阅读说明：本技术 用于负性光刻胶的聚酰亚胺树脂及包含其的负性光刻胶 (Polyimide resin for negative photoresist and negative photoresist comprising same ) 是由 不公告发明人 于 2021-08-03 设计创作，主要内容包括：本申请提供了一种新型聚酰亚胺,其通过在惰性气体保护下,在催化剂、除水剂以及溶剂的存在下,使含咪唑基二胺、非含咪唑基二胺与二酐反应而得到。本申请还提供了由该新型聚酰亚胺制备得到的负性光刻胶。该负性光刻胶具备良好的灵敏度和分辨率。(The application provides a novel polyimide, which is obtained by reacting diamine containing imidazolyl and diamine not containing imidazolyl with dianhydride in the presence of a catalyst, a water removal agent and a solvent under the protection of inert gas. The application also provides a negative photoresist prepared from the novel polyimide. The negative photoresist has good sensitivity and resolution.)

1. A polyimide resin for a negative photoresist, wherein the polyimide resin has a chemical structure of formula I:

wherein x is 0.05 to 0.95, preferably 0.4 to 0.7; n is 5 to 200, preferably 8 to 60;

Ar₁、Ar₂each independently selected from the group consisting of:

R₁selected from the group consisting of: R₃selected from single bond, oxygen atom, sulfur atom, benzene ring, methylene, carbonyl, sulfuryl, isopropyl or trifluoro isopropyl,

R₂Selected from the group consisting of:

2. the polyimide resin for a negative photoresist of claim 1, wherein the chemical structure of the polyimide resin is:

3. a method of preparing a polyimide resin for a negative photoresist, comprising: under the protection of inert gas, in the presence of a catalyst, a water removal agent and a solvent, reacting diamine containing imidazolyl and diamine not containing imidazolyl with dianhydride to obtain the polyimide resin;

wherein the catalyst is selected from triethylamine, pyridine or isoquinoline;

the water removing agent is toluene;

the solvent is selected from the group consisting of: n, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, Propylene Glycol Methyl Ether Acetate (PGMEA), γ -butyrolactone;

the imidazole-containing diamine is selected from the group consisting of:

R₃selected from single bond, oxygen atom, sulfur atom, benzene ring, methylene, carbonyl, sulfuryl, isopropyl or trifluoro isopropyl,

4. The negative photoresist is characterized by comprising the following components in parts by weight:

100 parts by weight of a solvent;

10 to 30 parts by weight of the polyimide resin for a negative photoresist according to claim 1 or 2;

1 to 10 parts by weight of a photoacid generator, preferably an acid generator capable of generating sulfonic acid; and

0.1-2 parts of auxiliary agent.

5. The negative photoresist of claim 4, comprising, in parts by weight:

100 parts by weight of a solvent;

15 to 25 parts by weight of the polyimide resin for a negative photoresist according to claim 1 or 2;

1-9 parts by weight of a photoacid generator, preferably an acid generator capable of generating sulfonic acid; and

0.1-1 weight parts of assistant.

6. The negative photoresist of claim 4, wherein the solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, m-cresol, p-cresol, Propylene Glycol Methyl Ether Acetate (PGMEA), and γ -butyrolactone.

7. The negative photoresist of claim 4, wherein the photoacid generator is one or more selected from the group consisting of sulfonium salts, iodonium salts, triazines, sulfonate compounds, and p-toluenesulfonic acid derivatives.

8. The negative photoresist of claim 4, wherein the auxiliary is selected from one or more of a sensitizer, a antisolvent, and an acid quencher.

9. The negative photoresist of claim 4, wherein the auxiliary is selected from one or more of triethanolamine, tripentylamine, and tri-n-dodecylamine.

10. Use of the polyimide resin for a negative photoresist according to claim 1 or 2 in the preparation of a negative photoresist.

Technical Field

The invention relates to the technical field of polymers, in particular to polyimide resin for a negative photoresist and the negative photoresist comprising the polyimide resin.

