CN110016154A - A kind of preparation of photon band gap adjustable type polyethyleneimine amino-functionalization photon crystal film - Google Patents
A kind of preparation of photon band gap adjustable type polyethyleneimine amino-functionalization photon crystal film Download PDFInfo
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- CN110016154A CN110016154A CN201910298748.7A CN201910298748A CN110016154A CN 110016154 A CN110016154 A CN 110016154A CN 201910298748 A CN201910298748 A CN 201910298748A CN 110016154 A CN110016154 A CN 110016154A
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- polyethyleneimine
- crystal film
- photon crystal
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- photon
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- 239000013078 crystal Substances 0.000 title claims abstract description 93
- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 77
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000001548 drop coating Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- -1 alkene imines Chemical class 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000010408 film Substances 0.000 description 69
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 37
- 235000019441 ethanol Nutrition 0.000 description 26
- 239000000377 silicon dioxide Substances 0.000 description 23
- 239000004038 photonic crystal Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 235000012239 silicon dioxide Nutrition 0.000 description 14
- 238000000985 reflectance spectrum Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000002077 nanosphere Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229960002050 hydrofluoric acid Drugs 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011022 opal Substances 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- 241000252506 Characiformes Species 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
- G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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Abstract
The present invention provides a kind of preparations of photon band gap adjustable type polyethyleneimine amino-functionalization photon crystal film.It configures certain density aq. polyethyleneimine first, and drop coating is on polymer photon crystal film, air blast and obtains polyethyleneimine functionalized polymer photon crystal film after drying at 30~40 DEG C.Then by changing the number of plies of polyethyleneimine drop coating, the photon band gap of linear regulation polyethyleneimine functionalized polymer photon crystal film.Obtain photon band gap adjustable type polyethyleneimine amino-functionalization photon crystal film.The corresponding minimal wave length of photon crystal film diffraction maximum prepared by the present invention is 505~510 nm, and the corresponding longest wavelength of diffraction maximum is 555~560 nm.By changing the polyethyleneimine drop coating number of plies, photon band gap can continuously adjust between 2.2~2.4 eV.Under the conditions of 1.0~pH of pH 10.0, the continuous ultraviolet light of 30 min, the M of 1 nM~1 ion concentration, 25 DEG C~50 DEG C of temperature, diffraction maximum position is held essentially constant photon crystal film prepared by the present invention.
Description
Technical field
The present invention relates to photon crystal film technical field, especially a kind of photon band gap adjustable type polyethyleneimine amine functions
Change the preparation of photon crystal film.
Background technique
Photonic crystal refers to the artificial periodicity with photon band gap (PhotonicBand-Gap, referred to as PBG) characteristic
Dielectric medium structure, otherwise referred to as PBG photon crystal structure.So-called photon band gap refers to that the wave of a certain frequency range cannot be
It is propagated in this periodic structure, i.e., this structure itself has " forbidden band ".So far, there are many based on the complete of photonic crystal
Newly photonic device is proposed in succession, the laser including no threshold value, loss-free reflecting mirror and bending optical path, high-quality-factor
Optical microcavity, the nonlinear switching and amplifier of low driving energy, wavelength resolution is high and super prism that volume is minimum, tool
There is the photonic crystal fiber of dispersion compensation functions, and light emitting diode improved efficiency etc..
Photon crystal film has the visible light of shielding specific frequency, these visible lights that cannot continue to propagate can be by photon
Crystal film reflection finally forms coherent diffraction in the photon crystal surface with periodic structure, to generate various face
Color, the prepared photon crystal film overwhelming majority is nonadjustable at present, i.e., after photonic crystal is made, photon band gap
Size is difficult to change.It needs to realize by the parameters of complicated process reform photonic crystal to photon crystal film
Photon band gap carries out small range adjusting.Such as in the photonic crystal after filling liquid crystal, by electric field to liquid crystal be modulated to
Adjust its photon band gap.But the method that photonic crystal is filled using liquid crystal is very complicated, therefore, it is difficult to be used for practical application.
