Photoresist composition and preparation method thereof

Abstract

The invention relates to the technical field of photoresist, in particular to a photoresist composition and a preparation method thereof, and the photoresist composition comprises the following components in parts by weight: 10-30 parts of polymer resin; 50-80 parts of an organic solvent; 2-5 parts of a photosensitizer; 1-2 parts of an auxiliary agent; 1-3 parts of an additive; wherein the additive is a mixture composed of a compound A and 1, 2-cyclohexene oxide according to a molar ratio of (1-20): 1. According to the photoresist composition provided by the invention, through the synergistic effect of the compound A, the 1, 2-cyclohexene oxide, the polymer resin and the photosensitizer, on the premise that the polymer resin does not need to be modified, the stability of the photoresist composition is improved, the preservation difficulty of the photoresist composition is reduced, and the shelf life of the photoresist composition is prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of photoresists, and in particular to a photoresist composition and a preparation method thereof. Background Art

[0002] Photoresist is a core material in the semiconductor manufacturing process. The photoresist currently widely used in high-end chip manufacturing is usually ArF photoresist.

[0003] Both positive and negative photoresists utilize the instability of the film-forming resin. After exposure and development, the solubility of the film-forming resin in the developer changes, thereby achieving pattern transfer from the template to the substrate. Because photoresists contain numerous groups that are easily polymerized or decomposed, they are extremely unstable. Changes in the external environment can cause changes in physical and chemical parameters such as viscosity, content, and photosensitivity. In particular, exposure to light can reduce or even eliminate the photoresist's development performance, directly impacting the accuracy and resolution of pattern transfer. For these reasons, current photoresists exhibit poor stability and require refrigerated storage in the dark, requiring stringent storage conditions. Summary of the Invention

[0004] In order to solve the problem of poor stability of photoresists in the prior art, the present invention provides a photoresist composition. By introducing mixed additives, the photoresist composition can extend the shelf life of the photoresist while ensuring the accuracy of the photolithographic pattern, thereby solving the problem of poor stability of photoresists in the prior art.

[0005] The technical solution adopted by the present invention to solve its technical problem is: A photoresist composition, comprising the following components in parts by weight: 10-30 parts of polymer resin; 50-80 parts of organic solvent; 2-5 parts of photosensitizer; 1-2 parts of additives; 1-3 parts of additives; Wherein, the additive is a mixture of compound A and 1,2-epoxycyclohexane in a molar ratio of (1-20):1; The structural formula of the compound A is shown below: .

[0006] Alternatively, the compound A is prepared as follows: S1: Add benzaldehyde and 2,4-dimethylpyrrole to anhydrous tetrahydrofuran and react at room temperature in the dark to obtain reaction solution I; S2: adding 2,3-dichloro-5,6-dicyano-p-benzoquinone to the reaction solution I, and continuing the reaction at room temperature under the protection of an inert gas to obtain a reaction solution II; S3: Add triethylamine and boron trifluoride etherate to the reaction solution II under ice bath conditions, react in the dark, filter, wash, and separate by silica gel column chromatography to obtain compound A.

[0007] Optionally, the molar ratio of the benzaldehyde to the 2,4-dimethylpyrrole is 1:(2-2.3).

[0008] Optionally, the molar ratio of the benzaldehyde to the 2,3-dichloro-5,6-dicyano-p-benzoquinone is 1:10.

[0009] Optionally, the polymer resin is a poly(meth)acrylate resin or a polystyrene resin.

[0010] Optionally, the polymer resin is selected from at least one of polymethacrylate and polymethacrylate containing an adamantyl group.

[0011] Optionally, the organic solvent is selected from at least one of propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, and diethylene glycol methyl ether.

[0012] Optionally, the photosensitizer is selected from at least one of triphenylsulfonium perfluorobutanesulfonate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and bis(trifluoromethylsulfonyl)diazomethane.

[0013] Optionally, the auxiliary agent is selected from at least one of a leveling agent, a thickener, and an adhesive.

