CN101560061B - Method for preparing patterned polymer brush - Google Patents
Method for preparing patterned polymer brush Download PDFInfo
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- CN101560061B CN101560061B CN2009100521493A CN200910052149A CN101560061B CN 101560061 B CN101560061 B CN 101560061B CN 2009100521493 A CN2009100521493 A CN 2009100521493A CN 200910052149 A CN200910052149 A CN 200910052149A CN 101560061 B CN101560061 B CN 101560061B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 55
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 14
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims 3
- 239000011259 mixed solution Substances 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- IKZZMZXDVDRISR-UHFFFAOYSA-N trimethyl 4-(oxiran-2-yl)butyl silicate Chemical compound CO[Si](OC)(OC)OCCCCC1CO1 IKZZMZXDVDRISR-UHFFFAOYSA-N 0.000 claims 1
- 238000001338 self-assembly Methods 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000001259 photo etching Methods 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 238000007654 immersion Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000005286 illumination Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- WKEXHTMMGBYMTA-UHFFFAOYSA-N trimethyl propyl silicate Chemical compound CCCO[Si](OC)(OC)OC WKEXHTMMGBYMTA-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000018 DNA microarray Methods 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- -1 methoxyl group Chemical group 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention relates to a method for preparing a patterned polymer brush, which belongs to the technical field of micro nano material preparation. The micron patterned polymer brush is obtained by fixing a thioxanthone photoinitiator containing coinitiator amine on the surface of a base material by covalent bond self-assembly technology, performing patterned photobleaching on the initiator through mask photoetching and performing photo-initiation monomer polymerization. The method is simple and effective, is suitable for large-scale preparation of various patterned polymer brushes, can prepare functional patterned polymer brushes and develops direction for potential application of the polymer brush.
Description
Technical field
The present invention relates to a kind of preparation method of patterned polymer brush.Belong to technical field of micro nano material preparation.
Background technology
The surface micronano patternization can realize artificially controlled to material surface character and structure becoming the previous ten minutes active research of order focus.The patternization of especially surperficial high molecular polymer has a wide range of applications in fields such as microelectronic industry, chemistry and bioanalysis, microfluid, photonic crystal and biochips.Polymkeric substance pattern method commonly used is vacuum ultraviolet (VUV) photetching technology (" the submicron order patterning on polymethyl methacrylate film surface ", " material Leader: a research piece of writing " the 23rd the 4th phase of volume of in April, 2009 (descending)).This technology has higher requirement to light transmission, the photosensitivity of polymkeric substance, and the hardness of polymkeric substance has very big influence to the stability of surface micro-structure, has limited the use of this method.And polymer brush surface stability height has obtained broad research, so researchdevelopment is simple effectively, extensively the polymer brush preparation method of suitable micro-nano patternization has great importance.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of simple effectively, preparation method that can the various patterned polymer brush of mass preparation.
For realizing this purpose, the present invention is fixed on substrate material surface by the thioxanthone photo initiator that the covalent linkage self-assembling technique will contain coinitiator amine, initiator is carried out the photobleaching of patternization by the mask photoetching.Trigger monomer polymerization then obtains the polymer brush of micron order pattern.
The detailed process that the present invention prepares patterned polymer brush is as follows:
1) substrate is carried out surface treatment.Substrate is placed on boil in the mixing solutions of the vitriol oil and hydrogen peroxide and handles 1-2h, the mass ratio of the vitriol oil and hydrogen peroxide is 7: 3 in the mixing solutions, then substrate is placed the ultrasonic 10-30min of acetone, use deionized water rinsing, oven dry at last, remove the organism and the impurity of substrate surface.
2) epoxy silane coupling agent self-assembly.The concentration that the substrate of cleaning oven dry is immersed 3-R-GLYCIDOL propoxy-Trimethoxy silane is to leave standstill 2h-24h in the toluene solution of 1-10mM, then with the substrate ultrasonic cleaning in toluene and acetone successively of taking out, dry, obtain the substrate of epoxy silane coupling agent self-assembly.
3) light trigger grafting.With the substrate immersion photoinitiator concentration of epoxy silane coupling agent self-assembly is in the chloroformic solution of 2-10mM, and 40 ℃ of heating of lucifuge 2-12h takes out back ultrasonic cleaning in chloroform, and oven dry obtains surperficial initiator grafted substrate; Described light trigger is the thioxanthone photo initiator that contains coinitiator amine.
4) mask photobleaching.Mask is covered surperficial initiator grafted substrate surface, place illumination 30-60 second under the ultraviolet lamp, obtain the substrate behind the surperficial initiator photobleaching.
5) polymer brush of light-initiated preparation patternization.It is the solution of 0.5-5M that substrate behind the surperficial initiator photobleaching is immersed monomer concentration, ultraviolet lighting after the logical nitrogen 30min deoxygenation, light application time 30min-5h; With substrate ultrasonic cleaning in toluene, chloroform, acetone or straight alcohol, dry after the reaction, obtain the polymer brush of micron order patternization.
