CN109305955B - Preparation method of molecular glass photoresist containing tetraphenylthiophenol structure - Google Patents
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
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Abstract
The invention relates to a method for preparing a molecular glass photoresist containing a tetraphenylthiophenol structureThe preparation method is as follows. The method simplifies the subsequent treatment process while improving the yield, and makes the industrial production possible. Specifically, the product is purified by selecting a proper solvent and a reprecipitation method to replace a silica gel chromatographic column, so that the complexity of post-treatment is reduced, and the post-treatment time is shortened. And under the condition of keeping the purity, the yield of the compounds (III) and (V) is greatly improved: the yield of the compound (III) is improved by more than 50 percent, and the yield of the compound (V) is improved by more than 25 percent.
Description
Technical Field
The invention relates to a tetraphenylthiophenol structure-containing molecular glass photoresist and a preparation method of the compound.
Background
In recent decades, the rapid development of microelectronic technology has promoted the sustainable development of national economy, and the related semiconductor industry has occupied a significant position in the field of national economy, and the future development trend of the semiconductor industry is more worthy of being longized along with the implementation of national internet +, "national big data strategy", and the like. Modern semiconductor technology requires smaller and smaller integrated circuits in electronic devices, and higher integration levels, which can meet the prediction of moore's law.
At present, the minimum feature size of integrated circuits has reached the nanometer level, and one of the core technologies on which the development of integrated circuits depends is lithography, which has undergone the development process from ultraviolet (UV, G-line 436nm and I-line 365nm), deep ultraviolet (DUV, 248nm and 193nm) to extreme ultraviolet (EUV, 13.5nm) lithography, nanoimprint, electron beam, etc., which are the most influential in the next-generation lithography.
With the development of photolithography, the sensitivity, resolution and line edge roughness of 193nm lithography have been difficult to meet the requirements of the semiconductor industry. The extreme ultraviolet lithography technology uses a light source with short wavelength of 13.5nm, can reach 22nm and 10nm technical nodes, even 7nm technical nodes, and occupies an important position in the next generation lithography technology.
Changes in the photolithography technique have led to changes in the photoresist material, and the currently used photoresist is likely to fail to meet the requirements of the next generation photolithography technique. Extreme ultraviolet photoresists need to have high resolution, high etch resistance, low exposure dose, low absorbance, high environmental stability, high transparency, low gassing, low line edge roughness, and the like. Therefore, it is very urgent to develop an euv photoresist capable of satisfying the above requirements.
The molecular glass is an organic micromolecule material with higher glass transition temperature (Tg), generally has a non-coplanar and irregular structure, is in an amorphous state, can avoid the tendency that conventional micromolecules are easy to crystallize, has the glass transition process peculiar to macromolecules, has high thermal stability, has the dual characteristics of micromolecules and polymers, and is an ideal photoresist material. Due to the excellent performance of the molecular glass photoresist, the molecular glass photoresist can be used in 193nm lithography and is more likely to become a main body material of next-generation lithography (such as extreme ultraviolet lithography, electron beam lithography, nanoimprint lithography and the like).
Patent ZL201210070713.6 reports a molecular glass containing tetraphenyl furan, tetraphenyl pyrrole, tetraphenyl thiophene and pentaphenyl pyridine structures and a synthesis method thereof:
the method has the advantages of few reaction steps of the synthetic route and few byproducts, but the method disclosed by the patent has the problems of harsh reaction conditions, complex treatment after reaction, low reaction yield, long reaction time consumption and the like.
Disclosure of Invention
The invention aims to provide a synthesis method of a molecular glass photoresist containing a tetraphenylthiophenol structure, which is economical and feasible and is suitable for industrial production.
