阅读说明：本技术 一种高对比度三电极电调光器件及其制备和控制方法 (A kind of three electrode electricity light modulation device of high contrast and its preparation and control method ) 是由 宋爱民 贺丹丹 辛倩 于 2018-05-18 设计创作，主要内容包括：本发明的高对比度三电极电调光器件,包括第一电调光材料层、第二电调光材料层、第三电调光材料层和透明电解质层,透明电解质层固定于第一电调光材料层的上表面上,第二电调光材料层和第三电调光材料层均固定于透明电解质层的上表面上,第三电调光材料层与第二电调光材料层不连接。本发明的高对比度三电极电调光器件,在第二电调光材料层的同侧引入了作为“牺牲电极”的第三电调光材料层,实现了第一、第二电调光材料层的着色、褪色或保持原状态不变的控制,解决了现有三明治结构的同种材料的透射型双电调光电极器件无法褪色的问题,且可使第一、第二电调光材料层可在本征色、叠加色之间进行切换显示,丰富了可调控颜色。(Three electrode electricity light modulation device of high contrast of the invention, including the first electric light control material layer, the second electric light control material layer, third electricity light control material layer and transparent electrolyte layer, transparent electrolyte layer is fixed on the upper surface of the first electric light control material layer, second electric light control material layer and third electricity light control material layer are both secured on the upper surface of transparent electrolyte layer, and third electricity light control material layer is not connected to the second electric light control material layer.Three electrode electricity light modulation device of high contrast of the invention, in the ipsilateral third electricity light control material layer introduced as " sacrificial electrode " of the second electric light control material layer, it realizes the coloring of the first, second electric light control material layer, fade or the constant control that maintains the original state, solve the problems, such as that the double electricity light modulation electrode devices of the transmission-type of the same material of existing sandwich structure can not fade, and can make the first, second electric light control material layer that can switch over display between intrinsic color, superposition color, enrich controllable color.)

1. a kind of three electrode electricity light modulation device of high contrast, it is characterised in that: including the first electric light control material layer (1), the second electricity Light control material layer (2), third electricity light control material layer (3) and transparent electrolyte layer (4), transparent electrolyte layer, which is fixed on the first electricity, to be adjusted On the upper surface of optical material layer, the second electric light control material layer and third electricity light control material layer are both secured to the upper of transparent electrolyte layer On surface, third electricity light control material layer is not connected to the second electric light control material layer.

2. three electrode electricity light modulation device of high contrast according to claim 1, it is characterised in that: the first electricity light modulation material On the lower surface of the bed of material (1), on the upper surface of the second electric light control material layer (2), on the upper surface of third electricity light control material layer (3) It is respectively fixed with the first conductive electrode layer (5), the second conductive electrode layer (6) and third conductive electrode layer (7), the second conductive electrode Layer is not connected to third conductive electrode layer, at least one in the first conductive electrode layer and the second conductive electrode layer is electrically conducting transparent Layer；First conductive electrode layer is denoted as electrode A, and the first electric light control material layer is denoted as to electrode, and the second conductive electrode layer is denoted as Electrode B, the second electric light control material layer are denoted as working electrode, and third conductive electrode layer is denoted as electrode C, third electricity light control material layer note For sacrificial electrode.

3. three electrode electricity light modulation device of high contrast according to claim 1 or 2, it is characterised in that: described first is conductive Electrode layer (5), the second conductive electrode layer (6) and third conductive electrode layer (7) are both secured on substrate (8).

4. three electrode electricity light modulation device of high contrast according to claim 1 or 2, it is characterised in that: first electricity is adjusted Electric light control material in optical material layer (1), the second electric light control material layer (2) and third electricity light control material layer (3) is such as poly- thiophene Pheno analog derivative, polyaniline compound derivative, multi-metal polypyrrole derivative organic polymer electricity light control material, such as purple sieve essence class is derivative The small organic molecule electricity light control material of object, such as Prussian blue organometallic complex electricity light control material or inorganic transition gold Belong to oxide electricity light control material；The material of first conductive electrode layer (5) and the transparency conducting layer in the second conductive electrode layer (6) is Such as indium tin oxide ITO, Al-Doped ZnO AZO, fluorine-doped tin oxide FTO, graphene, carbon nanotube transparent conductive metal oxygen Compound；The transparent electrolyte layer (4) is using such as LiNbO₃Solid-state version, such as LiClO₄The gel-type of system, PSSNa system, Or such as dilute hydrochloric acid, dilute sulfuric acid, NaCl solution solution-type.

