A series of heterocyclic aromatic photoinitiators and their photoinitiator applications

Abstract

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

Description

TECHNICAL FIELD

[0001] The application discloses a series of polycyclic aromatic hydrocarbon non-conjugated benzene ring compounds and photo-initiator applications thereof, and belongs to the technical field of photochemistry. BACKGROUND

[0002] Photoetching technology is widely used in the electronic industry, and is a main process in the production of planar transistors and integrated circuits.

[0003] Photoresists can be classified into photo-polymerization type, photo-decomposition type, photo-crosslinking type and chemical amplification type according to chemical structures, wherein the photoresist of the photo-decomposition type commonly adopts a photosensitive agent made of diazonaphthoquinone (DNQ), which, after light irradiation, undergoes a photo-decomposition reaction and is called a positive photoresist. The positive photoresist is mainly composed of resin, photo-initiator, organic solvent, additive and the like. The photo-initiator plays a key role in various process technologies in the electronic industry. The photo-initiator molecule has a certain light absorption capacity in the ultraviolet light region (250-400 nm) or the visible light region (400-800 nm), and after directly or indirectly absorbing light energy, the initiator molecule jumps from the ground state to the excited singlet state, and then undergoes intersystem crossing to the excited triplet state. After experiencing monomolecular or bimolecular chemical action in the excited singlet state or the excited triplet state, active fragments capable of initiating monomer polymerization are generated, and these active fragments can be free radicals, cations, anions and the like. According to different initiation mechanisms, the photo-initiator can be divided into free radical polymerization photo-initiators and cationic photo-initiators, wherein the free radical polymerization photo-initiators are most widely used.

[0004] In the past few years, more efforts have been devoted to developing new photo-initiators with a larger light absorption range and solving the above challenges. The present application develops a new type of hybrid photo-initiator with a polycyclic aromatic hydrocarbon skeleton. The cationic-radical hybrid photo-initiator has good initiation efficiency and good light curing performance. SUMMARY

[0005] The purpose of the present application is to synthesize a photo-initiator with a hybrid non-conjugated polycyclic structure by a simple method, so as to solve the problems of lack of new photo-initiators and single type of precursor skeleton of new photo-initiators. A synthesis method of a class of polycyclic aromatic hydrocarbon non-conjugated benzene ring compounds and photo-initiators thereof is proposed, and the functionality of the photo-initiator is described.

[0006] The application discloses a series of polycyclic aromatic hydrocarbon non-conjugated benzene ring compounds and photo-initiator applications thereof, and belongs to the technical field of photochemistry.

[0007] R1 is N or P; D is .

[0008] The heterocyclic aromatic hydrocarbon photoinitiator can also be

[0009] R1 is N or P; R2 and R3 are , R4 is H, or , wherein R4 and D have a substituent which is .

[0010] In some compounds, the general formula of the heterocyclic aromatic hydrocarbon photoinitiator can also be

[0011]

[0012] In the structural formula, D represents: hydrogen and diazonaphthoquinone ester group

[0013] (wherein at least one substituent of D is a diazonaphthoquinone ester group)

[0014] 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.

[0015] The structural formula of the benzene ring hydroxy heterocyclic anthracene skeleton compound is:

[0016]

[0017] In the above structural formula, D is H.

[0018] The present invention uses this series of compounds as precursors for preparing G / I-ray photoinitiators. When the hydroxyl groups in the above compounds are substituted, the photoinitiators can be applied to the semiconductor field related to I-ray photoresists.

[0019] Basic catalysts include triethylamine.

[0020] 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.

[0021] During the esterification reaction, the diazonaphthoquinone compound realizes the esterification reaction of the hydroxyl groups of the respective compounds in the benzene ring hydroxy heterocyclic anthracene skeleton compound, and the esterification reaction includes one or more of monoesterification, diesterification, triesterification, tetraesterification, and pentaesterification.

[0022] The present invention also provides a G / I line photoinitiator, which includes the heterocyclic aromatic hydrocarbon photoinitiator.

[0023] Another technical solution of the present invention is to use the heterocyclic aromatic hydrocarbon photoinitiator in the field of I-line photoresist semiconductors.

