Series of heterocyclic aromatic hydrocarbon photoinitiators and photoinitiator application thereof

Abstract

The invention relates to synthesis and application of a series of polycyclic aromatic hydrocarbon compounds and photoinitiators thereof, in particular to a synthesis method and application of polycyclic aromatic hydrocarbon non-conjugated photoinitiators, and the synthesis method is base-catalyzed esterification reaction. The polycyclic aromatic hydrocarbon non-conjugated compound screened by the invention has active hydroxyl with multiple benzene rings uniformly distributed, and when a corresponding photoinitiator is further synthesized, the reaction steric hindrance is small, the photosensitivity of the product is strong, and the polycyclic aromatic hydrocarbon non-conjugated compound has excellent photochemical application performance.

Description

Technical Field

[0001] The invention discloses a series of polycyclic aromatic hydrocarbon non-conjugated benzene ring compounds and photoinitiator applications thereof, belonging to the technical field of photochemistry. Background Art

[0002] Photolithography is a major process in the electronics industry and is used in the production of planar transistors and integrated circuits.

[0003] Photoresists can be classified into photopolymerization type, photodecomposition type, photocrosslinking type and chemical amplification type according to their chemical structure. Among them, the common photodecomposition type photoresist is made of a photosensitive agent with diazonaphthoquinone (DNQ). After exposure to light, it undergoes a photodecomposition reaction and is called a positive photoresist. Positive photoresists are mainly composed of resins, photoinitiators, organic solvents, additives, etc. Photoinitiators play a key role in various process technologies in the electronics industry. Photoinitiator molecules have a certain light absorption capacity in the ultraviolet light region (250~400 nm) or the visible light region (400~800 nm). After directly or indirectly absorbing light energy, the initiator molecules transition from the ground state to the excited singlet state, and then to the excited triplet state through intersystem crossing; after the excited singlet state or triplet state undergoes a single-molecule or bimolecular chemical reaction, active fragments that can initiate monomer polymerization are generated. These active fragments can be free radicals, cations, anions, etc. According to different initiation mechanisms, photoinitiators can be divided into free radical polymerization photoinitiators and cationic photoinitiators, among which free radical polymerization photoinitiators are the most widely used.

[0004] In the past few years, more efforts have been devoted to developing new photoinitiators with a larger light absorption range and solving the above challenges. The present invention uses polycyclic aromatic hydrocarbons as the skeleton to develop a new type of hybrid photoinitiator. The cation-free radical hybrid photoinitiator has good initiation efficiency and good photocuring performance. Summary of the invention

[0005] The purpose of the present invention is to synthesize a photoinitiator with a hybrid non-conjugated polycyclic structure by a simple method, so as to solve the problems of insufficient output of new photoinitiators and single type of new photoinitiator precursor skeleton, propose a synthesis method of a class of polyhydroxyheterocyclic anthracene skeleton compounds and their photoinitiators, and explain the functionality of the photoinitiator. The present invention discloses a series of polycyclic aromatic hydrocarbon non-conjugated benzene ring compounds and their photoinitiator applications, which belong to the field of near-ultraviolet photoinitiators, and their chemical structural formulas are as follows: R 1 is N or P; D is .

[0006] The heterocyclic aromatic hydrocarbon photoinitiator may also be R 1 N or P; R 2 , R 3 for , R 4 H, or , where R 4 and D has a substituent that is .

[0007] In some compounds, the general formula of the heterocyclic aromatic hydrocarbon photoinitiator can also be

[0008] In the structural formula, D represents: hydrogen and diazonaphthoquinone ester group (Wherein D has at least one substituent which is a diazonaphthoquinone ester group) The synthesis method of the heterocyclic aromatic hydrocarbon photoinitiator is characterized in that, under alkaline conditions, a benzene ring hydroxy heterocyclic anthracene skeleton compound and a diazonaphthoquinone type photosensitizer DNQ undergo an esterification reaction to generate a diazonaphthoquinone type photoinitiator.

[0009] The structural formula of the benzene ring hydroxy heterocyclic anthracene skeleton compound is:

[0010] In the above structural formula, D is H.

[0011] The present invention uses this series of compounds as precursors for preparing G / I line photoinitiators. When the hydroxyl groups in the above compounds are substituted, the photoinitiators can be applied to the semiconductor field related to I line photoresists.

