CN104199254B - A kind of phase transformation photoresist and preparation method thereof - Google Patents
A kind of phase transformation photoresist and preparation method thereof Download PDFInfo
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- CN104199254B CN104199254B CN201410493318.8A CN201410493318A CN104199254B CN 104199254 B CN104199254 B CN 104199254B CN 201410493318 A CN201410493318 A CN 201410493318A CN 104199254 B CN104199254 B CN 104199254B
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- proton pump
- photoresist
- dimaleoyl imino
- responsive polymers
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Abstract
The present invention provides a kind of preparation method of phase transformation photoresist, including：End dimaleoyl imino pH responsive polymers and sulfhydrylation light-driven proton pump are subjected to cross-linking reaction, obtain phase transformation photoresist.Preparation method provided by the invention is to hold dimaleoyl imino pH responsive polymers with sulfhydrylation light-driven proton pump as raw material, will be to hold dimaleoyl imino pH responsive polymers and sulfhydrylation light-driven proton pump to carry out a step cross-linking reaction, you can obtain phase transformation photoresist.Compared with prior art, the preparation method step of photoresist provided by the invention is few, easy to operate, shortens technological process, reduces using and putting into for industrial production equipment, beneficial to large-scale industrial production.
Description
Technical field
The present invention relates to technical field of lithography, more particularly to a kind of phase transformation photoresist and preparation method thereof.
Background technology
Photoresist is also known as photoresist, main by three kinds of photosensitive resin, sensitizer (see spectral sensitizing dye) and solvent
The photosensitive mixing liquid of component composition.After illumination, in exposure region photocuring reaction can soon occur for photosensitive resin,
So that significant change occurs for the physical property of this material, particularly dissolubility, compatibility etc..Handled through appropriate solvent, it is molten
Soluble part is removed, obtains required image.The technical sophistication of photoresist, kind are more.According to photoresist chemical reaction mechanism and
Development principle, can be divided into two class of negative photoresist and positive photoresist.
In recent years, photoresist becomes bio-microelectromechanical field, particularly the micro element system such as biochip, biology sensor
Key function material in standby.The fast development of biotechnology, makes requirement day of the micro-nano technology field to photoetching technique resolving capability
Benefit improves, and promotes the continuous innovation of exposure sources and photoetching process and improves, various new photoresists also continue to bring out.Such as public affairs
The number of opening is that the Chinese patent of CN101192005 discloses a kind of preparation method of heat resisting negative photoresist, with poly- cyclized butadiene
For glue matrix, with double (nitrine the benzal) -4- methyl cyclohexanones of 2,6- for crosslinking agent, using benzophenone as photosensitizer, with ring
Hexane is solvent, and by feed purification, impregnation and filtering technique and preliminary drying four techniques of film forming, it is cured resistance to obtain ultraviolet light
Hot negative photoresist.It is this prepare photoresist method technique it is tediously long, cumbersome.
The content of the invention
It is an object of the invention to provide a kind of phase transformation photoresist and preparation method thereof, preparation method letter provided by the invention
Just.
The present invention provides a kind of preparation method of phase transformation photoresist, including：
End dimaleoyl imino pH responsive polymers and sulfhydrylation light-driven proton pump are subjected to cross-linking reaction, obtain phase transformation
Photoresist.
Preferably, the preparation method of the end dimaleoyl imino pH responsive polymers comprises the following steps：
A pH) is responded into monomer, initiator and chain-transferring agent and carries out polymerisation in organic solvent, obtains Amino End Group pH
Responsive polymer, the end group of the initiator and/or chain-transferring agent is amino；
B) by the step A) obtained Amino End Group pH responsive polymers and 4- (N- maleimidomehyls) hexamethylene-
1- carboxylic acid sulfonic group succinimide reactant salts, obtain end dimaleoyl imino pH responsive polymers.
Preferably, the pH responses monomer includes the one or more in acrylic acid and acrylic homolog.
Preferably, the step B) in 4- (N- maleimidomehyls) hexamethylene -1- carboxylic acid sulfonic group succinimides
The molar ratio of salt and Amino End Group pH responsive polymers is (1~10):1.
Preferably, the step B) in reaction temperature be 10 DEG C~45 DEG C；
The step B) in reaction time be 10min~2.5h.
Preferably, the preparation method of the sulfhydrylation light-driven proton pump includes：
Light-driven proton pump and 2- iminothiolane hydrochlorides are reacted, obtain sulfhydrylation light-driven proton pump.
Preferably, the light-driven proton pump includes bacteriorhodopsin, the amino acid mutants of bacteriorhodopsin, mycetozoan
One or more in the amino acid mutants of rhodopsin and deformation bacteriorhodopsin.
Preferably, the molar ratio of the 2- iminothiolanes hydrochloride and light-driven proton pump is (10~15):1.
Preferably, the temperature of the light-driven proton pump and 2- iminothiolane hydrochloric acid reactant salts is 10 DEG C~45 DEG C；
The time of the light-driven proton pump and 2- iminothiolane hydrochloric acid reactant salts is 30min~60min.
Preferably, the molar ratio of the sulfhydrylation light-driven proton pump and end dimaleoyl imino pH responsive polymers is (1
~8):1.
Preferably, the sulfhydrylation light-driven proton pump and the temperature of end dimaleoyl imino pH responsive polymers reaction are
10 DEG C~45 DEG C；
The time of the sulfhydrylation light-driven proton pump and end dimaleoyl imino pH responsive polymers reaction for 10min~
2h。
The present invention provides a kind of phase transformation photoresist, by end dimaleoyl imino pH responsive polymers and sulfhydrylation optical drive
Proton pump cross-linking reaction obtains.
The present invention provides a kind of preparation method of phase transformation photoresist, including：End dimaleoyl imino pH is responded and is polymerize
Thing carries out cross-linking reaction with sulfhydrylation light-driven proton pump, obtains phase transformation photoresist.Preparation method provided by the invention is to hold horse
It is raw material to carry out imide pH responsive polymers with sulfhydrylation light-driven proton pump, will be polymerize with holding dimaleoyl imino pH to respond
Thing carries out a step cross-linking reaction with sulfhydrylation light-driven proton pump, you can obtains phase transformation photoresist.Compared with prior art, this hair
The preparation method step of the photoresist of bright offer is few, easy to operate, shortens technological process, reduces industrial production equipment
Use and put into, beneficial to large-scale industrial production.
