G / I line photoresist

Abstract

The invention relates to the technical field of photoresist, in particular to G / I line photoresist suitable for manufacturing liquid crystal display panels and semiconductors. The photoresist is a positive photoresist and comprises phenolic polymer resin, a diazo naphthoquinone type photoinitiator, a solvent and an additive. According to the invention, the multi-carbon-based enol compound is used as a precursor to prepare the diazo naphthoquinone sulfonate type photosensitive compound, and the photosensitive compound is matched with the phenolic polymer resin, the solvent and the additive, so that the prepared photoresist has high resolution, good sensitivity, excellent thermal stability and etching resistance.

Description

Technical Field

[0001] The invention relates to the technical field of photoresists, and in particular to a G / I line photoresist suitable for liquid crystal display panels and semiconductor manufacturing. Background Art

[0002] Photoresist is a key material in the photolithography process in semiconductor manufacturing. It is an electronic chemical consumable with the highest added value and the highest technical barriers in the semiconductor industry. Photoresist is mainly composed of polymer resin, photoinitiator, solvent and additives. According to the different photosensitivity 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 intensification of the reverse globalization of the semiconductor industry chain, the domestic semiconductor manufacturing industry faces an increasing risk of supply cuts of key materials such as photoresist. At present, the domestic self-sufficiency rate of G / I line photoresist is less than 10%, the self-sufficiency rate of KrF and ArF photoresist is only 5%, and EUV photoresist is almost blank. In addition to the urgent need to develop formulation technology, the lack of key raw materials is also one of the main reasons for the low localization rate of high-end photoresist.

[0003] The main photoinitiator used in G / I line photoresist is naphthoquinone diazo type photosensitive compound (PAC). After PAC and phenolic resin are configured into photoresist, a coupling effect will occur between the two, thereby reducing the solubility of the resin in a specific solvent. When the photoresist is exposed to ultraviolet light, the structure of PAC will change after exposure, and the hydrogen bonds between the PAC and the resin molecules will be destroyed, resulting in an increase in the solubility of the polymer molecules. Therefore, the exposed part of the photoresist can be dissolved and removed, thereby completing the transfer of the photolithographic pattern. The commonly used naphthoquinone diazo type photoinitiator is prepared and synthesized by esterification reaction of 2-diazo-1-naphthoquinone-5-sulfonyl chloride and a polyphenol backbone compound.

[0004] However, to apply DNQ photoinitiators to the field of semiconductor photoresists, they also need to be able to cooperate with polymer resins. The photosensitivity of DNQ photoinitiators and their ability to inhibit the dissolution of resins determine key indicators such as the resolution and etching resistance of photoresists. Therefore, the use of suitable raw materials and appropriate formulas is the basis for producing photoresists with excellent performance. 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 positive photoresist, including a phenolic polymer resin, a diazo naphthoquinone type photoinitiator, a solvent, and an additive. The present invention uses a multi-carbon-based enol compound as a precursor to prepare a diazo naphthoquinone sulfonate type photosensitive compound. The photosensitive compound is combined with a phenolic polymer resin, a solvent and an additive to prepare a photoresist with high resolution, good sensitivity, excellent thermal stability and anti-etching performance.

[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 an additive.

[0007] Wherein, the naphthoquinone diazine type photoinitiator has a structure shown in Formula I:

[0008]

[0009] Wherein X each independently represents N, C, Si, benzene ring and aromatic heterocycle, R each independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, C3-C12 cycloalkyl group, wherein 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] Wherein, the naphthoquinone diazine type photoinitiator is selected from at least one of the following structural compounds:

[0011]

[0012] Wherein, the naphthoquinone diazide type photoinitiator is prepared by the following method:

[0013] Step A1, mixing a polycarbonyl enol compound and diazonaphthoquinone sulfonyl chloride in an organic solvent, and reacting by adding an alkaline activator to obtain the diazonaphthoquinone type photoinitiator product system;

[0014] Step A2, adding hydrochloric acid to the diazonaphthoquinone type photoinitiator system obtained in A1, filtering to remove inorganic salt by-products, and then adding a large amount of water to the organic phase to precipitate the diazonaphthoquinone type photoinitiator.

[0015] Wherein, the carbonyl enol compound has a structure shown in Formula II:

[0016]

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

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

[0019]

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

[0021]

[0022] Step A1, synthesizing an acetyl compound by an acylation reaction of a raw aromatic compound;

[0023] Step A2, synthesizing a carboxylic acid compound by Willgerodt-Kindler reaction;

[0024] Step A3, preparing a Vilsmeier-Haack-Arnold reagent, adding a carboxylic acid compound to the Vilsmeier-Haack-Arnold reagent to synthesize an onium salt compound;

[0025] Step A4, hydrolyzing the onium salt compound to obtain a polycarbonyl enol compound;

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

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

[0028] According to the second part of the present invention, a method for configuring the photoresist is provided, wherein 20-30 parts of phenolic polymer resin and 5-8 parts of naphthoquinone diazide 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 are mixed under stirring at room temperature to form a clear solution, and then the temperature is slowly raised to 50-60 degrees Celsius for reaction for 16-24 hours to obtain the photoresist.

