Preparation method and application of photosensitive resin with aggregation-induced emission effect

Abstract

The application provides a preparation method and application of a photosensitive resin with an aggregation-induced emission effect, and the preparation method is as follows: a tetraphenyl ethylene with a carboxyl group is mixed and dissolved with allyl polyethylene glycol in an organic solvent; a dehydrating agent is added into the system and uniformly dissolved and stirred; after the reaction system is removed of air, nitrogen is introduced, and stirring is carried out at room temperature for 12-36h under anhydrous and oxygen-free environment; after the reaction is completed, filtration is carried out to remove by-products generated by the dehydrating agent, and the filtered product is collected; the filtered product is poured into a rotary evaporator, and residual organic solvents in the system are removed, so that the photosensitive resin tetraphenyl ethylene allyl polyethylene glycol ester is obtained. The preparation process is simple, by-products in the reaction process are easy to separate and remove, and the introduced rigid group can enhance the etching resistance and adhesion of the system; the photosensitive resin of the application is used to prepare a negative photoresist bottom antireflection coating, and after being cured to form a film, the photosensitive resin is more easy to increase the development effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of photoresist, in particular to a preparation method and application of a photosensitive resin with aggregation-induced emission effect. BACKGROUND

[0002] Photoresist, also known as photoresist, is a colloidal liquid formed by mixing photosensitive compounds, matrix resin and organic solvents, etc. After the photoresist is affected by a specific wavelength of light, its chemical structure changes, which changes the solubility of the photoresist in a certain specific solution, and there are positive and negative photoresists. The exposed part of the positive photoresist can be dissolved in the developer, and the unexposed part of the negative photoresist can be dissolved in the developer. The photoetching process can be divided into three main stages: light-resistant coating, alignment and exposure, and development. In the final development inspection process, find out the unqualified products of photoetching and development, and avoid the scrap of raw materials caused by subsequent etching. How to determine the uniformity of the coated glue and the thickness of the coated glue, the traditional process mainly observes through a microscope, and the ordinary development effect is poor and the resolution is low. The present application provides a preparation method and application of a photosensitive resin with aggregation-induced emission effect, which has the characteristics of fluorescent light and is used for negative photoresist BARC bottom anti-reflective coating, has stronger light absorption characteristics, and is easier to eliminate light reflected from the substrate to the photoresist, prevents impurities on the substrate from diffusing into the photoresist, and achieves the purpose of increasing the photoetching process window and improving the photoetching strip width control. SUMMARY

[0003] The technical problem to be solved is to provide a preparation method and application of a photosensitive resin with aggregation-induced emission effect, which adds tetraphenyl ethylene with carboxyl, introduces a rigid group, enhances the etching resistance and adhesion of the system, and is easier to eliminate light reflected from the substrate to the photoresist, prevents impurities on the substrate from diffusing into the photoresist.

[0004] Technical scheme: A photosensitive resin with aggregation-induced emission effect, comprising the following components in weight percentage:

[0005]

[0006] A preparation method of a photosensitive resin with aggregation-induced emission effect, the preparation method is as follows:

[0007] Step one: Dissolve tetraphenyl ethylene with carboxyl and allyl polyethylene glycol in an organic solvent;

[0008] Step two: Add a dehydrating agent to the system and dissolve and stir uniformly;

[0009] Step three: After removing air from the reaction system, introduce nitrogen, and stir at room temperature for 12-36 hours in anhydrous and oxygen-free environment.

[0010] Step four: after the reaction, filter to remove the by-products produced by the dehydrating agent, and collect the filtered product;

[0011] Step five: pour the filtered product of step four into a rotary evaporator, and remove the residual organic solvent in the system by rotating and vacuumizing for 0.5-1h at 60-80℃, to obtain the photosensitive resin tetraphenyl ethenyl-allyl polyethylene glycol ester.

[0012] Preferably, the tetraphenyl ethylene with carboxyl group includes monocarboxylic tetraphenyl ethylene, dicarboxylic tetraphenyl ethylene and tetracarboxylic tetraphenyl ethylene, whose structural formulas are shown in I, II and III respectively:

[0013]

[0014] Preferably, the molecular weight of the allyl polyethylene glycol ranges from 800 to 4000.

[0015] Preferably, the dehydrating agent is dicyclohexyl carbodiimide.

[0016] Preferably, the polymerization inhibitor is hydroquinone.