Phase transformation photoresist provided by the invention, for end dimaleoyl imino pH responsive polymers and sulfhydrylation optical drive proton
Pump carries out the product of cross-linking reaction.Phase transformation photoresist provided by the invention light-operated can deform upon, and the pattern of formation shows just
Property photoresist characteristic.Phase transformation photoresist provided by the invention is efficient, sensitive, environmentally friendly, good biocompatibility, especially suitable for miniflow
Control the micro-nano technology fields such as chip, biology sensor.
Brief description of the drawings
Fig. 1 is prepared for phase transformation photoresist provided in an embodiment of the present invention and photolithography process schematic diagram；
Fig. 2 be the photoresist that is prepared of the embodiment of the present invention before phase change after atomic force microscopy.
Embodiment
The present invention provides a kind of preparation method of phase transformation photoresist, including：
End dimaleoyl imino pH responsive polymers and sulfhydrylation light-driven proton pump are subjected to cross-linking reaction, obtain phase transformation
Photoresist.
Method provided by the invention is to hold dimaleoyl imino pH responsive polymers with sulfhydrylation light-driven proton pump as original
Material, will be to hold dimaleoyl imino pH responsive polymers and sulfhydrylation light-driven proton pump to carry out a step cross-linking reaction, you can
To phase transformation photoresist.Compared with prior art, the preparation method step of photoresist provided by the invention is few, easy to operate, shortens
Technological process, reduces using and putting into for industrial production equipment, beneficial to large-scale industrial production.
End dimaleoyl imino pH responsive polymers and sulfhydrylation light-driven proton pump are carried out cross-linking reaction by the present invention, are obtained
To phase transformation photoresist.In the present invention, the end dimaleoyl imino pH responsive polymers are preferably to hold dimaleoyl imino third
Olefin(e) acid homopolymer, end dimaleoyl imino acrylic homolog homopolymer, end dimaleoyl imino acrylic acid-co- water-soluble monos
Body polymer, end dimaleoyl imino acrylic acid-b- polymerisations thing, end dimaleoyl imino acrylic homolog-
Co- polymerisations thing and end dimaleoyl imino acrylic homolog-b- polymerisation things in one kind or
It is several, more preferably hold maleimide based polyacrylic acid, end poly- (acrylic acid)-co- (the Alpha-Methyl propylene of dimaleoyl imino
Acid) or end poly- (the dimethylamino methyl ethyl acrylate)-embedding-polyacrylic acid of dimaleoyl imino.
In the present invention, when the end dimaleoyl imino pH value responsive polymer is end dimaleoyl imino acrylic acid
Homopolymer, end dimaleoyl imino acrylic homolog homopolymer, end dimaleoyl imino acrylic acid-co- water-soluble monomers gather
When compound or end dimaleoyl imino acrylic homolog-co- polymerisation things, the end dimaleoyl imino pH is rung
Emergencing copolymer is preferably prepared according to following steps：
A pH) is responded into monomer, initiator and chain-transferring agent and carries out polymerisation in organic solvent, obtains Amino End Group pH
Responsive polymer, the end group of the initiator and/or chain-transferring agent is amino；
B) by the step A) obtained Amino End Group pH responsive polymers and 4- (N- maleimidomehyls) hexamethylene-
1- carboxylic acid sulfonic group succinimide reactant salts, obtain end dimaleoyl imino pH responsive polymers.
It is poly- to have synthesized Amino End Group pH responses in order to which end dimaleoyl imino pH responsive polymers are prepared first by the present invention
Compound, is preferably specially：PH is responded into monomer, initiator and chain-transferring agent and carries out polymerisation in organic solvent, is held
Amino pH responsive polymers；In the present invention, the end group of the initiator and/or chain-transferring agent is amino.
In the present invention, the pH responses monomer preferably includes the one or more in acrylic acid and acrylic homolog,
More preferably include acrylic acid and/or methacrylic acid.In the present invention, the pH responses monomer preferably further includes water-soluble mono
Body, the water-soluble mono is known from experience to be polymerize with acrylic acid or acrylic homolog, obtains copolymer.In the present invention, it is described water-soluble
Property monomer preferably includes ethylene oxide and/or amino acid.
In the present invention, the end group of the initiator and/or chain-transferring agent is amino, so that in the knot of pH responsive polymers
Amino End Group is introduced in structure.In the present invention, the initiator is preferably azo-initiator, more preferably azodiisobutyronitrile,
Azobisisoheptonitrile or azo-bis-iso-dimethyl；The chain-transferring agent is preferably 2- aminoethanethiol hydrochlorides.In this hair
In bright, the molar ratio of the initiator and pH response monomers is preferably (150~200):1, more preferably (170~195):
1, be most preferably (185~190):1；The molar ratio of the chain-transferring agent and pH response monomers is preferably (30~50):1,
More preferably (35~45):1, be most preferably (38~40):1.
The organic solvent that the present invention uses the polymerisation does not have special limitation, ripe using those skilled in the art
That knows is used for the organic solvent of chain transfer polymerization reaction, can such as use tetrahydrofuran.The present invention is to the organic solvent
Dosage there is no special limitation, reaction medium can be provided for the polymerisation.
The pH is preferably responded monomer, initiator, chain-transferring agent and organic solvent and mixed by the present invention, after the mixing
Solution polymerisation is carried out under conditions of condensing reflux.In the present invention, the temperature of the polymerisation is preferably 50 DEG C
~70 DEG C, more preferably 55 DEG C~65 DEG C, are most preferably 60 DEG C；The time of the polymerisation is preferably 1.5h~2.5h, more
Preferably 1.75h~2.25h, is most preferably 2h.
It is of the invention preferably by the sedimentation separation in methyl alcohol of obtained polymeric reaction product after completing the polymerisation, then
Precipitation after the sedimentation separation is washed with methanol, is dry, obtains Amino End Group pH responsive polymers.The present invention is to the drying
Method there is no special limitation, such as can be vacuum using the technical solution of drying well known to those skilled in the art
It is dry.
