CN103201676B - Display device - Google Patents
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- CN103201676B CN103201676B CN201180047280.6A CN201180047280A CN103201676B CN 103201676 B CN103201676 B CN 103201676B CN 201180047280 A CN201180047280 A CN 201180047280A CN 103201676 B CN103201676 B CN 103201676B
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Classifications
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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
- G02F1/1514—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
- G02F1/153—Constructional details
- G02F1/155—Electrodes
- G02F2001/1552—Inner electrode, e.g. the electrochromic layer being sandwiched between the inner electrode and the support substrate
-
- 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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Abstract
Disclosed herein is a kind of electrochromic passive-matrix display (100), the most each passive addressed pixel cell (111,112,113) includes the electrolyte (113) being connected by the polymer (121) of electrochromism and electro-chemical activity with layer (122) ion of conductive carbon.Thus, each pixel has the significant threshold voltage that be enough to reduce the crosstalk in electrochromic display device (ECD).
Description
Invention field
The present invention relates to electro-chemical activity organic pixel device, and particularly relate to printable based on Organic Electricity mutagens
The electro-chemical activity pixel arrangement of color material.
Background technology
In direct addressin electrochromic display device (ECD), each pixel passes through the externally connected driving voltage of single conductor wire
Independent electric control while all pixels in source, beneficially display.When in display, the number of pixel is big, to each pixel
Connect a single line or the most impossible or unpractical.For overcoming this problem, generally pixel is pacified
It is set to matrix structure, wherein they is addressed via row and column from matrix edge by time multiplex technique.By this aobvious
Show device and the method for they addressing is called matrix display and matrix addressing.
In Active Matrix Display, each pixel equipped with the respective electronic circuit with at least one transistor,
The conduction state of the most each transistor controls the color state of respective pixel.
The matrix display not having the single transistor of each pixel is referred to as passive matrix display.Show at active matrix
Show that the image element circuit in device improves the addressability of pixel, but, compare with passive matrix display, Active Matrix Display
Manufacture more complicated and expensive.On the other hand, several shortcomings are the slowest response time, image blurring and crosstalk limit passive
The actual application of matrix addressing electrochromic device.Image blurring can classify as crosstalk effect in a broad sense.It is picture
The phenomenon interacted by electrolyte between element, and cause the slight coloration of neighbor on the row and column selected.This not
Suitable coloring increases along with the distance with selected pixel and weakens.The conventional technology minimizing image blurring effect is independent
Display pixel physically isolated from one another.
Another source of crosstalk is the interaction between pixel via the electrode being connected with matrix.I.e., not only in institute
The pixel of the intersection of a pair columns and rows of addressing changes its color, and other adjacent pixels also change its color.String
The reason disturbing generation is, crosses over and there is also voltage difference around the electrolyte in the pixel around the pixel addressed.Additionally, with
The most charged pixel ratio emptied relatively, cross over its electrode and be generally of different voltage by the coloured display pixel of electric isolution.When by two
When individual pixel is charged as different color state and links together, the pixel of coloring trends towards being discharged by electric capacity and driving
Or the pixel that coloring empties.
WO 2004/114008 describes an example of electrochromic passive-matrix display.Pixel comprises and is clipped in two
Electrolyte between individual organic layer, each organic layer comprises electrochromic polymeric compounds.Additionally, this pixel be clipped in two electrodes it
Between.And, passive matrix display is formed by the layer with diode characteristic between and organic layer in electrode.Change
Yan Zhi, before pixel can change its color, it is necessary to exceed threshold voltage.Therefore, in display, the amount of crosstalk reduces.Except
Introducing has outside the layer of diode function within the pixel, and this application also proposes to be obtained by the combination that pixel materials is careful
Can passive addressed pixel, but about should how to select these materials with obtain this effect entirely without providing any information
Or example.
Summary of the invention
The purpose of the present invention is to propose to a kind of combination of materials, described combination of materials provides one to need not within the pixel individually
Diode layer can passive addressed pixel.
These and other purposes are achieved by the theme provided in the independent claim.Give in the independent claim
The preferred embodiments of the invention are gone out.
According to its first aspect, the present invention relates to a kind of passive matrix display device, described display device includes:
One group of pixel cell being arranged as matrix,
The most each pixel cell includes:
First pixel layer, described first pixel layer is included between the most perceptible different color state can electrification
Learn electrochromism and the organic polymer material of electro-chemical activity of conversion,
Second pixel layer, described second pixel layer in the face of described first pixel layer, and
3rd pixel layer of electrolyte of solidification, described 3rd pixel layer be spatially placed in described first pixel layer with
Between described second pixel layer, and with described first pixel layer and described second pixel layer contacted with ions, and
Described second pixel layer of the most each pixel cell is arranged as conductive carbon.
According to its second aspect, the present invention relates to a kind of passive matrix display device, described display device includes:
One group of pixel cell being arranged as matrix,
The most each pixel cell includes:
First pixel layer, described first pixel layer is included between the most perceptible different color state can electrification
Learn electrochromism and the organic polymer material of electro-chemical activity of conversion,
Second pixel layer, described second pixel layer in the face of described first pixel layer, and
3rd pixel layer of electrolyte of solidification, described 3rd pixel layer be spatially placed in described first pixel layer with
Between described second pixel layer, and with described first pixel layer and described second pixel layer contacted with ions, and
Described second pixel layer of the most each pixel cell is arranged as conductive carbon, thus it is described to provide at least response to cross over
The threshold voltage of the voltage that electrolyte applies.
The color of each pixel is by described electrochromism and the redox state of the organic polymer material of electro-chemical activity
On change provide.In other words, electrolyte usually not coloring agent such as pH dyestuff, i.e. response environment pH changes the dyestuff of color.
The most in other words, in the color conversion processes of pixel, the color of electrolyte generally remains constant or substantially constant.