In addition, the preparation method of photon crystal film mainly has a photoetch method, magnetron sputtering and electron beam lithography etc., but
It is that these methods mostly expend the time and need expensive instrument and equipment.The present invention is prepared for a kind of poly- second using hard template method
Alkene imines functionalization photon crystal film realizes its photon to prepared photonic crystal by the way that different layers of PEI are added
Band gap is by the consecutive variations 2.2 eV to 2.4 eV.It realizes brilliant from all relatively easy photon of band gap adjusting is prepared into
Body.
Summary of the invention
The present invention relates to a kind of preparation method of photon band gap adjustable type polyethyleneimine amino-functionalization thin film photonic crystal, packets
Include following steps:
(1) agitating and heating legal system prepared silicon dioxide nanosphere
(a) silicon source is (0.04~0.07) with alcohol by volume: 1 mixes, and stirs under the revolving speed of 600 r/min, obtains 180
ML just mixes object；
(b) configuration volume ratio be 1:(3~4) water and 20 mL of ammonium hydroxide (25 %) mixed liquor, then above-mentioned solution is slowly dropped into
In first mixed object into step (a), 10~15 h are stirred at 25~30 DEG C, obtain silicon dioxide nanosphere；
(c) use water and alcohol centrifuge washing three times respectively and drying silicon dioxide nanosphere in step (b).
(2) preparation of the silica photon film of opal structural
(a) by the alcoholic solution (100 mL) of 1%~3 % silicon dioxide nanosphere of mass fraction in step (1), ultrasonic disperse is obtained
To silicon dioxide microsphere solution, it is poured into and carries in cylinder, so as to subsequent experimental；
(b) clean glass slide is put into configured Piranha washing lotion, impregnates 24~30 h, be put into ultrapure water and surpass after taking-up
20~30 min of sound, is blown off with inert gas.Glass slide is then put into the load containing silicon dioxide microsphere solution in step (a)
In cylinder, dry 24~30 h, obtain silica photon crystal film under 30~40 DEG C of vacuum environment.
(3) preparation of the polymer photon crystal film of counter opal structure
(a) by amount of substance ratio be (20~40): it be 1:(3~5 that 1 monomer 1 and monomer 2, which is added to volume ratio) crosslinking agent and
In the solution of alcohol, wherein the volume ratio of monomer 2 and crosslinking agent is 1:(1~3), it is ultrasonic under conditions of logical inert gas after shaking up
10~30 min obtain 0.75 mL of alcoholic solution containing first mixed object；
(b) the first mixed object in step (a) is stored into 12~15 h at 0~4 DEG C；
(c) be 1:(0.03~0.05 by the first mixed object of 0.75 mL in step (b) and volume ratio) photoinitiator be uniformly mixed,
Lead to inert gas and 10~30 min of ultrasound under ice bath, is then added dropwise to silica photon crystal film in step (2) rapidly
On, obtain thin film precursor；
(d) 0.5~2 h is irradiated to thin film precursor room temperature in step (c) with ultraviolet lamp, be subsequently placed into hydrofluoric acid, after taking-up
Obtain the polymer photon crystal film of counter opal structure.
(4) preparation of polyethyleneimine functionalized polymer photon crystal film
(a) certain density aq. polyethyleneimine is configured, and drop coating is in step (3) on polymer photon crystal film,
Air blast and at 30~40 DEG C dry after obtain polyethyleneimine functionalized polymer photon crystal film；
(b) by changing the number of plies of polyethyleneimine drop coating, polyethyleneimine functionalized polymer in linear regulation step (a)
The photon band gap of photon crystal film.
Preferably, silicon source is ethyl orthosilicate, butyl silicate, positive silicic acid propyl ester or positive silicic acid first in the step (1)
Ester.
Preferably, alcohol is methanol, ethyl alcohol or ethylene glycol in the step (1).
