CN102414610A - Electrochromic display apparatus - Google Patents

Electrochromic display apparatus Download PDF

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Publication number
CN102414610A
CN102414610A CN2010800187342A CN201080018734A CN102414610A CN 102414610 A CN102414610 A CN 102414610A CN 2010800187342 A CN2010800187342 A CN 2010800187342A CN 201080018734 A CN201080018734 A CN 201080018734A CN 102414610 A CN102414610 A CN 102414610A
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CN
China
Prior art keywords
electrochromic
display device
electrode
show
show electrode
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Pending
Application number
CN2010800187342A
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Chinese (zh)
Inventor
平野成伸
八代彻
涩谷毅
近藤浩
中村有希
安部由希子
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Ricoh Co Ltd
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Ricoh Co Ltd
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Priority claimed from JP2009112006A external-priority patent/JP5487709B2/en
Application filed by Ricoh Co Ltd filed Critical Ricoh Co Ltd
Publication of CN102414610A publication Critical patent/CN102414610A/en
Pending legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1347—Arrangement of liquid crystal layers or cells in which the final condition of one light beam is achieved by the addition of the effects of two or more layers or cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G02F1/15165—Polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F2001/164—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect the electrolyte is made of polymers

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

An electrochromic display apparatus includes a display substrate; an opposite substrate disposed opposite the display substrate; an opposite electrode disposed on the opposite substrate; a plurality of display electrodes disposed between the display substrate and the opposite electrode, the display electrodes being electrically isolated from each other; a plurality of electrochromic layers disposed on the corresponding display electrodes; and an electrolyte disposed between the display electrodes and the opposite electrode. An electric resistance between one display electrode and another display electrode is greater than an electric resistance of the one or the other display electrode. One or more display electrodes that are disposed between the display electrode closest to the display substrate and the opposite electrode are configured to be permeable to the electrolyte.

Description

Electrochromic display device
Technical field
Present invention relates in general to electrochromic display device, and the method for making and drive electrochromic display device.Particularly, the present invention relates to can the multiple color of independent displaying electrochromic display device, and the method for making and drive this electrochromic display device.
Background technology
Developed the technological Electronic Paper that can replace paper of various Electronic Paper (electronic paper) as display medium with realization.Electronic Paper is often referred to the display unit of the characteristic of simulation paper.For this reason, Electronic Paper requires and conventional display unit, for example cathode ray tube (CRT) and LCD, desired characteristic different characteristic.The ask for something of Electronic Paper comprises making uses up reflection (rather than light emission) displaying principle; High white reflecting rate; High contrast; High display resolution; Storage (image-maintenance) effect; The low voltage drive ability; Size is little and in light weight; And it is low-cost.In above-mentioned characteristic, particularly relevant with the display quality high level of those characteristic requirements, said characteristic be white reflecting rate (the white reflecting rate of expecting itself and paper is suitable) and contrast for example.
Developed the multiple principle of work of Electronic Paper.Instance comprises reflective liquid crystal type, electrophoretype and toner mobile model.Yet, use any technique known, it is very difficult that multicolor displaying is provided when keeping high white reflecting rate and high-contrast.Though through using color filter can realize multicolor displaying, the absorbing light of color filter own causes reflectivity to reduce.Further, because color filter is red (R), green (G) and blue (B) with single pixel separation, the reflectivity of display device reduces, the result, and its contrast also reduces.The reduction of white reflecting rate and/or contrast influences visibility (visibility) unfriendly, therefore makes to be difficult to display device is used as the Electronic Paper of practicality.
Another kind of electronic paper technology adopts electrochromic principle to realize reflection display device, and does not use above-mentioned color filter.Electrochromism be meant the color of compound can be based on apply the reversible redox reaction that causes by voltage the phenomenon of reversible variation.The electrochromic display device utilization demonstrates the upward appearing and subsiding of color of compound (" electrochromic compounds ") of electrochromism phenomenon.Electrochromic display device is reflexive, has memory effect, and can under low pressure operate.Owing to these reasons, the electrochromism Study on Technology is just actively carried out from the many aspects that comprise developing material and designs with exploitation, so that the possible technique that realizes useful Electronic Paper to be provided.
Yet the disadvantage of electrochromic display is because the principle of its color appearing and subsiding is based on redox reaction, so color occurs or the speed (" color appearances/disappearance " response speed) that disappears slowly.The open No.2001-510590 (patent documentation 1) of Japanese patent application has discussed through electrochromic compounds being fixed near the electrode, improves color appearance/disappearance response speed.Patent documentation 1 is pointed out, is perhaps being disappeared under the colourless situation by blueness by colourless appearance is blue, and the time that color appearance/disappearance needs was improved as about 1 second from tens of approximately seconds.Yet this improvement is not enough, and the exploitation of useful electrochromic display device needs the further improvement of color appearance/disappearance response speed.
However, still the ability of the multiple color of desired display depends on that the electrochromic display of employed electrochromic compounds structure provides the multi-color display device of usefulness.Some multi-color display devices that utilize electrochromic display are known.For example, the open No.2003-121883 (patent documentation 2) of Japanese patent application has disclosed a kind of multi-color display device, and it adopts the electrochromic layer of multiple electrochromic compounds particulate.Special, patent documentation 2 has been discussed the multi-color display device that adopts the multilayer electrochromic compounds, and this electrochromic compounds comprises macromolecular compound, and this macromolecular compound has the different a plurality of functional groups of developing voltage.
The open No.2006-106669 (patent documentation 3) of Japanese patent application has disclosed a kind of display device that can show multiple color through a plurality of electrochromic layers of formation on electrode, above-mentioned layer Show Color under different voltages with different or current value.Especially, patent documentation 3 has been discussed a kind of multi-color display device that closes or mix the display layer of multiple electrochromic compounds formation through layer that has, and said multiple electrochromic compounds the desired threshold voltage of color occurs or the quantity of electric charge is different.
The open No.2003-270671 (patent documentation 4) of Japanese patent application has disclosed a kind of multi-color display device, and it has the sandwich construction unit that comprises that transparency electrode is right, said transparency electrode between be provided with electrochromic layer and electrolyte.The open No.2004-151265 (patent documentation 5) of Japanese patent application has disclosed a kind of multi-color display device that holds with RGB three form and aspect, wherein through using the structural unit in the patent documentation 4 to form passive matrix panel and active matrix panel.
The multi-color display device of these known employing electrochromic displaies has disadvantage.In the technology of patent documentation 2 because the electrochromic compounds of stratiform shows various colors under different voltages with different, though any color all can show through the voltage that control applies, can not show multiple color simultaneously.
In the technology of patent documentation 3, though because existence can show the multiple electrochromic compounds of different colours, thereby can show multiple color simultaneously, in order optionally to show the color of wanting, need complicated voltage and current control.
The a pair of transparent electrode layer of Technology Need in the patent documentation 4 and 5 is so that one deck electrochromic layer Show Color.Therefore, when a plurality of electrochromic layers pile up, need a large amount of electrode layers, cause the reduction of reflectivity and contrast.
Summary of the invention
Shortcoming of the prior art can overcome through the present invention, and the present invention is electrochromic display device on the one hand, comprises display base plate; The relative substrate that is oppositely arranged with display base plate; Be arranged on the comparative electrode on the relative substrate; Be arranged on a plurality of show electrodes between display base plate and the comparative electrode, show electrode is separated from each other; Be arranged on a plurality of electrochromic layers on the corresponding show electrode; And be arranged on the electrolyte between show electrode and the comparative electrode.Resistance between a show electrode and another show electrode is greater than the resistance of said one or another show electrode.It is porous that the one or more show electrodes that are provided with between near the show electrode of display base plate setting and comparative electrode are configured to electrolyte.
Description of drawings
Through with reference to following instructions and combine accompanying drawing, can better understand above-mentioned advantage of the present invention and further advantage, wherein:
Fig. 1 is the xsect of the electrochromic display device of first embodiment of the invention;
Fig. 2 is the skeleton view of display base plate of the electrochromic display device of first embodiment;
Fig. 3 is the xsect of electrochromic display device of first distortion of first embodiment;
Fig. 4 is the skeleton view of electrochromic display device of second distortion of first embodiment;
Fig. 5 is the xsect of electrochromic display device of the 3rd distortion of first embodiment;
Fig. 6 A is the xsect of electrochromic display device of the 4th distortion of first embodiment;
Fig. 6 B is the skeleton view of relative substrate of the electrochromic display device of the 4th distortion;
Fig. 7 is the process flow diagram of method of making the electrochromic display device of first embodiment;
Fig. 8 is the xsect of the image display device of second embodiment of the invention;
Fig. 9 is the skeleton view of the display base plate of image display device;
Figure 10 explains the driving circuit of image display device;
Figure 11 A is the planimetric map of the electrochromic display device of embodiment 1;
Figure 11 B is the xsect along the line A-A intercepting of Figure 11 A;
Figure 11 C is the xsect along the line B-B intercepting of Figure 11 A;
Figure 12 is the figure of the resistance between electrode measurement result between first and second show electrodes of electrochromic display device of illustrative embodiment 1 and 2;
The figure that concerns between the number of times of Figure 13 pulse voltage that to be explanation apply first show electrode of the electrochromic display device of embodiment 4 and the white reflecting rate;
The figure that concerns between the number of times of Figure 14 pulse voltage that to be explanation apply second show electrode of the electrochromic display device of embodiment 4 and the white reflecting rate;
Figure 15 is the figure that the reflectance spectrum in the blue process appears in the electrochromic display device of illustrative embodiment 4;
Figure 16 is the figure that the reflectance spectrum in the green process appears in the electrochromic display device of illustrative embodiment 4;
Figure 17 is the figure that the reflectance spectrum in the process of black appears in the electrochromic display device of illustrative embodiment 4;
Figure 18 A is the planimetric map of the electrochromic display device of embodiment 5;
Figure 18 B is the xsect along the line A-A intercepting of Figure 18 A;
Figure 18 C is the xsect along the line B-B intercepting of Figure 18 A;
Figure 19 A is applied to the electrochromic display device of embodiment 5 so that this electrochromic display device shows the multiple mode of multiple color to the 19C explanation with voltage;
Figure 20 is the figure that the reflectance spectrum in the process of magenta appears in the electrochromic display device of illustrative embodiment 6; And
Figure 21 is the figure that the reflectance spectrum in the yellow process appears in the electrochromic display device of illustrative embodiment 6.
