CN106054523A - Double response type degradable photoresist as well as preparation method and use method therefor - Google Patents

Abstract

The invention relates to a dual-response degradable photoresist, a preparation method and a use method thereof. The present invention uses molecules capable of cross-linking and de-cross-linking under different wavelengths of ultraviolet light as cross-linking agents to realize cross-linking and de-cross-linking of photoresist by irradiation with different wavelengths of ultraviolet light; a hydrolyzable structure is used as a polymer skeleton , can degrade in alkaline aqueous solution with pH>7 at room temperature, and finally obtain small molecules soluble in water. The photoresist system is obtained by mixing crosslinking agent, photoinitiator, active monomer and linking molecule, and then this photoresist is applied to nanoimprinting, which shows excellent imprinting performance and degradation performance, and solves the problem of The problem of photoresist damage to the template. In addition, it is also environmentally friendly and is an environmentally friendly degradable photoresist.

Description

A dual-response degradable photoresist and its preparation method and use method

technical field

The invention relates to a dual-response degradable photoresist, a preparation method and a use method thereof.

Background technique

With the advancement of science and technology, human society has entered the information age, and various communication devices and mobile terminals emerge in an endless stream. Multi-function, small size, and easy portability are the main directions of development. Integrated circuit (IC), as an important part of electronic equipment, directly affects its application and development, and the traditional photolithography technology for preparing integrated circuits cannot meet the requirements of producing higher integrated ICs due to various limitations. In 1995, the University of Houston, USA Professor Zhou Yu invented the low-cost, high-efficiency and high-resolution nanoimprint technology.

The main components of the nanoimprint process are the template (stamp), photoresist and substrate. The template is expensive, and the photoresist is in contact with the template throughout the process, which directly affects the service life of the template. At present, photoresists are mainly divided into three types: thermoplastic, thermosetting and ultraviolet curing. Among them, thermoplastic nanoimprinting adhesive is composed of polymers, which are heated above the glass transition temperature (T _g ) before imprinting to increase molecular mobility. Then the template is embossed on the polymer composition, and after cooling and solidification, the embossed pattern is obtained by demolding, so the pressure required is relatively high, and the template is seriously damaged; the main component of the thermosetting nano-imprinting adhesive is a prepolymer. Polymerization and curing, so the adhesion to the template is strong, the residual glue of the template is serious, and the damage is serious; the main components of the UV-curable photoresist are photopolymerizable monomers, resins and photoinitiators, and the reaction conditions are mild and the reaction The speed is fast and has received widespread attention, but it also faces the problem of damage to the template by residual glue.

In order to solve the interface problem between the photoresist and the template, the current main methods are: adding fluorine to the photoresist (such as the article Lin H, Wan X, Jiang X, et al.Journal of Materials Chemistry, 2012, 22 (6): 2616-2623) and silicon-containing (such as the article Choi P, Fu PF, Guo L J. Advanced Functional Materials, 2007, 17(1): 65-70), reduce the surface energy of the photoresist, Thereby reduce the interactive force between photoresist and template, but antisticking effect is limited, also reduced the adhesive force between photoresist and base material simultaneously, easily occurs debonding phenomenon; To template (as patent CN10103576447A) and The surface of the photoresist (such as patent CN102604454A) is processed so that its surface is connected with fluorine-containing groups to reduce the interaction force, but the process is complicated and the cost is high; prepare acid-degradable photoresist (such as article Hu, XinYang, Tao Gu, Ronghua Cui.Journal of Materials Chemistry C, 2014 2(10):836-842), the main principle is that the photoacid generator generates H ⁺ under ultraviolet light, and the crosslinking point is broken under heating conditions, increasing Its solubility in organic solvents, however, requires high temperature conditions for degradation, and acid damages the template protective layer; preparation of thermally degradable photoresists (such as articles Wiriya, Thongsomboon, Mark Sherwood, Noel Arellano, ACS MacroLetters.2013 2 (1): 19-22), the principle is that the crosslinking point breaks under heating conditions, which increases the solubility of photoresist in organic solvents, but the use of high temperature conditions limits its applicable range; preparation of reversible photoresist Glue (such as patent CN101957559A), using monomers that can cross-link and de-cross-link under different ultraviolet wavelengths as a cross-linking agent in the side chain, controls the degree of cross-linking through ultraviolet light, so as to control its dissolution in organic solvents performance, but its decrosslinking degree is limited, and after decrosslinking, it is still a macromolecule, and the dissolution effect is not obvious.

