CN102515282A - Biological template based preparation method for magnetic photonic crystals - Google Patents
Biological template based preparation method for magnetic photonic crystals Download PDFInfo
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- CN102515282A CN102515282A CN201110406913XA CN201110406913A CN102515282A CN 102515282 A CN102515282 A CN 102515282A CN 201110406913X A CN201110406913X A CN 201110406913XA CN 201110406913 A CN201110406913 A CN 201110406913A CN 102515282 A CN102515282 A CN 102515282A
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Abstract
Belonging to the field of material science, the invention relates to a biological template preparation based preparation method for magnetic photonic crystals. The method comprises the following steps of: step one, conducting surface pretreatment on a biological template; step two, preparing a precursor metal sol-gel solution; step three, putting the well treated biological template into the prepared precursor solution for dipping treatment; step four, after dipping, taking out of a sample, flushing it with distilled water, and conducting drying and roasting to remove the biological template, thus obtaining a ferric oxide material maintaining a photonic crystal structure; and step five, carrying out further sintering and reducing in a mixed gas of hydrogen and argon, thus obtaining a magnetic ferroferric oxide material maintaining a photonic crystal structure. Compared with prior art, the magnetic material with a natural photonic crystal structure prepared in the invention has good response to magnetism-light, thus having potential application prospects in the field of magneto-optical communication devices.
Description
Technical field
The invention belongs to material science; Especially relate to a kind of preparation method with magneto-optic memory technique of butterfly's wing photon crystal structure; Specifically, what relate to is a kind of on biological template, utilizes the method for the method material prepn magnetic photonic crystal of double sintering.
Background technology
Under the effect in magnetic field; The electromagnetic property of material (like magnetic permeability, the specific magnetising moment, domain structure etc.) can change, make light wave within it the phenomenon that also thereupon changes of the transport property of portion (like polarization state, light intensity, phase place, transmission direction etc.) be called magneto-optic effect.Magneto-optic effect comprises Faraday effect, Kerr effect, Zeeman effect, magnetic double refraction effect and magnetic circular dichroism, the magnet-wire found afterwards shake dichroism, the scattering of magnetic exciting light, magnetic field photoabsorption, magnetic ion gunn and photomagnetic effect etc.
Utilize the magneto-optic storage of Kerr magnetooptical effect; Utilize polarized light to rotate the magneto-optic modulator of modulated beam of light through magnet-optical medium generation polarization plane; Change through externally-applied magnetic field changes the effect of magneto-optical crystal to the incident polarized light polarization plane, thereby reaches the magneto-optic shutter of the effect of switching-over light path.Magnetic photonic crystal is regulated and control electromagnetic characteristic is with a wide range of applications it.
And how to prepare the magnetic photonic crystal material is the primary problem that solves.Through the retrieval of prior art document is found, general method is, the material of magnetic is incorporated in the material with photon crystal structure, Kodama T etc. " physica status solidi (b) " (<ning Jutaiwuli>) in 2004 241 phases, reported that " Opal photonic crystals impregnated with magnetite " (Z 250 is filled in the opal photonic crystal) is with SiO on 1597 pages
2The film with opal structural that ball is piled up is a template, at its surface coverage one deck Fe
3O
4, realized SiO
2/ Fe
3O
4The preparation of magneto-optical response material.Inoue M etc. are gone up in 2006 16 phases at " Journal of Materials Chemistry " (< materials chemistry magazine >); Reported " Magnetophotonic crystals-a novel magneto-optic material with artificial on 678 pages
Periodic structures " (magnetic photonic crystal-a kind of novel magneto-optic memory technique has the artificial periodic structure), adopt one deck SiO