[0014] Another object of the present invention is to provide a method for preparing the photoresist composition as described above, comprising the following steps: mixing a polymer resin, a photosensitizer, an organic solvent, additives and auxiliary agents according to the formula, filtering and packaging, and obtaining a photoresist composition.

[0015] The beneficial effects of the present invention are: The photoresist composition provided by the present invention improves the stability of the photoresist composition, reduces the difficulty of preserving the photoresist composition, and extends the shelf life of the photoresist composition through the synergistic effect of compound A and 1,2-epoxycyclohexane with a polymer resin and a photosensitizer, without modifying the polymer resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The present invention will be further described below with reference to the accompanying drawings and examples.

[0017] Figure 1 This is the photolithographic pattern of the photoresist composition prepared in Examples 1-3 of the present invention. DETAILED DESCRIPTION

[0018] The present invention will now be described in further detail. The embodiments described below are exemplary and intended to explain the present invention, but should not be construed as limiting the present invention. All other embodiments obtained by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are intended to fall within the scope of protection of the present invention.

[0019] In order to solve the problem of poor stability of photoresists in the prior art, the present invention provides a photoresist composition, which comprises the following components in parts by weight: 10-30 parts of polymer resin; 50-80 parts of organic solvent; 2-5 parts of photosensitizer; 1-2 parts of additives; 1-3 parts of additives; The additive is a mixture of compound A and 1,2-epoxycyclohexane in a molar ratio of (1-20):1, and the additive is preferably a mixture of compound A and 1,2-epoxycyclohexane in a molar ratio of (5-10):1; The structural formula of compound A is shown below: .

[0020] In the prior art, it is difficult to directly obtain a photoresist composition that simultaneously meets the requirements of adhesion, etching resistance and long shelf life without modifying the polymer resin. The process of modifying the polymer resin is relatively complicated, and the modified polymer resin is prone to produce many uncontrollable effects on photoetching. Based on this, the present invention starts from the physical structure of the photoresist composition, combines the interaction mechanism of the complex, introduces additives into the system, and through the interaction of the introduced additives with other components, the stability of the photoresist composition is improved without modifying the polymer resin, thereby not only extending the shelf life of the photoresist composition, but also ensuring that the photoresist composition does not need to be refrigerated and has a long shelf life when stored at room temperature.

[0021] The photoresist composition provided by the present invention improves the stability of the photoresist composition, reduces the difficulty of preserving the photoresist composition, and extends the shelf life of the photoresist composition through the synergistic effect of compound A and 1,2-epoxycyclohexane with a polymer resin and a photosensitizer, without modifying the polymer resin.

[0022] The photoresist composition provided by the present invention has reduced temperature sensitivity, high singlet oxygen quantum yield and high stability; the shelf life of the photoresist composition is significantly prolonged, the preparation method is simple, and there is no need to modify the synthetic resin to increase the shelf life.

[0023] Specifically, the preferred compound A of the present invention is prepared according to the following method: S1: Add benzaldehyde and 2,4-dimethylpyrrole to anhydrous tetrahydrofuran and react at room temperature in the dark to obtain reaction solution I; S2: adding 2,3-dichloro-5,6-dicyano-p-benzoquinone to reaction solution I, and continuing the reaction at room temperature under inert gas protection to obtain reaction solution II; S3: Add triethylamine and boron trifluoride etherate to reaction solution II in an ice bath, react in the dark, filter, wash, and separate by silica gel column chromatography to obtain compound A.

[0024] In order to balance reaction efficiency and economy, the present invention preferably has a molar ratio of benzaldehyde to 2,4-dimethylpyrrole of 1:(2-2.3); preferably has a molar ratio of benzaldehyde to 2,3-dichloro-5,6-dicyano-p-benzoquinone of 1:10; preferably has a molar ratio of benzaldehyde to boron trifluoride ether of 1:(1-1.5); and preferably has a molar ratio of benzaldehyde to triethylamine of 1:1.

