CN110109197A - Photon crystal material and preparation method thereof and photonic crystal ink and its application - Google Patents
Photon crystal material and preparation method thereof and photonic crystal ink and its application Download PDFInfo
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- CN110109197A CN110109197A CN201810456443.XA CN201810456443A CN110109197A CN 110109197 A CN110109197 A CN 110109197A CN 201810456443 A CN201810456443 A CN 201810456443A CN 110109197 A CN110109197 A CN 110109197A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
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- 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
Abstract
The present invention relates to a kind of photon crystal material and preparation method thereof and photonic crystal ink and its application, which includes kernel and the polyvinylpyrrolidone shell being coated on kernel, wherein kernel is formed by several nano ferriferrous oxide crystal grain clusters.The photon crystal material can be realized schemochrome and show and can prepare electrochromic display by way of printing.
Description
Technical field
The present invention relates to the field of display device more particularly to a kind of photon crystal material and preparation method thereof and photonic crystals
Ink and its application.
Background technique
Photonic crystal is a kind of substance with property specific cycle structure, and this periodic structure can adjust light wave
Control, enables to produce colour, i.e. schemochrome under the irradiation of ambient white light.This schemochrome is different from the color of traditional sense
Plain color, when it is that light passes through this substance, since the microstructure of substance itself makes light generate interference, diffraction and scattering
And generate.There is schemochrome the common pigments colors such as high brightness, high chroma, colour-fast, iris phenomenon and polarization effect can not reach
The excellent properties arrived have obtained people and have more and more paid close attention to and study, so that it obtains the property changed in terms of showing colour generation
Using.
The micro-nano granules that suitable size is prepared with chemical synthesis carry out outfield regulation to colloidal solid, it is possible to
Form three-dimensional photon crystal structure.Traditional display colour generation is three kinds of luminescent materials of RGB under certain voltage or electric current
The light of specific wavelength is issued, is then occurred by coloured light superposition colored.It folds color different from three primary colors to show, this schemochrome can be with
By constantly changing the size in outfield, the continuous spacing for changing colloidal solid reaches to continuously change the wavelength of emergent light
The effect of full-color EL display has very big potential using value in display field.
With the development of flexible display technologies of new generation, printed electronic manufacture shows wide application space.By target
Material is configured to ink, and electronic manufacture can be realized in the method by printing, and reduces production cost, improves production efficiency, makes
It obtains and the basis that ink chemical conversion is entire printed electronic industry is carried out to material.However, although this be based on schemochrome display technology
Tool has great advantage and application prospect, but is really not much for the research of display industry, and application industryization is also far from enough.
Summary of the invention
Based on this, it is necessary to provide the new schemochrome that can be realized of one kind and show and can be prepared by way of printing
The photon crystal material of electrochromic display.
In addition, also providing a kind of photon crystal material, photonic crystal ink and its application.
A kind of photon crystal material, the photon crystal material include kernel and the polyethylene pyrrole being coated on the kernel
Pyrrolidone shell, wherein the kernel is formed by several nano ferriferrous oxide crystal grain clusters.
Above-mentioned photon crystal material is a kind of new photon crystal material, can not only realize that schemochrome is shown, Er Qieshang
The ink that photon crystal material can also be fabricated to printing is stated, so that above-mentioned photon crystal material can pass through printing
Mode is prepared in display device.
The partial size of the kernel is 100 nanometers~250 nanometers in one of the embodiments,；The oxidation of nanometer four three
The partial size of iron crystal grain is 5 nanometers~15 nanometers.
In one of the embodiments, the polyvinylpyrrolidone shell with a thickness of 10 nanometers~30 nanometers.
It in one of the embodiments, further include the silicon dioxide layer being coated on the polyvinylpyrrolidone shell.
The silicon dioxide layer is porous structure in one of the embodiments,.
In one of the embodiments, the silicon dioxide layer with a thickness of 15 nanometers~40 nanometers.
A kind of preparation method of photon crystal material, includes the following steps:
Under alkaline environment, by water-soluble trivalent ferric salt, polyvinylpyrrolidone, glucose, reproducibility solvent and highly basic
Salt of weak acid mixing carries out hydro-thermal reaction, obtains Fe3O4@PVP particle, wherein Fe3O4Represent several nano ferriferrous oxides crystalline substance
Kernel made of grain cluster ,@indicate cladding, and PVP is shell.
In one of the embodiments, the water-soluble trivalent ferric salt in iron chloride, ferric nitrate and ferric sulfate extremely
Few one kind.
It is described under alkaline environment in one of the embodiments, by water-soluble trivalent ferric salt, polyvinylpyrrolidone,
The step of glucose, reproducibility solvent and strong base-weak acid salt mixing carry out hydro-thermal reaction are as follows: by the polyvinylpyrrolidone, institute
It states glucose to be dissolved in the reproducibility solvent, then sequentially adds the water-soluble trivalent ferric salt and the strong base weak acid
Salt, so that reaction system then carries out hydro-thermal reaction in alkalinity.
The temperature of the hydro-thermal reaction is 180 DEG C~230 DEG C in one of the embodiments,；And/or the polyethylene
The mass ratio of ferro element in pyrrolidones and the water-soluble trivalent ferric salt is 20:1~30:1；And/or the glucose with
The molar ratio of ferro element in the water-soluble trivalent ferric salt is 0.5:1~1:1；And/or the reproducibility solvent is second two
Alcohol；And/or the strong base-weak acid salt is acetate.
It in one of the embodiments, further include in the Fe3O4On@PVP particle the step of coated silica layer: will
The Fe3O4@PVP particle and silicon source, catalyst, the water hybrid reaction in alcohol, obtain being coated with the silicon dioxide layer
Fe3O4@PVP particle.
The molar ratio of the element silicon in silicon source and the water is 1:115~1:290 in one of the embodiments,；And/
Or, element silicon and the Fe in the silicon source3O4The molar ratio of ferro element in@PVP particle is 1:1~3:1；And/or institute
Stating catalyst is ammonium hydroxide；And/or the silicon source is selected from one of esters of silicon acis and organosilicon.
It in one of the embodiments, further include by the Fe for being coated with the silicon dioxide layer3O4@PVP particle and water
Mixing carries out surface modification treatment, so that the step of silicon dioxide layer is in porous structure.
The alcohol is selected from one of dehydrated alcohol, anhydrous methanol and anhydrous isopropyl alcohol in one of the embodiments,.
A kind of photonic crystal ink, including photon crystal material and solvent, photon crystal material are any of the above-described kind of photon
The photon crystal material that the preparation method of crystalline material or any of the above-described kind of photon crystal material is prepared.
The photon crystal material further includes being coated on the polyvinylpyrrolidone shell in one of the embodiments,
Silicon dioxide layer, the solvent be alcohol or water, the surface of the silicon dioxide layer is combined with silanol group.
The silicon dioxide layer is porous structure in one of the embodiments,.