[0024] The advantages and beneficial effects of the present invention are:

[0025] (1) The synthesis method of the parent structure of the polycyclic aromatic hydrocarbon non-conjugated benzene ring of the present invention is simple, and the raw materials are easily available.

[0026] (2) The present invention has a polycyclic aromatic hydrocarbon non-conjugated benzene ring type photoinitiator, which makes its UV-visible absorption peak red-shift 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-UV absorption. The photoinitiator together constitutes a photosensitive system to initiate monomer polymerization under near-UV light irradiation or serve as a photocurable material.

[0027] (3) Polycyclic aromatic hydrocarbon non-conjugated benzene ring compounds have active hydroxyl groups evenly distributed across multiple benzene rings. When further synthesized into corresponding photoinitiators, the reaction steric hindrance is small and the product is highly photosensitive, possessing excellent photochemical application properties. Diazonaphthoquinone compounds can be used as photosensitive compounds; the photoinitiator synthesized from the two exhibits excellent photocuring properties. DETAILED DESCRIPTION

[0028] 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 method of the present invention and are not intended to limit the remainder of the present invention in any way.

[0029] The present invention is further described below in conjunction with embodiments:

[0030] Example 1

[0031] Synthesis of compound c

[0032] Synthesis steps:

[0033] 1) Dissolve 1 mmol of compound b (hydroxyanthracene-based skeleton compound) and 1 mmol of compound a (DNQ) in 1,4-dioxane and stir at 35°C to dissolve.

[0034] 2) After the reaction system is cooled to 30°C, slowly add the same volume of triethylamine catalyst and triethylamine solvent dropwise (addition time is about 1 hour), maintaining the temperature between 30-31°C. After the addition is complete, react for 30 minutes.

[0035] 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter, and collect the filtrate;

[0036] 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 a pulping operation;

[0037] 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. The yield was 99%.

[0038] Example 2

[0039] Synthesis of compound c

[0040] 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.

[0041] Synthesis steps:

[0042] 1) Dissolve 1 mmol (polyhydroxyanthracene skeleton compound) and 2 mmol (DNQ) in 1,4-dioxane and stir to dissolve at 35°C;

[0043] 2) After the reaction system is cooled to 30°C, slowly add the same volume of triethylamine catalyst and triethylamine solvent dropwise (addition time is about 1 hour), maintaining the temperature between 30-31°C. After the addition is complete, react for 30 minutes.

[0044] 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter, and collect the filtrate;

[0045] 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 a pulping operation;

[0046] 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH of the filtrate was 6-7. The solid was collected and dried at 40°C. The yield was 97%.

[0047] Example 3

[0048] Synthesis of compound c

[0049] Wherein D has at least one diazonaphthoquinone sulfonyl group, that is, a mixture is obtained, wherein the mixture contains a compound in which D is a diazonaphthoquinone sulfonyl group, a compound in which D is a diazonaphthoquinone sulfonyl group, a compound in which D is a diazonaphthoquinone sulfonyl group, a compound in which D is a diazonaphthoquinone sulfonyl group, a compound in which D is a diazonaphthoquinone sulfonyl group, and a compound in which D is a diazonaphthoquinone sulfonyl group.

[0050] Synthesis steps

[0051] 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;

[0052] 2) After the reaction system is cooled to 30°C, slowly add the same volume of triethylamine catalyst and triethylamine solvent dropwise (addition time is about 1 hour), maintaining the temperature between 30-31°C. After the addition is complete, react for 30 minutes.

[0053] 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter, and collect the filtrate;

[0054] 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 a pulping operation;

[0055] 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH of the filtrate was 6-7. The solid was collected and dried at 40°C. The yield was 98%.

[0056] Example 4

[0057] Synthesis of compound c

[0058] Synthesis steps:

[0059] 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;

[0060] 2) After the reaction system is cooled to 30°C, slowly add the same volume of triethylamine catalyst and triethylamine solvent dropwise (addition time is about 1 hour), maintaining the temperature between 30-31°C. After the addition is complete, react for 30 minutes.

[0061] 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter, and collect the filtrate;

[0062] 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 a pulping operation;

[0063] 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH of the filtrate was 6-7. The solid was collected and dried at 40°C. The yield was 96%.