[0030] By applying the scheme provided in the present application, a diazo naphthoquinone sulfonate type photosensitive compound is prepared by using a multi-carbon enol compound as a precursor. The photosensitive compound is combined with a phenolic polymer resin, a solvent and an additive, and the photoresist configured in a specific proportion has high resolution, good sensitivity, excellent thermal stability and anti-etching performance. DETAILED DESCRIPTION

[0031] The technical solution of the present invention is further explained below in conjunction with 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 protection scope of the present invention shall be subject to the contents recorded in the claims. Any modification or replacement made by a person skilled in the art to the technical solution of the present invention without creative work shall fall within the protection scope of the present invention.

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

[0033] Wherein, the naphthoquinone diazine type photoinitiator has a structure shown in Formula I:

[0034]

[0035] Wherein X each independently represents N, C, Si, benzene ring and aromatic heterocycle, R each independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, C3-C12 cycloalkyl group, wherein 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] Wherein, the naphthoquinone diazine type photoinitiator is selected from at least one of the following structural compounds:

[0037]

[0038] Wherein, the naphthoquinone diazide type photoinitiator is prepared by the following method:

[0039] Step A1, mixing a polycarbonyl enol compound and diazonaphthoquinone sulfonyl chloride in an organic solvent, and reacting by adding an alkaline activator to obtain the diazonaphthoquinone type photoinitiator product system;

[0040] Step A2, adding hydrochloric acid to the diazonaphthoquinone type photoinitiator system obtained in A1, filtering to remove inorganic salt by-products, and then adding a large amount of water to the organic phase to precipitate the diazonaphthoquinone type photoinitiator.

[0041] Wherein, the carbonyl enol compound has a structure shown in Formula II:

[0042]

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

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

[0045]

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

[0047]

[0048] Step A1, synthesizing an acetyl compound by an acylation reaction of a raw aromatic compound;

[0049] Step A2, synthesizing a carboxylic acid compound by Willgerodt-Kindler reaction;

[0050] Step A3, preparing a Vilsmeier-Haack-Arnold reagent, adding a carboxylic acid compound to the Vilsmeier-Haack-Arnold reagent to synthesize an onium salt compound;

[0051] Step A4, hydrolyzing the onium salt compound to obtain a polycarbonyl enol compound;

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

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

[0054] According to the 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. Solutions 1 and 2 are mixed into a clear solution under stirring at room temperature, and then slowly heated to 50-60 degrees Celsius for reaction for 16-24 hours to obtain the photoresist.

[0055] By applying the scheme provided in the present application, a diazo naphthoquinone sulfonate type photosensitive compound is prepared by using a multi-carbon enol compound as a precursor. The photosensitive compound is combined with a phenolic polymer resin, a solvent and an additive, and the photoresist configured in a specific proportion has high resolution, good sensitivity, excellent thermal stability and anti-etching performance.

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

[0057] Example 1

[0058] 50g of phenolic polymer resin (a mixture of 2000 molecular weight and 10000 molecular weight resins in a ratio of 1:4) and 10g of diazonaphthoquinone type photoinitiator S1 were dissolved in 135g of PGMEA solvent to form solution 1, and then 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 slowly heated to 50 degrees Celsius for reaction for 16 hours to obtain photoresist 1.

[0059] Example 2

[0060] The difference from Example 1 is that the naphthoquinone diazide type photoinitiator is replaced by S2 from S1.

[0061] 50g of phenolic polymer resin (a mixture of 2000 molecular weight and 10000 molecular weight resins in a ratio of 1:4) and 10g of diazonaphthoquinone type photoinitiator S2 were dissolved in 135g of PGMEA solvent to form solution 1, and then 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 slowly heated to 50 degrees Celsius for reaction for 16 hours to obtain photoresist 2.

[0062] Example 3

[0063] The difference from Example 1 is that the naphthoquinone diazide photoinitiator is replaced by S3 from S1.

[0064] 50g of phenolic polymer resin (a mixture of 2000 molecular weight and 10000 molecular weight resins in a ratio of 1:4) and 10g of diazonaphthoquinone type photoinitiator S3 were dissolved in 135g of PGMEA solvent to form solution 1, and then 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 slowly heated to 50 degrees Celsius for reaction for 16 hours to obtain photoresist 3.

[0065] Example 4

[0066] The difference from Example 1 is that the usage amount of naphthoquinone diazide type photoinitiator S1 is increased.

[0067] 50g of phenolic polymer resin (a mixture of 2000 molecular weight and 10000 molecular weight resins in a ratio of 1:4) and 20g of diazonaphthoquinone type photoinitiator S1 were dissolved in 135g of PGMEA solvent to form solution 1, and then 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 slowly heated to 50 degrees Celsius for reaction for 16 hours to obtain photoresist 4.