In the present invention, when the pH responsive polymers are end dimaleoyl imino acrylic acid-b- polymerisations
Thing or end dimaleoyl imino acrylic homolog-b- polymerisation things, specially poly- (dimethylamino methyl acrylic acid
Ethyl ester)-embedding-polyacrylic acid (PDMA-b-PAA) when, the preparation method of Amino End Group pH responsive polymers preferably includes following steps：
Using 2- bromines ethamine as initiator, PDMA-b-PAA precursors are synthesized using atom transfer free crowd (ATRP) method；
The PDMA-b-PAA precursors are subjected to acidolysis, obtain Amino End Group PDMA-b-PAA.
The present invention is preferably by 2- bromines ethamine, cuprous bromide, 2,2 '-bipyridine and N, TMSDMA N dimethylamine methyl acrylate
React in organic solvent, obtain PDMA-b-PAA precursor intermediate products；
The PDMA-b-PAA precursors intermediate product and cuprous bromide, 2,2 '-bipyridine and tert-butyl acrylate are existed
Reacted in organic solvent, obtain PDMA-b-PAA precursors.
The present invention is preferably under protective atmosphere, by 2- bromines ethamine, cuprous bromide, 2,2 '-bipyridine and N, and TMSDMA N dimethylamine
Methyl acrylate mixes in organic solvent to be reacted.The present invention does not have special limit to the species of the protective atmosphere
System, using inert protective gas well known to those skilled in the art, can such as use nitrogen protection atmosphere.
In the present invention, the 2- bromines ethamine, cuprous bromide, 2,2 '-bipyridine and N, TMSDMA N dimethylamine ylmethyl propylene
The molar ratio of acid esters is preferably 1:(0.5~2):(1~5):(1~5), more preferably 1 (1.0~1.5):(2.0~2.5):
(2.0~2.5).The present invention does not have special limitation to the species of the organic solvent, and use is well known to those skilled in the art
In ATRP method frequently with organic solvent, such as can be ethyl acetate；The 2- bromines ethamine is in the organic solvent
Molar concentration is preferably 0.01mol/L~0.05mol/L, more preferably 0.02mol/L~0.03mol/L, is most preferably
0.0218mol/L。
In the present invention, the 2- bromines ethamine, cuprous bromide, 2,2 '-bipyridine and N, TMSDMA N dimethylamine ylmethyl propylene
The temperature of acid esters reaction is preferably 35 DEG C~55 DEG C, more preferably 40 DEG C~50 DEG C, is most preferably 45 DEG C；The 2- bromines ethamine,
Cuprous bromide, 2,2 '-bipyridine and N, the time of TMSDMA N dimethylamine methyl acrylate reaction is preferably 2h~4h, more preferably
It is most preferably 3h for 2.5h~3.5h.
It is of the invention by the PDMA-b-PAA precursors intermediate product and bromination after obtaining PDMA-b-PAA precursor intermediate products
It is cuprous, 2,2 '-bipyridine and tert-butyl acrylate react in organic solvent, obtain PDMA-b-PAA precursors.The present invention is excellent
It is selected under protective atmosphere, by the PDMA-b-PAA precursors intermediate product and cuprous bromide, 2,2 '-bipyridine and acrylic acid uncle
Butyl ester is reacted in organic solvent mixing；The present invention does not have special limitation to the species of the protective atmosphere, using ability
Inert protective gas known to field technique personnel, can such as use nitrogen protection atmosphere.
In the present invention, the PDMA-b-PAA precursors intermediate product, cuprous bromide, 2,2 '-bipyridine and acrylic acid
The molar ratio of the tert-butyl ester is preferably 1:(0.5~2):(1~5):(1~5), more preferably 1 (1.0~1.5):(2.0~2.5):
(2.0~2.5).The present invention does not have special limitation to the species of the organic solvent, and use is well known to those skilled in the art
In ATRP method frequently with organic solvent, such as can be ethyl acetate；The PDMA-b-PAA precursors intermediate product is in institute
It is preferably 0.01mol/L~0.05mol/L to state the molar concentration in organic solvent, more preferably 0.02mol/L~0.03mol/
L, is most preferably 0.0218mol/L.
In the present invention, the PDMA-b-PAA precursors intermediate product and cuprous bromide, 2,2 '-bipyridine and acrylic acid
The temperature of tert-butyl ester reaction is preferably 35 DEG C~55 DEG C, more preferably 40 DEG C~50 DEG C, is most preferably 45 DEG C；The PDMA-b-
The time of PAA precursors intermediate product and cuprous bromide, 2,2 '-bipyridine and tert-butyl acrylate reaction is preferably 2h~4h,
More preferably 2.5h~3.5h, is most preferably 3h.
After obtaining PDMA-b-PAA precursors, the PDMA-b-PAA precursors are preferably carried out acidolysis by the present invention, obtain end ammonia
Base PDMA-b-PAA.The PDMA-b-PAA is preferably carried out acidolysis by the present invention in the mixed solution of hydrochloric acid and dioxane；
In the present invention, the volume ratio of the hydrochloric acid and dioxane is preferably 1:(3~7), more preferably 1:(4~6), are most preferably
1:5；The present invention does not have special limitation to the concentration of hydrochloric acid, and the commercial goods using hydrochloric acid well known to those skilled in the art are
Can.In the present invention, the temperature of the acidolysis is preferably 80 DEG C~100 DEG C, more preferably 85 DEG C~95 DEG C, is most preferably 90
℃；The time of the acidolysis is preferably 10h~14h, more preferably 11h~13h, is most preferably 12h.
After completing the acidolysis, the present invention preferably removes the solvent in the acid hydrolysate, obtains Amino End Group PDMA-b-
PAA.The present invention does not have special limitation to the method for removing solvent, using well known to those skilled in the art except the technology of solvent
Scheme, can such as use the solvent in the method removing acid hydrolysate of revolving.
The number-average molecular weight for the Amino End Group pH responsive polymers that the present invention obtains is preferably 3000~7000.
It is of the invention by the Amino End Group pH responsive polymers and 4- (N- Malaysias acyls after obtaining Amino End Group pH responsive polymers
Formimino group) hexamethylene -1- carboxylic acid sulfonic group succinimide reactant salts, obtain end dimaleoyl imino pH responsive polymers.