Embodiment
Multiple embodiments of the present invention is described with reference to the drawings below, and wherein identical Reference numeral is represented identical or corresponding part all the time in several views.
Embodiment 1
Fig. 1 is the xsect of the electrochromic display device 10 of embodiment of the present invention.Electrochromic display device 10 comprises display base plate 11, with the relative substrate 12 that display base plate 11 is oppositely arranged, is arranged on the comparative electrode 15 on the relative substrate 12, and chamber 19.Chamber 19 forms with relative substrate 12 through connected display base plate 11 by spacer 18.Fig. 2 is the skeleton view of electrochromic display device 10.The structure of the electrochromic display device 10 of this embodiment at first, is described.
As shown in figs. 1 and 2, electrochromic display device 10 comprises the first show electrode 13a that is formed on the display base plate 11; Be arranged on the first electrochromic layer 14a on the first show electrode 13a; Be arranged on the insulation course 22 on the first electrochromic layer 14a; Be arranged on the second show electrode 13b on the insulation course 22; And be arranged on the second electrochromic layer 14b on the second show electrode 13b.Therefore, display base plate 11 carries the multiple layer that piles up.
First show electrode 13a configuration is used for controlling the electromotive force between the first electrochromic layer 14a and the comparative electrode 15, so that the first electrochromic layer 14a Show Color.The first electrochromic layer 14a comprises the first electrochromic compounds 16a and the metal oxide 17 that carries the first electrochromic compounds 16a.The first electrochromic compounds 16a is based on the redox reaction Show Color.Metal oxide 17 is except carrying the first electrochromic compounds 16a, and also configuration is used for accelerating the speed of color appearance/disappearance.
Though shown in Fig. 1 be the molecular adsorption of single electrochromic compounds 16a on metal oxide 17, this only is the explanation to perfect condition.In fact, the structure of the first electrochromic compounds 16a does not receive special restriction, if electrochromic compounds 16a be fix and have an electrical connection, make by the oxidation of electrochromic compounds 16a interference-free with the electron exchange that reduction causes.Preferably, electrochromic compounds 16a and metal oxide 17 can be blended in the individual layer.
Insulation course 22 is set makes the first show electrode 13a and the second show electrode 13b electrical isolation.Preferably, if can guarantee the enough resistance between the first and second show electrode 13a and the 13b, insulation course 22 can be set.Resistance between the first and second show electrode 13a and the 13b can increase through the film thickness that increases the first electrochromic layer 14a.
The similar part of the second show electrode 13b and the first show electrode 13a is that its configuration is used for controlling the electromotive force between the second electrochromic layer 14b and the comparative electrode 15, so that the second electrochromic layer 14b Show Color.The second electrochromic layer 14b comprises the second electrochromic compounds 16b and the metal oxide 17 that carries the second electrochromic compounds 16b.The second electrochromic compounds 16b is configured to respond the redox reaction Show Color.Metal oxide 17 also is provided with the speed that is used for increasing color appearance/disappearance except carrying the second electrochromic compounds 16b.The second electrochromic compounds 16b and the first electrochromic compounds 16a are configured to show various colors.
Resistance between the first and second show electrode 13a and the 13b (" resistance between electrode ") needs enough height, so that the electromotive force of they and comparative electrode 15 can be controlled independently.Especially, resistance between electrode needs at least the sheet resistance greater than the first show electrode 13a or the second show electrode 13b.If resistance between electrode is less than the sheet resistance of the first show electrode 13a or the second show electrode 13b, when voltage was applied to the first or second show electrode 13a or 13b, roughly the same voltage can be applied to other show electrode.As a result, become and to make the corresponding electrochromic layer 14a of the first and second show electrode 13a and 13b and 14b shows independently or Show Color not.Preferably, resistance between electrode is 500 times of sheet resistance of each show electrode or more.
In order to obtain appropriate insulation, resistance between electrode can be controlled through the thickness that changes the first electrochromic layer 14a.Perhaps, resistance between electrode can be controlled through the thickness that change is arranged on the insulation course 22 on the first electrochromic layer 14a.
The resistance between electrode of the first and second show electrode 13a and 13b can be equivalent to the resistance between in a plurality of show electrodes one and a plurality of show electrode another.
Comparative electrode 15 configurations that are arranged on the relative substrate 12 are used for controlling the electromotive force between the first and second show electrode 13a and 13b and the comparative electrode 15, so that the first and second electrochromic layer 14a and 14b Show Color.Chamber 19 usefulness electrolyte 20 are filled.Electrolyte 20 is provided with and is used for making ion (electric charge) between the first or second show electrode 13a or 13b and comparative electrode 15, to move, so that the first or second electrochromic layer 14a or 14b Show Color.Electrolyte 20 can be carried by polymkeric substance.In this case, color appearance/disappearance zone (being pixel) can be easy to form through making polymer patternization.
White reflecting layer 21 can also be contained in chamber 19.White reflecting layer 21 can be provided with the white reflecting rate that is used for improving electrochromic display device 10.White reflecting layer 21 can form through in chamber 19, injecting the electrolyte 20 that is dispersed with the Chinese white particle.Perhaps, white reflecting layer 21 can be through forming with the resin-coated comparative electrode that is dispersed with the Chinese white particle 15.
White reflecting layer 21 can be arranged between the one deck (the for example electrochromic layer 14b among Fig. 1) and comparative electrode 15 in the multiple layer (comprising the first and second show electrode 13a and 13b, the first and second electrochromic layer 14a and 14b and insulation course 22) that is provided with near relative substrate 12.Preferably, white reflecting layer 21 can be arranged on the relative side of the side with being formed with comparative electrode 15 of relative substrate 12.
More preferably, can the first or second electrochromic layer 14a or 14b in the face of the surface of the side of display base plate 11 on form the protective seam of organic polymer materials.Like this; What can between the first or second electrochromic layer 14a or 14b and their adjacent layers separately, be improved adheres to/seals; And can improve the solvent resistance of the first or second electrochromic layer 14a or 14b, thereby improve the permanance of electrochromic display device 10.
Preferably, can between the second electrochromic layer 14b and electrolyte 20, form inorganic protective layer.Like this, can obtain antilysis property and corrosion stability that the second electrochromic layer 14b improves electrolyte 20, thereby strengthen the permanance of electrochromic display device 10.
Below, the multicolor displaying operation of electrochromic display device 10 is described.The said structure of electrochromic display device 10 easily makes multicolor displaying become possibility.That is, because the first and second show electrode 13a and 13b separate through insulation course 22, the electromotive force of the first and second show electrode 13a and 13b and comparative electrode 15 can be controlled independently.This make be arranged on the first show electrode 13a the first electrochromic layer 14a be arranged on that the second electrochromic layer 14b on the second show electrode 13b shows independently or not Show Color become possibility.
Because the first and second electrochromic layer 14a and 14b are laminated on the display base plate 11, rely on the color appearance/nonvolatile mode of the first and second electrochromic layer 14a and 14b that multicolor displaying can be provided.That is, can produce three kinds of various colors appearance/nonvolatile mode: (1) color only occurs from the first electrochromic layer 14a; (2) color only occurs from the second electrochromic layer 14b; And (3) color occurs from the first and second electrochromic layer 14a and 14b.For example, the first and second electrochromic layer 14a and 14b can be configured to show and be selected from two kinds of red, green and blue different colours, to realize multicolor displaying.
In this embodiment, be arranged on the white reflecting rate that white reflecting layer 21 in the chamber 19 provides enhancing.As a result, can be compensated, make the multicolor displaying of visibility become possibility thus with improvement because the reflectivity that the layer structure of the first and second electrochromic layer 14a and 14b causes reduces.
Further, according to this embodiment, the first and second electrochromic compounds 16a and 16b carry through metal oxide 17 separately.This structure makes the multicolor displaying of the color appearance/disappearance response speed with increase become possibility.When use had the organic compound material of low electronics (or hole) mobility in the first or second electrochromic compounds 16a and 16b, this structure was effective especially.This be because; According to this embodiment; Electronics (or hole) can be from first or second show electrode 13a or the 13b; Do not move, but move via the metal oxide 17 that has higher electronics (or hole) mobility than the first or second electrochromic compounds 16a or 16b via the first or second electrochromic compounds 16a or 16b.Thus, can cause the appearance/disappearance of color at high speed, make the multicolor displaying of color appearance/disappearance response speed become possibility with increase.
According to this embodiment, along with the electrochromic display device of the whole electrochromic display device 10 of electrolyte 20 infiltrations, each electrochromic layer 14a and 14b iunjected charge are to carry out color appearance/reaction of disappearance.This means to apply the influence that voltage and response speed can receive electrolyte 20 penetration degrees, so that according to the degree of electrolyte osmosis, color produces reaction and possibly not take place.Therefore, should make electrolyte suitably infiltration in all first and second show electrode 13a and 13b, insulation course 22, the first and second electrochromic layer 14a and 14b and white reflecting layer 21.
This can pass through accomplished in many ways.For example, a kind of method can be included in the process of making element, in electrolyte solution infiltration show electrode 13a and 13b, insulation course 22 and electrochromic layer 14a and 14b, their layers is closed.Another kind method can be included in interlayer and apply and contain electrolytical polymkeric substance.In another method, contain electrolytical polymer film etc. and can be used as insulation course 22.In another method, containing electrolytical resin can be as the bonding agent of white particle in the white reflecting layer.Thus, white reflecting layer can comprise the dispersion of white particle in containing electrolytical resin.