2The method of one deck Bi:YIG sputter has prepared the unidimensional magnetic photonic crystal; And the Ge Jianping seminar of Tongji University; In " Angew.Chem.Int.Ed. " (German applied chemistry) in 2007; 46 phases, reported " Highly Tunable Superparamagnetic Colloidal Photonic Crystals " (regulatable superparamagnetism gel photonic crystal) on 7428 pages, adopt the method for the aqueous solution; Let the bead of Z 250 be self-assembled into the magnetic photonic crystal structure, thereby under the magnetic field that adds, obtain the magnetic photonic crystal of different structure parameter.In the preparation method of these experiments; All adopt surface coverage, perhaps method such as water-sol, reason is the magnetic interaction power of the nano particle of magnetic itself; Make it be easy to reunite, the power that need add is come the interaction force of this magneticsubstance of balance self.Why many about the report of magnetic photonic crystal in theory this also is, and very limited of work of experiment.Because the preparation of three-dimensional magnetic photonic crystal remains challenging work in every particular, this has just greatly limited the theoretical investigation and the application of magnetic-optic devices.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of natural photonic crystal with occurring in nature to be provided; The classification fine structure of butterfly's wing is as template; Through dipping, the method for collosol and gel is utilized the different chemical reactivity of biochemical composition; Through the processing and the chemical modification on surface, preparation earlier has the Fe of butterfly's wing photon crystal structure
2O
3Functional materials, and then through MC H
2The reductive method prepares the photonic crystal Fe of magnetic
3O
4Functional materials.The utilization of the invention property double sintering technology, synthetic magneticsubstance with photon crystal structure, this magnetic photonic crystal structure has improved the response to magnetic-light greatly, thereby has wide practical use in magneto-optic communication device field.
The object of the invention can be realized through following technical scheme:
A kind ofly prepare the method for the photonic crystal of magnetic, may further comprise the steps based on biological template:
The first step: selecting the biomaterial with photon crystal structure for use is template, and it is carried out surface preparation;
Second step: configuration precursor metal-salt sol gel solution, concentration is 0.1mol/L～1mol/L, heated and stirred;
The 3rd step: the biological template of handling well is put into the precursor solution impregnation for preparing handle;
The 4th step: after dipping finishes, take out sample, with distilled water flushing, drying, biological template is removed in roasting, just obtains keeping the red oxide of iron functional materials of biological template photon crystal structure;
The 5th step: sintering and reducing is handled and is obtained magnetic photonic crystal Z 250 hierarchy under the atmosphere of hydrogen-argon-mixed body.
Described biomaterial is the biomaterial with photon crystal structure of butterfly's wing, peacock feather, parrot feather or extra large mouse hair, adopts acetum that surface preparation is carried out on the biological template surface and handles.
The solute of precursor is muriate, nitrate salt or the vitriol of iron, cobalt, nickel.
The solvent of precursor is water, ethanol, glycerine or its mixture.
Described roasting, its temperature are 450 ℃-800 ℃, and soaking time is 1-6 hour.
Described reduction sintering, its temperature are 300 ℃-500 ℃, and soaking time is 3-12 hour.
In the described hydrogen-argon-mixed body, the volumetric concentration ratio of hydrogen is 5～20%.
The present invention with the biomaterial with photon crystal structure of occurring in nature as template; Utilize dip treating and a series of chemical reaction to realize the preparation of magnetic photonic crystal, created a kind of quick, simple; Effectively, the method for preparing the specific function novel material of environmental protection.The reservation that prepared material is complete the meticulous three-dimensional photon crystal structure of biological template, improved response performance greatly to magnetic-light.Through selecting different biological templates for use, the magnetic-light that can prepare various structure has the magneticsubstance of response, will wide application prospect occur in fields such as magneto-optic storage and communications by its magnetic-optic devices that makes.
Compared with prior art, the present invention has substantive distinguishing features and marked improvement, need be by surface coverage, perhaps the reactive force that adds such as hydrogel solution come equilibrium magnetism material itself interaction force to realize the preparation of magnetic photonic crystal.And technology is simple, and controllability is good.The reservation that the synthetic magneticsubstance is complete the photon crystal structure of biological template.
Description of drawings
Fig. 1 is to be the 3 D stereo microscope figure that utilizes biological template double sintering technology synthetic magnetic photonic crystal.
Fig. 2 is the sem photograph that utilizes biological template double sintering technology synthetic magnetic photonic crystal.
