CN111996595A - Method for preparing crack-free photonic crystal with inverse opal structure - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 58
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000002073 nanorod Substances 0.000 claims abstract description 22
- 239000011022 opal Substances 0.000 claims abstract description 20
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- 239000004005 microsphere Substances 0.000 claims description 49
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- 229910000859 α-Fe Inorganic materials 0.000 claims description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
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- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 238000001338 self-assembly Methods 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052946 acanthite Inorganic materials 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 238000001548 drop coating Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 2
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 abstract 1
- -1 hydroxyl ferric oxide Chemical compound 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract 1
- 229910052976 metal sulfide Inorganic materials 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 238000009958 sewing Methods 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 4
- 239000008204 material by function Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000001553 co-assembly Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910004042 HAuCl4 Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention discloses a preparation method of a crack-free photonic crystal with an inverse opal structure. Filling ferric salt in the traditional colloidal crystal containing cracks as a template, then carrying out in-situ hydrolysis under certain temperature and humidity conditions to form a hydroxyl ferric oxide nanorod, and sewing the cracks in the colloidal crystal by the nanorod to obtain a composite opal structure. Calcining the composite opal structure under a certain condition, and converting the hydroxyl iron oxide nano rod into FeP or alpha-Fe2O3Nanoparticles to obtain FeP or alpha-Fe2O3A crack-free photonic crystal. According to the method, a series of crack-free photonic crystals with inverse opal structures of metal simple substances, metal oxides or metal sulfides are obtained through reactions such as reduction, replacement, oxidation, vulcanization and the like. The crack-free inverse opal structure photonic crystal prepared by the invention has high specific surface area and good photonic band gap, and has important application prospect in the fields of catalysis, lithium ion battery electrode materials, high-performance optical devices and the like.
Description
Technical Field
The invention relates to a preparation method of a photonic crystal, in particular to a method for preparing a crack-free photonic crystal with an inverse opal structure, belonging to the technical field of photonic device preparation.
Background
As an alternative technology to the traditional top-down physical processing, chemical self-assembly methods that can easily prepare ordered macroporous structures have stimulated scientific interest, for example, colloidal crystals with opal structures can be obtained by chemical self-assembly, and the colloidal crystals can be used as templates to guide the filling and deposition of functional materials therein, so that inverse opal-structured photonic crystals with ordered macroporous structures can be conveniently obtained (B.T. Holland, C.F. bland and A.Stein, Synthesis of macroporous minerals with high order ordered porous structures of photonic crystals of porous arrays of porous composites, Science,1998,281, 538-540; F.F.Fuc, Z.Y.Chen, Z.ZHao, H.Wang, L.R.Sha, Z.Z.Gu and Y.J.Zoo, Bioins-porous-photonic crystals, H.W.201599. ZnO.05. gradient, K.K, Z.K.K.K.K.K.K.K.C.K.K.K.C.K., Z.K.K.K.K.K.K.K.K.K.K.K.C.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K. K. K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K4Telephones for solar water oxidation, Energy environ. Sci.,2014,7, 1402-1408). The inverse opal structure has through and numerous nano-pores, highly uniform pore diameter and periodic pore distribution, and has important application prospects in numerous fields of high-performance photonic devices, structural color, sensing and detection, filtration and separation, catalysis and the like. However, serious cracks in photonic crystals with inverse opal structures and the problem of light scattering loss caused by cracks have largely limited their widespread use in practice. Although, by optimizing the evaporation process (X.J.Wu, R.hong, J.K.Meng, R.Cheng, Z.J.Zhu, G.Wu, Q.Li, C.F.Wang and S.Chen, Hydrophobic po(water-butyl acrylate) photoresist coatings such as polyethylene glycol acrylate, polyethylene glycol acrylate, 2005,5, 2646-. However, the preparation of crack-free photonic crystals with inverse opal structures by using the brittle colloidal crystals as templates has not been successful. This is mainly because the filling of the functional material or the subsequent calcination process easily causes the generation of cracks. Although some well-designed co-Assembly processes may directly help one obtain crack-free inverse opal structure photonic crystals (k.r. phillips, t.shiran, e.shiran, a.v. shneidman, t.m.kay and j.aizenberg, nanocristalline precursors for the co-Assembly of crack-free metal oxide inverter optics, adv.mater, 2018,30, e1706329, b.hatton, l.michhenko, s.davis, k.h.sandh and j.aizenberg, Assembly of large-area, high hly ordered, crack-ee optics, proc.natl.ad.sci.s.a., 1035.2010, 9) such materials are susceptible to cracking. At present, once cracks in the photonic crystal occur, no effective repair technology exists. The development of crack repair techniques in photonic crystals or other functional materials is critical to driving their wide-spread practical applications.