Generally, the second pixel layer is arranged as the effect to electrode playing in electrochemical process, wherein the first pixel layer
Form the active photochromic layer of pixel arrangement.The layer of pixel arrangement is substantially parallel with each other disposed.According to an embodiment,
The layer in described first pixel layer front, the most described first insulating barrier and described first electrode are preferably transparent or semitransparent,
So that the variable color of pixel arrangement can visually be discovered.
In other words, the second pixel layer is electronic conductivity.And, the second pixel layer comprises carbon, or is arranged as comprising
The electronic conductivity material of carbon.
According to the third aspect of the invention we, it is provided that one group of pixel cell is for providing at least response to cross over described pixel cell
The purposes of the threshold voltage of the voltage applied, described pixel cell each includes:
-the first pixel layer, described first pixel layer is included between the most perceptible different color state can electricity
The electrochromism of chemical conversion and the organic polymer material of electro-chemical activity,
-the second pixel layer, described second pixel layer in the face of described first pixel layer, and
3rd pixel layer of the electrolyte of-solidification, described 3rd pixel layer is spatially placed in described first pixel layer
And between described second pixel layer, and with described first pixel layer and described second pixel layer contacted with ions, wherein,
Described electrolyte there is no PH dyestuff, and
Described second pixel layer of each pixel cell is arranged as comprising the material of conductive carbon.
By disposing the device described about described first, second or the third aspect, it is provided that one has and be enough to reduce
The pixel of the significant threshold voltage of the crosstalk in electrochromic display device (ECD).Although controlling the threshold value of electrochrome pixel device
The chemically and physically mechanism of matter still needs to be disclosed, it is possible to use obtained voltage threshold behavior is to minimize in matrix display
Crosstalk effect, such as the electric current of non-linear to voltage relatively applied and color contrast change.
According to an embodiment, this display device also includes one group of first electrode and one group of second electrode, and they are each other
Electric isolution, and be positioned so as to certain pattern:
-each described first electrode only intersects in a cross point with each described second electrode,
-each described second electrode only intersects in a cross point with each described first electrode, and
-each described pixel cell is placed in a respective described intersection, and described cross point is by respective first
Electrode and respective second electrode are formed, wherein:
Described first pixel layer of-each described pixel cell is consistent with a part for described respective first electrode, or
Person contacts with described respective first electrodic electron, and
Described second pixel layer of-each described pixel cell is consistent with a part for described respective second electrode, or
Person contacts with described respective second electrodic electron.
Benefit uniformly correlated with pixel layer and electrode layer is to need less print steps, i.e. can obtain more effectively
The manufacture method of rate.
Relevant benefits different from electrode layer with pixel layer are, it is possible to use different materials is used for pixel layer and electrode.
By selecting to compare with pixel layer, there is the conductive electrode material of more high electrode, it is provided that the less significant electricity along electrode
Pressure drop, and thus provide the more preferable conversion of each pixel cell.
An embodiment according to display device, it does not comprise the most each control element and a respective described picture
It is single for a group of transistor function of the color of pixel cell described in Active control that element unit combines and be arranged as offer
Control element.Relate to the present invention, individually control the control element that element is the part not as pixel cell.That is, control
Component positioning is in the electricity upstream of pixel cell or downstream.
An embodiment according to display device, is placed on flexible base board or flexible carrier, and is preferably wrapped
Containing paper and/or the substrate of plastics or carrier.It is that it is advantageously used for manufacturing display to the relevant benefit that uses of flexible base board
The use of printing process.
An embodiment according to display device, is arranged as multilamellar, and described multilamellar has impressionability and flexibility
In at least one.
An embodiment according to display device, described first electrode of described pixel cell and the first pixel layer are all pacified
It is set to identical material or is formed from the same material, and/or described second electrode of described pixel cell and the second pixel layer
All it is arranged as identical material or is formed from the same material.It is this letter about the benefit that several assemblies are used identical material
Change and accelerate preparation method.
An embodiment according to display device, described first electrode of each described pixel cell and the first pixel layer
It is all a part for identical layer, and/or described second electrode of each described pixel cell and the second pixel layer are identical
The part of layer.Benefit about this embodiment is, the structure of its commonly provided simplification, thus brings less printing
Step, and more have cost-efficient production.
Alternatively, although described second pixel layer and the second electrode are both mounted in identical plane, but for the second picture
Element layer and the second electrode use different materials respectively.Electrode can be arranged as the material with more high conductivity, thus reduces
The conversion time of described first pixel layer so that lower operation voltage can be used and/or provide higher color contrast.Electricity
Have and reduce the voltage drop along electrode than the described first higher electrical conductivity of pixel layer.
An embodiment according to display device, described display device includes insulating barrier, and preferably plastic insulating layer is described
Described second electrode that insulating barrier is placed in each pixel cell of described one group of pixel cell and described second pixel layer it
Between, and described insulating barrier also includes the passage that is each mounted with electronic conductor, described electronic conductor is each by respective pixel
Second pixel layer of unit electrically connects with described second electrode.The advantage that this this embodiment is relevant is, enabling only with one
Individual intermediate carrier layer manufacture.
An embodiment according to display device, it is described that described second pixel layer covers in each described pixel cell
The core of the 3rd pixel layer.In more detail, described second pixel layer and described 3rd pixel layer can be arranged as so that each
From the center of layer consistent along the normal orientation of described layer, described layer has stacked structure, and is arranged to be parallel to each other.
An embodiment according to display device, the surface area of the second pixel layer in each pixel cell is electrolyte
Surface area at least 60%, or at least 75%, or at least 90%, or at least 95%.In other words, described second pixel layer is permissible
It is placed in described electrolyte behind or to be covered by described electrolyte.
An embodiment according to display device, the electrolyte of solidification is polycation electrolyte.According to alternative reality
Executing scheme, the electrolyte of solidification is polyanion electrolyte.
According to an example, electrolyte is arranged as so that it is divided into less ionic complex and the biggest ion to join
Compound, the least ionic complex has the first electric charge and bigger ionic complex has contrary electric charge.Bigger
Ionic complex preferably comprise long polymer chain or macromole, and be cation or anion.In other words, according to a reality
Example, electrolyte is the polyelectrolyte or low polyelectrolyte comprising bigger cationic complexes.According to alternative example, electrolyte
For comprising the polyelectrolyte of bigger anionic complex or low polyelectrolyte.