Background

The polyimide material is a functional material with excellent performance, particularly high temperature resistance, insulating property and dielectric property, so that the polyimide material is widely applied to the fields of military industry and aerospace; polyimide is widely used in the field of microelectronics as a consumer product, in which photosensitive polyimide (PSPI) is used as a buffer layer, a passivation layer, and an α -particle barrier layer of an integrated circuit. Polyimide for photoresist has become one of the three main applications of polyimide in parallel with polyimide films and polyimide liquid crystal alignment agents.

Polyimide is mainly classified into a photodegradable type (positive resist) and a photocrosslinkable type (negative resist) as a photoresist, and currently commercially available photocrosslinkable polyimides are mainly classified into Hitachi-DuPont HD4000 series of Hitachi, Photoneece of Toray, and Durimide7000 series of Fuji. The technical route of the negative photoresist is that a precursor of polyamic acid is connected with a lateral group of acrylate, and after illumination, double bonds of the acrylate are opened under the action of an initiator to generate crosslinking, so that a crosslinking structure is formed and cannot be dissolved and removed by a developing solution to form a pattern.

However, as described above, the mainstream design concept of polyimide negative photoresist in the prior art is mainly to introduce acrylate or allyl double bond, and to use a sensitized benzophenone dianhydride system, and the formed cross-linked structure thereof can cause the activity and the movement capability of the photo-acid generator to be limited by the main polymer chain, which results in low sensitivity and poor resolution of the negative photoresist, and affects the product quality.

Therefore, it is very necessary to provide a new polyimide negative photoresist to achieve higher sensitivity and resolution.

Disclosure of Invention

In order to solve the above problems, a first aspect of the present invention provides a polyimide resin for a negative photoresist, wherein the polyimide resin has a chemical structure of the following formula I:

wherein x is 0.05 to 0.95, preferably 0.4 to 0.7; n is 5 to 200, preferably 8 to 60;

Ar₁、Ar₂each independently selected from the group consisting of:

R₁selected from the group consisting of: R₃selected from single bond, oxygen atom, sulfur atom, benzene ring, methylene, carbonyl, sulfuryl, isopropyl or trifluoro isopropyl,

R₂Selected from the group consisting of:

preferably, the chemical structure of the polyimide resin is:

a second aspect of the present invention provides a method of preparing a polyimide resin for a negative photoresist, comprising: under the protection of inert gas, in the presence of a catalyst, a water removal agent and a solvent, reacting diamine containing imidazolyl and diamine not containing imidazolyl with dianhydride to obtain the polyimide resin;

wherein the catalyst is selected from triethylamine, pyridine or isoquinoline;

the water removing agent is toluene;

the solvent is selected from the group consisting of: n, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, Propylene Glycol Methyl Ether Acetate (PGMEA), γ -butyrolactone;

the imidazole-containing diamine is selected from the group consisting of:

R₃selected from single bond, oxygen atom, sulfur atom, benzene ring, methylene, carbonyl, sulfuryl, isopropyl or trifluoro isopropyl,

A third aspect of the invention provides a negative photoresist comprising, in parts by weight:

100 parts by weight of a solvent;

10 to 30 parts by weight of the polyimide resin for a negative photoresist according to claim 1 or 2;

1 to 10 parts by weight of a photoacid generator, preferably an acid generator capable of generating sulfonic acid; and

0.1-2 parts of auxiliary agent.

Preferably, the negative photoresist comprises the following components in parts by weight:

100 parts by weight of a solvent;

15 to 25 parts by weight of the polyimide resin for a negative photoresist according to claim 1 or 2;

1-9 parts by weight of a photoacid generator, preferably an acid generator capable of generating sulfonic acid; and

0.1-1 weight parts of assistant.

In one embodiment, the solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, m-cresol, p-cresol, Propylene Glycol Methyl Ether Acetate (PGMEA), and γ -butyrolactone.

In one embodiment, the photoacid generator is selected from one or more of sulfonium salts, iodonium salts, triazines, sulfonate compounds, and p-toluenesulfonic acid derivatives.

In one embodiment, the adjuvant is selected from one or more of a sensitizer, a antisolvent, and an acid quencher.