The invention is an improved patent of Chinese patent ZL201210070713.6, and compared with the original patent, the synthetic route of the invention is simpler and easier, is convenient to operate and is suitable for industrial production.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a molecular glass photoresist containing a tetraphenylthiophenol structure comprises the following steps:
wherein R is1Optionally halogen (e.g. bromine), R2Optionally is-OC1-6Alkyl (e.g. -OCH)3) (ii) a R' is optionally H, OH; r is optionally H, OH or an acid labile group, wherein at least one R is an acid labile group;
(A) reacting a compound (I) with a compound (II) in a solvent, wherein R1Optionally halogen (e.g. bromine), R2Optionally is-OC1-6Alkyl (e.g. -OCH)3) After the reaction is finished, filtering to obtain a solid, washing with water and ethanol respectively, and filtering to obtain a compound (III);
(B) dealkylation of the compound (III) obtained in step (a) to produce compound (IV), wherein R' is optionally H, OH;
(C) reacting the compound (IV) obtained in step (B) with (COOR)3)2O or R4Z is reacted, wherein R3Is optionally C1-8Alkyl radical, R4Is optionally C1-8Alkyl, aryl, heteroaryl, and heteroaryl,
Z is halogen (preferably chlorine) to generate tetraphenyl thiophene molecular glass with partially or fully protected hydroxyl, namely the compound of the general formula (V); after the reaction is finished, concentrating the reaction solution, adding a poor solvent of the product into the system, refluxing and filtering to obtain the product.
According to the present invention, in step (a), the reaction is preferably carried out in the presence of a palladium catalyst such as tetrakis (triphenylphosphine) palladium. Preferably in the presence of a base, such as potassium carbonate. The solvent is preferably dioxane-water, the reaction temperature is preferably 60-160 ℃, the reaction time is preferably 6-24h, and the feeding molar ratio of the compound (I) to the compound (II) is preferably 2: 9.
According to the invention, in the step (A), after the reaction is finished, the reaction solution is filtered to obtain a light yellow solid, the light yellow solid is respectively washed by water and ethanol, the filtrate is filtered to be clear, and the obtained solid is dried to obtain the compound (III).
According to the invention, in step (B), the dealkylation is carried out in the presence of a Lewis acid, preferably boron tribromide, preferably in dichloromethane, at a temperature of preferably 0 to 10 ℃, more preferably 4 to 8 ℃ and for a time of preferably 2 to 15 hours. Preferably, boron tribromide is mixed with compound (III) at a temperature of 0 to 10 ℃ and then the reaction is carried out.
According to the present invention, in the step (B), preferably, after the reaction is completed, the obtained product is precipitated in a good solvent and a poor solvent to obtain the compound (IV). The good solvent is preferably ethyl acetate, and the poor solvent is n-hexane. Preferably, the product is dissolved in ethyl acetate, and the solution is added to a poor solvent for the compound of formula (IV) to precipitate a solid, thereby obtaining compound (IV).
According to the invention, in the step (B), boron tribromide is added into a 1000ml three-neck flask with dichloromethane under the protection of nitrogen at 5 ℃, the compound (III) is dissolved in dichloromethane, the mixture is slowly dripped at 0-10 ℃, then the reaction is carried out for 2-6h at the temperature, and after 2-6h, the reaction liquid is slowly dripped into water at room temperature for hydrolysis reaction, and white solid is generated in the water. After the dropwise addition, stirring. Adding ethyl acetate to dissolve the white solid, and standing the system for layering. The aqueous phase was collected by draining, extracted with ethyl acetate, and the organic phase was washed with saturated brine to neutrality. The obtained organic phase is dried over anhydrous magnesium sulfate, and then subjected to rotary evaporation concentration treatment, and the concentrated solution is added to a poor solvent (for example, n-hexane) for the compound of formula (IV), and a solid is precipitated and filtered to obtain the compound (IV).
According to the present invention, in the step (C), the reaction is preferably carried out in the presence of 4-Dimethylaminopyridine (DMAP) or potassium carbonate, the reaction temperature is preferably 5-45 ℃ and the reaction solvent is preferably tetrahydrofuran.
