiment of the present application further provides a photosensitive resin composition, which includes a resin or a resin precursor, a cross-linking agent, the photoacid generator mentioned in the embodiment of the present application, and an organic solvent.

[0102] 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 portion is washed away, and the exposed portion is retained. The patterning principle of the negative photosensitive resin composition of the present application embodiment is: the photoacid generator is irradiated by a light source to generate acid (substituted or unsubstituted sulfonic acid), and during the subsequent heat treatment process, the generated acid continuously catalyzes the cross-linking agent to cross-link, or the cross-linking agent and the polymer resin to cross-link, resulting in an obvious solubility difference between the exposed area and the unexposed area of ​​the polymer resin in the developer, that is, the solubility of the exposed area drops sharply due to cross-linking, while the unexposed area still maintains good solubility, and finally the unexposed area is washed away, and the exposed area is retained, thereby displaying a photolithographic pattern.

[0103] 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 is retained. The patterning principle of the positive photosensitive resin composition of the present application embodiment is: during the pre-baking process, the vinyl ether in the composition reacts with the hydroxyl group on the resin molecular chain and is insoluble in the alkaline developer. 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 remains insoluble.

[0104] 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 parts. 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 strong photoacid generating ability, so that the acid can be better formed, catalyzing the occurrence of the cross-linking reaction, improving the solubility difference between the exposure area and the non-exposure area, and improving the resolution of the pattern.

[0105] The photoacid generator of the embodiment of the present application is universal for resin and has no special requirements. In the embodiment of the present application, the resin or resin precursor in the photosensitive resin composition can be selected according to the actual application requirements, and the resin or resin precursor can be prepared by itself or purchased commercially. 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 one or more of phenolic resin precursor, epoxy resin precursor, acrylic resin precursor, benzocyclobutene resin precursor, benzoxazole resin precursor, and polyimide resin precursor. In the embodiment of the present application, the weight average molecular weight of the resin may be 5000-100000; in some embodiments, the weight average molecular weight of the resin may be 10000-80000; in some embodiments, the weight average molecular weight of the resin may be 20000-50000.

[0106] In the embodiment of the present application, the crosslinking agent includes a polyhydroxy crosslinking agent, and specifically the crosslinking agent can be a compound monomer containing a benzyl alcohol structure. The monomer can be crosslinked under acidic conditions to form a polymerized macromolecule with reduced solubility. In some embodiments, the compound monomer containing a benzyl alcohol structure can be a compound 2,6-bis(hydroxymethyl)-4-methylphenol as shown in formula A, or a compound (MBHP) as shown in formula B.

[0107]

[0108] 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.

[0109] 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.

[0110] In the embodiment of the present application, the organic solvent may be one or more of ester, ketone, ether or amide organic solvents. Among them, the ester organic solvent may be ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxy acetic acid alkyl esters, 3-alkoxy propionic acid alkyl esters, 2-alkoxy propionic acid alkyl esters, 2-alkoxy-2-methyl propionic acid methyl esters and 2-alkoxy-2-methyl propionic acid ethyl esters, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. The ketone organic solvent may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. The ether organic solvent can be diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol 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.

[0111] In the embodiment of the present application, the photosensitive resin composition can be prepared by uniformly mixing a resin or a resin precursor, a cross-linking agent, a photoacid generator, and an organic solvent.

[0112] 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 80 mJ / cm 2 -170 mJ / cm 2 In a specific embodiment, the exposure energy may be 80 mJ / 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 .

[0113] The present application also provides a method for forming a pattern, comprising:

[0114] S01, coating the photosensitive resin composition of the embodiment of the present application on a substrate to form a coating film;

[0115] The substrate can be a silicon-based material or a metal material (such as copper), and the thickness of the coating can be adjusted according to actual needs. After the coating is formed, the coating can be dried by heating to volatilize part of the solvent.

[0116] S02, exposing the coating film according to a preset pattern;

[0117] In the embodiment of the present application, a 365 nm mercury lamp light source can be used for exposure, and the exposure energy can be 80 mJ / cm 2 -170 mJ / cm 2 . After exposure, drying can be performed.

[0118] S03, developing the exposed coating film with a developer to obtain a resin pattern;

[0119] In the embodiment of the present application, the developer can be determined according to the solubility of the photosensitive resin composition, for example, it can be an alkaline developer. For a negative photosensitive resin composition, the exposed area is retained, while the non-exposed area is washed away, thereby forming a resin pattern.

[0120] S04, heat-treating the resin pattern. Heat treatment can cure the resin to form a cured film. The temperature of the heat treatment can be 100-350°C. The specific temperature can be determined according to the curing properties of the resin. In some embodiments, the heat treatment can be programmed temperature curing, for example, it can be programmed temperature curing from 100°C (1h) → 200°C (1h) → 300°C (1h). Curing with a certain degree of temperature rise is conducive to complete curing, forming a uniform, stable, and high-quality cured film.

[0121] The embodiment of the present application also provides a cured film, which is a cured film of the above-mentioned photosensitive resin composition, obtained by curing the above-mentioned photosensitive resin composition. The cured film is a patterned cured film, obtained by photolithography curing of the above-mentioned photosensitive resin composition.

[0122] 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 can be 4 μm, 3 μm, 2 μm, 1 μm, or 0.5 μm.

[0123] 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 can 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. The closer the inclination angle is to 90°, the better the patterning effect is.