Light trigger described in the present invention is DAB-16-TX, DAB-4-TX, DAB-64-TX or HPTX.
Described monomer is the monomer that can carry out light initiation polymerization, as methyl methacrylate (MMA), and N-isopropylacrylamide (NIPAM), glycidyl methacrylate (GMA) or the like.
It is simple to operate that the present invention prepares the method for patterned polymer brush, and the initiator grafting density is big, the fast efficient height of velocity of initiation.The pattern of the used mask of the present invention is varied, and is widely used in carrying out the monomer of light initiation polymerization.By causing functional monomer, can prepare graphical polymer brush to environment such as temperature, pH value sensitivity.And further polymer brush is carried out modification, and some biomolecules such as polysaccharide, polypeptide, protein are incorporated in the patterned polymer brush, can obtain having different bioactive surfaces in the micron order zone.These researchs lay the first stone for the micro-nano transmitter of preparation, biochip.
Description of drawings
Fig. 1 is the schema of the inventive method.
The PMMA patterned polymer brush figure that Fig. 2 obtains for example of the present invention.
The PNIPAM patterned polymer brush figure that Fig. 3 obtains for example of the present invention.
Embodiment
Below in conjunction with drawings and Examples technical scheme of the present invention is further described.Following examples are to further specify of the present invention, rather than limit the scope of the invention.
Fig. 1 is the schema of the inventive method.As shown in Figure 1, at first substrate (silicon chip or quartz plate) is cleaned and obtain the silicon hydroxyl surface, immerse then in the toluene solution of 3-R-GLYCIDOL propoxy-Trimethoxy silane.The silane coupling agent that contains methoxyl group reacts with the substrate surface hydroxyl, and self-assembly is in substrate surface.The silane coupling agent of flush away substrate surface absorption, initiator solution is immersed in the oven dry back, obtains initiator grafting individual layer behind 40 ℃ of heating of lucifuge 2-12h.The initiator of ultrasonic flush away individual layer surface adsorption, oven dry.Mask is covered initiator grafted substrate surface, place illumination 30-60 second under the ultraviolet lamp.Immerse monomer solution medium ultraviolet illumination 30min-5h then, obtain the polymer brush of patternization.
Embodiment 1
1, the processing of substrate
Handle 1h with being placed at the bottom of the silicon wafer-based to boil in the mixing solutions of the vitriol oil and hydrogen peroxide, the mass ratio of the vitriol oil and hydrogen peroxide is 7: 3 in the mixing solutions, then substrate is placed the ultrasonic 30min of acetone, use deionized water rinsing, oven dry at last, remove the organism and the impurity of substrate surface.
2, epoxy silane coupling agent self-assembly
Leave standstill 12h with cleaning in the toluene solution that the substrate immersion 3-R-GLYCIDOL propoxy-Trimethoxy silane concentration of drying is 5mM.With the substrate ultrasonic cleaning in toluene and acetone successively of taking out, dry then, obtain the silicon chip of epoxy silane coupling agent self-assembly.
3, initiator DAB-16-TX grafting
With the substrate immersion light trigger DAB-16-TX concentration of epoxy silane coupling agent self-assembly is in the chloroformic solution of 2mM, and 40 ℃ of heating of lucifuge 12h takes out back ultrasonic cleaning in chloroform, and oven dry obtains surperficial initiator grafted silicon chip.
4, mask photobleaching
Mask is covered surperficial initiator grafted substrate surface, placed under the ultraviolet lamp illumination 30 seconds.Obtain the substrate behind the surperficial initiator photobleaching.
5, light-initiated preparation patterned polymer brush
Substrate behind the surperficial initiator photobleaching is immersed the toluene solution of the MMA of monomer concentration 1M, ultraviolet lighting 1h after the logical nitrogen 30min deoxygenation, with substrate ultrasonic cleaning in toluene, chloroform, acetone or straight alcohol, dry after the reaction, obtain the PMMA polymer brush of patternization.
Figure 2 shows that the PMMA polymer brush of the patternization of 50 times of magnifications.
Embodiment 2
1, the processing of substrate
Handle 1.5h with being placed at the bottom of the silicon wafer-based to boil in the mixing solutions of the vitriol oil and hydrogen peroxide, the mass ratio of the vitriol oil and hydrogen peroxide is 7: 3 in the mixing solutions, then substrate is placed the ultrasonic 20min of acetone, use deionized water rinsing, oven dry at last, remove the organism and the impurity of substrate surface.
2, epoxy silane coupling agent self-assembly
Leave standstill 12h with cleaning in the toluene solution that the silicon chip immersion 3-R-GLYCIDOL propoxy-Trimethoxy silane concentration of drying is 5mM.With the silicon chip ultrasonic cleaning in toluene and acetone successively of taking out, dry then, obtain the substrate of epoxy silane coupling agent self-assembly.
