CN106054523B - A kind of degradable photoresist of double-response type and preparation method thereof and application method - Google Patents
A kind of degradable photoresist of double-response type and preparation method thereof and application method Download PDFInfo
- Publication number
- CN106054523B CN106054523B CN201610348839.3A CN201610348839A CN106054523B CN 106054523 B CN106054523 B CN 106054523B CN 201610348839 A CN201610348839 A CN 201610348839A CN 106054523 B CN106054523 B CN 106054523B
- Authority
- CN
- China
- Prior art keywords
- photoresist
- acid
- double
- band
- linking agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
The present invention relates to a kind of degradable photoresist of double-response type and preparation method thereof and application methods.Molecule of the present invention can crosslink reconciliation crosslinking under different wave length ultraviolet light realizes that the reconciliation that is crosslinked of photoresist is crosslinked by different wave length ultraviolet light as crosslinking agent；Using hydrolyzable structure as polymer backbone, it can degrade in the aqueous alkali of pH > 7 under room temperature, finally obtain the small molecule for being dissolved in water.Crosslinking agent, photoinitiator, activated monomer and connection molecule are mixed to get photoresist system, this photoresist is then applied to nano impression, excellent coining performance and degradation property is shown, has well solved photoresist to the damage problem of template.In addition, it also has the characteristic of environmental protection, it is a kind of degradable photoresist of environment-friendly type.
Description
Technical field
The present invention relates to a kind of degradable photoresist of double-response type and preparation method thereof and application methods.
Background technique
With the progress of science and technology, human society enters the information age, and various communication apparatus, mobile terminal layer go out not
Thoroughly, multi-functional, small size, easily it is portable be development Main way.Important composition portion of the integrated circuit (IC) as electronic equipment
Point, its application and development are directly influenced, and tradition prepares the photoetching technique of integrated circuit since various limitations can not expire
The requirement of foot production more high integration IC, nineteen ninety-five houston, U.S.A university week strongly fragrant teaching inventive low cost, high efficiency and
High-resolution nanometer embossing.
The chief component of nanoimprinting process has template (seal), photoresist and substrate, and wherein the price of template is high
Expensive, photoresist then in the whole process with template contacts, directly influences the service life of template.Photoresist is broadly divided at present
Thermoplasticity, thermosetting property and ultraviolet light solidify three types, and wherein thermoplastic nanofibers coining glue is made of macromolecule, by it before coining
It is heated to glass transition temperature (Tg) on increase molecular mobility, then template is impressed on macromolecular composition again, it is cold
But curing and demolding obtains coining pattern, it is therefore desirable to pressure it is larger, template is damaged serious；Thermosetting property nano impression glue
Chief component is performed polymer, heats polymerizing curable, therefore stronger to the adhesiveness of template, and template residue glue is serious, and damage is tight
Weight；The main composition of ultraviolet curing type photoresist is the monomer, resin and photoinitiator of photopolymerization, reaction condition temperature
With reaction speed is fast, has received widespread attention, but similarly face residue glue to the damage problem of template.
To solve the interface problem between photoresist and template, current main method has: being added in the photoresist fluorine-containing
(such as article Lin H, Wan X, Jiang X, et al.Journal of Materials Chemistry, 2012,22 (6):
2616-2623) and it is siliceous (such as article Choi P, Fu P F, Guo L J.Advanced Functional Materials,
2007,17 (1): 65-70) ingredient, reduce photoresist surface can, to reduce the interaction between photoresist and template
Power, but anti-adhesion effects are limited, while also reducing the adhesion strength between photoresist and substrate, degumming phenomenon easily occur；To template
(such as patent CN10103576447A) and photoresist surface (such as patent CN102604454A) is handled, and is connected its surface and is contained
Fluorin radical reduces interaction force, but process is complicated, at high cost；Prepare photoresist (such as the article Hu, Xin of acid-degradable
Yang, Tao Gu, Ronghua Cui.Journal of Materials Chemistry C, 2,014 2 (10): 836-842),
Its cardinal principle is that photoacid generator generates H under ultraviolet lighting+, it is broken crosslinking points under heating conditions, increasing it is having
Dissolubility in solvent, still, degradation need hot conditions, and acid has damage template protection layer；Prepare thermal degradation type light
Photoresist (such as article Wiriya, Thongsomboon, Mark Sherwood, Noel Arellano, ACS Macro
Letters.2013 2 (1): 19-22), principle is crosslinking points fracture in a heated condition, increases photoresist in organic solvent
In dissolubility, but use hot conditions, limit its applicable range；Prepare reversible photoresist (such as patent
CN101957559A), using the monomer for conciliating crosslinking can be crosslinked under different ultraviolet wavelengths in side chain as crosslinking agent, lead to
Ultraviolet light is crossed to control crosslinking degree, thus reach the solubility property for controlling it in organic solvent, but it solves crosslinking degree
It is limited, and be still macromolecular after solution crosslinking, solute effect is unobvious.