The above methods reduce the damage of the photoresist to the template to a certain extent, but there are still the following problems, such as heating limits the application range, low reversibility makes the degradation not obvious, and the use of organic solvents pollutes the environment and so on. Therefore, there is an urgent need for a photoresist that can rapidly degrade at room temperature and is environmentally friendly.

Contents of the invention

The present invention aims to provide a dual-response degradable photoresist and its preparation method and use method. The present invention uses molecules capable of cross-linking and de-cross-linking under different wavelengths of ultraviolet light as cross-linking agents, through different wavelengths of ultraviolet light Photoresist is crosslinked and decrosslinked by light irradiation; a hydrolyzable structure is used as the polymer skeleton, which can be degraded in an alkaline aqueous solution with pH>7 at room temperature, and finally small molecules soluble in water are obtained. The photoresist system is obtained by mixing crosslinking agent, photoinitiator, active monomer, linking molecule and solvent, and then this photoresist is applied to nanoimprinting, which shows excellent imprinting performance and degradation performance, and is well The problem of photoresist damage to the template is solved. In addition, it is also environmentally friendly and is an environmentally friendly degradable photoresist.

The composition and mass parts of a kind of dual response type degradable photoresist provided by the present invention are:

A reversible crosslinking agent 10-40 parts, preferably 10-25 parts

B active monomer 5-30 parts, preferably 5-20 parts

10-30 parts of C linking molecules, preferably 10-20 parts

D photoinitiator 1-5 parts, preferably 1-3 parts

E organic solvent 0-60 parts, preferably 40-60 parts

The above-mentioned active monomer B is an acid anhydride with two double bonds, preferably selected from one of the following substances or a mixture thereof: acrylic anhydride, methacrylic anhydride, 4-pentene anhydride, butenoic anhydride, citric anhydride, 3 - Methyl-2-butyric anhydride or 2-hexenoic anhydride. More preferred is acrylic anhydride, 4-pentene anhydride or crotene anhydride.

The linker C above is a thiol with two or more mercapto groups, preferably one or a mixture of the following substances: 1,2-ethanedithiol, 1,4-butanedithiol, 1, 3-propanedithiol, 2-hydroxy-1,3-propanedithiol, 1,6-hexanedithiol, 1,6-dimercapto-3-hexanethiol, 1,8-octanedithiol , 3,6-dioxa-1,8-octanedithiol, 1,9-nonanedithiol, 3,7-dithia-1,9-nonanedithiol, 2,6-naphthalene dithiol, 4,4'-dimercaptodiphenyl ether, ethylene glycol dimercaptoacetate, 2-methyl-1,2,3-propanetriol tris(3-mercaptopropionic acid), trimethylol propane tris(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionic acid). Further preferred are 3,6-dioxa-1,8-octanedithiol, 1,6-dimercapto-3-hexylsulfide, 3,7-dithia-1,9-nonaneedithiol or 1,8-octanedithiol.

Above-mentioned photoinitiator D is selected from one or their mixtures in the photoinitiator commonly used in the following art: α-hydroxyketone (such as: 1-hydroxyl-cyclohexyl benzophenone, 2-hydroxyl-2-methyl-1 -phenylacetone or 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenylacetone), benzil (such as: α,α'-dimethylbenzil ketal), acylphosphine Oxides (such as: 2,4,6-trimethylbenzoyldiphenylphosphine oxide or 2,4,6-trimethylbenzoylphenyl phosphate ethyl ester).

The above-mentioned organic solvent E is selected from one of the following substances or a mixture thereof: acetone, chloroform, dichloromethane, ethanol, isopropanol, n-butanol, ethyl acetate, cyclohexane 1,4-diox six rings. The organic solvent is an optional component. When the reversible cross-linking agent is completely soluble in the linking molecule and the active monomer, no organic solvent can be added.

