CN104102060A - Preparation method for intelligent color changing window - Google Patents
Preparation method for intelligent color changing window Download PDFInfo
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- CN104102060A CN104102060A CN201410130604.8A CN201410130604A CN104102060A CN 104102060 A CN104102060 A CN 104102060A CN 201410130604 A CN201410130604 A CN 201410130604A CN 104102060 A CN104102060 A CN 104102060A
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Abstract
The invention provides a preparation method for an intelligent color changing window. The preparation method for the intelligent color changing window comprises the following steps: growing a conducting material on a substrate by adopting a chemical vapor deposition method to form a first conducting layer; growing transition metal oxides and a mixture thereof on the first conducting layer by adopting the chemical vapor deposition method to form an electrochromic layer; performing ion implantation on the electrochromic layer by adopting a two-electrode or three-electrode electrochemical method; growing oxides or inorganic solid state lithium salts on the electrochromic layer by adopting a method for performing lithiation on the electrochromic layer or the chemical vapor deposition method to form an ion conduction layer; growing the transition metal oxides and the mixture thereof on the ion conduction layer by adopting the chemical vapor deposition method to form an ion storage layer; growing the conducting material on the ion storage layer by the chemical vapor deposition method to form a second conducting layer; growing a protective layer on the second conducting layer to obtain the intelligent color changing window. The preparation method is low in production cost, and can prepare an electrochromic device on glass with a certain curved surface.
Description
Technical field
The present invention relates to Material Field, particularly a kind of method of utilizing chemistry and galvanochemistry integrated approach to prepare intelligent color-changing window.
Background technology
Electrochromic device (Electrochromic Device) refers under two electrode application voltage effects, the class device that its optical property changes.The optical property of device generally comprises its color, transmissivity, reflectivity, refractive index and emissivity etc.Utilize the windowpane of this characteristic structure of electrochromic material to realize the dynamic adjustments to sunshine according to surrounding environment actual needs or people's wish, such device glass is called as smart window (Smart Window).Enter the energy of buildings just because of controllable adjustment sunshine as required, smart window can significantly save architectural lighting energy consumption, for thermal energy consumption and refrigeration energy consumption, thereby realizes building energy conservation object.At present approximately 50,000,000,000 square metres of China's existing buildings, more than 95% be the common individual layer of employing or common double-deck plate glass window, comfortable quality of building is low, heat supply refrigeration energy consumption is high.And approximately 5,000,000,000 square metres of China's annual town and country construction newly constructed house floor area of building and keep approximately 10% annual growth.Promote and replace existing business and civilian common individual layer or common double window by smart window, can improve the quality of living, reducing building energy consumption, meeting national energy-saving environmental protection industry development policy, thering is wide domestic and international market prospect.
Electrochromic device, is shown in Fig. 1, conventionally by five layer materials stacking forming on substrate 1: the first conductive layer 2, electrochromic layer 3, ion conductive layer 4, ion storage 5 and the second conductive layer 6.Electrochromic layer 3 is under electrochemical reaction effect, and its optical property changes.When apply relative voltage on two conductive layers 2 and 6 in the situation that, ion (H+ or Li+) carrys out transmission back by ionic conduction layer 4 under electromotive force effect between electrochromic layer 3 and ion storage 5, realizes bleaching and the colored state of device.
Wherein, electrochromic layer 3 is made up of inorganic solid-state electrochromic material conventionally, inorganic solid-state electrochromic material is generally the oxide of transition metal, as the metal oxide of cathode electrochromic material W, Mo, V, Nb, Ti and Ta and its mixed oxide, the metal oxide of anode electrochromic material Ni, Cr, Mn, Fe, Co, Rh and Ir or its mixed oxide.
With the typical cathode electrochromic material WO of one
3for example, under the insertion of ion and extracting, there is following electrochemical reaction and cause that material color changes:
Colourless blueness
Wherein, M+ is H
+, Li
+deng alkali metal ion, or other D
+, K
+, Na
+, Ca
2+, Mg
2+deng alkali metal ion and alkaline-earth metal ions.When in electronics and the transparent tungsten oxide film of Implantation, film will become blueness.In the time that ion and electronics are drawn out of, film is reduced into again original pellucidity.
In addition can there is following electrochemical reaction and cause that material color changes in other cathode electrochromic materials:
Colourless blueness
Yellow light blue
Colourless light blue
Colourless blueness
Taking the typical anode electrochromic material of one NiO as example, under the insertion of ion and extracting, there is following electrical reactions and cause that material color changes:
Light green color brownish black
Wherein, the extraction model of (1) corresponding proton H+ is extracted proton out from film, and material color is changed; (2), corresponding to the insertion model of OH-, OH-is injected in film and material color changes thereupon.
In addition can there is following electrochemical reaction and cause that material color changes in other cathode electrochromic materials:
Colourless black-and-blue
Although electrochromic intelligent window has plurality of advantages, but it is applied and still has many difficulties.
One, the whole or most of magnetron sputtering physical gas-phase deposite methods of using of the main above-mentioned five layer material preparation methods of existing commercialization electrochromic intelligent window.The method needs high vacuum, apparatus expensive, and production cost is high, mainly contains several the enterprises such as the U.S. and uses the method to prepare large area intelligent window for building.At present, intelligent window for building is expensive, is 5 to 10 times of general ordinary glazed window price, is the high-grade energy-saving glass window of other kind, as low-E (Low-E) glass 3-5 times.The degree of accepting extensively in market is also very low.
The 2nd,, the linear deposit characteristic that existing business preparation method's physical gas-phase deposite method is intrinsic, if i.e. substrate surface out-of-flatness will cause deposit film in uneven thickness.This just limits it can only prepare electrochromic device on flat glass.Can't on bend glass, prepare in the world at present large scale intelligent color-changing device.And we know at automobile, train, on the vehicles such as aircraft and pleasure boat, glazing is all to have certain curved surface.
The 3rd,, existing smart window device in the world at present, all adopts conductive ion Li+ to realize electrochromism, and the less H+ variable color slewing rate that compares is slower.
The 4th,, the ionic conduction layer that early stage electrochromic device adopts is liquid phase electrolyte form, such devices owing to existing in the dead of night, yielding, painted inhomogeneous, be not suitable for the shortcomings such as large area production, can not really realize and commercially producing.
The 5th,, existing other electrochromic devices adopt that organic electrochromic materials or colloidal sol ion-conductive material also exist that chemical stability is bad, thermal radiation resistance ability, adhere to the shortcomings such as not firm with substrate inorganic material (as glass).
Summary of the invention
Goal of the invention: for overcoming deficiency of the prior art, the invention provides a kind of method of utilizing chemistry and galvanochemistry integrated approach to prepare intelligent color-changing window.
Technical scheme: the preparation method of a kind of intelligent color-changing window provided by the invention, comprises the following steps:
Step 1, adopts chemical vapour deposition technique, at Grown conductive material, forms the first conductive layer;
Step 2, adopts chemical vapour deposition technique, and on the first conductive layer, grow transition metal oxide or its potpourri form electrochromic layer;
Step 3, adopts two electrodes or three-electrode electro Chemical method, and electrochromic layer is carried out to Implantation;
Step 4, method or the chemical vapour deposition technique of employing lithiumation electrochromic layer, grow oxide or inorganic solid-state lithium salts on electrochromic layer, form ionic conduction layer;
Step 5, adopts chemical vapour deposition technique, and on ionic conduction layer, grow transition metal oxide or its potpourri form ion storage layer;
Step 6, adopts chemical vapour deposition technique, and the conductive material of growing in ion storage layer forms the second conductive layer, makes intelligent color-changing window.