Above method reduces damage of the photoresist to template to a certain extent, but there is a problem in that, such as plus
Heat limits use scope, and degree of reversibility is low to be made to degrade unobvious, uses organic solvent environmental pollution etc..Therefore, it is badly in need of
It is a kind of can at normal temperature fast degradation and environmental protection photoresist.
Summary of the invention
The present invention is intended to provide a kind of degradable photoresist of double-response type and preparation method thereof and application method, the present invention
Molecule can crosslink reconciliation crosslinking under different wave length ultraviolet light passes through different wave length ultraviolet light as crosslinking agent
To realize the crosslinking reconciliation crosslinking of photoresist；It, can be in the alkali of pH > 7 under room temperature using hydrolyzable structure as polymer backbone
It degrades in aqueous solution, finally obtains the small molecule for being dissolved in water.By crosslinking agent, photoinitiator, activated monomer, connection molecule with
Solvent is mixed to get photoresist system, this photoresist is then applied to nano impression, shows excellent coining performance and drop
Performance is solved, has well solved photoresist to the damage problem of template.In addition, it also has the characteristic of environmental protection, it is a kind of environmental protection
The degradable photoresist of type.
The composition and mass fraction of a kind of degradable photoresist of double-response type provided by the invention are as follows:
10-40 parts of A reversible cross-linking agent, preferably 10~25 parts
5-30 parts of B activity monomer, preferably 5~20 parts
10-30 parts of C connection molecule, preferably 10~20 parts
1-5 parts of D photoinitiator, preferably 1~3 part
0-60 parts of E organic solvent, preferably 40~60 parts
Above-mentioned activated monomer B is the acid anhydrides of two double bonds of band, preferably is selected from one of following substance or their mixture:
Acrylic anhydride, methacrylic anhydride, 4- amylene acid anhydride, crotonic anhydride, tiglic acid acid anhydride, 3- methyl -2- butyric anhydride or 2- hexene acid anhydrides.
Further preferred acrylic anhydride, 4- amylene acid anhydride or crotonic anhydride.
Above-mentioned connection molecule C be the mercaptan with two or more sulfydryls, preferably be selected from one of following substance or it
Mixture: 1,2- dithioglycol, 1,4- succinimide mercaptans, 1,3- dimercaptopropane, 2- hydroxyl -1,3- dimercaptopropane, 1,6- oneself
Two mercaptan, the own thioether of 1,6- dimercapto -3-, pungent two mercaptan of 1,8-, 3,6- dioxa -1,8- octanedithiol, two sulphur of 1,9- nonyl
Alcohol, two mercaptan of 3,7- dithia -1,9- nonyl, two mercaptan of 2,6- naphthalene, 4,4'- dimercapto diphenyl ether, dimercapto acetic acid ethylene glycol
Ester, 2- methyl-1,2,3- glycerine three (3- mercaptopropionic acid), trimethylolpropane tris (2- mercaptoacetate), pentaerythrite four
(3- mercaptopropionic acid).Further preferred 3,6- dioxa -1,8- octanedithiol, the own thioether of 1,6- dimercapto -3-, bis- sulphur of 3,7-
Miscellaneous two mercaptan of -1,9- nonyl or pungent two mercaptan of 1,8-.
Above-mentioned photoinitiator D is selected from one of following photoinitiator commonly used in the art or their mixture: Alpha-hydroxy
(such as: 1- hydroxy-cyciohexyl Benzophenone, 2- hydroxy-2-methyl -1- phenylacetone or 2- hydroxy-2-methyl -1- are to ethoxy for ketone
Ether phenylacetone), benzil (such as: α, α '-dimethyl benzil ketals), acylphosphine oxide (such as: 2,4,6- trimethylbenzene
Formoxyl diphenyl phosphine oxide or 2,4,6- trimethylbenzoyl phenyl etherophosphoric acid).
Above-mentioned organic solvent E is selected from one of following substance or their mixture: acetone, chloroform, dichloromethane
Alkane, ethyl alcohol, isopropanol, n-butanol, ethyl acetate, hexamethylene 1,4- dioxane.Organic solvent is selective component, when reversible
When crosslinking agent is completely dissolved in connection molecule and activated monomer, organic solvent can be not added.