Substantially, the thickness of described first pixel layer of pixel arrangement is not limited or limits, but an enforcement
In scheme, primarily for manufacturing and flexible viewpoint, it can be typically between 0.1 μm to 7 μm, the thickness selected in it
Device performance needed for dependence；Relatively thin layer is generally equal to the shorter pixel arrangement conversion time, and thicker layer is generally equal to
Higher color contrast.Additionally, the thickness of described second pixel layer of pixel arrangement can be in one embodiment
0.1 μm is to 40 μm.The following is should be taken into account: the second the thinnest pixel layer can reduce described first when selecting the thickness of layer
The tinctorial property of pixel layer, and the thickest layer may reduce resistance to bend(ing) and/or the mechanical resistant pressure of pixel arrangement.This
Outward, the thickness of described 3rd pixel layer of pixel arrangement can be between 1 μm to 20 μm in one embodiment, or not 1 μ
M to 100 μm.Generally, layer gets thinner, and flexibility is the best, but simultaneous contrast declines.The thickness of each pixel layer is along each pixel layer
The direction of observation of normal is measured.According to the optional method of offer pixel layer, they can pass through multiple usual printing techniques
It is provided, as spin coating, ink jet printing, silk screen printing, ion self assembling multilayer, aerosol injection printing or rod are coated with.
According to an example, by the way of laser technology, by the way of laser drill, preferably provide described insulating barrier
In passage.When manufacturing the passage in insulating barrier by the way of boring or laser drill, preferably select the most dystectic
Material so that damage the risk minimization in channel circumference region.
In one embodiment, the cross-sectional area of the passage of pixel arrangement can be such as 10 μm2To 2mm2.According to separately
One example, this area is 100 μm2To 0.5mm2.According to yet another instance, this area is 500 μm2To 0.2mm2.According to again
Another example, this area is 1000 μm2To 0.1mm2.Cross-sectional area is measured in extension with described passage orthogonally, i.e. if
Channel formation is the conventional hollow cylinder with base radius r, and the cross-sectional area of passage is pi*r2.Relatively large passage rank street
Area has an advantage that it provides higher levels of electrical conductivity.But, the biggest cross-sectional area can cause manufacture process
In problem, if the 3rd pixel layer is through the leakage of passage.
For some technologies of preparing, it is arranged on the electric conductor in described passage and is only simply disposed in the inner side of described passage, this
Meaning that described electric conductor has hollow or tubular form, have interior girth and outer perimeter, at least a part of which outer perimeter corresponds to institute
State the girth of passage.In described passage, other arrangements of electric conductor are possible, condition be this conductor described conduction alignment with
Electronics is provided to connect between described second pixel layer.
Generally, operate in the following manner according to assembly of the invention: apply the first electromotive force to described first pixel layer, and
Second electromotive force different from described first electromotive force is applied so that set up in the electrolyte of described solidification to described second pixel layer
Electric field.As long as electromotive force maintains to obtain long enough, electric field causes the redox reaction of described pixel layer, and described reaction causes described electricity
Cause the color change of off-color material.
Should be appreciated that conversion time or the color change of pixel arrangement often rely on such as:
Ionic mobility in-electrolyte, mobility is the highest, and the conversion time is the shortest；
The size of the ion current in-electrolyte, this is determined by the ionic mobility in electrolyte and electrolyte volume
Fixed；
-electro-chemical activity and/or the selection of electrochromic material；
-in order to change the electro-chemical activity and/or the body of electrochromic material reacted needed for the color of electrochromic material
Long-pending；
-the amplitude of voltage that applied；The voltage the highest conversion time is the shortest, and vice versa.
Can be by disposing multiple electrochrome pixel devices as above, it is provided that there is several individually addressable pixel
Display.It is advantageous that pixel arrangement is arranged as allowing the matrix arrangement of passive matrix addressing concept.
The scheme applicable, routine or known of any addressing for passive matrix display may be used for operation originally
Device.Such as, dispose rows of electrode to provide electrochrome pixel element or the first pixel layer, and dispose electrode in column to provide
Second pixel layer of matrix display.Each respective row and column is connected to the output lead of digital integrated electronic circuit, and it is the most logical
Cross applying voltage to drive.The image storage that hope can be shown by display in programmable circuit, its by once or
Repeatedly update whole display output image.Matrix display updates the most line by line, even if scanning by column or single picture element scan
It is other possible addressing replacement schemes.In progressive scan, it is allowed to the corresponding row of output activation signal, so that required picture
Element can update by applying a voltage to corresponding alignment.The output of un-activation row and non-addressed column is prohibited from.Afterwards,
The output lead of the row being updated over is set as that output is forbidden, and updates row subsequently by identical method.So
Addressing scheme in, threshold voltage combine with forbid do not address row and column allow passive matrix display there is the least crosstalk
In the case of renewal.
In another example, the combination of the external circuit utilizing threshold voltage and only there is simulation output.Here, suppose that
In a pixel cell, colour completely by applying voltage V realization.So, addressed row is set to the general of this voltage, and
Addressed column is also configured as the half of this voltage, but opposite polarity.Therefore, the total voltage crossing over pixel cell is V.To not address
Row and column is set to ground connection.At addressed row and the pixel cell of the intersection of non-addressed column or in non-addressed row and addressed column
The pixel cell of intersection experiences the half updating voltage V.Thus, as long as threshold voltage is about as much as renewal voltage V
General, threshold voltage in respective pixel cell thus minimize crosstalk.
About the present invention, described one group of first electrode and described one group of second electrode are sometimes as a example by row electrode and row electrode
Explanation.The content stated about row electrode and row electrode can be used for described one group of first electrode and described one group of second electricity
Pole, even if these electrodes do not have arranged parallel or orthogonal arrangement.
