G / i line photoresist

Abstract

The application relates to the technical field of photoresists, in particular to a G / I line photoresist suitable for liquid crystal display panels and semiconductor manufacturing. The photoresist is a kind of positive photoresist, which comprises a phenolic polymer resin, a diazonaphthoquinone type photo initiator, a solvent and an additive. A diazonaphthoquinone sulfonate type photosensitive compound is prepared by using a multi-carbon-based enol compound as a precursor, and the photosensitive compound is matched with the phenolic polymer resin, the solvent and the additive to configure the photoresist, which has high resolution, good photosensitivity, excellent thermal stability and good etching resistance.

Description

Technical Field

[0001] This invention relates to the field of photoresist technology, and more specifically to a G / I line photoresist suitable for liquid crystal display panels and semiconductor manufacturing. Background Technology

[0002] Photoresist is a key material in the photolithography process of semiconductor manufacturing. It is the electronic chemical consumable with the highest added value and the highest technological barriers in the semiconductor industry. Photoresist is mainly composed of polymer resin, photoinitiator, solvent, and additives. According to different photosensitive wavelengths, it is mainly divided into: g-line (436nm), i-line (365nm), KrF type (248nm), ArF type (193nm), and EUV type (13.5nm). With the increasing deglobalization of the semiconductor industry chain, the risk of supply disruption of key materials such as photoresist in the domestic semiconductor manufacturing industry is constantly increasing. At present, the self-sufficiency rate of domestic g / i-line photoresist is less than 10%, the self-sufficiency rate of KrF and ArF type photoresist is only 5%, and EUV type photoresist is almost non-existent. In addition to the urgent need for formulation technology development, the lack of key raw materials is also one of the main reasons for the low domestic production rate of high-end photoresist.

[0003] The photoinitiator primarily used in G / I line photoresists is a diazonoquinone-type photosensitive compound (PAC). When PAC is formulated with phenolic resin to form a photoresist, a coupling effect occurs between the two, reducing the resin's solubility in specific solvents. When the photoresist is exposed to ultraviolet light, the structure of the PAC changes after exposure, the hydrogen bonds between it and the resin molecules are broken, leading to increased polymer solubility. Therefore, the exposed portion of the photoresist can be dissolved and removed, thus completing the transfer of the photolithographic pattern. Commonly used diazonoquinone-type photoinitiators are synthesized by esterification of 2-diazo-1-naphthoquinone-5-sulfonyl chloride with a polyphenolic backbone compound.

[0004] However, for DNQ-type photoinitiators to be applied in the field of semiconductor photoresists, they also need to be compatible with polymer resins. The photosensitivity and resin solubility inhibition properties of DNQ-type photoinitiators determine key indicators of photoresists such as resolution and etching resistance. Therefore, using appropriate raw materials and suitable formulations is the foundation for producing high-performance photoresists. Summary of the Invention

[0005] In view of the above reasons, the present invention provides a G / I line photoresist for liquid crystal display panels and semiconductor manufacturing. The photoresist is a type of positive photoresist, comprising a phenolic polymer resin, a diazonaphthoquinone-type photoinitiator, a solvent, and additives. The present invention uses a multi-carbon-based enol compound as a precursor to prepare a diazonaphthoquinone sulfonate-type photosensitive compound. This photosensitive compound, combined with the phenolic polymer resin, solvent, and additives, produces a photoresist with high resolution, good photosensitivity, excellent thermal stability, and etching resistance.

[0006] To achieve the above objectives, according to the first part of the present invention, a G / I line photoresist is provided, comprising a phenolic polymer resin, a diazonaphthoquinone type photoinitiator, a solvent, and additives.

[0007] The diazonoquinone-type photoinitiator has the structure shown in Formula I:

[0008]

[0009] Where X independently represents N, C, Si, benzene ring, and aromatic heterocycle, and R independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, and C3-C12 cycloalkyl, where k represents any integer between 1 and 4, n represents an integer between 0 and 2, and m represents an integer between 2 and 4.

[0010] The diazonoquinone type photoinitiator is selected from at least one of the following structural compounds:

[0011]

[0012] The diazonoquinone type photoinitiator is prepared by the following method:

[0013] Step A1: Mix the polycarbonyl enol compound and diazonaquinone sulfonyl chloride in an organic solvent, and react them by adding an alkaline activator to obtain the diazonaquinone-type photoinitiator product system;

[0014] In step A2, hydrochloric acid is added to the diazonoquinone-type photoinitiator system obtained in A1 and filtered to remove inorganic salt byproducts. Then, a large amount of water is added to the organic phase to precipitate the diazonoquinone-type photoinitiator.