[0124] The present invention also provides an electronic device 100, which includes the cured film of the present invention. The cured film can be used as a protective layer, a passivation layer, an interlayer insulating layer, a buffer layer, a planarization layer, an α-ray shielding layer or a rewiring layer in the electronic device 100. Figure 1 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, a rewiring layer 40 is formed on the passivation 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, a via hole is formed on the first dielectric layer 401 to expose the pad 20, the rewiring seed layer 403 and the 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 is formed on the second dielectric layer 402 to expose the rewiring metal layer 404, and a metal connection layer 501, an under bump metal layer 502, and a solder bump 503 are sequentially formed in the via hole. The semiconductor chip 10 can be a chip of any form, for example, it can be an integrated circuit (IC) in a bare state, the pad 20 can include a conductive material such as aluminum, and the passivation layer 30 can include oxides, nitrides, etc. The first dielectric layer 401 and the second dielectric layer 402 can be a patterned cured film formed by curing the photosensitive resin composition of the embodiment of the present application. The rewiring metal layer 404 is a copper layer. The metal connection layer 501 can be a Ti / Cu sputtered layer, and the under-bump metal layer 502 can be a Ni layer. In the packaging structure of the semiconductor chip, there is usually a bonding interface between the cured film and silicon and copper. The embodiment of the present application uses the photosensitive resin composition of the embodiment of the present application to form a cured film, which can effectively improve the bonding interface between the cured film and silicon and copper, and enhance the stability of the packaging structure.

[0125] In the embodiment of the present application, the cured film is disposed on the silicon wafer or the metal layer, and the adhesion between the cured film and the silicon wafer reaches the national standard reliability 100 grid test 3B or 4B standard; the adhesion between the cured film and the metal layer reaches the national standard reliability 100 grid test 4B or 5B standard. The metal layer can be, for example, a copper layer.

[0126] 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, photolithography materials, etc.

[0127] The embodiments of the present application are further described below with reference to a plurality of embodiments.

[0128] Example 1

[0129] (I) Synthesis of photoacid generator 1-a

[0130] (1) Compound 1a was dissolved in DMF, and an aqueous solution of sodium azide in an equimolar ratio was added dropwise at room temperature, and the mixture was reacted at high temperature for 2 h. After the reaction was completed, the reaction solution was cooled to room temperature and poured into ice water for precipitation. The yellow precipitate was collected by filtration and dried with air for 7 h to obtain compound 1b.

[0131] (2) Compound 1b and excess phenylacetylene (about 4 times the molar amount) were dissolved in a mixed solution of tetrahydrofuran (THF) and water. An equimolar amount of copper sulfate pentahydrate and a 5-fold molar amount of sodium ascorbate were added successively under a nitrogen atmosphere, and the mixture was refluxed at high temperature for 5 h. The reaction solution was poured into ice water for precipitation, and the yellow-green precipitate was collected by filtration and dried by air for 4 h to obtain compound 1c.

[0132] (3) Compound 1c, 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, repeatedly washed with ethanol and deionized water, and dried with air to obtain an orange-yellow powder compound 1d.

[0133] (4) Compound 1d was dissolved in acetonitrile, and 2 times the molar amount of pyridine and 2 times the molar amount of trifluoromethanesulfonic anhydride were added dropwise under nitrogen atmosphere and ice bath, and the reaction was carried out at high temperature for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature and directly filtered. The filter residue was rinsed with acetonitrile and then pumped dry with an oil pump to obtain a white powder compound, namely, photoacid generator 1-a. Characterization results of photoacid generator 1-a: 1HNMR (400MHz, CDCl3, 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] + : The calculated value is 489.0, and the experimental value is 489.1.

[0134] The synthetic reaction process of the above steps (1) to (4) is as follows:

[0135]

[0136] (II) Preparation of photosensitive resin composition

[0137] After 6FAP (36.6 g, 100 mmol) and p-aminophenol (0.655 g, 6 mmol) were added to N-methylpyrrolidone (NMP) and stirred to dissolve completely, 6FDA (45.6 g, 103 mmol) was added under nitrogen and the solid content was adjusted to 25 wt.%, and stirred at room temperature for 14 hours to obtain a 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 hours. All the toluene in the system was evaporated, cooled to room temperature, precipitated in a mixed solvent with a volume ratio of ethanol: water of 1:1, and vacuum dried at 120 ° C for 12 hours to obtain an off-white solid polyimide resin PHI with a molecular weight of about 30,000. The reaction formula for the preparation process of polyimide resin PHI is shown below, where n represents the degree of polymerization.

[0138]

[0139] 100 parts by mass of a PHI resin having a molecular weight of about 30,000, 10 parts by mass of a photoacid generator prepared in Example 1, and 20 parts by mass of a crosslinker MBHP were dissolved in 303 parts by mass of N-methylpyrrolidone (NMP) to make the total solid content of the composition (the total mass fraction of the three solids of the resin, the acid generator, and the crosslinker in the solvent) be 30 wt.%, and the mixture was stirred and mixed evenly, and then vacuum degassed to form a photosensitive resin composition.

[0140] (III) Preparation of patterned cured film

[0141] The prepared photosensitive resin composition was spin-coated on a silicon wafer to form a film, and then pre-baked on a hot plate at 110°C for 3 minutes to evaporate part of the solvent, thereby obtaining a dried composition coating film. The film was placed under a mask and exposed using a contact exposure machine with a 365nm mercury lamp light source, with an exposure energy range of 100-150mJ / cm 2 The exposed film was baked on a hot plate at 130°C for 2 minutes; after spray development in a developer, it was rinsed with deionized water. The film layer in the exposed area was retained, and the film layer in the non-exposed area was removed. Nitrogen was blown away the residual liquid on the silicon wafer, and then the temperature was raised and cured according to the program of 100°C (1h) → 200°C (1h) → 300°C (1h) to form a patterned cured film.