[0064] Example 5

[0065] Synthesis of compound c

[0066] 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.

[0067] Synthesis steps:

[0068] 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;

[0069] 2) After the reaction system is cooled to 30°C, slowly add the same volume of triethylamine catalyst and triethylamine solvent dropwise (addition time is about 1 hour), maintaining the temperature between 30-31°C. After the addition is complete, react for 30 minutes.

[0070] 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter, and collect the filtrate;

[0071] 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 a pulping operation;

[0072] 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH of the filtrate was 6-7. The solid was collected and dried at 40°C. The yield was 98%.

[0073] Example 6

[0074] Synthesis of compound c

[0075] Wherein D has at least one diazonaphthoquinone sulfonyl group, that is, a mixture is obtained, wherein the mixture contains a compound in which D is a diazonaphthoquinone sulfonyl group, a compound in which D is a diazonaphthoquinone sulfonyl group, a compound in which D is a diazonaphthoquinone sulfonyl group, a compound in which D is a diazonaphthoquinone sulfonyl group, a compound in which D is a diazonaphthoquinone sulfonyl group, and a compound in which D is a diazonaphthoquinone sulfonyl group.

[0076] Synthesis steps:

[0077] 1) Dissolve 1 mmol of compound b (polyhydroxyanthracene-based compound) and 3 mmol of compound a (DNQ) in 1,4-dioxane and stir at 35°C to dissolve.

[0078] 2) After the reaction system is cooled to 30°C, slowly add the same volume of triethylamine catalyst and triethylamine solvent dropwise (addition time is about 1 hour), maintaining the temperature between 30-31°C. After the addition is complete, react for 30 minutes.

[0079] 3) Add 30% by volume hydrochloric acid to the reaction system for quenching, filter, and collect the filtrate;

[0080] 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 a pulping operation;

[0081] 5) The mixed solution was filtered and the solid product was washed with ultrapure water until the pH of the filtrate was 6-7. The solid was collected and dried at 40°C. The yield was 96%.

[0082] Example 7

[0083] 5g of each of the photoinitiators prepared in Examples 1, 2, 3, 4, 5, and 6 were mixed with 20g of phenolic resin and 65g of the organic solvent PGMEA to prepare photosensitive compositions, numbered as compositions (1-2), (2-2), (3-2), (4-2), (5-2), and (6-2), respectively. Each of the six compositions was subjected to a photolithography process under identical conditions, including spin coating, pre-bake, exposure, post-bake, and development. The process parameters are shown in the table below:

[0084]

[0085] The height difference of the film covered by each group of substrates was tested by profilometer. The test results are shown in the table:

[0086]

[0087] It can be observed that the compositions have significant photosensitivity, with the differences between compositions (2-2), (3-2), (5-2), and (6-2) being significant. It can also be observed that the greater the number of hydroxyl groups in the backbone compound, the greater the amount of 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.

[0088] It should be noted that the embodiments of the present invention have better practicability and do not limit the present invention in any form. 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 modifications 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 method for synthesizing a heterocyclic aromatic hydrocarbon photoinitiator, 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 photoinitiator. The structural formula of the benzene ring hydroxy heterocyclic anthracene skeleton compound is: In the structural formula, D represents: hydrogen; The structural formula of diazonaphthoquinone photosensitizer DNQ is: ; The structural formula of the heterocyclic aromatic hydrocarbon photoinitiator is any one of the following: ； In the structural formula of the heterocyclic aromatic hydrocarbon photoinitiator, at least one substituent of D is a diazonaphthoquinone ester group.

2. The method for synthesizing a heterocyclic aromatic hydrocarbon photoinitiator according to claim 1, wherein: The base is triethylamine.

3. The method for synthesizing a heterocyclic aromatic hydrocarbon photoinitiator according to claim 1, wherein: 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 minutes.

4. Heteroaromatic hydrocarbon photoinitiator, characterized in that The method according to any one of claims 1 to 3 is synthesized.

5. G / I line photoinitiator, characterized in that The initiator comprises the heterocyclic aromatic hydrocarbon photoinitiator according to claim 4.

6. Use of the heterocyclic aromatic hydrocarbon photoinitiator according to claim 4 in the field of preparing I-line photoresist semiconductors.

Images