[0015] The carbonyl enol compound has the structure shown in Formula II:

[0016]

[0017] Where X independently represents N, C, Si, benzene ring and aromatic heterocycle, R independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, C3-C12 cycloalkyl, n represents an integer between 0 and 2, and m represents an integer between 2 and 4.

[0018] The polycarbonyl enol compound is selected from at least one of the following structural compounds:

[0019]

[0020] The polycarbonyl enol compound is prepared by the following method:

[0021]

[0022] Step A1: Acetyl compounds are synthesized from the starting aromatic compounds via an acylation reaction;

[0023] Step A2: Synthesis of carboxylic acid compounds via the Willgerodt-Kindler reaction;

[0024] Step A3: Prepare the Vilsmeier-Haack-Arnold reagent by adding carboxylic acid compounds to the Vilsmeier-Haack-Arnold reagent to synthesize onium salt compounds;

[0025] Step A4: Hydrolyze the onium salt compound to obtain a polycarbonyl enol compound;

[0026] X, R, m, n, and the polycarbonyl enol compound have the same meaning as in any one of claims 1 above.

[0027] The phenolic polymer resin has a molecular weight distribution of 2000-10000. The solvent is propylene glycol methyl ether acetate (PGMEA), and the additives include one or more of surfactants S-381, S-382, S-386, and adhesion promoters KP-341 and X-70-092.

[0028] According to a second part of the present invention, a method for preparing the photoresist is provided, wherein 20-30 parts of phenolic polymer resin and 5-8 parts of diazonaphthoquinone type photoinitiator are dissolved in 50-60 parts of PGMEA solvent to form solution 1, and then 2-6 parts of additives are dissolved in 10 parts of PGMEA solvent to form solution 2.

[0029] Solutions 1 and 2 were mixed at room temperature with stirring to form a clear solution, and then the temperature was slowly raised to 50-60 degrees Celsius and reacted for 16-24 hours to obtain the photoresist.

[0030] Using the solution provided in this invention application, a diazonaphthoquinone sulfonate type photosensitive compound is prepared by using a multicarbon-based enol compound as a precursor. The photosensitive compound, combined with phenolic polymer resin, solvent and additives, forms a photoresist with high resolution, good photosensitivity, excellent thermal stability and etching resistance when prepared in a specific ratio. Detailed Implementation

[0031] The technical solution of the present invention will be further explained and described below with reference to specific embodiments. It is worth noting that the following embodiments are only preferred embodiments of the present invention and should not be construed as limiting the present invention. The scope of protection of the present invention should be determined by the contents of the claims. Modifications and substitutions made by those skilled in the art to the technical solution of the present invention without creative effort all fall within the scope of protection of the present invention.

[0032] In a first typical embodiment of this application, this application provides a polycarbonyl enol compound and a G / I line photoresist, comprising a phenolic polymer resin, a diazonaphthoquinone type photoinitiator, a solvent, and additives.

[0033] The diazonoquinone-type photoinitiator has the structure shown in Formula I:

[0034]

[0035] Where X independently represents N, C, Si, benzene ring, and aromatic heterocycle, and R independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, and C3-C12 cycloalkyl, where k represents any integer between 1 and 4, n represents an integer between 0 and 2, and m represents an integer between 2 and 4.

[0036] The diazonoquinone type photoinitiator is selected from at least one of the following structural compounds:

[0037]

[0038] The diazonoquinone type photoinitiator is prepared by the following method:

[0039] Step A1: Mix the polycarbonyl enol compound and diazonaquinone sulfonyl chloride in an organic solvent, and react them by adding an alkaline activator to obtain the diazonaquinone-type photoinitiator product system;

[0040] In step A2, hydrochloric acid is added to the diazonoquinone-type photoinitiator system obtained in A1 and filtered to remove inorganic salt byproducts. Then, a large amount of water is added to the organic phase to precipitate the diazonoquinone-type photoinitiator.

[0041] The carbonyl enol compound has the structure shown in Formula II:

[0042]

[0043] Where X independently represents N, C, Si, benzene ring and aromatic heterocycle, R independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, C3-C12 cycloalkyl, n represents an integer between 0 and 2, and m represents an integer between 2 and 4.

[0044] The polycarbonyl enol compound is selected from at least one of the following structural compounds:

[0045]

[0046] The polycarbonyl enol compound is prepared by the following method:

[0047]

[0048] Step A1: Acetyl compounds are synthesized from the starting aromatic compounds via an acylation reaction;

[0049] Step A2: Synthesis of carboxylic acid compounds via the Willgerodt-Kindler reaction;

[0050] Step A3: Prepare the Vilsmeier-Haack-Arnold reagent by adding carboxylic acid compounds to the Vilsmeier-Haack-Arnold reagent to synthesize onium salt compounds;

[0051] Step A4: Hydrolyze the onium salt compound to obtain a polycarbonyl enol compound;

[0052] X, R, m, n, and the polycarbonyl enol compound have the same meaning as in any one of claims 1 above.