The mass percentage of the photon crystal material is 10%~50% in one of the embodiments, described molten
The mass percentage of agent is 50%~90%.
The solvent is selected from at least one of water and alcohol in one of the embodiments,.
Any of the above-described kind of photonic crystal ink is preparing the application in electrochromic display.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of the photon crystal material of an embodiment；
Fig. 2 is the structural schematic diagram for the electrochromic device that the photonic crystal ink of embodiment 9~32 is fabricated to.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give preferred embodiment of the invention.But the invention can be realized in many different forms, however it is not limited to herein
Described embodiment.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more saturating
It is thorough comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more phases
Any and all combinations of the listed item of pass.
The photon crystal material of one embodiment, the photon crystal material include kernel and the polyethylene that is coated on kernel
Pyrrolidones shell, wherein kernel is formed by several nano ferriferrous oxide crystal grain clusters.I.e. at this point, photon crystal material knot
Structure indicates are as follows: Fe3O4@PVP particle, wherein Fe3O4Kernel made of several nano ferriferrous oxide crystal grain clusters is represented,
Indicate cladding, PVP is shell.
Since nano ferriferrous oxide crystal grain can show the performance advantage of superparamagnetism, and several nanometers four aoxidize three
Kernel made of iron crystal grain cluster is also able to maintain such performance；PVP is coated on kernel, can not only control the big of kernel
It is small, and the steric hindrance of PVP is big, will not influence the magnetism of kernel, so that the monodisperse of kernel is realized, so that Fe3O4@PVP
Grain can be realized under magnetic field condition, the adjusting to the distance between monodispersed kernel, to meet the requirement of discoloration.
Specifically, the partial size of kernel is 100 nanometers~250 nanometers；The partial size of nano ferriferrous oxide crystal grain be 5 nanometers~
15 nanometers.It is above-mentioned partial size by control nano ferriferrous oxide crystal grain and kernel, Fe can be made3O4@PVP particle has magnetic field
There is preferable response.
Specifically, polyvinylpyrrolidone shell with a thickness of 10 nanometers~30 nanometers.
Further, photon crystal material further includes the silicon dioxide layer being coated on polyvinylpyrrolidone shell.At this point,
Photon crystal material can indicate are as follows: Fe3O4@PVP@SiO2.By in Fe3O4Coated silica layer on@PVP particle, can be with
Make Fe3O4@PVP@SiO2Negatively charged group (silanol group (- SiOH)) is generated under the dicyandiamide solution of water or alcohol, and will not
The magnetism of material is influenced, but also can be realized Fe3O4@PVP@SiO2Response to electric field, so that between monodispersed kernel
The adjusting of distance under the electric field, meets the requirement of electric field colour changing.That is Fe3O4@PVP@SiO2Discoloration is not only realized under magnetic field, also
Discoloration can be realized under the electric field.
Specifically, silicon dioxide layer with a thickness of 15 nanometers~40 nanometers.
Further, silicon dioxide layer is porous structure.At this point, photon crystal material can be expressed as Fe3O4@PVP@
p-SiO2, wherein p- indicates porous.The silicon dioxide layer of porous structure can generate more under the dicyandiamide solution of water or alcohol
More negatively charged group (silanol group (- SiOH)), so that the negative electrical charge that the surface for increasing photon crystal material carries, increases material
The color change interval of material in the electric field；And a part of PVP in material can also be stretched out from the hole of porous silicon dioxide layer,
So that PVP can preferably play space steric effect, the long-range control of material is further increased, material can not only be increased
Color change interval in the electric field, additionally it is possible to increase color change interval of the material in magnetic field.
Above-mentioned photon crystal material is a kind of new photon crystal material, can not only realize that schemochrome is shown, Er Qieshang
The ink that photon crystal material can be fabricated to printing is stated, so that above-mentioned photon crystal material can pass through printing
Mode is prepared in display device.
As shown in Figure 1, the preparation method of the photon crystal material of an embodiment, is one kind of above-mentioned photon crystal material
Preparation method.The preparation method of the photon crystal material includes the following steps:
Step S110: under alkaline environment, by water-soluble trivalent ferric salt, polyvinylpyrrolidone (PVP), glucose (D-
(+)-Glucose, C6H12O6), reproducibility solvent and strong base-weak acid salt mixing carry out hydro-thermal reaction, obtain Fe3O4@PVP particle.
Wherein, Fe3O4Kernel made of several nano ferriferrous oxide crystal grain clusters is represented, indicates cladding, PVP is
Shell.
Specifically, polyvinylpyrrolidone shell with a thickness of 10 nanometers~30 nanometers.
Water-soluble trivalent ferric salt is selected from least one of iron chloride, ferric nitrate and ferric sulfate.
Specifically, polyvinylpyrrolidone is PVP (K30).
Specifically, the mass ratio of polyvinylpyrrolidone and the ferro element in water-soluble trivalent ferric salt is 20:1~30:1.
Since the size of the kernel of formation will affect the spacing between kernel, so that the display of schemochrome is affected, and polyethylene
The additive amount of pyrrolidones directly affects the size of the kernel generated.So suitable polyvinylpyrrolidone can
So that kernel has suitable size, so that with suitable between particle in subsequent magnetic field or electric field response
Spacing range.
Glucose can be under hydrothermal conditions by the reactions generation glucosan derivative such as polymerization, aromatization, and glucose
Derivative is incorporated between PVP and kernel by hydrogen bond action, and glucosan derivative can limit nanometer Fe3O4The life of crystal grain
It is long, and make that there is stronger binding force between PVP and kernel, if PVP is difficult to the firm table for being coated on kernel without glucose
Face.
The molar ratio of glucose and water-soluble trivalent ferric salt affects nanometer Fe to a certain extent3O4Grain size, because
This, the molar ratio of glucose and water-soluble trivalent ferric salt needs to meet certain proportional region.Glucose and water-soluble ferric iron
The molar ratio of ferro element in salt is 0.5:1~1:1.
Reproducibility solvent is can be by ferric ion (Fe3+) it is reduced into ferrous ion (Fe2+) solvent, by portion
Divide ferric ion (Fe3+) it is reduced into ferrous ion (Fe2+)。
Specifically, reproducibility solvent is ethylene glycol, and ethylene glycol acts not only as reducing agent in hydro-thermal reaction, can be by trivalent
Iron ion (Fe3+) partial reduction is at ferrous ion (Fe2+), but also be the solvent of reaction system.
Wherein, the quality of reproducibility solvent accounts for the 60%~90% of the quality of the reaction system of step S110.That is reproducibility
The quality of solvent is water-soluble trivalent ferric salt, the quality of polyvinylpyrrolidone, glucose, strong base-weak acid salt and reproducibility solvent
The sum of 60%~90%.
Strong base-weak acid salt can provide alkaline environment to system, be conducive to presoma made from above-mentioned substance in subsequent high temperature
It is reacted under hyperbaric environment.Alkaline environment enables to residue not by the Fe of reduction of ethylene glycol3+With the Fe of generation2+It generates
Fe(OH)3With Fe (OH)2, pass through Fe (OH)2With Fe (OH)3Dehydration forms nanometer Fe in water-heat process3O4Crystal grain.