The present invention is preferably by the Amino End Group pH responsive polymers and 4- (N- maleimidomehyls) hexamethylene -1- carboxylic acid sulfonic group ambers
Amber imide salts are reacted in buffer solution.Specifically, it is preferred that the Amino End Group pH responsive polymers are dissolved in buffer solution, then
4- (N- maleimidomehyls) hexamethylene -1- carboxylic acid sulfonic group succinimide salt is added thereto, and reaction obtains end Malaysia
Imide pH responsive polymers.In the present invention, the buffer solution is preferably phosphate buffer solution；The buffer solution
Molar concentration be preferably 40mmol/L~60mmol/L, more preferably 45mmol/L~55mmol/L, be most preferably 50mmol/
L；The pH value of the buffer solution is preferably 6.5~7.5, and more preferably 7.0~7.2.
In the present invention, 4- (N- maleimidomehyls) hexamethylene -1- carboxylic acids sulfonic group succinimide salt with
The molar ratio of the Amino End Group pH responsive polymers is preferably (1~10):1, more preferably (2~8):1, be most preferably (3~
6):1。
In the present invention, 4- (N- maleimidomehyls) hexamethylene -1- carboxylic acids sulfonic group succinimide salt with
The temperature of the Amino End Group pH responsive polymers reaction is preferably 10 DEG C~45 DEG C, more preferably 15 DEG C~40 DEG C；4- (the N-
Maleimidomehyl) reaction of hexamethylene -1- carboxylic acids sulfonic group succinimide salt and the Amino End Group pH responsive polymers
Time is preferably 10min~2.5h, more preferably 15min~2.25h, is most preferably 20min~2h.
4- (N- maleimidomehyls) hexamethylene -1- carboxylic acids sulfonic group succinimide salt and the Amino End Group pH
After the completion of responsive polymer reaction, the reaction product desalination of the invention that will preferably obtain, then de-, drying is washed with deionized water, obtain
To end dimaleoyl imino pH responsive polymers.The present invention does not have special limitation to the method for the desalination, using this area
The technical solution of desalination known to technical staff, can such as use desalting column to the 4- (N- maleimidomehyls) ring
Hexane -1- carboxylic acids sulfonic group succinimide salt and the reaction product of the Amino End Group pH responsive polymers carry out desalination.This hair
The bright method to the drying is not particularly limited, using the technical solution of drying well known to those skilled in the art；This
Invention drying under protective gas air-flow preferably by the reaction product after elution；The present invention does not have the species of the protective gas
Special limitation, such as can be nitrogen using protective gas well known to those skilled in the art.
After obtaining end dimaleoyl imino pH responsive polymers, the present invention, which responds the end dimaleoyl imino pH, to be polymerize
Thing carries out cross-linking reaction with sulfhydrylation light-driven proton pump, obtains phase transformation photoresist.In the present invention, the sulfhydrylation optical drive
The preparation method of proton pump preferably includes：
Light-driven proton pump and 2- iminothiolane hydrochlorides are reacted, obtain sulfhydrylation light-driven proton pump.
The present invention is preferably reacted light-driven proton pump and 2- iminothiolane hydrochlorides in buffer solution, is obtained
Sulfhydrylation light-driven proton pump.Specifically, light-driven proton pump is preferably dissolved in buffer solution by the present invention；It is mixed by what is obtained again
Close solution to mix with 2- iminothiolane hydrochlorides, reacted, obtain sulfhydrylation light-driven proton pump.In the present invention, institute
It is preferably PBST-EDTA buffer solutions to state buffer solution, the PBST-EDTA buffer solutions include phosphate, Tween-20 and
EDTA；In the present invention, in the PBST-EDTA buffer solutions, phosphatic molar concentration be preferably 20mmol/L~
30mmol/L, more preferably 22mmol/L~28mmol/L, are most preferably 25mmol/L；In the PBST-EDTA buffer solutions,
The mass concentration of Tween-20 is preferably 3%~7%, and more preferably 4%~6%, it is most preferably 5%；The PBST-EDTA delays
Rush in solution, the molar concentration of EDTA is preferably 5mmol/L~15mmol/L, more preferably 7mmo/L~12mmol/L, optimal
Elect 10mmol/L as.In the present invention, the pH value of the PBST-EDTA buffer solutions is preferably 8.0~9.5, and more preferably 8.5
~9.2, it is most preferably 9.0.
In the present invention, mass concentration of the light-driven proton pump in the buffer solution be preferably 5mg/mL~
15mg/mL, more preferably 7mg/nL~13mg/mL, are most preferably 10mg/mL.
In the present invention, the light-driven proton pump preferably includes the amino acid mutation of bacteriorhodopsin, bacteriorhodopsin
One or more in the amino acid mutants of body, deformation bacteriorhodopsin and deformation bacteriorhodopsin；More preferably include bacterium
Rhodopsin and/or deformation bacteriorhodopsin.The present invention does not have special limitation to the source of the light-driven proton pump, uses
The commercial goods of above-mentioned light-driven proton pump well known to those skilled in the art.In the present invention, the 2- imino group mercaptans
The molar ratio of heptane hydrochloride salt and light-driven proton pump is (10~15):1, more preferably (11~14):1, be most preferably (12~
13):1。
In the present invention, the temperature of the light-driven proton pump and 2- iminothiolane hydrochloric acid reactant salts be preferably 10 DEG C~
45 DEG C, more preferably 15 DEG C~40 DEG C；The time of the light-driven proton pump and 2- iminothiolane hydrochloric acid reactant salts is preferably
30min~60min, more preferably 35min~55min, are most preferably 40min~50min.
The light-driven proton pump and the reaction that after the completion of 2- iminothiolane hydrochloric acid reactant salts, the present invention will preferably obtain
Product desalination, obtains sulfhydrylation light-driven proton pump.The present invention does not have special limitation to the method for the desalination, using ability
The technical solution of desalination known to field technique personnel, can such as use desalting column to light-driven proton pump and 2- imino group mercaptans
The reaction product of heptane hydrochloride salt carries out desalination.
It is of the invention by the end after obtaining end dimaleoyl imino pH responsive polymers and sulfhydrylation light-driven proton pump
Dimaleoyl imino pH responsive polymers carry out cross-linking reaction with sulfhydrylation light-driven proton pump, obtain phase transformation photoresist.At this
In invention, the sulfhydrylation light-driven proton pump with end dimaleoyl imino pH responsive polymers molar ratio be preferably (1~
8):1, more preferably (2~6):1；In an embodiment of the present invention, the sulfhydrylation light-driven proton pump and end maleimide
The molar ratio of base pH responsive polymers can be 2:1、3:1、4:1、5:1 or 6:1.