Perhaps, near another show electrode that is provided with between show electrode of display base plate 11 and the comparative electrode 15, i.e. the second show electrode 13b in this embodiment, it is porous to be configured to electrolyte 20.It is porous that insulation course 22 also can be configured to electrolyte 20.Dielectric substrate can be arranged between any two-layer in the first and second show electrode 13a and 13b, the first and second electrochromic layer 14a and 14b and the insulation course 22.
Therefore, according to this embodiment, a plurality of show electrodes and electrochromism are closed layer by layer, wherein single show electrode and electrochromic layer are insulated from each other.Therefore, can make the separately corresponding electrochromic layer of each show electrode, i.e. electrochromic layer between comparative electrode and this specific show electrode, demonstration or Show Color not.How Here it is can control separately that first and second electrochromic layers show or Show Color not.Yet; If (the for example second show electrode 13b) applies high voltage to a show electrode; Not only to corresponding electrochromic layer (the for example second electrochromic layer 14b) diffusion in the face of comparative electrode 15, also the opposite side (for example to the first electrochromic layer 14a) to this show electrode spreads electric charge.As a result, can cause color appearance/disappearance in the face of first electrochromic layer (the for example first electrochromic layer 14a) on the opposite side of display base plate 11 at this show electrode.
In order to prevent above-mentioned phenomenon, near one deck of display base plate 11, the first electrochromic layer 14a for example can possess the high threshold voltage that the color of making occurs or disappears in the electrochromic layer.Like this, owing to do not have electrochromic layer, the second show electrode 13b is applied high voltage can not cause aforementioned unwanted color appearance/reaction of disappearance in the face of on the opposite side of comparative electrode 15 at show electrode (the for example first show electrode 13a).
Next, the material that uses in the electrochromic display device 10 of first embodiment is described.At first, display base plate 11 and the material that is formed on the various layers on the display base plate 11 are described.The material of display base plate 11 does not receive special restriction, as long as it is transparent.Instance comprises glass and plastic foil.
The material of the first and second show electrode 13a and 13b does not receive special restriction, if its be the conduction with optically transparent.Need the visibility of these character with the color of enhancing electrochromic layer 14a and 14b demonstration.The instance of this transparent conductive material comprises inorganic material, for example the indium oxide of doped tin (" ITO "); The tin oxide of doped with fluorine (" FTO "); And the tin oxide of antimony dopant (" ATO ").Preferred examples is the electrochromic film that contains inorganic material at least a in indium oxide (" In oxide "), tin-oxide (" Sn oxide ") and the zinc oxide (" Zn oxide "), and said film forms through the vacuum film formation method.This In oxide, Sn oxide and Zn oxide can easily form film through sputter, and they also provide suitable transparency and conductivity.Wherein, InSnO, GaZnO, SnO, In 2O 3, ZnO is preferred especially.
First and second electrochromic compounds 16a among the first and second electrochromic layer 14a and the 14b and the material of 16b can comprise the material that changes based on the redox reaction Show Color.The instance of this material comprises known polymer-type, color type, metal complex type and metal oxide type electrochromic compounds.
The instance of polymer-type and color type electrochromic compounds comprises low-molecular-weight organic electrochromic compound, for example azobenzene, anthraquinone, diarylethene, dihydropyrene, styrene base class, styryl spiro-pyrans, spiral shell
Figure BDA0000103049950000091
piperazine, spiral shell thiapyran, thioindigo, tetrathiafulvalene, terephthalic acid (TPA), triphenyl methane, triphenylamine, aphthopyrans, viologen, pyrazoline, azophenlyene, phenylenediamine, fen
Figure BDA0000103049950000092
piperazine, phenothiazine, phthalocyanine, fluorane, fulgide, chromene and metallocene compound.Instance also comprises the conducting polymer compound, for example polyaniline and polythiophene.
In above-mentioned substance, the terephthalic acid compounds of the viologen compound of preferred especially following general formula (1) expression or following general formula (2) expression.
Figure BDA0000103049950000093
Because these materials have low color appearance/disappearance electromotive force, they can provide suitable colour in having the electrochromic display device of a plurality of show electrodes.
Preferably, the first and second electrochromic compounds 16a and 16b can comprise the compound of following general formula (3) expression, and wherein the heterogeneous ring compound derivant structure is between two pyridine ring alkyl cationic structurals.This material has high memory characteristic, so it helps to increase image holding time and reduces power consumption.
Figure BDA0000103049950000101
Preferably, the first and second electrochromic compounds 16a and 16b can comprise the viologen compound.Preferably, they can comprise terephthalic acid compounds.Preferably, they can comprise the wherein compound of heterogeneous ring compound derivant structure between two pyridine ring alkyl cationic structurals.Have the material of similar molecular structure through use, the first and second show electrode 13a and 13b can possess substantially the same color appearance/disappearance electromotive force, make it possible to use identical electrolyte to be easy to their color appearance/disappearance of control.
The instance of metal complex type and metal oxide type electrochromic compounds comprises the inorganic electrochromic compound, for example titanium dioxide, vanadium oxide, tungsten oxide, indium oxide, yttrium oxide, nickel oxide and Prussian blue.The material of metal oxide 17 does not receive special restriction.Instance comprises having any following metal oxide as major constituent: titanium dioxide, zinc paste, tin oxide, aluminium oxide (" alumina "), zirconia, cerium oxide, monox (" silicon dioxide "), yttria, boron oxide, magnesium oxide, strontium titanates, potassium titanate, barium titanate, calcium titanate, calcium oxide, ferrite, hafnia, tungsten oxide, iron oxide, cupric oxide, nickel oxide, cobalt oxide, baryta, strontium oxide strontia, vanadium oxide, alumina silicate, calcium phosphate and aluminosilicate.These metal oxides can use separately perhaps with two kinds in the said components or more kinds of potpourri uses.
From electricity and physical characteristics; The viewpoint of conductivity and optical property for example; Be selected from following compound through use; Can realize having the multicolor displaying of high color appearance/disappearance response speed: titanium dioxide, zinc paste, tin oxide, aluminium oxide, zirconia, iron oxide, magnesium oxide, indium oxide and tungsten oxide or their potpourri.Especially, through using titanium dioxide, can realize having the multicolor displaying of high color appearance/disappearance response speed.
The shape of metal oxide 17 does not receive special restriction.Preferably, the shape of metal oxide 17 is such, and the surface area of its per unit volume (" specific surface area ") is big, so that metal oxide 17 can carry first and second electrochromic compounds 16a and the 16b effectively.For example; Form metal oxide 17 through aggregation by nano particle; Can obtain bigger serface,, make color appearance/disappearance show that the multicolor displaying of contrast becomes possibility with improvement so that metal oxide 17 can carry electrochromic compounds effectively.
More preferably, can mix multiple particle with variable grain diameter.Existence with particle of variable grain diameter provides the gap in electrochromic layer, the electrolyte osmosis property that can be improved thus.The layer that comprises such granulate mixture with variable grain diameter can also have intensity of distortion in the anti-layer that when it is coated with, improves or the like, therefore in the manufacture process of this element, improves productive rate.
Electrochromic compounds 16a and 16b can be carried on the metal oxide 17 via the mixture layer of electrochromic compounds 16a or 16b and metal oxide 17.Yet,, preferably use electrochromic compounds 16a or 16b to be adsorbed on the structure on the metal oxide 17 via adsorption group for the color appearance/disappearance that improves in the multicolor displaying shows contrast.
The material of insulation course 22 does not receive special restriction, if its be porous and have a suitable insulation performance.Preferably, material is highly durable and has excellent filming performance.Preferably, material can comprise ZnS.ZnS provides it to form film on electrochromic layer 14a fast through sputtering at, and does not damage the advantage of electrochromic layer 14a.Contain ZnS and comprise ZnO-SiO as the instance of the material of major constituent 2, ZnS-SiC, ZnS-Si and ZnS-Ge, wherein the content of ZnS can be preferably at about 50mol% in the scope of about 90mol%, so that when forming insulation course 22, can keep suitable crystallization property.Therefore, special preferred examples is ZnS-SiO 2(8/2), ZnS-SiO 2(7/3), ZnS and ZnS-ZnO-In 2O 3-Ga 2O 3(60/23/10/7).
Through in insulation course 22, using such material as stated, can obtain the suitable insulation effect by film, and the intensity reduction (this can cause peeling off of insulation course 22) of the insulation course 22 that can prevent to cause owing to multiple-level stack.Through insulation course 22 is formed as membrana granulosa, can obtain the perforated membrane of insulation course 22.For example, when sputter ZnS,, can form the perforated membrane of ZnS through being pre-formed membrana granulosa as undercoat.In this case, though metal oxide 17 can form such membrana granulosa, comprise that the porous particle film of silicon dioxide or aluminium oxide for example can be used as the part formation of insulation course 22.Through forming insulation course 22 thus as perforated membrane, allow electrolyte 20 transmission through insulation course 22, promote migration thus in response to ion (electric charge) in the electrolyte 20 of redox reaction.Thereby, the multicolor displaying of the color appearance/disappearance response speed with improvement possibility that becomes is provided.
The film thickness of insulation course 22 can be preferably in the scope of 20nm to 500nm, more preferably in the scope of 50nm to 150nm.If film thickness, possibly can not get the insulation of needs less than above-mentioned scope.If film thickness surpasses above-mentioned scope, manufacturing cost can increase, and visibility possibly reduce owing to painted.