[0017] Preferably, the organic solvent includes any one or a combination of two or more of butyl acetate, dimethylbenzene, acetone and tetrahydrofuran.

[0018] Preferably, the water content in the anhydrous and anaerobic environment in step three should be less than 100ppm, and the oxygen content should be less than 100ppm.

[0019] Preferably, the photosensitive resin is applied in the field of photoresist.

[0020] Further, a negative photoresist with aggregation-induced emission effect applied in BARC bottom anti-reflective coating is prepared, which is composed of the photoresist prepolymer tetraphenyl ethenyl-allyl polyethylene glycol ester, the photoinitiator 2-isopropyl thioxanthone (ITX), the leveling agent diphenyl polysiloxane, the organic solvent propylene glycol methyl ether acetate (PMX), wherein the following ingredients are included in percentage by weight:

[0021]

[0022] The preparation steps are as follows:

[0023] Step one: dissolve the photosensitive resin tetraphenyl ethenyl-allyl polyethylene glycol ester prepared in the organic solvent propylene glycol methyl ether acetate (PMX);

[0024] Step two: add the leveling agent diphenyl polysiloxane and stir until uniform, stirring speed is 300-800 r / min, stirring time is 10-30 min;

[0025] Step three: add the photoinitiator 2-isopropylthioxanthone (ITX) to the reaction system in a light-proof environment and stir until uniform, stirring speed is 300-800 r / min, stirring time is 5-10 min, to obtain the negative photoresist with aggregation-induced emission effect for BARC bottom anti-reflective coating that can be used.

[0026] Advantages: the present application has the following advantages:

[0027] 1. The present application adds tetraphenyl ethylene with carboxyl, introduces rigid groups, which can enhance the etching resistance and adhesion of the system.

[0028] 2. The preparation process of the present application is simple, and the by-products obtained in the reaction process can be easily separated and removed. The photosensitive resin of the present application is used to prepare the negative photoresist BARC bottom anti-reflective coating, which can more easily eliminate the light reflected from the substrate to the photoresist and prevent impurities on the substrate from diffusing into the photoresist. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The GPC test data graph of the photosensitive resin tetraphenyl ethylene allyl polyethylene glycol ester prepared for Example 1;

[0030] Figure 2 The cured layer picture of the negative photoresist with aggregation-induced emission effect prepared for Example 1;

[0031] Figure 3 The fluorescence emission behavior graph of the cured coating of the negative photoresist with aggregation-induced emission effect prepared for Example 1 under ultraviolet lamp irradiation;

[0032] Figure 4 The scanning electron microscope microsurface morphology graph of the cured coating of the negative photoresist with aggregation-induced emission effect prepared for Example 1;

[0033] Figure 5 The fluorescence spectrum comparison graph of the cured coating of the negative photoresist of Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0034] The present application will be further described below in combination with the drawings and examples, and the following examples are an explanation of the present application and the present application is not limited to the following examples:

[0035] Example 1

[0036] A photosensitive resin with aggregation-induced emission effect, comprising the following components in percentage by weight:

[0037] Monocarboxy tetraphenyl ethylene 20wt%, allyl polyethylene glycol 35wt%, dehydrating agent dicyclohexyl carbodiimide 2.5wt%, polymerization inhibitor hydroquinone 0.1wt%, organic solvent butyl acetate 42.4wt%.

[0038] The preparation method is as follows:

[0039] Step one: dissolve monocarboxy tetraphenyl ethylene and allyl polyethylene glycol in organic solvent butyl acetate;

[0040] Step two: add dehydrating agent dicyclohexyl carbodiimide to the system and stir until uniform;

[0041] Step three: after removing air from the reaction system, introduce nitrogen, and stir at room temperature for 12h in anhydrous and oxygen-free environment;

[0042] Step four: after the reaction is completed, filter to remove byproduct dicyclohexyl urea generated by the dehydrating agent, and collect the filtered product;

[0043] Step five: pour the filtered product of step four into a rotary evaporator, remove the residual organic solvent in the system by rotating and vacuumizing at 60℃ for 0.5h, to obtain the photosensitive resin tetraphenyl vinyl-allyl polyethylene glycol ester.