Preferably, inert gas used in the step (2) is nitrogen or argon gas, the alcohol ethyl alcohol used or second two
Alcohol.
Preferably, monomer 1 used in the step (3) is acrylamide or acrylic acid alkyl rouge；Monomer 2 is methyl
Acrylic acid or acrylic acid；Crosslinking agent be ethylene glycol dimethacrylate, Diacetone Acrylamide or N hydroxymethyl acrylamide,
Alcohol is methanol, ethyl alcohol or ethylene glycol, and inert gas used is nitrogen or argon gas.
Preferably, photoinitiator used in the step (3) be -2 methyl phenyl ketone of 2 hydroxyl, azodiisobutyronitrile or
Dibenzoyl peroxide；
Preferably, the volume fraction of hydrofluoric acid is the % of 2 %~3 in the step (3).
Preferably, alcohol source used in the step (3) is methanol, ethyl alcohol or ethylene glycol.
Preferably, 220~250 μM of concentration of (4) aq. polyethyleneimine in the step, blast temperature is 30~
40 DEG C, drying time is 0.5~2 h
Preferably, it is 220~250 μM that (4), which adjust polyethyleneimine amine concentration used in photonic crystal, in the step, each
The polyethyleneimine of 90~100 μ L is coated on the photon crystal film of 10*10 cm by layer.
The present invention provides a kind of poly- second of photon band gap adjustable type that preparation method described in above-mentioned technical proposal is prepared
Alkene imines functionalized polymer photon crystal film.Process is simple, easy to operate, and mild condition, time-consuming are short.It is preferably based on step
(4) the corresponding minimal wave length of polyethyleneimine functionalized polymer photon crystal film diffraction maximum synthesized is 505~510 nm,
The corresponding longest wavelength of diffraction maximum is 555~560 nm.By changing the polyethyleneimine drop coating number of plies, photon band gap can be
It continuously adjusts between the eV of 2.2 eV~2.4 (see Fig. 3).
Detailed description of the invention
Fig. 1 is polymer photon crystal film scanning electron microscope.
Fig. 2 is the scanning electron microscope (SEM) photograph of polyethyleneimine functionalized polymer photon crystal film.
Fig. 3 is that polyethyleneimine amino-functionalization photon crystal film diffraction maximum position and polyethyleneimine drop coating number of plies relationship are bent
Line chart.
Relationship between Fig. 4 photon crystal film and polyethyleneimine amino-functionalization photon crystal film diffraction maximum position and pH
Curve graph.
Fig. 5 photon crystal film and polyethyleneimine amino-functionalization photon crystal film diffraction maximum position and ultraviolet light
Graph of relation between time.
Fig. 6 photon crystal film and polyethyleneimine amino-functionalization photon crystal film diffraction maximum position and solion are strong
Graph of relation between degree.
Fig. 7 photon crystal film and polyethyleneimine amino-functionalization photon crystal film diffraction maximum position and solution temperature it
Between graph of relation.
Specific embodiment
The present invention provides a kind of preparations of photon band gap adjustable type polyethyleneimine amino-functionalization photon crystal film, including
Following steps:
(1) silicon dioxide nanosphere is prepared using heating；
(2) preparation of the silica photon film of opal structural；
(3) preparation of the polymer photon crystal film of counter opal structure；
(4) preparation of polyethyleneimine functionalized polymer photon crystal film.
Silicon source and alcohol are mixed to get just mixed object in the step (1) of the present invention.The silicon source and alcohol in the present invention
Volume ratio is preferably (0.04~0.07): 1, more preferably (0.05~0.07): 1, most preferably (0.05~0.06): 1.,
In the present invention, the silicon source is preferably ethyl orthosilicate, and the alcohol is preferably ethyl alcohol, and the water is ultrapure water.
The present invention does not have the mixed method of the silicon source and alcohol special restriction, using known to those skilled in the art
Material mixing technical solution.
It configures the mixed liquor of ammonium hydroxide and water and above-mentioned solution is slowly dropped into above-mentioned just mixed object, at 25~30 DEG C
10~15 h are stirred, silicon dioxide nanosphere is obtained.