Below, relative substrate 12 and the material that is formed on the comparative electrode 15 on the relative substrate 12 are described.The material of substrate 12 does not receive special restriction relatively.The material of comparative electrode 15 does not receive special restriction yet, as long as it conducts electricity.When relative substrate 12 comprised glass substrate or plastic foil, the instance of the material of comparative electrode 15 comprised the nesa coating of ITO, FTO or zinc paste; The conductive metal film of zinc or platinum; And carbon.The nesa coating of this comparative electrode 15 or conductive metal film can be coated on the relative substrate 12.When the sheet metal that uses zinc etc. during as substrate 12 relatively, substrate 12 can also serve as comparative electrode 15 relatively.
When the material configuration of comparative electrode 15 is when showing the opposite reaction of the redox reaction that shows with the first electrochromic layer 14a or the second electrochromic layer 14b, can realize stable color appearance/disappearance.Especially, as the first and second electrochromic layer 14a and 14b during through the oxidation Show Color, the material of comparative electrode 15 can be configured to show reduction reaction.When the first and second electrochromic layer 14a and 14b were configured to through the reduction Show Color, the material of comparative electrode 15 can be configured to show oxidation reaction.Like this, can make the color appearance/reaction of disappearance among the first and second electrochromic layer 14a and the 14b more stable.
Below, the material of description electrolyte 20 and white reflecting layer 21.Usually, the material of electrolyte 20 comprises the support salt (supporting salt) that is dissolved in the solvent.Support the instance of salt to comprise inorganic ion salt, for example alkali metal salt and alkali salt; Quaternary ammonium salt; Acid; And alkali.Instantiation comprises LiClO 4, LiBF 4, LiAsF 6, LiPF 6, LiCF 3SO 3, LiCF 3COO, KCl, NaClO 3, NaCl, NaBF 4, NaSCN, KBF 4, Mg (ClO 4) 2And Mg (BF 4) 2The instance of solvent comprises carbonic allyl ester, acetonitrile, gamma-butyrolacton, ethylene carbonate, sulfolane, dioxolanes, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1; 2-dimethoxy-ethane, 1,2-ethoxy methoxy base ethane, polyglycol and alcohols.The material of electrolyte 20 is not limited to comprise the liquid electrolyte of the support salt that is dissolved in the solvent.Preferably, electrolyte 20 can comprise the electrolyte or the solid electrolyte of gel form, for example polymer dielectric.
The instance of the material of the Chinese white particle that contains in the white reflecting layer 21 comprises titanium dioxide, aluminium oxide, zinc paste, silicon dioxide, cesium oxide and yttria.Through in granules of pigments, mixing the particle with optical storage performance, the brightness in reflection horizon 21 can improve through outside luminous energy, makes and can implement brighter demonstration.Therefore, white reflecting layer 21 can preferably include the material with optical storage performance.White reflecting layer 21 can improve reflection contrast and visibility.As will be described with reference to the 4th distortion of first embodiment, through mixture of white granules of pigments in polymer dielectric, the function of white reflecting layer can be provided
Therefore, according to this embodiment, the electromotive force of the first and second show electrode 13a and 13b in the independent control electrochromic display device 10 is so that can make the first and second electrochromic layer 14a and 14b independently implement the color appearing and subsiding.Therefore, can provide the color that needs can be through the electrochromic display device of simple control procedure demonstration.
From closely being attached to the viewpoint of electrochromic layer 14, the organic polymer materials that is formed on the aforementioned protective seam on the first and/or second electrochromic layer 14a and the 14b can be selected from conventional resin.The instance of this resin comprises polyvinyl alcohol (PVA), poly-N-vinyl acid amides, polyester, polystyrene and polypropylene.
Distortion 1
With reference to figure 3, first distortion of embodiment 1 is described.Fig. 3 is the schematic cross-section of the electrochromic display device 10a of distortion 1.The difference of the electrochromic display device 10 of electrochromic display device 10a and embodiment 1 is that it comprises three show electrode layers and three electrochromic layers.
As shown in Figure 3, electrochromic display device 10a comprises display base plate 11a; Be formed on the first show electrode 13a on the display base plate 11a; Be arranged on the first electrochromic layer 14a on the first show electrode 13a; Be arranged on the first insulation course 22a on the first electrochromic layer 14a; Be arranged on the second show electrode 13b on the first insulation course 22a; Be arranged on the second electrochromic layer 14b on the second show electrode 13b; Be arranged on the second insulation course 22b on the second electrochromic layer 14b; Be arranged on the 3rd show electrode 13c on the second insulation course 22b; And be arranged on the 3rd electrochromic layer 14c on the 3rd show electrode 13c.
This structure of electrochromic display device 10a easily makes multicolor displaying become possibility.Because first, second is separated through the first and second insulation course 22a and 22b with the 3rd show electrode 13a, 13b and 13c each other, the electromotive force between first, second and the 3rd show electrode 13a, 13b and 13c and the comparative electrode 15 can be controlled independently.As a result, make and be separately positioned on first, second and can carry out color appearance/disappearance independently with first, second and the 3rd electrochromic layer 14a, 14b and 14c on the 3rd show electrode 13a, 13b and the 13c.Because first, second is laminated on the display base plate 11a with the 3rd electrochromic layer 14a, 14b and 14c, can realize the color appearance/disappearance of various modes, and multicolor displaying is provided thus.
For example, 1) can make first, second or the 3rd electrochromic layer 14a, 14b or 14c Show Color; 2) can make the first and second electrochromic layer 14a and 14b Show Color; 3) can make the first and the 3rd electrochromic layer 14a and 14c Show Color; 4) can make the second and the 3rd electrochromic layer 14b and 14c Show Color; And 5) can make all first, second and the 3rd electrochromic layer 14a, 14b and the equal Show Color of 14c;
Preferably, first, second can be configured to show yellow, magenta and cyan respectively with the 3rd electrochromic layer 14a, 14b and 14c.Like this, through independently controlling the electromotive force of first, second and the 3rd show electrode 13a, 13b and 13c, electrochromic display device 10a can carry out panchromatic demonstration.
Therefore, according to this distortion of embodiment 1, electrochromic display device 10a can show shades of colour through simple control operation.
Distortion 2
With reference to figure 4, second distortion of embodiment 1 is described.Fig. 4 is the perspective schematic view of the display base plate 11b of distortion 2 electrochromic display device.The electrochromic display device of distortion 2 is that with the difference of the electrochromic display device 10 of distortion 1 the second show electrode 13b has trellis with holes in planimetric map.The whole lip-deep embodiment 1 that this structure and the second show electrode 13b are formed on display base plate 11 forms contrast.
The trellis with holes of the second show electrode 13b promotes the transmission in response to electrolyte 20 intermediate ions (electric charge) of redox reaction, so that can improve the color appearance/disappearance response speed of multicolor displaying.Therefore, according to the distortion 2 of embodiment 1, electrochromic display device can be carried out multicolor displaying at a high speed based on simple control operation.
Distortion 3
Next, the 3rd distortion of embodiment 1 is described with reference to figure 5.Fig. 5 is the schematic cross-section of the electrochromic display device 10c of distortion 3.The difference of the electrochromic display device 10 of electrochromic display device 10c and embodiment 1 is not to be provided with dielectric film 22.
With reference to figure 5, according to distortion 3, in electrochromic display device 10c, the first electrochromic layer 14a that is arranged on the first show electrode 13a separates with the second show electrode 13b basically, and between them, does not place insulation course.Through controlling the resistance of the first electrochromic layer 14a, can set the resistance between electrode between the first and second show electrode 13a and the 13b for be higher than arbitrary show electrode sheet resistance.
Therefore, under the situation that insulation course 22 is not provided, the electromotive force of the first and second show electrode 13a and 13b can be controlled independently.Owing to can make the first and second electrochromic layer 14a and 14b carry out the appearance/disappearance of color independently, electrochromic display device 10c can show shades of colour through simple control operation.
Distortion 4
With reference to figure 6A and 6B, the electrochromic display device 10d of the 4th distortion of embodiment 1 is described.Fig. 6 A is the schematic cross-section of electrochromic display device 10d.Fig. 6 B is the perspective schematic view of the relative substrate 12a of electrochromic display device 10d.
The difference of the electrochromic display device 10 of electrochromic display device 10d and embodiment 1 is the form patterning of electrolyte 20a with matrix.Preferably, also patternization similarly of white reflecting layer 21.In this case, white reflecting layer 21 can be laminated on the electrolyte 20a of patterning.Perhaps, shown in Fig. 6 A, white reflecting layer 21 can mix with electrolyte 20a.
Electrolyte 20a can pass through the several different methods patterning.In an example, electrolyte 20a is patterning in the following manner: electrolyte 20a and solvent and transparent ink or white ink are mixed, use ink-jet method or silk screen print method then, use this potpourri according to predetermined pattern.This printing ink can comprise conventional UV cured printing ink or thermo-cured ink.In order to keep electrolyte 20a or solvent, can use having the material of low density structures and low cross-linking ratio.
Electrolyte 20a can comprise polymer dielectric.In this case, insulation course 22 can comprise electrolyte 20a, and this electrolyte 20a comprises polymer dielectric.Usually, a plurality of show electrodes and electrochromic layer being patterned as matrix shape causes manufacturing cost excessively to increase.The straightforward procedure of electrolyte 20a through using this embodiment is used polymer dielectric with the predetermined matrix pattern thus, can prevent the increase of this manufacturing cost.
When electrolyte 20a was patterned as the matrix shape shown in Fig. 6 A and 6B, comparative electrode 15a also can patterning, so that the voltage between electrolyte 20a and the show electrode separately can independently be controlled.
Preferably, electrolyte 20a can with the pixel electrode union patternization, single thus pixel can drive through active matrix independently, and does not make a plurality of show electrodes or a plurality of electrochromism patterned, this describes reference implementation scheme 2 after a while.
Make the method for the electrochromic display device of embodiment 1
Make the method for the electrochromic display device 10 of embodiment 1 with reference to the flow chart description of figure 7.
Form first show electrode
In step S11, for example,,, on display base plate 11, form the first show electrode 13a like vapour deposition, sputter or ion plating through the vacuum film formation technology.