According to the invention, in the step (C), after the reaction is finished, the reaction solution is concentrated, n-hexane is added into the system for refluxing, the solid is obtained after filtration, the solid is washed, and the product is obtained after filtration.
According to the invention, the preparation method comprises the following steps:
(A) tetrabromothiophene reacts with 3, 4-dimethoxyphenylboronic acid in a solvent, after the reaction is finished, the reaction liquid is filtered to obtain solid, the solid is respectively washed by water and ethanol, the filtrate is filtered until the filtrate is clear, and the obtained solid is dried to obtain a compound (3);
(B) carrying out dealkylation on the compound (3) obtained in the step (A) to generate a compound (4);
(C) reacting the compound (4) obtained in the step (B) with di-tert-butyl dicarbonate to obtain a compound (5); after the reaction is finished, the reaction solution is concentrated, a poor solvent (such as n-hexane) of the product is added into the system, reflux is carried out, a solid is obtained after filtration, and the product is obtained after washing and filtration.
Through a large number of experiments, the invention finally realizes the product purification by using a solvent washing method or a reprecipitation method in a good solvent and a poor solvent to replace a silica gel chromatographic column to purify the product, thereby reducing the complexity of post-treatment and shortening the post-treatment time. And by the method, the yield of the compounds (III) and (V) is greatly improved under the condition of keeping the purity: the yield of the compound (III) is improved by more than 50 percent, and the yield of the compound (V) is improved by more than 25 percent. And under the condition of ensuring the yield and the purity, the dropping temperature of the boron tribromide in the step (B) is increased from-78 ℃ to higher than 0 ℃, such as 0-10 ℃, so that the reaction condition is optimized, no side reaction occurs, and the cost of industrial production is greatly reduced.
The method has the advantages of reasonable process conditions, simple and convenient post-treatment operation, short reaction time, high reaction yield and no side reaction, and is suitable for large-scale industrial production.
Detailed Description
The following series of specific examples are given to further illustrate the teaching of the present invention, but the present invention is not limited to these specific examples, and any modification of the present invention that would be obvious to those skilled in the art can be made to achieve similar results and is also included in the present invention.
Example 1
Preparation of Compound (3)
Under the protection of nitrogen, 300ml of dioxane, 90g (0.23mol) of tetrabromothiophene and 250g (1.4mol) of 3, 4-dimethoxyphenylboronic acid are added into a 1000ml three-neck flask, 160g of potassium carbonate is dissolved in 300ml of water and then added into the three-neck flask, the temperature is set to 100 ℃, after all solid materials are dissolved, 3g of tetrakis (triphenylphosphine) palladium is added, and the reaction is carried out for 10 hours. Filtering the product to obtain a light yellow solid, washing with water and ethanol respectively, filtering until the filtrate is clear, and drying the obtained solid to obtain the product with the yield of about 83%.
Comparative example 1:
preparation of Compound (3)
In a three-neck flask (three necks are respectively connected with an air duct, a constant pressure dropping funnel and a rubber turning-over plug), 1g of palladium tetrakis (triphenylphosphine) and 15g, K of 3, 4-dimethoxyphenylboronic acid are firstly added2CO310g, vacuumizing and filling argon for three times, enabling the reaction to be carried out under the protection of argon, dropwise adding 12ml of distilled water and 24ml of 1, 4-dioxane, finally heating the reaction system to 110 ℃, dropwise adding 24ml of 1, 4-dioxane solution of tetrabromothiophene (2.4g), completing the dropwise adding within one hour, and finishing the reaction within 48 hours. The product was washed with a large amount of saturated brine and ethyl acetate, and then washed with waterThe organic phase was separated by filtration, and the filtrate was spin-dried and subjected to column chromatography (developing solvent was ethyl acetate: petroleum ether: 1: 4) to isolate 1g of compound (3) with a yield of about 26.5%.