[0044] A negative photoresist with aggregation-induced emission effect for BARC bottom anti-reflective coating, comprising the following components: photoresin prepolymer tetraphenyl vinyl-allyl polyethylene glycol ester prepared in this embodiment 30wt%, photoinitiator 2-isopropyl thioxanthone (ITX) 0.5wt%, leveling agent diphenyl polysiloxane 0.3wt%, organic solvent propylene glycol methyl ether acetate (PMX) 69.2wt%. The preparation steps are as follows:

[0045] Step one: dissolve the prepared photosensitive resin tetraphenyl vinyl-allyl polyethylene glycol ester in organic solvent propylene glycol methyl ether acetate (PMX);

[0046] Step two: add leveling agent diphenyl polysiloxane and stir until uniform, at a stirring speed of 300r / min for 10min;

[0047] Step three: in a light-proof environment, add photoinitiator 2-isopropyl thioxanthone (ITX) to the reaction system and stir to mix uniformly, at a stirring speed of 300r / min for 5min, to obtain the negative photoresist with aggregation-induced emission effect for BARC bottom anti-reflective coating.

[0048] Example 2

[0049] A photosensitive resin with aggregation-induced emission effect, comprising the following components by weight percentage:

[0050] p-Dicarboxy tetraphenyl ethylene 25wt%, allyl polyethylene glycol 25wt%, dehydrating agent dicyclohexyl carbodiimide 3wt%, polymerization inhibitor hydroquinone 0.3wt%, organic solvent xylene 46.7wt%.

[0051] The preparation method is as follows:

[0052] Step one: mix and dissolve p-dicarboxy tetraphenyl ethylene and allyl polyethylene glycol in organic solvent xylene;

[0053] Step two: add dehydrating agent dicyclohexyl carbodiimide to the system, dissolve and stir uniformly;

[0054] Step three: after removing air from the reaction system, introduce nitrogen, stir at room temperature for 20h in anhydrous and oxygen-free environment;

[0055] Step four: after the reaction is completed, filter to remove by-product dicyclohexyl urea generated by the dehydrating agent, and collect the filtered product;

[0056] Step five: pour the filtered product of step four into a rotary evaporator, remove the residual organic solvent in the system by rotating vacuum for 0.5h at 65℃, to obtain the photosensitive resin tetraphenyl ethylene-allyl polyethylene glycol ester.

[0057] A BARC bottom anti-reflective coating negative photoresist with aggregation-induced emission effect, its composition includes the photoresist prepolymer tetraphenyl ethylene-allyl polyethylene glycol ester prepared in this embodiment 35wt%, photoinitiator 2-isopropyl thioxanthone (ITX) 1wt%, leveling agent diphenyl polysiloxane 1wt%, organic solvent propylene glycol methyl ether acetate (PMX) 63wt%. The preparation steps are as follows:

[0058] Step one: dissolve the prepared photosensitive resin tetraphenyl ethylene-allyl polyethylene glycol ester in organic solvent propylene glycol methyl ether acetate (PMX);

[0059] Step two: add leveling agent diphenyl polysiloxane and stir uniformly, the stirring speed is 500r / min, and the stirring time is 15min;

[0060] Step three: in a light-proof environment, add photoinitiator 2-isopropyl thioxanthone (ITX) to the reaction system and stir to mix uniformly, the stirring speed is 500r / min, and the stirring time is 6min, to obtain the BARC bottom anti-reflective coating negative photoresist with aggregation-induced emission effect that can be used.

[0061] Example 3

[0062] A photosensitive resin with aggregation-induced emission effect, comprising the following components in weight percentage:

[0063] Tetracarboxy tetraphenyl ethylene 30wt%, allyl polyethylene glycol 35wt%, dehydrating agent dicyclohexyl carbodiimide 4.5wt%, polymerization inhibitor hydroquinone 0.4wt%, organic solvent acetone 30.1wt%.

[0064] The preparation method is as follows:

[0065] Step one: dissolve tetracarboxy tetraphenyl ethylene and allyl polyethylene glycol in organic solvent acetone;

[0066] Step two: add dehydrating agent dicyclohexyl carbodiimide to the system and stir until uniform;

[0067] Step three: after removing air from the reaction system, introduce nitrogen, and stir at room temperature for 30h in anhydrous and oxygen-free environment;

[0068] Step four: after the reaction is completed, filter to remove by-product dicyclohexyl urea generated by the dehydrating agent, and collect the filtered product;

[0069] Step five: pour the filtered product of step four into a rotary evaporator, remove the residual organic solvent in the system at 75°C under vacuum for 0.8h, and obtain the photosensitive resin tetracarboxy tetraphenyl ethylene-allyl polyethylene glycol ester.