The present invention above-mentioned reversible cross-linking agent A's the preparation method comprises the following steps:
(1) the reversible cross-linking agent main body of two hydroxyls of band is prepared:
Be 1:(1~5 by molar ratio): the benzenetriol substance of (0.1~1), ethyl acetoacetate substance, catalyst with
Solvent mixing, is heated to 30~90 DEG C, is stirred to react 3~12 hours.Then cleaning filtering, vacuum drying, obtains two hydroxyls of band
The reversible cross-linking agent main body of base.
Benzenetriol substance is selected from: phloroglucin, pyrogallol, oxyhydroquinone, 2,4,6- trihydroxytoluene, 2,4,
6- trihydroxy benzene acetone, 2,4- dihydroxy-benzyl alcohol, 3,4- dihydroxy-benzyl alcohol or 3,4,5- trihydroxytoluene.Further preferred isophthalic
Triphenol, pyrogallol or oxyhydroquinone.
Ethyl acetoacetate substance is selected from: ethyl acetoacetate, trifluoroacetic ethyl acetoacetate, 2- acetyl fluoride acetic acid second
Ester, 4- chloroacetyl acetacetic ester, 2- methyl-acetoacetic ester, 4- ethyl bromoacetoacetate, 2- acetoacetate chloroethene ester, second
Ethyl acetoacetic acid n-propyl, Propionylacetic acid ethyl ester, 3- propionic acid methyl ester, 3- ethyl 3-oxopropanoate, fluoro propionyl ethyl or
3- chloro-2-methyl -3- ethyl 3-oxopropanoate.Further preferred ethyl acetoacetate, 2- methyl-acetoacetic ester, 2- acetyl fluoride
Ethyl acetate or 4- chloroacetyl acetacetic ester.
Catalyst is selected from: 70~98% concentrated sulfuric acids, 85~98% phosphoric acid, 31~36% hydrochloric acid, p-methyl benzenesulfonic acid, iodine, ammonia
Base sulfonic acid, silver trifluoromethanesulfonate, methanesulfonic acid, sodium bisulfate, trifluoroacetic acid, oxalic acid, benzene sulfonic acid or ammonium ceric nitrate.Further preferably
70~98% concentrated sulfuric acids, 85~98% phosphoric acid, iodine or p-methyl benzenesulfonic acid.
Solvent is selected from: deionized water, six alkane of 1,4- dioxy, acetone, toluene, methanol, hexamethylene, methylene chloride, tetrahydro furan
It mutters, second cyanogen or chloroform.
(2) the reversible cross-linking agent main body of two long chain allcyls of band is prepared:
Reversible cross-linking agent main body, halohydrin and acid binding agent by two hydroxyls of band in above-mentioned (1) be in molar ratio 1:(2~
5): the ratio of (4~10) is mixed with solvent, is heated to 60~100 DEG C, is condensed back, is stirred to react 12~48 hours.It crosses and filters out
Acid binding agent is removed, it is dry, obtain the reversible cross-linking agent main body of two long chain allcyls of band.
Above-mentioned halohydrin is selected from: ethylene bromohyrin, 2- (2- bromine oxethyl) ethyl alcohol, ethylene chlorhydrin, 2- (2- chloroethoxy) second
The bromo- 2- methyl-1-propyl alcohol of the bromo- 1- propyl alcohol of alcohol, 3- bromopropyl alcohol, 2-, 3-, the bromo- 2,2- dimethyl-1- propyl alcohol of 3-, the chloro- 1- third of 3-
The chloro- 2- propyl alcohol of alcohol, 1-, the chloro- 2,2- dimethyl -1- propyl alcohol of 3-, 4- bromobutanol, the iodo- n-butyl alcohol of 4-, the chloro- n-butyl alcohol of 4-, 5- bromine penta
The chloro- 1- amylalcohol of alcohol, 5-, 6- bromine hexanol or the chloro- 1- hexanol of 6-.Further preferred ethylene bromohyrin, 3- bromopropyl alcohol, 4- bromobutanol, 5-
Bromine amylalcohol or 6- bromine hexanol.
Acid binding agent is selected from: Anhydrous potassium carbonate, natrium carbonicum calcinatum, sodium hydroxide, potassium hydroxide, potassium iodide, triethylamine or pyrrole
Pyridine.
Solvent is selected from: acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, tetrahydrofuran or toluene.