Fig. 3 is the magnetic hysteresis loop that utilizes biological template double sintering technology synthetic magnetic photonic crystal.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Embodiment 1
The first step is put into 40wt%CH with butterfly's wing
3After 4 hours,, then, use distilled water flushing, drying for standby in the COOH solution to dissolve the mineral substance that goes sintering to be difficult for removing.
Second step, the preparation of precursor solution.FeCl
3The preparation program of solution: under the condition of hot water bath, configuration concentration is the iron(ic)chloride ethanolic soln of 0.1mol/L.
In the 3rd step, the butterfly's wing of handling well is put into the precursor solution that configures soaked 12 hours
The 4th step, after immersion finishes, take out sample, use distilled water flushing, put into 50 ℃ of TR inner dryings of baking oven then 10 hours.After the drying, remove biological template, obtain having the red oxide of iron functional materials of biological template photon crystal structure at 450 ℃ of sintering temperatures;
In the 5th step, above-mentioned product is the magnetic ferroferric oxide material that 400 ℃ of sintering of hydrogen-argon-mixed body of 20% obtain having photon crystal structure at density of hydrogen further again.The magnetic photonic crystal material for preparing has kept the classifying porous morphological structure of original butterfly's wing.And has a response of magnetics and optical.
Fig. 1 is the 3 D stereo microscope figure that utilizes biological template double sintering technology synthetic magnetic photonic crystal.As can be seen from the figure prepare Z 250 and have the biological template photon crystal structure, and demonstrate the metal iris.
Fig. 2 is the sem photograph that utilizes biological template double sintering technology synthetic magnetic photonic crystal.As can be seen from the figure the Z 250 of preparation has kept the three-dimensional photon crystal structure of biological template, and the fine structure on the ridge.
Fig. 3 is the magnetic hysteresis loop that utilizes biological template double sintering technology synthetic magnetic photonic crystal.The Z 250 that as can be seen from the figure prepares has magnetic performance.
Embodiment 2
The first step is put into 40wt%CH with butterfly's wing
3After 4 hours,, then, use distilled water flushing, drying for standby in the COOH solution to dissolve the mineral substance that goes sintering to be difficult for removing.
Second step, the preparation of precursor solution.FeCl
3The preparation program of solution: under the condition of hot water bath, configuration concentration is the iron(ic)chloride ethanolic soln of 0.1mol/L.
In the 3rd step, the butterfly's wing of handling well is put into the precursor solution that configures soaked 20 hours
The 4th step, after immersion finishes, take out sample, use distilled water flushing, put into 60 ℃ of TR inner dryings of baking oven then 10 hours.After the drying, remove biological template, obtain having the red oxide of iron functional materials of biological template photon crystal structure at 500 ℃ of sintering temperatures;
In the 5th step, above-mentioned product is the magnetic ferroferric oxide material that 450 ℃ of sintering obtain having photon crystal structure under 10% the hydrogen-argon-mixed body at density of hydrogen further again.The analysis revealed of scanning and transmission electron microscope, the magnetic photonic crystal material for preparing has kept the classifying porous morphological structure of original butterfly's wing.The analysis revealed of magnetic hysteresis loop, the saturation magnetization rate of preparation material is 35emu/g, has magnetic, the reflection spectrum analysis revealed, the preparation material has schemochrome.
Embodiment 3
The first step is put into 40wt%CH with butterfly's wing
3After 4 hours,, then, use distilled water flushing, drying for standby in the COOH solution to dissolve the mineral substance that goes sintering to be difficult for removing.
Second step, the preparation of precursor solution.FeCl
3The preparation program of solution: under the condition of hot water bath, configuration concentration is the iron(ic)chloride ethanolic soln of 1mol/L.
In the 3rd step, the butterfly's wing of handling well is put into the precursor solution that configures soaked 48 hours
The 4th step, after immersion finishes, take out sample, use distilled water flushing, put into 80 ℃ of TR inner dryings of baking oven then 10 hours.After the drying, remove biological template, obtain having the red oxide of iron functional materials of biological template photon crystal structure at 800 ℃ of sintering temperatures;
In the 5th step, above-mentioned product is 500 ℃ of sintering under 5% the hydrogen-argon-mixed body at density of hydrogen further again, is incubated 12 hours, obtains having the magnetic ferroferric oxide material of photon crystal structure.The analysis revealed of scanning and transmission electron microscope, the magnetic photonic crystal material for preparing has kept the classifying porous morphological structure of original butterfly's wing.The analysis revealed of magnetic hysteresis loop, the saturation magnetization rate of preparation material is 40emu/g, has magnetic, the reflection spectrum analysis revealed, the preparation material has schemochrome.