Disclosure of Invention
The invention aims to provide a method for preparing a crack-free photonic crystal with an inverse opal structure.
The object of the invention is thus achieved.
Firstly, taking a colloidal crystal with micro cracks prepared by a chemical self-assembly method as a template, and filling an iron salt solution with a certain concentration in the colloidal crystal by dip coating, lifting, drop coating, spin coating and other modes;
secondly, hydrolyzing an iron salt solution in a colloidal crystal template under the conditions of certain temperature and humidity, and growing the hydroxyl iron oxide nanorods in the microsphere gaps and cracks in the colloidal crystal template until the hydroxyl iron oxide nanorods are completely filled to obtain the photonic crystal with the composite opal structure;
thirdly, the photonic crystal with the composite opal structure is placed in NaH2PO2Calcining in the presence of iron oxyhydroxide nanorod and NaH2PO2PH generated by pyrolysis3Reacting to generate FeP, eliminating cracks in the colloidal crystal template by volume shrinkage caused in the conversion process, and simultaneously decomposing the colloidal microspheres by heating to obtain crack-free FeP inverse opal structure photonic crystals;
or directly calcining the composite opal structure photonic crystal at a certain temperature to convert the iron oxyhydroxide nanorod into alpha-Fe2O3The nano particles and the colloidal microspheres are heated to decompose to obtain alpha-Fe2O3Crack-free photonic crystals with inverse opal structures;
the fourth step of converting alpha-Fe2O3Calcining crack-free inverse opal structure photonic crystal in hydrogen atmosphere, alpha-Fe2O3Is reduced to Fe3O4To obtain Fe3O4Crack-free photonic crystals with inverse opal structures;
or calcining the alpha-Fe 2O3 crack-free inverse opal structure photonic crystal in a CO atmosphere, and reducing the alpha-Fe 2O3 into an Fe simple substance to obtain the Fe simple substance crack-free inverse opal structure photonic crystal.
On the basis, a series of photonic crystals with the metal simple substance crack-free inverse opal structure can be prepared through a displacement reaction, such as: co, Ni, Sn, Cu, Pb, Ag, Pt, Au, etc. to obtain the above-mentioned simple metalThe crack-free photonic crystal with inverse opal structure can oxidize the metal simple substance to obtain the metal oxide (CoO, NiO, SnO)2、PbO、Ag2O, etc.) and sulfides (CoS, NiS, SnS, PbS, Ag)2S, etc.).
The fifth step of adding Fe3O4The photonic crystal with crack-free inverse opal structure is oxidized at high temperature in air to form Fe3O4Conversion to gamma-Fe2O3To obtain gamma-Fe2O3Crack-free photonic crystal with inverse opal structure.
In the method, the colloidal crystal template is formed by arranging polymer microspheres in a face-centered cubic manner, the polymer microspheres are divided into single crystal regions of 5-10 mu m by cracks, and the polymer microspheres are selected from polystyrene colloidal microspheres or polymethyl methacrylate colloidal microspheres or polystyrene-polymethyl methacrylate-polyacrylic acid colloidal microspheres or poly (tert-butyl acrylate) colloidal microspheres and the like. The particle size is 200-1000 nm.
The ferric salt solution is Fe2(SO4)3、FeCl3、Fe(NO3)3And the concentration of any one or a mixture of two or more of the aqueous solutions is 1.0-2.5 mol/L.
The hydrolysis temperature of the ferric salt solution filled into the colloidal crystal template is 50-85 ℃, the humidity condition is 50-90%, and the hydrolysis time is 0.5-5 h.
The alpha-Fe2O3The calcination temperature of the crack-free photonic crystal is 300-550 ℃, and the calcination time is 0.5-5 h.