5. a kind of preparation method of the electrode electricity light modulation device of high contrast three described in claim 1, which is characterized in that pass through Following steps are realized:

A) buys or prepares conductive electrode layer, and the technique of such as vacuum evaporation, plating or printing is used in insulation transparent substrate Certain thickness transparent conductive material is deposited, or directly purchase obtains required lead now with the substrate of transparent conductive material Electric electrode layer；

B) deposits electric light modulation layer, and certain thickness is deposited on conductive electrode layer using such as printing, spin coating or vacuum-deposited technique The electric light control material of degree controls electric light modulation as electric light modulation layer, and by regulation film thickness, stoichiometric ratio or heat treatment Membrane structure, quality and the discoloration contrast of layer, to form satisfactory electric light modulation layer；

C) prepares three electric light control material layers, prepares first that 3 areas do not wait using the method in step a) and step b) Electric light control material layer, the second electric light control material layer and third electricity light control material layer, and first, second, third is adjusted as needed The area ratio of electric light modulation layer；

D) prepares electrolyte, and the electrolyte as transparent electrolyte layer is prepared into the thick or non-solwution method technique system of use It is standby to help solid film, it is spare；

E) bonds electric light control material layer, and the thick electrolyte prepared in step d) is existed using the technique for being such as coated with, printing It forms a film on the electric light control material layer of 3 prepared in step c), by the lesser electricity light modulation material of 2 areas when matter to be electrolysed will solidify The bed of material is bonded on the biggish electric light control material layer of area, obtains three electrode electricity light modulation devices.

6. the preparation method of three electrode electricity light modulation device of high contrast according to claim 5, it is characterised in that: step a) In substrate be such as glass, PET or PEN insulation transparent substrate, in the first conductive electrode layer and the second conductive electrode layer at least There is one for transparency conducting layer, the material of transparency conducting layer is such as indium tin oxide ITO, Al-Doped ZnO AZO or fluorine doped oxygen Change the transparent conductive metal oxide of tin FTO, the conductive oxide nitride of such as titanium nitride, graphene or carbon nanotube；Step B) heat treatment mode described in is that silicon or substrate toast, and regulation film thickness mode is that Multiple depositions electricity dims material Material；Prepared electrolyte is such as LiNbO in step d)₃Solid-state version, such as LiClO₄The gel of system, PSSNa system Type, or such as dilute hydrochloric acid, dilute sulfuric acid, NaCl solution solution-type electrolyte, using PSSNa polymer gel as electrolyte The preparation method comprises the following steps: being in mass ratio 40:10:10:40 by kayexalate PSSNa, glycerol, sorbierite, deionized water Ratio mix at normal temperature, mixed liquor after mixing, then obtained uniformly through ultrasound, deaeration technique through magnetic agitation 1 hour Colorless and transparent sticky electrolyte；It is half-dried or in sky using being dried to after electrolyte forms a film on electric light control material layer in step e) The mode that solvent flashing is placed in gas, reaches the state that electrolyte will solidify.

7. a kind of control method of the electrode electricity light modulation device of high contrast three described in claim 1, note electrode A and electrode B, Voltage between electrode A and electrode C is respectively V_AB、V_AC, which is characterized in that in the first electric light control material layer, the second electricity light modulation material When electric light control material in the bed of material and third electricity light control material layer is all made of cathodic reduction off-color material, the control of electric light modulation device Method is realized by following steps:

1) first tests the transmitance of workspace when three electrode electricity light modulation devices are in original state；

2) the electric light control material layer coloring of second, applies 1.5V voltage, i.e. V between electrode A and electrode B_AB=1.5V, so that second Electric light control material layer coloring, the first electric light control material layer fade；

3) sacrificial electrode co-pigmentation removes the V in step 2_ABVoltage keeps electrode B hanging, then the second electric light control material layer Keep the coloured state in step 2 constant, application -1.5V voltage, i.e. V between electrode A and electrode C_AC=-1.5V, so that first Electric light control material layer coloring, the second electric light control material layer keep colored state constant, and result is that working electrode region is Color reinforces display；

4) the electric light control material layer of second fades, and removes the V in step 3)_ACVoltage keeps electrode C hanging, in electrode A and electrode B Between application -1.5V voltage, i.e. V_AB=-1.5V, so that the second electric light control material layer fades, the first electric light control material layer coloring；

5) sacrificial electrode auxiliary is faded, and removes the V in step 4)_ABVoltage keeps electrode B hanging, then the second electric light control material Layer keeps the colour fading state in step 4) constant, applies 1.5V voltage, i.e. V between electrode A and electrode C_AC=1.5V, the first electricity are adjusted Optical material layer fades, the second electric light control material layer keeps bleached state constant；As a result be working electrode region be auxiliary take off Color is shown；

Electric light control material in the first electric light control material layer, the second electric light control material layer and third electricity light control material layer is all made of When anodic oxidation off-color material, the voltage applied in step 2) to step 5) takes opposite direction, and electric light modulation device can be realized Color control.

Technical field

The present invention relates to a kind of three electrode electricity light modulation devices and its preparation and control methods, more specifically, more particularly to A kind of two electric light control material layers in working region can switch over the high contrast three of display between intrinsic color, superposition color Electrode electricity light modulation device and its preparation and control method.

Background technique

It comes out so far from first electric light modulation device, people conveniently have been achieved for very big achievement, such as automotive rear-view at this Mirror, smart window, display, camouflage etc., in addition to this, in optical modulator, Electronic Paper and sensor and analysis field etc. Also have quite high researching value and good application prospect, this have benefited from its low-power consumption, low cost, high contrast, without visual angle Limitation (compared with liquid crystal display), open a way state memory effect, be easy to the advantages such as flexibility.Wherein, the research of smart window is expected to It plays a key effect in terms of energy conservation and environmental protection, therefore, it is always one of the emphasis of domestic and international researcher concern.