(3) reversible cross-linking agent of two double bonds of band is prepared:
The reversible cross-linking agent main body of two long chain allcyls of two hydroxyls of step (1) band or step (2) band, catalyst are massaged
You than be 1:(2~5) ratio mixed with solvent, at 30~80 DEG C, be uniformly mixed, mixture be then cooled to 0
DEG C, then the acyl chloride compound that molar equivalent is 2~5 is slowly added dropwise into mixture, it is stirred to react 1.5~6 hours, control is anti-
Answering temperature is 0 ± 2 DEG C.After the reaction was completed, it is filtered, washed, is dried in vacuo, obtain the reversible cross-linking agent of two double bonds of band.
Acyl chloride compound is selected from: acryloyl chloride, methacrylic chloride, 2- fluoropropene acyl chlorides, crotonyl chloride, 3- methyl bar
Beans acyl chlorides, (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.It is further preferred: acryloyl chloride, methacrylic chloride, crotonyl chloride,
3- methyl crotonic acyl chlorides or (E) -2- methyl-2-butene acyl chlorides.
Catalyst is selected from: triethylamine, pyridine, Anhydrous potassium carbonate or natrium carbonicum calcinatum.
Solvent is selected from: tetrahydrofuran, methylene chloride, chloroform, acetone, dimethylformamide (DMF), dimethyl sulfoxide
(DMSO), second cyanogen, toluene, hexamethylene or 1,4- dioxane.
A kind of degradable photoresist of double-response type provided by the invention the preparation method comprises the following steps: by the reversible of two double bonds of band
Crosslinking agent A and activated monomer B, connection molecule C, photoinitiator D are dissolved in proportion in organic solvent E, are stirred under conditions of being protected from light
Mix it is uniformly mixed, through filter be made.Preferably 0.2~2 μm of filter pore size size.
The application method of a kind of degradable photoresist of double-response type provided by the invention are as follows: photoresist is coated on substrate
On, photoresist film is formed, is placed on marking press and is imprinted, through 365nm (20~35mw/cm2) ultraviolet photoetching (2~10
Minute), it demoulds after photoresist curing molding, the coining pattern of photoresist is obtained on substrate, then will be in pattern transfer to substrate
(such as: ion etching or lift-off technology), then through 254nm (14~25mw/cm2) ultraviolet photoetching (10~30 minutes), by base
Plate is immersed in the alkaline aqueous solution of pH=9~12 (such as: sodium hydroxide or potassium hydroxide aqueous solution) removing photoresist.
The template of coining will be completed in 254nm (14~25mw/cm2) exposed under UV light (10~30 minutes), then impregnate
Remaining photoresist in template (such as: sodium hydroxide or potassium hydroxide aqueous solution) is removed into the alkaline aqueous solution of pH=9~12.
The photoresist removal process of substrate and template can carry out respectively, can also complete together.
The degradable photoresist of double-response type prepared by the present invention overcomes the difficult problem of template cleaning, can be by ultraviolet
Light (254nm) and buck (pH > 7) processing, make crosslinking points and main chain while being broken, promote the quick dissolution of residue glue in template, mention
The high service life and service efficiency of template.In addition, reducing the pollution to environment using aqueous cleaning.This photoresist is also
It can be applied to prepare the micro-nano pattern under other specific conditions, such as prepare flexible circuit.
Detailed description of the invention
Fig. 1 is the degradation reaction schematic diagram of photoresist of the present invention；
Fig. 1 (a) is the photoresist reticular structure after crosslinking curing, is broken through 254nm UV Light processing post-crosslinking point,
Linear molecule shown in Fig. 1 (b) is obtained, then is handled through buck, water-soluble small molecule shown in Fig. 1 (c) is obtained.
Fig. 2 is micro-pattern prepared by embodiment 1；
Fig. 2 (a) and Fig. 2 (c) is impression block (20 × 20 μm of square groove, 20 μm of stripeds of line width), Fig. 2 (b) and Fig. 2
(d) it is corresponding photoresist coining pattern (20 × 20 μm of square cylinder, the striped that 20 μm of line width).
Specific embodiment:
Embodiment 1:
(1) the reversible cross-linking agent main body of two hydroxyls of band is prepared
The phloroglucin for taking 7.2g is added in 85% phosphoric acid solution of 20ml, stirs evenly, and is heated to 60 DEG C, is added dropwise
The ethyl acetoacetate of 5.6ml continues stirring to being completely dissolved.Heat preservation 2 hours, is stirred at room temperature 6 hours.After the reaction was completed, it uses
Filter paper filtering, and it is neutral for being cleaned with a large amount of deionized waters to solution.Vacuum drying, obtains faint yellow solid powder, is band two
The reversible cross-linking agent main body of a hydroxyl.