The preparation method of above-mentioned reversible cross-linking agent A of the present invention is:

(1) Preparation of a reversible cross-linking agent body with two hydroxyl groups:

Mix glucinol substances, ethyl acetoacetate substances, catalysts and solvents with a molar ratio of 1:(1-5):(0.1-1), heat to 30-90°C, and stir for 3-12 hours. Then wash, filter, and dry in vacuum to obtain a reversible cross-linking agent body with two hydroxyl groups.

Glycinols are selected from: phloroglucinol, pyrogallol, 1,2,4-glucinol, 2,4,6-trihydroxytoluene, 2,4,6-trihydroxypropiophenone, 2 , 4-dihydroxybenzyl alcohol, 3,4-dihydroxybenzyl alcohol or 3,4,5-trihydroxytoluene. More preferred are phloroglucinol, pyrogallol, or 1,2,4-pyrogallol.

Ethyl acetoacetate substances are selected from: ethyl acetoacetate, ethyl trifluoroacetoacetate, ethyl 2-fluoroacetoacetate, ethyl 4-chloroacetoacetate, ethyl 2-methylacetoacetate, 4-bromoacetyl Ethyl acetate, chloroethyl 2-acetylacetate, n-propyl acetoacetate, ethyl propionyl acetate, methyl 3-oxopropionate, ethyl 3-oxopropionate, ethyl fluoropropionyl acetate Or 3-chloro-2-methyl-3-oxopropanoic acid ethyl ester. Further preferred is ethyl acetoacetate, ethyl 2-methylacetoacetate, ethyl 2-fluoroacetoacetate or ethyl 4-chloroacetoacetate.

The catalyst is selected from: 70-98% concentrated sulfuric acid, 85-98% phosphoric acid, 31-36% hydrochloric acid, p-toluenesulfonic acid, iodine, sulfamic acid, silver trifluoromethanesulfonate, methanesulfonic acid, sodium bisulfate, three Fluoroacetic acid, oxalic acid, benzenesulfonic acid, or ceric ammonium nitrate. More preferably 70-98% concentrated sulfuric acid, 85-98% phosphoric acid, iodine or p-toluenesulfonic acid.

The solvent is selected from: deionized water, 1,4-dioxane, acetone, toluene, methanol, cyclohexane, dichloromethane, tetrahydrofuran, acetonitrile or chloroform.

(2) Preparation of a reversible cross-linking agent body with two long-chain hydroxyl groups:

Mix the reversible crosslinking agent main body with two hydroxyl groups in the above (1), halohydrin and acid binding agent with the solvent in a molar ratio of 1:(2~5):(4~10), and heat to 60~ 100°C, condensed and refluxed, stirred and reacted for 12 to 48 hours. The acid-binding agent was removed by filtration and dried to obtain the main body of the reversible cross-linking agent with two long-chain hydroxyl groups.

Above-mentioned haloalcohol is selected from: 2-bromoethanol, 2-(2-bromoethoxy)ethanol, 2-chloroethanol, 2-(2-chloroethoxy)ethanol, 3-bromopropanol, 2-bromoethanol -1-propanol, 3-bromo-2-methyl-1-propanol, 3-bromo-2,2-dimethyl-1-propanol, 3-chloro-1-propanol, 1-chloro- 2-propanol, 3-chloro-2,2-dimethyl-1-propanol, 4-bromobutanol, 4-iodo-1-butanol, 4-chloro-1-butanol, 5-bromopentyl alcohol, 5-chloro-1-pentanol, 6-bromohexanol or 6-chloro-1-hexanol. Further preference is given to 2-bromoethanol, 3-bromopropanol, 4-bromobutanol, 5-bromopentanol or 6-bromohexanol.

The acid-binding agent is selected from: anhydrous potassium carbonate, anhydrous sodium carbonate, sodium hydroxide, potassium hydroxide, potassium iodide, triethylamine or pyridine.

The solvent is selected from: acetone, dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetonitrile, tetrahydrofuran or toluene.