In the present invention, the volume ratio of water and ammonium hydroxide is preferably 1:(3~4), more preferably 1:(3.5~4), optimal
It is selected as 1:(3.5~3.75)；Temperature is preferably 25~30 DEG C, more preferably 25.5~28 DEG C, most preferably 26~27
℃；Mixing time is preferably 10~15 h, more preferably 10.5~13 h, most preferably 11~12 h.
Obtained silicon dioxide nanosphere in step (1) is configured to 20 mL mass in step (2) of the present invention
Score is the alcoholic solution of the % of 1 %~2, using 10~30 min of ultrasonic disperse, uniformly mixed solution is poured into and is carried in cylinder, so as to
Subsequent experimental.In the present invention, the mass fraction of silicon dioxide nanosphere alcoholic solution is preferably the % of 1 %~2, and more preferably 1
The % of %~1.75, the most preferably % of 1.2 %~1.5, the time of ultrasonic disperse are preferably 10~30 min, more preferably 15~25
Min, most preferably 15~20 min.
In the present invention, alcohol used is preferably ethyl alcohol.
The present invention does not have the mixed method of the silicon dioxide nanosphere and ethyl alcohol special restriction, using ability
The technical solution of the mixing of material known to field technique personnel.
Clean glass slide is put into configured Piranha washing lotion, 20~28 h is impregnated, is put into ultrapure water after taking-up
10~30 min of ultrasound, are blown off with inert gas.Then glass slide is put into the load cylinder containing silicon dioxide microsphere solution,
Dry 20~28 h under 30~50 DEG C of vacuum environment.
In the present invention, wherein glass slide soaking time in Piranha washing lotion is preferably 20~28 h, more preferably 22
~26 h, most preferably 24~25 h, the time of ultrasonic disperse are preferably 10~30 min, more preferably 15~25 min,
Most preferably 15~20 min；Drying temperature is preferably 30~50 DEG C of h, more preferably 35~45 DEG C, most preferably 40~
45 ℃；Drying time is preferably 20~28 h, more preferably 22~26 h, most preferably 24~25 h.
Acrylamide is added to containing methacrylic acid, dimethyl allene glycol ester in step (3) of the present invention
Methanol solution in, after shaking up under conditions of logical inert gas 10~30 min of ultrasound, 10~15 h of refrigeration at 0~4 DEG C.
Said mixture is added into -2 methyl phenyl ketone of 2 hydroxyl, inert gas and 10~30 min of ultrasound are led under ice bath, it is then fast
Speed is added dropwise on the glass slide of the film with opal structural prepared in step (2), shines 0.5~2 with ultraviolet lamp in the dark
It after h, is put into the hydrofluoric acid of 2~3 %, obtains the silica photonic crystal (note with counter opal structure after removing template
For I).
In the present invention, wherein used monomer 1 is preferably acrylamide；Monomer 2 is preferably methacrylic acid；Crosslinking
Agent is preferably ethylene glycol dimethacrylate, and photoinitiator is preferably -2 methyl phenyl ketone of 2 hydroxyl, and alcohol source is preferably methanol,
Inert gas used is preferably nitrogen.The amount of substance of monomer 1 and monomer 2 is than being preferably (20~40): 1, more preferably (25~
35): 1, most preferably (25~35): 1；The volume ratio of crosslinking agent and alcohol is preferably 1:(3~5), more preferably 1:(4~5),
Most preferably 1:(4~4.5)；Wherein the volume ratio of monomer 2 and crosslinking agent is preferably 1:(1~3), more preferably 1:(1.5~
2.5), most preferably 1:(2~2.5)；Wherein just mixed object and photoinitiator volume ratio are preferably 1:(0.03~0.05) it is more excellent
It is selected as 1:(0.035~0.045), most preferably 1:(0.04~0.045)；In the present invention, refrigerated storage temperature is preferably 0~4
DEG C, more preferably 2~4 DEG C, most preferably 1~4 DEG C；Cold preservation time is preferably 10~15 h, more preferably 11~13 h
Min, most preferably 11~12 h；The time of ultrasonic disperse is preferably 10~30 min, more preferably 15~25 min, optimal
It is selected as 15~20 min；Ultraviolet lamp is preferably 0.5~2 h according to the time, more preferably 1~2 h, most preferably 1~1.5 h；Hydrogen
The volume fraction of fluoric acid is preferably the % of 2 %~3, more preferably the % of 2 %~2.5, most preferably the % of 2.25 %~2.5.