(2) reversible cross-linking agent of two double bonds of band is prepared
Product and 4.6g triethylamine in 4.3g above-mentioned (1) are taken, is added in 50ml tetrahydrofuran solution, is heated to 60 DEG C,
Stirring 30 minutes.Temperature is reduced to 0 DEG C, and 4.5g acryloyl chloride is slowly added dropwise into mixture, is stirred to react 2 hours.Reaction knot
Deionized water is added into mixture by Shu Hou, white solid, filtering is precipitated, and rinsed with deionized water, is dried in vacuo, obtains
White powder, the as reversible cross-linking agent of two double bonds of band.
(3) preparation method of the degradable photoresist of double-response type
Take step (2) reversible cross-linking agent (17.5wt%), acrylic anhydride (8.0wt%), 3,6- dioxa -1,8- octane two
Mercaptan (23.0wt%) and photoinitiator 1- hydroxy-cyciohexyl Benzophenone (1173) (1.5wt%) and acetone (50.0wt%) are mixed
It closes, is protected from light stirring 1 hour.0.2 μm of filter filtration, purification is used after mixing.
(4) application method of the degradable photoresist of double-response type
By silicon wafer substrate in the 30wt%H that volume ratio is 1:32O2And 98wt%H2SO4170 DEG C are heated in mixed solution,
It is kept for 5 hours, in 0.2wt%3- (trimethoxysilyl) propyl -2- methyl -2- acrylate after cleaning-drying
(MPTES) it impregnates 6 hours in toluene solution, is then cleaned and dried.The silicon wafer substrate that is added drop-wise to that treated in right amount is taken again,
Spin coating 20 seconds, obtain photoresist film under the conditions of 3000rpm.It is imprinted on marking press, through 365nm (25mw/cm2) ultraviolet
Light lamp exposes 5 minutes, and curing and demolding obtains the coining pattern of photoresist, will using ion etching by pattern transfer to substrate
Substrate and the template just demoulded are in 254nm (20mw/cm2) illumination 15 minutes under ultraviolet lamp, then it is dipped into the hydrogen-oxygen of pH=12
Change in sodium or potassium hydroxide aqueous solution 5 minutes, is cleaned and dried to obtain surface with deionized water, ethyl alcohol and acetone respectively after taking-up and does
Net template and substrate.
Embodiment 2:
(1) the reversible cross-linking agent main body of two hydroxyls of band is prepared
The phloroglucin for taking 7.2g is added in 20ml 85wt% phosphoric acid solution, stirs evenly, and is heated to 60 DEG C, is added dropwise
The 4- chloroacetyl acetacetic ester of 6ml continues stirring to being completely dissolved.Heat preservation 2 hours, is stirred at room temperature 6 hours.After the reaction was completed,
It is filtered with filter paper, and it is neutral for being cleaned with a large amount of deionized waters to solution.Vacuum drying, obtains faint yellow solid powder, is band
The reversible cross-linking agent main body of two hydroxyls.
(2) reversible cross-linking agent of two double bonds of band is prepared
Product and 4.6g triethylamine in 5.1g above-mentioned (1) are taken, is added in 60ml tetrahydrofuran solution, is heated to 60 DEG C,
Stirring 30 minutes.Temperature is reduced to 0 DEG C, and 4.5g acryloyl chloride is slowly added dropwise into mixture, is stirred to react 2 hours.Reaction knot
Deionized water is added into mixture by Shu Hou, white solid, filtering is precipitated, and rinsed with deionized water, is dried in vacuo, obtains
White powder, the as reversible cross-linking agent of two double bonds of band.
(3) preparation method of the degradable photoresist of double-response type
Weigh step (2) reversible cross-linking agent (19.8wt%), acrylic anhydride (7.7wt%), 3,6- dioxa -1,8- octane
Two mercaptan (21.0wt%) and photoinitiator 1- hydroxy-cyciohexyl Benzophenone (1173) (1.5wt%) and acetone (50.0wt%)
Mixing is protected from light stirring 1 hour.0.2 μm of filter filtration, purification is used after mixing.
(4) application method of the degradable photoresist of double-response type
With embodiment 1.
Embodiment 3:
(1) the reversible cross-linking agent main body of two hydroxyls of band is prepared
With embodiment 1.