High contrast is the important parameter for determining smart window application prospect, and color abundant is then a pass of display device Key technology index.Currently, the research about this respect, is mostly focused on the exploitation of Novel electric light control material and transparent electrode material And optimization and the performance improvement etc. of these materials, and grinding for electricity light modulation device performance is improved from device structure design and optimization aspect It is seldom to study carefully report.Document [Kalagi S S, Mali S S, Dalavi D S, et al. Limitations of dual and complementary inorganic–organic electrochromic device for smart window application and its colorimetric analysis[J]. Synthetic Metals, 2011, 161(11- 12) WO is used in: 1105-1112.]₃Make cathode and anodic coloration layer preparation complementary type electricity light modulation device respectively with polyaniline, Middle WO₃The method of magnetron sputtering and chemical polymerization is used to prepare respectively with polyaniline, LiClO₄Carbonic allyl ester solution be electrolysed Matter, the contrast of device are 57%, much higher (WO when colouring respectively than the two off-color materials₃: 23.02%, polyaniline: 31.63%).This complementary type structure containing double coloring layer can effectively improve the contrast of device, but dim to electricity in device The type of material is restricted, i.e., two kinds of materials cannot be the identical same polarity coloured material of same or coloured state color, institute Do not have universality with this structure.Reynolds professor team deliver 2 documents [Unur E, Beaujuge P M, Ellinger S, et al. Black to transmissive switching in a pseudo three- electrode electrochromic device[J]. Chemistry of Materials, 2009, 21(21): 5145-5153.] and [Bulloch R H, Kerszulis J A, Dyer A L, et al. Mapping the broad CMY subtractive primary color gamut using a dual-active electrochromic device [J] ACS applied materials & interfaces, 2014,6 (9): 6623-6630.] in be prepared for one kind The electric light modulation device of " pseudo- three electrodes ", device architecture are that the transmissive type devices of the double electricity light modulation electrode structures of two tradition are vertically folded It places and sets, make 2 transparent conductive electrode short circuits adjacent among two devices, form " pseudo- three electrodes ".That reports in text should be " pseudo- There are two independent electricity to dim working electrode (the different off-color material of coloured state color) for three electrodes " electricity light modulation device, and two same Kind of material to electrode, altogether containing there are three types of electric light control material, may be implemented black and it is transparent between color change.Li Jun et al. Also the electric light modulation device of same structure is prepared in the patent of invention of [a kind of lamination electrochomeric glass and its application] of application. For device compared to the traditional structure of double electric light modulation layers, " pseudo- three electrodes " structure can realize the shear between more kinds of colors, The contrast of device can also be effectively improved.But device architecture is complicated, and the preparation process of each electrode material is complicated, and it is at high cost, And at least need two kinds of electric light control materials.In view of the demand of practical application, the off-color material in device will draw materials extensive, square Just, device preparation technology is simple, so the applicability of the preparation method of device in practical applications is not strong in above-mentioned document.

As previously mentioned, the contrast of device can be improved in the complementary type structure of double coloring layer, but requires to use two kinds Off-color material, and the superposition color that must satisfy 2 coloring layers positive, under backward voltage is different, wants to the collocation of 2 kinds of light control materials Ask higher；Although the lamination photo chromic glass of the device and Li Jun of " pseudo- three electrodes " structure of Reynolds team preparation et al. preparation Contrast is high, and color category is more, but the preparation process of each electrode material and device architecture are complicated, at high cost, in practical applications Applicability it is not strong.And the performances such as contrast and the simple document report of process flow are improved by optimised devices structure very It is few, so, we are prepared for novel " three electrodes " electric light modulation device, not only effectively improve the contrast of device, also solve The problems such as complex process, collocation at high cost, light control material (single off-color material can also realize dimming function) of having determined.In addition, It is somebody's turn to do the combination of " three electrodes " structure and transparent electrolyte, superposition of the also controllable a variety of off-color materials in their the intrinsic colors of difference Change between color, to keep the color change of device richer.

Summary of the invention

The present invention in order to overcome the shortcomings of the above technical problems, provides a kind of two electric light control materials in working region Layer can switch over the three electrode electricity light modulation device of high contrast and its preparation and controlling party of display between intrinsic color, superposition color Method.

Three electrode electricity light modulation device of high contrast of the invention, including the first electric light control material layer, the second electric light control material Layer, third electricity light control material layer and transparent electrolyte layer, transparent electrolyte layer are fixed on the upper surface of the first electric light control material layer On, the second electric light control material layer and third electricity light control material layer are both secured on the upper surface of transparent electrolyte layer, third electricity tune Optical material layer is not connected to the second electric light control material layer.

Three electrode electricity light modulation device of high contrast of the invention, on the lower surface of the first electric light control material layer, second The first conductive electrode layer, are respectively fixed on the upper surface of electric light control material layer, on the upper surface of third electricity light control material layer Two conductive electrode layers and third conductive electrode layer, the second conductive electrode layer are not connected to third conductive electrode layer, the first conductive electricity At least one in pole layer and the second conductive electrode layer is transparency conducting layer；First conductive electrode layer is denoted as electrode A, and first Electric light control material layer is denoted as to electrode, and the second conductive electrode layer is denoted as electrode B, and the second electric light control material layer is denoted as working electrode, Third conductive electrode layer is denoted as electrode C, and third electricity light control material layer is denoted as sacrificial electrode.