(3) Preparation of a reversible cross-linking agent with two double bonds:

Mix the main body of the reversible crosslinking agent with two hydroxyl groups in step (1) or two long-chain hydroxyl groups in step (2), and the catalyst in a molar ratio of 1:(2~5) with a solvent, and heat it at 30~80°C Stir and mix evenly, then cool the mixture to 0°C, then slowly add acid chloride compounds with a molar equivalent of 2 to 5 into the mixture, stir and react for 1.5 to 6 hours, and control the reaction temperature to 0±2°C. After the reaction is completed, the reversible cross-linking agent with two double bonds is obtained by filtering, washing and vacuum drying.

Acyl chloride compounds are selected from: acryloyl chloride, methacryloyl chloride, 2-fluoroacryloyl chloride, crotonoyl chloride, 3-methylcrotonoyl chloride, (E)-2-methyl-2-butenoyl chloride, fumaric acid mono Acetyl chloride, 4-pentenoyl chloride, 3-ethoxyacryloyl chloride, (E)-2-heptenoyl chloride or trans-8-methyl-6-nonanoyl chloride. More preferred: acryloyl chloride, methacryloyl chloride, crotonoyl chloride, 3-methylcrotonoyl chloride or (E)-2-methyl-2-butenoyl chloride.

The catalyst is selected from: triethylamine, pyridine, anhydrous potassium carbonate or anhydrous sodium carbonate.

The solvent is selected from: tetrahydrofuran, dichloromethane, chloroform, acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, toluene, cyclohexane or 1,4-dioxane ring.

The preparation method of a dual-response degradable photoresist provided by the present invention is: dissolving the reversible crosslinking agent A with two double bonds, the active monomer B, the linking molecule C, and the photoinitiator D in proportion to the organic In solvent E, stir and mix uniformly under the condition of avoiding light, and obtain it by filtration. The filter pore size is preferably 0.2-2 μm.

A method for using a dual-response degradable photoresist provided by the present invention is as follows: coating the photoresist on the substrate to form a photoresist film, placing it on an embossing machine for embossing, /cm ² ) UV exposure (2 to 10 minutes), the photoresist is cured and molded, and the mold is released, and the imprinted pattern of the photoresist is obtained on the substrate, and then the pattern is transferred to the substrate (such as: ion etching or stripping technology), and then exposed to 254nm (14-25mw/cm ² ) ultraviolet light (10-30 minutes), soak the substrate in an alkaline aqueous solution with a pH of 9-12 (such as sodium hydroxide or potassium hydroxide aqueous solution) Remove photoresist.

Expose the imprinted template to 254nm (14-25mw/cm ² ) ultraviolet light (10-30 minutes), and then soak it in an alkaline aqueous solution with a pH of 9-12 (such as sodium hydroxide or potassium hydroxide aqueous solution) to remove residual photoresist on the template.

The photoresist removal process of the substrate and the template can be performed separately or together.

The double-response degradable photoresist prepared by the present invention overcomes the problem of difficult template cleaning, and can be treated by ultraviolet light (254nm) and alkaline water (pH>7), so that the crosslinking point and the main chain are broken at the same time, so as to promote the formation of the template. The rapid dissolution of residual glue improves the service life and efficiency of the template. In addition, cleaning with an aqueous solution reduces environmental pollution. This photoresist can also be applied to the preparation of micro-nano patterns under other special conditions, such as the preparation of flexible circuits.

Description of drawings

Fig. 1 is the schematic diagram of the degradation reaction of photoresist of the present invention;

Figure 1(a) shows the photoresist network structure after cross-linking and curing. After being treated with 254nm ultraviolet light, the cross-linking points are broken, and the linear molecules shown in Figure 1(b) are obtained, and then treated with alkaline water to obtain the graph. 1(c) shows a water-soluble small molecule.