Compared with the traditional sacrificial template method for preparing the photonic crystal with the inverse opal structure, the method has the unique characteristics that the cracks are sewed by the iron oxyhydroxide nanorods generated by the in-situ hydrolysis reaction of the ferric salt, and the cracks disappear by the volume shrinkage caused by the nanostructure transformation (from the nanorods to the nanoparticles) in the subsequent calcination process. Continuous in-situ conversion reaction between ferric salt-hydroxyl ferric oxide-ferric oxide (or FeP) combined with favorable nano-structure change is a key factor for realizing crack-free inverse opal structure photonic crystals by adopting a template method. The traditional sacrificial template method can not effectively fill cracks only by using simple chemical reaction, so that the cracks are kept in the final photonic crystal with the inverse opal structure.
The method has the beneficial effects that the historical problem of preparing the inverse opal structure photonic crystal by using a sacrificial template method is solved, the universal method for preparing the crack-free inverse opal structure photonic crystal is developed, the wide practical use of the inverse opal structure photonic crystal in the fields of high-performance photonic devices, catalysis and the like is promoted, and theoretical and technical guidance is provided for eliminating cracks in other functional materials.
Drawings
FIG. 1: in example 1 of the present invention, a scanning electron microscope photograph of a colloidal crystal template was obtained using polystyrene-polymethylmethacrylate-polyacrylic acid microspheres having a particle size of 285 nm. We can find that the template has a face-centered cubic structure, divided by cracks into monocrystalline regions <10 μm.
FIG. 2: scanning electron microscope photographs of the composite opal structure photonic crystals in example 1 of the present invention. The hydroxyl iron oxide nano rod is filled in the gaps between the cracks and the microspheres, and the cracks are effectively sewed.
FIG. 3: scanning electron microscope photographs of the crack-free FeP inverse opal structure photonic crystals in example 1 of the present invention. The periodic structure of the template is replicated into the inverse opal structure and cracks are eliminated.
FIG. 4: the reflection spectrum of the crack-free inverse opal structure photonic crystal in examples 1,5, 6, 7, and 8 of the present invention.
Detailed Description
The following examples serve to illustrate the invention.
Example 1
FeCl with the concentration of 1mol/L3The aqueous solution is coated in polystyrene-polymethyl methacrylate-polyacrylic microsphere colloidal crystal template (particle size of microsphere is 285nm), the microstructure of the polystyrene-polymethyl methacrylate-polyacrylic microsphere colloidal crystal template is as shown in figure 1, and the colloidal crystal template is divided into 5-10 μm by criss-cross cracksAnd (4) a region. Subsequently, will be filled with FeCl3And (3) placing the colloidal crystal template of the aqueous solution at 80 ℃ and under the condition of 80% relative humidity, hydrolyzing for 2h, and growing needle-shaped iron oxyhydroxide nanorods in gaps and cracks of the colloidal crystal template to obtain the photonic crystal with the composite opal structure (figure 2). Then, the composite opal structure photonic crystal and NaH are combined2PO2The powder was calcined in a muffle furnace at a temperature of 300 ℃ for 5 h. During the calcination process, the rodlike iron oxyhydroxide is converted into FeP nano particles, and meanwhile, the polystyrene-polymethyl methacrylate-polyacrylic acid microsphere colloidal crystal template is heated and decomposed, so that the FeP crack-free inverse opal photonic crystal is obtained (figure 3). The sample had a sharp reflection peak (fig. 4), indicating a good periodic structure (fig. 3), with a reflection peak position of 528 nm.
Example 2
Fe with the concentration of 2.0mol/L2(SO4)3The aqueous solution was spin-coated into a polystyrene microsphere colloidal crystal template (particle size of microsphere 1000nm), and then filled with Fe2(SO4)3And (3) putting the colloidal crystal template of the aqueous solution under the conditions of 50 ℃ and 90% of relative humidity, hydrolyzing for 5h, and growing needle-shaped iron oxyhydroxide nanorods in gaps and cracks of the colloidal crystal template to obtain the photonic crystal with the composite opal structure. Then, the composite opal structure photonic crystal was placed in a muffle furnace and calcined at 550 ℃ for 5 hours. Conversion of rod-like iron oxyhydroxides to alpha-Fe during calcination2O3The nano particles and the polystyrene microsphere colloidal crystal template are heated and decomposed to obtain alpha-Fe2O3Crack-free inverse opal photonic crystals. Then, alpha-Fe is added2O3Crack-free inverse opal photonic crystal with 5% H2Calcining for 1h, alpha-Fe at 350 ℃ in the atmosphere of 95% Ar2O3Is reduced to Fe3O4To obtain Fe3O4Crack-free inverse opal photonic crystals. Further, adding Fe3O4Calcining crack-free inverse opal photonic crystal at 400 ℃ for 1h, Fe3O4Is oxidized into gamma-Fe2O3To obtain gamma-Fe2O3Crack-free photonic crystal with inverse opal structure.