[0142] The prepared photosensitive resin composition was spin-coated on a copper sheet to form a film, and then heated on a hot plate at 110°C for 3 minutes to evaporate part of the solvent, thereby obtaining a dried composition coating. The film was placed under a mask and exposed using a 365nm mercury lamp light source with an exposure energy of 100-150mJ / cm 2The exposed film was baked on a hot plate at 130°C for 2 minutes; after spray development in a developer, it was rinsed with deionized water, and nitrogen was blown off the residual liquid on the copper sheet. Then, the film was cured according to the program of 100°C (1h) → 200°C (1h) → 300°C (1h) to form a patterned cured film.

[0143] The photoacid generator prepared in Example 1 was tested using an ultraviolet-visible spectrometer, and it was found that the photoacid generator prepared in Example 1 had good absorbance at i-line, good absorption of 365 nm light, and high photosensitivity.

[0144] The photosensitive resin composition of Example 1 of the present application was used for patterning, and the results showed that the stripes of the photolithography pattern under the mask with a line width of 4 μm were clear and flat without residual adhesive adhesion, and the pattern resolution that can be obtained by the photosensitive resin composition is 4 μm.

[0145] The adhesion between the cured film of Example 1 and the silicon wafer, and between the cured film and the copper sheet were tested by the 100-grid test method. The results showed that the adhesion between the cured film of Example 1 and the silicon wafer, and between the cured film and the copper sheet reached the national standard reliability 100-grid test 3B and 4B standards respectively.

[0146] The 100-grid test is carried out in accordance with the standard "GBT9286-1998". The national standard 100-grid test includes the following 6 levels: 5B standard: the edge of the cut is completely smooth and there is no peeling at the edge of the grid; 4B standard: there is small peeling at the intersection of the cut, and the actual damage to the grid area does not exceed 5%; 3B standard: there is peeling at the edge or intersection of the cut, and the damage area is greater than 5% and less than 15%; 2B standard: there is partial peeling or large peeling at the edge of the cut, or some grids are peeled off in full, and the damage area is greater than 15% and less than 35%; 1B standard: large peeling at the edge of the cut, or some grids are peeled off in full, and the damage area is greater than 35% and less than 65%; 0B standard: the damage area is greater than 65%.

[0147] The photoacid generator of the embodiment of the present application introduces an azole ring on the naphthalene ring of naphthaleneimide and introduces a phenyl group on the azole ring, and uses the special electronic effect of the phenyl group and the azole ring to control the optimal absorption wavelength of the photoacid generator to fall within 345-355 nm, while at the same time making the adhesion between the cured film and silicon and copper have a high level.

[0148] Example 2

[0149] (I) Synthesis of photoacid generator 6-a

[0150] (1) 4-bromophenol and potassium hydroxide were dissolved in 2-propanol at a molar ratio of 3:4, and 0.3 mL of formaldehyde aqueous solution was added dropwise, followed by heating and stirring at 40° C. for 48 hours. After cooling to room temperature, 1 mL of hydrochloric acid was added and the mixture was allowed to stand for 6 hours to form a red precipitate. The red precipitate was removed by suction and allowed to stand for two days to precipitate a white precipitate, which was dried to obtain compound 4a as a white solid.

[0151] (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 mixture was washed with copper sulfate pentahydrate solution to remove pyridine. The organic layer was dried and concentrated by rotary evaporation. After column chromatography with ethyl acetate and n-hexane, a white solid compound 4b was obtained.

[0152] (3) Dissolve 128 mg of compound 4b and 0.07 mL of trimethylsilylacetylene in triethylamine, and add 6.7 mg of triphenylphosphine, 8.3 mg of cuprous iodide and 5.2 mg of bis(triphenylphosphine)palladium dichloride under nitrogen atmosphere. Heat and reflux for 24 h. Filter, remove the solvent by rotary evaporation, and obtain brown liquid compound 4c after column chromatography with ethyl acetate and n-hexane.

[0153] (4) Add the THF solution of compound 4c to the THF solution of lithium aluminum hydride under ice-water bath conditions, stir at room temperature for 2 h, and then add 1 mL of deionized water under ice-water bath conditions. Continue stirring the reaction solution at room temperature for 12 h. Add 10 mL of HCl aqueous solution to the reaction solution to precipitate aluminum salt. Filter, evaporate under reduced pressure, dissolve in ethyl acetate and then wash with saturated brine. Dry the organic layer with anhydrous magnesium sulfate, filter, and evaporate to remove the solvent to obtain white solid compound 4d (i.e., hydroxymethyl-substituted hydroxyphenylacetylene).

[0154] The synthetic reaction process of the above steps (1) to (4) is as follows:

[0155]

[0156] (5) Compound 1b, 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 dried with air to obtain an orange-yellow powder compound 4e.