Three electrode electricity light modulation device of high contrast of the invention, first conductive electrode layer, the second conductive electrode layer and Third conductive electrode layer is both secured on substrate.

Three electrode electricity light modulation device of high contrast of the invention, the described first electric light control material layer, the second electric light control material Electric light control material in layer and third electricity light control material layer is such as polythiophene-based derivatives, polyaniline compound derivative, polypyrrole The organic polymer electricity light control material of analog derivative, the small organic molecule electricity light control material of such as purple sieve essence analog derivative, such as general Shandong The organometallic complex electricity light control material or inorganic transition metal oxide electricity light control material of scholar's indigo plant；First conductive electrode The material of transparency conducting layer in layer and the second conductive electrode layer is such as indium tin oxide ITO, Al-Doped ZnO AZO, fluorine doped The transparent conductive metal oxide of tin oxide FTO, the conductive oxide nitride of such as titanium oxide, graphene or carbon nanotube；It is described Transparent electrolyte layer uses such as LiNbO₃Solid-state version, such as LiClO₄The gel-type of system, PSSNa system, or such as dilute salt Acid, dilute sulfuric acid, NaCl solution solution-type.

The preparation method of three electrode electricity light modulation device of high contrast of the invention, which is characterized in that by following steps come It realizes:

A) buys or prepares conductive electrode layer, and the technique of such as vacuum evaporation, plating or printing is used in insulation transparent substrate Certain thickness transparent conductive material is deposited, or directly buys the existing substrate with transparent conductive material, needed for acquisition Conductive electrode layer；

B) deposits electric light modulation layer, and certain thickness is deposited on conductive electrode layer using such as printing, spin coating or vacuum-deposited technique The electric light control material of degree controls electric light modulation as electric light modulation layer, and by regulation film thickness, stoichiometric ratio or heat treatment Membrane structure, quality and the discoloration contrast of layer, to form satisfactory electric light modulation layer；

C) prepares three electric light control material layers, prepares first that 3 areas do not wait using the method in step a) and step b) Electric light control material layer, the second electric light control material layer and third electricity light control material layer, and first, second, third is adjusted as needed The area ratio of electric light modulation layer；

D) prepares electrolyte, and the electrolyte as transparent electrolyte layer is prepared into the thick or non-solwution method technique system of use It is standby to help solid film, it is spare；

E) bonds electric light control material layer, and the thick electrolyte prepared in step d) is existed using the technique for being such as coated with, printing It forms a film on the electric light control material layer of 3 prepared in step c), by the lesser electricity light modulation material of 2 areas when matter to be electrolysed will solidify The bed of material is bonded on the biggish electric light control material layer of area, obtains three electrode electricity light modulation devices.

The preparation method of three electrode electricity light modulation device of high contrast of the invention, the substrate in step a) be such as glass, At least one in PET or PEN insulation transparent substrate, the first conductive electrode layer and the second conductive electrode layer is transparency conducting layer, The material of transparency conducting layer is the electrically conducting transparent gold of such as indium tin oxide ITO, Al-Doped ZnO AZO or fluorine-doped tin oxide FTO Belong to oxide, the conductive oxide nitride of such as titanium nitride, graphene or carbon nanotube；Heat treatment side described in step b) Formula is that silicon or substrate toast, and regulation film thickness mode is Multiple depositions electricity light control material；Prepared by step d) Electrolyte is such as LiNbO₃Solid-state version, such as LiClO₄The gel-type of system, PSSNa system, or such as dilute hydrochloric acid, dilute The solution-type electrolyte of sulfuric acid, NaCl solution, using PSSNa polymer gel as electrolyte preparation method are as follows: by polyphenyl Vinyl sulfonic acid sodium PSSNa, glycerol, sorbierite, deionized water are that the ratio of 40:10:10:40 mixes at normal temperature in mass ratio, Mixed liquor after mixing, then through ultrasound, deaeration technique obtained the transparent sticky electrolysis of uniform colorless through magnetic agitation 1 hour Matter；In step e), after electrolyte forms a film on electric light control material layer, using being dried to half-dried or in air place solvent flashing Mode reaches the state that electrolyte will solidify.

The control method of three electrode electricity light modulation device of high contrast of the invention, note electrode A and electrode B, electrode A and electrode Voltage between C is respectively V_AB、V_AC, which is characterized in that in the first electric light control material layer, the second electric light control material layer and third When electric light control material in electric light control material layer is all made of cathodic reduction coloured material, the control method of electric light modulation device by with Lower step is realized:

1) first tests the transmitance of workspace when three electrode electricity light modulation devices are in original state；

2) the electric light control material layer coloring of second, applies 1.5V voltage, i.e. V between electrode A and electrode B_AB=1.5V, so that the Two electric light control material layer coloring, the first electric light control material layer fade；

3) sacrificial electrode co-pigmentation removes the V in step 2_ABVoltage keeps electrode B hanging, then the second electric light control material Layer keeps the coloured state in step 2 constant, application -1.5V voltage, i.e. V between electrode A and electrode C_AC=-1.5V, so that the One electric light control material layer coloring, the second electric light control material layer keep colored state constant, and result is that working electrode region is Display is reinforced in coloring；