Fig. 2 is the miniature pattern prepared by embodiment 1;

Figure 2(a) and Figure 2(c) are imprint templates (20×20μm square grooves, line width 20μm stripes), and Figure 2(b) and Figure 2(d) are corresponding photoresist imprinting Graphics (square cylinders of 20×20 μm, stripes with a line width of 20 μm).

detailed description:

Example 1:

(1) Preparation of a reversible cross-linking agent body with two hydroxyl groups

Take 7.2g of phloroglucinol, add it to 20ml of 85% phosphoric acid solution, stir evenly, heat to 60°C, add 5.6ml of ethyl acetoacetate dropwise, and continue stirring until completely dissolved. Keep warm for 2 hours and stir at room temperature for 6 hours. After the reaction is completed, filter with filter paper and wash with a large amount of deionized water until the solution is neutral. Dry in vacuo to obtain a light yellow solid powder, which is the main body of a reversible cross-linking agent with two hydroxyl groups.

(2) Preparation of a reversible cross-linking agent with two double bonds

Take 4.3g of the product in (1) above and 4.6g of triethylamine, add it to 50ml of tetrahydrofuran solution, heat to 60°C, and stir for 30 minutes. The temperature was lowered to 0° C., 4.5 g of acryloyl chloride was slowly added dropwise to the mixture, and the reaction was stirred for 2 hours. After the reaction, deionized water was added to the mixture to precipitate a white solid, which was filtered, rinsed with deionized water, and dried in vacuum to obtain a white powder, which was a reversible cross-linking agent with two double bonds.

(3) Preparation method of dual responsive degradable photoresist

Get step (2) reversible cross-linking agent (17.5wt%), acrylic anhydride (8.0wt%), 3,6-dioxa-1,8-octanedithiol (23.0wt%) and photoinitiator 1- Hydroxy-cyclohexylbenzophenone (1173) (1.5 wt%) was mixed with acetone (50.0 wt%), and stirred for 1 hour in the dark. After mixing evenly, use a 0.2 μm filter to filter and purify.

(4) How to use dual-response degradable photoresist

Heat the silicon substrate to 170°C in a mixed solution of 30wt% H ₂ O ₂ and 98wt% H ₂ SO ₄ with a volume ratio of 1:3, keep it for 5 hours, wash and dry it in 0.2wt% 3-(trimethoxy Soak in a toluene solution of silyl)propyl-2-methyl-2-acrylate (MPTES) for 6 hours, then wash and dry. Then take an appropriate amount and add it dropwise to the treated silicon wafer substrate, and spin-coat at 3000 rpm for 20 seconds to obtain a photoresist film. Carry out imprinting on the embossing machine, expose to 365nm (25mw/cm ² ) ultraviolet light for 5 minutes, release the mold after curing, and obtain the embossed pattern of photoresist, use ion etching to transfer the pattern to the substrate, and the substrate and The template just released from the mold was exposed to 254nm (20mw/cm ² ) ultraviolet light for 15 minutes, then soaked in sodium hydroxide or potassium hydroxide aqueous solution with pH = 12 for 5 minutes, after taking it out, wash it with deionized water, ethanol and Wash and dry with acetone to obtain templates and substrates with clean surfaces.

Example 2:

(1) Preparation of a reversible cross-linking agent body with two hydroxyl groups

Take 7.2g of phloroglucinol, add it into 20ml of 85wt% phosphoric acid solution, stir evenly, heat to 60°C, add 6ml of ethyl 4-chloroacetoacetate dropwise, and continue stirring until completely dissolved. Keep warm for 2 hours and stir at room temperature for 6 hours. After the reaction is completed, filter with filter paper and wash with a large amount of deionized water until the solution is neutral. Dry in vacuo to obtain a light yellow solid powder, which is the main body of a reversible cross-linking agent with two hydroxyl groups.

(2) Preparation of a reversible cross-linking agent with two double bonds

Take 5.1 g of the product in (1) above and 4.6 g of triethylamine, add it to 60 ml of tetrahydrofuran solution, heat to 60° C., and stir for 30 minutes. The temperature was lowered to 0° C., 4.5 g of acryloyl chloride was slowly added dropwise to the mixture, and the reaction was stirred for 2 hours. After the reaction, deionized water was added to the mixture to precipitate a white solid, which was filtered, rinsed with deionized water, and dried in vacuum to obtain a white powder, which was a reversible cross-linking agent with two double bonds.