Specifically, strong base-weak acid salt is acetate, but is not limited to thus.Specifically, carboxylate is selected from sodium acetate, potassium acetate
Equal strong base-weak acid salts, but not limited to this.
Specifically, the molar ratio of acetate and the ferro element in water-soluble trivalent ferric salt is 14:1~21:1.
Specifically, under alkaline environment, by water-soluble trivalent ferric salt, polyvinylpyrrolidone, glucose, reproducibility solvent
The step of carrying out hydro-thermal reaction with strong base-weak acid salt are as follows: polyvinylpyrrolidone, glucose are dissolved in reproducibility solvent, so
After water-soluble trivalent ferric salt is added, obtain mixed liquor, add strong base-weak acid salt, then carry out hydro-thermal reaction the step of are as follows: will
Polyvinylpyrrolidone, glucose are dissolved in reproducibility solvent, then sequentially add water-soluble trivalent ferric salt and strong base weak acid
Salt, so that reaction system then carries out hydro-thermal reaction in alkalinity.
By the way that first polyvinylpyrrolidone and glucose are dissolved in reproducibility solvent, to guarantee polyvinylpyrrolidone
It can be uniformly mixed with the water-soluble trivalent ferric salt of subsequent addition, undissolved PVP is avoided to mix not with water-soluble trivalent ferric salt
Viscoelastic fluid uniformly is formed, and the visco elastic fluids are known from experience and are climbed along stirring parts (such as rotating rod), and cannot shape well
At reaction system, subsequent Fe is influenced3O4The generation of@PVP particle.
It specifically, is at 80 DEG C~120 DEG C by the step that polyvinylpyrrolidone, glucose are dissolved in reproducibility solvent
Lower progress.
It should be noted that under alkaline environment, by water-soluble trivalent ferric salt, polyvinylpyrrolidone, glucose, reduction
Property solvent and strong base-weak acid salt the step of carrying out hydro-thermal reaction be not limited to aforesaid way, for example, it is also possible to for first by polyethylene
Pyrrolidones is dissolved in reproducibility solvent, and glucose and water-soluble trivalent ferric salt is then added, and strong base-weak acid salt is being added, is connecing
Carry out hydro-thermal reaction.
Specifically, the temperature of hydro-thermal reaction is 180 DEG C~230 DEG C.The time of hydro-thermal reaction is 6 hours~24 hours.
Further, after hydro-thermal reaction, further include the steps that purifying the product of hydro-thermal reaction: by hydro-thermal reaction
Product afterwards is separated by solid-liquid separation, and then cleaning is separated by solid-liquid separation obtained solid, then solid is dry.
Specifically, the method for separation of solid and liquid is Magneto separate.Pass through the removal supernatant liquid of the method for Magneto separate.
Specifically, cleaning is separated by solid-liquid separation the step of obtained solid are as follows: clear using at least one of water and ethyl alcohol ultrasound
Solid is washed, to dissolve reaction residue, impurity etc..That is, the step of ultrasonic cleaning solid can be that water is used to clean solid；Or
Person cleans solid using EtOH Sonicate；Alternatively, alternately cleaning solid using water and ethyl alcohol.Wherein, water is deionized water, ethyl alcohol
For dehydrated alcohol.
Specifically, dry temperature is 20 DEG C~50 DEG C.
Specifically, the partial size of nano ferriferrous oxide crystal grain is 5 nanometers~15 nanometers；The partial size of kernel be 100 nanometers~
250 nanometers.
Step S120: by Fe3O4@PVP particle and silicon source, catalyst and the water hybrid reaction in alcohol, obtain being coated with dioxy
The Fe of SiClx layer3O4@PVP particle.
Wherein, be coated with silicon oxide the Fe of layer3O4@PVP particle indicates are as follows: Fe3O4@PVP@SiO2。
Specifically, silicon dioxide layer with a thickness of 15 nanometers~40 nanometers.
Specifically, step S120 is carried out at room temperature.
Specifically, by Fe3O4@PVP particle and silicon source, catalyst and water are in alcohol the step of hybrid reaction are as follows: by Fe3O4@
PVP particle is dispersed in alcohol, and water then is added and catalyst is sufficiently mixed, adds silicon source, then react at room temperature.
More specifically, silicon source is added in a manner of the alcoholic solution of silicon source.And the alcoholic solution of silicon source is added by way of dropwise addition
Enter into reaction system.The molar ratio of the ferro element in element silicon and water-soluble trivalent ferric salt in silicon source is 1:1~3:1.
Wherein, silicon source is selected from one of esters of silicon acis and organosilicon.The esters of silicon acis is selected from ethyl orthosilicate, positive silicic acid first
One of ester and positive silicic acid propyl ester, but not limited to this.
Catalyst is the ammonium hydroxide that mass percentage concentration is 25%~28%.NH in step S120, in ammonium hydroxide3With addition
The molar ratio of water (water not comprising ammonium hydroxide itself) is 1:2~1:10.
In step S120, water is reactant.Specifically, the element silicon in silicon source and the water of addition (do not include ammonium hydroxide itself
Water) molar ratio be 1:115~1:290.
Specifically, alcohol is selected from one of dehydrated alcohol, anhydrous methanol and anhydrous isopropyl alcohol.And the alcoholic solution of silicon source is selected from
One of the ethanol solution of silicon source, the absolute methanol solution of silicon source and anhydrous isopropanol solution of silicon source.
Step S130: by the Fe for the layer that is coated with silicon oxide3O4@PVP particle and water mixing carry out surface modification treatment, with
Make silicon dioxide layer in porous structure.
Wherein, the material that step S130 is obtained indicates are as follows: Fe3O4@PVP@p-SiO2；P- indicates porous.At this point, if will
Fe3O4@PVP@p-SiO2It dissolves in water and/or alcoholic solvent, generates porous surface, make SiO2Surface area increases, can be in conjunction with more
More silanol groups has the surface of silicon dioxide layer higher so as to increase the surface charge density of silicon dioxide layer
Charge density.
Specifically, by the Fe for the layer that is coated with silicon oxide3O4The step of@PVP particle and water mixing carry out surface modification treatment
Specifically: by the Fe for the layer that is coated with silicon oxide3O4@PVP particle and water are blended at 80 DEG C~120 DEG C and carry out back flow reaction.
Specifically, by Fe3O4@PVP@SiO2The step of colloidal solid and water mix are as follows: by Fe3O4@PVP@SiO2Colloid
Grain ultrasonic disperse is in deionized water.
Wherein, the principle that photon crystal material different colours are shown are as follows:
Molten liquefied photonic crystal is also referred to as colloidal crystal, obtains size uniformity by various chemical synthesis process first
Nano particle, then with water or other solvents (such as alcohols) for medium, in the presence of outfield, colloidal solid can be in space
Periodic arrangement is presented.This colloidal crystal can regulate and control light, and the diffraction crest location of specific photonic crystal meets cloth
Glug diffraction law, it may be assumed that
N λ=2mdsin θ
Wherein, n indicate diffraction progression, λ indicate diffraction wavelength, d be colloidal solid spacing, θ be glancing angle (incident ray with
The angle of crystal face), m indicates mean refractive index.As can be seen from the above equation, diffraction wavelength is positively correlated with colloidal solid spacing, glue
Body crystal spacing is bigger, and diffraction wavelength is longer；Conversely, colloidal crystal spacing is smaller, diffraction wavelength is bigger.Colloidal solid spacing
Consecutive variations occur, then corresponding consecutive variations also occur for diffraction wavelength.So being adjusted by the variation of control colloidal particle spacing
That saves colloidal photon crystal goes out light color.
Make colloidal particle be assembled into photonic crystal and produce bright schemochrome, first has to guarantee that synthesize size equal
One, the similar micro-nano granules of surface nature, secondary so that being separated from each other into certain distance between nano particle, also requirement is logical
Cross the controllability that certain means makes colloidal particle spacing.
And the preparation method of above-mentioned photon crystal material synthesizes a kind of Fe by the method for solvent heat3O4@PVP particle,
Fe3O4For kernel made of several nano ferriferrous oxide crystal grain clusters, PVP is shell, is coated on above-mentioned kernel, due to poly-
The presence of ethylene ratio pyrrolidone (PVP) long chain can control several nano ferriferrous oxide grain colonies in synthesis process
The size and homogeneity of the kernel of cluster, so that the kernel of preparation has uniform size, and due to the nanometer of composition kernel
The size of ferroso-ferric oxide crystal grain is less than critical dimension and superparamagnetism is presented, can be by external magnetic field one-to-one correspondence come dynamic
Regulate and control its grain spacing size.It is mutually exclusive between the PVP strand of core surface cladding to make to separate one between its colloidal particle
Fixed spacing, at this point, PVP chain can produce telescopic variation, and then reaches and adjust colloidal particle spacing by control magnetic field size
Purpose.This particle size is suitable, size uniformity, is separated between particle by the effect based on steric hindrance repelling effect, in magnetic
It can be assembled into the colloidal photon crystal of tunable band gap off field, diffraction goes out wavelength variable schemochrome.
And since PVP in the solution is almost in electroneutral, in order to enable Fe3O4@PVP photonic crystal structure color applies to electricity
In mutagens color device, the preparation method of above-mentioned photon crystal material utilizes improvedMethod is to above-mentioned Fe3O4@PVP is carried out
Coated with silica forms Fe3O4@PVP@SiO2, so that Fe3O4@PVP@SiO2Dicyandiamide solution following table of the particle in water or alcohol
Face can be bonded a large amount of silanol groups, and elecrtonegativity is shown, due to negatively charged and can respond under the electric field between particle.
In order to increase the responsiveness and modification scope of this electric field or magnetic field, to Fe3O4@PVP@SiO2It is surface-treated,
With easy boiling reflux method to Fe3O4@PVP@SiO2It is handled, obtains Fe3O4@PVP@p-SiO2Colloidal solid, from
And form the SiO of porous structure2Layer.The water of boiling is by corroding SiO2Superficial layer, so that under the dicyandiamide solution of water or alcohol more
More silanol group (Si-OH) bond energys are enough connected to particle surface, maintain the electrostatic repulsion of long-range between particle；Meanwhile it mentioning
High SiO2Layer ion permeability, so that certain PVP molecules are occurred steric restriction effect, substantially increased orderly by hole
The long-range control of nano particle.
It is appreciated that step S130 can be omitted, at this point, obtained photon crystal material is then the layer that is coated with silicon oxide
Fe3O4@PVP particle；Step S120 also can be omitted, and obtained photon crystal material is then Fe3O4@PVP particle.
And the experiment proved that, above-mentioned Fe3O4The Fe of@PVP particle, the layer that is coated with silicon oxide3O4@PVP particle and
Fe3O4@PVP@p-SiO2Particle can be realized structure coloring, and display device can be prepared by way of printing
Photon crystal material.
The photonic crystal ink of one embodiment, including photon crystal material and solvent.In photonic crystal ink, photon
The mass percentage of crystalline material is 10%~50%, and the mass percentage of solvent is 50%~90%.
Photon crystal material is Fe3O4The Fe of@PVP particle, the layer that is coated with silicon oxide3O4@PVP particle or Fe3O4@PVP@
p-SiO2Particle.
Solvent is selected from least one of water and alcohol.Specifically, alcohol is selected from least one of ethyl alcohol and isopropanol.
Specifically, when photon crystal material is the Fe of layer of being coated with silicon oxide3O4@PVP particle or Fe3O4@PVP@p-
SiO2When particle, the surface of silicon dioxide layer is combined with silanol group.
Specifically, the preparation process of photonic crystal ink is as follows: in a solvent by photon crystal material dissolution, photonic crystal
Ink.
The photonic crystal ink can change colour under the influence of a magnetic field, and color change interval covers entire visible light.Meanwhile
Be coated with silicon oxide the Fe of layer3O4@PVP particle and Fe3O4@PVP@p-SiO2The photonic crystal ink of particle production, additionally it is possible to
Change colour under the action of electric field, or even can also be in the common lower discoloration in magnetic field and electric field, and color change interval covering is entire visible
Light.
Above-mentioned photonic crystal ink can be applied in electrochromic display, realize that the mode of printing prepares color changing display
Part.Wherein, electrochromic display can be electrochromic device.
The following are specific embodiment part, (following embodiment unless otherwise specified, does not then contain and removes inevitable impurity
Other components not yet explicitly pointed out in addition.):
Embodiment 1
The preparation process of the photon crystal material of the present embodiment is as follows:
(1) polyvinylpyrrolidone-K30 (PVP-K30), glucose and ethylene glycol are added in 100mL three-necked bottle,
It is stirred 30 minutes at 100 DEG C, is then cooled to room temperature；Then FeCl is added into three-necked bottle3·6H2O, stirring are formed to dissolving
The transparent mixed liquor of yellowish orange；Sodium acetate is added into mixed liquor again, stirring obtains reaction system to dissolving, then will be anti-
Answer system to be transferred in the hydrothermal reaction kettle of 50mL to seal, be then placed in baking oven 200 DEG C heat preservation hydro-thermal 12 hours, be then cooled to
Room temperature obtains black dispersion liquid, and black dispersion liquid is carried out Magneto separate, and solid washes with water, and finally puts it into vacuum drying
50 DEG C drying 12 hours, obtain Fe in case3O4@PVP particle, and through transmission electron microscope detection and XRD detection it is found that Fe3O4@PVP
In grain, Fe3O4The partial size of kernel is 100 nanometers~250 nanometers；The partial size of the nano ferriferrous oxide crystal grain of kernel is formed to receive for 5
Rice~15 nanometers, PVP shell with a thickness of 10 nanometers~30 nanometers.Wherein, PVP-K30 and FeCl3·6H2The matter of ferro element in O
Amount is than being 20:1；Glucose and FeCl3·6H2The molar ratio of ferro element in O is 1:1；The quality of ethylene glycol accounts for reaction system
The 75% of quality；Sodium acetate and FeCl3·6H2The molar ratio of ferro element in O is 18:1.