Definition
Layer: according to an embodiment, pixel arrangement has laminated construction, and is made up of " layer " of different materials.This
A little layers can be continuous print and/or patterning, and can put on each other (self-supporting device) or apply to supporter or
Carrier (support means).These terms " self-supporting/support " can be used for single layer.Self-supporting layer is can be with himself
Carry out operating and, such as install to printer in the case of not damaging and need not extra supporting layer.Additionally, art
Language " layer " can include all identical material in identical plane, no matter is that this is material patterned or with in the planes
The mode forming discontinuous " island " is interrupted.
Insulating barrier: insulating barrier preferably comprises plastics, or by comprising the layer of plastics, plastic insulating layer, plastic foil or plastics
Paper tinsel such as polyester foil is formed.For plastic insulating layer or the insulating barrier that comprises plastics, it can include such as film, foam films or its layer
Press mold, including, such as: polyolefin such as polyethylene, polypropylene etc.；Polyester such as polyethylene terephthalate, poly-naphthalenedicarboxylic acid
Glycol ester, polybutylene terephthalate (PBT) etc.；Polrvinyl chloride, polystyrene, polyurethane, Merlon, polyamide, polyamides
Imines, polymethyl methacrylate, polybutene, polybutadiene, polymethylpentene, vinyl-vinyl acetate copolymer, ethylene
(methyl) acrylic copolymer, ethylene (methyl) acrylate copolymer, ABS resin, ionomer resin etc., but it is not limited to these
Example.And, for layer, it is possible to use commercial membranes, and can also use and utilize process materials to be formed by cast film process
Film.
Additionally, the display with several pixel can include the pantostrat of insulant, its formation is the plurality of electroluminescent
At least some of described insulating barrier of electrochrome pixel device.In other words, the insulating barrier of several pixels can be individually one continuously
The single part of insulating barrier.
Electrochromic layer: " electrochromic layer " that the present invention relates to is continuous geometry body, it can be patterned as different
Shape, and be made up of the combination of a kind of material or multiple material.One or more materials described can be organic or inorganic
, low molecular or high molecular.This electrochromic layer, is to be made up of a kind of material or more than one material whole with it
Body is unrelated, is combined with following character: at least one material is conduction at least one oxidation state, and at least one material is
Electrochromic, i.e. as the result presentation color change of the electrochemical redox reaction in material.Optionally, electrochromism
Layer can comprise electrochemical active material.
Electro-chemical activity: according to " electro-chemical activity " layer of the present invention be a piece of have can by change described material
The material of the electronic conductivity that redox state electrochemistry changes.Generally, at least some of and electrolysis of electrochemically active element
Matter contacted with ions, and electrochemically active element can also be integrated with the electrode being made up of identical or different material.Electrode is also
The top of described electrochemical active material can be placed in.
Electrochromic display device (ECD): " electrochromic display device (ECD) " that the present invention relates to is to include at least one electrochrome pixel
The device of layer, disposes described device so that the color change of electrochromic layer visually can be examined in reflection and/or transmission
Feel.
Color change: when mentioning " color change ", this also means to include the change on optical density (OD) or reflectance, so that
" color change " such as also allow for from Lan Zhihong, blue to colourless, colourless to blue, dark green to light green, grey to white or dark-grey to
The change etc. of light gray.
Passive matrix: in Active Matrix Display, each pixel provides transistor function equipped with having at least one
Control element electronic circuit.In other words, passive matrix display device is not have the most each control element with respective
Be connected one group of one pixel cell individually controls the display device of element.Control element is arranged as offer further and can control
Make the transistor function of the color of described pixel cell.The example controlling element is field-effect transistor and electrochemical transistor.
" individually " means that key-course is placed in electricity upstream or the downstream of described pixel cell.
Pixel layer: " pixel layer " that the present invention relates to is by the interface definition between electrolyte and conductive layer.In more detail, as
Element layer is the volume of the electronic conductive layer being covered with an electrolyte in its side.When pixel layer is electrochromic layer, the variable color of layer
The interface between electrolyte and electrochromic layer, the scope of i.e. defined pixel layer may not corresponded to.Color change may
Such as extend to outside the interface between electrolyte and electrochromic layer, and extremely covered by electrolyte through electrochromic layer
The side that side is contrary.
According to an example, electrolyte is clipped in the electrode layer that comprises carbon and comprises electrochromism and electro-chemical activity organic
Between the electrode layer of polymer, described electrode layer intersects each other at a point or intersects.As explained above, pixel layer is by electrode
With the corresponding interface definition between electrolyte.In other words, pixel layer is consistent with the appropriate section of electrode.
In the optional embodiment of pixel arrangement, electronic conductor may include that electrically conductive material such as, and electronics conduction is poly-
Compound such as PEDOT:PSS (poly-(3,4-rthylene dioxythiophene) poly-(styrene sulfonate)), carbon, inert metal or electrochemicaUy inert
Metals like gold, or it is suitable for other conductive materials contacted with electrochemically active layer, or the group of these electrically conductive materials
Close.Generally, the conductive material being suitable to contact with electrochemically active layer is inert, so that they do not cause the electrochemistry of essence
Reaction.These materials can such as provide as the ink disposed in preparation process or prefabrication process in the channel or serosity.
Electrode: electrode can include any electrically conductive material, such as conducting polymer, metal, conductive carbon, titanium, platinum, stone
Ink, Graphene, noble metal and inert metal or the combination of these electrically conductive materials.Electrode can also comprise electrochemicaUy inert gold
Belong to as gold or other be suitable for the conductive material that contacts with electrochemically active layer.Generally, it is suitable for contacting with electrochemically active layer
Conductive material be inert so that they do not cause the electrochemical reaction of essence.These materials can be such as in system
Standby process or prefabrication process are placed in the ink on described dielectric film or serosity provides.