(2) the reversible cross-linking agent main body of two long chain allcyls of band is prepared
It takes product, 7g Anhydrous potassium carbonate in 3g above-mentioned (1) to be added in the three-necked flask equipped with 100ml acetone, is heated to
80 DEG C, then the middle bromo- 1- propyl alcohol of dropwise addition 4.3g 3- into mixture, it is stirred to react 20 hours.After reaction, it is filtered to remove carbon
Sour potassium, filtrate decompression is rotated, and obtains oily object, then mention by column chromatography for separation (leacheate is acetone: petroleum ether=2:1)
It is pure, white solid is obtained, is obtained as the reversible cross-linking agent main body of two long chain allcyls of band.
(3) reversible cross-linking agent of two double bonds of band is prepared
Product and 0.7g triethylamine in 1g above-mentioned (2) are taken, is added in 30ml tetrahydrofuran solution, is heated to 60 DEG C, stirs
It mixes 30 minutes.Temperature is reduced to 0 DEG C, and 0.6g acryloyl chloride is slowly added dropwise into mixture, is stirred to react 2 hours.Reaction terminates
Afterwards, deionized water is added into mixture, white solid, filtering is precipitated, and rinsed with deionized water, is dried in vacuo, obtains white
Color powder, the as reversible cross-linking agent of two double bonds of band.
(4) preparation method of the degradable photoresist of double-response type
Weigh step (3) reversible cross-linking agent (21.5wt%), acrylic anhydride (7.0wt%), 3,6- dioxa -1,8- octane
Two mercaptan (20.0wt%) and photoinitiator 1- hydroxy-cyciohexyl Benzophenone (1173) (1.5wt%) and acetone (50.0wt%)
Mixing is protected from light stirring 1 hour.0.2 μm of filter filtration, purification is used after mixing.
(5) application method of the degradable photoresist of double-response type
With embodiment 1.
Embodiment 4:
(1) the reversible cross-linking agent main body of two hydroxyls of band is prepared
With embodiment 1.
(2) reversible cross-linking agent of two double bonds of band is prepared
With embodiment 1.
(3) preparation method of the degradable photoresist of double-response type
Weigh step (2) reversible cross-linking agent (16.1wt%), 4- amylene acid anhydride (9.6wt%), glycol dimercaptosuccinate
(22.8wt%) and photoinitiator 1- hydroxy-cyciohexyl Benzophenone (1173) (1.5wt%) are mixed with acetone (50.0wt%), are kept away
Light stirs 1 hour.0.2 μm of filter filtration, purification is used after mixing.
(4) application method of the degradable photoresist of double-response type
With embodiment 1.
Embodiment 5:
(1) the reversible cross-linking agent main body of two hydroxyls of band is prepared
With embodiment 1.
(2) reversible cross-linking agent of two double bonds of band is prepared
With embodiment 1.
(3) preparation method of the degradable photoresist of double-response type
Weigh step (2) reversible cross-linking agent (21.9wt%), 4- amylene acid anhydride (13.6wt%), 1,2- dithioglycol
(13.0wt%) and photoinitiator 1- hydroxy-cyciohexyl Benzophenone (1173) (1.5wt%) are mixed with acetone (50.0wt%), are kept away
Light stirs 1 hour.0.2 μm of filter filtration, purification is used after mixing.
(4) application method of the degradable photoresist of double-response type
With embodiment 1.
Claims (8)
1. a kind of degradable photoresist of double-response type, substantially composition and mass fraction are as follows:
10-40 parts of A reversible cross-linking agent
5-30 parts of B activity monomer
10-30 parts of C connection molecule
1-5 parts of D photoinitiator
0-60 parts of E organic solvent
Wherein activated monomer B is the acid anhydrides of two double bonds of band；Connection molecule C is the mercaptan with two or more sulfydryls；It can
Inverse crosslinking agent A is prepared with the following method:
(1) the reversible cross-linking agent main body of two hydroxyls of band is prepared:
It is 1:(1~5 by molar ratio): benzenetriol substance, ethyl acetoacetate substance, catalyst and the solvent of (0.1~1)
Mixing, is heated to 30~90 DEG C, is stirred to react 3~12 hours, then cleaning filtering, vacuum drying obtains two hydroxyls of band
Reversible cross-linking agent main body；
Benzenetriol substance is selected from: phloroglucin, 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 substance 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
Sour n-propyl, Propionylacetic acid ethyl ester, 3- propionic acid methyl ester, 3- ethyl 3-oxopropanoate, fluoro propionyl ethyl or 3- are chloro-
2- methyl -3- ethyl 3-oxopropanoate；