(3) Preparation method of dual responsive degradable photoresist

Weigh step (2) reversible crosslinking agent (19.8wt%), acrylic anhydride (7.7wt%), 3,6-dioxa-1,8-octanedithiol (21.0wt%) and photoinitiator 1 -Hydroxy-cyclohexylbenzophenone (1173) (1.5 wt%) was mixed with acetone (50.0 wt%) and stirred for 1 hour in the dark. After mixing evenly, use a 0.2 μm filter to filter and purify.

(4) How to use dual-response degradable photoresist

With embodiment 1.

Example 3:

(1) Preparation of a reversible cross-linking agent body with two hydroxyl groups

With embodiment 1.

(2) Preparation of a reversible cross-linking agent body with two long-chain hydroxyl groups

Take 3g of the product in (1) above and 7g of anhydrous potassium carbonate and add it to a three-necked flask filled with 100ml of acetone, heat it to 80°C, then add 4.3g of 3-bromo-1-propanol dropwise to the mixture, and stir the reaction 20 hours. After the reaction, potassium carbonate was removed by filtration, and the filtrate was rotary evaporated under reduced pressure to obtain an oily substance, which was then purified by column chromatography (eluent: acetone:petroleum ether=2:1) to obtain a white solid. A reversible cross-linking agent body with a long-chain hydroxyl group.

(3) Preparation of a reversible cross-linking agent with two double bonds

Take 1 g of the product in (2) above and 0.7 g of triethylamine, add it to 30 ml of tetrahydrofuran solution, heat to 60° C., and stir for 30 minutes. The temperature was lowered to 0° C., 0.6 g of acryloyl chloride was slowly added dropwise to the mixture, and the reaction was stirred for 2 hours. After the reaction, deionized water was added to the mixture to precipitate a white solid, which was filtered, rinsed with deionized water, and dried in vacuum to obtain a white powder, which was a reversible cross-linking agent with two double bonds.

(4) Preparation method of dual responsive degradable photoresist

Weigh step (3) reversible crosslinking agent (21.5wt%), acrylic anhydride (7.0wt%), 3,6-dioxa-1,8-octanedithiol (20.0wt%) and photoinitiator 1 -Hydroxy-cyclohexylbenzophenone (1173) (1.5 wt%) was mixed with acetone (50.0 wt%) and stirred for 1 hour in the dark. After mixing evenly, use a 0.2 μm filter to filter and purify.

(5) How to use dual-response degradable photoresist

With embodiment 1.

Example 4:

(1) Preparation of a reversible cross-linking agent body with two hydroxyl groups

With embodiment 1.

(2) Preparation of a reversible cross-linking agent with two double bonds

With embodiment 1.

(3) Preparation method of dual responsive degradable photoresist

Weigh step (2) reversible cross-linking agent (16.1wt%), 4-pentene anhydride (9.6wt%), ethylene glycol dimercaptoacetate (22.8wt%) and photoinitiator 1-hydroxyl-cyclohexylbenzene Ketone (1173) (1.5wt%) was mixed with acetone (50.0wt%) and stirred for 1 hour in the dark. After mixing evenly, use a 0.2 μm filter to filter and purify.

(4) How to use dual-response degradable photoresist

With embodiment 1.

Example 5:

(1) Preparation of a reversible cross-linking agent body with two hydroxyl groups

With embodiment 1.

(2) Preparation of a reversible cross-linking agent with two double bonds

With embodiment 1.

(3) Preparation method of dual responsive degradable photoresist

Weigh step (2) reversible crosslinking agent (21.9wt%), 4-pentene anhydride (13.6wt%), 1,2-ethanedithiol (13.0wt%) and photoinitiator 1-hydroxyl-cyclohexylbenzene Methanone (1173) (1.5wt%) and acetone (50.0wt%) were mixed and stirred for 1 hour in the dark. After mixing evenly, use a 0.2 μm filter to filter and purify.

(4) How to use dual-response degradable photoresist

With embodiment 1.