Electrode is preferably elongation, and can be band-shaped, or is arranged as line or linear.Electrode can such as be arranged as leading
The layer of electric polymer or be arranged as tinsel or line.According to an embodiment, first group of electrode is placed in parallel with each other
In one plane.Second group of electrode is placed in the second plane in parallel with each other, and described second plane is different from described first plane,
And wherein said first plane is arranged as parallel to each other with described second plane.Preferably, the first and second planes are only separated
Little distance, described distance is at least equal to the height of electrolyte.Additionally, described first and second groups of electrodes are generally arranged as each other
Vertically.According to another embodiment, the electrode of described first and/or second group of electrode is not arranged as parallel to each other, or the
One and second plane be not arranged as parallel to each other.Additionally, electrode can dispose with straight line but it also may be curve or have not
Regular shape.In other words, the pixel cell being arranged as matrix is necessarily placed in straight row and column, but can be less to advise
Mode then disposes, condition be each electrode in described first group of electrode only with each electrode in described second group of electrode only
Intersect in a cross point.
Directly electrical contact: allow biphase (such as electro-chemical activity organic material and electrolyte) that electric charge is exchanged by interface
Between direct physical contact (public interface).By the charge-exchange at interface may include that electronics shift between conductive phase,
Ion ionic conduction mutually between shift, or such as between element and electrolyte or electrolyte and electric driven color-changing part it
Between interface, by the way of electrochemistry, or by owing to the electric capacity of the charging of helmholtz layer on this interface
The appearance of electric current, the conversion between electronic current and ion current.
The ion between two elements is provided to connect by least one material that can transmit ion between the two elements
Touch.The electrolyte directly contacting (public interface) with the first and second electrochemically active layer is to provide two electro-chemical activities
One example of the material of the contacted with ions between Ceng.Therefore this electrolyte and two electrochemically active layer ions can be claimed to connect
Touch.
Bi-material can be such as via the 3rd material mutual electronics contact.Electronics between two elements contacts by extremely
Few a kind of material that can transmit electronics between the two elements provides.Directly contact with the first and second electrochemically active layer
The carbon-coating of (public interface) is an example of the material that electronics can be provided between the two layers to contact.Therefore carbon-coating can be claimed
For electronic conductor, or electronics conduction.
Direct electron contacts: direct physical contact (public interface) between two electronic conductors.
Electrochrome pixel device can include that the polymer at least conducted electricity an oxidation state is as electrochromic material
And/or electrochemical active material, and the most also comprise polyanionic compound.
Electrochromic polymeric compounds for using in the electrochrome pixel device of the present invention is selected from by following
The group of composition: electrochromic polythiophenes, electrochromic polypyrroles, electrochromic polyanilines, electrochromism gather different sulfur naphthalene, electroluminescent
Variable color p-phenylene vinylene, and their copolymer.In one embodiment, electrochromic polymeric compounds is 3,4-dialkoxy
The homopolymer of thiophene or copolymer, wherein said two alkoxyls can be same or different, or represents together optionally
Epoxide-alkylidene-epoxide bridge of being replaced.In a further embodiment, electrochromic polymeric compounds is that choosing is the most following
The 3 of the group of item composition, the homopolymer of 4-dialkoxythiophene or copolymer: poly-(3,4-methylene dioxy thiophene), poly-(3,4-Asias
Methyl dioxy thiophene) derivant, poly-(3,4-ethyldioxythiophene), poly-(3,4-ethyldioxythiophene) derivant, poly-(3,
4-popylenedioxythiphene), poly-(3,4-popylenedioxythiphene) derivant, poly-(3,4-butylidene dioxy thiophene), poly-(3,4-
Butylidene dioxy thiophene) derivant and their copolymer.Polyanionic compound is then preferably poly styrene sulfonate.
As easily understood technician, in the alternative embodiment of the present invention, electrochromic material includes the most non-
The combination of polymeric material, the combination of different non-polymer materials, or polymeric material and non-polymer material, they
At least one oxidation state represents conductivity and electrochromism behavior.Such as, people can use conductive material and electrochromism
The composite of material, as with polymer or non-polymer electrochromic material such as polyaniline, polypyrrole, polythiophene, oxidation
Nickel, polyethylene ferrocene, poly-viologen, tungsten oxide, yttrium oxide, molybdenum oxide and the conducting particles of Prussian blue (ferric ferrocyanide)
Such as stannum oxide, ITO or ATO particle.As the limiting examples of the electric driven color-changing part for assembly of the invention, Ke Yiti
To have: a piece of conduction and electrochromic PEDOT-PSS；A piece of have Fe2+/SCN-Conduction and electrochromic
PEDOT-PSS, and Fe2+/SCN-As additional electrochromism component (see below)；Direct with electrochromism WO3 coating
The sheet that the contiguous network by the electroconductive ITO particle in insulating polymer matrix of electrical contact is constituted；With dissolving in the electrolyte
The sheet that constitutes of the contiguous network by the electroconductive ITO particle in insulating polymer matrix of electrochromism component contact.As above institute
Stating, electrochrome pixel device could be included for realizing other electrochromism materials of the display with more than one color
Material.These other electrochromic materials can be arranged in electrochrome pixel element or in the electrolyte that solidifies, then such as its
Including electrochromic redox system, as being colourless Fe2+With the redox couple of SCN-ion, another side is red
Fe3+(SCN)(H2O)5Coordination compound.By the way of other non-limiting examples, such material can be selected from different fens
Piperazine class, such as DMPA-5,10-dihydro-5,10-dimethylphenazine, DEPA-5,10-dihydro-5,10-diethyl azophenlyene and DOPA-5,
10-dihydro-5,10-dioctylphenazine, selected from TMPD-N, N, N', N'-durol diamidogen, TMBZ-N, N, N', N'-tetramethyl
Benzidine, TTF-tetrathiafulvalene, phenanthroline-iron complex, erioglaucine A, diphenylamine, p-ethyoxyl chrysol, methylene blue,
Different indigo-blue and phenosafraine, and their mixture.
