CN115453819A - Chemically amplified photoresist composition for flat panel display manufacturing process - Google Patents

Abstract

The invention discloses a chemical amplification type photoresist composition used for a flat panel display manufacturing process, which comprises the following components in percentage by mass of 10-30:100 of a solid component and an organic solvent, the solid component comprising a film-forming resin, a photosensitizer, and a surfactant; compared with the conventional PAC TYPE PHOTORESIST (photosensitizer TYPE PHOTORESIST), the resolution is higher, a more precise pattern (pattern) can be manufactured, and a more precise panel can be manufactured.

Description

Chemically amplified photoresist composition usable in flat panel display manufacturing process

technical field

The invention relates to a chemically amplified photoresist composition that can be used in the manufacturing process of high-resolution flat panel displays.

Background technique

In order to improve the picture quality, people have higher and higher requirements for the pixels of the flat panel display, and the higher the pixel per inch value (PPI=pixel per inch) of the display, the clearer the picture quality will be. For example, in the existing TV screen models, the number of pixels of 2K TV in the same area is 1920×1080; the number of pixels of 4K TV is increased to 3840×2160; and the number of pixels of 8K TV is further increased to 7680×4320. In order to produce flat-panel displays with higher image values, flat-panel display manufacturers need to further reduce the size of thin-film transistors (TFTs) in the production process to make high-resolution products; and to further miniaturize TFTs, it is necessary to improve the resolution of the photolithography process. Rate.

R=resolution, K1=process factor, NA=numerical aperture, λ=exposure wavelength

In theory, Rayleigh's formula (Rayleigh's formula) reveals how to realize the principle of fine graphics production. To improve the resolution of graphics, under certain conditions, it can be achieved by shortening the wavelength of the light source of the exposure machine or using a high numerical aperture exposure machine.

However, at present, the exposure machine light source used in the manufacturing process of flat panel displays generally adopts a wavelength of 365nm i-line, or uses a broadband light source including 365nm i-line, 400nm h-line, and 436nm g-line. It is impossible to shorten the wavelength of the exposure light source. At the same time, in the flat panel display manufacturing process, if the numerical aperture of the lens is increased, the exposure time needs to be extended, resulting in a decrease in actual productivity. Therefore, the use of a high numerical aperture exposure machine to improve the flat panel display Resolution is also not feasible. At present, the numerical aperture of exposure machines commonly used in the manufacturing process of flat panel displays is about 0.08–0.1.

Therefore, using a low numerical aperture exposure machine and existing photoresists, the limit resolution that can be achieved in the mass production of flat panel displays is about 2 μm, and the production of high-definition displays requires high-resolution flat panel displays with a value of more than 1000 pixels. . For example, a display with a resolution of about 1.5 μm is required for the production of virtual simulation equipment. However, with the exposure machine equipment and photoresist commonly used at present, it is impossible to stably achieve a resolution of about 1.5 μm in the mass production of panel displays.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art and provide a chemically amplified photoresist composition that can be used in the manufacturing process of flat panel displays.

Technical scheme of the present invention is summarized as follows:

The chemically amplified photoresist composition that can be used in the manufacturing process of flat panel displays is composed of a solid component and an organic solvent with a mass ratio of 10-30:100, and the solid component includes a film-forming resin, a photosensitizer and a surfactant ;

The film-forming resin is at least one of the polymers shown in formulas III to XII;

In formula III～XII:

R1 is selected from -H, -OH or -CH ₃ ;

R2 is selected from -H, -OH or -CH ₃ ;

The weight average molecular weight of the polymer represented by formula III-XII is 1000-20000.

The mass of the film-forming resin accounts for 65%-80% of the mass of the solid component, the mass of the photosensitizer accounts for 15%-30% of the mass of the solid component; the mass of the surfactant accounts for 0.001%-5% of the mass of the solid component.

The photosensitizer is preferably a photoacid generator, or is formed by mixing a diazoquinone photosensitizer and a photoacid generator in any mass ratio.

The photoacid generator is any one of the compounds shown in formula 1 to formula 6:

The diazoquinone photosensitizer is any one of the compounds described in formulas 7-10:

In formula 7 to formula 10, D is selected from formula 11 or formula 12:

The surfactant is Si-Type: TEGO 440 (EVONIK) or F-Type F-560 (DIC).

The organic solvent is at least one of (2-ethoxyethyl) acetate, (2-methoxyethyl) acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and butyl acetate .

Advantages of the present invention:

Compared with the existing PAC TYPE PHOTORESIST (photosensitizer type photoresist), the resolution is higher, more precise patterns can be produced, and more precise panels can be produced.

Description of drawings

Fig. 1 is the pattern state of 1.5μm L/S measured by scanning electron microscope (SEM).