[0070] A BARC bottom anti-reflective coating with aggregation-induced emission effect negative photoresist, the composition includes the photoresist prepolymer tetracarboxy tetraphenyl ethylene-allyl polyethylene glycol ester prepared in this embodiment 40wt%, photoinitiator 2-isopropyl thioxanthone (ITX) 1.5wt%, leveling agent diphenyl polysiloxane 1.5wt%, organic solvent propylene glycol methyl ether acetate (PMX) 57wt%. The preparation steps are as follows:

[0071] Step one: dissolve the photosensitive resin tetracarboxy tetraphenyl ethylene-allyl polyethylene glycol ester prepared in this embodiment in organic solvent propylene glycol methyl ether acetate (PMX);

[0072] Step two: add leveling agent diphenyl polysiloxane and stir until uniform, the stirring speed is 700r / min and the stirring time is 25min;

[0073] Step three, in the dark environment, add photoinitiator 2-isopropyl thioxanthone (ITX) to the reaction system and stir to mix evenly, the stirring speed is 650 r / min, the stirring time is 10 min, to obtain the negative photoresist with aggregation-induced emission effect for BARC bottom anti-reflective coating which can be used.

[0074] Example 4

[0075] A photosensitive resin with aggregation-induced emission effect, comprising the following components by weight percentage:

[0076] Tetracarboxy tetraphenyl ethylene 38wt%, allyl polyethylene glycol 25.5wt%, dehydrating agent dicyclohexyl carbodiimide 5wt%, polymerization inhibitor hydroquinone 0.5wt%, organic solvent tetrahydrofuran 31wt%.

[0077] The preparation method is as follows:

[0078] Step one: dissolve tetracarboxy tetraphenyl ethylene and allyl polyethylene glycol in organic solvent tetrahydrofuran;

[0079] Step two: add dehydrating agent dicyclohexyl carbodiimide to the system and dissolve and stir evenly;

[0080] Step three: after removing air from the reaction system, introduce nitrogen, and stir at room temperature for 36 h in anhydrous and oxygen-free environment;

[0081] Step four: after the reaction is completed, filter to remove by-product dicyclohexyl urea generated by the dehydrating agent, and collect the filtered product;

[0082] Step five: pour the filtered product of step four into a rotary evaporator, remove the residual organic solvent in the system at 80°C under vacuum for 1 h, to obtain the photosensitive resin tetraphenyl ethylene-allyl polyethylene glycol ester.

[0083] A negative photoresist with aggregation-induced emission effect for BARC bottom anti-reflective coating, which comprises tetracarboxy tetraphenyl ethylene-allyl polyethylene glycol ester 42wt% prepared by the method of the embodiment, photoinitiator 2-isopropyl thioxanthone (ITX) 2wt%, leveling agent diphenyl polysiloxane 2wt%, and organic solvent propylene glycol methyl ether acetate (PMX) 54wt%. The preparation steps are as follows:

[0084] Step one: dissolve the photosensitive resin tetracarboxy tetraphenyl ethylene-allyl polyethylene glycol ester prepared by the method of the embodiment in organic solvent propylene glycol methyl ether acetate (PMX);

[0085] Step two: add leveling agent diphenyl polysiloxane and stir evenly, the stirring speed is 800 r / min, and the stirring time is 30 min.

[0086] Step three, in the dark environment, add photoinitiator 2-isopropylthioxanthone (ITX) in the reaction system and stir to mix it evenly, the stirring speed is 800 r / min, the stirring time is 10 min, to get the BARC bottom anti-reflective coating with the application of the negative photoresist with aggregation-induced emission effect.

[0087] Comparative Example 1

[0088] The difference between the present comparative example and Example 1 is that the resin used for preparing the BARC bottom anti-reflective coating negative photoresist is a commercially available photosensitive resin epoxy acrylate (brand EBECRYL1710, manufacturer: Zhenxin Resin), specifically:

[0089] A BARC bottom anti-reflective coating negative photoresist, the composition includes epoxy acrylate 30wt%, photoinitiator 2-isopropylthioxanthone (ITX) 0.5wt%, leveling agent diphenyl polysiloxane 0.3wt%, organic solvent propylene glycol methyl ether acetate (PMX) 69.2wt%.