Example 2
Preparation of Compound (4)
50ml (0.5mol) of boron tribromide and 200ml of dichloromethane were charged in a 1000ml three-necked flask, 60g of the compound (3) obtained in example 1 was dissolved in 350ml of dichloromethane, and a dichloromethane solution of the compound (3) was slowly dropped into the three-necked flask under nitrogen protection at 5 ℃ to react for 4 hours. After the reaction is finished, after 2-5h, the reaction solution is slowly dripped into water at room temperature through a constant pressure dropping funnel for hydrolysis reaction, and white solid is generated in the water. After the dropwise addition, stirring. Adding ethyl acetate to dissolve the white solid, and standing the system for layering. The aqueous phase was collected by draining, extracted with ethyl acetate, and the organic phase was washed with saturated brine to neutrality. Drying the obtained organic phase by using anhydrous magnesium sulfate, then carrying out rotary evaporation concentration treatment, adding the concentrated solution into n-hexane, and filtering to obtain the product with the yield of about 90%.
Comparative example 2
Preparation of Compound (4)
0.8g of the compound (3) obtained in the comparative example 2 is added into a three-neck flask (three necks are respectively connected with a gas guide tube, a constant-pressure dropping funnel and a rubber turning plug), then the mixture is vacuumized and filled with argon gas for three times, so that the reaction system is carried out under the protection of the argon gas, the temperature of the reaction system is adjusted to-78 ℃ by acetone liquid nitrogen, 20ml of dichloromethane is firstly dropwise added, 10ml of dichloromethane solution containing boron tribromide (containing 2ml of boron tribromide) is slowly dropwise added, the reaction is shifted to the normal temperature for 12 hours after the dropwise addition is finished, and finally distilled water is dropwise added to terminate the reaction. The reaction mixture was washed with a large amount of distilled water to precipitate a white solid matter, which was then filtered to obtain 0.5g of the compound (4) in a yield of about 76.07%.
Example 3
Preparation of Compound (5)
400ml of tetrahydrofuran, 500g (Boc)2O and 100g (0.20mol) of the compound (4) are sequentially added into a 1000ml three-necked flask, 2g of DMAP is added into the three-necked flask after dissolution, and the reaction is carried out for 12 hours. After the reaction is finished, concentrating the reaction solution, adding n-hexane into a three-necked bottle, heating the system to 60 ℃, refluxing for 6h, filtering to obtain a solid, washing the solid, and filtering to obtain a product with the yield of about 75%. Melting point: 136 + -1 deg.C. 1H-NMR (400MHz, DMSO, ppm)7.31(d, J ═ 9.1Hz, 1H), 7.18(m, 3H), 7.08(d, J ═ 2.0Hz, 1H), 6.95(dd, J ═ 8.4; 2.0Hz, 1H), 1.47(d, J ═ 5.3Hz, 18H), 1.45(d, J ═ 6.0Hz, 18H). Elemental analysis (C)68H84O24S) theoretical calculation value C, 61.99%; h, 6.43%, found: c, 61.89%; h, 6.49 percent.
Comparative example 3
Preparation of Compound (5)
In a two-necked flask (two necks connected to a constant pressure dropping funnel and a rubber cock respectively), 0.5g of the compound (4) and K were added2CO30.5g, then the reaction flask is moved to an ice-water bath, 10ml of tetrahydrofuran (anhydrous) is added dropwise, 5ml of tetrahydrofuran (anhydrous) solution of di-tert-butyl dicarbonate (0.64g) and 18-crown-6 (0.01g) is added dropwise, and the reaction is moved to 30 ℃ for reaction for 24 hours after the dropwise addition is finished. The reaction solution was filtered, and the filtrate was spin-dried and then subjected to column chromatography (the developing solvent was ethyl acetate: petroleum ether: 1: 5), and finally, recrystallization and purification were performed with ethanol to obtain 0.6g of the objective compound (5) with a yield of about 47.04%. Melting point: 136 + -1 deg.C. Elemental analysis (C)68H84O24S): 62.19 percent of C and 6.42 percent of H; theoretical calculation value: 61.99 percent of C and 6.43 percent of H.1H-NMR(400MHz,CDCl3)7.23(s,1H),7.10(q,J＝8.5Hz,2H),6.97(d,J＝8.7Hz,1H),6.89(s,1H),6.78(d,J＝8.4Hz,1H),1.47(s,36H)。
The physical and chemical properties of the compound (5) prepared by the invention are the same as those of the compound obtained in Chinese invention patent ZL201210070713.6, and the compound can be used for 193nm photoetching, EUV photoetching, electron beam photoetching and the like.