[0025] The preferred polymer resin of the present invention is a poly(meth)acrylate resin or a polystyrene resin. Further, the preferred polymer resin is at least one selected from polymethacrylate and polymethacrylate containing an adamantyl group; the preferred polystyrene resin is a poly(p-hydroxystyrene) resin.

[0026] Specifically, the number average molecular weight of the polymer resin of the present invention is preferably in the range of 10,000-80,000, and its molecular weight distribution PDI is preferably less than 2.5, more preferably, PDI is less than 2.0.

[0027] In the present invention, the organic solvent is preferably selected from at least one of propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, and diethylene glycol methyl ether; the photosensitizer is preferably selected from at least one of triphenylsulfonium perfluorobutyl sulfonate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethane sulfonate, diphenyliodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethane sulfonate, and bis(trifluoromethylsulfonyl)diazomethane; the auxiliary agent is preferably selected from at least one of a leveling agent, a thickener, and an adhesive, and the leveling agent is preferably selected from one or more of siloxane and perfluorooctane sulfonate, and the leveling agent is further preferably siloxane.

[0028] Another object of the present invention is to provide a method for preparing the photoresist composition as described above, the method comprising the following steps: uniformly mixing a polymer resin, a photosensitizer, an organic solvent, additives and auxiliary agents according to the formula, and adjusting the various indicators of the photoresist to meet the requirements; and finally filtering and packaging the photoresist, wherein the photoresist is first coarsely filtered through a plate-and-frame filter and then ultra-clean filtered with a filter membrane pore size of 0.2 mm. The ultra-clean filtered glue solution is packaged as a finished product to obtain a photoresist composition.

[0029] The preparation method of the photoresist composition provided by the present invention is simple. The prepared photoresist composition improves the stability of the photoresist composition, reduces the difficulty of preserving the photoresist composition, and extends the shelf life of the photoresist composition through the synergistic effect of additives, polymer resins, and photosensitizers without modifying the polymer resin.

[0030] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0031] Unless otherwise specified, compound A in each example and comparative example of the present invention was prepared as follows: Benzaldehyde and 2,4-dimethylpyrrole (molar ratio of 1:2.1) were added to tetrahydrofuran (anhydrous), with the ratio of formaldehyde to tetrahydrofuran (anhydrous) being 1 mol:15 mL. The mixture was reacted at room temperature in the dark for 24 h. 2,3-dichloro-5,6-dicyano-p-benzoquinone was added, and the reaction was continued at room temperature under nitrogen protection for 10 h. The molar ratio of benzaldehyde to 2,3-dichloro-5,6-dicyano-p-benzoquinone was 1:10. Triethylamine and boron trifluoride etherate were added to the reaction solution under ice bath conditions, with the molar ratio of benzaldehyde, triethylamine and boron trifluoride etherate being 1:1:1.1. After being protected from light overnight, the mixture was filtered to remove impurities, washed with water and saturated sodium bicarbonate solution, respectively, and then separated by silica gel column chromatography using petroleum ether and methanol as eluents to obtain compound A with a yield of 65%. 1 H NMRR (400 MHz, CDCl3 ): =1.39 (s,6H,CH3), 2.66 (s,6H,CH3), 8.10(d,J=8.4Hz,2H,ArH),7.53(d,J =8.4Hz,2H,ArH),6.20(s,2H,pyrrole-H).

[0032] 1,2-Epoxycyclohexane in the Examples and Comparative Examples of the present invention was purchased from Sigma, CAS: 1436-34-6. The remaining reagents were all commercially available products purchased from reagent companies such as Sigma.

[0033] Example 1 This embodiment provides a photoresist composition, which is prepared according to the following method: Take 10g of commercially available polymethacrylate resin (MW 45000; PDI: <1.05), 80g of propylene glycol methyl ether acetate, 4g of bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, 3g of additives, and 2.5g of siloxane, mix the above ingredients to prepare glue, filter and package, and the glue solution that has been ultra-cleaned and packaged is the finished product.