The electrolyte of solidification: for the purposes of the present invention, " electrolyte of solidification " represents such a electrolyte, this electrolysis
Matter uses temperature to be sufficiently rigid at it so that its body mutually in particle/thin slice substantially by the high viscosity of electrolyte/just
Property is fixed, and it does not flows or leaks.In the preferred situation, this electrolyte has the suitable rheological equationm of state, to allow
By this material, such as, by conventional print process, it is coated on supporter with the form of full wafer or pattern.After deposition, electricity
Solving matter preparation should to solidify after the evaporation of solvent or because of chemical crosslink reaction, described chemical crosslink reaction is by adding
Chemical reagent or by physical effect as by ultraviolet, infrared or microwave radiation, cooling or any other such effect
Bring.The electrolyte of solidification can such as comprise aqueous or containing organic solvent gel, such as gelatin or polymeric gel.But,
Solid polyelectrolyte is also expected, and falls within the scope of this invention.Additionally, this definition also includes by suitable matrix
Material, the liquid electrolyte leaching such as paper, fiber or porous polymer or keeping in any other manner.In some of the present invention
In embodiment, this material actually disposes the supporter of electrochromic device, so that above support forms electroluminescent change
The global facility of the operation of color device.
The electrolyte of solidification can comprise binding agent.Preferably this binding agent has gelling.Binding agent can be selected from
The group being made up of the following: gelatin, gelatine derivative, polyacrylic acid, polymethylacrylic acid, PVP,
Polysaccharide, polyacrylamide, polyurethane, poly(propylene oxide), poly(ethylene oxide), poly-(styrene sulfonic acid) and poly-(vinyl alcohol), and
Their salt and copolymer；And can optionally be crosslinked.Electrolyte can by the one in materials listed above or these
The two or more combination of material is formed.
In a word, select according to the material of the pixel arrangement of the present invention and vertical stratification structure allows to include conventional printing techniques
Manufacture method.This conventional printing techniques can include rod painting, silk screen printing, spin coating, ink jet printing, aerosol injection print
Brush, or any other such fabrication schedule.The structure of pixel arrangement also allows for use can be amplified to bigger chi simply
The fabrication schedule of very little manufacture, this allows faster to manufacture with low price therewith.Such as, including the multiple pixel arrangements according to the present invention
Display array can manufacture in roll-to-roll fabrication schedule.
In an embodiment of pixel arrangement, conduction alignment, described passage in electronic conductor, the second pixel layer,
3rd pixel layer and the first pixel layer can dispose by the way of printing technology.Therefore it provides described second pixel layer with lead
The electronic conductor of electrical connection between electricity alignment can be preferably arranged comprise can the material of printing material to be conducive to manufacturing,
I.e. in order to the material with the suitable rheological equationm of state can be printed.The ink comprising conducting polymer or conductive carbon is this to print material
The example of material.In the manufacture process of pixel arrangement, electrically conductive material can be placed in described passage in the following manner:
By multiple different printing technology such as rod painting, silk screen printing, ink jet printing, aerosol injection printing, spin coating etc., or pass through
Material it is coated at passage and is pressed into described passage by such as crossing over described passage and drawing squeegee.Will also be understood that
, having the insulating barrier of the passage being mounted with electronic conductor can be preassembled or part is preassembled.For example, it is possible to
It is coated with or disposes passage and electronic conductor during preprocessing.
Usually, other targets, feature and the benefit of the present invention will be from described below, dependent claims and accompanying drawing
Manifest.Embodiment of the present invention will be described with reference to the drawings by the way of embodiment now.Should be appreciated that accompanying drawing is not by very
Full scale, and to those skilled in the art it can be readily appreciated that within the scope of this invention, with the chi shown in accompanying drawing
Very little different size be it is also possible that.
Accompanying drawing is sketched
Fig. 1 a schematically shows the decomposition diagram of passive matrix display, and wherein pixel layer is consistent with electrode.
Fig. 1 b schematically shows the sectional view according to the pixel in the pixel arrangement disposed described in Fig. 1 a.
Fig. 2 a schematically shows the decomposition diagram of passive matrix display, wherein the first pixel layer and the first electrode
Unanimously.
Fig. 2 b schematically shows the sectional view according to the pixel in the pixel arrangement disposed described in Fig. 2 a.
Fig. 3 a schematically shows the decomposition diagram of passive matrix display, and it comprises the insulating barrier with passage.
Fig. 3 b schematically shows the sectional view according to the pixel in the pixel arrangement disposed described in Fig. 3 a.
Fig. 4 shows the parameter of the fill factor for calculation display.
Fig. 5-9 shows the I-V characteristic of the different samples disposed according to the present invention.
Figure 10 a is the photo of display device.
Figure 10 b is the diagram of photo based on Figure 10 a, and reflects a part for display device.
Figure 11-14 shows the I-V characteristic of the different samples comprising different electrolyte disposed according to the present invention.
Describe in detail
In Fig. 1 a and 1b, it is schematically shown that according to an example of the passive matrix display of the present invention.Fig. 1 a
Being the decomposition diagram of passive matrix display, wherein pixel layer is consistent with electrode.Arrange the first of one group of electrochromic material
Electrode 121, and one group of second electrode 122 comprising carbon.Each electrode is all formed as the element of linear extension.First electrode
121, the electrode in the most described one group of first electrode, it is placed in parallel with each other in the first common plane.Second electrode 122,
Electrode in the most described one group of second electrode, is placed in the second common plane in parallel with each other.Additionally, dependently of each other pacify
Put two arrays of electrodes 121,122, so that each described first electrode only intersects in a cross point with each described second electrode.
In fig 1 a, the first electrode disposes orthogonally with described second electrode, and i.e. electrode is each other with the angular cross of 90 degree.Alternatively,
Electrode can be such as, mutual with the angle in the interval of 10 ° to 170 ° with the substantially any angle of enough deviations 0 and 180 degree
Dispose across.
Each infall between described first and second electrodes, Existential Space disposes and is electrolysed between two electrodes
The layer of matter 113.In other words, electrolyte 113 be clipped in a first electrode 121a of described one group of first electrode with described one group the
Between one the second electrode 122a of two electrodes.Additionally, between the first pixel layer 111 is by electrolyte 113 and the first electrode 121a
Interface scope definition.Second pixel layer 112 is defined by the scope at the interface between electrolyte 113 and the second electrode 122a.