Example 3
Fe with the concentration of 1.5mol/L2(SO4)3、FeCl3(molar ratio is 1:1) is dripped into a polymethyl methacrylate microsphere colloidal crystal template (the particle diameter of the microsphere is 200nm), and then the microsphere is filled with Fe2(SO4)3、FeCl3And (3) placing the colloidal crystal template of the mixed aqueous solution at 60 ℃ and under the condition of relative humidity of 50%, hydrolyzing for 0.5h, and growing needle-shaped iron oxyhydroxide nanorods in gaps and cracks of the colloidal crystal template to obtain the photonic crystal with the composite opal structure. Then, the composite opal structure photonic crystal and NaH are combined2PO2The powders were placed together in a muffle furnace and calcined at a temperature of 300 ℃ for 0.5 h. During the calcination process, the rodlike iron oxyhydroxide is converted into FeP nano particles, and meanwhile, the polystyrene microsphere colloidal crystal template is heated and decomposed, so that the FeP crack-free inverse opal structure photonic crystal is obtained.
Example 4
Fe (NO) with a concentration of 2.5mol/L3)3The aqueous solution was drop-coated into a colloidal crystal template of t-butyl polyacrylate colloidal microspheres (particle size of 245nm), which were subsequently filled with Fe2(NO3)3And (3) placing a colloidal crystal template of the aqueous solution at 75 ℃ and under the condition of relative humidity of 80%, hydrolyzing for 0.5h, and growing needle-shaped iron oxyhydroxide nanorods with the length of 250nm in gaps and cracks of the colloidal crystal template to obtain the photonic crystal with the composite opal structure. Then, the composite opal structure photonic crystal and NaH are combined2PO2The powders were placed together in a muffle furnace and calcined at a temperature of 300 ℃ for 5 h. During the calcination process, the rodlike iron oxyhydroxide is converted into FeP nano particles, and meanwhile, the polystyrene microsphere colloidal crystal template is heated and decomposed, so that the FeP crack-free inverse opal structure photonic crystal is obtained.
Example 5
Fe with the concentration of 1.5mol/L2(SO4)3、FeCl3、Fe(NO3)3(molar ratio is 1:3:2) mixed waterThe solution was drop coated into a polymethylmethacrylate microsphere colloidal crystal template (particle size of microsphere 300nm) and then filled with Fe2(SO4)3、FeCl3、Fe(NO3)3And (3) placing the colloidal crystal template of the mixed aqueous solution at 60 ℃ and under the condition of relative humidity of 60%, hydrolyzing for 1.5h, and growing needle-shaped iron oxyhydroxide nanorods in gaps and cracks of the colloidal crystal template to obtain the photonic crystal with the composite opal structure. Then, the composite opal structure photonic crystal NaH is added2PO2The powders were placed together in a muffle furnace and calcined at a temperature of 300 ℃ for 5 h. During the calcination process, the rodlike iron oxyhydroxide is converted into FeP nano particles, and meanwhile, the polystyrene microsphere colloidal crystal template is heated and decomposed, so that the FeP crack-free inverse opal structure photonic crystal is obtained. The peak position of the emission spectrum of the sample was 639nm (FIG. 4).