In one embodiment, the adjuvant is selected from one or more of triethanolamine, tripentylamine, and tri-n-dodecylamine.

A fourth aspect of the invention provides use of the polyimide resin for a negative photoresist according to claim 1 or 2 for producing a negative photoresist.

The invention has the beneficial technical effects that:

the novel negative polyimide photoresist can be obtained by matching the novel polyimide resin and the photoacid generator. After spin coating exposure, the photoacid generator generates protons to protonate the imidazole groups, the solubility of the polyimide resin in a solvent is greatly reduced, and a negative resist image is obtained during development. Different from polyimide resin which is sold in the market and has two negative photoresist systems of side chain grafted vinyl and benzophenone as the main chain, the photo-acid generator has good solubility and is uniformly distributed in a photoresist coating film, and the activity and the movement capability are not limited by the main chain of the polymer, so the negative polyimide photoresist related by the invention has high sensitivity and good resolution.

Drawings

FIG. 1 is an infrared spectrum of a polyimide resin according to one to eight examples of the present invention.

FIG. 2 is a photoresist pattern of a negative photoresist according to a first embodiment of the invention.

FIG. 3 is a photolithography pattern of a negative photoresist according to a second embodiment of the present invention.

FIG. 4 is a photolithography pattern of a negative photoresist of example three of the present invention.

FIG. 5 is a photoresist pattern of a negative photoresist of example four of the present invention.

FIG. 6 is a photolithography pattern of a negative photoresist of example five of the present invention.

Figure 7 a photolithography pattern of a negative photoresist of example six of the present invention.

Fig. 8 is a photolithography pattern of a negative photoresist according to a seventh embodiment of the present invention.

Fig. 9 a photoresist pattern of a negative photoresist of example eight of the invention.

Detailed Description

The first embodiment is as follows:

a dry clean glass bottle was charged with NMP solvent 50ml, purged with nitrogen, followed by 4.92g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (12mmol) and 1.344 g (6mmol) of 2- (4-aminophenyl) -5-aminobenzimidazole, after all dissolved, 3.860g (17.7mmol) of pyromellitic dianhydride was slowly added in portions, reacted at room temperature and kept under stirring for 12 hours, toluene was slowly added dropwise, warmed to 160 ℃ and stirred for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 6 hours to obtain polyimide resin containing imidazolyl;

2g of the dried polyimide resin is dissolved in 10ml of a solvent gamma-butyrolactone, 0.2g of acid generator TME-triazine is added, and 0.05g of triethanolamine is dissolved uniformly to prepare a sample No. 1 to be tested.

The chemical structure of the polyimide resin is as follows:

example two:

in a dry clean glass bottle 70ml of NMP solvent are added, nitrogen is passed for protection, then 0.82g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (2mmol) and 6.656 g (16mmol) of 2,2 ' -bis (4-aminophenyl) -5,5 ' -biphenylimidazole are added, after complete dissolution 7.734g (17.4mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride are slowly added in portions, the reaction is carried out at room temperature and stirring is maintained for 12 hours, toluene is slowly added dropwise, the temperature is raised to 160 ℃ and stirring is continued for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 8 hours to obtain polyimide resin containing imidazolyl;

2g of the dried polyimide resin is dissolved in 10ml of NMP solvent, 0.4g of acid generator PIW-501(Heraeus) is added, and 0.1g of tripentylamine is uniformly dissolved to prepare a sample No. 2 to be detected.

The chemical structure of the polyimide resin is as follows:

example three:

after adding 60ml of NMP solvent into a dry and clean glass bottle and introducing nitrogen for protection, 1.44g of 2,2 ' -bis-trifluoromethyl-4, 4' -benzidine (5.4mmol) is added until all is dissolved, 2.353g (5.3mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride are slowly added in portions and stirred at room temperature for 2 hours; then 2.75g (6.6mmol) of 2,2 '-bis (3-aminophenyl) -5, 5' -biphenylimidazole and 1.973g (6.1mmol) of 3,3', 4' -benzophenonetetracarboxylic dianhydride were added thereto, and the reaction was continued at room temperature while maintaining stirring for 12 hours, and toluene was slowly added dropwise while warming to 160 ℃ and the stirring was continued for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 8 hours to obtain polyimide resin containing imidazolyl;

2g of the dried polyimide resin is dissolved in 10ml of NMP solvent, then 0.5g of acid generator trifluoromethyl sulfonic acid group triphenyl sulfonium salt is added, and 0.1g of tripentylamine is uniformly dissolved to prepare a sample No. 3 to be tested.