In the present invention, the light-driven proton pump and the temperature of end dimaleoyl imino pH responsive polymers reaction
Preferably 10 DEG C~45 DEG C, more preferably 15 DEG C~40 DEG C；Specifically, in an embodiment of the present invention, the optical drive proton
Pump with the end dimaleoyl imino pH responsive polymers reaction temperature can be 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C or
40℃.In the present invention, the driving proton pump and the time that the end dimaleoyl imino pH responsive polymers react are preferred
For 10min~2h；Specifically, in an embodiment of the present invention, the light-driven proton pump and the end dimaleoyl imino pH
The time of responsive polymer reaction can be 10min, 30min, 1h, 1.5h or 2h.
After the completion of the light-driven proton pump is reacted with the end dimaleoyl imino pH responsive polymers, the present invention is preferably
Obtained reaction product is purified, to remove Tween-20 therein.The present invention does not have special limit to the method for the purifying
System, using the technical solution of purifying well known to those skilled in the art, such as can by the light-driven proton pump with it is described
The reaction product of dimaleoyl imino pH responsive polymers is held through Extractigel column purifications.
Described in completing after purification, the present invention preferably centrifuges product after purification, obtains supernatant.The present invention to it is described from
The method of the heart does not have special limitation, using the technical solution of centrifugation well known to those skilled in the art.
After obtaining supernatant, the present invention preferably removes the solvent in the supernatant, obtains phase transformation photoresist.The present invention is right
The method for removing solvent does not have special limitation, using well known to those skilled in the art except the technical solution of solvent, such as
The supernatant can be rotated, preferably rotates the supernatant under nitrogen protection, to remove solvent therein.
Referring to Fig. 1, Fig. 1 is prepared for phase transformation photoresist provided in an embodiment of the present invention and photolithography process schematic diagram, first
PH responsive polymers and sulfhydrylation light-driven proton pump are first subjected to cross-linking reaction, obtain phase transformation photoresist；The phase that will be obtained again
Become photoresist and be spun to stromal surface, form photoresist film；Patterned, made using electron beam irradiation photoresist film again
Photoresist is crosslinked；Again under dark condition, the photoresist film after will be patterned into is placed in water, photoresist swelling；Finally to molten
Swollen photoresist film carries out illumination, and photoresist film precipitation is swollen, shows positive photoetching rubber characteristic.
The present invention provides a kind of phase transformation photoresist, for end dimaleoyl imino pH responsive polymers and the CD-ROM drive of sulfhydrylation
Dynamic proton pump carries out the product of cross-linking reaction.
In the present invention, the kind of the light-driven proton pump of the end dimaleoyl imino pH responsive polymers and sulfhydrylation
Class, source and the light-driven proton pump of end dimaleoyl imino pH responsive polymers and sulfhydrylation carry out the technology of cross-linking reaction
Scheme is consistent with described in above-mentioned technical proposal, and details are not described herein.
Phase transformation photoresist provided by the invention light-operated can deform upon, and the pattern of formation shows positive photoresist characteristic.
Phase transformation photoresist provided by the invention is efficient, sensitive, environmentally friendly, good biocompatibility, is passed especially suitable for micro-fluidic chip, biology
The micro-nano technology such as sensor field.
Phase transformation photoresist provided by the invention can be used for electron beam lithography field, specifically, the phase transformation photoresist
Application method preferably include following steps：
Glass slide after cleaning is subjected to silication；
The organic solution of phase transformation photoresist is coated on the glass slide after silication, obtains phase transformation photoresist film；
Patterned using photoresist film described in electron beam or ion beam irradiation；
Under the conditions of lucifuge, the phase transformation photoresist film after will be patterned into is dipped in ultra-pure water；
The phase transformation photoresist film being dipped in ultra-pure water is exposed.
Glass slide after cleaning is carried out silication by the present invention.It is special that the present invention does not have the clean method of the glass slide
Limitation, using the technical solution of cleaning glass slide well known to those skilled in the art.Glass slide can such as be carried out successively
Ethanol cleaning, ultraviolet light, Low Pressure Oxygen corona treatment.In we, the time of the ultraviolet irradiation is preferably
6min~12min, more preferably 8min~11min, are most preferably 10min；The time of the Low Pressure Oxygen corona treatment is excellent
Elect 6min~12min as, more preferably 8min~11min, be most preferably 10min；The pressure of the Low Pressure Oxygen corona treatment
Power is preferably 40Pa；The power of the Low Pressure Oxygen corona treatment is preferably 1.75W.
After completing to the cleaning of glass slide, the glass slide after cleaning is carried out silicidation by the present invention, after preferably cleaning
Glass slide be dipped in silane reagent, to glass slide carry out silication.In the present invention, the silane reagent is preferably vinyl first
The methanol solution of oxysilane；The mass concentration of the silane reagent is preferably 2%；The time of the silicidation is preferably
6min~12min, more preferably 8min~11min, are most preferably 10min.
After completing to the silicidation of glass slide, the glass slide after silicidation is preferably cleaned, done by the present invention with ethanol
It is dry.The present invention does not have special limitation to the method for the drying, using the technical side of drying well known to those skilled in the art
Case；In the present invention, the temperature of the drying is preferably 100 DEG C~120 DEG C, more preferably 105 DEG C~115 DEG C, optimal
Elect 110 DEG C as；The time of the drying is preferably 6min~12min, more preferably 8min~11min, is most preferably 10min.
After obtaining the glass slide after silication, the organic solution of phase transformation photoresist is coated in the glass slide after silication by the present invention
On, obtain phase transformation photoresist film.In the present invention, the solvent in the organic solution of the phase transformation photoresist is preferably dimethyl
Formamide；The mass concentration of the organic solution of the phase transformation photoresist is preferably 1%~3%, and more preferably 1.5%~2.5%,
Most preferably 2%.
The present invention does not have special limitation to the method for the coating, using the skill of coating well known to those skilled in the art
Art scheme, such as can be spin coating；In the present invention, the rotating speed of the spin coating is preferably 4000rpm.