[0157] (6) Compound 4e was dissolved in acetonitrile, and 2 times the molar amount of pyridine and 2 times the molar amount of trifluoromethanesulfonic anhydride were added dropwise under nitrogen atmosphere and ice bath, and the reaction was carried out at high temperature for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature and directly filtered. The filter residue was rinsed with acetonitrile and then pumped dry with an oil pump to obtain compound 4f as a yellow powder. (7) Compound 4f and compound 4d were dissolved in THF solution in an equimolar ratio, and equimolar amounts of copper sulfate pentahydrate and 5 times the molar amount of sodium ascorbate were added successively under nitrogen atmosphere, and the reaction was refluxed at high temperature for 5 hours. The reaction solution was poured into ice water for precipitation, and the yellow-green precipitate was collected by filtration and dried with air for 4 hours to obtain the photoacid generator 6-a. Mass spectrum [M+H]+: calculated value is 564.0, and the experimental value is 564.1.

[0158] The synthetic reaction process of the above steps (5) to (7) is as follows:

[0159]

[0160] (II) Preparation of photosensitive resin composition

[0161] Take 100 parts by mass of a PHI resin with a molecular weight of about 30,000, 8 parts by mass of a photoacid generator prepared in Example 2, and 20 parts by mass of a crosslinking agent MBHP, dissolve them in 298 parts by mass of N-methylpyrrolidone (NMP) so that the total solid content of the composition is 30 wt.%, stir and mix evenly, and then vacuum degasse to form a photosensitive resin composition.

[0162] (III) Preparation of patterned cured film

[0163] The prepared photosensitive resin composition is spin-coated on a silicon wafer to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process is 80-150 mJ / cm 2 .

[0164] The prepared photosensitive resin composition was spin-coated on a copper sheet to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process was 80-150 mJ / cm 2 .

[0165] The photoacid generator prepared in Example 2 was tested using an ultraviolet-visible spectrometer, and it was found that the photoacid generator prepared in Example 2 had good absorbance at i-line, good absorption of 365 nm light, and high photosensitivity.

[0166] The photosensitive resin composition of Example 2 of the present application was used for patterning, and the results showed that the stripes of the photolithography pattern under the mask with a line width of 2 μm were clear and flat without residual adhesive adhesion, and the pattern resolution that can be obtained by the photosensitive resin composition is 2 μm.

[0167] The adhesion between the cured film of Example 2 and the silicon wafer, and between the cured film and the copper sheet were tested by the 100-grid test method. The results showed that the adhesion between the cured film of Example 2 and the silicon wafer, and between the cured film and the copper sheet reached the national standard reliability 100-grid test 3B and 4B standards respectively.

[0168] The photoacid generator of the embodiment of the present application introduces an azole ring on the naphthalene ring of naphthalimide and introduces a polyhydroxyphenyl group on the azole ring. On the one hand, the electronic effect of the polyhydroxyphenyl group and the azole ring can be used to adjust the optimal absorption wavelength of the photoacid generator to fall within 350-360 nm; at the same time, the adhesion between the cured film and silicon and copper can be made higher; in addition, the polyhydroxyphenyl group can improve the solubility of the resin composition in the alkaline developer, thereby ultimately improving the resolution of the pattern and reducing the residual adhesive phenomenon in the non-exposed area.

[0169] Example 3

[0170] (I) Synthesis of Photoacid Generator 10-a

[0171] (1) Compound 1a was dissolved in DMF (N,N-dimethylformamide), and an equimolar amount of an aqueous solution of sodium azide was added to the reaction system at room temperature for 2 hours at high temperature. After the reaction was completed, the reaction solution was cooled to room temperature and poured into ice water for precipitation. The yellow precipitate was collected by filtration and dried at 50°C for 7 hours to obtain compound 1b. (2) Compound 1b and 4-ethynylphenol were dissolved in DMF in an equimolar ratio, and an equimolar amount of copper sulfate pentahydrate and a 5-fold molar amount of sodium ascorbate were added. The reaction mixture was stirred at high temperature for 14 hours, poured into ice water, and filtered to obtain a solid precipitate. The precipitate was washed with cold water and dried to obtain compound 6a.

[0172] (3) Compound 6a and NaH were added to anhydrous tetrahydrofuran in 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. The mixture was heated to reflux for 8 hours, cooled to room temperature, poured into water, and extracted with ether. The organic layers were combined, dried over anhydrous Na2SO4, the solvent was removed by rotary evaporation, and purified by column chromatography to obtain compound 6b.

[0173] (4) Compound 6b, hydroxylamine hydrochloride and sodium bicarbonate were dissolved in ethanol at a molar ratio of 5:6:6. The mixture was refluxed for 3 h, cooled to room temperature and filtered, washed repeatedly with ethanol and deionized water, and dried under air at 70°C to obtain an orange-yellow powder compound 6c.

[0174] (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. The reaction was carried out at high temperature for 15 h, and the solvent was removed by rotary evaporation. The photoacid generator 10-a was purified by silica gel column chromatography. Mass spectrum [M+H]+: calculated value is 560.1, and the experimental value is 560.2.

[0175] The synthetic reaction process of the above steps (1) to (5) is as follows:

[0176]

[0177] (II) Preparation of photosensitive resin composition

[0178] Take 100 parts by mass of a PHI resin with a molecular weight of about 30,000, 8 parts by mass of the photoacid generator synthesized in Example 3, and 20 parts by mass of a crosslinking agent MBHP, dissolve them in 298 parts by mass of N-methylpyrrolidone (NMP) so that the total solid content of the composition is 30 wt.%, stir and mix evenly, and then vacuum degasse to form a photosensitive resin composition.

[0179] (III) Preparation of patterned cured film

[0180] The prepared photosensitive resin composition is spin-coated on a silicon wafer to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process is 100-150 mJ / cm 2 .