Example 6
Fe with the concentration of 1.5mol/L2(SO4)3、Fe(NO3)3(molar ratio is 1:2) is dripped into a polymethyl methacrylate microsphere colloidal crystal template (the particle size of the microsphere is 210nm), and then the microsphere is filled with Fe2(SO4)3、Fe(NO3)3And (3) placing the colloidal crystal template of the mixed aqueous solution at 80 ℃ and under the condition of relative humidity of 80%, hydrolyzing for 0.5h, and growing needle-shaped iron oxyhydroxide nanorods in gaps and cracks of the colloidal crystal template to obtain the photonic crystal with the composite opal structure. Then, the composite opal structure photonic crystal NaH is added2PO2The powders were placed together in a muffle furnace and calcined at a temperature of 300 ℃ for 5 h. During the calcination process, the rodlike iron oxyhydroxide is converted into FeP nano particles, and meanwhile, the polystyrene microsphere colloidal crystal template is heated and decomposed, so that the FeP crack-free inverse opal structure photonic crystal is obtained. The peak position of the emission spectrum of the sample was 472nm (FIG. 4).
Example 7
Fe with the concentration of 1.0mol/L2(SO4)3The aqueous solution was spin-coated into a polystyrene microsphere colloidal crystal template (particle size of microsphere 250nm), and then filled with Fe2(SO4)3And (3) placing the colloidal crystal template of the aqueous solution at 80 ℃ and under the condition of relative humidity of 80%, hydrolyzing for 2h, and growing needle-shaped iron oxyhydroxide nanorods in gaps and cracks of the colloidal crystal template to obtain the photonic crystal with the composite opal structure. Then, the composite opal structure photonic crystal was placed in a muffle furnace and calcined at 550 ℃ for 5 hours. Conversion of rod-like iron oxyhydroxides to alpha-Fe during calcination2O3The nano particles and the polystyrene microsphere colloidal crystal template are heated and decomposed to obtain alpha-Fe2O3Crack-free inverse opal photonic crystals. Then, alpha-Fe is added2O3Calcining crack-free inverse opal photonic crystal at 500 ℃ for 3h in the atmosphere of CO, wherein the temperature of the crystal is alpha-Fe2O3Is reduced into Fe simple substance to obtain the crack-free inverse opal photonic crystal of the Fe simple substance. Further, the Fe simple substance crack-free inverse opal photonic crystal is placed in CuSO4And obtaining the Cu simple substance crack-free photonic crystal in the solution. And further oxidizing the Cu simple substance crack-free photonic crystal for 1 hour at the temperature of 200 ℃ in air to obtain the CuO crack-free photonic crystal. Or calcining the Cu simple substance in steam of the sulfur simple substance for 1 hour at 500 ℃ to obtain Cu2S is a crack-free photonic crystal with an inverse opal structure. The peak position of the emission spectrum was 590nm (FIG. 4).
Example 8
Fe with the concentration of 1.0mol/L2(SO4)3The aqueous solution was spin-coated into a polystyrene microsphere colloidal crystal template (particle size of microsphere 250nm), and then filled with Fe2(SO4)3And (3) placing the colloidal crystal template of the aqueous solution at 80 ℃ and under the condition of relative humidity of 80%, hydrolyzing for 2h, and growing needle-shaped iron oxyhydroxide nanorods in gaps and cracks of the colloidal crystal template to obtain the photonic crystal with the composite opal structure. Then, the composite opal structure photonic crystal was placed in a muffle furnace and calcined at 550 ℃ for 5 hours. Conversion of rod-like iron oxyhydroxides to alpha-Fe during calcination2O3The nano particles and the polystyrene microsphere colloidal crystal template are heated and decomposed to obtain alpha-Fe2O3Crack-free inverse opal photonic crystals. Then, the product is processedThen, alpha-Fe is added2O3Calcining crack-free inverse opal photonic crystal at 500 ℃ for 3h in the atmosphere of CO, wherein the temperature of the crystal is alpha-Fe2O3Is reduced into Fe simple substance to obtain the crack-free inverse opal photonic crystal of the Fe simple substance. Further, the Fe crack-free inverse opal photonic crystal is placed in CoCl2、Ni(NO3)2、SnCl2、Pb(NO3)2、AgNO3、Pt(NO3)2、HAuCl4In the solution, the crack-free photonic crystal of Co, Ni, Sn, Pb, Ag, Pt and Au simple substances is obtained through a displacement reaction. Further oxidizing the Co, Ni, Sn, Pb, Ag, Pt and Au elementary substance crack-free photonic crystals in the air at the temperature of 300 ℃, 450 ℃, 150 ℃,200 ℃ and 150 ℃ for 1 hour to obtain CoO, NiO and SnO2、PbO、Ag2And O is a crack-free photonic crystal. Or the simple substance is in sulfur or H2Calcining in the steam of S at 300 deg.C, 450 deg.C, 150 deg.C, 200 deg.C, 150 deg.C for 1 hr to obtain CoS, NiS, SnS, PbS, Ag2S is a crack-free photonic crystal with an inverse opal structure. The peak position of the emission spectrum was 590nm (FIG. 4).