After completing the coating, one layer of phase transformation photoresist film is formed in slide surface；The phase transformation photoresist film
Thickness be preferably 35nm~45nm, more preferably 38nm~42nm, be most preferably 45nm；
After completing the coating, preferably obtained phase transformation photoresist film is dried by the present invention, therein to remove
Residual solvent.The present invention does not have special limitation to the method for the drying, using drying well known to those skilled in the art
Technical solution；In the present invention, the drying is preferably to be dried in vacuo；The vacuum drying temperature is preferably 40 DEG C~
50 DEG C, more preferably 45 DEG C；The vacuum drying time is preferably 1.5h~2.5h, is most preferably 1.75h~2.25h.
After obtaining phase transformation photoresist film, the present invention carries out figure using photoresist film described in electron beam or ion beam irradiation
Case.The present invention does not have special limitation to the equipment of the patterned method and use, ripe using those skilled in the art
The lithographic equipment known, can such as use FEI XL30 field emission scanning electron microscopes and NPGS electron beam lithographic etching systems.
In the present invention, the maximum electron energy of the beam current of the electron beam irradiation is preferably 2kV.
After completing the patterning, the present invention soaks the phase transformation photoresist film after the patterning under the conditions of lucifuge
In ultra-pure water.Phase transformation photoresist film after the present invention will be patterned into is dipped in ultra-pure water, since pH is rung in phase transformation photoresist
The aquation of emergencing copolymer so that photoresist film is swollen in ultra-pure water；When pH is higher than the pKa of hydrogel, acrylic acid
The carboxylic acid group of institute's band starts to dissociate on monomer, causes osmotic pressure gradually to accumulate, and causes macromolecular chain significantly to stretch and hydrogel
Further swelling.In the present invention, the pH value of the ultra-pure water is preferably 9.0；The phase transformation photoresist film that will be patterned into
The time being dipped in ultra-pure water is preferably 6min~12min, more preferably 8min~11min, is most preferably 10min.
After phase transformation photoresist film after will be patterned into is dipped in ultra-pure water, the present invention will soak the phase darkening of ultra-pure water
Photoresist film exposes.Surpass specifically, the present invention can use the irradiation of Dolan-Jenner MI-150 fiber optic illuminators to soak
Phase transformation photoresist film after pure water, is exposed the phase transformation photoresist film；The power setting of the irradiation is 1%
(about 500mV)；The wavelength of the irradiation is the characteristic absorption wavelength of light-driven proton pump, is preferably 420nm~580nm, more excellent
Elect 490nm~550nm as, be most preferably 515nm~525nm.During exposure, the optical drive in phase transformation photoresist film
Proton pump absorbs the energy in illumination ripple, plays it and transports the ability of proton, reduces the pH value of local environment, make phase transformation photoresist
Film is shunk because precipitation is swollen, causes volume significant change, so that positive photoresist characteristic be presented.
The present invention provides a kind of preparation method of phase transformation photoresist, including：End dimaleoyl imino pH is responded and is polymerize
Thing carries out cross-linking reaction with sulfhydrylation light-driven proton pump, obtains phase transformation photoresist.Preparation method provided by the invention is to hold horse
It is raw material to carry out imide pH responsive polymers with sulfhydrylation light-driven proton pump, will be polymerize with holding dimaleoyl imino pH to respond
Thing carries out a step cross-linking reaction with sulfhydrylation light-driven proton pump, you can obtains phase transformation photoresist.Compared with prior art, this hair
The preparation method step of the photoresist of bright offer is few, easy to operate, shortens technological process, reduces industrial production equipment
Use and put into, beneficial to large-scale industrial production.
Phase transformation photoresist provided by the invention, for end dimaleoyl imino pH responsive polymers and sulfhydrylation optical drive proton
Pump carries out the product of cross-linking reaction.Phase transformation photoresist provided by the invention light-operated can deform upon, and the pattern of formation shows just
Property photoresist characteristic.Phase transformation photoresist provided by the invention is efficient, sensitive, environmentally friendly, good biocompatibility, especially suitable for miniflow
Control the micro-nano technology fields such as chip, biology sensor.
In order to further illustrate the present invention, with reference to embodiment to phase transformation photoresist provided by the invention and its preparation side
Method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Under nitrogen protection, 10g acrylic acid, 0.4g 2- aminoethanethiol hydrochlorides, 0.12g are added into 100mL flasks
Azodiisobutyronitrile and 20mL tetrahydrofurans, when 60 DEG C of condensing reflux reactions 2 are small, reaction product pours into sedimentation separation in methanol,
Methanol washing precipitation, vacuum drying, obtains the polyacrylic acid that end is amino；
It is that 50mmol/L phosphate delays that the polyacrylic acid that the end that above-mentioned steps synthesize is amino is dissolved in 2mL molar concentrations
Solution (PBS, pH value=7.2) is rushed, adds 4- (N- maleimide of 6 times of ends for the polyacrylic acid molal quantity of amino thereto
Amine methyl) hexamethylene -1- carboxylic acid sulfonic group succinimides salt (being purchased from Thermo Scientific companies of the U.S.), it will obtain
Mixed solution react 2h at 15 DEG C after, using desalting column desalination, de-, nitrogen stream drying is washed with deionized water, obtains end
For the polyacrylic acid of maleimide；
5mg deformation bacteriorhodopsins (EBAC31A08) are dissolved in 0.5mL PBST-EDTA buffer solutions (25mmol/L PBS+
5%Tween-20+10mmol/L EDTA, pH value=9.0), 13 times of deformation bacteriorhodopsin molal quantity Traut ' are added thereto
S reagents (are purchased from Thermo Scientific companies of the U.S.), and obtained mixed solution is reacted 45min at 15 DEG C, will be obtained
Reaction product use desalting column desalination, complete to deform bacteriorhodopsin sulfhydrylation, obtain sulfhydrylation mycetozoan rhodopsin
Matter；
It is 2 by molar ratio:The deformation bacteriorhodopsin of 1 sulfhydrylation is mixed with end for the polyacrylic acid of maleimide
Afterwards, 1h is reacted at 15 DEG C.Reaction product is purified through Extractigel columns (being purchased from Thermo Scientific companies of the U.S.)
To remove Tween-20.Gained eluent is slightly cloudy, centrifuging and taking supernatant.Solvent is evaporated off in nitrogen protection backspin, obtains phase darkening
Photoresist.