Wherein, in step 1, described substrate is glass substrate, tempered glass substrate or plastic; The substrate that the present invention uses can be not limited to the substrates such as ordinary plate glass, tempered glass and the plastics that additive method uses, any material with applicable optics, electricity, calorifics and engineering properties can be used as substrate, particularly can adopt the glass of other various shapes, size and thickness to substrate are also not particularly limited.Described conductive material is thin metal, nanotube, transparent conductive oxide or transparent conductive nitride, and described transparent conductive oxide comprises metal oxide and blended metal oxide, preferably, comprises fluorine doped tin oxide (SnO
2: F), tin-doped indium oxide (In
2o
3: Sn, ITO), antimony doped tin oxide (SnO
2: Sb), Al-Doped ZnO (ZnO: Al) and mix fluorine zinc paste (ZnO:F); The thickness of described the first conductive layer is 100-1000nm, and transmittance is that more than 80% sheet resistance is less than 50 Ω/.Conventionally apply for intelligent color-changing window, it is transparent requiring the first conductive layer in visible wavelength range, the electrical properties (for example conduction) being necessary and optical property (for example transmissivity), sheet resistance is less, cross over large area conducting stratum potential drop lower, can increase ion-drive power and conduction of velocity, effectively shorten electricity and cause and fade and painted switching time.
Wherein, in step 2, described transition metal oxide is selected from one or more the mixing in cathode electrochromic material and anode electrochromic material; Preferably, described transition metal oxide is the potpourri of potpourri, tungsten oxide and vanadium oxide or the potpourri of tungsten oxide and titanium dioxide of tungsten oxide, molybdena, vanadium oxide, tungsten oxide and molybdena; The thickness of described electrochromic layer is 50-500nm.Electrochromic layer can be crystalline state, amorphous state or its mixed state, can receive from ion storage and shift the ion of coming, and changes thereby produce optical property.
Wherein, in step 3, the ion being injected into is H
+, Li
+, or H
+and Li
+mixing.If inject H
+, can use H
2sO
4or other contains H+ acid solution; Select to inject Li as crossed
+, available LiClO
4solution, LiClO
4 -acetonitrile solution or LiClO
4other organic solution, working electrode is the glass substrate that deposits electrochromic layer.
Wherein, in step 4, described oxide comprises monox, sieve and silica-sesquioxide (SiAlO) and tantalum oxide, and described inorganic solid-state lithium salts comprises silicic acid reason, tungstate lithium, lithium niobate, lithium tantalate, lithium borate, meta-aluminate and lithium metaborate; The thickness of described ionic conduction layer is 1-100nm.Ionic conduction layer serves as carries the medium of ion (in electrolytical mode) when electrochromic device transforms between bleaching state and coloured state; The thin ionic conduction layer conducting ion rapidly with high ion-conductivity, allows high-performance electrochromic device to change fast thus; Require to have enough low electron conductivity, electronics transmission is in the normal operation period little, minimizes two interelectrode leakage currents simultaneously.The present invention prepares ionic conduction layer by multiple non-magnetron sputtering physical gas-phase deposite method technique, and the ionic conduction layer making can be crystallization, nanocrystal or amorphous.
Wherein, in step 5, described transition metal oxide is selected from one or more the mixing in cathode electrochromic material and anode electrochromic material; Preferably, described transition metal oxide is nickel oxide, nickel tungsten oxide, nickel barium oxide, nickel chromium triangle oxide or nickel aluminum oxide; The thickness of described ion storage layer is 50-500nm.Preferably, select to present with electrochromic layer anode electrochromic material or the cathode electrochromic material of complementary state,, in the time that ion inserts this layer, it is Transparent color, and in the time that ion leaves this layer, it presents colored state; The ion storage layer of growing by chemical vapour deposition technique of the present invention can be crystalline state, amorphous state or its mixed state.
Wherein, in step 6, described conductive material is thin metal, nanotube, transparent conductive oxide or transparent conductive nitride, and described transparent conductive oxide comprises metal oxide and blended metal oxide; The thickness of described the second conductive layer is 100-1000nm, and transmittance is that more than 80% sheet resistance is less than 50 Ω/; Described the second conductive layer can be same or different transparent conductive oxide with the first conductive layer.
Wherein, described intelligent color-changing window also comprises protective seam, and its preparation method is: adopt chemical vapour deposition technique, the potpourri of one or more of grow on the second conductive layer SiOx, SiNy and SiAlO, forms protective seam; Wherein, x is 1-3, and y is 1-3, and the thickness of described protective seam is 10-1000nm.Protective seam not only can increase the durability of device, and can also play the function such as protection against the tide, anti-scratch, under varying environment, uses, and all can effectively increase the durability of device.
Beneficial effect: the present invention adopts chemical deposition and electrochemical method, and integrated to prepare intelligent color-changing window production cost low, can realize and have the electrochromic device of preparing on glass of certain curved surface, the electrochromic intelligent window making has advantages of quick color-changing ability and long service life.
Particularly, the present invention, with respect to prior art, has following outstanding advantage:
(1) production cost is low: existingly commercially produce that electrochromic intelligent window all adopts or large portion adopts magnetron sputtering physical gas-phase deposite method to deposit each functional layer, and therefore high vacuum, apparatus expensive, production cost is high; And the inventive method adopts the combination of chemical deposition and electrochemical method, do not need high vacuum, expensive equipment and starting material, greatly reduce production cost and technology difficulty;
(2) applied range: the existing electrochromic intelligent window method of commercially producing can only be prepared electrochromic device on flat glass; And the inventive method adopts the combination of chemical deposition and electrochemical method, can realize and have the electrochromic device of preparing on glass of certain curved surface, can be applicable to and need to have the windowpane of radian as on the vehicles such as automobile, greatly increased intelligent color-changing window applications scope and commercial market prospect;
(3) the present invention can adopt H
+, Li
+, or H
+and Li
+hybrid ionic, the electrochromic intelligent window making has advantages of quick color-changing ability and long service life.
Brief description of the drawings
Fig. 1 is the structural representation of electrochromic device.
The structural representation of the intelligent color-changing window that in Fig. 2, the present invention makes.
Fig. 3 is chemical vapor deposition unit structural representation of the present invention.
Fig. 4 is electrochemical ion injection device structural representation of the present invention.
Fig. 5 is that chemistry and galvanochemistry integrating device are prepared intelligent electrochromic production line schematic diagram
Embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
Embodiment 1
The preparation method of intelligent color-changing window, comprises the following steps:
(1) substrate is prepared: adopt tempered glass substrate, by structural glass cutting, moulding, edging and tempering processing, be prefabricated into the needed size and shape of the concrete application of building glass or glass for vehicle window, concrete technology can adopt glass industry or the standard method of solar cell industry to carry out.Cleaned substrate is carried out to optical check, reject and have the substrate of obvious surface imperfection, thereby can effectively improve production yield, reduce product average production cost.
(2) adopt chemical vapour deposition technique, the conductive material of growing on substrate 1, forms the first conductive layer 2; Chemical gaseous phase depositing process all adopts chemical vapour deposition reaction device as shown in Figure 3 to implement.
The present invention adopts chemical vapour deposition technique first conductive layer 2 of growing, and chemical vapor deposition unit adopts existing apparatus, as shown in Figure 3, adopts pre-reaction material In (C
5h
7o
2)
3as In source, pre-reaction material Sn (C
5h
7o
2)
2as Sn source, reacting gas is oxygen, and current-carrying gas is nitrogen, the first transparent conductive layer 2 of reaction preparation ITO at 500 DEG C; This reaction is carried out under normal pressure, does not have other reacting gas to participate in, and does not also need RF generator and pumped vacuum systems.
The ITO transparency conducting layer Sn/In atomic ratio making is between 0.01-0.2.Transmission of visible light is more than 85%, and sheet resistance is in 4 to 20 Ω/ left and right.
Adopt above method to make five batches of samples of numbering 01-05, measure in Table 1-1.
Five batches of properties of sample of table 1-1 lot number 01-05 are measured
(3) adopt chemical vapour deposition technique, the transition metal oxide of growing on the first conductive layer 2, forms electrochromic layer 3;
The present invention adopts chemical vapour deposition technique to grow and prepare electrochromic layer 3 on the first conductive layer 2.Adopt pre-reaction material WF
6as W source, reacting gas is oxygen and hydrogen, does not have other pre-reaction material or current-carrying gas to participate in; Reaction is carried out at normal temperatures and pressures, and additional RF power 200-2000W, frequency 13.56MHz, make WO
3electrochromic layer; Prepared electrochromic layer 3 thickness 100-500nm.