[0012] Basic catalysts include triethylamine.

[0013] The molar feed ratio of the raw material DNQ to the polyhydroxy heterocyclic anthracene skeleton compound is 1-3:1, the synthesis temperature is controlled at 30-35°C, and the reaction time is 5-30 min.

[0014] During the esterification reaction, the diazonaphthoquinone compound realizes the esterification reaction of the hydroxyl groups of the respective compounds in the benzene ring hydroxyl heterocyclic anthracene skeleton compound, and the esterification reaction includes one or more of monoesterification, diesterification, triesterification, tetraesterification, and pentaesterification.

[0015] The present invention also provides a G / I line photoinitiator, wherein the initiator comprises the heterocyclic aromatic hydrocarbon photoinitiator.

[0016] Another technical solution of the present invention is to use the heterocyclic aromatic hydrocarbon photoinitiator in the field of I-line photoresist semiconductors.

[0017] The advantages and beneficial effects of the present invention are: (1) The synthesis method of the parent structure having a polycyclic aromatic hydrocarbon non-conjugated benzene ring of the present invention is simple, and the source of raw materials is convenient and easily available.

[0018] (2) The present invention has a polycyclic aromatic hydrocarbon non-conjugated benzene ring type photoinitiator, which makes its UV-visible absorption peak red-shifted to 350 nm, with a half-peak width of about 50 nm, and extends to around 420 nm, which fully meets the requirements of near-ultraviolet absorption. The photoinitiator together constitutes a photosensitive system to initiate monomer polymerization under near-ultraviolet light irradiation or serve as a photocurable material.

[0019] (3) Polycyclic aromatic hydrocarbon non-conjugated benzene ring compounds have active hydroxyl groups evenly distributed on multiple benzene rings. When further synthesizing the corresponding photoinitiator, the reaction steric hindrance is small and the product has strong photosensitivity, which has excellent photochemical application performance. Diazo naphthoquinone compounds can be used as photosensitive compounds; the photoinitiator synthesized by the two has excellent photocuring performance. DETAILED DESCRIPTION

[0020] The features and advantages of the present invention can be further understood through the following detailed description. The examples provided are merely illustrative of the methods of the present invention and are not intended to limit the remainder of the present invention in any way.

[0021] The present invention is further described below in conjunction with embodiments: Example 1 Synthesis of compound c Synthesis steps: 1) Dissolve 1 mmol of compound b (hydroxyanthracene skeleton compound) and 1 mmol of compound a (DNQ) in 1,4-dioxane and stir to dissolve at 35 °C; 2) After the reaction system is cooled to 30 °C, slowly add the same volume of triethylamine catalyst and triethylamine solvent (addition time is about 1 h), keep the temperature between 30-31 °C, and react for 30 min after the addition is completed; 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter and collect the filtrate; 4) Slowly pour the filtrate into ultrapure water (mixed with 30% hydrochloric acid) containing 5 times the volume of the organic solution, and stir vigorously to perform pulping operation; 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH value of the filtrate was 6-7. The solid was collected and dried at 40°C with a yield of 99%.

[0022] Example 2 Synthesis of compound c Wherein D has at least one diazonaphthoquinonesulfonyl group, that is, a mixture is obtained, wherein the mixture contains a compound in which D is a diazonaphthoquinonesulfonyl group, a compound in which D is a diazonaphthoquinonesulfonyl group, and a compound in which D is a diazonaphthoquinonesulfonyl group. Synthesis steps: 1) Dissolve 1 mmol (polyhydroxyanthracene skeleton compound) and 2 mmol (DNQ) in 1,4-dioxane and stir to dissolve at 35°C; 2) After the reaction system is cooled to 30 °C, slowly add triethylamine catalyst and the same volume of triethylamine solvent (addition time is about 1 h), keep the temperature between 30-31 °C, and react for 30 min after the addition is completed; 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter and collect the filtrate; 4) Slowly pour the filtrate into ultrapure water (mixed with 30% hydrochloric acid by volume) containing 5 times the volume of the organic solution, and stir vigorously to perform pulping operation; 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH value of the filtrate was 6-7. The solid was collected and dried at 40°C with a yield of 97%.