[0181] The prepared photosensitive resin composition is spin-coated on a copper sheet to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process is 100-150 mJ / cm 2 .

[0182] The photoacid generator prepared in Example 3 was tested using an ultraviolet-visible spectrometer, and it was found that the photoacid generator prepared in Example 3 had good absorbance at i-line, good absorption of 365 nm light, and high photosensitivity.

[0183] Figure 2 and Figure 3 This is a photolithography effect diagram of the photosensitive resin composition of Example 3 of the present application, specifically Figure 2 This is the photolithography pattern under the mask with a line width of 8μm (after curing); Figure 3 The photolithography pattern under the mask with a line width of 4 μm (after curing). Figure 2 It can be seen that the photolithography pattern under the mask with a line width of 8μm is steep and has no collapse, and the pattern is clear and flat. Figure 3 It can be seen that the photolithography pattern under the mask with a line width of 4 μm can be basically developed, and the best pattern resolution that can be obtained by the photosensitive resin composition is about 4 μm.

[0184] The adhesion between the cured film of Example 3 and the silicon wafer, and between the cured film and the copper sheet was tested by the 100-grid test method. The results showed that the adhesion between the cured film of Example 3 and the silicon wafer, and between the cured film and the copper sheet reached the national standard reliability 100-grid test 4B standard.

[0185] The photoacid generator of the embodiment of the present application introduces an oxadiazole ring on the naphthalene ring of naphthalimide and introduces an epoxyalkoxy group to replace the phenyl group on the oxadiazole ring. On the one hand, the electronic effect of the epoxyalkoxy group to replace the phenyl group and the oxadiazole ring can be used to adjust the optimal absorption wavelength of the photoacid generator to fall within 355-380nm; at the same time, the adhesion between the cured film and silicon and copper can be made to have a high level; in addition, the epoxy group can undergo a cross-linking reaction under acid catalysis and high temperature, which can improve the cross-linking degree 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 about 90°.

[0186] Example 4

[0187] (I) Preparation of photoacid generator 13-a

[0188] (1) A catalytic amount of copper chloride and N,N-diisopropylethylamine were dissolved in diethyl ether. An equimolar mixture of 3-chloropropyne and trichlorosilane was slowly added dropwise in an ice-water bath. The mixture was heated to room temperature and stirred for 2 h. The solid in the reaction solution was filtered and then distilled under reduced pressure at 80° C. to obtain compound 3a.

[0189] (2) Compound 1b and an excess of compound 3a (about 4 times the molar amount) were dissolved in THF, and an equimolar amount of copper sulfate pentahydrate and a 5-fold molar amount of sodium ascorbate were added successively under a nitrogen atmosphere, and the mixture was refluxed at high temperature for 5 h. The reaction solution was poured into ice water for precipitation, and the yellow-green precipitate was collected by filtration and dried with air for 4 h to obtain compound 3b.

[0190] (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 dried at 70°C to obtain an orange-yellow powder compound 3c.

[0191] (4) Compound 3c was dissolved in acetonitrile, and 2 times the molar amount of pyridine and 2 times the molar amount of trifluoromethanesulfonic anhydride were added dropwise under nitrogen atmosphere and ice bath, reacted at 60°C for 3 hours, cooled to room temperature, and directly filtered. The filter residue was rinsed with acetonitrile and then dried with an oil pump to obtain a photoacid generator 13-a as a white powder. Mass spectrum [M+H] + : The calculated value is 588.1, and the experimental value is 588.2.

[0192] The synthetic reaction process of the above steps (1) to (4) is as follows:

[0193]

[0194] (II) Preparation of photosensitive resin composition

[0195] Take 100 parts by mass of a PHI resin with a molecular weight of about 30,000, 12 parts by mass of the photoacid generator synthesized in Example 4, and 20 parts by mass of a crosslinking agent MBHP, dissolve them in 308 parts by mass of N-methylpyrrolidone (NMP) so that the total solid content of the composition is 30 wt.%, stir and mix evenly, and then vacuum degasse to form a photosensitive resin composition.

[0196] (III) Preparation of patterned cured film

[0197] The prepared photosensitive resin composition is spin-coated on a silicon wafer to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process is 120-170 mJ / cm 2 .

[0198] The prepared photosensitive resin composition was spin-coated on a copper sheet to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process was 120-170 mJ / cm 2 .

[0199] The photoacid generator prepared in Example 4 was tested using an ultraviolet-visible spectrometer, and it was found that the photoacid generator prepared in Example 4 had good absorbance at i-line, good absorption of 365 nm light, and high photosensitivity.

[0200] Figure 4 The photolithography effect diagram of the photosensitive resin composition of Example 4 of the present application, specifically, the photolithography patterns under the mask with different line widths (after curing). Figure 4 It can be seen that the photolithography pattern under the mask with a line width of 2 μm is clear and flat without residual adhesive adhesion, and the pattern resolution that can be obtained by the photosensitive resin composition is 2 μm.

[0201] The adhesion between the cured film of Example 4 and the silicon wafer, and between the cured film and the copper sheet were tested by the 100-grid test method. The results showed that the adhesion between the cured film of Example 4 and the silicon wafer, and between the cured film and the copper sheet reached the national standard reliability 100-grid test 4B and 5B standards respectively.