Specific implementation method

The present invention will be further described below by specific examples.

Film-forming resin III-XII, the structure is as follows:

In formula III～XII:

R1 is selected from -H, -OH or -CH ₃ ;

R2 is selected from -H, -OH or -CH ₃ ;

The weight average molecular weight of the polymer represented by formula III-XII is 1000-20000.

The photoacid generator is any one of the compounds shown in formula 1 to formula 6:

Diazoquinone photosensitizers such as any one of the compounds described in formulas 7 to 10:

In formula 7 to formula 10, D is selected from formula 11 or formula 12:

Example 1

A chemically amplified photoresist composition that can be used in the manufacturing process of flat panel displays, consisting of a solid component and an organic solvent with a mass ratio of 20:100, the solid component including a film-forming resin, a photosensitizer and a surfactant;

The film-forming resin is a polymer shown in formula III. In formula III, R1 is -CH ₃ ; R2 is -CH ₃ ; the weight average molecular weight is 10000;

The mass of the film-forming resin accounts for 70% of the mass of the solid component, the mass of the photosensitizer accounts for 25% of the mass of the solid component, and the mass of the surfactant accounts for 5% of the mass of the solid component.

The photosensitizer is a photoacid generator, and the photoacid generator is shown in Formula 1.

The surfactant is Si-Type: TEGO 440 (EVONIK);

The organic solvent is (2-ethoxyethyl) acetate.

Preparation of each embodiment: Mix the film-forming resin and the photosensitizer evenly, dissolve them with an organic solvent, add a surfactant, and mix evenly to obtain a chemically amplified photoresist composition that can be used in the manufacturing process of flat panel displays.

The above-mentioned chemically amplified photoresist composition that can be used in the flat panel display manufacturing process is uniformly coated on a glass substrate of 10 cm * 10 cm, baked on a hot plate at 100 ° C for 60 seconds, and then use Canon MPA 500F ( equipment model) for exposure, and the substrate was baked again on a 110°C hot plate for 60 seconds, and then developed in (mass concentration) 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds, and a scanning electron microscope (SEM) was used to measure 1.5 μm L /S graphics state. see picture 1.

Example 2

A chemically amplified photoresist composition that can be used in the manufacturing process of flat panel displays, consisting of a solid component and an organic solvent with a mass ratio of 15:100, the solid component including a film-forming resin, a photosensitizer and a surfactant;

The film-forming resin is a polymer shown in formula IV. In formula IV, R1 is-H; R2 is- _CH3 ; the weight average molecular weight is 1000,

The mass of the film-forming resin accounts for 65% of the mass of the solid component, the mass of the photosensitizer accounts for 30% of the mass of the solid component, and the mass of the surfactant accounts for 5% of the mass of the solid component.

The photosensitizer is a photoacid generator, and the photoacid generator is shown in formula 2.

Surfactant is Si-Type: TEGO 440 (EVONIK)

The organic solvent is (2-methoxyethyl) acetate.

Example 3

A chemically amplified photoresist composition that can be used in the manufacturing process of flat panel displays, consisting of a solid with a mass ratio of 30:100

Components and organic solvents, the solid components include film-forming resins, photosensitizers and surfactants;

The film-forming resin is a polymer shown in formula V. In formula V, R1 is -CH ₃ ; R2 is -H; the weight average molecular weight is 5000,

The quality of the film-forming resin accounts for 80% of the mass of the solid component, the quality of the photosensitizer accounts for 15% of the mass of the solid component; the quality of the surfactant accounts for 5% of the mass of the solid component;

The photosensitizer is a photoacid generator, and the photoacid generator is shown in formula 3.

Surfactant is F-Type F-560 (DIC)

The organic solvent is propylene glycol methyl ether acetate.

Example 4

A chemically amplified photoresist composition that can be used in the manufacturing process of a flat panel display, consisting of a solid component and an organic solvent with a mass ratio of 10:100, the solid component including a film-forming resin, a photosensitizer and a surfactant;

Film-forming resin is polymer shown in formula VI, and in formula VI, R1 is-H; R2 is H; Weight average molecular weight is 7000,

The mass of the film-forming resin accounts for 75% of the mass of the solid component, the mass of the photosensitizer accounts for 24.999% of the mass of the solid component; the mass of the surfactant accounts for 0.001% of the mass of the solid component;

The photosensitizer is a photoacid generator, and the photoacid generator is shown in formula 4.

Surfactant is Si-Type: TEGO 440 (EVONIK)

The organic solvent is propylene glycol monomethyl ether.