Claims (10)
1. A method for preparing crack-free photonic crystals with inverse opal structures is characterized by comprising the following steps:
firstly, taking a colloidal crystal with micro cracks prepared by a chemical self-assembly method as a template, and filling an iron salt solution with a certain concentration in the colloidal crystal by dip coating, lifting, drop coating, spin coating and other modes;
secondly, hydrolyzing an iron salt solution in a colloidal crystal template under the conditions of certain temperature and humidity, and growing the hydroxyl iron oxide nanorods in the microsphere gaps and cracks in the colloidal crystal template until the hydroxyl iron oxide nanorods are completely filled to obtain the photonic crystal with the composite opal structure;
thirdly, the photonic crystal with the composite opal structure is placed in NaH2PO2Calcining in the presence of iron oxyhydroxide nanorod and NaH2PO2PH generated by pyrolysis3Reaction to generate FeP, introducing in the conversion processThe volume shrinkage eliminates cracks in the colloidal crystal template, and the colloidal microspheres are heated and decomposed to obtain crack-free FeP inverse opal structure photonic crystals.
2. The method of claim 1, wherein: thirdly, calcining the composite opal structure photonic crystal at a certain temperature to convert the iron oxyhydroxide nanorod into alpha-Fe2O3The nano particles and the colloidal microspheres are heated to decompose to obtain alpha-Fe2O3Crack-free photonic crystal with inverse opal structure.
3. The method of claim 2, wherein: alpha-Fe is mixed2O3Calcining crack-free inverse opal structure photonic crystal in hydrogen atmosphere, alpha-Fe2O3Is reduced to Fe3O4To obtain Fe3O4Crack-free photonic crystal with inverse opal structure.
4. The method of claim 2, wherein: alpha-Fe is mixed2O3Calcining crack-free inverse opal structure photonic crystal in CO atmosphere, alpha-Fe2O3Is reduced into Fe simple substance to obtain the photonic crystal with the Fe simple substance crack-free inverse opal structure.
5. The method of claim 4, wherein: preparing any single metal of Co, Ni, Sn, Cu, Pb, Ag, Pt and Au into crack-free inverse opal structure photonic crystals through a replacement reaction, and oxidizing the single metal of Co, Ni, Sn, Cu, Pb, Ag to obtain metal oxides of CoO, NiO and SnO2、PbO、Ag2O or sulfides CoS, NiS, SnS, PbS, Ag2S。
6. The production method according to claim 3, characterized in that: mixing Fe3O4The photonic crystal with crack-free inverse opal structure is oxidized at high temperature in air to form Fe3O4Conversion to gamma-Fe2O3To obtain gamma-Fe2O3Crack-free photonic crystal with inverse opal structure.
7. The method of claim 1, wherein: the colloidal crystal template is formed by arranging polymer microspheres in a face-centered cubic manner, the polymer microspheres are divided into single crystal areas with the particle size of 5-10 mu m by cracks, the polymer microspheres are selected from polystyrene colloidal microspheres or polymethyl methacrylate colloidal microspheres or polystyrene-polymethyl methacrylate-polyacrylic acid colloidal microspheres or poly (tert-butyl acrylate) colloidal microspheres, and the particle size of the polymer microspheres is 200-1000 nm.
8. The method of claim 1, wherein: the ferric salt solution is Fe2(SO4)3、FeCl3、Fe(NO3)3One or a mixture of two or more of the above in the aqueous solution, the concentration is 1.0-2.5 mol/L.
9. The method of claim 1, wherein: the hydrolysis temperature of the ferric salt solution filled into the colloidal crystal template is 50-85 ℃, the humidity condition is 50-90%, and the hydrolysis time is 0.5-5 h.
10. The production method according to claim 3 or 4, characterized in that: alpha-Fe2O3The calcination temperature of the crack-free inverse opal structure photonic crystal is 300-550 ℃, and the calcination time is 0.5-5 h.
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