Claims (9)

1. a double-response type degradable photoresist, it substantially forms and with mass fraction is:

A reversible cross-linking agent 10-40 part

B activity monomer 5-30 part

C connects molecule 10-30 part

D light trigger 1-5 part

E organic solvent 0-60 part

Wherein activated monomer B is the anhydride with two double bonds；Connecting molecule C is the mercaptan with two or more sulfydryls.

Double-response type degradable photoresist the most according to claim 1, is characterized in that: activated monomer B is selected from following thing A kind of in matter or their mixture: acrylic anhydride, methacrylic anhydride, 4-amylene acid anhydride, crotonic anhydride, tiglic acid acid anhydride, 3- Methyl-2-butyryl oxide. or 2-hexene anhydride.

Double-response type degradable photoresist the most according to claim 1, is characterized in that: connect molecule C selected from following thing A kind of in matter or their mixture: 1,2-dithioglycol, 1,4-succinimide mercaptans, 1,3-dimercaptopropane, 2-hydroxyl-1,3-third Two mercaptan, 1,6-ethanthiol, the own thioether of 1,6-dimercapto-3-, pungent two mercaptan of 1,8-, 3,6-dioxa-1,8-octane two sulfur Alcohol, 1,9-nonyl two mercaptan, 3,7-dithia-1,9-nonyl two mercaptan, 2,6-naphthyl two mercaptan, 4,4'-dimercapto diphenyl ether, two mercaptos Guanidine-acetic acid glycol ester, 2-methyl isophthalic acid, 2,3-glycerol three (3-mercaptopropionic acid), trimethylolpropane tris (2-TGA Ester), tetramethylolmethane four (3-mercaptopropionic acid).

Double-response type degradable photoresist the most according to claim 1, is characterized in that: light trigger D is selected from following thing A kind of in matter or their mixture: alpha-alcohol ketone, benzil, acylphosphine oxide.

Double-response type degradable photoresist the most according to claim 4, is characterized in that: light trigger is selected from: 1-hydroxyl- Phenylcyclohexyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-hydroxy-2-methyl-1-are to ethoxy ether phenyl third Ketone, α, α '-dimethyl benzil ketals, 2,4,6-trimethyl benzoyl diphenyl base phosphine oxide or 2,4,6-trimethylbenzoyl Base phosphenylic acid ethyl ester.

Double-response type degradable photoresist the most according to claim 1, is characterized in that: reversible cross-linking agent A uses as follows Prepared by method:

(1) preparation reversible cross-linking agent main body with two hydroxyls:

It is 1:(1～5 by mol ratio): the benzenetriol class material of (0.1～1), ethyl acetoacetate class material, catalyst and solvent Mixing, is heated to 30～90 DEG C, stirring reaction 3～12 hours, then cleans filtration, and vacuum drying obtains with two hydroxyls Reversible cross-linking agent main body；

Benzenetriol class material is selected from: phloroglucinol, pyrogallol, oxyhydroquinone, 2,4,6-trihydroxytoluene, 2,4,6-tri- Hydroxypropiophenonepreparation, 2,4-dihydroxy-benzyl alcohol, 3,4-dihydroxy-benzyl alcohol or 3,4,5-trihydroxytoluene；

Ethyl acetoacetate class material is selected from: ethyl acetoacetate, trifluoroacetic ethyl acetoacetate, 2-acetyl fluoride ethyl acetate, 4- Chloroacetyl acetacetic ester, 2-methyl-acetoacetic ester, 4-ethyl bromoacetoacetate, 2-acetoacetate chloroethene ester, acetyl second Acid n-propyl, Propionylacetic acid ethyl ester, 3-propionic acid methyl ester, 3-oxopropanoate, fluoro propiono ethyl acetate or 3-are chloro- 2-methyl-3-oxopropanoate；

Catalyst is selected from: 70～98% concentrated sulphuric acid, 85～98% phosphoric acid, 31～36% hydrochloric acid, p-methyl benzenesulfonic acid, iodine, amino sulphur Acid, silver trifluoromethanesulfonate, methanesulfonic acid, sodium bisulfate, trifluoroacetic acid, oxalic acid, benzenesulfonic acid or ammonium ceric nitrate；