[0023] Example 3 Synthesis of compound c Wherein D has at least one diazonaphthoquinone sulfonyl group, that is, a mixture is obtained, wherein the mixture contains a compound in which 1 D is a diazonaphthoquinone sulfonyl group, a compound in which 2 Ds are diazonaphthoquinone sulfonyl groups, a compound in which 3 Ds are diazonaphthoquinone sulfonyl groups, a compound in which 4 Ds are diazonaphthoquinone sulfonyl groups, and a compound in which 5 Ds are diazonaphthoquinone sulfonyl groups. Synthesis steps 1) Dissolve 1 mmol of compound b (polyhydroxyanthracene skeleton compound) and 3 mmol of compound a (DNQ) in 1,4-dioxane at a certain molar ratio and stir to dissolve at 35°C; 2) After the reaction system is cooled to 30 °C, slowly add triethylamine catalyst and the same volume of triethylamine solvent (addition time is about 1 h), keep the temperature between 30-31 °C, and react for 30 min after the addition is completed; 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter and collect the filtrate; 4) Slowly pour the filtrate into ultrapure water (mixed with 30% hydrochloric acid by volume) containing 5 times the volume of the organic solution, and stir vigorously to perform pulping operation; 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH value of the filtrate was 6-7. The solid was collected and dried at 40°C with a yield of 98%.

[0024] Example 4 Synthesis of compound c Synthesis steps: 1) Dissolve 1 mmol of compound b (polyhydroxyanthracene skeleton compound) and 1 mmol of compound a (DNQ) in 1,4-dioxane at a certain molar ratio and stir to dissolve at 35°C; 2) After the reaction system is cooled to 30 °C, slowly add the same volume of triethylamine catalyst and triethylamine solvent (addition time is about 1 hour), keep the temperature between 30-31 °C, and react for 30 minutes after the addition is completed; 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter and collect the filtrate; 4) Slowly pour the filtrate into ultrapure water (mixed with 30% hydrochloric acid) containing 5 times the volume of the organic solution, and stir vigorously to perform pulping operation; 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH value of the filtrate was 6-7. The solid was collected and dried at 40°C with a yield of 96%.

[0025] Example 5 Synthesis of compound c Wherein D has at least one diazonaphthoquinonesulfonyl group, that is, a mixture is obtained, wherein the mixture contains a compound in which D is a diazonaphthoquinonesulfonyl group, a compound in which D is a diazonaphthoquinonesulfonyl group, and a compound in which D is a diazonaphthoquinonesulfonyl group.

[0026] Synthesis steps: 1) Dissolve 1 mmol of compound b (polyhydroxyanthracene skeleton compound) and 2 mmol of compound a (DNQ) in 1,4-dioxane and stir to dissolve at 35°C; 2) After the reaction system is cooled to 30 °C, slowly add the same volume of triethylamine catalyst and triethylamine solvent (addition time is about 1 h), keep the temperature between 30-31 °C, and react for 30 min after the addition is completed; 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter and collect the filtrate; 4) Slowly pour the filtrate into ultrapure water (mixed with 30% hydrochloric acid) containing 5 times the volume of the organic solution, and stir vigorously to perform pulping operation; 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH value of the filtrate was 6-7. The solid was collected and dried at 40°C with a yield of 98%.

[0027] Example 6 Synthesis of compound c Wherein D has at least one diazonaphthoquinone sulfonyl group, that is, a mixture is obtained, wherein the mixture contains a compound in which 1 D is a diazonaphthoquinone sulfonyl group, a compound in which 2 Ds are diazonaphthoquinone sulfonyl groups, a compound in which 3 Ds are diazonaphthoquinone sulfonyl groups, a compound in which 4 Ds are diazonaphthoquinone sulfonyl groups, and a compound in which 5 Ds are diazonaphthoquinone sulfonyl groups.

[0028] Synthesis steps: 1) Dissolve 1 mmol of compound b (polyhydroxyanthracene skeleton compound) and 3 mmol of compound a (DNQ) in 1,4-dioxane and stir to dissolve at 35 °C; 2) After the reaction system is cooled to 30 °C, slowly add the same volume of triethylamine catalyst and triethylamine solvent (addition time is about 1 h), keep the temperature between 30-31 °C, and react for 30 min after the addition is completed; 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter and collect the filtrate; 4) Slowly pour the filtrate into ultrapure water (mixed with 30% hydrochloric acid) containing 5 times the volume of the organic solution, and stir vigorously to perform pulping operation; 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH value of the filtrate was 6-7. The solid was collected and dried at 40°C with a yield of 96%.