As can be seen from example 2 and comparative example 2, such dealkylation is carried out by bringing BBr, generally at-78 ℃3The reaction solution is added dropwise, and in example 2, in the preparation of the compound (4) from the compound (3), the dropwise addition temperature is raised from-78 ℃ to more than 0 ℃ (e.g., 5 ℃), and the yield is improved. The increase of the dripping temperature greatly reduces the cost of industrial production and leads the production to be more economical and feasible.
As can be seen from examples 1 to 3 and comparative examples 1 to 3, the present invention abandons the purification of the product by silica gel chromatography in the post-reaction treatment, but purifies the product by using a suitable solvent or reprecipitating in a good solvent and a poor solvent. Greatly reduces the complexity of post-processing and shortens the post-processing time. Most importantly, the method greatly improves the yield of the compounds (3), (4) and (5) under the condition of keeping the purity unchanged, and comprises the following steps: the yield of the compound (3) was increased from 26.5% to 83%, the yield of the compound (4) was increased from 76% to 90%, and the yield of the compound (5) was increased from 47% to 75%.
Claims (23)
1. A process for the preparation of a compound of formula (V) comprising:
wherein R is1Is halogen, R2Is selected from-OC1-6An alkyl group; r' is selected from H, OH; r is selected from H, OH or an acid labile group, wherein at least one R is an acid labile group which is-OCO-OC1-8Alkyl, -OC1-8Alkyl, aryl, heteroaryl, and heteroaryl,
(A) Reacting a compound (I) with a compound (II) in a solvent, wherein R1Is halogen, R2Is selected from-OC1-6After the reaction is finished, filtering to obtain a solid, washing with water and ethanol respectively, and filtering to obtain a compound (III);
(B) dealkylation of compound (III) obtained in step (a) to form compound (IV), wherein R' is selected from H, OH;
(C) reacting the compound (IV) obtained in step (B) with (COOR)3)2O or R4Z is reacted, wherein R3Is selected from C1-8Alkyl radical, R4Is selected from C1-8Alkyl, aryl, heteroaryl, and heteroaryl,
Z is halogen to generate tetraphenyl thiophene molecular glass with partially or completely protected hydroxyl, namely a compound of a general formula (V); after the reaction is finished, concentrating the reaction solution, adding a poor solvent of the product into the system, refluxing and filtering to obtain the product.
2. The method of claim 1, wherein R1Is bromine.
3. The method of claim 1, wherein R2is-OCH3。
4. The method according to claim 1, wherein Z is chlorine.
5. The production method according to claim 1, wherein in the step (A), the reaction is carried out in the presence of a palladium catalyst and a base.
6. The production method according to claim 5, wherein the palladium catalyst is tetrakis (triphenylphosphine) palladium.
7. The method of claim 5, wherein the base is potassium carbonate.
8. The production method according to claim 1, wherein in the step (A), the reaction is carried out in a solvent which is dioxane-water.
9. The process according to claim 1, wherein in the step (A), after the reaction, the reaction solution is filtered to obtain a solid, the solid is washed with water and ethanol, the filtrate is filtered to be clear, and the solid is dried to obtain the compound (III).
10. The production process according to claim 1, wherein, in the step (B), the dealkylation reaction is carried out in the presence of a Lewis acid.