Example 5

A chemically amplified photoresist composition that can be used in the manufacturing process of flat panel displays, consisting of a solid component and an organic solvent with a mass ratio of 15:100, the solid component including a film-forming resin, a photosensitizer and a surfactant;

Film-forming resin is polymer shown in formula VII, and in formula VII, R1 is-OH; R2 is-OH; Weight average molecular weight is 9000,

The mass of the film-forming resin accounts for 70% of the mass of the solid component, the mass of the photosensitizer accounts for 25% of the mass of the solid component, and the mass of the surfactant accounts for 5% of the mass of the solid component.

The photosensitizer is a photoacid generator, and the photoacid generator is shown in formula 5.

The surfactant is Si-Type: TEGO 440 (EVONIK);

The organic solvent is ethyl lactate.

Example 6

A chemically amplified photoresist composition that can be used in the manufacturing process of flat panel displays, consisting of a solid component and an organic solvent with a mass ratio of 20:100, the solid component including a film-forming resin, a photosensitizer and a surfactant;

The film-forming resin is a polymer shown in formula VIII. In formula VIII, R1 is -OH; R2 is -CH ₃ ; the weight average molecular weight is 11000,

The mass of the film-forming resin accounts for 65% of the mass of the solid component, the mass of the photosensitizer accounts for 30% of the mass of the solid component, and the mass of the surfactant accounts for 5% of the mass of the solid component.

The photosensitizer is a mixture of photoacid generator and diazoquinone photosensitizer in a mass ratio of 5:1;

Wherein the photoacid generator is shown in formula 6, the diazoquinone photosensitizer is shown in formula 7, and D in formula 7 is selected from formula 11;

Surfactant is F-Type F-560 (DIC)

Described organic solvent is butyl acetate.

Example 7

A chemically amplified photoresist composition that can be used in the manufacturing process of flat panel displays, consisting of a solid component and an organic solvent with a mass ratio of 15:100, the solid component including a film-forming resin, a photosensitizer and a surfactant;

The film-forming resin is a polymer shown in formula IX. In formula IX, R1 is-H; R2 is- _CH3 ; the weight average molecular weight is 13000,

The mass of the film-forming resin accounts for 75% of the mass of the solid component, the mass of the photosensitizer accounts for 24% of the mass of the solid component, and the mass of the surfactant accounts for 1% of the mass of the solid component.

The photosensitizer is a photoacid generator and a diazoquinone photosensitizer mixed in a mass ratio of 1:1. The photoacid generator is shown in formula 6, and the diazoquinone photosensitizer is shown in formula 8. Formula 8 D in is selected from formula 12;

Surfactant is Si-Type: TEGO 440 (EVONIK)

The organic solvent is composed of butyl acetate and ethyl lactate with a volume ratio of 1:1.

Example 8

A chemically amplified photoresist composition that can be used in the manufacturing process of a flat panel display, consisting of a solid component and an organic solvent with a mass ratio of 10:100, the solid component including a film-forming resin, a photosensitizer and a surfactant;

The film-forming resin is a polymer shown in formula X. In formula X, R1 is -H; R2 is _-CH3 ; the weight average molecular weight is 15000,

The mass of the film-forming resin accounts for 70% of the mass of the solid component, the mass of the photosensitizer accounts for 29.95% of the mass of the solid component, and the mass of the surfactant accounts for 0.05% of the mass of the solid component.

The photosensitizer is formed by mixing a photoacid generator and a diazoquinone photosensitizer in a mass ratio of 10:1; the photoacid generator is shown in formula 1, and the diazoquinone photosensitizer is shown in formula 9, wherein D is selected from formula 11;

Surfactant is Si-Type: TEGO 440 (EVONIK)

The organic solvent is (2-ethoxyethyl) acetate.

Example 9

A chemically amplified photoresist composition that can be used in the manufacturing process of a flat panel display, consisting of a solid component and an organic solvent with a mass ratio of 30:100, the solid component including a film-forming resin, a photosensitizer and a surfactant;

The film-forming resin is a polymer shown in formula XI. In formula XI, R1 is-H; R2 is- _CH3 ; the weight average molecular weight is 20000,

The mass of the film-forming resin accounts for 70% of the mass of the solid component, the mass of the photosensitizer accounts for 29% of the mass of the solid component, and the mass of the surfactant accounts for 1% of the mass of the solid component.

The photosensitizer is formed by mixing a photoacid generator and a diazoquinone photosensitizer in a mass ratio of 5:1; the photoacid generator is shown in formula 2, and the diazoquinone photosensitizer is shown in formula 10, wherein D is selected from formula 12;

Surfactant is F-Type F-560 (DIC)

The organic solvent is (2-ethoxyethyl) acetate.

Comparative example 1

Mix 20 grams of phenolic resin with a weight average molecular weight of 8000 (the weight ratio of m-cresol and p-cresol is 50:50), 5 grams of photosensitizer BP PAC435 and 75 grams of propylene glycol methyl ether acetate, and add 500 ppm of silicone-type surface Activator, mixed uniformly to obtain a typical m/p phenolic resin type photoresist.