Embodiment 2
Under nitrogen protection, 8.2mL acrylic acid, 5.1mL methacrylic acids, 0.58g 2- amino are added into 100mL flasks
Ethanethiol hydrochloride, 0.18g azodiisobutyronitriles and 30mL tetrahydrofurans, 60 DEG C of reaction 2.5h, product is with distilled water immersion
48h, changes water to remove unreacted monomer and impurity, 80 DEG C of drying, obtain poly- (acrylic acid)-co- (α-first that end is amino
Base acrylic acid)；
It is as a result 4860~6050 using the number-average molecular weight of the product after gel exclusion chromatography measure drying.
The end that above-mentioned steps are prepared is dissolved in 2mL for poly- (the acrylic acid)-co- (α-methacrylic acid) of amino and rubs
The phosphate buffer solution (PBS, pH value=7.2) that your concentration is 50mmol/L, adds 5 times of ends as the poly- of amino thereto
4- (N- maleimidomehyls) hexamethylene -1- carboxylic acid sulfonic group ambers of (acrylic acid)-co- (α-methacrylic acid) molal quantity
Imide salts, after obtained mixed solution is reacted 2h at room temperature, using desalting column desalination, are washed with deionized water de-, nitrogen
Drying is flowed, obtains poly- (the acrylic acid)-co- (α-methacrylic acid) that end is maleimide；
5mg bacteriorhodopsins (being purchased from Sigma Co., USA) are dissolved in 0.5mL PBST-EDTA buffer solutions (25mmol/L
PBS+5%Tween-20+10mmol/L EDTA, pH value=9.0), 10 times of bacteriorhodopsin molal quantitys are added thereto
Traut ' s reagents, react 45min at room temperature by obtained mixed solution, using reaction product desalination of the desalting column to obtaining,
The sulfhydrylation to bacteriorhodopsin is completed, obtains sulfhydrylation bacteriorhodopsin；
It is 6 by molar ratio:The bacteriorhodopsin of 1 sulfhydrylation and poly- (the acrylic acid)-co- that end is maleimide
After (α-methacrylic acid) mixing, 1h is reacted at room temperature, reaction product is after Extractigel column purifications, centrifuging and taking supernatant,
Supernatant is rotated under nitrogen protection and removes solvent, obtains phase transformation photoresist.
Embodiment 3
Under nitrogen protection, added into 100mL round-bottomed flasks 1.09mmol 2- bromines ethamine, 1.08mmol cuprous bromides,
0.218mmol 2,2 '-bipyridine, 0.218mmol N, TMSDMA N dimethylamine amino ethyl methacrylate (DMA) and 50mL acetic acid second
Ester, reacts 3h by obtained mixed solution at 45 DEG C；
Products therefrom 1.09mmol is taken, adds 1.08mmol cuprous bromides, 0.218mmol 2,2 '-union II pyrrole thereto
Pyridine, 0.218mmol tert-butyl acrylates and 50mL ethyl acetate, react 3h, before obtaining by obtained mixed solution at 45 DEG C
Body；
Precursor PDMA-b-PtBuA is dissolved in volume ratio for 1:5 hydrochloric acid and the in the mixed solvent of dioxane, obtain
Obtained reaction product is rotated removing solvent, obtains end as amino by solution under nitrogen protection in 90 DEG C of acidolysis 12h
PDMA-b-PAA；
Use number-average molecular weight of the end that gel exclusion chromatography measures for the PDMA-b-PAA of amino, as a result for
6000~7000；
It is 50mmol/L phosphate-buffereds that the PDMA-b-PAA for the Amino End Group that above-mentioned steps are obtained, which is dissolved in 2mL molar concentrations,
Solution (PBS, pH value=7.2), adds 4- (N- maleimide of 5 times of ends for the PDMA-b-PAA molal quantitys of amino thereto
Amine methyl) hexamethylene -1- carboxylic acid sulfonic group succinimide salt, after obtained mixed solution is reacted 10min at 40 DEG C, make
With desalting column desalination, it is washed with deionized water de-, nitrogen stream drying, obtains the PDMA-b-PAA that end is maleimide；
5mg deformation bacteriorhodopsins (EBAC31A08) are dissolved in 0.5mL PBST-EDTA buffer solutions (25mmol/L PBS+
5%Tween-20+10mmol/L EDTA, pH value=9.0), 13 times of deformation bacteriorhodopsin molal quantity Traut ' are added thereto
S reagents (are purchased from Thermo Scientific companies of the U.S.), and obtained mixed solution is reacted 45min at 15 DEG C, will be obtained
Reaction product use desalting column desalination, complete to deform bacteriorhodopsin sulfhydrylation, obtain sulfhydrylation mycetozoan rhodopsin
Matter；
It is 5 by molar ratio:The deformation bacteriorhodopsin of 1 sulfhydrylation is mixed with end for the PDMA-b-PAA of maleimide
After conjunction, 10min is reacted at 40 DEG C, reaction product is after Extractigel column purifications, centrifuging and taking supernatant, and nitrogen protection is lower will
Supernatant revolving removes solvent, obtains phase transformation photoresist.
Embodiment 4~6
By glass slide using irradiation 10min, low pressure oxygen plasma treatment (40Pa, 1.75W) under ethanol cleaning, ultraviolet lamp
10min；The methanol that glass slide is dipped in the vinyl methoxy silane (being purchased from traditional Chinese medicines chemical company) that mass concentration is 2% again is molten
10min carries out silication in liquid, is cleaned afterwards with ethanol, dry 10min at 110 DEG C；
The phase transformation photoresist that embodiment 1~3 is prepared is dissolved in dimethylformamide respectively, mass concentration, which is made, is
2% phase transformation photoresist solution, by obtained photoresist solution spin coating (4000rpm) in the matrix after silication, forms thickness
The photoresist film of about 40nm, 2h is dried in vacuo at 45 DEG C, removes all residual solvents；
Using FEI XL30 field emission scanning electron microscopes (being purchased from FEI Co. of the U.S.) and NPGS electron beam lithographic etching systems
(being purchased from JC Nabity companies of the U.S.) patterns photoresist film.Beam current is measured using Faraday cup, used
Maximum electron energy is 2kV.
Under the conditions of lucifuge, the film sample after will be patterned into is dipped in ultra-pure water (pH 9.0) 10min；
Using Dolan-Jenner MI-150 fiber optic illuminators (being purchased from Edmund companies of the U.S.) irradiating step C)
The film sample arrived, power setting are 1% (about 500mV), wavelength 525nm.