Form first electrochromic layer
In step S12,, on the first show electrode 13a, form the first electrochromic layer 14a that comprises the first electrochromic compounds 16a and metal oxide particle 17 through for example spin coating or serigraphy.Special; Can be through metal oxide particle 17 being disperseed with electrochromic compounds 16a or being dissolved in the solvent; Preparation liquid coating printing ink can be administered to the first show electrode 13a through spin coating with coating printing ink then, forms the first electrochromic layer 14a thus.Perhaps, can coating printing ink be administered to display base plate 11 through serigraphy, form the first electrochromic layer 14a thus.
Be used to regulate the solvent that is coated with printing ink and can comprise various well known solvents (for example water, alcohol, cellosolve, halo carbon, ketone and ether).Can be coated with the first electrochromic layer 14a through in a collection of, using the potpourri of electrochromic compounds 16a and metal oxide particle 17.Perhaps, can on the layer of metal oxide particle 17, use electrochromic compounds 16a then, be coated with the first electrochromic layer 14a through using the dispersion liquid of metal oxide particle 17.
Form first insulation course
In the step S13 of Fig. 7, through the vacuum film formation method, for example vapour deposition, sputter and ion plating form first insulation course 22 on the first electrochromic layer 14a.
Form second show electrode and electrochromic layer
In step S14 and S15, form the second show electrode 13b and the second electrochromic layer 14b.Step S14 and S15 can be similar to step S11 and S12 carries out.
Form comparative electrode
In step S16, through the vacuum film formation method, for example vapour deposition, sputter and ion plating are forming comparative electrode 15 on the substrate 12 relatively.
Fixing base
In step S17, the relative substrate 12 that forms comparative electrode 15 on it is fixed to display base plate 11 via the electrolyte that contains the particle that is useful on white reflecting layer 21 20, formed on this display base plate 11 up to and comprise the various layers of first insulation course 22.Especially, display base plate 11 forms chamber 19 with substrate 12 is fixed to one another via spacer 18 relatively.Then, through the opening (not shown) in the chamber 19, vacuum impregnating is penetrated electrolyte solution 20 in chamber 19, and this electrolyte solution 20 contains the particle that is useful on white reflecting layer 21.Then with this opening seal.White reflecting layer 21 can be administered to through the resin dispersion with the Chinese white particle on the comparative electrode 15 and form.
Perhaps, can blended polymer electrolyte and UV cured printing ink, and this potpourri can be administered to display base plate 11 according to predetermined pattern or relatively on the substrate 12 through serigraphy or ink jet printing.Then that display base plate 11 is fixed to one another with relative substrate 12, so that their electrode faces with each other.Fill the space between the substrate with electrolyte solution then, use UV photoirradiation UV cured printing ink afterwards, thereby make the curing of UV cured printing ink and make display base plate fixed to one another with relative substrate.
Embodiment 2
With reference to figure 8 to 10, the image display device 30 of another embodiment of the invention is described.Image display device 30 comprises the electrochromic display device 10 of embodiment 1.Especially, image display device 30 comprises a plurality of electrochromic display device 10, and they electrochromic display devices 31 as the single pixel of demonstration.Electrochromic display device 31 can keep color show state or color closed condition for a long time, makes image display device 30 can keep image display status or non-image show state for a long time.
Image display device 30 can be used as reflection display device, for example Electronic Paper.
Fig. 8 is the schematic cross-section of image display device 30.Image display device 30 comprises display base plate 11 and relative substrate 12.Fig. 9 is the perspective schematic view of display base plate 11.On relative substrate 12, a plurality of comparative electrodes 15 that are used for electrochromic display device 31 separately are provided.On display base plate 11, be provided with the first show electrode 13a, the first electrochromic layer 14a, dielectric film 22, the second show electrode 13b and the second electrochromic layer 14b of the electrochromic display device 31 that is used for separately.Each electrochromic display device 31 comprises one group of first show electrode 13a, the first electrochromic layer 14a, dielectric film 22, the second show electrode 13b and the second electrochromic layer 14b.A plurality of electrochromic display devices 31 with cells arranged in matrix in the face of display base plate 11.
Image display device 30 comprises the white reflecting layer 21 in the chamber 19.White reflecting layer 21 can be injected in the chamber 19 through the electrolyte 20 that will have the Chinese white particle that is dispersed in wherein and form.Perhaps, white reflecting layer 21 can be administered on the comparative electrode 15 through the resin dispersion with the Chinese white particle and form.More preferably, as stated, polymer dielectric can form according to the pattern of matrix electrodes shape.This last method possibly be more favourable aspect manufacturing cost.
Below, the method for the electrochromic display device 31 of description driven image display device 30.Can adopt various unit or circuit, electric field is applied to the electrochromic display device 31 of image display device 30.For example, can adopt known active matrix driving circuit to drive electrochromic display device 31 according to known driven with active matrix method.Active matrix driving circuit can comprise that wherein the electrode as the thin film transistor (TFT) (TFT) of driven with active matrix element is connected to the circuit of electrochromic display device 31.The circuit of the type can the single electrochromic display device 31 of high-speed driving, therefore can make image display device 30 high speed display of high resolution images.
Next, the driving circuit of the electrochromic display device 31 that uses driven with active matrix method driven image display device 30 is described with reference to Figure 10.As shown in Figure 10, image display device 30 comprises a plurality of electrochromic display devices 31; Be connected respectively to first and second show electrode 13a of a plurality of electrochromic display devices 31 and thin film transistor (TFT) 33a and the 33b of 13b; Be provided with in the horizontal direction and be connected to the lead 34a and the 34b of the gate electrode of thin film transistor (TFT) 33a and 33b; And the lead 35a and the 35b that are provided with in vertical direction and are connected to the source electrode of thin film transistor (TFT) 33a and 33b.The drain electrode of thin film transistor (TFT) 33a is connected to the first show electrode 13a of electrochromic display device 31.The drain electrode of thin film transistor (TFT) 33b is connected to the second show electrode 13b of electrochromic display device 31.The comparative electrode 15 of electrochromic display device 31 has constant current potential, for example earthing potential.
In image display device shown in Figure 10 30; When applying voltage across one of lead 35a of one of the lead 34a of horizontal direction and vertical direction; Voltage is administered to the gate electrode of the thin film transistor (TFT) 33a that is connected with 35a with the lead 34a that selects; Thin film transistor (TFT) 33a opens thus, and the resistance between its source electrode and the drain electrode reduces.As a result, voltage is applied to the first show electrode 13a of the electrochromic display device 31 that is connected with thin film transistor (TFT) 33a.This makes first electrochromic compounds that is included in the electrochromic display device 31 show predetermined color.
Similarly, when when one of the lead of one of the lead of horizontal direction 34b and vertical direction 35b applies voltage, voltage applies across the second show electrode 13b that selects and the comparative electrode 15 of selection.This makes second electrochromic compounds that is included in the corresponding electrochromic display device 31 show predetermined color.Through these operations, can make pixel between the comparative electrode of show electrode of selecting and selection show the color that causes by first electrochromic compounds separately, the color that causes by second electrochromic compounds separately, or the color that causes by first and second electrochromic compounds.
Therefore, through between the first and/or second show electrode 13a and 13b and comparative electrode 15, optionally applying voltage, image display device 30 can show the image of needs.
Color in order in the duration that prolongs, to keep showing should not have the low resistance part between the show electrode of selecting and other show electrode or comparative electrode.That is, the show electrode of selection should be an electrical isolation with other electrode.This electrical isolation makes might prevent that electrochromic compounds from partly discharging electric charge via electrode or low resistance, and perhaps the electric charge of electrochromic compounds release injects via low resistance part or electrode.Like this, can improve the color retention time.
Preferably, when making the show electrode Show Color, can earlier color be eliminated voltage and be applied to each show electrode, can make the electrochromic layer Show Color through above-mentioned color display drive method then, each one deck.Apply color elimination voltage to show electrode and make that the electriferous state (redox reaction state) of electrochromic compounds can initialization.After this, color is occurred based on mode successively.Like this, can control the color appearance/obliteration procedure of single electrochromic layer with high repeatability.
The redox reaction state of each electrochromic layer may be controlled to the intermediateness between the state of oxidation and the reducing condition, all electrochromic particles complete oxidation all under the state of oxidation, all reduction fully of electrochromic particles under reducing condition.This intermediateness make electrochromic layer can the Show Color show state and the color closed condition between middle color.
Be applied to voltage and the product of time (promptly through controlling the injection and the emission measure of electric charge) through control, can be controlled to be the state of mediating by the electrochromic layer that this is specific corresponding to the show electrode of electrochromic layer.In this case, apply voltage and time, color in the middle of can controlling through continuous change.Perhaps, through change potential pulse apply number of times can control in the middle of color, this potential pulse has predetermined maximum voltage value and predetermined pulse width.
Therefore, according to embodiment of the present invention 2, in the face of the substrate of image display device 30, with the stack layer of cells arranged in matrix show electrode and electrochromic layer, so that image display device 30 can show various images.
The first show electrode 13a and thin film transistor (TFT) 33a and the 33b of the second show electrode 13b that are connected respectively on the display base plate 11 can be formed on the relative substrate 12, so that thin film transistor (TFT) 33a and 33b do not reduce the visibility of the color that shows through electrochromic display device 31.
Though image display device 30 is described as comprising two show electrodes and is arranged on two electrochromic layers on the show electrode that the number of show electrode and/or electrochromic layer can be three or more.
Embodiment 1
The formation of show electrode and electrochromic layer
Preparation is of a size of the glass substrate of 30mm * 30mm, forms the ITO film in the zone through the 16mm * 23mm on the upper surface that sputters at glass substrate then, and the about 100nm of thickness forms first show electrode thus.First show electrode is about 200 Ω across the sheet resistance of its electrode tip.