The photoresist prepared above is uniformly coated on a glass substrate of 10 cm × 10 cm, baked on a hot plate at 100 ° C for 60 seconds, then uses Canon MPA 500F (it is the equipment model) to expose, and again The substrate was baked on a hot plate at 110°C for 60 seconds, and then developed in an aqueous solution of 2.38% tetramethylammonium hydroxide for 60 seconds, and the pattern state of 1.5 μm L/S was measured with a scanning electron microscope (SEM). see picture 1.

Comparative example 2

20 grams of phenolic resin with a weight average molecular weight of 6000 (the weight ratio of m-cresol, p-cresol and 3,5-xylenol is 45:45:10), 5 grams of photosensitizer BP PAC435 with 75 grams of propylene glycol methyl ether acetic acid Esters are mixed, and 500ppm of silicone-type surfactant is added, and mixed uniformly to obtain a typical m/p/xylenol resin type photoresist.

The photoresist prepared above was uniformly coated on a glass substrate of 10 cm × 10 cm, baked on a hot plate at 100 ° C for 60 seconds, and then exposed using Canon MPA 500F (equipment model), and the substrate was placed on the Bake on a hot plate at 110°C for 60 seconds, then develop in 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds, and measure the pattern state of 1.5 μm L/S with a scanning electron microscope (SEM). see picture 1.

Comparative example 3

20 grams of phenolic resin with a weight average molecular weight of 4000 (m-cresol and p-cresol and 3,5-xylenol weight ratio are 45:45:10), 2 grams of photosensitizer BP PAC325 and 3 grams of BP PAC435, with Mix 75 grams of propylene glycol methyl ether acetate, add 500ppm of silicone type surfactant, mix well, obtain typical m/p/xylenol resin type photoresist.

Coat the photoresist prepared above evenly on a 10 cm × 10 cm glass substrate, bake on a 100°C hot plate for 60 seconds, then use Canon MPA 500F (it is the equipment model) to expose, and again the substrate Baked on a hot plate at 110°C for 60 seconds, then developed in (mass concentration) 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds, and measured the pattern state of 1.5 μm L/S with a scanning electron microscope (SEM). see picture 1.

Figure 1 shows that,

In Comparative Example 1, a typical photoresist used in a large display process cannot be used in a 1.5μm process due to severe image loss;

In Comparative Example 2, the high-resolution photoresist commonly used for large high-definition displays cannot be used in the 1.5μm process due to severe image loss;

In Comparative Example 3, the high-resolution photoresist used for mobile OLED displays has less severe image loss than the photoresist used for large displays, but outline clarity and resolution Not high, so it still cannot be used in 1.5μm process.

In contrast, in Example 1 of the present invention, it was confirmed that no image loss occurred, and a 1.5 μmL/S image could be clearly presented.

Experiments have shown that the chemically amplified photoresist composition prepared in Examples 2-9 of the present application and which can be used in the manufacturing process of flat panel displays can confirm that no image loss occurs, and can clearly present 1.5 μm L/S images.

Claims (7)

1. The chemically amplified photoresist composition that can be used for the flat panel display manufacturing process is characterized in that it is composed of a solid component and an organic solvent with a mass ratio of 10-30:100, and the solid component includes a film-forming resin and a photosensitizer and surfactants; The film-forming resin is at least one of the polymers shown in formulas III to XII;

In formula III～XII: R1 is selected from -H, -OH or -CH ₃ ; R2 is selected from -H, -OH or -CH ₃ ; The weight average molecular weight of the polymer represented by formula III-XII is 1000-20000. 2. composition according to claim 1 is characterized in that the quality of described film-forming resin accounts for 65%～80% of solid component quality, and the quality of photosensitizer accounts for 15%～30% of solid component quality; The mass of the agent accounts for 0.001% to 5% of the mass of the solid component. 3. The composition according to claim 1 or 2, characterized in that the photosensitizer is a photoacid generator, or is formed by mixing a diazoquinone photosensitizer and a photoacid generator in any mass ratio. 4. The composition according to claim 3, characterized in that the photoacid generator is any one of the compounds shown in formula 1 to formula 6:

5. The composition according to claim 3, characterized in that the diazoquinone photosensitizer is any one of the compounds described in formulas 7-10:

In formula 7 to formula 10, D is selected from formula 11 or formula 12:

6. The composition according to claim 1, characterized in that the surfactant is Si-Type: TEGO 440 or F-Type F-560. 7. composition according to claim 1 is characterized in that described organic solvent is (2-ethoxy ethyl) acetate, (2-methoxy ethyl) acetate, propylene glycol methyl ether acetate, At least one of propylene glycol monomethyl ether, ethyl lactate and butyl acetate.

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