The present invention is for the acrylamide, methacrylic acid, ethylene glycol dimethacrylate, -2 methylbenzene of 2 hydroxyl
The mixed method of acetone does not have special restriction, the technical solution mixed using material well known to those skilled in the art.
In the present invention, the present invention preferably first mixes acrylamide with methacrylic acid, then sequentially adds surplus materials.
The photonic crystal of counter opal structure prepared by step (3) is immersed into polyethylene in step (4) of the present invention
Imide liquor (1.5 × 10-4M~3.0 × 10-4 M in), 5 min are waited, dry (being denoted as II) at 30~50 DEG C after taking-up,
Then above steps may be repeated multiple times, and the photonic crystal for obtaining being respectively provided with 2,3,4 layers of polyethyleneimine amino-functionalization (is denoted as respectively
III, IV, V).In the present invention, the concentration of polyethylenimine solution used in the step is preferably 1.5 × 10-4M~
3.0×10-4 M, more preferably 2.0 × 10-4M~3.0 × 10-4 M, most preferably 2.0 × 10-4M~2.5 × 10-4 M；It is dry
Dry temperature is preferably 30~50 DEG C of h, more preferably 35~45 DEG C, most preferably 40~45 DEG C.Polyethylene used in each layer
Imide liquor volume is preferably 80~100 μ L, is more selected as 90~100 μ L, the most preferably step of 95~100 μ L.
In in (4) polyethyleneimine be coated on the photon crystal film of 10*10 cm.
The present invention provides a kind of poly- second of photon band gap adjustable type that preparation method described in above-mentioned technical proposal is prepared
Alkene imines functionalization photon crystal film.The polyethyleneimine functionalized polymer photon crystal film diffraction maximum of synthesis is corresponding
Minimal wave length is 505~510 nm, and the corresponding longest wavelength of diffraction maximum is 555~560 nm.By changing polyethyleneimine drop
The number of plies is applied, photon band gap can continuously adjust between the eV of 2.2 eV~2.4.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, the described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, every other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
The scope of protection of the invention.
Embodiment 1
Ethyl orthosilicate and ethyl alcohol alcohol that volume ratio is 0.05:1 are mixed to get 180 mL just mixed object, are 1:3.5 by volume ratio
Ammonium hydroxide and 20 mL of mixed liquor of water be slowly dropped into above-mentioned just mixed object, stir and be dried to obtain silica for 40 DEG C after 12 h
Nanosphere, the ethanol solution for being 1.5 % by the mass fraction that obtained silicon dioxide nanosphere is configured to 100 mL, makes
It is carried in cylinder with uniformly mixed solution is poured into after 20 min of ultrasonic disperse, is obtained after 40 DEG C of vacuum drying with opal
The glass slide of the film of structure.Acrylamide is added to the methanol solution containing methacrylic acid, dimethyl allene glycol ester
In (0.75 mL), refrigerated after ultrasound under logical nitrogen after shaking up, said mixture added into 2 with the volume ratio 1:4 of ethyl alcohol
- 2 methyl phenyl ketone of hydroxyl leads to nitrogen and 20 min of ultrasound under ice bath, be then added dropwise to rapidly prepare with opal
On the glass slide of the film of structure, after being protected from light the lower photograph using 1 h of ultraviolet lamp, it is put into 2 % hydrofluoric acid, is had after removing template
There is the silica photonic crystal (being denoted as I) of counter opal structure.It is swept to resulting silica crystal film with photon is prepared
Electronic Speculum observation is retouched, the scanning electron microscope (SEM) photograph of the photonic crystal is obtained.