4) the electric light control material layer of second fades, and removes the V in step 3)_ACVoltage keeps electrode C hanging, in electrode A and electrode Application -1.5V voltage, i.e. V between B_AB=-1.5V, so that the second electric light control material layer fades, the first electric light control material layer coloring；

5) sacrificial electrode auxiliary is faded, and removes the V in step 4)_ABVoltage keeps electrode B hanging, then the second electricity light modulation material The bed of material keeps the colour fading state in step 4) constant, applies 1.5V voltage, i.e. V between electrode A and electrode C_AC=1.5V, the first electricity Light control material layer fades, the second electric light control material layer keeps bleached state constant；It as a result be working electrode region is auxiliary It fades and shows；

Electric light control material in the first electric light control material layer, the second electric light control material layer and third electricity light control material layer is all made of When anode oxidation coloration material, the voltage applied in step 2) to step 5) takes opposite direction, and electric light modulation device can be realized Color control.

The beneficial effects of the present invention are: three electrode electricity light modulation device of high contrast of the invention, transparent by being respectively arranged at The electric light control material layer of the first of electrolyte layer two sides and the second electric light control material layer and third electricity light control material layer composition, the The ipsilateral third electricity light control material layer introduced as " sacrificial electrode " of two electric light control material layers, realizes the first, second electricity The coloring of light control material layer is faded or the constant control that maintains the original state, and solves existing Sanming City by introducing " sacrificial electrode " The double electricity of transmission-type for controlling the same material of structure dim what electrode devices can not fade, and can make the first, second electric light control material Layer can switch over display between intrinsic color, superposition color, enrich controllable color.

Three electrode electricity light modulation device of high contrast of the invention has the beneficial effect that:

1) device contrast is improved by simply improving device architecture, such as the electric light modulator of " three electrodes " structure in experiment Part introduces " sacrificial electrode " and significantly reduces the transmitance of device coloured state, can improve device colour fading state down to 2.7% Transmitance (compared to initial state), to improve device contrast.This has very well in " smart window " class electricity light modulation device field Application prospect.

2) due in existing electric light control material type abundant and this " three electrodes " structure off-color material it is non-limiting, Using transparent electrolyte, also controllable a variety of off-color materials change between the superposition color of their the intrinsic color of difference, thus very Color control is enriched to big degree, this has very high potential in the application aspect of colorful display.

3) area ratio that " sacrificial electrode " and working electrode can be adjusted according to practical application, without influencing device performance.Separately Outside, device can carry out complete colour fading under the voltage window of ± 1.5 V, and functional.These advantages further mention Its high application prospect in smart window and colored display, such as sunglasses, other passive drives such as mobile phone display screen, low-power consumption The fields such as electronic device.

2. technique and cost advantages: 1) electricity light control material type and number used in device are unrestricted, can be used one Kind or a variety of electric light control materials, 2) device architecture is simple, do not need multiple-layer stacked, 3) each layer electrode material preparation process is simple, It is at low cost.

Detailed description of the invention

Fig. 1 is the structural schematic diagram of three electrode electricity light modulation device of high contrast of the invention；

Fig. 2 is the area ratio S of sacrificial electrode and working electrode_{It sacrifices}:S_Work=1:1 uses PEDOT:PSS for electric light control material institute shape At three electrode electricity light modulation devices under the applied voltage successively applied, the transmitance of workspace with wavelength change curve；

Fig. 3 is the area ratio S of sacrificial electrode and working electrode_{It sacrifices}:S_Work=1:4 uses PEDOT:PSS for electric light control material institute shape At three electrode electricity light modulation devices under the applied voltage successively applied, the transmitance of workspace with wavelength change curve；

Fig. 4 is the device that electric light control material is PEDOT:PSS, and application voltage is V_ABWhen=1.5V, electronics and ion in device Mobile schematic diagram；

Fig. 5 is the device that electric light control material is PEDOT:PSS, removes the voltage V of 1.5V_AB, then applying voltage is V_AC=-1.5V When, the mobile schematic diagram of electronics and ion in device；

Fig. 6 is the device that electric light control material is PEDOT:PSS, removes the voltage V of -1.5V_AC, then apply voltage V_AB=-1.5V When, the mobile schematic diagram of electronics and ion in device；

Fig. 7 is the device that electric light control material is PEDOT:PSS, removes the voltage V of -1.5V_AB, then apply voltage V_AC=1.5V When, the mobile schematic diagram of electronics and ion in device.

In figure: 1 first electric light control material layer, 2 second electric light control material layers, 3 third electricity light control material layers, 4 transparent electrolysis Matter layer, 5 first conductive electrode layers, 6 second conductive electrode layers, 7 third conductive electrode layers, 8 substrates, 9 workspaces.

Specific embodiment

The invention will be further described with embodiment with reference to the accompanying drawing.

As shown in Figure 1, the structural schematic diagram of three electrode electricity light modulation device of high contrast of the invention is given, by first The electric light control material layer 2 of electric light control material layer 1, second, third electricity light control material layer 3 and transparent electrolyte layer 4 form, and the first electricity is adjusted Optical material layer 1 is fixed on the lower surface of transparent electrolyte layer 4, and the second electric light control material layer 2 and third electricity light control material layer 3 are solid Due on the upper surface of transparent electrolyte layer 4, the area of third electricity light control material layer 3 is smaller than the second electric light control material layer 2 Area, and third electricity light control material layer 3 is not connected with the second electric light control material layer 2.In the first electric light control material layer 1, second When the conductive matter of electric light control material employed in electric light control material layer 2, third electricity light control material layer 3, then it can not set Conductive electrode layer is set, if the electric light control material used does not have conduction property, the outer surface Ying Qi is respectively set first Conductive electrode layer 5, the second conductive electrode layer 6 and third conductive electrode layer 7.The second electric light control material layer 2 and corresponding thereto Region where first electric light control material layer 1, transparent electrolyte layer 4 is workspace 9.