[0029] Example 7 5 g of the photoinitiator prepared in Examples 1, 2, 3, 4, 5, and 6 were weighed respectively, mixed with 20 g of phenolic resin and 65 g of organic solvent PGMEA to prepare photosensitive compositions, which were numbered as compositions (1-2), (2-2), (3-2), (4-2), (5-2), and (6-2). The six compositions were subjected to photolithography processes under the same conditions, and the process flow included spin coating, pre-baking, exposure, post-baking, and development, and the process parameters of the process were shown in the table:

[0030] The height difference of the film covered by each group of substrates was tested by a profilometer, and the test results are shown in the table:

[0031] It can be observed that the composition has significant photosensitivity, among which the high difference values ​​of composition (2-2), composition (3-2), composition (5-2) and composition (6-2) are significant. It can also be observed that the more hydroxyl groups in the skeleton compound, the more photosensitive compound (DNQ) generated by esterification, the more photosensitivity is significantly enhanced (such as compositions 3-2 and 6-2), and the better the developing effect.

[0032] It should be noted that the embodiments of the present invention have better practicability and do not impose any form of limitation on the present invention. Any technician familiar with the field may use the technical content disclosed above to change or modify it into an equivalent effective embodiment. However, any modification or equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A series of heterocyclic aromatic hydrocarbon photoinitiators, characterized in that: The heterocyclic aromatic hydrocarbon photoinitiator system compound structure is: R1 is N or P; D is .

2. The heterocyclic aromatic hydrocarbon photoinitiator according to claim 1, characterized in that The heterocyclic aromatic hydrocarbon photoinitiator can also be R1 is N or P; R2 and R3 are , R4 is H, or , wherein R4 and D have a substituent which is .

3. The heterocyclic aromatic hydrocarbon photoinitiator according to claim 1 or 2, characterized in that: The structural formula of the heterocyclic aromatic hydrocarbon photoinitiator includes any one of the following: In the structural formula, D represents: hydrogen and diazonaphthoquinone ester group, that is, at least one substituent of D is diazonaphthoquinone ester group.

4. The method for synthesizing a heterocyclic aromatic hydrocarbon photoinitiator according to any one of claims 1 to 3, characterized in that: Under alkaline conditions, the benzene ring hydroxy heterocyclic anthracene skeleton compound undergoes an esterification reaction with the diazonaphthoquinone type photosensitizer DNQ to generate a diazonaphthoquinone type photoinitiator.

5. The method for synthesizing a heterocyclic aromatic hydrocarbon photoinitiator according to claim 4, characterized in that: The structural formula of the benzene ring hydroxy heterocyclic anthracene skeleton compound is In the structural formula, D is H.

6. The method for synthesizing a heterocyclic aromatic hydrocarbon photoinitiator according to claim 4, characterized in that: Basic catalysts include triethylamine.

7. The method for synthesizing a heterocyclic aromatic hydrocarbon photoinitiator according to claim 4, characterized in that: The molar feed ratio of the raw material DNQ to the polyhydroxy heterocyclic anthracene skeleton compound is 1-3:1, the synthesis temperature is controlled at 30-35°C, and the reaction time is 5-30min.

8. The method for synthesizing a heterocyclic aromatic hydrocarbon photoinitiator according to claim 4, characterized in that: During the esterification reaction, the diazonaphthoquinone compound realizes the esterification reaction of the hydroxyl groups of the respective compounds in the benzene ring hydroxyl heterocyclic anthracene skeleton compound, and the esterification reaction includes one or more of monoesterification, diesterification, triesterification, tetraesterification, and pentaesterification.

9. G / I line photoinitiator, characterized in that The initiator comprises the heterocyclic aromatic hydrocarbon photoinitiator according to any one of claims 1 to 3.

10. Use of the heterocyclic aromatic hydrocarbon photoinitiator according to any one of claims 1 to 3 in the field of I-line photoresist semiconductors.

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