Fig. 1 is the electromicroscopic photograph of silica photon crystal film, as shown in Figure 1, the photonic crystal is with complete and equal
Even counter opal structure, diameter are about 0.16 μm.
Embodiment 2
It is 2.5 × 10 that embodiment 1, which is prepared obtained silica photon crystal film to be immersed in concentration,-4 M polyethyleneimine
In solution, the photon crystal film (being denoted as II) of polyethyleneimine amino-functionalization is obtained after 40 DEG C of drying after taking-up.Polyethyleneimine
Liquor capacity is 100 μ L.Electronic Speculum observation is scanned to film, has obtained the scanning electron microscope (SEM) photograph of the photonic crystal.
As shown in Fig. 2, the photonic crystal is reduced in its gap after PEI processing, diameter is about 0.12 μm,
About 0.04 μm is reduced before comparing functionalization.
Embodiment 3
It is 2.5 × 10 that the photon crystal film that embodiment 2 prepares obtained polyethyleneimine amino-functionalization, which is again dipped into concentration,-4 In M polyethylenimine solution, the photon crystal film of two layers of polyethylene imines functionalization is obtained after 40 DEG C of drying after taking-up
(being denoted as III) repeats aforesaid operations, obtains the photon crystal film (being denoted as IV, V respectively) that the polyethyleneimine number of plies is three, four.
Reflectance spectrum test is carried out to the photonic crystal of preparation, has obtained the reflectance spectrum of the photonic crystal of the different polyethyleneimine numbers of plies
Spectrogram.
As shown in figure 3, the redshift effect of photonic crystal constantly increases with the increase (0~4 layer) of the polyethyleneimine number of plies
By force, reflectance spectrum diffraction maximum position is respectively 505,520,530,550 and 555 nm.
Embodiment 4
Photon crystal film before and after polyethyleneimine amino-functionalization in embodiment 1,2 is subjected to different pH(1~10) under the conditions of it is anti-
Spectrum test is penetrated, the pass between polyethyleneimine amino-functionalization front and back photon crystal film reflectance spectrum diffraction maximum position and pH is obtained
System's figure.The functionalization photon crystal film used in embodiment 4 is the photon crystal film labeled as IV.
As shown in figure 4, pH 10, reflectance spectrum diffraction maximum red shift~30 nm of photon crystal film are increased to from 1 with pH,
The reflectance spectrum diffraction maximum position of polyethyleneimine amino-functionalization photon crystal film minor change within the scope of 555~565 nm.
Embodiment 5
Ultraviolet light (~365 nm) irradiation under different time is carried out to photon crystal film before and after functionalization in embodiment 1,2,
Study the relationship between ultraviolet light time and reflectance spectrum diffraction maximum position.The functionalization photon used in embodiment 5 is brilliant
Body thin film is the photon crystal film labeled as IV.
As shown in figure 5, photon crystal film and polyethyleneimine amino-functionalization photon crystal film are in the purple for continuing 30 min
Diffraction maximum position under the irradiation of the outer light minor change within the scope of 555~565 nm.
Embodiment 6
Reflectance spectrum test under different ions concentration is carried out to photon crystal film before and after functionalization in embodiment 1,2, is obtained
The relation curve of reflectance spectrum diffraction maximum position and solution ion concentration.The functionalization photon crystal film used in embodiment 6
For the photon crystal film labeled as IV.
As shown in fig. 6, the photon crystal film reflectance spectrum diffraction maximum position before and after polyethyleneimine amino-functionalization is 0~1
μM ion concentration under within the scope of 555~565 nm minor change.
Embodiment 7
Reflectance spectrum test under different temperatures is carried out to photon crystal film before and after functionalization in embodiment 1,2, has been obtained not
The reflectance spectrum spectrogram of photonic crystal under synthermal.The functionalization photon crystal film used in embodiment 7 is labeled as IV
Photon crystal film.
As shown in fig. 7, as temperature changes between 25 DEG C~50 DEG C, the diffraction maximum of photon crystal film is from 510 nm
Drop to 480 nm, polyethyleneimine amino-functionalization photon crystal film minor change within the scope of 555~565 nm.
It should also be noted that, specific embodiments of the present invention are used only to exemplary illustration, do not limit in any way
Determining protection scope of the present invention, the related technical personnel of this field can be improved or be changed according to above-mentioned some explanations, but
All these improvements and changes all should belong to the protection scope of the claims in the present invention.
Claims (10)
1. the preparation of polyethyleneimine functionalized polymer photon crystal film: (1) configuring certain density polyethyleneimine aqueous amine
Solution, and drop coating is on polymer photon crystal film, air blast and obtains polyethyleneimine function after drying at 30~40 DEG C
It can fluidized polymer photon crystal film；(2) by changing the number of plies of polyethyleneimine drop coating, poly- second in linear regulation step (1)
The photon band gap of alkene imines functionalized polymer photon crystal film.
2. preparation method according to claim 1, in the step concentration of (1) aq. polyethyleneimine be 220~
250 μM, drying time is 0.5~2 h.
3. preparation method according to claim 1 or 2, (2) aq. polyethyleneimine drop coating number of plies point in the step
Wei not be 1,2,3,4 layer, the polyethyleneimine functionalized polymer photon crystal film of the corresponding number of plies be respectively labeled as II, III,
IV,V；Each layer is by polyethyleneimine is coated onto the photon crystal film of 10*10 cm in (2) in the step of 80~100 μ L
On.
4. preparation method according to claims 1 to 3, which is characterized in that in the step in (1) polyethyleneimine point
Son amount is 5000~10000Da.
5. the polyethyleneimine amino-functionalization photon crystal film packet that any one of Claims 1 to 4 preparation method is prepared
Include polyethyleneimine and the polymer photon crystal film amine-modified by polyethyleneimine.
6. polyethyleneimine amino-functionalization photon crystal film according to claim 5, which is characterized in that the polyethyleneimine
The corresponding minimal wave length of amino-functionalization photon crystal film diffraction maximum is 505~510 nm, and the corresponding longest wavelength of diffraction maximum is
555~560 nm；By changing the polyethyleneimine drop coating number of plies, photon band gap can continuously be adjusted between the eV of 2.2 eV~2.4
Section.
7. polyethyleneimine amino-functionalization photon crystal film according to claims 1 to 6, which is characterized in that labeled as V's
Polyethyleneimine functionalized polymer photon crystal film diffraction peak is set to 555~560 nm's.
8. polyethyleneimine amino-functionalization photon crystal film according to claim 7, which is characterized in that range be 1.0
Under the conditions of~10.0 pH, polyethyleneimine amino-functionalization photon crystal film diffraction maximum position is micro- within the scope of 555~565 nm
Small variation.
9. polyethyleneimine amino-functionalization photon crystal film according to claim 7, which is characterized in that range be 0~
Under continuous ultraviolet light (~365 nm) irradiation condition of 30 min, polyethyleneimine amino-functionalization photon crystal film diffraction maximum position
The minor change within the scope of 555~565 nm.
10. polyethyleneimine amino-functionalization photon crystal film according to claim 7, which is characterized in that range be 1
Under the conditions of the ion concentration of the M of nM~1, polyethyleneimine amino-functionalization photon crystal film diffraction maximum position is in 555~565 nm models
Enclose interior minor change；Polyethyleneimine amino-functionalization photon crystal film according to claim 7, which is characterized in that in model
Under the conditions of enclosing the temperature for 25 DEG C~50 DEG C, polyethyleneimine amino-functionalization photon crystal film diffraction maximum position is 555~565
Minor change within the scope of nm.
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