In the case where being not provided with conductive electrode layer, the first electric light control material layer 2 of electric light control material layer 1, second, third electricity Light control material layer 3 itself is respectively formed electrode A, electrode B and electrode C, in the case where conductive electrode layer is arranged, conductive electrode layer Form electrode A, electrode B, electrode C.In this way, applying positive voltage or negative voltage between electrode A and electrode B, the first electricity can be made to adjust Optical material layer 1 and the second electric light control material layer 2 colour, fade or maintain the original state it is constant, by between electrode A and electrode C Apply positive voltage or negative voltage, the first electric light control material layer 1 can be assisted to colour or fade, realize the first electric light control material layer 1, Second electric light control material layer 2 switches over display between intrinsic color, superposition color, enriches controllable color.

Electric light control material in the first electric light control material layer 2 of electric light control material layer 1, second and third electricity light control material layer 3 Can be organic polymer electricity light control material (such as polythiophene-based derivatives, polyaniline compound derivative, multi-metal polypyrrole derivative), Small organic molecule electricity light control material (such as purple sieve essence analog derivative), organometallic complex electricity light control material (such as Prussian blue), Inorganic transition metal oxide electricity light control material etc..Wherein organic off-color material have can spin coating, spraying and silk screen print method at Film, the advantages that low in cost, contrast is high, various colors；Organometallic complex electricity light control material have can solwution method film forming, Low in cost, the advantages that contrast is high, stability is good；No electromechanical light control material have stability is good, the service life is long, it is anti-radiation, can The advantages that spatter film forming.

At least one in first conductive electrode layer 5 and the second conductive electrode layer 6 is transparent electrode, and transparent electrode material can Think the transparent conductive metal oxide or conductive nitrogen oxygen of indium tin oxide ITO, Al-Doped ZnO AZO, fluorine-doped tin oxide FTO etc. Compound (such as titanium nitride) and graphene, carbon nanotube.Transparent electrolyte layer 4 uses transparent electrolyte, common are solid State type (such as LiNbO₃), gel-type (such as LiClO₄System, PSSNa system) and solution-type (such as dilute hydrochloric acid, dilute sulfuric acid, NaCl solution Deng).Substrate is determined according to the actual situation, can not have substrate layer.

The preparation method of 1 high contrast, three electrode electricity light modulation device is given below:

A) deposition (such as vacuum evaporation, plating, printing technique) is certain thickness transparent respectively on substrate (such as glass, PET) by Electrode, or existing transparent conductive material is directly bought, such as conductive metal oxide (containing blended metal oxide) (such as ITO Deng) or conductive nitride (such as titanium nitride) and graphene, carbon nanotube etc..

B) deposits (such as printing, spin coating, vacuum deposition) certain thickness (such as micro/nano level) electricity on conductive electrode layer Light control material can pass through regulation film thickness (such as Multiple depositions), heat treatment (such as substrate heating, baking as electric light modulation layer Deng), controlled material stoichiometric ratio (oxygen flow when such as regulation vacuum deposition) regulate and control membrane structure, quality and discoloration Contrast etc..

C) prepares the first not equal electric light control material layer 1 of 3 areas, the using the method in step a) and step b) Two electric light control material layers 2 and third electricity light control material layer 3；

D) preparation of electrolyte prepares such as LiNbO₃Solid-state version, such as LiClO₄The gel-type of system, PSSNa system, Or such as dilute hydrochloric acid, dilute sulfuric acid, NaCl solution solution-type electrolyte, here with a kind of PSSNa gel-form solid polymer electrolyte For illustrate: by kayexalate (PSSNa), glycerol, sorbierite and deionized water 40:10:10:40 in mass ratio ratio Example is uniformly mixed (such as magnetic agitation 1 hour) at normal temperature, obtains the transparent sticky electricity of uniform colorless through techniques such as ultrasound, deaerations Xie Zhi.

E) is by the electrolyte prepared in d) film forming (such as coating, printing) on photochromic layer in c), be dried to it is half-dried or Solvent flashing is placed in air, by two components and third in three electrode assemblies in d) when matter to be electrolysed will solidify Electrode assembly is bonded together, and obtains the electric light modulation device of " three electrodes " structure.

The first conductive electrode layer 5, the second conductive electrode layer 6 and third conductive electrode layer 7 are denoted as electrode A, electricity respectively in Fig. 1 Pole B, electrode C, interelectrode voltage difference are denoted as V respectively_AB、V_AC、V_BC.The first electric light control material layer of electric light control material layer 1, second 2, third electricity light control material layer 3 is referred to as to electrode, working electrode, sacrificial electrode.