Adopt above method to process respectively five batches of samples of numbering 01-05, measure in Table 1-2.
Five batches of sample preparation conditions of table 1-2 lot number 01-05 and electrochromism layer thickness
| ? | 01 | 02 | 03 | 04 | 05 |
| RF power W | 200 | 500 | 1000 | 1500 | 2000 |
| Thickness nm | 100 | 160 | 250 | 310 | 500 |
(4) adopt two electrodes or three-electrode electro Chemical method, electrochromic layer is carried out to Implantation;
Adopt two electrode electro Chemical methods to carry out the needed ion of Implantation electrochromism to electrochromic layer, Implantation carries out in two electrode electro Chemical grooves as shown in Figure 5.
First, preparation H+ concentration is the sulfuric acid solution to 10Mol/L at 0.5Mol/L, while injecting ion, adds negative voltage at substrate base, adds positive voltage on to electrode; Being Pt to electrode, can be also the glass that deposits conductive layer; Voltage can be constant voltage, also with the voltage gradient of certain form ripple.Inject the common polarity that does not change voltage of ion process and ensure that ion continues to inject.Between two electrodes, also adding the power supply of Current Control, can be the gradual change current and power supply of constant-current supply or certain form ripple.Inject ionic weight and be advisable to realize needed transmittance, if transmittance is below 4%.
Adopt above method to process respectively five batches of samples of numbering 01-05, condition is in Table 1-3.
Five batches of sample preparation conditions of table 1-3 lot number 01-05
| ? | 01 | 02 | 03 | 04 | 05 |
| H+ concentration Mol/L | 0.5 | 2 | 4 | 7 | 10 |
| Transmittance % | 4 | 3.5 | 3 | 2.5 | 2 |
After Implantation, also can heat-treat sedimentary pile lamination, to improve the performance of variable color device.
(5) method or the chemical vapor deposition of employing lithiumation electrochromic layer, grow oxide or inorganic solid-state lithium salts on electrochromic layer 3, form ionic conduction layer 4;
The method of employing lithiumation electrochromic layer is grown and is prepared ionic conduction layer 4 on electrochromic layer 3.After step (4), to the product 200-500 DEG C thermal treatment of step (4), its surperficial self-forming wolframic acid lithium salts LixW (1-x) O3 thin layer, this x is 0.01-0.5, thin layer is ionic conduction layer.
Adopt above method to process respectively five batches of samples of numbering 01-05, condition is in Table 1-4.
Five batches of sample preparation conditions of table 1-4 lot number 01-05 and performance
| ? | 01 | 02 | 03 | 04 | 05 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 1 | 20 | 50 | 80 | 100 |
| x | 0.01 | 0.1 | 0.2 | 0.4 | 0.5 |
(6) adopt chemical vapour deposition technique, the transition metal oxide of growing, ion storage 5 on ionic conduction layer 4;
Adopt chemical vapour deposition technique growth preparation ion storage 5; Pre-reaction material is Ni (CO)
4as Ni source, reacting gas is O
2, current-carrying gas is inert argon, does not have other pre-reaction material or reacting gas to participate in, reaction is carried out under 200-500 DEG C, normal pressure, makes ion storage 5; Prepared ion storage is NiO; Prepared ion storage 5 thickness 100-500nm.
Adopt above method to process respectively five batches of samples of numbering 01-05, condition is in Table 1-5.
Five batches of sample preparation conditions of table 1-5 lot number 01-05 and performance
| ? | 01 | 02 | 03 | 04 | 05 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 170 | 210 | 410 | 500 |
(7) adopt (2) identical chemical vapour deposition technique, the conductive material of growing in ion storage 5, forms second conductive layer 6 identical with the first conductive layer 2, makes intelligent color-changing window.
Adopt above method five batches of samples of the numbering 01-05 for the treatment of step (6) respectively, measure in Table 1-6.
Five batches of properties of sample of table 1-6 lot number 01-05 are measured
(8) adopt chemical vapour deposition technique, the potpourri of one or more of grow on the second conductive layer 6 SiOx, SiNy and SiAlO, forms protective seam 7;
Adopt chemical vapour deposition technique, on the second conductive layer 6, protective seam 7 is prepared in growth.Pre-reaction material is SiH
4, reacting gas is O
2, do not have other pre-reaction material or current-carrying gas to participate in, reaction is carried out under 300-500 DEG C, normal pressure, and prepared protective seam 7 is thin layer SiO
2, thickness 100nm is to 1000nm.
Adopt above method to process respectively five batches of samples of numbering 01-05, measure in Table 1-7.
Five batches of sample preparation conditions of table 1-7 lot number 01-05 and performance
| ? | 01 | 02 | 03 | 04 | 05 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 290 | 480 | 760 | 1000 |
Embodiment 2
The preparation method of intelligent color-changing window, comprises the following steps:
(1) substrate is prepared: adopt simple glass substrate, by structural glass cutting, moulding, edging.Cleaned substrate is carried out to optical check, reject and have the substrate of obvious surface imperfection, thereby can effectively improve production yield, reduce product average production cost.
(2) adopt chemical vapour deposition technique, the conductive material of growing on substrate 1, forms the first conductive layer 2; Chemical gaseous phase depositing process all adopts chemical vapour deposition reaction device to implement.
The present invention adopts chemical vapour deposition technique first conductive layer 2 of growing, and chemical vapor deposition unit adopts existing apparatus.Adopt pre-reaction material F
3cCOOH is as mixing agent F source, adopting pre-reaction material Sn (C
3h
7) Cl
3as Sn source, reacting gas is oxygen, and current-carrying gas is nitrogen, and at 400 DEG C, fluorine doped tin oxide (SnO is prepared in reaction
2: F) transparent the first conductive layer 2; This reaction is carried out under normal pressure, does not have other reacting gas to participate in, and does not also need RF generator and pumped vacuum systems.
Fluorine doped tin oxide (the SnO making
2: F) its F doping content of transparency conducting layer is at 0.1at. % to 1at. %, and transmission of visible light is 85% to 95%, and sheet resistance is in 4 to 20 Ω/ left and right.
Adopt above method to make five batches of samples of numbering 06-10, measure in Table 2-1.
Five batches of properties of sample of table 2-1 lot number 06-10 are measured
(3) adopt chemical vapour deposition technique, the transition metal oxide of growing on the first conductive layer 2, forms electrochromic layer 3;
The present invention adopts chemical vapour deposition technique to grow and prepare electrochromic layer 3 on the first conductive layer 2.Adopt pre-reaction material Mo (CO)
6as Mo source, reacting gas is oxygen, and current-carrying gas is inert argon, does not have other pre-reaction material or current-carrying gas to participate in; Reaction is carried out at normal temperatures, and temperature of reaction, at 200-500 DEG C, makes MoO
3electrochromic layer; Prepared electrochromic layer 3 thickness 100-500nm.
Adopt five batches of samples of the numbering 06-10 that above method processes respectively, measure in Table 2-2.
Five batches of sample preparation conditions of table 2-2 lot number 06-10 and electrochromism layer thickness
| ? | 06 | 07 | 08 | 09 | 10 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 130 | 280 | 350 | 500 |
(4) adopt two electrodes or three-electrode electro Chemical method, electrochromic layer is carried out to Implantation;
Adopt two electrode electro Chemical methods to carry out the needed ion of Implantation electrochromism to electrochromic layer, Implantation carries out in two electrode electro Chemical grooves.
First, preparation Li
+concentration is the LiClO to 10Mol/L at 0.5Mol/L
4solution, injects when ion, adds negative voltage, adds positive voltage on to electrode at substrate base; But to electrode Pt, can be also the glass that deposits conductive layer; Voltage can be constant voltage, also with the voltage gradient of certain form ripple.Inject the common polarity that does not change voltage of ion process and ensure that ion continues to inject.Between two electrodes, also adding the power supply of Current Control, can be the gradual change current and power supply of constant-current supply or certain form ripple.Inject ionic weight and be advisable to realize needed transmittance, if transmittance is below 4%.