Solvent is selected from: deionized water, 1,4-dioxy six alkane, acetone, toluene, methanol, hexamethylene, dichloromethane, oxolane, second Cyanogen or chloroform；

(2) preparation reversible cross-linking agent main body with two long chain allcyl:

It is 1:(2～5 in molar ratio by middle for step (1) reversible cross-linking agent main body, halohydrin and the acid binding agent with two hydroxyls): (4 ～10) ratio mix with solvent, be heated to 60～100 DEG C, condensing reflux, stirring reaction 12～48 hours, be filtered to remove and tie up Acid agent, is dried, obtains the reversible cross-linking agent main body with two long chain allcyl；

Halohydrin is selected from: ethylene bromohyrin, 2-(2-bromine oxethyl) ethanol, ethylene chlorhydrin, 2-(2-chloroethoxy) ethanol, 3-bromine third Alcohol, 2-bromo-1-propanol, 3-bromo-2-methyl isophthalic acid-propanol, 3-bromo-2,2-dimethyl-1-propanol, trimethylene chlorohydrin, the chloro-2-of 1- Propanol, 3-chloro-2,2-dimethyl-1-propanol, 4-bromobutanol, the iodo-n-butyl alcohol of 4-, the chloro-n-butyl alcohol of 4-, 5-bromine amylalcohol, the chloro-1-of 5- Amylalcohol, 6-bromine hexanol or 6-chloro-1-hexanol；

Acid binding agent is selected from: Anhydrous potassium carbonate, natrium carbonicum calcinatum, sodium hydroxide, potassium hydroxide, potassium iodide, triethylamine or pyridine；

Solvent is selected from: acetone, dimethylformamide, dimethyl sulfoxide, acetonitrile, oxolane or toluene；

(3) preparation reversible cross-linking agent with two double bonds:

By step (1) with reversible cross-linking agent main body with two long chain allcyl of two hydroxyls or step (2), catalyst in molar ratio For 1:(2～5) ratio mix with solvent, at 30～80 DEG C, be uniformly mixed, then mixture be cooled to 0 DEG C, then In mixture, it is slowly added dropwise the acyl chloride compound that molar equivalent is 2～5, stirring reaction 1.5～6 hours, controls reaction temperature Degree is 0 ± 2 DEG C, after having reacted, through filtering, wash, being vacuum dried, obtains the reversible cross-linking agent with two double bonds；

Catalyst is selected from: triethylamine, pyridine, Anhydrous potassium carbonate or natrium carbonicum calcinatum；

Acyl chloride compound is selected from: acryloyl chloride, methacrylic chloride, 2-fluoropropene acyl chlorides, crotonyl chloride, 3-tiglyl Chlorine, (E)-2-methyl-2-butene acyl chlorides, monomethyl ester acyl chlorides, 4-prenyl chloride, 3-ethoxy propylene acyl chlorides, (E)-2- Heptene acyl chlorides or trans-8-methyl-6-pelargonyl chloride.

7. a preparation method for the double-response type degradable photoresist described in claim 1, by reversible cross-linking agent A and activity Monomer B, connection molecule C, light trigger D are mixed in proportion or are dissolved in organic solvent E, and under conditions of lucifuge, stirring mixing is all Even, prepare through filtering.

8. a using method for the double-response type degradable photoresist described in claim 1, is coated on substrate by photoresist On, form photoresist film, be placed on marking press and imprint, de-after 365nm ultraviolet photoetching, photoresist curing molding Mould, obtains the coining pattern of photoresist on substrate, then is transferred on substrate by figure, then exposes through 254nm ultra-violet lamp, Substrate is immersed in the alkaline aqueous solution of pH=9～12 removing photoresist again；

The template completing impressing is exposed under 254nm ultra-violet lamp, then is dipped in the alkaline aqueous solution of pH=9～12 removing The photoresist of residual in template.

The using method of double-response type degradable photoresist the most according to claim 8, is characterized in that: substrate and template Under the ultra-violet lamp of photoresist removal process, exposure has processed together with alkaline aqueous solution immersion.