Catalyst is selected from: 70~98% concentrated sulfuric acids, 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, benzene sulfonic acid or ammonium ceric nitrate；
Solvent is selected from: deionized water, six alkane of 1,4- dioxy, acetone, toluene, methanol, hexamethylene, methylene chloride, tetrahydrofuran, second
Cyanogen or chloroform；
(2) the reversible cross-linking agent main body of two long chain allcyls of band is prepared:
Reversible cross-linking agent main body, halohydrin and acid binding agent by two hydroxyls of band in step (1) are 1:(2~5 in molar ratio): (4
~10) ratio is mixed with solvent, is heated to 60~100 DEG C, is condensed back, is stirred to react 12~48 hours, is filtered to remove and ties up
Sour agent, it is dry, obtain the reversible cross-linking agent main body of two long chain allcyls of band；
Halohydrin is selected from: ethylene bromohyrin, 2- (2- bromine oxethyl) ethyl alcohol, ethylene chlorhydrin, 2- (2- chloroethoxy) ethyl alcohol, 3- bromine third
The bromo- 2- methyl-1-propyl alcohol of the bromo- 1- propyl alcohol of alcohol, 2-, 3-, the bromo- 2,2- dimethyl-1- propyl alcohol of 3-, trimethylene chlorohydrin, the chloro- 2- of 1-
The chloro- 2,2- dimethyl -1- propyl alcohol of propyl alcohol, 3-, 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 the chloro- 1- hexanol of 6-；
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, tetrahydrofuran or toluene；
(3) reversible cross-linking agent of two double bonds of band is prepared:
In molar ratio by the reversible cross-linking agent main body of two long chain allcyls of two hydroxyls of step (1) band or step (2) band, catalyst
For 1:(2~5) ratio mixed with solvent, at 30~80 DEG C, be uniformly mixed, mixture be then cooled to 0 DEG C, then
The acyl chloride compound that molar equivalent is 2~5 is slowly added dropwise into mixture, is stirred to react 1.5~6 hours, control reaction temperature
Degree is 0 ± 2 DEG C, after the reaction was completed, is filtered, washed, is dried in vacuo, obtains the reversible cross-linking agent of two double bonds of band；
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.
2. the degradable photoresist of double-response type according to claim 1, it is characterized in that: activated monomer B is selected from following object
One of matter or their mixture: acrylic anhydride, methacrylic anhydride, 4- amylene acid anhydride, crotonic anhydride, tiglic acid acid anhydride, 3-
Methyl -2- butyric anhydride or 2- hexene acid anhydrides.
3. the degradable photoresist of double-response type according to claim 1, it is characterized in that: connection molecule C is selected from following object
One of 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-, two sulphur of 3,6- dioxa -1,8- octane
Alcohol, two mercaptan of 1,9- nonyl, two mercaptan of 3,7- dithia -1,9- nonyl, two mercaptan of 2,6- naphthalene, 4,4'- dimercapto diphenyl ether, two mercaptos
Guanidine-acetic acid glycol ester, 2- methyl-1,2,3- glycerine three (3- mercaptopropionic acid), trimethylolpropane tris (2- thioacetic acid
Ester), pentaerythrite four (3- mercaptopropionic acid).
4. the degradable photoresist of double-response type according to claim 1, it is characterized in that: photoinitiator D is selected from following object
One of matter or their mixture: alpha-alcohol ketone, benzil, acylphosphine oxide.
5. the degradable photoresist of double-response type according to claim 4, it is characterized in that: photoinitiator 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.
6. a kind of preparation method of the degradable photoresist of double-response type described in claim 1, by reversible cross-linking agent A and activity
Monomer B, connection molecule C, photoinitiator D are mixed or are dissolved in proportion in organic solvent E, are stirred under conditions of being protected from light
It is even, it is made through filtering.
7. photoresist is coated on substrate by a kind of application method of the degradable photoresist of double-response type described in claim 1
On, photoresist film is formed, is placed on marking press and is imprinted, through 365nm ultraviolet photoetching, is taken off after photoresist curing molding
Mould obtains the coining pattern of photoresist on substrate, then by pattern transfer to substrate, then exposes through 254nm ultraviolet lamp,
Substrate is immersed in the alkaline aqueous solution of pH=9~12 again and removes photoresist；
The template for completing coining is exposed under 254nm ultraviolet lamp, then is dipped into the alkaline aqueous solution of pH=9~12 and removes
Remaining photoresist in template.