[0202] The photoacid generator of the embodiment of the present application introduces an azole ring on the naphthalene ring of naphthalimide, and introduces a substituted phenyl group containing an alkoxysilane at the terminal on the azole ring. On the one hand, the electronic effect of the substituted phenyl group and the azole ring can be used to adjust the optimal absorption wavelength of the photoacid generator to fall near 380nm, thereby improving the i-line photosensitivity; at the same time, the adhesion between the cured film and the silicon wafer and the copper sheet can be further improved through the terminal alkoxysilane group, thereby eliminating the adhesive drift phenomenon and improving the structural stability of the cured film layer.

[0203] Example 5

[0204] (I) Preparation of photoacid generator 2-a

[0205] (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 a 5-fold molar amount of sodium ascorbate were added successively under a nitrogen atmosphere, and the mixture was refluxed at high temperature for 5 h. The reaction solution was poured into ice water for precipitation, and the yellow-green precipitate was collected by filtration and dried with air for 4 h to obtain compound 2a.

[0206] (2) Compound 2a, 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 dried with air to obtain an orange-yellow powder compound 2b.

[0207] (3) Compound 2b was dissolved in acetonitrile, and 2 times the molar amount of pyridine and 2 times the molar amount of trifluoromethanesulfonic anhydride were added dropwise under nitrogen atmosphere and ice bath, reacted at 60°C for 3 hours, cooled to room temperature, and directly filtered. The filter residue was rinsed with acetonitrile and then pumped dry with an oil pump to obtain a photoacid generator 2-a as a white powder. Mass spectrum [M+H]+: calculated value is 489.0, experimental value is 489.1.

[0208] The synthetic reaction process of the above steps (1) to (3) is as follows:

[0209]

[0210] (II) Preparation of photosensitive resin composition

[0211] Take 100 parts by mass of a PHI resin with a molecular weight of about 30,000, 10 parts by mass of the photoacid generator synthesized in Example 5, and 20 parts by mass of a crosslinking agent MBHP, dissolve them in 303 parts by mass of N-methylpyrrolidone (NMP) so that the total solid content of the composition is 30 wt.%, stir and mix evenly, and then vacuum degasse to form a photosensitive resin composition.

[0212] (III) Preparation of patterned cured film

[0213] The prepared photosensitive resin composition is spin-coated on a silicon wafer to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process is 100-150 mJ / cm 2 .

[0214] The prepared photosensitive resin composition is spin-coated on a copper sheet to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process is 100-150 mJ / cm 2 .

[0215] The photoacid generator prepared in Example 5 was tested using an ultraviolet-visible spectrometer, and it was found that the photoacid generator prepared in Example 5 had good absorbance at i-line, good absorption of 365 nm light, and high photosensitivity.

[0216] The photosensitive resin composition of Example 4 of the present application was used for patterning, and the results showed that the photolithography pattern under the mask with a line width of 4 μm was clear and flat without adhesion, and the best pattern resolution that could be obtained by the photosensitive resin composition was about 4 μm.

[0217] The adhesion between the cured film of Example 4 and the silicon wafer, and between the cured film and the copper sheet were tested by the 100-grid test method. The results showed that the adhesion between the cured film of Example 5 and the silicon wafer, and between the cured film and the copper sheet reached the national standard reliability 100-grid test 3B and 4B standards respectively.

[0218] The photoacid generator of the embodiment of the present application introduces a tetrazole ring on the naphthalene ring of naphthaleneimide and introduces a substituted phenyl group on the tetrazole ring. The electronic effect of the phenyl group and the tetrazole ring can be used to adjust the optimal absorption wavelength of the photoacid generator to fall around 345-360nm, thereby improving the i-line photosensitivity. At the same time, the adhesion between the cured film and silicon and copper can be made to have a higher level.

[0219] Comparative Example 1

[0220] Preparation of a photosensitive resin composition: 100 parts by mass of the PHI-30000 resin synthesized in Example 1, 12 parts by mass of a photoacid generator PTMA ((5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile) and 20 parts by mass of a crosslinking agent MBHP were dissolved in 298 parts by mass of N-methylpyrrolidone (NMP) to make a total solid content of the composition of 30 w.t.%, stirred and mixed evenly, and then vacuum degassed to form a photosensitive resin composition.

[0221] The prepared photosensitive resin composition is spin-coated on a silicon wafer to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process is 150-200 mJ / cm 2 .

[0222] The prepared photosensitive resin composition is spin-coated on a copper sheet to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process is 150-200 mJ / cm 2 .

[0223] In Comparative Example 1, the best absorption wavelength of the photoacid generator PTMA is 415 nm, and the absorbance at the i-line is poor.

[0224] Figure 5The photolithography effect diagram of the photosensitive resin composition of Comparative Example 1 of the present application, specifically, the photolithography patterns under the mask with different line widths (after curing). Figure 5 It can be seen that after photolithography development using the photosensitive resin composition of Comparative Example 1 of the present application, the photosensitive resin composition has severe bleaching, the adhesion between the base film and the silicon wafer is insufficient, and stripes with a resolution of 10 μm can barely be obtained.

[0225] The adhesion between the cured film of comparative example 1 and the silicon wafer, and between the cured film and the copper sheet was tested using the 100-grid test method. The results showed that the adhesion between the cured film of comparative example 1 and the silicon wafer, and between the cured film and the copper sheet reached the national standard reliability 100-grid test 2B standard.

[0226] Comparative Example 2

[0227] (I) Synthesis of unsubstituted naphthaleneimide-type photoacid generator

[0228] (1) 1,8-naphthalene dianhydride, hydroxylamine hydrochloride and sodium bicarbonate were dissolved in ethanol in a ratio of 5:6:6 and refluxed at high temperature for 3 h. The reaction mixture was filtered under reduced pressure, washed repeatedly with ethanol and water, and dried at 80° C. to obtain dark yellow powder NI-OH.

[0229] (2) NI-OH and pyridine were dissolved in acetonitrile in a molar ratio of 2:3, and trifluoromethanesulfonic anhydride was slowly added dropwise in an ice bath in an amount equimolar to pyridine. After stirring at high temperature for 12 hours (TLC monitoring the reaction, the product point no longer increased), a brown solid was obtained by rotary evaporation under reduced pressure. The crude product was subjected to silica gel column chromatography to obtain a white solid, i.e., the unsubstituted naphthalene imide 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 value is 346.0, and the experimental value is 346.0.

[0230]

[0231] (II) Preparation of photosensitive resin composition

[0232] 100 parts by mass of PHI-30000 resin, 10 parts by mass of PAG synthesized in Comparative Example 2, and 20 parts by mass of crosslinking agent MBHP were dissolved in 303 parts by mass of N-methylpyrrolidone (NMP) so that the total solid content of the composition was 30 w.t.%, and the mixture was stirred and mixed evenly, and then vacuum degassed to form a photosensitive resin composition.

[0233] The prepared photosensitive resin composition is spin-coated on a silicon wafer to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process is 150-200 mJ / cm 2 .

[0234] The prepared photosensitive resin composition is spin-coated on a copper sheet to obtain a patterned cured film in the same manner as in Example 1, wherein the exposure energy during the exposure process is 150-200 mJ / cm 2 .

[0235] The photoacid generator of Comparative Example 2 has an optimal absorption wavelength of 340 nm and an average absorbance at the i-line.

[0236] Figure 6 and Figure 7 This is a photolithography effect diagram of the photosensitive resin composition of Comparative Example 2 of the present application, wherein: Figure 6 This is the photolithography pattern under the mask with a line width of 8μm (after curing); Figure 7 This is the photolithography pattern under the mask with a line width of 4μm (after curing). Figure 6 It can be seen that the stripes of the photolithography pattern under the mask with a line width of 8μm are dissolved and shrunk, resulting in poor flatness. Figure 7 It can be seen that the stripes of the photolithographic pattern under the mask with a line width of 4 μm are not developed cleanly, resulting in serious adhesion. The pattern resolution of the photosensitive resin composition of Comparative Example 2 is 8 μm.

[0237] The adhesion between the cured film of Comparative Example 2 and the silicon wafer, and between the cured film and the copper sheet were tested using the 100-grid test method. The results showed that the adhesion between the cured film of Comparative Example 2 and the silicon wafer, and between the cured film and the copper sheet reached the national standard reliability 100-grid test 3B standard.

[0238] The results of the best absorption wavelength of the photoacid generator in Examples 1-5 and Comparative Examples 1-2, the photolithographic performance of the photosensitive resin composition, and the adhesion between the cured film of the photosensitive resin composition and the silicon and copper interfaces are summarized in Table 1.

[0239] Table 1. Experimental results of examples and comparative examples

[0240]

[0241] From the results in Table 1, it can be seen that compared with Comparative Examples 1-2, the optimal absorption wavelength of the photoacid generator of Examples 1-5 of the present application is close to 365nm, and the absorbance at the i-line is higher, so the resolution of the photolithography pattern is improved, and Examples 1-5 show that at least a resolution of 4μm can be obtained. Compared with Comparative Examples 1-2, the adhesion of the photosensitive resin composition cured film of Examples 1-5 of the present application to the silicon and copper interfaces is improved. In some embodiments, the use of the photoacid generator of the embodiments of the present application can also reduce the exposure dose required during the exposure process to a certain extent.

Claims

1. A photosensitive molecule, characterized in that The molecular structure of the photosensitive molecule includes a naphthalene imide structure, a substituted sulfonic acid group connected to a nitrogen atom in the naphthalene imide structure, a heterocyclic group X connected to a naphthalene ring in the naphthalene imide structure, and R2 connected to the heterocyclic group; The substituted sulfonic acid group is represented by -SO3R1, wherein R1 is a halogenated alkyl group, and the number of carbon atoms of R1 is 1-20; The heterocyclic group X is selected from triazole or tetrazole, wherein one of the nitrogen atoms of the triazole or tetrazole is connected to the carbon atom of the naphthalene ring; the R2 is selected from an aryl group, an aralkyl group, an alkylaryl group, a halogenated aryl group, an alkoxyaryl group, an epoxy aryl group, a hydroxyaryl group, a hydroxyalkyl substituted hydroxyaryl group, an aminoaryl group, an aryl ether group, an epoxy alkoxy substituted aryl group, and a group containing alkoxysilane, wherein the group containing alkoxysilane is selected from γ-aminopropyltriethoxysilane, γ- Aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, wherein the number of carbon atoms of R2 is 1-20.

2. The photosensitive molecule according to claim 1, characterized in that The molecular structure of the photosensitive molecule also includes R3 connected to the naphthalene ring in the naphthaleneimide structure, R3 is selected from a group including hydrogen, halogen, alkyl, alkenyl, alkynyl, and halogenated alkyl, and when R3 is a carbon-containing group, the number of carbon atoms is 1-20.