The glass substrate that is formed with first show electrode on it is used as the SP210 of TiOx nano particle dispersion (from Showa Titanium Co.; Ltd. buy) be coated with through spin coating; Then, form the titan oxide particles film thus at 15 minutes (min) of 120 ℃ of annealing.Afterwards, through with 2,2,3 of the viologen compound of the following general formula (4) of 5wt%, 3-tetrafluoropropanol solution and aforementioned SP210 prepare coating fluid with 2.4/4 mixed.
Figure BDA0000103049950000191
Coating fluid is administered to glass substrate through spin coating, at 120 ℃ of annealing 10min, forms first electrochromic layer that comprises titan oxide particles and electrochromic compounds thus subsequently.
Then, be formed with above that on the glass substrate of first electrochromic layer, use the ethanolic solution of 0.1 weight % poly-N-vinyl acid amides and the WS of 0.5 weight % polyvinyl alcohol (PVA), form protective seam through spin coating.Be that to form ratio of components through sputter be 8/2 ZnS-SiO subsequently 2Film form inorganic insulation layer, film thickness at 25nm to the scope of 150nm.Further, in the 10mm of the inorganic insulation layer on glass baseplate surface * 20mm zone, forming thickness through sputter is the ZnS-SiO of about 100nm 2The ITO film, form second show electrode thus.Second show electrode is about 200 Ω across its terminal sheet resistance.
Be formed with above that on the glass substrate of second show electrode, (Showa Titanium Co. Ltd.), at 120 ℃ of annealing 15min, forms the titan oxide particles film subsequently further to use SP210 as the TiOx nano particle dispersion through spin coating.
Through with 2,2,3 of the viologen compound of the following general formula (5) of 1wt% expression, 3-tetrafluoropropanol solution and SP210 prepare coating fluid with 2.4/4 mixed.
Figure BDA0000103049950000201
This coating fluid is used through spin coating, at 120 ℃ of annealing 10min, forms second electrochromic layer that contains titan oxide particles and electrochromic compounds thus subsequently, thereby accomplishes display base plate.
The formation of comparative electrode
Prepare to be of a size of the glass substrate of 30mm * 30mm independently with above-mentioned glass substrate, and on the entire upper surface of glass substrate, form the transparent conductive film of tin oxide.The acetate 2-ethoxy ethyl ester of 25wt% is joined among the CH10 (from Jujo Chemical Co., Ltd. buys) as the thermosetting electric conductive carbon printing ink preparation solution.Subsequently this solution is administered to the upper surface of glass substrate, forms the transparent conductive film of tin oxide through spin coating above that.At 120 ℃ of annealing 15min, accomplish relative substrate subsequently.
The assembling of electrochromic display device
Is that the spacer of 75 μ m is fixed to one another with display base plate and relative substrate via length, forms the chamber thus.(the Ishihara Sangyo Kaisha of the titan oxide particles with 300nm primary particle size with 35wt%; Ltd. make) be distributed in the carbonic allyl ester solution; Prepare electrolyte solution, dissolved the perchlorate chloride of 0.1M in this carbonic allyl ester solution.This electrolyte solution is put into the chamber with the mode of seal, obtains the electrochromic display device 10e shown in Figure 11.
The electrochromic display device 10e of Figure 11 A, 11B and 11C illustrative embodiment 1.Figure 11 A, 11B and 11C be respectively the planimetric map of electrochromic display device 10e, along the xsect of the line A-A intercepting of Figure 11 A with along the xsect of the line B-B intercepting of Figure 11 A.
With reference to figure 11B and 11C, electrochromic display device 10e comprises the first show electrode 13a (ITO1), the first electrochromic layer 14a (EC1), insulation course 22a, the second show electrode 13b (ITO2) and the second electrochromic layer 14b (EC2).Shown in Figure 11 A, electrochromic display device 10e has its middle level and has closed the central area of all ITO1, EC1, ITO2 and EC2 (shade is arranged).This central area with shade is called color appearance/disappearance evaluation region hereinafter, and it is used for color appearance/disappearance test, and this will be described below.
The measurement of resistance between electrode
The first and second show electrode 13a of the electrochromic display device 10e of measurement embodiment 1 and the resistance between electrode between the 13b.Figure 12 is measurement result figure.From the figure of Figure 12, can find out, be 50nm or bigger through the film thickness that makes inorganic insulation layer, obtains the good insulation properties of 100k Ω or higher (it is about 500 times across the terminal sheet resistance of show electrode).
Color appearance/disappearance test
Through under the situation of the film thickness that changes inorganic insulation layer, apply voltage to the electrochromic display device 10e of embodiment 1, carry out color and occur estimating.Voltage is 1.7V, applies 2s (second).Show electrode is connected to negative pole, and comparative electrode is connected to positive pole.
When the film thickness of inorganic insulation layer is that 50nm or bigger and resistance between electrode are 100k Ω or when higher, when voltage being applied to first or second show electrode, independently, first show electrode occurs blue or second show electrode occurs green.Further, the color that has shown can stably keep.
At the film thickness of inorganic insulation layer less than 50nm and resistance between electrode during less than 100k Ω; When first show electrode applies voltage; Though at the initial stage that color occurs; First show electrode is Show Color independently, but second show electrode begins Show Color in time gradually, thereby in case has stoped the color of stable maintenance independent displaying.
Embodiment 2
Except the formation of omitting the titan oxide particles film, the electrochromic display device (not shown) of embodiment 2 is to prepare with embodiment 1 identical mode.Resistance between electrode between first and second show electrodes of measurement electrochromic display device.Figure 12 has explained measurement result.As as can beappreciated from fig. 12, be set at 75nm or bigger through film thickness with inorganic insulation layer, obtain the good insulation properties of 100k Ω or higher (it is about 500 times across the terminal sheet resistance of show electrode).
Color appearance/disappearance test
According to embodiment 1, through under the situation of the film thickness that changes inorganic insulation layer, apply voltage to the electrochromic display device of embodiment 2, carry out color appearances/disappearance evaluation.Especially, the voltage that applies is 1.7V, and the duration is 2s.Show electrode is connected to negative pole, and comparative electrode is connected to positive pole.
When the film thickness of inorganic insulation layer is that 75nm or bigger and resistance between electrode are 100k Ω or when higher, when voltage being applied to first or second show electrode, independently, first show electrode occurs blue or second show electrode occurs green.The color of independent displaying can stably keep.
At the film thickness of inorganic insulation layer less than 75nm and resistance between electrode during less than 100k Ω; When first show electrode applies voltage; Though at the initial stage that color occurs; First show electrode is Show Color independently, but second show electrode begins to show its oneself color in time gradually, thereby in case has stoped the color of stable maintenance independent displaying.
Embodiment 3
Two electrochromic display device (not shown) of embodiment 3 with embodiment 2 in identical mode make, except the material of the inorganic insulation layer of a device comprises ZnS, the material of the inorganic insulation layer of another device comprises ZnO-ZnO-In 2O 3-Ga 2O 3(60/23/10/7), and the film thickness of inorganic insulation layer be 140nm.
Resistance between electrode between first and second show electrodes of measurement electrochromic display device.As a result, in two electrochromic display device, all obtain the good insulation properties of about 10M Ω.
Embodiment 4
With with embodiment 1 in identical mode make the electrochromic display device (not shown), except show electrode and electrochromic layer through the following steps manufacturing.
The manufacturing of electrochromic display device
Preparation is of a size of the glass substrate of 30mm * 30mm.Form the ITO film in the zone through the 16mm * 23mm on the upper surface that sputters at glass substrate, the about 100nm of thickness forms first show electrode thus.First show electrode is about 200 Ω across its terminal sheet resistance.
The glass substrate that is formed with first show electrode on it is used as the SP210 of TiOx nano particle dispersion, and (Showa Titanium Co. Ltd.) is coated with through spin coating, then at 120 ℃ of annealing 15min, forms the titan oxide particles film thus.This glass substrate further is coated with through spin coating with coating fluid.This coating fluid comprise 1wt% general formula (5) expression the viologen compound 2,2,3,3-tetrafluoropropanol solution.After this, at 120 ℃ of 10min that anneal, form first electrochromic layer that contains titan oxide particles and electrochromic compounds.
Be formed with above that on the glass substrate of first electrochromic layer, form the ZnS-SiO of film thickness 140nm through sputter 2The film of (ratio of components 8/2) forms inorganic insulation layer thus.Further, on glass baseplate surface, form the ITO film through sputter in the zone of 10mm * 20mm, the about 100nm of thickness, thus form second show electrode.Second show electrode is approximately 200 Ω across its terminal sheet resistance.
On it, be formed with the glass substrate of second show electrode, (Showa Titanium Co. Ltd.), subsequently at 120 ℃ of 15min that anneal, thereby forms the titan oxide particles film further to use SP210 as the TiOx nano particle dispersion through spin coating.This glass substrate further is coated with through spin coating with coating fluid, this coating fluid comprise 1wt% general formula (4) expression the viologen compound 2,2,3,3-tetrafluoropropanol solution.Subsequently,, form second electrochromic layer that contains titan oxide particles and electrochromic compounds thus, accomplish display base plate at 120 ℃ of 10min that anneal.After this, the similar step of step that enforcement and reference implementation example 2 are described obtains electrochromic display device.
The measurement of resistance between electrode
Resistance between electrode between first and second show electrodes of electrochromic display device is about 10M Ω, expression good insulation performance property.
Color appearance/disappearance test
With with embodiment 2 in identical mode the electrochromic display device of embodiment 4 is carried out color appearance/disappearance evaluation.Color appearance/disappearance evaluation comprises uses Otsuka Electronics Co., and the LCD-5000 spectrophotometer that Ltd. makes shines with scattered light.Apply for voltage, use FG-02 function generator (Toho Giken).The voltage that applies is 2.55V, and the duration that applies be 100ms, when applying a plurality of pulse, the recurrent interval is 10ms.