The chemical structure of the polyimide resin is as follows:

example four:

after adding 50ml of gamma-butyrolactone as a solvent into a dry and clean glass bottle, introducing nitrogen for protection, adding 1.4g (7.0mmol) of 4,4' -diaminodiphenyl ether and 2.912g (7.0mmol) of 2,2 ' -dibenzoimidazole benzidine, after all the components are dissolved, slowly adding 5.639g (12.7mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride in portions, reacting at room temperature and keeping stirring for 12 hours, slowly adding toluene dropwise, heating to 160 ℃, and continuing stirring for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 8 hours to obtain polyimide resin containing imidazolyl;

2g of the dried polyimide resin is dissolved in 10ml of NMP solvent, then 0.8g of acid generator trifluoromethyl sulfonic acid group triphenyl sulfonium salt is added, and 0.1g of tri-n-dodecylamine is uniformly dissolved to prepare a sample No. 4 to be tested.

The chemical structure of the polyimide resin is as follows:

example five:

40ml of solvent PGMEA was added to a dry clean glass bottle, nitrogen protected, followed by 0.16g of 2,2 ' -bis trifluoromethyl-4, 4' -benzidine (0.5mmol) and 3.952g (9.5mmol) of 2,2 ' -bis (4-aminophenyl) -5,5 ' -biphenylimidazole, after complete dissolution 4.396g (9.9mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride were slowly added in portions, reacted at room temperature and kept stirring for 8 hours, toluene was slowly added dropwise, warmed to 160 ℃ and stirred for 12 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 8 hours to obtain polyimide resin containing imidazolyl;

2g of the dried polyimide resin is dissolved in 10ml of NMP solvent, 0.8g of acid generator TME-triazine and 0.05g of tri-n-dodecylamine are added and uniformly dissolved to prepare a sample No. 5 to be tested.

The chemical structure of the polyimide resin is as follows:

example six:

a dry clean glass bottle was charged with NMP (50 ml solvent), nitrogen purged, 5.166g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (12.6mmol) was added, 2.747g (12.6mmol) of phthalic anhydride was added, and after stirring at room temperature for 2 hours, 2.246g (5.4mmol) of 2,2 '-dibenzoimidazolbiphenylamine was added and, after complete dissolution, 1.674g (5.4mmol) of 4,4' -oxydiphthalic anhydride was slowly added in portions, reacted at room temperature and kept stirring for 12 hours, toluene was slowly added dropwise, and the temperature was raised to 160 ℃ and stirring was continued for 12 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 6 hours to obtain polyimide resin containing imidazolyl;

3g of the dried polyimide resin is dissolved in 15ml of gamma-butyrolactone solvent, 0.5g of acid generator PIW-501(Heraeus) is added, and 0.05g of tri-n-dodecylamine is uniformly dissolved to prepare a sample No. 6 to be tested.

The chemical structure of the polyimide resin is as follows:

example seven:

30ml of NMP solvent is added into a dry and clean glass bottle, nitrogen is introduced for protection, then 1.813g (3.5mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane and 2.21g (6.5mmol) of 1, 4-bis (5-aminobenzimidazole) benzene are added, after all the solvent is dissolved, 3.157g (9.8mmol) of 3,3', 4' -benzophenone tetracarboxylic dianhydride are slowly added in portions, the reaction is carried out at room temperature and the stirring is kept for 12 hours, toluene is slowly added dropwise, the temperature is raised to 160 ℃, and the stirring is continued for 12 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 6 hours to obtain polyimide resin containing imidazolyl;

2g of the dried polyimide resin is dissolved in 10ml of a solvent gamma-butyrolactone, 0.2g of acid generator N-hydroxyphthalimide-p-methylbenzenesulfonate and 0.01g of tri-N-dodecylamine are added and uniformly dissolved to prepare a sample No. 7 to be tested.