[0034] The additive is a mixture of compound A and 1,2-epoxycyclohexane in a molar ratio of 8:1.

[0035] Example 2 This embodiment provides a photoresist composition, which is prepared according to the following method: Take 10g of commercially available adamantyl-substituted acrylic resin (MW 55000; PDI: <1.08), 80g of propylene glycol methyl ether acetate, 4g of bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, 3g of additives, and 2.5g of siloxane, mix the above ingredients to prepare glue, filter and package, and the glue solution that has been ultra-cleaned and packaged is the finished product.

[0036] The additive is a mixture of compound A and 1,2-epoxycyclohexane in a molar ratio of 8:1.

[0037] Example 3 This embodiment provides a photoresist composition, which is prepared according to the following method: Take 10g of poly(p-hydroxystyrene) resin (MW 50000; PDI: <1.07), 80g of propylene glycol methyl ether acetate, 4g of bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate), 3g of additives, and 2.5g of siloxane, mix the above ingredients to prepare glue, filter and package, and the glue solution that has been ultra-cleaned and packaged is the finished product.

[0038] The additive is a mixture of compound A and 1,2-epoxycyclohexane in a molar ratio of 8:1.

[0039] The following comparative examples are all compared with Example 1.

[0040] Comparative Example 1 This comparative example provides a photoresist composition, which is prepared according to the following method: Take 10g of commercially available polymethacrylate resin (MW 45000; PDI: <1.05), 80g of propylene glycol methyl ether acetate, 4g of bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, 3g of additives, and 2.5g of siloxane, mix the above ingredients to prepare glue, filter and package, and the glue solution that has been ultra-cleaned and packaged is the finished product.

[0041] The additive is 2,3,4,4'-tetrahydroxybenzophenone.

[0042] Comparative Example 2 This comparative example provides a photoresist composition, which is prepared according to the following method: Take 10g of commercially available polymethacrylate resin (MW 45000; PDI: <1.05), 80g of propylene glycol methyl ether acetate, 4g of bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, 3g of additives, and 2.5g of siloxane, mix the above ingredients to prepare glue, filter and package, and the glue solution that has been ultra-cleaned and packaged is the finished product.

[0043] The additive is compound A.

[0044] Comparative Example 3 This comparative example provides a photoresist composition, which is prepared according to the following method: Take 10g of commercially available polymethacrylate resin (MW 45000; PDI: <1.05), 80g of propylene glycol methyl ether acetate, 4g of bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, 3g of additives, and 2.5g of siloxane, mix the above ingredients to prepare glue, filter and package, and the glue solution that has been ultra-cleaned and packaged is the finished product.

[0045] The additive is 1,2-epoxycyclohexane.

[0046] The properties of the photoresist compositions prepared in the above embodiments and comparative examples were tested.

[0047] 1. High temperature accelerated test (aging test) 10g of each of the photoresist compositions prepared in the above examples and comparative examples was weighed, diluted with propylene glycol methyl ether acetate, and placed in a dark oven at 60°C. After 12 hours and 24 hours, the sample dilutions were compared with the refrigerated sample dilutions. Changes in clarity and color difference of each sample dilution in the oven were recorded. The results are shown in Table 1: Table 1 time Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 2 Example 3 12h √ O √ √ √ √ 24h √ X O X √ √ Among them, √: no change in appearance, no yellowing, no turbidity, no precipitation, etc.; O: basically no change in appearance, with slight color change or turbidity; X: obvious change in appearance, such as yellowing, turbidity or no precipitation, etc.

[0048] The photoresist compositions prepared in Examples 1-3 showed no changes in appearance after 12 and 24 hours.

[0049] The photoresist composition provided in Comparative Example 1 showed yellowing and reduced clarity after 12 hours of observation. The photoresist compositions prepared in Comparative Examples 2 and 3 showed significantly reduced clarity after 24 hours of observation.