In other words, described first pixel layer 111 is consistent with a part of described first electrode 121a；And described second pixel layer 112
Consistent with a part of described second electrode 122a.In more detail, described first pixel layer 111 and described second pixel layer 112
A described 121a and whole volumes of the 2nd 122a electrode are respectively constituted.
According to an embodiment, described one group of first electrode is placed in the first carrier layer 116, and described one group
Two electrodes are placed on Second support layer 117.First and second carriers are preferably arranged as insulant.When manufacturing pixel arrangement
Time, electrolyte can be placed in the one or both of the electrode at the electrode crossings of each of which.Afterwards, carrier is closed
Together, so that the intersection between respective first and second electrodes ion can be provided to connect.
Fig. 1 b shows the amplification of the schematic sectional view according to a pixel in the pixel arrangement disposed described in Fig. 1 a.
The layer of pixel has the vertical or arrangement of stacking.In more detail, electrolyte 113 is clipped in the first pixel comprising electrochromic material
Between layer 111 and the second pixel layer 112 comprising carbon.Additionally, the first pixel layer is spatially placed in first substrate 116 and electricity
Solve between matter 113；And the second pixel layer is spatially placed between second substrate 117 and electrolyte.Observe described pixel
Direction be the normal direction of described first carrier layer, and pointed out by arrow 130.
Fig. 2 a schematically shows the decomposition diagram of passive matrix display.Pixel arrangement shown in fig. 2 a
200 dispose according to described in Fig. 1 a and 1b, and difference is, described second pixel layer is inconsistent with described second electrode.Instead of
For, described second pixel layer 212 is the single layer comprising conductive carbon, is spatially placed in the second electrode 222a and described the
Between the electrolyte 213 of one and second intersection between electrode 221a, 222a.And, the second pixel layer is arranged as and institute
State the second electrode 222 directly to make electrical contact with.Second electrode can be arranged as the material identical with described second pixel layer, or has
The material of higher electronic conductivity such as silver.In more detail, each between the first electrode 221a with the second electrode 222a is intersected
At Dian, the layer of respective electrolyte 213 and the second pixel layer 212 of material with carbon element are laminated to each other, and are placed in described first He
Between second electrode 221a, 222a；So that described pixel layer 212 contacts with described second electrode 222a direct electron, and
Described electrolyte 213 and described second pixel layer 212 and described first picture of the electrochromic material of described first electrode 221a
Element both layers 211 contacted with ions.
In more detail, and according to an embodiment, described one group of first electrode 221 is placed in the first carrier layer 216
On, and described one group of second electrode 222 be placed on Second support layer 217.First and second carrier layer 216,217 are preferably pacified
It is set to insulant.Additionally, the second pixel layer 212 of carbon be placed between described first and second electrodes 221,222 each
On the described second electrode 222a of cross point or some intersections.Additionally, the layer of electrolyte 213 can be placed in respective
In one or both in one and second the first and second electrodes at electrode crossings.Afterwards, carrier is combined, so that
Obtain between first and second pixel layer 211,212 of intersection between respective first and second electrode 221a, 222a
Offer ion connects.
Fig. 2 b is the amplification of the schematic sectional view according to a pixel in the pixel arrangement disposed described in Fig. 2 a.Pixel
Layer there is the vertical or arrangement of stacking.In more detail, electrolyte 213 is clipped in the first pixel layer comprising electrochromic material
Between 211 and the second pixel layer 212 comprising carbon.Additionally, the first pixel layer 211 be spatially placed in first substrate 216 with
Between electrolyte 213；And the second pixel layer 212 is spatially placed between the second electrode 222 and electrolyte 213.Additionally,
Second electrode is spatially placed between the second pixel layer and Second support layer 217.The direction observing described pixel is described
The normal direction of the first carrier layer, and pointed out by arrow 230.
Fig. 3 a schematically shows the decomposition diagram of passive matrix display.Pixel arrangement 300 shown in Fig. 3 a
Disposing according to described in Fig. 2 a and 2b, difference is, described second pixel layer 312 is not straight with described second electrode 322
Connect electronics contact.It is instead of that the insulating barrier 318 comprising passage 319 is placed in described second pixel layer 312 and described second electrode
Between 322.Electronic conductor 320 is placed in each described passage 319.Additionally, dispose insulating barrier so that each electronic conductor
Second electrode 322 is connected by 320 with the second pixel layer 312 electronics.
In more detail, according to an embodiment, the first carrier layer 316 of insulant is set, disposes one group thereon
First electrode 321.Additionally, arrange the intermediate carrier layer 318 of insulant, and dispose one group of passage 319 wherein.In described
Between carrier layer 318 the first side on dispose one group of second electrode 322, and electronic conductor 320 is set in described passage 319.
And, the opposition side of described intermediate carrier layer 318 arranges one group of second pixel layer 312 comprising conductive carbon, and each
Described second pixel layer 312 is arranged as contacting with respective described electronic conductor 320 electronics, so that each electronic conductor
Respective second pixel layer 312a is connected by 320 with its respective second electrode 322a electronics.In all embodiments, second
Pixel layer disposes the most in isolation from each other.The 3rd pixel layer comprising electrolyte 313 is placed in each of described second pixel layer 312
On individual.Afterwards, the first carrier and intermediate carrier 316,318 are combined, so that each described first electrode 321 is with each
Described second electrode 322 only intersects in a cross point.As follows the first carrier and intermediate carrier 316,318 are combined in one
Rise: make the intersection between the first electrode 321a and 322a, at respective described first electrode 321a and respective
Between individual described second pixel layer 312a, ion is set via respective described 3rd pixel layer 313 and connects.In this group the
Contacted with ions one group of first pixel layer 311 provided as described above between three pixel layers 313 and the first electrode 321.