(2) by Fe3O4Then@PVP particle ultrasonic disperse is added water and mass percentage concentration is in 50mL dehydrated alcohol
26% ammonium hydroxide, stirring allow solution to mix well, obtain mixed solution；Measure the nothing that ethyl orthosilicate (TEOS) is dissolved in 10mL
In water-ethanol, the ethanol solution of TEOS is obtained.Under continuous agitation, by the ethanol solution of TEOS with 2 drops/sec of speed
It being added drop-wise in mixed solution, the ethanol solution to TEOS is added dropwise to complete, continues to react 5 hours under conditions of continuing and room temperature,
It is centrifuged, obtains Fe3O4@PVP@SiO2Particle, and SiO2Layer with a thickness of 15 nanometers~40 nanometers.Silicon in ethyl orthosilicate
Element and FeCl3·6H2The molar ratio of the ferro element in ferro element in O is 1:1.Element silicon and addition in ethyl orthosilicate
Water molar ratio be 1:200.NH in ammonium hydroxide3Molar ratio with the water of addition is 1:6.
(3) by Fe3O4@PVP@SiO2Particle ultrasonic disperse goes to three necks of condensing unit in the deionized water of 30mL
It stirs, and back flow reaction 2 hours at 100 DEG C, then cooled to room temperature, then is washed with deionized in bottle, obtain
Fe3O4@PVP@p-SiO2Particle.
Embodiment 2
The preparation process of the photon crystal material of the present embodiment is as follows:
(1) PVP-K30, glucose and ethylene glycol are added in 100mL three-necked bottle, are stirred 1 hour at 80 DEG C, it is then cold
But to room temperature；Then FeCl is added into three-necked bottle3·6H2O particle, stirring form the transparent mixing of yellowish orange to dissolving
Liquid；Potassium acetate is added into mixed liquor again, stirring obtains reaction system, reaction system is then transferred to 50mL's to dissolving
Sealed in hydrothermal reaction kettle, be then placed in baking oven 180 DEG C heat preservation hydro-thermal 24 hours, be then cooled to room temperature, obtain black dispersion
Black dispersion liquid is carried out Magneto separate by liquid, and solid washes with water, and it is small finally to put it into 20 DEG C of dryings 24 in vacuum oven
When, obtain Fe3O4@PVP, and through transmission electron microscope detection and XRD detection it is found that Fe3O4In@PVP particle, Fe3O4The partial size of kernel
It is 100 nanometers~250 nanometers；The partial size for forming the nano ferriferrous oxide crystal grain of kernel is 5 nanometers~15 nanometers, PVP shell
With a thickness of 10 nanometers~30 nanometers.Wherein, PVP-K30 and FeCl3·6H2The mass ratio of ferro element in O is 30:1；Glucose
With FeCl3·6H2The molar ratio of ferro element in O is 0.8:1；The quality of ethylene glycol accounts for the 60% of the quality of reaction system；Acetic acid
Potassium and FeCl3·6H2The molar ratio of ferro element in O is 14:1.
(2) by Fe3O4Then@PVP particle ultrasonic disperse is added water and mass percentage concentration is in 50mL dehydrated alcohol
25% ammonium hydroxide, stirring allow solution to mix well, obtain mixed solution；It measures organosilicon to be dissolved in 10mL dehydrated alcohol, obtain
To the ethanol solution of organosilicon.Under continuous agitation, the ethanol solution of organosilicon is added drop-wise to 2 drops/sec of speed
In mixed solution, the ethanol solution to organosilicon is added dropwise to complete, and is continued continuing and reaction 2 hours under conditions of room temperature, through from
The heart obtains Fe3O4@PVP@SiO2Particle, and SiO2Layer with a thickness of 15 nanometers~40 nanometers.Element silicon in organosilicon with
FeCl3·6H2The molar ratio of ferro element in O is 2:1.The molar ratio of the water of element silicon and addition in organosilicon is 1:115.
NH in ammonium hydroxide3Molar ratio with the water of addition is 1:9.
(3) by Fe3O4@PVP@SiO2Particle ultrasonic disperse goes to three necks of condensing unit in the deionized water of 10m
It stirs, and back flow reaction 1 hour at 120 DEG C, then cooled to room temperature, then is washed with deionized in bottle, obtain
Fe3O4@PVP@p-SiO2Particle.
Embodiment 3
The preparation process of the photon crystal material of the present embodiment is as follows:
(1) PVP-K30, glucose and ethylene glycol are added in 100mL three-necked bottle, stir 10 minutes at 120 DEG C, then
It is cooled to room temperature；Then FeCl is added into three-necked bottle3·6H2O, stirring form the transparent mixed liquor of yellowish orange to dissolving；
Sodium acetate is added into mixed liquor again, stirring obtains reaction system, reaction system is then transferred to the hydro-thermal of 50mL to dissolving
Sealed in reaction kettle, be then placed in baking oven 230 DEG C heat preservation hydro-thermal 6 hours, be then cooled to room temperature, obtained black dispersion liquid,
Black dispersion liquid is subjected to Magneto separate, solid washes with water, finally puts it into 50 DEG C drying 6 hours in vacuum oven, obtain
To Fe3O4@PVP, and through transmission electron microscope detection and XRD detection it is found that Fe3O4In@PVP particle, Fe3O4The partial size of kernel is 100
Nanometer~250 nanometers；Form kernel nano ferriferrous oxide crystal grain partial size be 5 nanometers~15 nanometers, PVP shell with a thickness of
10 nanometers~30 nanometers.Wherein, PVP-K30 and FeCl3·6H2The mass ratio of ferro element in O is 24:1；Glucose with
FeCl3·6H2The molar ratio of ferro element in O is 0.8:1；The quality of ethylene glycol accounts for the 90% of the quality of reaction system；Sodium acetate
With FeCl3·6H2The molar ratio of ferro element in O is 21:1.
(2) by Fe3O4Then@PVP ultrasonic disperse is added water and mass percentage concentration is in 50mL anhydrous isopropyl alcohol
28% ammonium hydroxide, stirring allow solution to mix well, obtain mixed solution；It measures methyl orthosilicate and is dissolved in 10mL anhydrous isopropyl alcohol
In, obtain the aqueous isopropanol of methyl orthosilicate.Under continuous agitation, by the ethanol solution of TEOS with 2 drops/sec of speed
Degree is added drop-wise in mixed solution, and the aqueous isopropanol to methyl orthosilicate is added dropwise to complete, under conditions of lasting stirring and room temperature
Reaction 10 hours, is centrifuged, obtains Fe3O4@PVP@SiO2Particle, and SiO2Layer with a thickness of 15 nanometers~40 nanometers.Positive silicic acid
Element silicon and FeCl in methyl esters3·6H2The molar ratio of ferro element in O is 2.5:1.Element silicon in methyl orthosilicate with plus
The molar ratio of the water entered is 1:290.NH in ammonium hydroxide3Molar ratio with the water of addition is 1:3.
(3) by Fe3O4@PVP@SiO2Particle ultrasonic disperse goes to three necks of condensing unit in the deionized water of 50mL
It stirs, and back flow reaction 3 hours at 80 DEG C, then cooled to room temperature, then is washed with deionized in bottle, obtain
Fe3O4@PVP@p-SiO2Particle.
Embodiment 4
The preparation process of the photon crystal material of the present embodiment is as follows:
(1) PVP-K30, glucose and ethylene glycol are added in 100mL three-necked bottle, stir 40 minutes at 110 DEG C, then
It is cooled to room temperature；Then FeCl is added into three-necked bottle3·6H2O, stirring form the transparent mixed liquor of yellowish orange to dissolving；
Potassium acetate is added into mixed liquor again, stirring obtains reaction system, reaction system is then transferred to the hydro-thermal of 50mL to dissolving
Sealed in reaction kettle, be then placed in baking oven 210 DEG C heat preservation hydro-thermal 12 hours, be then cooled to room temperature, obtain black dispersion liquid, will
Black dispersion liquid carries out Magneto separate, and solid washes with water, finally puts it into 30 DEG C drying 18 hours in vacuum oven, obtain
Fe3O4@PVP, and through transmission electron microscope detection and XRD detection it is found that Fe3O4In@PVP particle, Fe3O4The partial size of kernel is received for 100
Rice~250 nanometers；Form kernel nano ferriferrous oxide crystal grain partial size be 5 nanometers~15 nanometers, PVP shell with a thickness of 10
Nanometer~30 nanometers.Wherein, PVP-K30 and FeCl3·6H2The mass ratio of ferro element in O is 28:1；Glucose and FeCl3·
6H2The molar ratio of ferro element in O is 0.7:1；The quality of ethylene glycol accounts for the 80% of the quality of reaction system；Potassium acetate with
FeCl3·6H2The molar ratio of ferro element in O is 16:1.
(2) by Fe3O4Then H is added in 50mL anhydrous methanol in@PVP ultrasonic disperse2The mass percentage concentration of O sum is
26% ammonium hydroxide, stirring allow solution to mix well, obtain mixed solution；It is anhydrous that measurement 0.2mL positive silicic acid propyl ester is dissolved in 10mL
In methanol, the methanol solution of positive silicic acid propyl ester is obtained.Under continuous agitation, by the ethanol solution of positive silicic acid propyl ester with 2
Drop/sec speed be added drop-wise in mixed solution, the methanol solution to positive silicic acid propyl ester is added dropwise to complete, under continuous agitation
It reacts 7 hours at room temperature, is centrifuged, obtains Fe3O4@PVP@SiO2Particle, and SiO2Layer is received with a thickness of 15 nanometers~40
Rice.The molar ratio of the water of element silicon and addition in positive silicic acid propyl ester is 1:150.NH in ammonium hydroxide3With mole of the water of addition
Than for 1:8.
(3) by Fe3O4@PVP@SiO2Particle ultrasonic disperse goes to three necks of condensing unit in the deionized water of 40mL
It stirs, and back flow reaction 2.5 hours at 90 DEG C, then cooled to room temperature, then is washed with deionized in bottle, obtain
Fe3O4@PVP@p-SiO2Particle.
Embodiment 5
The preparation process of the photon crystal material of the present embodiment is roughly the same with embodiment 1, and difference is:
The water-soluble trivalent ferric salt used in step (1) is ferric nitrate.The matter of PVP-K30 and the ferro element in ferric nitrate
Amount is than being 20:1；The molar ratio 0.6:1 of ferro element in glucose and ferric nitrate, sodium acetate rub with the ferro element in ferric nitrate
You are than being 15:1.
The molar ratio of the water of element silicon and addition in step (2) ethyl orthosilicate is 1:250, the silicon in ethyl orthosilicate
The molar ratio of ferro element in element and ferric nitrate is 2.5:1, the NH in ammonium hydroxide3Molar ratio with the water of addition is 1:2.
Embodiment 6
The preparation process of the photon crystal material of the present embodiment is roughly the same with embodiment 1, and difference is:
The water-soluble trivalent ferric salt used in step (1) is ferric sulfate.The matter of PVP-K30 and the ferro element in ferric sulfate
Amount is than being 24:1；The molar ratio 0.8:1 of ferro element in glucose and ferric sulfate, sodium acetate rub with the ferro element in ferric sulfate
You are than being 17:1.
The molar ratio of the water of element silicon and addition in step (2) ethyl orthosilicate is 1:180, the silicon in ethyl orthosilicate
The molar ratio of ferro element in element and ferric sulfate is 1.8:1, the NH in ammonium hydroxide3Molar ratio with the water of addition is 1:10.
Embodiment 7
The preparation process of the photon crystal material of the present embodiment is roughly the same with embodiment 1, and difference is:
The FeCl that the water-soluble trivalent ferric salt used in step (1) is 1:13·6H2The mixture of O and ferric sulfate.PVP-
The mass ratio of K30 and the ferro element in water-soluble trivalent ferric salt is 28:1；Ferro element in glucose and water-soluble trivalent ferric salt
Molar ratio 1:1, the molar ratio 20:1 of the ferro element in sodium acetate and water-soluble trivalent ferric salt.
The molar ratio of the water of element silicon and addition in step (2) ethyl orthosilicate is 1:220, the silicon in ethyl orthosilicate
The molar ratio of ferro element in element and water-soluble trivalent ferric salt is 2.6:1, the NH in ammonium hydroxide3Molar ratio with the water of addition is
1:5。
Embodiment 8
The preparation process of the photon crystal material of the present embodiment is roughly the same with embodiment 1, and difference is:
The FeCl that the water-soluble trivalent ferric salt used in step (1) is 1:13·6H2The mixture of O and ferric sulfate.PVP-
The mass ratio of K30 and the ferro element in water-soluble trivalent ferric salt is 25:1；Ferro element in glucose and water-soluble trivalent ferric salt
Molar ratio 0.7:1, the molar ratio 19:1 of the ferro element in sodium acetate and water-soluble trivalent ferric salt.
The molar ratio of the water of element silicon and addition in step (2) ethyl orthosilicate is 1:130, the silicon in ethyl orthosilicate
The molar ratio of ferro element in element and water-soluble trivalent ferric salt is 3:1, the NH in ammonium hydroxide3Molar ratio with the water of addition is 1:
4。
9~embodiment of embodiment 32
The preparation process of the photonic crystal ink of 9~embodiment of embodiment 32 is as follows:
The Fe that (1) the step of 1~embodiment of embodiment 8 is prepared according to table 33O4@PVP particle is dissolved in molten respectively
In agent, the photonic crystal ink of 9~embodiment of embodiment 16 is obtained.
The Fe that (2) the step of 1~embodiment of embodiment 8 are prepared according to table 43O4@PVP@SiO2Particle dissolves respectively
In a solvent, the photonic crystal ink of 17~embodiment of embodiment 24 is obtained.
The Fe that (3) the step of 1~embodiment of embodiment 8 are prepared according to table 53O4@PVP@p-SiO2Particle difference is molten
Solution in a solvent, obtains the photonic crystal ink of 25~embodiment of embodiment 32.
Table 3
Table 4
Table 5
Test:
(1) electric field colour changing is tested:
The photonic crystal ink of embodiment 9~32 is fabricated to electrochromic device respectively, successively obtains electrochromism device
Part 1~24.
Wherein, electrochromic device is produced as follows: the method for photonic crystal ink pressure injection is placed in two
Between the ito glass electrode that piece is sealed with epoxy resin, structure electrochromic device 200 as shown in Figure 2, two intervals are obtained
The ITO electro-conductive glass 210 of setting and two epoxy resin packaging parts 220 are enclosed jointly and are set as accommodating photonic crystal ink 230
Cavity, ito glass electrode 210 includes glassy layer 212 and ITO layer 214, and the ITO layer 214 of two ito glass electrodes 210 is close
Setting.Wherein, epoxy resin packaging part 220 is with a thickness of 250 microns.
Discoloration test: two ito glass electrodes 210 of each electrochromic device 200 are respectively connected to adjustable voltage
DC power supply positive and negative anodes on, open DC power supply, adjust voltage swing (0~10V of adjustable range).Wherein, electrochromism
Discoloration of the device 1~24 in the range of voltage is 0~10V is as follows:
The discoloration of electrochromic device 1~8 is equal are as follows: does not change colour.
The discoloration of electrochromic device 9~16 is equal are as follows: when loading upper voltage, voltage is adjusted, when voltage adjusting is arrived
When to a certain degree, there is color in device.Continue to adjust voltage, may occur in which color change phenomenon, but the variation range of color is smaller,
And there can be no brighter red.
The discoloration of electrochromic device 17~24 is equal are as follows: not powered pressure, i.e. voltage are 0V, do not load electric field, device
The original brown of ink is presented in part；When loading certain certain voltage, color is presented in device；When increasing voltage, that is, increase electric-field strength
Degree, device color blue shift reduce voltage, device color red shift.The amplitude of variation of color is big, and the brightness of color also improves, and
Brighter red can occur.Change voltage swing, can be realized and covered from red, orange, yellow, green, cyan, blue etc.
The continuous color change of entire visible-range, i.e. electrochromism.This explanation can be realized by changing electric field intensity size
Electrochromic device successively becomes orange, yellow, green, cyan, blue etc. from red, and covers the company of entire visible-range
Continuous color change, i.e. electrochromism.
This is because the Fe in the photonic crystal ink of electrochromic device 17~243O4@PVP@p-SiO2Colloid grains sublist
Face carries a large amount of negative electrical charges, so that Fe3O4@PVP@p-SiO2Colloidal particle has enough dispersibilities.Under extra electric field, glue
Body particle has electrostatic repulsion due to a large amount of negative electrical charges in surface, reaches dynamic equilibrium with external electrical field power, so that particle
It is arranged as oldered array.Equilibrium state can be changed by adjusting extra electric field, and then change the spacing of particle, and pass through Prague
Diffraction generates variable photon band gap feature.Carry the Fe of negative electrical charge3O4@PVP@p-SiO2Particle is inhaled by positive terminal electrostatic
Guide positive polar motion (electrophoresis) into；And Fe3O4@PVP@p-SiO2Strong electrostatic row is generated due to carrying like charges between particle
Reprimand effect hinders Fe3O4@PVP@p-SiO2The electrophoresis of particle.When external voltage increases, electrophoresis is strong, and grain spacing becomes smaller；Voltage
When reduction, electrophoresis is weaker, and grain spacing increases.By external voltage size control grain spacing, to be made by Bragg diffraction
Photonic crystal structure color wavelength shift is obtained, to achieve the purpose that tune photon band gap, then reaches electrochromic purpose.
And electrochromic device 1~8 is due to being Fe3O4@PVP colloidal solid, surface are almost in electroneutral, will not be responded outer
Boundary's electric field.Electrochromic device 9~16 is through surface coated Si O2Colloidal solid afterwards, surface carry more negative electrical charge, energy
Enough respond the variation of external electrical field.But the negative electrical charge on surface is limited, and only relies on the negative electrical charge between particle to respond the external world
Electric field, modification scope are limited.Electrochromic device 17~24 is by the modified Fe in surface3O4@PVP@p-SiO2Form surface
Porous colloidal solid, the Zeta electric potential of modified system are substantially reduced (absolute value increase), it is bigger to illustrate that area load has
Negative charge density, response external electrical field that can be stronger, furthermore by the modified SiO for increasing layer2The permeability of layer, can shape
At porous structure, several PVP molecules can be made to increase the long-range control under the electric field of colloidal solid by hole.
(2) magnetic field changes colour:
The photonic crystal ink of embodiment 9~32 is loaded in cuvette respectively, is successively obtained equipped with embodiment 9~32
The cuvette 1~24 of photonic crystal ink.
Discoloration test: cuvette is placed in by magnet, is changed cuvette at a distance from magnet, is observed the light in each cuvette
The color of sub- crystal ink.
Wherein, the color change of the photonic crystal ink in cuvette 1~24 is equal are as follows: when cuvette is placed in by magnet, than
Photonic crystal ink in color ware becomes colour by the variation of original dark brown；Change the relative distance of each cuvette and magnet,
It can observe that different colors occurs；And the mobile cuvette of continuous reversible and the relative distance of magnet in a certain range, just
The colored display of continuous reversible variation can be observed.It is compared to cuvette 1~16, the photonic crystal ink in cuvette 17~24
More preferably, response color gamut is wider, it can be achieved that from red, green to the entire visible wavelength range of blue for water electric field response performance
Reversible color change.
This is to illustrate to constitute Fe3O4@PVP particle, Fe3O4@PVP@SiO2Particle and Fe3O4@PVP@p-SiO2The core of particle
Heart Fe3O4Particle scale very little has superparamagnetic characteristic, responds under magnetic field rapidly, and stimulation is corresponded with response, will not be gone out
Existing hysteresis；Under the action of an external magnetic field dipole moment can be generated along magnetic line of force direction.Between dipole between adjacent particle
Active force is showing as repulsion perpendicular to outer magnetic field direction, shows as attraction being parallel to outer magnetic field direction.This not Tongfang
To gravitation and repulsion and interparticle electrostatic repulsion forces mutually act synergistically and reach dynamic equilibrium so that Fe3O4@PVP
Particle, Fe3O4@PVP@SiO2Particle and Fe3O4@PVP@p-SiO2Particle can be assembled into orderly chain knot along magnetic direction
Structure.With to Fe3O4@PVP colloidal particle carries out surface modification treatment, so that particle surface carries more negative electrical charges, PVP
Also can be by porous, so that collective effect increases the response to externally-applied magnetic field, response range is bigger.When magnetic field is strong, this collaboration
Effect is so that grain spacing becomes smaller, and makes schemochrome wavelength blue shift by Bragg diffraction (n λ=2d sin θ)；Magnetic field is weak
When, so that grain spacing becomes larger, schemochrome red shift of wavelength is made by Bragg diffraction, reaches the mesh of the reversible tuning of photon band gap
's.
(3) magnetic field and electric field act on lower discoloration simultaneously:
By above-mentioned electrochromic device 9~24, ito glass electrode is being respectively connected to the DC power supply of adjustable voltage just
On cathode, electrochromic device 9~24 is fixed on the integrating device being made of multiple electromagnet；Ito glass electrode
It accesses on extraneous DC power supply, each electromagnet is individually controlled by different circuits respectively.Regulate and control the voltage of each circuit respectively
Or size of current, the Electrochromic device under magnetic field electric field can be realized while controlling.
By control voltage swing, it can be achieved that the entire color change of device, by individually controlling electromagnet current
Size, i.e. adjusting magnetic field size realize the magneto discoloration in whole face device zonule, realize on the basis of integral color variation
The magneto discoloration of part.By comparison, 9~16 color response wave-length coverage of device is relatively narrow, 17~24 color response range of device
Bigger, color is more vivider.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (20)
1. a kind of photon crystal material, which is characterized in that the photon crystal material includes kernel and is coated on the kernel
Polyvinylpyrrolidone shell, wherein the kernel is formed by several nano ferriferrous oxide crystal grain clusters.
2. photon crystal material according to claim 1, which is characterized in that the partial size of the kernel is 100 nanometers~250
Nanometer；The partial size of the nano ferriferrous oxide crystal grain is 5 nanometers~15 nanometers.
3. photon crystal material according to claim 1, which is characterized in that the polyvinylpyrrolidone shell with a thickness of
10 nanometers~30 nanometers.
4. photon crystal material according to claim 1, which is characterized in that further include being coated on the polyvinylpyrrolidine
Silicon dioxide layer on ketone shell.
5. photon crystal material according to claim 4, which is characterized in that the silicon dioxide layer is porous structure.
6. photon crystal material according to claim 4 or 5, which is characterized in that the silicon dioxide layer with a thickness of 15
Nanometer~40 nanometers.
7. a kind of preparation method of photon crystal material, which comprises the steps of:
Under alkaline environment, by water-soluble trivalent ferric salt, polyvinylpyrrolidone, glucose, reproducibility solvent and strong base weak acid
Salt mixing carries out hydro-thermal reaction, obtains Fe3O4@PVP particle, wherein Fe3O4Represent several nano ferriferrous oxide grain colonies
Kernel made of cluster ,@indicate cladding, and PVP is shell.
8. the preparation method of photon crystal material according to claim 7, which is characterized in that the water-soluble trivalent ferric salt
Selected from least one of iron chloride, ferric nitrate and ferric sulfate.
9. the preparation method of photon crystal material according to claim 7, which is characterized in that it is described under alkaline environment,
Water-soluble trivalent ferric salt, polyvinylpyrrolidone, glucose, reproducibility solvent and strong base-weak acid salt are mixed and carry out hydro-thermal reaction
The step of are as follows: the polyvinylpyrrolidone, the glucose are dissolved in the reproducibility solvent, institute is then sequentially added
Water-soluble trivalent ferric salt and the strong base-weak acid salt are stated, so that reaction system then carries out hydro-thermal reaction in alkalinity.
10. the preparation method of photon crystal material according to claim 7, which is characterized in that the temperature of the hydro-thermal reaction
Degree is 180 DEG C~230 DEG C；And/or the quality of the ferro element in the polyvinylpyrrolidone and the water-soluble trivalent ferric salt
Than for 20:1~30:1；And/or the molar ratio of the ferro element in the glucose and the water-soluble trivalent ferric salt is 0.5:1
~1:1；And/or the reproducibility solvent is ethylene glycol；And/or the strong base-weak acid salt is acetate.
11. the preparation method of photon crystal material according to claim 7, which is characterized in that further include in the Fe3O4@
On PVP particle the step of coated silica layer: by the Fe3O4@PVP particle mixes instead with silicon source, catalyst, water in alcohol
It answers, obtains the Fe for being coated with the silicon dioxide layer3O4@PVP particle.
12. the preparation method of photon crystal material according to claim 11, which is characterized in that the silicon member in the silicon source
The plain molar ratio with the water is 1:115~1:290；And/or the element silicon in the silicon source and the Fe3O4In@PVP particle
Ferro element molar ratio be 1:1~3:1；And/or the catalyst is ammonium hydroxide；And/or the silicon source be selected from esters of silicon acis and
One of organosilicon.
13. the preparation method of photon crystal material according to claim 11 or 12, which is characterized in that further including will be described
It is coated with the Fe of the silicon dioxide layer3O4@PVP particle and water mixing carry out surface modification treatment, so that the silicon dioxide layer
The step of in porous structure.
14. the preparation method of photon crystal material according to claim 11, which is characterized in that the alcohol is selected from anhydrous second
One of alcohol, anhydrous methanol and anhydrous isopropyl alcohol.
15. a kind of photonic crystal ink, which is characterized in that including photon crystal material and solvent, wherein the photonic crystal material
Material is the described in any item photon crystal materials of claims 1 to 3 or the described in any item photonic crystal materials of claim 7~10
The photon crystal material that the preparation method of material is prepared.
16. photonic crystal ink according to claim 15, which is characterized in that the photon crystal material further includes cladding
Silicon dioxide layer on the polyvinylpyrrolidone shell, the solvent are alcohol or water, and the surface of the silicon dioxide layer is tied
Conjunction has silanol group.
17. photonic crystal ink according to claim 16, which is characterized in that the silicon dioxide layer is porous structure.
18. 5~17 described in any item photonic crystal inks according to claim 1, which is characterized in that the photon crystal material
Mass percentage be 10%~50%, the mass percentage of the solvent is 50%~90%.
19. photonic crystal ink according to claim 15, which is characterized in that the solvent is selected from least the one of water and alcohol
Kind.
20. the described in any item photonic crystal inks of claim 15~19 are preparing the application in electrochromic display.
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| CN112552557A (en) * | 2020-12-19 | 2021-03-26 | 江南大学 | Magnetic field response photonic crystal anti-counterfeiting film and preparation method and application thereof |
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