[0050] 2. Long-term storage test The photoresist composition prepared in Examples 1-3 was stored at room temperature for 3 months. 50 ml of the photoresist composition stored at room temperature for 3 months was taken and compared with the photoresist composition stored in a refrigerator for one month.

[0051] The above product was ultrasonically stirred for 1 minute for uniform coating. After exposure, the film was developed. The photoresist film thickness was 100 nm. The developer was a 2.37% aqueous solution of TMAH. The photolithography process conditions were: bake at 120°C for 5 minutes, exposure energy of 33 mJ / cm², and development time of 60 seconds. The photolithography machine was an ASMLXT 1900i, and the optical electron microscope was a Hitachi CG4000. The voltage was 500 V and the current was set to 6 pA.

[0052] The photolithography results of Examples 1-3 were observed by electron microscope. Figure 1 As shown, the pictures are basically the same, with uniform lines and high resolution. There is no obvious difference between the samples stored at room temperature and refrigerated storage, indicating that the photoresist quality of the photoresist composition prepared in Examples 1-3 does not decrease after one month at room temperature.

[0053] In summary, the photoresist composition prepared by the technical solution of the present invention can improve the shelf life of poly(meth)acrylic resin photoresists at room temperature, which produces unexpected technical effects on the application and transportation of photoresist products and has broad research value and application prospects.

[0054] With the above-described preferred embodiments of the present invention as a guide, and with reference to the above description, relevant personnel are fully capable of making various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the contents of the specification and must be determined according to the scope of the claims.

Claims

1. A photoresist composition, characterized in that According to parts by weight, it includes the following components: 10-30 parts of polymer resin; 50-80 parts of organic solvent; 2-5 parts of photosensitizer; 1-2 parts of additives; 1-3 parts of additives; Wherein, the additive is a mixture of compound A and 1,2-epoxycyclohexane in a molar ratio of (1-20):1; The structural formula of the compound A is shown below: 。 2. The photoresist composition according to claim 1, wherein The compound A was prepared as follows: S1: Add benzaldehyde and 2,4-dimethylpyrrole to anhydrous tetrahydrofuran and react at room temperature in the dark to obtain reaction solution I; S2: adding 2,3-dichloro-5,6-dicyano-p-benzoquinone to the reaction solution I, and continuing the reaction at room temperature under the protection of an inert gas to obtain a reaction solution II; S3: Add triethylamine and boron trifluoride etherate to the reaction solution II under ice bath conditions, react in the dark, filter, wash, and separate by silica gel column chromatography to obtain compound A.

3. The photoresist composition according to claim 2, wherein The molar ratio of the benzaldehyde to the 2,4-dimethylpyrrole is 1:(2-2.3).

4. The photoresist composition according to claim 2, wherein The molar ratio of the benzaldehyde to the 2,3-dichloro-5,6-dicyano-p-benzoquinone is 1:

10.

5. The photoresist composition according to any one of claims 1 to 4, wherein The polymer resin is a poly(meth)acrylate resin or a polystyrene resin.

6. The photoresist composition according to claim 5, wherein The polymer resin is selected from at least one of polymethacrylate and polymethacrylate containing an adamantyl group.

7. The photoresist composition according to any one of claims 1 to 4, wherein The organic solvent is selected from at least one of propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, and diethylene glycol methyl ether.

8. The photoresist composition according to any one of claims 1 to 4, wherein The photosensitizer is selected from at least one of triphenylsulfonium perfluorobutanesulfonate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and bis(trifluoromethylsulfonyl)diazomethane.

9. The photoresist composition according to any one of claims 1 to 4, wherein The auxiliary agent is selected from at least one of a leveling agent, a thickener, and an adhesive.

10. A method for preparing the photoresist composition according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: mixing polymer resin, photosensitizer, organic solvent, additives and auxiliary agents according to the formula, filtering and packaging, and obtaining a photoresist composition.

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