Electric light control material in the first electric light control material layer, the second electric light control material layer and third electricity light control material layer is equal When using cathodic reduction coloured material, the coloring control method of three electrode electricity light modulation devices is realized by following steps:

Step 1: testing transmitance when three electrode electricity light modulation devices are in initial state；

Step 2: applying voltage V_AB=1.5 V, the second electric light control material layer 2 colour, and the first electric light control material layer 1 fades；

Step 3: removing the V in second step_ABVoltage keeps electrode B hanging, then the second electric light control material layer keeps coloured state not Become, applies voltage V_AC=-1.5 V, the electric light control material layer 1 of sacrificial electrode auxiliary first colour；

Step 4: removing the V in third step_ACVoltage keeps electrode C hanging, applies voltage V_AB=-1.5 V, the second electricity light modulation material The bed of material 2 fades, and the first electric light control material layer 1 colours；

Step 5: removing the V in the 4th step_ABVoltage keeps electrode B hanging, then the second electric light control material layer 2 keeps colour fading state It is constant, apply voltage V_AC=1.5 V, the electric light control material layer 1 of sacrificial electrode auxiliary first fade.

Electric light control material in the first electric light control material layer, the second electric light control material layer and third electricity light control material layer is equal When using anode oxidation coloration material, the voltage that second step applies into the 5th step takes opposite direction, and electric light modulator can be realized Part color control.

In order to illustrate the colour fading or coloring of electricity light modulation layer each in above-mentioned steps, below with the first, second, and third electricity light modulation Material layer (referred to as electric light modulation layer) is illustrated when being PEDOT:PSS.In PEDOT:PSS film, the PEDOT:PSS of extreme portions Molecule is in oxidation state, but minimal amount of Na in film⁺Or H⁺At the PEDOT:PSS molecule for making small part (can be ignored) In reduction-state.

As application V_ABWhen the voltage of=1.5V, the chemical reaction that the first, second electric light modulation layer occurs is respectively:

PEDOT⁰+PSSNa → PEDOT⁺PSS^- +Na⁺+e^-

PEDOT⁺PSS^- +Na⁺+e^- → PEDOT⁰+PSSNa

The PEDOT:PSS of first electric light modulation layer is in oxidation state, i.e. colour fading state；The PEDOT:PSS of second electric light modulation layer is reduced For PEDOT⁰, blue is shown, coloured state is in.As shown in figure 4, giving the device that electric light control material is PEDOT:PSS, apply electricity Pressure is V_ABWhen=1.5V, the mobile schematic diagram of electronics and ion in device.

As application V_ACWhen the voltage of=- 1.5V, first, third electricity light modulation layer occur chemical reaction be respectively:

PEDOT⁺PSS^- +Na⁺+e^- → PEDOT⁰+PSSNa

PEDOT⁰+PSSNa → PEDOT⁺PSS^- +Na⁺+e^-

As shown in figure 5, giving the voltage V for removing 1.5V_AB, then applying voltage is V_ACWhen=- 1.5V, in device electronics and from The PEDOT:PSS of the mobile schematic diagram of son, the first electric light modulation layer is reduced to PEDOT⁰, blue is shown, coloured state is in；Third electricity The PEDOT:PSS of light modulation layer is in oxidation state, i.e. colour fading state；At this point, the second electric light modulation layer is still in coloured state.

As application V_ABWhen the voltage of=- 1.5V, the chemical reaction that the first, second electric light modulation layer occurs is respectively:

PEDOT⁺PSS^- +Na⁺+e^- → PEDOT⁰+PSSNa

PEDOT⁰+PSSNa → PEDOT⁺PSS^- +Na⁺+e^-

The PEDOT:PSS of first electric light modulation layer is reduced to PEDOT⁰, blue is shown, coloured state is in；Second electric light modulation layer PEDOT⁰It is oxidized to PEDOT:PSS, is in colour fading state.As shown in fig. 6, giving the voltage V for removing -1.5V_AC, then apply Voltage V_ABWhen=- 1.5V, the mobile schematic diagram of electronics and ion in device.

As application V_ACWhen the voltage of=1.5V, first, third electricity light modulation layer occur chemical reaction be respectively:

PEDOT⁰+PSSNa → PEDOT⁺PSS^- +Na⁺+e^-

PEDOT⁺PSS^- +N^a++e^- → PEDOT⁰+PSSNa

As shown in fig. 7, giving V_ACThe mobile schematic diagram of electronics and ion when=1.5V, the PEDOT of the first electric light modulation layer⁰By oxygen PEDOT:PSS is turned to, colour fading state is in；The PEDOT:PSS of third electricity light modulation layer is reduced to PEDOT⁰, blue is shown, is in Color state.At this point, the second electric light modulation layer is still in colour fading state.

As shown in Figures 2 and 3, the area ratio that sacrificial electrode and working electrode is set forth is S_{It sacrifices}:S_Work=1:1 and S_{It sacrifices}:S_WorkWhen=1:4, electric light control material using PEDOT:PSS be formed by three electrode electricity light modulation devices in successively apply outer plus Under voltage, the transmitance of workspace with wavelength change curve；Table 1 is given electric light control material and is formed using PEDOT:PSS The different three electrode electricity light modulation devices of sacrificial electrode area to the transmitance of 650nm wavelength light.