Adopt above method to process respectively five batches of samples of numbering 06-10, condition is in Table 2-3.
Five batches of sample preparation conditions of table 2-3 lot number 06-10 and electrochromism layer thickness
| ? | 06 | 07 | 08 | 09 | 10 |
| Li +Concentration Mol/L | 0.5 | 2 | 4 | 7 | 10 |
| Transmittance % | 4 | 3.5 | 3 | 2.5 | 2 |
After Implantation, also can heat-treat sedimentary pile lamination, to improve the performance of variable color device.
(5) method or the chemical vapor deposition of employing lithiumation electrochromic layer, grow oxide or inorganic solid-state lithium salts on electrochromic layer 3, form ionic conduction layer 4;
Adopt chemical vapor deposition to grow on electrochromic layer 3 and prepare ionic conduction layer 4.Adopt pre-reaction material SiH
4, reacting gas (1) is O
2, do not have other pre-reaction material or current-carrying gas to participate in, under reaction normal pressure, carry out at 300-500 DEG C; Prepared ionic conduction layer 4 is thin layer SiO
2, thickness 5nm is to 50nm.
Adopt above method to process respectively five batches of samples of numbering 06-10, condition is in Table 2-4.
Five batches of sample preparation conditions of table 2-4 lot number 06-10 and performance
| ? | 06 | 07 | 08 | 09 | 10 |
| Temperature of reaction DEG C | 300 | 350 | 400 | 450 | 500 |
| Thickness nm | 5 | 15 | 40 | 30 | 50 |
(6) adopt chemical vapour deposition technique, the transition metal oxide of growing on ionic conduction layer 4, forms ion storage 5;
Adopt chemical vapour deposition technique growth preparation ion storage 5; Pre-reaction material is Ni (C
5h
7o
2)
2as Ni source, reacting gas is O
2, current-carrying gas is nitrogen, does not have other pre-reaction material or current-carrying gas to participate in.Under reaction normal pressure, carry out.Between temperature of reaction 200-500 DEG C, making NiO is ion storage 5; Obtained ion storage 5 thickness 100nm are to 500nm;
Adopt above method to process respectively five batches of samples of numbering 06-10, condition is in Table 2-5.
Five batches of sample preparation conditions of table 2-5 lot number 06-10 and performance
| ? | 01 | 02 | 03 | 04 | 05 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 180 | 290 | 360 | 500 |
(7) adopt the chemical vapour deposition technique identical with (2), the conductive material of growing in ion storage 5, forms the second conductive layer 6, makes intelligent color-changing window;
Adopt above method to process respectively five batches of samples of numbering 06-10, measure in Table 2-6.
Five batches of properties of sample of table 2-6 lot number 06-10 are measured
(8) adopt chemical vapour deposition technique, the potpourri of one or more of grow on the second conductive layer 6 SiOx, SiNy and SiAlO, forms protective seam 7;
Adopt chemical vapour deposition technique, on the second conductive layer 6, protective seam (8) is prepared in growth.Pre-reaction material is SiH
4and 2Al (OC
3h
7)
3, reacting gas is O
2, do not have other pre-reaction material or current-carrying gas to participate in, reaction is carried out under 300-500 DEG C, normal pressure; Prepared protective seam 7 is thin layer SiAlO, and thickness 100nm is to 1000nm.
Adopt above method five batches of samples of the numbering 06-10 for the treatment of step (7) respectively, measure in Table 2-7.
Five batches of sample preparation conditions of table 2-7 lot number 06-10 and performance
| ? | 01 | 02 | 03 | 04 | 05 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 400 | 600 | 800 | 1000 |
Embodiment 3
The preparation method of intelligent color-changing window, comprises the following steps:
(1) substrate is prepared: adopt plastic, non-glass substrate, as flexible substrate such as plastics, cuts, the pre-service such as moulding, edging.Pretreated substrate is cleaned, as adopted mechanical scrub and/or Ultrasonic Cleaning, to remove the surface impurity such as organic marking and inorganic particle of substrate material surface.Cleaned substrate is checked, reject and have the substrate of obvious surface imperfection, thereby can effectively improve production yield, reduce product average production cost.
(2) adopt chemical vapour deposition technique, the conductive material of growing on substrate 1, forms the first conductive layer 2; Chemical gaseous phase depositing process all adopts chemical vapour deposition reaction device to implement.
The present invention adopts chemical vapour deposition technique first conductive layer 2 of growing, and chemical vapor deposition unit adopts existing apparatus.Adopt pre-reaction material HF as mixing agent F source, adopting pre-reaction material SnCl
4as Sn source, pre-reaction material H
2o is as oxidation source, and current-carrying gas is nitrogen, and at 350 DEG C, fluorine doped tin oxide (SnO is prepared in reaction
2: F) the first transparent conductive layer 2; This reaction is carried out under normal pressure, does not have other reacting gas to participate in, and does not also need RF generator and pumped vacuum systems.
Fluorine doped tin oxide (the SnO making
2: F) its F of its transparency conducting layer of transparency conducting layer mix concentration at 0.05at.% to 2at.%, transmission of visible light is 85% to 95%, sheet resistance is in 3 to 30 Ω/ left and right.
Adopt above method to make five batches of samples of numbering 11-15, measure in Table 3-1.
Five batches of properties of sample of table 3-1 lot number 11-15 are measured
(3) adopt chemical vapour deposition technique, the transition metal oxide of growing on the first conductive layer 2, forms electrochromic layer 3;
The present invention adopts chemical vapour deposition technique to grow and prepare electrochromic layer 3 on the first conductive layer 2.Adopt pre-reaction material V (OC
2h
5)
5as V source, reacting gas is oxygen, does not have other pre-reaction material or current-carrying gas to participate in; Reaction is carried out at normal temperatures, and temperature of reaction is at 200-500 DEG C; Prepared electrochromic layer is V
2o
5; The electrochromic layer 3 thickness 100-500nm that make.
Adopt above method to process respectively five batches of samples of numbering 01-05, measure in Table 3-2.
Five batches of sample preparation conditions of table 3-2 lot number 11-15 and electrochromism layer thickness
| ? | 11 | 12 | 13 | 14 | 15 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 150 | 270 | 390 | 500 |
(4) adopt two electrodes or three-electrode electro Chemical method, electrochromic layer is carried out to Implantation;
Adopt three-electrode electro Chemical method to carry out the needed ion of Implantation electrochromism to electrochromic layer, three electrode chemical tanks, increase a contrast electrode, as Ag/AgCl or Hg/HgCl
2deng.
First, preparation H+ concentration is the sulfuric acid solution to 10Mol/L at 0.5Mol/L, while injecting ion, adds negative voltage at substrate base, adds positive voltage on to electrode; Being Pt to electrode, can be also the glass that deposits conductive layer; Voltage can be constant voltage, also with the voltage gradient of certain form ripple.Inject the common polarity that does not change voltage of ion process and ensure that ion continues to inject.Between two electrodes, also adding the power supply of Current Control, can be the gradual change current and power supply of constant-current supply or certain form ripple.Inject ionic weight and be advisable to realize needed transmittance, if transmittance is below 4%.
Adopt above method to process respectively five batches of samples of numbering 11-15, condition is in Table 3-3.
Five batches of sample preparation conditions of table 3-3 lot number 11-15 and electrochromism layer thickness
| ? | 11 | 12 | 13 | 14 | 15 |
| Li +Concentration Mol/L | 0.5 | 2 | 4 | 7 | 10 |
| Transmittance % | 4 | 3.5 | 3 | 2.5 | 2 |
After Implantation, also can heat-treat sedimentary pile lamination, to improve the performance of variable color device.