[0068] Example 5

[0069] The difference from Example 1 is that the usage amount of naphthoquinone diazide photoinitiator S1 is reduced.

[0070] 50g of phenolic polymer resin (a mixture of 2000 molecular weight and 10000 molecular weight resins in a ratio of 1:4) and 5g of diazonaphthoquinone type photoinitiator S1 were dissolved in 135g of PGMEA solvent to form solution 1, and then 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 slowly heated to 50 degrees Celsius for reaction 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 is used as the photoinitiator.

[0073] 50g of phenolic polymer resin (a mixture of 2000 molecular weight and 10000 molecular weight resins in a ratio of 1:4) and 10g of 2,3,4,4'-tetrahydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate were dissolved in 135g of PGMEA solvent to form solution 1, and then 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 slowly heated to 50 degrees Celsius for reaction for 16 hours to obtain photoresist 6.

[0074] Comparative Example 2

[0075] The commercially available photoresist product 7 was directly purchased for comparison, and its main components were phenolic polymer resin, photoinitiator 435, PGMEA, and additives.

[0076] The above-mentioned photoresists 1-7 were respectively coated on silicon wafers by spin coating, and after vacuum drying, they were baked on a hot plate at a temperature of 110°C for 90 seconds to form a photoresist coating with a coating thickness of about 1.5μm. Then a mercury lamp was used as a light source to expose the photoresist coating, and the total exposure energy was between 200 and 400mJ / cm2. After exposure, it was developed with a tetramethylammonium hydroxide aqueous solution with a mass concentration of 2.38wt%, and the development time was 20s. After washing with water for 30s, it was dried to remove the exposed part to form a photoresist pattern. The photoresist pattern was inspected using a scanning electron microscope to compare the resolution of the photoresist. The resolution was based on the minimum line width that could be achieved. The resolution test results of 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] The resolution test results show that the minimum resolution tested for photoresist 1, photoresist 3, photoresist 6, and photoresist 7 is 1.5 μm, and their performance is better than that of photoresist 2, photoresist 4, and photoresist 5.

Claims

1. A G / I line photoresist, characterized in that: The photoresist comprises a phenolic polymer resin, a diazonaphthoquinone type photoinitiator, a solvent and an additive.

2. The G / I line photoresist according to claim 1, characterized in that: The naphthoquinone diazide photoinitiator has a structure shown in Formula I:

3. Formula I Wherein X each independently represents N, C, Si, benzene ring and aromatic heterocycle, R each independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, C3-C12 cycloalkyl group, wherein 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.

4. The naphthoquinone diazide type photoinitiator according to claim 2, characterized in that: The naphthoquinone diazide type photoinitiator is selected from at least one of the following structural compounds: 。 5. The naphthoquinone diazide photoinitiator according to claim 3, characterized in that: The naphthoquinone diazide type photoinitiator is prepared by the following method: Step A1, mixing a polycarbonyl enol compound and diazonaphthoquinone sulfonyl chloride in an organic solvent, and reacting by adding an alkaline activator to obtain the diazonaphthoquinone type photoinitiator product system; Step A2, adding hydrochloric acid to the diazonaphthoquinone type photoinitiator system obtained in A1, filtering to remove inorganic salt by-products, and then adding a large amount of water to the organic phase to precipitate the diazonaphthoquinone type photoinitiator.

6. The method for preparing a naphthoquinone diazide photoinitiator according to claim 4, characterized in that: The carbonyl enol compound has a structure shown in Formula II:

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

8. The polycarbonyl enol compound according to claim 5, characterized in that The polycarbonyl enol compound is selected from at least one of the following structural compounds: 。 9. The polycarbonyl enol compound according to claim 6, characterized in that: The polycarbonyl enol compound is prepared by the following method: Step A1, synthesizing an acetyl compound by an acylation reaction of a raw aromatic compound; Step A2, synthesizing a carboxylic acid compound by Willgerodt-Kindler reaction; Step A3, preparing a Vilsmeier-Haack-Arnold reagent, adding a carboxylic acid compound to the Vilsmeier-Haack-Arnold reagent to synthesize an onium salt compound; Step A4, hydrolyzing the onium salt compound to obtain a polycarbonyl enol compound; X, R, m, n and the polycarbonyl enol compound have the same meanings as in any one of the above claim 1.

10. The G / I line photoresist according to claim 1, characterized in that: The molecular weight of the phenolic polymer resin is distributed in the range of 2000-10000.

11. The G / I line photoresist according to claim 1, characterized in that: According to the weight percentage, the composition comprises 20-30 parts of phenolic polymer resin, 5-8 parts of diazonaphthoquinone type photoinitiator, 60-70 parts of solvent and 2-6 parts of additive.

12. According to claim 9, it is characterized in that: The solvent is propylene glycol methyl ether acetate PGMEA, The additives include one or more of the surfactants S-381, S-382, S-386 and the adhesion promoter KP-341\X-70-092.

Images