8. the application method of the degradable photoresist of double-response type according to claim 7, it is characterized in that: substrate and template
Exposure and alkaline aqueous solution impregnate processing together and complete under the ultraviolet lamp of photoresist removal process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610348839.3A CN106054523B (en) | 2016-05-24 | 2016-05-24 | A kind of degradable photoresist of double-response type and preparation method thereof and application method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610348839.3A CN106054523B (en) | 2016-05-24 | 2016-05-24 | A kind of degradable photoresist of double-response type and preparation method thereof and application method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106054523A CN106054523A (en) | 2016-10-26 |
| CN106054523B true CN106054523B (en) | 2019-10-18 |
Family
ID=57175162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610348839.3A Active CN106054523B (en) | 2016-05-24 | 2016-05-24 | A kind of degradable photoresist of double-response type and preparation method thereof and application method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106054523B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111025846B (en) * | 2019-12-12 | 2021-09-03 | Tcl华星光电技术有限公司 | Color photoresist, color filter and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101883797A (en) * | 2007-11-30 | 2010-11-10 | 昭和电工株式会社 | Curable composition for transfer materials and method for forming micropattern using the curable composition |
| CN101957559A (en) * | 2010-08-30 | 2011-01-26 | 上海交通大学 | Optical reversible nanoimprint photoresist as well as preparation method and application method thereof |
| CN102408332A (en) * | 2011-11-14 | 2012-04-11 | 无锡英普林纳米科技有限公司 | Ultraviolet curing degradable cross-linking monomer and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012074994A1 (en) * | 2010-11-29 | 2012-06-07 | The Regents Of The University Of Colorado, A Body Corporate | Novel thermoreversible network scaffolds and methods of preparing same |
-
2016
- 2016-05-24 CN CN201610348839.3A patent/CN106054523B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101883797A (en) * | 2007-11-30 | 2010-11-10 | 昭和电工株式会社 | Curable composition for transfer materials and method for forming micropattern using the curable composition |
| CN101957559A (en) * | 2010-08-30 | 2011-01-26 | 上海交通大学 | Optical reversible nanoimprint photoresist as well as preparation method and application method thereof |
| CN102408332A (en) * | 2011-11-14 | 2012-04-11 | 无锡英普林纳米科技有限公司 | Ultraviolet curing degradable cross-linking monomer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106054523A (en) | 2016-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101553549B (en) | Photobase generator and photocurable resin composition | |
| JP6627997B2 (en) | Self-assembled composition for pattern formation and pattern formation method | |
| CN101528660A (en) | Adamantane derivative, process for producing the same, resin composition, and cured product thereof | |
| JP2007536398A (en) | Derivatized polyhydroxystyrene having a novolac type structure and method for producing the same | |
| JP3914363B2 (en) | Re-dissolvable acid-crosslinking polymer and photosensitive resin composition combining the polymer and a photoacid generator | |
| JP5910245B2 (en) | Base generator, photosensitive resin composition, pattern forming material comprising the photosensitive resin composition, relief pattern manufacturing method using the photosensitive resin composition, and article | |
| CN106054523B (en) | A kind of degradable photoresist of double-response type and preparation method thereof and application method | |
| CN109232838B (en) | Preparation method of novel biodegradable rapid photocuring molding material | |
| CN110229257A (en) | Polymerizable monomer, solidification compound and resin component | |
| JP5128574B2 (en) | Photosensitive resin composition | |
| CN101957559A (en) | Optical reversible nanoimprint photoresist as well as preparation method and application method thereof | |
| JP2013194205A (en) | Base generator, photosensitive resin composition, pattern-forming material composed of the photosensitive resin composition, method for producing relief pattern by using the photosensitive resin composition, and article | |
| CN111007698B (en) | Bio-based water-soluble negative ultraviolet photoresist composition, photoresist and preparation method thereof | |
| JP2007164045A (en) | Photosensitive relief pattern forming material | |
| JP2878654B2 (en) | Photosensitive resin composition | |
| JP5768348B2 (en) | Thermal base generator, polymer precursor composition, and article using the composition | |
| CN114836033B (en) | Resin precursor composition, resin film thereof, preparation method and application | |
| JP6813028B2 (en) | Pattern formation method, base material and laminate | |
| CN114957758A (en) | Negative photochromic film and preparation method and application thereof | |
| CN112859520A (en) | Low-energy-curing photoresist, resist pattern and preparation method thereof | |
| JPS6071657A (en) | Photosensitive resin composition | |
| CN117341370B (en) | Preparation method of soft lithography seal attached to curved object without external force, product and application thereof | |
| JPH087436B2 (en) | Photosensitive diazoquinone compound and positive photosensitive resin composition using the same | |
| CN105045051B (en) | The minimizing technology of photoresist material | |
| CN101139427A (en) | Preparation and use of water-soluble phenol resin containing tertiary amine oxide lateral group |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |