CN107608156A - A kind of flexible tunable visible near-infrared bands branch fiber waveguide device and preparation method thereof - Google Patents
A kind of flexible tunable visible near-infrared bands branch fiber waveguide device and preparation method thereof Download PDFInfo
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Abstract
A kind of flexible tunable visible near-infrared bands branch fiber waveguide device and preparation method thereof, belongs to electrochromism technology and fiber waveguide device field.In the upper surface of flexible transparent substrate, tiling has normal light waveguide-layer, electrochromism light waveguide-layer, normal light waveguide-layer, electrochromism light waveguide-layer are at one layer, normal light waveguide-layer uses the branched structure of Y types two, the B strips and C strips after A strips, branch i.e. before branch, a side and the side of electrochromism light waveguide-layer one for the A strips before normal light waveguide-layer y-branch are closely coupled；Electrochromism light waveguide-layer also leads to conductive electrode, and conductive electrode overlaps with electrochromism light waveguide-layer, and conductive electrode is used for the effect to electrochromism light waveguide-layer on-load voltage, and conductive electrode tiling is fixed in flexible transparent substrate；Conductive electrode and normal light waveguide-layer are without directly contacting.Using Electro-optical Modulation effect, light modulation is realized with reference to all optical communication and transmittance.
Description
Technical field
The invention belongs to electrochromism technology and fiber waveguide device field, and in particular to a kind of flexible tunable visible-near
Infrared band branch waveguide device and preparation method thereof.
Background technology
Electrochromism refers to the optical properties (absorptivity, transmitance or reflectivity etc.) of material in the presence of extra electric field
The stable, phenomenon of reversible change occurs, shows as the reversible change of color and transparency in appearance.The essence of electrochromism phenomenon
It is a kind of process of electrochemical reaction, with alive change is applied, the thing of material mutually changes and causes device for Optical Properties of Materials
(such as light transmission, refractive index etc.) changes.The word of electrochromism one is to be proposed in 1961 by Piatt earliest.Until
Tungstic acid (WO is described in detail within 1969 and Deb in 19733) for film under certain voltage effect, its color can be colourless
The phenomenon of phase co-conversion between blueness.He uses the WO of amorphous for the first time3Film preparation electrochromic device, and propose
The Discoloration mechanism of " Lacking oxygen colour center ", indicate the beginning of electrochromism science and technology research.Hereafter, people are successive
It was found that new off-color material, including NiO, Co3O4、TiO2、MoO3Deng transition metal oxide and polyaniline (PANI), polypyrrole
And some high-molecular organic materials such as polythiophene (Polythiophene) (PPy).It is new organic after late 1980s
The preparation of Polymer Electrochromic material and electrochromic device are assembled into a research field to become increasingly active.Section of Sweden
The it is proposed such as scholar C.G.Granqvist and American scientist C.M.Lampert it is a kind of new based on electrochomeric films
Type Energy Saving Windows, i.e. smart window (Smart window), turn into a milestone of electrochromism technical research.So far, day
Originally, Europe and some industrial powers of the U.S. maintain the leading position in terms of electrochromism technology application study.China is in electroluminescent change
Research starting in terms of color material and device also has a certain distance than later with the advanced application study technology of foreign countries.At present,
The institution of higher learning such as Zhejiang University, Jilin University, Tsing-Hua University, University of Electronic Science and Technology and Chinese Academy of Sciences's Changchun applied chemistry study
Institute, Ningbo material engineering Suo Deng R＆D institutions achieve some relatively prominent achievements.
Fiber waveguide is that light can be limited in its internal or near surface by one kind, and direction of the guiding light wave along determination is propagated
Guide lighting channel, practical fiber waveguide has planar optical waveguide, strip optical waveguide and cylindrical light waveguide.Planar optical waveguide and strip light
Waveguide is mainly used in making active and passive optical waveguide components, such as laser, modulator and photo-coupler, and they are using half
Conductor thin film technique, it is adapted to the integrated optical circuit that planar structure is made.Fiber waveguide principle is widely used in acquisition of information, letter with device
Breath transmission, information processing and production and living field.In terms of information transfer, active, passive device is can be made into, optical fiber is may make up and leads to
Believe main line, light can be formed and exchange access network, AON, DWDM, OADM, OTDM and FTTC/B/O/H can be achieved.Optical branch waveguide device
It is one of indispensable passive device in optical communication network, the flexible light branch-waveguide device that luminous power is tunable is following
Development trend.
Tunable flexible light branch-waveguide device needs to reach three requirements：Tunable, flexible and branch-waveguide device,
Need meeting on the light transparent conductor material of traditional optical branch wave guide and thin-film technique basis, two kinds of redesign addition
Function.Mentality of designing：1st, using the transparent semiconductor film material of amorphous-nano-crystalline structure, flexible can be adapted to require；
2nd, using voltage tunable electrochromic material transmission characteristics, change the luminous power of refraction light, reflected light and refraction light are divided
Do not drawn from two branched bottoms, reach the requirement that voltage quantitatively controls branch's luminous power.
The content of the invention
The present invention seeks to invent a kind of flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device and its preparation side
Method, gained branch waveguide device have preferable luminous power tuning performance, stable optical branch under flexible substrate bending condition
Effect and the relatively low proportion of goods damageds.
A kind of flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device, it is characterised in that served as a contrast including flexible and transparent
Bottom, conductive electrode, normal light waveguide-layer, electrochromism light waveguide-layer, in the upper surface of flexible transparent substrate, tiling has normal light
Ducting layer, electrochromism light waveguide-layer, at one layer, normal light waveguide-layer uses Y for normal light waveguide-layer, electrochromism light waveguide-layer
The branched structure of type two, i.e., the B strips and C strips after A strips, branch before branch, the A bars before normal light waveguide-layer y-branch
A side and the side of electrochromism light waveguide-layer one for shape is closely coupled；Electrochromism light waveguide-layer also leads to conductive electrode,
Conductive electrode overlaps with electrochromism light waveguide-layer, and conductive electrode is used for electrochromism light waveguide-layer on-load voltage
Effect, conductive electrode tiling are fixed in flexible transparent substrate；Conductive electrode and normal light waveguide-layer are without directly contacting.
Flexible transparent substrate is PET or PDMS.
Conductive electrode uses layer structure, is metal nano-particle layer or graphene film layer.
Normal light waveguide-layer, the electrochromism light waveguide-layer of the present invention selects conventional normal light waveguide-layer, electrochromism
Light waveguide-layer.
Further preferably, normal light waveguide-layer is the transparent semiconductor film material of amorphous-nano-crystalline composite construction, preferably stone
Black alkene adulterates (In2O3)x(ZnO)y(Ga2O3)z(In, Zn, Ga mol ratio are 0.6-0.9 to thin-film material:0.2-0.05:0.2-
0.05), the preferred amorphous-nano-crystalline compound structure film material of electrochromism light waveguide-layer (region) material, more preferably (ITO)x
(Nb2O5)y(Ga2O3)zThin-film material, indium, tin, niobium, the mol ratio of gallium are 0.54-0.81:0.06-0.09:0.05-0.35:
0.05-0.35。
Conductive electrode and electrochromism light waveguide-layer overlap part, and conductive electrode is located at flexible transparent substrate and electricity
Between mutagens coloured light ducting layer.
Electrochromism light waveguide-layer is elongate configuration, electrochromism light waveguide-layer elongate configuration long side and normal light waveguide-layer
The long side lengths of A strips before y-branch are identical, and closely connect, the long side of A strips and pair of the branched structure of Y types two
Claim axle parallel, as shown in Fig. 1 top views.
The preparation method of the flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device of the present invention, it is characterised in that
Using the preparation method of routine, prepared by individual layer, pattern, collosol and gel spin coating legal system are etched in the photoresist using photoetching technique
For monolayer material film is gone out, remove photoresist and retain material requested pattern.
Electrochromic layer amorphous-nano-crystalline composite construction (ITO)x(Nb2O5)y(Ga2O3)zThe preparation of film includes following step
Suddenly：
Step 1, by inidum chloride (InCl3), butter of tin (SnCl4), columbium pentachloride (NbCl5) and gallium trichloride (GaCl3)
Ammoniacal liquor is added in mixed aqueous solution, regulation pH value is 8-10 so that cation is fully converted to hydroxide precipitation；
Step 2, clean mixed hydroxides repeatedly with deionized water, alcoholic solvent respectively to precipitate, separation of solid and liquid obtains hydrogen-oxygen
Compound presoma；
Step 3, hydroxide precursor is mixed with ethanol, adds monoethanolamine, ultrasonic disperse is into suspension, by suspension
Insert in autoclave and be heat-treated, obtain the nanocrystalline dispersion liquid of tin indium oxide gallium niobium, carry out spin coating and prepare amorphous-nano-crystalline composite junction
The flexible electrical mutagens coloured light thin film waveguide layer of structure.
Further, mole of the indium ion described in electrochromic layer preparation process 1, tin ion, niobium ion, gallium ion
Than for 0.54-0.81:0.06-0.09:0.05-0.35:0.05-0.35.
Further, the molar ratio of the hydroxide precursor described in electrochromic layer preparation process 3 and monoethanolamine
For 1：2, the heat treatment temperature of autoclave is 200 DEG C -260 DEG C, and the time is 10-40 hours.
Prepared by normal light waveguide-layer (i.e. transparent light waveguide-layer) comprises the following steps：
Step 1, graphene oxide water solution Ultrasonic Heating is reduced into graphene nanometer sheet, heating-up temperature and reducing agent are matched somebody with somebody
Than controlling graphene nano chip size, it is centrifuged repeatedly and is washed till neutral aqueous solution, ultrasound is broken up, and is heated to obtaining graphene nano
Particle is standby；
Step 2, by InCl3、Zn(OAC)2、GaCl3Reagent be dissolved in ethylene glycol solution heating stirring to colourless
It is bright, obtain the mixing of indium gallium zinc oxygen colloidal sol；
Step 3, graphene nano particle is mixed with indium gallium zinc oxygen colloidal sol, gained colourless transparent solution is ultrasonic in a water bath
Heating stirring is to colloidal sol shape；
Step 4, step 3 gained vitreosol is subjected to spin coating by spin coating instrument, is then annealed, be repeated a number of times
Spin coating and annealing, the transparent optical waveguide film of flexible nano level is made.
Further, InCl in light waveguide-layer preparation process3、Zn(OAC)2、GaCl3Mol ratio be 0.6-0.9:
0.2-0.05:0.2-0.05；InCl3、Zn(OAC)2、GaCl3Purity be 99.99%, graphene nano particle and InCl3's
The ratio between amount of material is 1:100-1:700.
Further, ultrasound 60 DEG C -95 DEG C of the heating-up temperature of reduction described in light waveguide-layer preparation process 1, time 1-3
Hour；Reducing agent is hydrazine hydrate, hydrazine hydrate and graphene oxide mass ratio 6:10-8:10.
Further, the InCl described in light waveguide-layer preparation process 23、Zn(OAC)2、GaCl3It is molten in ethylene glycol solution
During solution stirring, 20 DEG C -65 DEG C of temperature, mixing time 0.5-2 hours；
Further, the water bath heating temperature described in light waveguide-layer preparation process 3 is 25 DEG C -80 DEG C, the heat time
0.5h-4h。
Further, the Thin-film anneal temperature described in light waveguide-layer preparation process 4 is 50 DEG C -150 DEG C, annealing time
0.5h-2h, repeats spin coating annealing times 4-18 times, and optical waveguide film thickness is in 150nm-3000nm.
There is the tunable branch waveguide device of the present invention preferable pliability and Electro-optical Modulation branch luminous power to act on,
Using real Electro-optical Modulation effect, light modulation is realized with reference to all optical communication and transmittance.The present invention should in Passive Optical Components
With extensive, scalability is strong, and Making programme is simple, the advantages such as cost is cheap.
Normal light waveguide-layer of the invention uses to be occurred producing weight based on element doping to molecular structure change and functional performance
Influence, there is indium (In) element doping generation crystalline state nanometer and near infrared region light transmittance castering action, gallium (Ga) element to mix
Miscellaneous that there is molecule to keep non crystalline structure effect, zinc (Zn) element doping keeps nanocrystalline micro-nano covalent structure, so that in film
There is preferable mobility and amorphous-nano-crystalline mixed structure under the conditions of flexible bending.
Normal light waveguide-layer of the invention uses graphene nano structure doping techniques, effectively improves chemical method preparation
The problem of flexible and transparent oxide semiconductor thin-film electric property is poor.
Brief description of the drawings
Fig. 1 is flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device structure top view；
Fig. 2 is flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device structural front view；
1 flexible transparent substrate, 2 normal light waveguide-layers, 3 electrochromism light waveguide-layers, 4 conductive electrodes.
Fig. 3 is the electrochromism optical waveguiding region amorphous-nano-crystalline composite construction indium tin niobium gallium oxide film of embodiment 1
X ray diffracting spectrum.
The X of the amorphous-nano-crystalline composite construction graphene of Fig. 4 embodiments 1 doping indium gallium zinc oxide transparent conductive film is penetrated
Ray diffraction diagram is composed.
Embodiment
With reference to embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
A kind of flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device, including flexible substrate, conductive electrode layer,
Light waveguide-layer and coating, it is characterised in that:Flexible transparent substrate is PET or PDMS, and conductive electrode layer is metal nanoparticle
Layer or graphene film layer, light waveguide-layer are divided into normal optical waveguiding region and electrochromism optical waveguiding region, its structural representation
Fig. 1 and Fig. 2 are seen respectively；Normal light waveguide-layer is that the layer of amorphous-nano-crystalline state graphene doping is (In2O3)x(ZnO)y
(Ga2O3)zThin-film material, electrochromism optical waveguiding region material are amorphous-nanocomposite structures (ITO)x(Nb2O5)y
(Ga2O3)zThin-film material.
Specific embodiment comprises the following steps：
Step 1, standby 0.5 gram of graphene nanometer sheet is taken to be mixed with 2ml ethanol, ultrasonic disperse is suspended dispersed liquid.Soft
Property transparent substrates substrate on spin coating S1813 photoresists, utilize maskless direct-write photoetching system prepare planar structure, spin coating graphene
Dispersion liquid, photoresist is removed, graphene conductive micro-nano structure is obtained, as conductive electrode.
Step 2, the spin coating S1813 photoresists on the substrate obtained by step 1, utilize maskless direct write light
Etching system prepares planar structure, the nanocrystalline dispersion liquid of spin coating tin indium oxide gallium niobium, removes photoresist, obtains flexible electrical
Mutagens coloured light thin film waveguide layer, the end points of flexible electrical mutagens coloured light thin film waveguide layer and two conductive electrodes partially overlap；Specific bag
Include as follows：
(1), by 2.633 grams of inidum chloride (InCl3), 0.354 gram of butter of tin (SnCl4), 2.432 grams of columbium pentachlorides
(NbCl5) and 0.176 gram of gallium trichloride (GaCl3) 3ml ammoniacal liquor is added in mixed aqueous solution, regulation pH value is about 9 so that sun from
Son is fully converted to hydroxide precipitation；
(2), cleaned repeatedly 4 times with deionized water, alcoholic solvent respectively, mixed hydroxides precipitation, separation of solid and liquid obtains hydrogen
Oxide precursor；
(3), presoma is mixed with 20ml ethanol, adds 10ml monoethanolamines, ultrasonic disperse puts suspension into suspension
Enter in autoclave and be heat-treated, obtain the nanocrystalline dispersion liquid of tin indium oxide gallium niobium, carry out spin coating and prepare amorphous-nano-crystalline composite construction
Flexible electrical mutagens coloured light thin film waveguide layer.
Step 3, flexible electrical mutagens coloured light thin film waveguide layer side prepares the normal light wave of Y types in the substrate obtained by step 2
Conducting shell, specifically include as follows：
(1) 2g/ml graphene oxide water solutions are taken into 0.2ml ultrasounds 0.5 hour, adds hydrazine hydrate 0.3ml, 85 DEG C of water-baths
Middle heating is reduced into graphene nanometer sheet for 1 hour, after heating reduction reaction, adds ammoniacal liquor cleaning hydrazine hydrate, then use deionized water
It is centrifuged repeatedly and is washed till neutral aqueous solution, ultrasound is broken up and to be heated to graphene nano powder standby.
(2), by 5.865 grams of InCl3, 0.548 gram of Zn (OAC)2, 0.44 gram of GaCl3High purity reagent be dissolved in 10ml second two
In alcoholic solution, 50 DEG C of heating stirrings to colourless transparent solution；
(3), graphene nanometer sheet powder is mixed with indium gallium zinc oxygen solution, colourless transparent solution is ultrasonic in 30 DEG C of water-baths
Heating stirring is to colloidal sol shape；
(4), the spin coating under 3000 revs/min of rotating speed in spin coating instrument by vitreosol, anneal 45 minutes at 100 DEG C, instead
It is multiple 8 times, remove photoresist (removing photoresist after annealing repeatedly), the branch waveguide structure of Symmetric Y type two is made in substrate
Normal optical waveguiding region.Normally optical waveguide film thickness is to the refractive index of 1550nm laser in 1500nm-3000nm, film
2.4。
A kind of flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device provided by the invention and preparation method thereof,
Molecular structure is changed based on element doping and functional performance occurs producing material impact, indium (In) element doping is received with generation
There is molecule to keep non crystalline structure effect, zinc for rice crystalline state and near infrared region light transmittance castering action, gallium (Ga) element doping
(Zn) element doping keeps nanocrystalline micro-nano covalent structure, and niobium (Nb) element doping has electrochromic property, so that device
There is flexible tunable optical branch-waveguide characteristic under the conditions of flexible bending to Visible-to-Near InfaRed band of light.
Claims (10)
1. a kind of flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device, it is characterised in that served as a contrast including flexible and transparent
Bottom, conductive electrode, normal light waveguide-layer, electrochromism light waveguide-layer, in the upper surface of flexible transparent substrate, tiling has normal light
Ducting layer, electrochromism light waveguide-layer, at one layer, normal light waveguide-layer uses Y for normal light waveguide-layer, electrochromism light waveguide-layer
The branched structure of type two, i.e., the B strips and C strips after A strips, branch before branch, the A bars before normal light waveguide-layer y-branch
A side and the side of electrochromism light waveguide-layer one for shape is closely coupled；Electrochromism light waveguide-layer also leads to conductive electrode,
Conductive electrode overlaps with electrochromism light waveguide-layer, and conductive electrode is used for electrochromism light waveguide-layer on-load voltage
Effect, conductive electrode tiling are fixed in flexible transparent substrate；Conductive electrode and normal light waveguide-layer are without directly contacting.
2. according to the flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device of one kind described in claim 1, its feature exists
In flexible transparent substrate is PET or PDMS.
3. according to the flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device of one kind described in claim 1, its feature exists
In conductive electrode uses layer structure, is metal nano-particle layer or graphene film layer.
4. according to the flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device of one kind described in claim 1, its feature exists
In normal light waveguide-layer is the transparent semiconductor film material of amorphous-nano-crystalline composite construction, and electrochromism light waveguide-layer material is excellent
Select amorphous-nano-crystalline compound structure film material.
5. according to the flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device of one kind described in claim 4, its feature exists
In normal light waveguide-layer is that graphene adulterates (In2O3)x(ZnO)y(Ga2O3)zThin-film material, In, Zn, Ga mol ratio are
0.6-0.9:0.2-0.05:0.2-0.05；Electrochromism light waveguide-layer is (ITO)x(Nb2O5)y(Ga2O3)zThin-film material, indium,
Tin, niobium, the mol ratio of gallium are 0.54-0.81:0.06-0.09:0.05-0.35:0.05-0.35.
6. according to the flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device of one kind described in claim 1, its feature exists
Overlapped part in, conductive electrode and electrochromism light waveguide-layer, conductive electrode is located at flexible transparent substrate and electroluminescent change
Between coloured light ducting layer.
7. according to the flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device of one kind described in claim 1, its feature exists
In electrochromism light waveguide-layer is elongate configuration, electrochromism light waveguide-layer elongate configuration long side and normal light waveguide-layer Y types point
The long side lengths for the A strips supported the front are identical, and closely connect, and the symmetry axis of the long side and the branched structure of Y types two of A strips is put down
OK.