Table 1

Device	Ⅰ	Ⅱ
			Electrode area ratio	SIt sacrifices:SWork=1.00	SIt sacrifices:SWork=0.25
Tc1%(VAB=1.5 V)	12.5%	10.8%
			Tc2%(VAC=-1.5 V)	3.9%	2.7%
Tb1%(VAB=-1.5 V)	14.9%	10.7%
			Tb2%(VAC=1.5 V)	62.1%	57.4%
ΔT=Tc1% -Tc2%	8.6%	8.1%
			Optical contrast (Tb2% -Tc2%)	58.2%	54.7%

In table 1:

T_c1%: the second electric light control material layer 2 colours, and the first electric light control material layer 1 fades, and voltage is V at this time_AB=1.5 V(second Walk regulating and controlling voltage).

T_c2(i.e. sacrificial electrode assists all in coloured state for %: the second electric light control material layer 2 and the first electric light control material layer 1 Color), voltage V_AC=-1.5 V(third step regulating and controlling voltages).

T_b1%: the second electric light control material layer 2 fades, and the first electric light control material layer 1 colours, and voltage is V at this time_AB= -1.5 V (the 4th step regulating and controlling voltage).

T_b2(i.e. sacrificial electrode auxiliary takes off all in colour fading state for %: the second electric light control material layer 2 and the first electric light control material layer 1 Color), voltage V_ACThe 5th step regulating and controlling voltage of=1.5 V().

By the data in the curve and table 1 in Fig. 2 and Fig. 3 it is found that the introducing of " sacrificial electrode " significantly reduces device The transmitance of test zone (i.e. working region) coloured state, can be down to 2.7%.In addition, device workspace is taken off compared to initial state The transmission of color state is also obviously improved.Third electricity light control material layer, the second electric light control material layer area ratio be 1.00 and 0.25 In the case where, less, this explanation is dimmed the transmitance variation under device coloring or bleached state using the third electricity compared with small area Material layer, which can also meet the coloring of device and fade, to be required.From curve graph and T_c1%、T_b1%(its be respectively 10.8%, 10.7%) Value it is found that make electric light modulation layer (the second electric light control material layer 2) and ion storage (the first electricity tune with a kind of electric light control material simultaneously Optical material layer 1) to prepare the transmission-type electricity light modulation devices of double electricity light modulation electrodes of typical sandwich structure be infeasible, because Device cannot fade and (always have one layer to be in coloured state).The device of " three electrodes " structure prepared in the present invention efficiently solves This problem, and effect is obvious.In electric light modulation device of the invention, when the area of sacrificial electrode is only working electrode area 0.25 times when, still ensure that the good tinctorial property of device.

In addition, in addition to colouring single material (such as PEDOT:PSS, WO₃Deng) except, it should " three electrodes " structure and transparent electricity The combination of matter is solved, also controllable a variety of off-color materials change between the superposition color of their the intrinsic color of difference, to make device Color change it is richer.

Three electrode electricity light modulation device of high contrast of the invention has following advantages:

1. electric light modulation device of the invention, introduces " sacrificial electrode ", when the introducing of the electrode significantly reduces device coloring Transmitance, improve the contrast of device, penetrating when only being coloured with a kind of typical device of electric light control material based on the structure Rate can be down to 2.7%, and contrast is up to 58.2%.And there is no the double electricity light modulation electricity of tradition of sacrificial electrode using electric light control material of the same race The device of pole structure does not have color shear function.

2. reducing the area of " sacrificial electrode " in a certain range, the performance of device is had no effect on, when " sacrificial electrode " When area is only a quarter of working electrode area, device remains to work normally.

3. in device electric light control material using unrestricted, can for electric dimming function same material or A variety of off-color materials, existing electricity light control material includes transition metal oxide, conjugated polymer, organic micromolecule compound etc. It is applicable in, draws materials unrestricted.

4. display color is abundant, regulation flexibly, can realize multicolor displaying according to demand, non-to smart window and colour display Chang Youli.1) using single electric light control material, for visible transparent and nontransparent coloured state shear electric light control material (such as PEDOT:PSS、WO₃Deng), " transparent-coloured " that the double electricity light modulation electrode structures of same material tradition, which can be realized, cannot achieve is cut Become, and contrast is high, is highly suitable for the application such as smart window.2) using single electric light control material, in 2 kinds and the above face The material of shear between color (nontransparent), using " three electrodes " structure and transparent electrolyte layer, controllable off-color material it Change between intrinsic color (coloured state and colour fading state color) and the superposition color of intrinsic color, color control can be enriched, and uses same The devices of the double electricity light modulation electrode structures of the tradition of kind off-color material, can only be by using the nontransparent electrolyte realization intrinsic color of material Between shear.3) using two kinds (or more) electric light control material, i.e. electrolyte layer two sides are different electric light control materials, are utilized It is somebody's turn to do " three electrodes " structure and transparent electrolyte layer, superposition of the controllable off-color material in their the intrinsic colors (at least four kinds of) of difference Change between color (at least four kinds of), can largely enrich color control, and equally using the traditional of this 2 kinds of off-color materials Double electricity light modulation pole structure devices, the shear of the intrinsic color of material are only able to achieve using nontransparent electrolyte, only using transparent electrolyte The shear being able to achieve between limited superposed method color (usually 2 kinds).Therefore, " three electrodes " structure has colour display great Application potential.