(5) method or the chemical vapor deposition of employing lithiumation electrochromic layer, grow oxide or inorganic solid-state lithium salts on electrochromic layer 3, form ionic conduction layer 4;
Adopt chemical vapor deposition to grow on electrochromic layer 3 and prepare ionic conduction layer 4.Adopt pre-reaction material SiH4 and 2Al (OC
3h
7)
3, reacting gas (1) is O
2, do not have other pre-reaction material or current-carrying gas to participate in, under reaction normal pressure, carry out at 300-500 DEG C, the ionic conduction layer 4 making is thin layer SiAlO, thickness 5nm is to 50nm.
Adopt above method to process respectively five batches of samples of numbering 11-15, condition is in Table 3-4.
Five batches of sample preparation conditions of table 3-4 lot number 11-15 and performance
| ? | 11 | 12 | 13 | 14 | 15 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 5 | 10 | 24 | 30 | 50 |
(6) adopt chemical vapour deposition technique, the potpourri of the transition metal oxide of growing on ionic conduction layer 4, forms ion storage 5;
Adopt chemical vapour deposition technique growth preparation ion storage 5; Pre-reaction material be Ni (C5H7O2) 2 as Ni source, pre-reaction material is W (OC
2h
5)
5as W source, reacting gas is O
2, current-carrying gas is inert argon, does not have other pre-reaction material to participate in, and carries out, between 200 °-500 DEG C of temperature of reaction under reaction normal pressure; Prepared ion storage 5 is NiO and WO
3potpourri NixW (1-x) O, wherein x is between 0.2 to 0.8; Obtained ion storage 5 thickness 100 to 500nm.
Adopt above method to process respectively five batches of samples of numbering 11-15, condition is in Table 3-5.
Five batches of sample preparation conditions of table 3-5 lot number 11-15 and electrochromism layer thickness
| ? | 11 | 12 | 13 | 14 | 15 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 140 | 280 | 370 | 500 |
| x | 0.3 | 0.5 | 0.2 | 0.7 | 0.8 |
(7) adopt the chemical vapour deposition technique identical with (2), the conductive material of growing in ion storage 5, forms the second conductive layer 6, makes intelligent color-changing window;
Adopt above method to process respectively five batches of samples of numbering 11-15, measure in Table 3-6.
Five batches of properties of sample of table 3-6 lot number 11-15 are measured
(8) adopt chemical vapour deposition technique, the potpourri of one or more of grow on the second conductive layer 6 SiOx, SiNy and SiAlO, forms protective seam (8);
Adopt chemical vapour deposition technique, on the second conductive layer 6, protective seam 7 is prepared in growth.Pre-reaction material is SiH
4and NH
3, reacting gas is O
2, do not have other pre-reaction material or current-carrying gas to participate in, reaction is carried out under 300-500 DEG C, normal pressure, and prepared protective seam 7 is thin layer SiNx, and thickness 100nm is to 1000nm.
Adopt above method to process respectively five batches of samples of numbering 11-15, measure in Table 3-7.
Five batches of sample preparation conditions of table 3-7 lot number 11-15 and performance
| ? | 01 | 02 | 03 | 04 | 05 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 250 | 600 | 750 | 1000 |
| x | 1 | 1.5 | 2 | 2.5 | 3 |
Embodiment 4
The preparation method of intelligent color-changing window, comprises the following steps:
(1) substrate is prepared: adopt tempered glass substrate, by structural glass cutting, moulding, edging and tempering processing, be prefabricated into the needed size and shape of the concrete application of building glass or glass for vehicle window, concrete technology can adopt glass industry or the standard method of solar cell industry to carry out.Cleaned substrate is carried out to optical check, reject and have the substrate of obvious surface imperfection, thereby can effectively improve production yield, reduce product average production cost.
(2) adopt chemical vapour deposition technique, the conductive material of growing on substrate 1, forms the first conductive layer 2; Chemical gaseous phase depositing process all adopts chemical vapour deposition reaction device to implement.
The present invention adopts chemical vapour deposition technique first conductive layer 2 of growing, and chemical vapor deposition unit adopts existing apparatus.Adopt pre-reaction material HF as mixing agent F source, adopting pre-reaction material Sn (CH
3)
4as Sn source, reacting gas is oxygen, and current-carrying gas is nitrogen, and at 300 DEG C, fluorine doped tin oxide (SnO is prepared in reaction
2: F) the first transparent conductive layer 2; This reaction is carried out under normal pressure, does not have other reacting gas to participate in, and does not also need RF generator and pumped vacuum systems.
Fluorine doped tin oxide (the SnO making
2: F) its F of its transparency conducting layer of transparency conducting layer mix concentration at 0.1at.% to 3at.%, transmission of visible light is 85% to 95%, sheet resistance is in 2 to 20 Ω/ left and right.
Adopt above method to make five batches of samples of numbering 16-20, measure in Table 4-1.
Five batches of properties of sample of table 4-1 lot number 16-20 are measured
(3) adopt chemical vapour deposition technique, the potpourri of the transition metal oxide of growing on the first conductive layer 2, forms electrochromic layer 3;
The present invention adopts chemical vapour deposition technique to grow and prepare electrochromic layer 3 on the first conductive layer 2.Adopt pre-reaction material W (OC
2h
5)
5as W source, pre-reaction material V (OC
2h
5)
5as V source, reacting gas is oxygen, does not have other pre-reaction material or current-carrying gas to participate in; Reaction is carried out at normal temperatures, and temperature of reaction is at 200-500 DEG C; Prepared electrochromic layer is WO
3and V
2o
5potpourri VxW (1-x) O
3, wherein x is between 0.01 to 0.5; The electrochromic layer 3 thickness 100-500nm that make.
Adopt above method to process respectively five batches of samples of numbering 16-20, measure in Table 4-2.
Five batches of sample preparation conditions of table 4-2 lot number 16-20 and electrochromism layer thickness
| ? | 16 | 17 | 18 | 19 | 20 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 170 | 260 | 400 | 500 |
| x | 0.01 | 0.1 | 0.2 | 0.4 | 0.5 |
(4) adopt two electrodes or three-electrode electro Chemical method, electrochromic layer is carried out to Implantation;
Adopt two electrode electro Chemical methods to carry out the needed ion of Implantation electrochromism to electrochromic layer, Implantation carries out in two electrode electro Chemical grooves.
First, preparation Li
+concentration is the LiClO to 10Mol/L at 0.5Mol/L
4-acetonitrile solution, injects when ion, adds negative voltage, adds positive voltage on to electrode at substrate base; But to electrode Pt, can be also the glass that deposits conductive layer; Voltage can be constant voltage, also with the voltage gradient of certain form ripple.Inject the common polarity that does not change voltage of ion process and ensure that ion continues to inject.Between two electrodes, also adding the power supply of Current Control, can be the gradual change current and power supply of constant-current supply or certain form ripple.Inject ionic weight and be advisable to realize needed transmittance, if transmittance is below 4%.
Adopt above method to process respectively five batches of samples of numbering 16-20, condition is in Table 4-3.
Five batches of sample preparation conditions of table 4-3 lot number 16-20 and electrochromism layer thickness
| ? | 16 | 17 | 18 | 19 | 20 |
| Li +Concentration Mol/L | 0.5 | 2 | 4 | 7 | 10 |
| Transmittance % | 4 | 3.5 | 3 | 2.5 | 2 |
After Implantation, also can heat-treat sedimentary pile lamination, to improve the performance of variable color device.
(5) method or the chemical vapor deposition of employing lithiumation electrochromic layer, grow oxide or inorganic solid-state lithium salts on electrochromic layer 3, form ionic conduction layer 4;
Adopt chemical vapor deposition to grow on electrochromic layer 3 and prepare ionic conduction layer 4.Adopt pre-reaction material SiH
4and Al (OC
3h
7)
3, reacting gas (1) is O
2, do not have other pre-reaction material or current-carrying gas to participate in, under reaction normal pressure, carry out at 300-500 DEG C, the ionic conduction layer 4 making is thin layer SiAlO, thickness 5nm is to 50nm.