The chemical structure of the polyimide resin is as follows:

example eight:

a dry clean glass bottle was charged with 60ml of solvent GBL, purged with nitrogen, followed by 2.92g of 1, 3-bis (4-aminophenoxy) benzene (10mmol) and 4.32g (10mmol) of 4,4 '-bis (5-aminobenzimidazolyl) diphenyl ether, after complete dissolution 8.821g (19.87mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride was slowly added in portions, reacted at room temperature and kept under stirring for 12 hours, and toluene was slowly added dropwise, warmed to 160 ℃ and stirred for 12 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 6 hours to obtain polyimide resin containing imidazolyl;

2g of the dried polyimide resin is dissolved in 10ml of a solvent gamma-butyrolactone, 0.2g of acid generator N-hydroxyphthalimide-p-methylbenzenesulfonate and 0.02g of tri-N-dodecylamine are added and uniformly dissolved to prepare a sample No. 8 to be tested.

The chemical structure of the polyimide resin is as follows:

comparative example 1

Imidazole polyimide homopolymer: in a dry clean glass bottle 60ml of NMP solvent were added, nitrogen was passed through for protection, followed by 4.32g (10mmol) of 4,4 '-bis (5-aminobenzimidazolyl) diphenyl ether, after complete dissolution 4.18g (9.68mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride were added slowly in portions, reacted at room temperature and kept stirring for 12 hours, and toluene was slowly added dropwise, warmed to 160 ℃ and stirred for 12 hours. Precipitating the obtained polymer solution into methanol, stirring and washing the solution, and drying the solution in a vacuum oven for 6 hours to obtain polyimide resin containing imidazolyl;

2g of the dried polyimide resin is dissolved in 20ml of NMP solvent, 0.3g of acid generator N-hydroxyphthalimide-p-methylbenzenesulfonate and 0.01g of tri-N-dodecylamine are added and uniformly dissolved to prepare a to-be-detected reference sample No. 9.

The chemical structure of the polyimide resin is as follows:

comparative example No. two

Polyimide homopolymer without imidazole group: after completely dissolving 4,4 '-diaminodiphenyl ether (3.092 g, 6.97mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride (3.092 g) is added in portions slowly, the reaction is carried out at room temperature and stirring is maintained for 12 hours, toluene is slowly added dropwise, and the stirring is continued for 10 hours after the temperature is raised to 160 ℃. The obtained polymer solution is precipitated into methanol, stirred and washed, and dried in a vacuum oven for 8 hours to obtain polyimide resin containing imidazolyl, 2g of the dried resin is dissolved in 10ml of solvent NMP, then 0.8g of acid generator trifluoromethyl sulfonic acid group triphenyl sulfonium salt is added, and 0.05g of tri-n-dodecylamine is uniformly dissolved to prepare a sample No. 10 to be tested.

The chemical structure of the polyimide resin is as follows:

the above examples one to eight and comparative examples one and two were subjected to performance tests, and the results were as follows:

test method

1. The polymer was tested for infrared spectroscopy (FT-IR) using a Perkin-Elmer Paragon 1000 Fourier transform infrared spectrophotometer to verify its chemical structure.

2. Thickness, photosensitivity and resolution test: and under the condition of 800-. The exposure intensity is 1500mJ/cm by using i-line 365 nanometer exposure²5% -60% gray mask plate, developing in cyclopentanone/NMP (1:1) mixed solution, tetrahydrofuranFixing to obtain a photoetching pattern; thickness, sensitivity and resolution were observed under an olympus metallographic microscope.

Test results

The test results are shown in the following table I

TABLE-comparison of thickness, sensitivity and resolution of samples after Photoresist spin-on Exposure

As can be seen from the above table and fig. 2 to 9, compared with the first and second comparative examples, the photoresist of the present invention achieves significantly better technical effects in terms of sensitivity and resolution, and achieves significant technical progress.