Using step C) in same scanning electron microscope carry out magnification at high multiple imaging, accelerating potential 1.0keV, imaging results are such as
Shown in Fig. 2, Fig. 2 be the obtained photoresist of the embodiment of the present invention 4~6 before phase change after atomic force microscopy, wherein Fig. 2A
The photoresist obtained for the embodiment of the present invention 4 before phase change after atomic force microscopy, Fig. 2 B obtain for the embodiment of the present invention 5
Photoresist before phase change after atomic force microscopy, Fig. 2 C be the obtained photoresist of the embodiment of the present invention 6 before phase change after
Atomic force microscopy, in Fig. 2A and Fig. 2 C, illumination wavelength is 514.5nm in illumination wavelength 525nm, Fig. 2 B.
As seen from the above embodiment, preparation method provided by the invention is to hold dimaleoyl imino pH responsive polymers and mercapto
Base light-driven proton pump is raw material, and end dimaleoyl imino pH responsive polymers and sulfhydrylation light-driven proton pump are carried out one
Walk cross-linking reaction, you can obtain phase transformation photoresist.Compared with prior art, the preparation method step of photoresist provided by the invention
Less, it is easy to operate, technological process is shortened, reduces using and putting into for industrial production equipment, beneficial to heavy industrialization
Production.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of phase transformation photoresist, including：
End dimaleoyl imino pH responsive polymers and sulfhydrylation light-driven proton pump are subjected to cross-linking reaction, obtain phase transformation photoetching
Glue；
The end dimaleoyl imino pH responsive polymers are end dimaleoyl imino acrylate homopolymer, end dimaleoyl imino
Acrylic homolog homopolymer, end dimaleoyl imino acrylic acid-co- polymerisations thing, end dimaleoyl imino third
Olefin(e) acid-b- polymerisations thing, end dimaleoyl imino acrylic homolog-co- polymerisations thing and end horse
Carry out the one or more in imide acrylic homolog-b- polymerisation things；
The end dimaleoyl imino pH responsive polymers are prepared according to following steps：
A pH) is responded into monomer, initiator and chain-transferring agent and carries out polymerisation in organic solvent, obtains Amino End Group pH responses
Polymer, the end group of the initiator and/or chain-transferring agent is amino；
B) by the step A) obtained Amino End Group pH responsive polymers and 4- (N- maleimidomehyls) hexamethylene -1- carboxylic acids
Sulfonic group succinimide reactant salt, obtains end dimaleoyl imino pH responsive polymers；
The pH responses monomer includes the one or more in acrylic acid and acrylic homolog；
The initiator is azo-initiator；
The chain-transferring agent is 2- aminoethanethiol hydrochlorides；
The preparation method of the sulfhydrylation light-driven proton pump includes：
Light-driven proton pump and 2- iminothiolane hydrochlorides are reacted in buffer solution, obtain sulfhydrylation CD-ROM drive kinoplaszm
Son pump；
The light-driven proton pump include bacteriorhodopsin, bacteriorhodopsin amino acid mutants, deformation bacteriorhodopsin and
Deform the one or more in the amino acid mutants of bacteriorhodopsin.
2. in the preparation method described in claim 1, step B) in 4- (N- maleimidomehyls) hexamethylene -1- carboxylic acid sulfonic acid
Base succinimide salt and the molar ratio of Amino End Group pH responsive polymers are (1~10):1.
3. preparation method according to claim 1 or 2, it is characterised in that the step B) in reaction temperature be 10 DEG C
~45 DEG C；
The step B) in reaction time be 10min~2.5h.
4. preparation method according to claim 1, it is characterised in that the 2- iminothiolanes hydrochloride and CD-ROM drive kinoplaszm
The molar ratio of son pump is (10~15):1.
5. preparation method according to claim 1, it is characterised in that the light-driven proton pump and 2- iminothiolane salt
The temperature of hydrochlorate reaction is 10 DEG C~45 DEG C；
The time of the light-driven proton pump and 2- iminothiolane hydrochloric acid reactant salts is 30min~60min.
6. preparation method according to claim 1, it is characterised in that the sulfhydrylation light-driven proton pump and end Malaysia acyl
The molar ratio of imido grpup pH responsive polymers is (1~8):1.
7. preparation method according to claim 1, it is characterised in that the sulfhydrylation light-driven proton pump and end Malaysia acyl
The temperature of imido grpup pH responsive polymers reaction is 10 DEG C~45 DEG C；
The sulfhydrylation light-driven proton pump and the time of end dimaleoyl imino pH responsive polymers reaction are 10min~2h.
8. a kind of phase transformation photoresist, is prepared as the method described in claim 1.
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| EP0596668A2 (en) * | 1992-11-03 | 1994-05-11 | International Business Machines Corporation | Process for imaging of photoresist |
| WO2001042854A1 (en) * | 1999-12-09 | 2001-06-14 | Autologic Information International, Inc. | Platemaking system and method using an imaging mask made from photochromic film |
| US7291442B1 (en) * | 2001-11-28 | 2007-11-06 | University Of Central Florida Research Foundation, Inc. | Photosensitive polymeric material for WORM optical data storage with two-photon fluorescent readout |
| CN102037346A (en) * | 2008-04-16 | 2011-04-27 | 明智全像公司 | Photopolymerizable compositions |
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| US4728591A (en) * | 1986-03-07 | 1988-03-01 | Trustees Of Boston University | Self-assembled nanometer lithographic masks and templates and method for parallel fabrication of nanometer scale multi-device structures |
| EP0596668A2 (en) * | 1992-11-03 | 1994-05-11 | International Business Machines Corporation | Process for imaging of photoresist |
| WO2001042854A1 (en) * | 1999-12-09 | 2001-06-14 | Autologic Information International, Inc. | Platemaking system and method using an imaging mask made from photochromic film |
| US7291442B1 (en) * | 2001-11-28 | 2007-11-06 | University Of Central Florida Research Foundation, Inc. | Photosensitive polymeric material for WORM optical data storage with two-photon fluorescent readout |
| CN102037346A (en) * | 2008-04-16 | 2011-04-27 | 明智全像公司 | Photopolymerizable compositions |
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