3, initiator DAB-16-TX grafting
With the substrate immersion light trigger DAB-16-TX concentration of epoxy silane coupling agent self-assembly is in the chloroformic solution of 5mM, and 40 ℃ of heating of lucifuge 12h takes out back ultrasonic cleaning in chloroform, and oven dry obtains surperficial initiator grafted substrate;
4, mask photobleaching
Mask is covered initiator grafted silicon chip surface, placed under the ultraviolet lamp illumination 45 seconds.
5, light-initiated preparation patterned polymer brush
With the NIPAM solution of the immersion of the silicon chip behind surperficial initiator photobleaching monomer concentration 1M, solvent is methyl alcohol and 1: 1 mixing solutions of water volume ratio.Ultraviolet lighting 2h after the logical nitrogen 30min deoxygenation with substrate ultrasonic cleaning in toluene, chloroform, acetone or straight alcohol, is dried after the reaction, obtains the PNIPAM polymer brush of patternization.Fig. 3 A is the pattern PNIPAM polymer brush of 1250 times of magnifications.Fig. 3 B is the AFM figure of PNIPAM patterned polymer brush, because rolling up after the polymer chain oven dry, there is projection on the surface.
Embodiment 3
1, the processing of substrate
Handle 2h with being placed at the bottom of the silicon wafer-based to boil in the mixing solutions of the vitriol oil and hydrogen peroxide, the mass ratio of the vitriol oil and hydrogen peroxide is 7: 3 in the mixing solutions, then substrate is placed the ultrasonic 10min of acetone, use deionized water rinsing, oven dry at last, remove the organism and the impurity of substrate surface.
2, epoxy silane coupling agent self-assembly
Leave standstill 12h with cleaning in the toluene solution that the silicon chip immersion 3-R-GLYCIDOL propoxy-Trimethoxy silane concentration of drying is 10mM.With the silicon chip ultrasonic cleaning in toluene and acetone successively of taking out, dry then, obtain the substrate of epoxy silane coupling agent self-assembly.
3, initiator DAB-16-TX grafting
With the substrate immersion light trigger DAB-16-TX concentration of epoxy silane coupling agent self-assembly is in the chloroformic solution of 10mM, and 40 ℃ of heating of lucifuge 12h takes out back ultrasonic cleaning in chloroform, and oven dry obtains surperficial initiator grafted substrate;
4, mask photobleaching
Mask is covered initiator grafted silicon chip surface, placed under the ultraviolet lamp illumination 60 seconds.
5, light-initiated preparation patterned polymer brush
Silicon chip behind the surperficial initiator photobleaching is immersed glycidyl methacrylate (GMA) monomer solution of monomer concentration 1M.Ultraviolet lighting 2h after the logical nitrogen 30min deoxygenation with substrate ultrasonic cleaning in toluene, chloroform, acetone or straight alcohol, is dried after the reaction, obtains the PGMA polymer brush of patternization.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100521493A CN101560061B (en) | 2009-05-27 | 2009-05-27 | Method for preparing patterned polymer brush |
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| CN2009100521493A CN101560061B (en) | 2009-05-27 | 2009-05-27 | Method for preparing patterned polymer brush |
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| CN101560061A CN101560061A (en) | 2009-10-21 |
| CN101560061B true CN101560061B (en) | 2011-08-31 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030482B (en) * | 2010-10-13 | 2012-08-08 | 中国科学院化学研究所 | Method for preparing nanometer patterning bipolymer brush |
| CN102603361B (en) * | 2012-01-19 | 2013-08-21 | 广东石油化工学院 | Preparation method of polymer brush with stimulation stability |
| CN102701602B (en) * | 2012-06-12 | 2014-08-06 | 常州大学 | Method for initiating graft polymer through ultraviolet induction on surface of glass |
| CN102952244A (en) * | 2012-08-31 | 2013-03-06 | 郑州大学 | Preparation method of N-hydroxymethyl acrylamide hydrophilic polymer brush |
| CN102952245A (en) * | 2012-08-31 | 2013-03-06 | 郑州大学 | Environment-friendly preparation method of multi-hydroxyl polymer molecular brush |
| CN102875195B (en) * | 2012-09-20 | 2014-03-12 | 华东理工大学 | A preparation method of multiple stimuli-responsive polymer brush film |
| CN110655622B (en) * | 2019-09-04 | 2023-05-05 | 华东理工大学 | Method for preparing polymer brush micropattern based on maskless lithography system |
| CN114573764B (en) * | 2020-11-30 | 2023-08-29 | 深圳市真迈生物科技有限公司 | Polymer, chip, preparation method and application thereof |
| CN113880974B (en) * | 2021-10-21 | 2022-10-25 | 天津理工大学 | Photocurable liquid based on pyrrolopyrrole structure photoinitiator and acrylate resin, and preparation method and application thereof |
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