8. prepare the side of the flexible tunable Visible-to-Near InfaRed bands branch fiber waveguide device described in claim any one of 1-7
Method, it is characterised in that comprise the following steps：Prepared by individual layer, pattern, collosol and gel are etched in the photoresist using photoetching technique
Spin-coating method prepares monolayer material film, removes photoresist and retains material requested pattern；
Wherein electrochromic layer amorphous-nano-crystalline composite construction (ITO)x(Nb2O5)y(Ga2O3)zThe preparation of film includes following step
Suddenly：
Step 1, by inidum chloride (InCl3), butter of tin (SnCl4), columbium pentachloride (NbCl5) and gallium trichloride (GaCl3) mixing
Ammoniacal liquor is added in the aqueous solution, regulation pH value is 8-10 so that cation is fully converted to hydroxide precipitation；
Step 2, clean mixed hydroxides repeatedly with deionized water, alcoholic solvent respectively to precipitate, separation of solid and liquid obtains hydroxide
Presoma；
Step 3, hydroxide precursor is mixed with ethanol, adds monoethanolamine, ultrasonic disperse inserts suspension into suspension
It is heat-treated in autoclave, obtains the nanocrystalline dispersion liquid of tin indium oxide gallium niobium, is carried out spin coating and prepare amorphous-nano-crystalline composite construction
Flexible electrical mutagens coloured light thin film waveguide layer；
Prepared by normal light waveguide-layer comprises the following steps：
Step 1, graphene oxide water solution Ultrasonic Heating is reduced into graphene nanometer sheet, heating-up temperature and reducing agent proportioning control
Graphene nano chip size processed, is centrifuged repeatedly and is washed till neutral aqueous solution, and ultrasound is broken up, and is heated to obtaining graphene nano particle
It is standby；
Step 2, by InCl3、Zn(OAC)2、GaCl3Reagent be dissolved in heating stirring in ethylene glycol solution and, to water white transparency, obtain
Mixed to indium gallium zinc oxygen colloidal sol；
Step 3, graphene nano particle is mixed with indium gallium zinc oxygen colloidal sol, gained colourless transparent solution Ultrasonic Heating in a water bath
Stir to colloidal sol shape；
Step 4, step 3 gained vitreosol is subjected to spin coating by spin coating instrument, is then annealed, be repeated a number of times spin coating
And annealing, the transparent optical waveguide film of flexible nano level is made.
9. according to the method for claim 8, it is characterised in that InCl in light waveguide-layer preparation process3、Zn(OAC)2、GaCl3's
Mol ratio is 0.6-0.9:0.2-0.05:0.2-0.05；InCl3、Zn(OAC)2、GaCl3Purity be 99.99%, graphene is received
The ratio between rice grain and the InCl3 amount of material are 1:100-1:700；Optical waveguide film thickness is in 150nm-3000nm；
The mol ratio of indium ion, tin ion, niobium ion, gallium ion described in electrochromic layer preparation process 1 is 0.54-
0.81:0.06-0.09:0.05-0.35:0.05-0.35。
10. according to the method for claim 8, it is characterised in that the ultrasound reduction heating temperature described in light waveguide-layer preparation process 1
60 DEG C -95 DEG C of degree, the time is 1-3 hours；Reducing agent is hydrazine hydrate, hydrazine hydrate and graphene oxide mass ratio 6:10-8:10；
InCl described in light waveguide-layer preparation process 23、Zn(OAC)2、GaCl3When stirring is dissolved in ethylene glycol solution, temperature
20 DEG C -65 DEG C, mixing time 0.5-2 hours；
Water bath heating temperature described in light waveguide-layer preparation process 3 is 25 DEG C -80 DEG C, heat time 0.5h-4h；
Thin-film anneal temperature described in light waveguide-layer preparation process 4 is 50 DEG C -150 DEG C, annealing time 0.5h-2h, repeats to revolve
Apply annealing times 4-18 times；
The molar ratio of hydroxide precursor and monoethanolamine described in electrochromic layer preparation process 3 is 1：2, autoclave
Heat treatment temperature is 200 DEG C -260 DEG C, and the time is 10-40 hours.
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