Claims (7)
1. one kind prepares the method for the photonic crystal of magnetic based on biological template, it is characterized in that this method may further comprise the steps:
The first step: selecting the biomaterial with photon crystal structure for use is template, and it is carried out surface preparation;
Second step: configuration precursor metal-salt sol gel solution, concentration is 0.1mol/L～1mol/L, heated and stirred;
The 3rd step: the biological template of handling well is put into the precursor solution impregnation for preparing handle;
The 4th step: after dipping finishes, take out sample, with distilled water flushing, drying, biological template is removed in roasting, just obtains keeping the red oxide of iron functional materials of biological template photon crystal structure;
The 5th step: sintering and reducing is handled and is obtained magnetic photonic crystal Z 250 hierarchy under the atmosphere of hydrogen-argon-mixed body.
2. a kind of method for preparing the photonic crystal of magnetic based on biological template according to claim 1; It is characterized in that; Described biomaterial is the biomaterial with photon crystal structure of butterfly's wing, peacock feather, parrot feather or extra large mouse hair, adopts acetum that surface preparation is carried out on the biological template surface and handles.
3. according to claim 1ly a kind ofly prepare the method for the photonic crystal of magnetic, it is characterized in that the solute of precursor is muriate, nitrate salt or the vitriol of iron, cobalt, nickel based on biological template.
4. according to claim 1ly a kind ofly prepare the method for the photonic crystal of magnetic, it is characterized in that the solvent of precursor is water, ethanol, glycerine or its mixture based on biological template.
5. according to claim 1ly a kind ofly prepare the method for the photonic crystal of magnetic, it is characterized in that based on biological template, described roasting, its temperature is 450 ℃-800 ℃, soaking time is 1-6 hour.
6. according to claim 1ly a kind ofly prepare the method for the photonic crystal of magnetic, it is characterized in that based on biological template, described reduction sintering, its temperature is 300 ℃-500 ℃, soaking time is 3-12 hour.
7. according to claim 1ly a kind ofly prepare the method for the photonic crystal of magnetic, it is characterized in that in the described hydrogen-argon-mixed body, the volumetric concentration ratio of hydrogen is 5～20% based on biological template.
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| CN102838173A (en) * | 2012-07-13 | 2012-12-26 | 上海交通大学 | Method for preparing magnetic photonic crystal on basis of biological templates of single scales of butterfly wing |
| CN102898586A (en) * | 2012-07-11 | 2013-01-30 | 上海交通大学 | Method for preparing composite intelligent high-molecular photonic crystal having pH response |
| CN103316615A (en) * | 2013-06-17 | 2013-09-25 | 东南大学 | Preparation and detection method of magnetic microspheres with visible glucose detection function |
| CN104183833A (en) * | 2014-08-14 | 2014-12-03 | 上海交通大学 | Preparation method of lithium ion battery cathode material biological template with photonic crystal structure |
| CN104437283A (en) * | 2014-11-05 | 2015-03-25 | 河北师范大学 | Super colloidal crystal assembly body particles with controllable morphology and sizes, and preparation method of super colloidal crystal assembly body particles |
| CN108190939A (en) * | 2017-12-07 | 2018-06-22 | 常州市沃兰特电子有限公司 | A kind of preparation method of hierarchical structure photonic crystal |
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| CN110907503A (en) * | 2019-10-28 | 2020-03-24 | 深圳大学 | Manufacturing method of hierarchical porous structure metal oxide and metal oxide semiconductor gas sensor |
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| CN109705838A (en) * | 2018-12-14 | 2019-05-03 | 江汉大学 | Naturally with warm off-color material, preparation method and containing described naturally with the container of warm off-color material |
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