Adopt above method to process respectively five batches of samples of numbering 16-20, condition is in Table 4-4.
Five batches of sample preparation conditions of table 4-4 lot number 16-20 and performance
| ? | 16 | 17 | 18 | 19 | 20 |
| Temperature of reaction DEG C | 300 | 350 | 400 | 450 | 500 |
| Thickness nm | 5 | 10 | 20 | 40 | 50 |
(6) adopt chemical vapour deposition technique, the potpourri of the transition metal oxide of growing on ionic conduction layer 4, forms ion storage 5;
Adopt chemical vapour deposition technique growth preparation to form ion storage 5; Pre-reaction material is Ni (C
5h
7o
2)
2as Ni source, pre-reaction material is V (OC
2h
5)
5as V source, reacting gas is O
2, current-carrying gas is inert argon, does not have other pre-reaction material to participate in, and under reaction normal pressure, carries out, between temperature of reaction 200-500 DEG C, prepared ion storage 5 is NiO and V
2o
5potpourri NixV (1-x) O, wherein x is between 0.2 to 0.8; Obtained ion storage 5 thickness 100 to 500nm.
Adopt above method to process respectively five batches of samples of numbering 16-20, condition is in Table 4-5.
Five batches of sample preparation conditions of table 4-5 lot number 16-20 and electrochromism layer thickness
| ? | 16 | 17 | 18 | 19 | 20 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 120 | 260 | 390 | 500 |
| x | 0.3 | 0.5 | 0.2 | 0.7 | 0.8 |
(7) adopt the chemical vapour deposition technique identical with (2), the conductive material of growing in ion storage 5, forms the second conductive layer 6, makes intelligent color-changing window;
Adopt above method to make five batches of samples of numbering 16-20, measure in Table 4-6.
Five batches of properties of sample of table 4-6 lot number 16-20 are measured
(8) adopt chemical vapour deposition technique, the potpourri of one or more of grow on the second conductive layer 6 SiOx, SiNy and SiAlO, forms protective seam 7;
Adopt chemical vapour deposition technique, on the second conductive layer 6, protective seam 7 is prepared in growth.Pre-reaction material is SiH
4and NH
3, reacting gas is O
2, do not have other pre-reaction material or current-carrying gas to participate in, reaction is carried out under 300-500 DEG C, normal pressure, and prepared protective seam 7 is thin layer SiNx, and thickness 100nm is to 1000nm.
Adopt above method to process respectively five batches of samples of numbering 16-20, measure in Table 4-7.
Five batches of sample preparation conditions of table 4-7 lot number 16-20 and performance
| ? | 16 | 17 | 18 | 19 | 20 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 450 | 670 | 790 | 1000 |
| x | 1 | 1.5 | 2 | 2.5 | 3 |
Embodiment 5
The preparation method of intelligent color-changing window, comprises the following steps:
(1) substrate is prepared: adopt tempered glass substrate, by structural glass cutting, moulding, edging and tempering processing, be prefabricated into the needed size and shape of the concrete application of building glass or glass for vehicle window, concrete technology can adopt glass industry or the standard method of solar cell industry to carry out.Cleaned substrate is carried out to optical check, reject and have the substrate of obvious surface imperfection, thereby can effectively improve production yield, reduce product average production cost.
(2) adopt chemical vapour deposition technique, the conductive material of growing on substrate 1, forms the first conductive layer 2; Chemical gaseous phase depositing process all adopts chemical vapour deposition reaction device to implement.
The present invention adopts chemical vapour deposition technique first conductive layer 2 of growing, and chemical vapor deposition unit adopts existing apparatus.Adopt pre-reaction material C
6h
5cOF is as mixing agent F source, adopting pre-reaction material (C
2h
5)
2zn (CH
3)
2nCH
2cH
2-n (CH
3)
2as Zn source, pre-reaction material ethanol (C2H5OH), as oxygen source, current-carrying gas is for being preheating to 100 DEG C of nitrogen, and at 250 DEG C, the first conductive layer 2 that fluorine zinc paste (ZnO:F) is transparent is mixed in reaction preparation; This reaction is carried out under normal pressure, does not have other reacting gas to participate in, and does not also need RF generator and pumped vacuum systems.
What make mixes fluorine zinc paste (ZnO:F); Its F of its transparency conducting layer of transparency conducting layer mixes concentration and arrives 1at.% at 0.1at.%, and transmission of visible light is 85% to 95%, and sheet resistance is in 2-10 Ω/ left and right.
Adopt above method to make five batches of samples of numbering 21-25, measure in Table 5-1.
Five batches of properties of sample of table 5-1 lot number 21-25 are measured
(3) adopt chemical vapour deposition technique, the potpourri of the transition metal oxide of growing on the first conductive layer 2, forms electrochromic layer 3;
The present invention adopts chemical vapour deposition technique to grow and prepare electrochromic layer 3 on the first conductive layer 2.Adopt pre-reaction material W (OC
2h
5)
5as W source, pre-reaction material Ti (OC
2h
5)
4as Ti source, reacting gas is oxygen, does not have other pre-reaction material or current-carrying gas to participate in; Reaction is carried out at normal temperatures, and temperature of reaction is at 200-500 DEG C; Prepared electrochromic layer is WO
3and TiO
2potpourri TixW (1-x) O
3, wherein x is between 0.01 to 0.5; The electrochromic layer 3 thickness 100-500nm that make.
Adopt above method to process respectively five batches of samples of numbering 21-25, condition is in Table 5-2.
Five batches of sample preparation conditions of table 5-2 lot number 21-25 and electrochromism layer thickness
| ? | 21 | 22 | 23 | 24 | 25 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 155 | 275 | 360 | 500 |
| x | 0.01 | 0.1 | 0.2 | 0.4 | 0.5 |
(4) adopt two electrodes or three-electrode electro Chemical method, electrochromic layer is carried out to Implantation;
Adopt two electrode electro Chemical methods to carry out the needed ion of Implantation electrochromism to electrochromic layer, Implantation carries out in two electrode electro Chemical grooves.
First, preparation Li
+concentration to the LiClO4-acetonitrile solution of 10Mol/L, while injecting ion, adds negative voltage at substrate base at 0.5Mol/L, add positive voltage on to electrode; But to electrode Pt, can be also the glass that deposits conductive layer; Voltage can be constant voltage, also with the voltage gradient of certain form ripple.Inject the common polarity that does not change voltage of ion process and ensure that ion continues to inject.Between two electrodes, also adding the power supply of Current Control, can be the gradual change current and power supply of constant-current supply or certain form ripple.Inject ionic weight and be advisable to realize needed transmittance, if transmittance is below 4%.
Adopt above method to process respectively five batches of samples of numbering 21-25, condition is in Table 5-3.
Five batches of sample preparation conditions of table 5-3 lot number 21-25 and electrochromism layer thickness
| ? | 21 | 22 | 23 | 24 | 25 |
| Li +Concentration Mol/L | 0.5 | 2 | 4 | 7 | 10 |
| Transmittance % | 4 | 3.5 | 3 | 2.5 | 2 |
After Implantation, also can heat-treat sedimentary pile lamination, to improve the performance of variable color device.
(5) method or the chemical vapor deposition of employing lithiumation electrochromic layer, grow oxide or inorganic solid-state lithium salts on electrochromic layer 3, form ionic conduction layer 4;
Adopt chemical vapor deposition to grow on electrochromic layer 3 and prepare ionic conduction layer 4.Adopt pre-reaction material SiH
4and 2Al (OC
3h
7)
3, reacting gas (1) is O
2, do not have other pre-reaction material or current-carrying gas to participate in, under reaction normal pressure, carry out at 300-500 DEG C, the ionic conduction layer 4 making is thin layer SiAlO, thickness 5nm is to 50nm.
Adopt above method to process respectively five batches of samples of numbering 21-25, condition is in Table 5-4.