[0090] The preparation steps are as follows:

[0091] Step one: dissolve epoxy acrylate in organic solvent propylene glycol methyl ether acetate (PMX);

[0092] Step two: add leveling agent diphenyl polysiloxane and stir evenly, the stirring speed is 300 r / min, the stirring time is 10 min;

[0093] Step three, in the dark environment, add photoinitiator 2-isopropylthioxanthone (ITX) in the reaction system and stir to mix it evenly, the stirring speed is 300 r / min, the stirring time is 5 min, to get the BARC bottom anti-reflective coating with the application of the negative photoresist with aggregation-induced emission effect.

[0094] From Figure 1 It can be seen that the number average molecular weight, weight average molecular weight and molecular weight distribution of the photosensitive resin prepared in Example 1, Figure 2 and Figure 3 It can be seen that the photoresist prepared in Example 1 shows strong fluorescent light behavior, Figure 4 It can be seen that the cured coating of the negative photoresist prepared in Example 1 shows a flat and uniform morphology under a microscope, Figure 5 The fluorescence spectrum of the cured coating of the negative photoresist prepared in Example 1 and the cured coating of the negative photoresist prepared in Comparative Example 1 is compared, from the figure it can be seen that the cured coating obtained by the present application shows strong fluorescent light behavior.

[0095] Obviously, the above embodiments are merely example for clearly illustrating but not limitation to the embodiments. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, all the embodiments need not and can not be enumerated. The obvious changes or variations derived from the above description are still within the protection scope of the present application.

Claims

1. A photosensitive resin exhibiting aggregation-induced emission effect, characterized in that: By weight percentage, it includes the following components: 20-40 wt% of tetraphenylethylene with carboxyl groups Allyl polyethylene glycol 20~45wt% Dehydrating agent 1~5wt% Polymerization inhibitor 0.1~0.5wt% Organic solvent 30~50wt%; The tetraphenylethylene containing a carboxyl group includes monocarboxylated tetraphenylethylene, p-dicarboxylated tetraphenylethylene, and tetracarboxylated tetraphenylethylene, the structural formulas of which are shown in I, II, and III, respectively: Ⅰ； Ⅱ ； Ⅲ。 2. A method for preparing a photosensitive resin with aggregation-induced emission effect, characterized in that: The preparation method is as follows: Step 1: Dissolve tetraphenylethylene with carboxyl groups in an organic solvent, wherein the tetraphenylethylene with carboxyl groups includes monocarboxylated tetraphenylethylene, dicarboxylated tetraphenylethylene, and tetracarboxylated tetraphenylethylene, the structural formulas of which are shown in I, II, and III, respectively. Ⅰ； Ⅱ ； Ⅲ； Step 2: Add the dehydrating agent to the system and stir until dissolved and homogeneous; Step 3: After removing air from the reaction system, nitrogen gas is introduced, and the mixture is stirred at room temperature for 12–36 hours in an anhydrous and oxygen-free environment. Step 4: After the reaction is complete, filter to remove the byproducts generated by the dehydrating agent and collect the filtered product; Step 5: Pour the filtered product from Step 4 into a rotary evaporator and evacuate it at 60-80°C for 0.5-1 hours to remove residual organic solvents from the system, thus obtaining the photosensitive resin tetraphenylvinyl-allyl polyethylene glycol ester.

3. The photosensitive resin with aggregation-induced emission effect according to claim 1, characterized in that: The molecular weight range of the allyl polyethylene glycol is 800 to 4000.

4. The photosensitive resin with aggregation-induced emission effect according to claim 1, characterized in that: The dehydrating agent is dicyclohexylcarbodiimide.

5. The photosensitive resin with aggregation-induced emission effect according to claim 1, characterized in that: The polymerization inhibitor is hydroquinone.

6. The photosensitive resin with aggregation-induced emission effect according to claim 1, characterized in that: The organic solvent includes any one or a combination of two or more of butyl acetate, xylene, acetone, and tetrahydrofuran.

7. The method for preparing a photosensitive resin with aggregation-induced emission effect according to claim 2, characterized in that: In step three, the water and oxygen content in the anhydrous and oxygen-free environment should be less than 100 ppm and less than 100 ppm, respectively.

8. The application of the photosensitive resin according to claim 1 in the preparation of a negative photoresist with aggregation-induced emission effect for a BARC bottom anti-reflection coating, characterized in that: The negative photoresist comprises the following components by weight percentage: 30-48 wt% of the photosensitive resin as described in claim 1 Photoinitiator 2-isopropylthioxanthone 0.5–2 wt% Leveling agent: diphenyl polysiloxane 0.3–2 wt% Organic solvent propylene glycol methyl ether acetate 50-70 wt.

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