3. A photosensitive molecule, characterized in that The molecular structure of the photosensitive molecule includes a naphthalene imide structure, a substituted sulfonic acid group connected to the nitrogen atom in the naphthalene imide structure, a heterocyclic group X connected to the naphthalene ring in the naphthalene imide structure, and R2 connected to the heterocyclic group; the photosensitive molecule is prepared by the following method: The bromine substitution position in 4-bromo-1,8-naphthalene dicarboxylic anhydride is grafted with a heterocyclic group -X-R2, and the anhydride group is amidated and then grafted with a sulfonic acid group to obtain a photosensitive molecule; wherein X is selected from triazole or tetrazole, and one of the nitrogen atoms of the triazole or tetrazole is connected to the carbon atom of the naphthalene ring; and R2 is selected from one of the groups selected from aryl, aralkyl, alkylaryl, halogenated aryl, alkoxyaryl, epoxy aryl, hydroxyaryl, aminoaryl, aryl ether, hydroxyalkyl substituted hydroxyaryl, epoxy alkyloxy substituted aryl, and alkoxysilane-containing groups, The alkoxysilane-containing group is selected from γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, and the carbon number of R2 is 1-20; The substituted sulfonic acid group is represented by -SO3R1, wherein R1 is a halogenated alkyl group, and the number of carbon atoms of R1 is 1-20.

4. A photosensitive molecule, characterized in that The molecular structure of the photosensitive molecule is shown below:

5. A method for preparing a photosensitive molecule, characterized in that: include: The bromine substitution position in 4-bromo-1,8-naphthalene dicarboxylic anhydride is grafted with a heterocyclic group -X-R2, and the sulfonic acid group is grafted with the anhydride group after amidation to obtain a photosensitive molecule, wherein the molecular structure of the photosensitive molecule includes a naphthalene imide structure, the substituted sulfonic acid group connected to the nitrogen atom in the naphthalene imide structure, and a heterocyclic group X connected to the naphthalene ring in the naphthalene imide structure, and R2 connected to the heterocyclic group; wherein X is selected from triazole or tetrazole, and one of the nitrogen atoms of the triazole or tetrazole is connected to the carbon atom of the naphthalene ring; and R2 is selected from aryl, aralkyl, alkaryl, halogenated aryl, alkoxyaryl, epoxyaryl, hydroxyaryl, aminoaryl, aryl ether A group selected from the group consisting of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltri(β-methoxyethoxy)silane, wherein R2 has a carbon atom number of 1-20; The substituted sulfonic acid group is represented by -SO3R1, wherein R1 is a halogenated alkyl group, and the number of carbon atoms of R1 is 1-20.

6. A photoacid generator, characterized in that The photoacid generator comprises the photosensitive molecule according to any one of claims 1 to 4 or the photosensitive molecule prepared by the preparation method according to claim 5.

7. Use of the photosensitive molecule according to any one of claims 1 to 4, or the photosensitive molecule prepared by the preparation method according to claim 5, or the photoacid generator according to claim 6 in patterning treatment.

8. 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 as claimed in claim 6.

9. The photosensitive resin composition according to claim 8, 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.

10. The photosensitive resin composition according to claim 8 or 9, characterized in that: The resin includes one or more of phenolic resin, epoxy resin, acrylic resin, benzocyclobutene resin, benzoxazole resin, and polyimide resin.

11. The photosensitive resin composition according to claim 8, characterized in that: The cross-linking agent includes a polyhydroxy cross-linking agent, and the polyhydroxy cross-linking agent includes a compound monomer containing a benzyl alcohol structure.

12. The photosensitive resin composition according to claim 8, 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.

13. The photosensitive resin composition according to claim 8, characterized in that: The photosensitive resin composition further includes an organic solvent.

14. The photosensitive resin composition according to claim 13, characterized in that: Based on 100 parts by mass of the resin, the organic solvent in the photosensitive resin composition is 130-740 parts by mass.

15. The photosensitive resin composition according to claim 13 or 14, characterized in that: The organic solvent includes one or more of ester, ketone, ether or amide organic solvents.

16. The photosensitive resin composition according to claim 8, characterized in that: When the photosensitive resin composition is used for patterning, the exposure energy required to act on the photosensitive resin composition is 80-170 mJ / cm 2 .

17. A pattern forming method, characterized in that: include: Applying the photosensitive resin composition according to any one of claims 8 to 16 on a substrate to form a coating film; exposing the coating film according to a preset pattern; Developing the exposed coating film with a developer to obtain a resin pattern; The resin pattern is heat-treated.

18. A cured film, characterized in that: The cured film is a cured film of the photosensitive resin composition according to any one of claims 8 to 16.

19. The cured film according to claim 18, wherein The cured film is a patterned cured film, and a resolution of a pattern on the cured film is less than or equal to 4 μm.

20. An electronic device, characterized in that: The electronic device comprises the cured film according to claim 18 or 19, or the electronic device comprises a cured film formed by curing a composition comprising the photosensitive molecule according to any one of claims 1 to 4.

21. The electronic device according to claim 20, characterized in that The electronic device includes a silicon wafer or a metal layer, and the cured film is arranged on the silicon wafer or the metal layer; the adhesion between the cured film and the silicon wafer reaches the national standard reliability test 3B or 4B standard; the adhesion between the cured film and the metal layer reaches the national standard reliability test 4B or 5B standard.

22. The electronic device according to claim 20 or 21, characterized in that: The cured film serves as a protective layer, a passivation layer, an interlayer insulating layer, a buffer layer, a planarizing layer, an α-ray shielding layer, or a rewiring layer in the electronic device.

Images