Five batches of sample preparation conditions of table 5-4 lot number 21-25 and performance
| ? | 21 | 22 | 23 | 24 | 25 |
| Temperature of reaction DEG C | 300 | 350 | 400 | 450 | 500 |
| Thickness nm | 5 | 15 | 20 | 35 | 50 |
(6) adopt chemical vapour deposition technique, the transition metal oxide of growing on ionic conduction layer 4, forms ion storage 5;
Adopt chemical vapour deposition technique growth preparation ion storage 5; Pre-reaction material is Ni (C
5h
7o
2)
2as Ni source, pre-reaction material is Cr (OC
2h
5)
3as Cr source, reacting gas is O
2, current-carrying gas is inert argon, does not have other pre-reaction material to participate in, under reaction normal pressure, carry out, between 200 DEG C-500 DEG C of temperature of reaction, nickel chromium triangle oxide mixture NixCr (1-x) O that prepared ion storage 5 is NiO and CrO, wherein x is between 0.2 to 0.8; Obtained ion storage 5 thickness 100 to 500nm.
Adopt above method to process respectively five batches of samples of numbering 21-25, condition is in Table 5-5.
Five batches of sample preparation conditions of table 5-5 lot number 21-25 and electrochromism layer thickness
| ? | 21 | 22 | 23 | 24 | 25 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 140 | 260 | 410 | 500 |
| x | 0.2 | 0.4 | 0.5 | 0.8 | 0.7 |
(7) adopt the chemical vapour deposition technique identical with (2), at the upper growth of ion storage (5) conductive material, form the second conductive layer 6, make intelligent color-changing window;
Adopt above method to make five batches of samples of numbering 21-25, measure in Table 5-6.
Five batches of properties of sample of table 5-6 lot number 21-25 are measured
(8) adopt chemical vapour deposition technique, the potpourri of one or more of grow on the second conductive layer 6 SiOx, SiNy and SiAlO, forms protective seam 7;
Adopt chemical vapour deposition technique, prepare protective seam 7 in the upper growth 6 of the second conductive layer (7).Pre-reaction material is SiH
4and NH
3, reacting gas is O
2, do not have other pre-reaction material or current-carrying gas to participate in, reaction is carried out under 300-500 DEG C, normal pressure, and prepared protective seam (8) is thin layer SiNx, and thickness 100nm is to 1000nm.
Adopt above method five batches of samples of the numbering 21-25 for the treatment of step (7) respectively, measure in Table 5-7.
Five batches of sample preparation conditions of table 5-7 lot number 21-25 and performance
| ? | 21 | 22 | 23 | 24 | 25 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 310 | 650 | 890 | 1000 |
| x | 1 | 1.5 | 2 | 2.5 | 3 |
Embodiment 6
The preparation method of intelligent color-changing window, comprises the following steps:
(1) substrate is prepared: adopt tempered glass substrate, by structural glass cutting, moulding, edging and tempering processing, be prefabricated into the needed size and shape of the concrete application of building glass or glass for vehicle window, concrete technology can adopt glass industry or the standard method of solar cell industry to carry out.Cleaned substrate is carried out to optical check, reject and have the substrate of obvious surface imperfection, thereby can effectively improve production yield, reduce product average production cost.
(2) adopt chemical vapour deposition technique, the conductive material of growing on substrate 1, forms the first conductive layer 2; Chemical gaseous phase depositing process all adopts chemical vapour deposition reaction device to implement.
The present invention adopts chemical vapour deposition technique first conductive layer 2 of growing, and chemical vapor deposition unit adopts existing apparatus.Adopt pre-reaction material Al (C
2h
5)
3as mixing agent Al source, adopting pre-reaction material Zn (C
2h
5)
2as Zn source, pre-reaction material ethanol (C
2h
5oH) as oxygen source, current-carrying gas is for being preheating to 150 DEG C of nitrogen, and at 200 DEG C, the first conductive layer 2 that Al-Doped ZnO (ZnO:Al) is transparent is prepared in reaction; This reaction is carried out under normal pressure, does not have other reacting gas to participate in, and does not also need RF generator and pumped vacuum systems.
The Al-Doped ZnO (ZnO:Al) making; Its Al doping content of transparency conducting layer is at 0.2at.% to 2at.%, and transmission of visible light is 85% to 95%, and sheet resistance is in 2-10 Ω/ left and right.
Adopt above method to make five batches of samples of numbering 26-30, measure in Table 6-1.
Five batches of properties of sample of table 6-1 lot number 26-30 are measured
(3) adopt chemical vapour deposition technique, the potpourri of the transition metal oxide of growing on the first conductive layer 2, forms electrochromic layer 3;
The present invention adopts chemical vapour deposition technique to grow and prepare electrochromic layer 3 on the first conductive layer 2.Adopt pre-reaction material W (OC
2h
5)
5as W source, pre-reaction material Mo (OC
2h
5)
5as Mo source, reacting gas is oxygen, does not have other pre-reaction material or current-carrying gas to participate in; Reaction is carried out at normal temperatures, and temperature of reaction is at 200-500 DEG C; Prepared electrochromic layer is WO
3and MoO
3mixture M oxW (1-x) O
3, wherein x is between 0.01 to 0.5; The electrochromic layer 3 thickness 100-500nm that make.
Adopt above method to process respectively five batches of samples of numbering 26-30, condition is in Table 6-2.
Five batches of sample preparation conditions of table 6-2 lot number 26-30 and electrochromism layer thickness
| ? | 26 | 27 | 28 | 29 | 30 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 180 | 260 | 390 | 500 |
| x | 0.01 | 0.1 | 0.2 | 0.4 | 0.5 |
(4) adopt two electrodes or three-electrode electro Chemical method, electrochromic layer is carried out to Implantation;
Adopt two electrode electro Chemical methods to carry out the needed ion of Implantation electrochromism to electrochromic layer, Implantation carries out in two electrode electro Chemical grooves.
First, preparation Li
+concentration is the LiClO to 10Mol/L at 0.5Mol/L
4-acetonitrile solution, injects when ion, adds negative voltage, adds positive voltage on to electrode at substrate base; But to electrode Pt, can be also the glass that deposits conductive layer; Voltage can be constant voltage, also with the voltage gradient of certain form ripple.Inject the common polarity that does not change voltage of ion process and ensure that ion continues to inject.Between two electrodes, also adding the power supply of Current Control, can be the gradual change current and power supply of constant-current supply or certain form ripple.Inject ionic weight and be advisable to realize needed transmittance, if transmittance is below 4%.
Adopt above method to process respectively five batches of samples of numbering 26-30, condition is in Table 6-3.
Five batches of sample preparation conditions of table 6-3 lot number 26-30 and electrochromism layer thickness
| ? | 26 | 27 | 28 | 29 | 30 |
| Li +Concentration Mol/L | 0.5 | 2 | 4 | 7 | 10 |
| Transmittance % | 4 | 3.5 | 3 | 2.5 | 2 |
After Implantation, also can heat-treat sedimentary pile lamination, to improve the performance of variable color device.
(5) method or the chemical vapor deposition of employing lithiumation electrochromic layer, grow oxide or inorganic solid-state lithium salts on electrochromic layer 3, form ionic conduction layer 4;
Adopt chemical vapor deposition to grow on electrochromic layer 3 and prepare ionic conduction layer 4.Adopt pre-reaction material SiH
4and 2Al (OC
3h
7)
3, reacting gas (1) is O
2, do not have other pre-reaction material or current-carrying gas to participate in, under reaction normal pressure, carry out at 300-500 DEG C, the ionic conduction layer 4 making is thin layer SiAlO, thickness 5nm is to 50nm.
Adopt above method to process respectively five batches of samples of numbering 26-30, condition is in Table 6--4.
Five batches of sample preparation conditions of table 6--4 lot number 26-30 and performance
| ? | 26 | 27 | 28 | 29 | 30 |
| Temperature of reaction DEG C | 300 | 350 | 400 | 450 | 500 |
| Thickness nm | 5 | 15 | 20 | 45 | 50 |
(6) adopt chemical vapour deposition technique, the potpourri of the transition metal oxide of growing on ionic conduction layer 4, forms ion storage 5;
Adopt chemical vapour deposition technique growth preparation to form ion storage 5; Pre-reaction material is Ni (C
5h
7o
2)
2as Ni source, pre-reaction material is Al (OC
2h
5)
3as Al source, reacting gas is O
2, current-carrying gas is inert argon, does not have other pre-reaction material to participate in, and carries out, between 200 DEG C-500 DEG C of temperature of reaction under reaction normal pressure; Prepared ion storage 5 is NiO and Al
2o
3potpourri NixAl (1-x) O, wherein x is between 0.2 to 0.8; Obtained ion storage 5 thickness 100 to 500nm.
Adopt above method to process respectively five batches of samples of numbering 26-30, condition is in Table 6-5.
Five batches of sample preparation conditions of table 6-5 lot number 26-30 and electrochromism layer thickness
| ? | 26 | 27 | 28 | 29 | 30 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 140 | 240 | 430 | 500 |
| x | 0.3 | 0.2 | 0.5 | 0.7 | 0.8 |
(7) adopt the chemical vapour deposition technique identical with (2), the conductive material of growing in formation ion storage 5, forms the second conductive layer 6, makes intelligent color-changing window;
Adopt above method to make five batches of samples of numbering 26-30, measure in Table 6-6.
Five batches of properties of sample of table 6-6 lot number 26-30 are measured
(8) adopt chemical vapour deposition technique, the potpourri of one or more of grow on the second conductive layer 6 SiOx, SiNy and SiAlO, forms protective seam 7;
Adopt chemical vapour deposition technique, on the second conductive layer 6, protective seam (8) is prepared in growth.Pre-reaction material is SiH
4and NH
3, reacting gas is O
2, do not have other pre-reaction material or current-carrying gas to participate in, reaction is carried out under 300-500 DEG C, normal pressure, and prepared protective seam 7 is thin layer SiNx, and thickness 100nm is to 1000nm.
Adopt above method five batches of samples of the numbering 26-30 for the treatment of step (7) respectively, measure in Table 6-7.
Five batches of sample preparation conditions of table 6-7 lot number 26-30 and performance
| ? | 26 | 27 | 28 | 29 | 30 |
| Temperature of reaction DEG C | 200 | 250 | 300 | 400 | 500 |
| Thickness nm | 100 | 350 | 680 | 860 | 1000 |
| x | 1 | 1.5 | 2 | 2.5 | 3 |
Compared with the present invention prepares electrochromic device with current commercialization physical vapour deposition (PVD), chemistry and electrochemical method energy consumption is low, equipment relatively cheap simple, be suitable for large area and prepare.
Although the present invention it should be noted that taking whole chemical vapour deposition techniques as preferential case study on implementation replaces physical vapour deposition (PVD) with integrated, wherein a step or multistep also can realize and being equal to or equivalent embodiment by other non-physical vapour deposition (PVD) sedimentations.As wherein a step or multistep sedimentary deposit, can replace with ald (ALD), sol-gel process deposition (sol-gel), electrochemical deposition method etc.For instance, in some embodiment of the present invention, chemogenic deposit step 303 is prepared electrochromic layer can prepare replacement with electrochemical deposition method.Electrochemical depositer is identical with Fig. 4, and working electrode is substrate base, is coating electro-conductive glass to electrode, contrast electrode is Ag/AgCl, and deposit solution is peroxide wolframic acid, and deposition voltage is between 0.1 to 20V, sedimentation time is at 10 to 100 minutes, deposit thickness 100 to 1000 nanometers.Heat-treat afterwards to regulate and optimize its electrochromic property, 100 to 300 DEG C of heat treatment temperatures, heat treatment time was at 10 to 180 minutes.
The above, each chemical gaseous phase depositing process, integrated with electrochemical ion injection, and intelligent color-changing window production line, be only certain preferred embodiment of the present invention, not the present invention is done to any pro forma restriction.Although the present invention with the concrete statement of preferred embodiment as above, but not in order to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, when can utilizing the technology contents of above-mentioned announcement to make a little change or being modified to the equivalent embodiment of equivalent variations, in every case be not depart from technical solution of the present invention content, any simple modification, equivalent variations and the modification above embodiment done according to technical spirit of the present invention, all still belong in the scope of technical solution of the present invention.
Claims (8)
1. a preparation method for intelligent color-changing window, is characterized in that: comprise the following steps:
Step 1, adopts chemical vapour deposition technique, at the upper growth of substrate (1) conductive material, forms the first conductive layer (2);
Step 2, adopts chemical vapour deposition technique, at the first conductive layer (2) upper growth transition metal oxide or its potpourri, forms electrochromic layer (3);
Step 3, adopts two electrodes or three-electrode electro Chemical method, and electrochromic layer is carried out to Implantation;
Step 4, method or the chemical vapour deposition technique of employing lithiumation electrochromic layer, at the upper grow oxide of electrochromic layer (3) or inorganic solid-state lithium salts, form ionic conduction layer (4);
Step 5, adopts chemical vapour deposition technique, at ionic conduction layer (4) upper growth transition metal oxide or its potpourri, forms ion storage layer (5);
Step 6, adopts chemical vapour deposition technique, at the upper growth of ion storage layer (5) conductive material, forms the second conductive layer (6), makes intelligent color-changing window.
2. the preparation method of a kind of intelligent color-changing window according to claim 1, is characterized in that: in step 1, described substrate (1) is glass substrate, tempered glass substrate or plastic; Described conductive material is transparent conductive oxide; Described transparent conductive oxide comprises metal oxide and blended metal oxide, preferably, comprises fluorine doped tin oxide, tin-doped indium oxide, Al-Doped ZnO and mixes fluorine zinc paste; The thickness of described the first conductive layer (2) is 100-1000nm, and transmittance is that more than 80% sheet resistance is below 50 Ω/.
3. the preparation method of a kind of intelligent color-changing window according to claim 1, is characterized in that: in step 2, described transition metal oxide is selected from one or more the mixing in cathode electrochromic material and anode electrochromic material; Preferably, described transition metal oxide is the potpourri of potpourri, tungsten oxide and vanadium oxide or the potpourri of tungsten oxide and titanium dioxide of tungsten oxide, molybdena, vanadium oxide, tungsten oxide and molybdena; The thickness of described electrochromic layer (3) is 50-500nm.
4. the preparation method of a kind of intelligent color-changing window according to claim 1, is characterized in that: in step 3, the ion being injected into is the mixing of H+, Li+ or H+ and Li+.
5. the preparation method of a kind of intelligent color-changing window according to claim 1, is characterized in that: in step 4, described ionic conduction layer is oxide or inorganic solid-state lithium salts, and preferential described oxide comprises monox, sieve and silica-sesquioxide; Described inorganic solid-state lithium salts is tungstate lithium; The thickness of described ionic conduction layer (4) is 1-100nm.
6. the preparation method of a kind of intelligent color-changing window according to claim 1, is characterized in that: in step 5, described transition metal oxide is selected from one or more the mixing in cathode electrochromic material and anode electrochromic material; Preferably, described transition metal oxide is nickel oxide, nickel tungsten oxide, nickel barium oxide, nickel chromium triangle oxide or nickel aluminum oxide; The thickness of described the second electrochromic layer (5) is 50-500nm.
7. the preparation method of a kind of intelligent color-changing window according to claim 1, is characterized in that: in step 6, described conductive material is transparent conductive oxide, and described transparent conductive oxide comprises metal oxide and blended metal oxide; The thickness of described the second conductive layer (6) is 100-1000nm, and transmittance is that more than 80% sheet resistance is less than 50 Ω/.
8. the preparation method of a kind of intelligent color-changing window according to claim 1, it is characterized in that: described intelligent color-changing window also comprises protective seam (7), its preparation method is: adopt chemical vapour deposition technique, at one or more the potpourri of the second conductive layer (6) upper growth SiOx, SiNy and SiAlO, form protective seam (7); Wherein, x is 1-3, and y is 1-3, and the thickness of described protective seam (7) is 10-1000nm.
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