11. The production process according to claim 1, wherein in the step (B), the dealkylation reaction is carried out using boron tribromide.
12. The process according to claim 1, wherein the solvent used in the reaction in the step (B) is dichloromethane.
13. The method according to claim 1, wherein the reaction temperature in the step (B) is 0 to 10 ℃.
14. The production method according to claim 13, wherein the reaction temperature is 4 to 8 ℃.
15. The production method according to claim 1, wherein in the step (B), after completion of the reaction, the obtained product is reprecipitated in a good solvent and a poor solvent to obtain the compound (IV).
16. The production method according to claim 15, wherein the good solvent is ethyl acetate and the poor solvent is n-hexane.
17. The process according to claim 15, wherein the product is dissolved in ethyl acetate, and the solution is added to a poor solvent for the compound of formula (IV) to precipitate a solid, thereby obtaining the compound (IV).
18. The preparation process according to claim 15, wherein in the step (B), after the reaction is completed, ethyl acetate is added to dissolve the solid, and the mixture is allowed to stand for layering; discharging the water phase in the system, collecting, extracting with ethyl acetate, and washing the organic phase with saturated saline solution to neutrality; the organic phase was dried and concentrated, and the concentrated solution was added to n-hexane and filtered to obtain compound (IV).
19. The process according to claim 1, wherein in the step (C), the reaction is carried out in the presence of 4-Dimethylaminopyridine (DMAP) or potassium carbonate.
20. The process according to claim 1, wherein in the step (C), the reaction temperature is 5 to 45 ℃ and the reaction solvent is tetrahydrofuran.
21. The process according to claim 1, wherein in the step (C), after the reaction is completed, the reaction mixture is concentrated, n-hexane is added to the system, and the mixture is refluxed and filtered to obtain the product.
22. The production method according to claim 1, wherein the production method comprises:
(A) tetrabromothiophene reacts with 3, 4-dimethoxyphenylboronic acid in a solvent, after the reaction is finished, the reaction liquid is filtered to obtain solid, the solid is respectively washed by water and ethanol, the filtrate is filtered until the filtrate is clear, and the obtained solid is dried to obtain a compound (3);
(B) carrying out dealkylation on the compound (3) obtained in the step (A) to generate a compound (4);
(C) reacting the compound (4) obtained in the step (B) with di-tert-butyl dicarbonate to obtain a compound (5); after the reaction is finished, concentrating the reaction solution, adding n-hexane into the system, refluxing, filtering to obtain a solid, washing, and filtering to obtain a product.
23. The process according to claim 1, wherein the compound of formula (V) is used as a resist host material for 193nm lithography, EUV lithography and electron beam lithography.
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Effective date of registration: 20211209 Address after: 101400 room 203-11, second floor, building 13, yard 53, Yanqi street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Guoke Tianji (Beijing) new material technology Co.,Ltd. Address before: Room 901, building 4a, Shenzhen software industry base, Haitian 1st Road, South District, Nanshan District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN QIANHAI GUANGYU TIANJI TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20230103 Address after: No. 333, Bohai 24th Road, Changjiang 5th Road, Binzhou Economic and Technological Development Zone, Shandong Province, 256606 Patentee after: Guoke Tianji (Binzhou) New Materials Co.,Ltd. Address before: 101400 room 203-11, second floor, building 13, yard 53, Yanqi street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: Guoke Tianji (Beijing) new material technology Co.,Ltd. |
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Address after: No. 333, Bohai 24th Road, Changjiang 5th Road, Binzhou Economic and Technological Development Zone, Shandong Province, 256606 Patentee after: Guoke Tianji (Shandong) New Material Co.,Ltd. Address before: No. 333, Bohai 24th Road, Changjiang 5th Road, Binzhou Economic and Technological Development Zone, Shandong Province, 256606 Patentee before: Guoke Tianji (Binzhou) New Materials Co.,Ltd. |
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