[0053] The phenolic polymer resin has a molecular weight distribution of 2000-10000. The solvent is propylene glycol methyl ether acetate (PGMEA), and the additives include one or more of surfactants S-381, S-382, S-386, and adhesion promoters KP-341 and X-70-092.

[0054] According to a second part of the present invention, a method for preparing the photoresist is provided, comprising dissolving 20-30 parts of phenolic polymer resin and 5-8 parts of diazonoquinone-type photoinitiator in 50-60 parts of PGMEA solvent to form solution 1, and then dissolving 2-6 parts of additives in 10 parts of PGMEA solvent to form solution 2. Solutions 1 and 2 are mixed under stirring at room temperature to form a clear solution, and then the temperature is slowly raised to 50-60 degrees Celsius and reacted for 16-24 hours to obtain the photoresist.

[0055] Using the solution provided in this invention application, a diazonaphthoquinone sulfonate type photosensitive compound is prepared by using a multicarbon-based enol compound as a precursor. The photosensitive compound, combined with phenolic polymer resin, solvent and additives, forms a photoresist with high resolution, good photosensitivity, excellent thermal stability and etching resistance when prepared in a specific ratio.

[0056] The beneficial effects of this application will be further illustrated below with reference to the embodiments.

[0057] Example 1

[0058] 50g of phenolic polymer resin (a mixture of resins with molecular weights of 2000 and 10000 in a 1:4 ratio) and 10g of diazonoquinone-type photoinitiator S1 were dissolved in 135g of PGMEA solvent to form solution 1. Subsequently, 2g of surfactant S-381 was dissolved in 5g of PGMEA to form solution 2. Solutions 1 and 2 were mixed under stirring at room temperature to form a clear solution, and then the temperature was slowly raised to 50 degrees Celsius and reacted for 16 hours to obtain photoresist 1.

[0059] Example 2

[0060] The difference from Example 1 is that the diazonoquinone type photoinitiator is replaced by S2 instead of S1.

[0061] 50g of phenolic polymer resin (a mixture of resins with molecular weights of 2000 and 10000 in a 1:4 ratio) and 10g of diazonoquinone-type photoinitiator S2 were dissolved in 135g of PGMEA solvent to form solution 1. Subsequently, 2g of surfactant S-381 was dissolved in 5g of PGMEA to form solution 2. Solutions 1 and 2 were mixed under stirring at room temperature to form a clear solution, and then the temperature was slowly raised to 50 degrees Celsius and reacted for 16 hours to obtain photoresist 2.

[0062] Example 3

[0063] The difference from Example 1 is that the diazonoquinone type photoinitiator is replaced by S3 instead of S1.

[0064] 50g of phenolic polymer resin (a mixture of resins with molecular weights of 2000 and 10000 in a 1:4 ratio) and 10g of diazonoquinone-type photoinitiator S3 were dissolved in 135g of PGMEA solvent to form solution 1. Subsequently, 2g of surfactant S-381 was dissolved in 5g of PGMEA to form solution 2. Solutions 1 and 2 were mixed under stirring at room temperature to form a clear solution, and then the temperature was slowly raised to 50 degrees Celsius and reacted for 16 hours to obtain photoresist 3.

[0065] Example 4

[0066] The difference from Example 1 is that the amount of diazonaphthoquinone type photoinitiator S1 used is increased.

[0067] 50g of phenolic polymer resin (a mixture of resins with molecular weights of 2000 and 10000 in a 1:4 ratio) and 20g of diazonoquinone-type photoinitiator S1 were dissolved in 135g of PGMEA solvent to form solution 1. Subsequently, 5g of surfactant S-381 was dissolved in 5g of PGMEA to form solution 2. Solutions 1 and 2 were mixed under stirring at room temperature to form a clear solution, and then the temperature was slowly raised to 50 degrees Celsius and reacted for 16 hours to obtain photoresist 4.

[0068] Example 5

[0069] The difference from Example 1 is that the amount of diazonoquinone-type photoinitiator S1 used was reduced.

[0070] 50g of phenolic polymer resin (a mixture of resins with molecular weights of 2000 and 10000 in a 1:4 ratio) and 5g of diazonoquinone-type photoinitiator S1 were dissolved in 135g of PGMEA solvent to form solution 1. Subsequently, 5g of surfactant S-381 was dissolved in 5g of PGMEA to form solution 2. Solutions 1 and 2 were mixed under stirring at room temperature to form a clear solution, and then the temperature was slowly raised to 50 degrees Celsius and reacted for 16 hours to obtain photoresist 5.