The electrochromic display device of embodiment 4 demonstrates about 50% high white reflecting rate not applying appearance white under the voltage condition.When first show electrode was connected to negative pole and comparative electrode and is connected to positive pole, electrochromic display device occurred green when applying pulse voltage.When second show electrode was connected to negative pole and comparative electrode and is connected to positive pole, electrochromic display device occurred blue when applying pulse voltage.Further, when first and second show electrodes were connected to negative pole and comparative electrode and are connected to positive pole, black appearred in electrochromic display device 10i when applying pulse voltage.
Figure 13 is the figure that concerns between number of times and the white reflecting rate of explanation pulse voltage that first show electrode is applied.Figure 14 is the figure that concerns between number of times and the white reflecting rate of explanation pulse voltage that second show electrode is applied.Figure 15 is the figure of the reflectance spectrum of explanation in blue process occurring.Figure 16 is the figure of the reflectance spectrum of explanation in green process occurring.Figure 17 is the figure of the reflectance spectrum of explanation in the process of black occurring.
Like what find out from Figure 13 and 14, when pulse voltage was applied to first show electrode and pulse voltage and is applied to second show electrode, along with pulse applies the increase of number of times, the white reflecting rate reduced continuously.That is, along with pulse applies the increase of number of times, color shows continuous deepening, the possibility of color in the middle of expression shows.
Applying between first show electrode and the comparative electrode under the situation of pulse voltage, Figure 15 has shown that the wavelength of reflectivity about 440nm increases, and expression occurs blue.Applying between second show electrode and the comparative electrode under the situation of pulse voltage, Figure 16 has shown that the wavelength of reflectivity about 490nm increases, and expression occurs green.Applying between first and second show electrodes and the comparative electrode under the situation of pulse voltage, Figure 17 has shown that reflectivity compares overall reduction with Figure 15 with 16, and black appears in expression.
Therefore, apply, can easily carry out multicolor displaying through selecting first show electrode or second show electrode to be used for voltage.Through the number of times that the control potential pulse applies, color in the middle of can showing.
Embodiment 5
Figure 18 A to the electrochromic display device 10j shown in the 18C with embodiment 1 in identical mode make, except it comprises three show electrode layers and three electrochromic layers.
The formation of show electrode and electrochromic layer
Preparation is of a size of the glass substrate of 30mm * 30mm, and forms the ITO film through sputter in the zone of the 16mm * 23mm on the upper surface of glass substrate, and thickness is about 100nm, forms first show electrode thus.First show electrode is about 200 Ω across its terminal sheet resistance.
Be formed with above that on the glass substrate of first show electrode, use SP210 (Showa Titanium Co., Ltd. system), then, form the titan oxide particles film at 120 ℃ of annealing 15min as the TiOx nano particle dispersion through spin coating.After this, this glass substrate further is coated with through spin coating with coating fluid, this coating fluid comprise 1wt% general formula (5) expression the viologen compound 2,2,3,3-tetrafluoropropanol solution.At 120 ℃ of 10min that anneal, form first electrochromic layer that contains titan oxide particles and electrochromic compounds then.
The glass substrate that is formed with first electrochromic layer on it further is coated with through spin coating with the ethanolic solution of 0.1wt% poly N-vinyl acid amides and the WS of 0.5wt% polyvinyl alcohol (PVA), to form protective seam.After this, the ratio of components that forms film thickness 140nm through sputter is 8/2 ZnS-SiO 2Film, thus inorganic insulation layer formed.Further, be formed with ZnS-SiO above that 2In the zone of 10mm * 20mm, form the ITO film through sputter on the surface of the glass substrate of inorganic insulation layer, the about 100nm of thickness forms second show electrode thus.Second show electrode is about 200 Ω across its terminal sheet resistance.
The glass substrate that is formed with second show electrode on it further is used as the SP210 of TiOx nano particle dispersion (Showa Titanium Co., Ltd. system) and is coated with through spin coating, then at 120 ℃ of annealing 15min, forms the titan oxide particles film.After this, this glass substrate is coated with through spin coating with coating fluid, this coating fluid comprise 1wt% general formula (5) expression the viologen compound 2,2,3, the mixing ratio of 3-tetrafluoropropanol solution and SP210 is 2.4/4 potpourri.After this, at 120 ℃ of annealing 10min, form second electrochromic layer that contains titan oxide particles and electrochromic compounds.
The glass substrate that is formed with first electrochromic layer on it is coated with through spin coating with the ethanolic solution of 0.1wt% poly N-vinyl acid amides and the WS of 0.5wt% polyvinyl alcohol (PVA), forms protective seam.After this, the ratio of components that forms film thickness 140nm through sputter is 8/2 ZnS-SiO 2Film, thereby form inorganic insulation layer.Further, be formed with ZnS-SiO above that 2In the zone of 10mm * 20mm, form the ITO film on the surface of the glass substrate of inorganic insulation layer through sputter, the about 100nm of thickness, thus form the 3rd show electrode.The 3rd show electrode is approximately 200 Ω across its terminal sheet resistance.
The glass substrate that is formed with the 3rd show electrode on it further is used as the SP210 of TiOx nano particle dispersion (Showa Titanium Co.; Ltd. make) be coated with through spin coating; Then, form the 3rd electrochromic layer that comprises titan oxide particles thus at 120 ℃ of annealing 15min.The glass substrate that is formed with the 3rd electrochromic layer on it further is coated with through spin coating with the ethanolic solution of 0.1wt% poly N-vinyl acid amides and the WS of 0.5wt% polyvinyl alcohol (PVA), thereby forms protective seam.After this, the ratio of components that forms film thickness 35nm through sputter is 8/2 ZnS-SiO 2Film, thereby form inorganic insulation layer.
The electrochromic display device 10j of Figure 18 A, 18B and 18C illustrative embodiment 5.Figure 18 A, 18B and 18C are respectively the planimetric map of electrochromic display device 10j, the xsect of Figure 18 A A-A intercepting along the line and the xsect of B-B intercepting along the line
Shown in Figure 18 B and 18C, electrochromic display device 10j comprises the first show electrode 13a (ITO1), the first electrochromic layer 14a (EC1), the first insulation course 22a, the second show electrode 13b (ITO2), the second electrochromic layer 14b (EC2), the second insulation course 22b, the 3rd show electrode 13c (ITO3) and the 3rd electrochromic layer 14c (EC3).Shown in Figure 18 A, electrochromic display device 10j has its middle level and has closed the central area of all ITO1, EC1, ITO2, EC2, ITO3 and EC3 (shade is arranged).This central area with shade is called the color appearance/disappearance evaluation region that wherein carries out color appearance/disappearance test, and this will be described later.
The measurement of resistance between electrode
Resistance between electrode between first and second show electrodes of electrochromic display device 10j is about 10M Ω, and the resistance between electrode between the second and the 3rd show electrode is about 0.5M Ω.
Color appearance/disappearance test
The electrochromic display device 10j of embodiment 5 is carried out color occur estimating, it comprises and applies voltage 2s, so that between show electrode and comparative electrode, demonstrate like Figure 19 A to the electric potential difference shown in the 19C.
Especially, under the situation of Figure 19 A, apply voltage, make ITO1/EC1 have the electromotive force of 0V, and comparative electrode has the electromotive force of 1.5V, and ITO2/EC2 and ITO3/EC3 are not applied voltage.Under the situation of Figure 19 B, apply voltage, make ITO2/EC2 have the electromotive force of 0V, and comparative electrode has the electromotive force of 1.5V, and ITO1/EC1 and ITO3/EC3 are not applied voltage.Under the situation of Figure 19 C, apply voltage, make ITO3/EC3 have the electromotive force of 0V, and comparative electrode has the electromotive force of 1.5V, and ITO1/EC1 and ITO2/EC2 are not applied voltage.
As a result, in Figure 19 A, has only the regional Show Color of ITO1/EC1.Under the situation of Figure 19 B, has only the regional Show Color of ITO2/EC2.Under the situation of Figure 19 C, has only the regional Show Color of ITO3/EC3.Therefore, can make first, second and the 3rd show electrode Show Color independently.
Embodiment 6
The electrochromic display device (not shown) with embodiment 1 in identical mode make; Contain through use except first electrochromic layer 4wt% general formula (6) expression terephthalic acid compounds and 20wt% AMT100 titan oxide particles (Tayca Corporation) 2; 2; 3,3-tetrafluoropropanol solution forms.With another difference of embodiment 1 be general formula (7) expression that contains 4wt% through use of second electrochromic layer terephthalic acid compounds and 20wt% AMT100 2,2,3, the formation of 3-tetrafluoropropanol solution.
Electrochromic display device 10k and embodiment 1 further difference are; 35wt% titan oxide particles (the Ishihara Sangyo Kaisha that will have the 300nm primary particle size; Ltd. make) be dispersed in the electrolyte solution of dimethyl sulfoxide, in the electrolyte solution of this dimethyl sulfoxide, dissolved the 0.1M TBAP.
Resistance between electrode between first and second show electrodes of electrochromic display device 10k is about 10M Ω, expression good insulation performance property.
Color appearance/disappearance test
The electrochromic display device of embodiment 6 is carried out color appearance/disappearance evaluation.Color appearance/disappearance evaluation comprises that (Otsuka Electronics Co. Ltd.) penetrates electrochromic display device 10k with light scattering to use LCD-5000 spectrophotometer.Apply for voltage, use FG-02 function generator (Toho Giken), the pulse 100ms of 4.5V is provided, when applying a plurality of pulse, the recurrent interval is 10ms.
Electrochromic display device is represented about 45% high white reflecting rate not applying appearance white under the voltage condition.When the first show electrode 13a was connected to negative pole and comparative electrode 12 and is connected to positive pole, magenta appearred when applying pulse voltage.When the second show electrode 13b is connected to negative pole and comparative electrode 12 and is connected to positive pole, occur yellow when applying pulse voltage.When the first and second show electrode 13a and 13b are connected to negative pole and comparative electrode 12 and are connected to positive pole, occur red when applying pulse voltage.