[0071] Comparative Example 1

[0072] The difference from Example 1 is that commercially available 2,3,4,4'-tetrahydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate was used as the photoinitiator.

[0073] 50g of phenolic polymer resin (a mixture of resins with molecular weights of 2000 and 10000 in a 1:4 ratio) was dissolved in 135g of PGMEA solvent to form solution 1. Subsequently, 2g of surfactant S-381 was dissolved in 5g of PGMEA to form solution 2. Solutions 1 and 2 were mixed under stirring at room temperature to form a clear solution, and then the temperature was slowly raised to 50 degrees Celsius and reacted for 16 hours to obtain photoresist 6.

[0074] Comparative Example 2

[0075] For comparison, commercially available photoresist product 7 was purchased directly. Its main components are phenolic polymer resin, photoinitiator 435, PGMEA, and additives.

[0076] Photoresists 1-7 were spin-coated onto a silicon wafer. After vacuum drying, they were baked on a hot plate at 110°C for 90 seconds to form a photoresist coating with a thickness of approximately 1.5 μm. A mercury lamp was then used as the light source to expose the photoresist coating, with a total exposure energy of 200–400 mJ / cm². After exposure, the coating was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 20 seconds. After rinsing with water for 30 seconds, the exposed portions were removed, forming a photoresist pattern. The photoresist pattern was examined using a scanning electron microscope to compare the resolution, with the minimum achievable linewidth as the standard. The resolution test results for different photoresist patterns are shown in Table 2.

[0077] Table 1

[0078] Photoresist Minimum resolution (μm) 1 1.5 2 2.0 3 1.5 4 5 5 4 6 1.5 7 1.5

[0079] Resolution test results show that the minimum resolution of photoresist 1, photoresist 3, photoresist 6, and photoresist 7 is 1.5μm, which is better than that of photoresist 2, photoresist 4, and photoresist 5.

Claims

1. A G / I line photoresist, characterized in that, The photoinitiator comprises 20-30 parts of phenolic polymer resin, 5-8 parts of diazonoquinone photoinitiator, 60-70 parts of solvent, and 2-6 parts of additives. The diazonoquinone photoinitiator has the following structure: Where D is not entirely H, Where X independently represents N and C, R independently represents hydrogen and C1 to C18 alkyl groups, k represents any integer between 1 and 3, n represents 1, and m represents an integer between 2 and 3.

2. The G / I line photoresist according to claim 1, characterized in that, The diazonoquinone-type photoinitiator is selected from at least one of the following structural compounds: ， D is not entirely H.

3. The G / I line photoresist according to claim 1 or 2, characterized in that, The diazonoquinone-type photoinitiator was prepared by the following method: Step A1: Mix the polycarbonyl enol compound and diazonaquinone sulfonyl chloride in an organic solvent, and react them by adding an alkaline activator to obtain the diazonaquinone-type photoinitiator product system; In step A2, hydrochloric acid is added to the diazonoquinone-type photoinitiator system obtained in A1 and filtered to remove inorganic salt byproducts. Then, a large amount of water is added to the organic phase to precipitate the diazonoquinone-type photoinitiator.

4. The G / I line photoresist according to claim 3, characterized in that, The carbonyl enol compound has the following structure: ， Where X independently represents N and C, R independently represents hydrogen and C1 to C18 alkyl groups, k represents any integer between 1 and 3, n represents 1, and m represents an integer between 2 and 3.

5. The G / I line photoresist according to claim 4, characterized in that, The polycarbonyl enol compound is selected from at least one of the following structural compounds: 。 6. The G / I line photoresist according to claim 4 or 5, characterized in that, The polycarbonyl enol compound was prepared by the following method: Step A1: Acetyl compounds are synthesized from aromatic raw materials via acylation reaction; Step A2: Synthesis of carboxylic acid compounds via the Willgerodt-Kindler reaction; Step A3: Prepare the Vilsmeier-Haack-Arnold reagent by adding carboxylic acid compounds to the Vilsmeier-Haack-Arnold reagent to synthesize onium salt compounds; Step A4: Hydrolyze the onium salt compound to obtain a polycarbonyl enol compound; Where X independently represents N and C, and R independently represents hydrogen and C1 to C18 alkyl groups, where n represents 1 and m represents an integer between 2 and 3.

7. The G / I line photoresist according to claim 1, characterized in that, The molecular weight distribution of the phenolic polymer resin is between 2000 and 10000.

8. The G / I line photoresist according to claim 1, characterized in that, The solvent is propylene glycol methyl ether acetate (PGMEA), and the additives include one or more surfactants and adhesion promoters.

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