Figure 20 is the figure of the reflectance spectrum of explanation when magenta occurring.Figure 21 is the figure of the reflectance spectrum of explanation when yellow occurring.Put in pulse voltage under the situation of the Figure 20 between the first show electrode 13a and the comparative electrode 12, reflectivity increases with 600nm or bigger wavelength about 420nm, and magenta appears in expression.Put in pulse voltage under the situation of the Figure 21 between the second show electrode 13b and the comparative electrode 12, reflectivity increases in the wavelength of 500nm to about the 600nm, and expression occurs yellow.
Therefore, apply, can easily realize multicolor displaying through selecting the first show electrode 13a or the second show electrode 13b to be used for voltage.Through the number of times that the control potential pulse applies, color in the middle of can showing.
Embodiment 7
The electrochromic display device (not shown) with embodiment 4 in identical mode make, different except making comparative electrode with the condition of assembling electrochromic display device.
The formation of comparative electrode
Prepare to be of a size of the glass substrate of 30mm * 30mm independently with the substrate that is formed with show electrode on it, and on the entire upper surface of glass substrate, form the transparent conductive film of tin oxide.The upper surface that is formed with the glass substrate of transparent conductive film on it is further used 2 of 20wt%; 2; 3,3-tetrafluoropropanol dispersion liquid is coated with through spin coating, the about 2 μ m of thickness; Dispersion liquid contains the granules of stannic oxide (Mitsubishi Materials Corporation) of dissolving, and this granules of stannic oxide has the primary particle size of 30nm.After this, at 120 ℃ of 15min that anneal, form comparative electrode thus.
The manufacturing of electrochromic display device
Through mix PTC10 UV cured printing ink (Jujo Chemical Co. with 10/1/2/2 weight ratio; Ltd.), perchlorate chloride, carbonic allyl ester and titan oxide particles (Ishihara Sangyo Kaisha; Ltd.); Preparation electrolyte white ink, this titan oxide particles has the primary particle size of 300nm.
Subsequently, the electrolyte white ink is administered to as stated the comparative electrode made from following pattern: the point of diameter 1mm, the about 5 μ m of thickness is that the mode of 2.5mm is arranged with the spacing of center to center.
Then, display base plate is placed on the relative substrate, make show electrode and the electrochromic layer of display base plate and the coating of the electrolyte white ink on the substrate is relative relatively.After placing 10min, carry out the ultraviolet ray irradiation, with the solidified electrolyte white ink, thereby display base plate is fixed on the relative substrate.
The measurement of resistance between show electrode
Resistance between electrode between first and second show electrodes of measurement electrochromic display device.Resistance is about 10M Ω, expression good insulation performance property.
Color appearance/disappearance test
Electrochromic display device through to embodiment 7 applies voltage, carries out color and occurs estimating.The voltage that applies is 2.5V, and the duration that applies is 2s.Show electrode is connected to negative pole, and comparative electrode is connected to positive pole.
As a result, it is blue and green that first show electrode and second show electrode can be distinguished demonstration independently.Can also only make the electrolyte white ink part Show Color of patterning.
Embodiment 8
Electrochromic display device with embodiment 1 in identical mode make; Substitute the viologen compound of general formula (4) expression except viologen compound with general formula (8) expression; In the viologen compound of general formula (8) expression, the heterogeneous ring compound furan structure is incorporated between the pyridine ring alkyl cationic structural.
Figure BDA0000103049950000281
Another difference is the viologen compound that substitutes general formula (5) expression with the viologen compound of general formula (9) expression, and in the viologen compound of general formula (9) expression, heterogeneous ring compound thiophene structure is incorporated between the pyridine ring alkyl cationic structural.
Figure BDA0000103049950000282
When voltage was applied to the show electrode of electrochromic display device, first and second show electrodes can be distinguished and show magenta and yellow independently.Further, the maintenance that color of independent displaying can be stable.
Comparative example 1
The electrochromic display device of comparative example 1 with embodiment 4 in identical mode make, except not forming insulation course.
Resistance between electrode between first and second show electrodes of measurement electrochromic display device.Measure the resistance that shows about 200 Ω, the insulativity of expression difference.
The electrochromic display device of comparative example 1 also with embodiment 4 in identical mode carry out color appearance/disappearance.When second show electrode is connected to negative pole and comparative electrode and is connected to positive pole; When applying pulse voltage; Black appears in electrochromic display device, and expression is shown blueness independently and shown green failure independently by second electrochromic layer by first electrochromic layer.
Though describe the present invention in detail, in scope of the present invention and spirit that claim is subsequently described and defined, have distortion and remodeling with reference to specific embodiment.
The Japan that the present invention is based on submission on May 1st, 2009 is at first to file No.2009-112006, and its full content is incorporated the present invention by reference into.

Claims (14)

1. electrochromic display device, it comprises:
Display base plate;
The relative substrate that is oppositely arranged with display base plate;
Be arranged on the comparative electrode on the relative substrate;
Be arranged on a plurality of show electrodes between display base plate and the comparative electrode, show electrode is separated from each other;
Be arranged on a plurality of electrochromic layers on the corresponding show electrode; With
Be arranged on the electrolyte between show electrode and the comparative electrode,
Resistance between one of them show electrode and another show electrode is greater than the resistance of said one or said another show electrode, and
Be arranged on wherein that to be configured to said electrolyte near the show electrode of display base plate and the one or more show electrodes between the comparative electrode porous.
2. electrochromic display device according to claim 1, wherein electrochromic layer comprises electrochromic compounds and metal oxide particle.
3. electrochromic display device according to claim 1 further comprises the reflection horizon, and this reflection horizon is arranged near between the electrochromic layer of relative substrate and the comparative electrode or be arranged on the side relative with comparative electrode of relative substrate.
4. electrochromic display device according to claim 1, wherein electrolyte is with the matrix form patterning.
5. electrochromic display device according to claim 1 further comprises the insulation course between the show electrode, so that show electrode insulate each other.
6. electrochromic display device according to claim 1, the one deck that wherein in each electrochromic layer Show Color is had high threshold voltage is corresponding near the show electrode setting of display base plate.
7. electrochromic display device according to claim 1, the one deck that wherein in each electrochromic layer Show Color is not had high threshold voltage is corresponding near the show electrode setting of display base plate.
8. electrochromic display device according to claim 1, the electrochromic layer that wherein is arranged on the corresponding show electrode is configured to show various colors.
9. electrochromic display device according to claim 1, wherein the one deck at least in the electrochromic layer comprises the viologen compound of general formula (1) expression:
Figure FDA0000103049940000021
Wherein R1, R2 and R3 are that carbon number is 1,2,3 or 4 alkyl or aryl, and said alkyl or aryl can comprise substituting group independently, wherein are selected from COOH, PO (OH) one of among R1 and the R2 2And Si (OC kH 2k+1) 3X is a univalent anion; N is 0,1 or 2; M is 0,1,2,3 or 4; And k is 0,1 or 2.
10. electrochromic display device according to claim 1, wherein the one deck at least in the electrochromic layer comprises the terephthalic acid compounds of general formula (2) expression:
Figure FDA0000103049940000022
Wherein R4, R5 and R6 are that carbon number is 1,2,3 or 4 alkyl, carbon alkoxy or aryl, wherein are selected from COOH, PO (OH) one of among R4 and the R5 2And Si (OC kH 2k+1) 3Q is 1 or 2; P is 0,1,2,3 or 4; And k is 0,1 or 2.
11. electrochromic display device according to claim 1, wherein the one deck at least in the electrochromic layer comprises the wherein compound of general formula (3) expression of heterogeneous ring compound derivant structure between two pyridine ring alkyl cationic structurals:
Figure FDA0000103049940000023
Wherein R1, R2 and R3 are that carbon number is 1,2,3 or 4 alkyl or aryl, and said alkyl or aryl can comprise substituting group independently, wherein are selected from COOH, PO (OH) one of among R1 and the R2 2And Si (OC kH 2k+1) 3X is a univalent anion; N is 0,1 or 2; M is 0,1 or 2; K is 0,1 or 2; And A is the heterogeneous ring compound derivant.
12. electrochromic display device according to claim 9, wherein all electrochromic layers include the viologen compound of general formula (1) expression:
Wherein R1, R2 and R3 are that carbon number is 1,2,3 or 4 alkyl or aryl, and said alkyl or aryl can comprise substituting group independently, wherein are selected from COOH, PO (OH) one of among R1 and the R2 2And Si (OC kH 2k+1) 3X is a univalent anion; N is 0,1 or 2; M is 0,1,2,3 or 4; And k is 0,1 or 2.
13. electrochromic display device according to claim 10, wherein all electrochromic layers include the terephthalic acid compounds of general formula (2) expression:
Figure FDA0000103049940000032
Wherein R4, R5 and R6 are that carbon number is 1,2,3 or 4 alkyl, carbon alkoxy or aryl, wherein are selected from COOH, PO (OH) one of among R4 and the R5 2And Si (OC kH 2k+1) 3Q is 1 or 2; P is 0,1,2,3 or 4; And k is 0,1 or 2.
14. electrochromic display device according to claim 11, wherein all electrochromic layers include the wherein compound of general formula (3) expression of heterogeneous ring compound derivant structure between two pyridine ring alkyl cationic structurals:
Figure FDA0000103049940000033
Wherein R1, R2 and R3 are that carbon number is 1,2,3 or 4 alkyl or aryl, and said alkyl or aryl can comprise substituting group independently, wherein are selected from COOH, PO (OH) one of among R1 and the R2 2And Si (OC kH 2k+1) 3X is a univalent anion; N is 0,1 or 2; M is 0,1 or 2; K is 0,1 or 2; And A is the heterogeneous ring compound derivant.
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