Additionally, or alternatively, before the first carrier layer and intermediate carrier layer 316,318 are combined, can be by
3rd pixel layer be set to corresponding to respective described first and second electrodes 321,322 between predetermined cross point
Position and described first electrode 321 contacted with ions.Afterwards, in the following manner the first carrier and intermediate carrier 316,318 are combined in
Together: make the intersection between respective first electrode and second electrode 321a, 322a, at respective one described
Between one electrode 321a and a respective described second pixel layer 312a, via respective described 3rd pixel layer 313
Arrange ion to connect.
Fig. 3 b is the amplification of the schematic sectional view according to a pixel in the pixel arrangement disposed described in Fig. 3 a.Pixel
Layer there is the vertical or arrangement of stacking.In more detail, electrolyte 313 is clipped in the first pixel layer comprising electrochromic material
Between 311 and the second pixel layer 312 comprising carbon.Additionally, the first pixel layer 311 is spatially placed in the first insulating barrier 316
And between the 3rd pixel layer 313.And, the second insulating barrier 318 comprising passage 319 be placed in described second pixel layer 312 with
Between described second electrode 322, and electronic conductor 320 is placed in described passage 319, and described electronic conductor is by described second
Pixel layer 312 is connected with described second electrode 322 electronics.Optionally, the second pixel layer 312 can be placed in described second insulation
Between layer and not other insulating barrier shown in Fig. 3 a and 3b.
Fig. 4 schematically shows the display comprising the pixel cell that a group is arranged as matrix described in Fig. 1 a and 1b
Device.Multiple pixel portion being placed in matrix structure, the most each pixel portion limits one according to the pixel described in Fig. 1 b
Device.The common property measuring display relates to fill factor.The effective area of fill factor and each pixel and whole display
The given Area comparison of device is relevant.Fill factor can obtain from shown size A and B.Distance A corresponds to two separate pictures
Distance between element part, and be that two pixels are positioned to how close, or the invalid existed in the display is great
Instruction.Distance B illustrates the typical sizes of pixel portion, and it is corresponding to the cross-sectional area of pixel element.Usually, the phase of distance A
To reducing the increase meaning fill factor, and the increase relatively of area B means the increase of fill factor.An enforcement
In scheme, based on 1 × 1mm2Single pixel portion area, comprise the pixel arrangement according to the present invention display filling because of
Number can be 90%.
There is the preparation of the passive matrix addressed displays of insulating barrier
There is provided comprise 50 μ m-thick polyethylene terephthalate (hereinafter referred to as PET) film (Melinex 454,
By DuPont Teijin film produce) insulating barrier, wherein irradiate by laser, with 20 × 20 net-like pattern set up lead to
Road, the distance between the passage that two of which is adjacent is 1cm.The inlet diameter of passage on the first side of described insulating barrier be～
30 μm, and on the opposite side of described insulating barrier be～70 μm.By using squeegee, by conductive carbon paste (7102 screen printings
Brush carbon is starched, DuPont produce) deposit to passage.Carbon slurry is that 120 DEG C were dried after 3 minutes, were repeated once carbon laydown
Process step, to guarantee the electronic conduction by passage.On the first side of described insulating barrier, by the 20 of brush deposition silver serosity
Bar parallel lines (Ag 5000 silk screen printing silver serosity, DuPont production), wherein every line is～2-3mm width and ＞ 200mm
It is long, so that every line electrically connects 20 passages in described insulating barrier.Afterwards by silver wire heat treatment；120 DEG C, continue 5 minutes.
In the second side of described insulating barrier, deposition conductive carbon paste (7102) each has～4-5mm to be formed in described channel roof2's
The square of area.It is dried serving as the carbon square to electrode member in electrochrome pixel device 3 minutes at 120 DEG C.By 20
(Luviquat Excellence, is produced × 20 electrolyte drops by BASF, comprises the TiO2 powder (Kronos of 10 weight %
2300, KRONOS produce)) deposit to carbon square, and be dried 1 minute at 60 DEG C.Luviquat is the second in aqueous solution
Vinyl pyrrolidone and the copolymer of quaternized vinyl imidazole.In order to make electrolyte the opaquest use TiO2.Carry
For being coated with the PET paper tinsel of PEDOT:PSS (Orgacon EL-350, AGFA production) in advance.PEDOT:PSS layer is passed through pocket knife
Drawing instrument is patterned as 20 rectangles, and each rectangle has 23 × 1cm2Area.In obtained matrix display,
PEDOT:PSS rectangle serves as the first electrode and the first pixel layer.According to identical with the electrolyte drop on the second electrode netted
20 × 20 electrolyte drops of pattern deposition, and be dried 1 minute at 60 DEG C.As final process step, by the second electrode with
First pixel layer is stacked together so that described layer in vertical stratification toward each other, and conductive silver wire and conduction
PEDOT:PSS rectangle is orientated in an orthogonal manner.The latter guarantees that matrix display comprises row and column.
Embodiment device and the preparation of comparable device
Can be by using material (carbon slurry, PEDOT:PSS and the electrolysis identical with the material for above-mentioned matrix display
Matter) and substrate (PET paper tinsel) manufacture electrochrome pixel device.In single pixel arrangement, need not comprise the conductor wire of silver.
According to the first embodiment of pixel arrangement, carbon is starched (7102, DuPont produce) and PEDOT:PSS serosity
(Clevios S V3 silk screen printing serosity, H.C.Starck offer) is screen printed onto on respective PET foil substrate, Mei Gechen
Lamination has 35x35mm2Area, and be separately dried 5 and 2 minutes at 110 DEG C afterwards.Afterwards, will have 2x2mm2Area
Dielectric substrate be deposited on the corner of substrate of respective pre-coating, to each substrate one electrolyte pattern.By electrolyte
Layer, after 60 DEG C are dried 1 minute, completes pixel arrangement by being stacked as vertical stratification layer by layer, the electrolyte being wherein clipped in the middle
Guarantee that the ion between first and second pixel layer connects.
Prepare the second embodiment of pixel arrangement, there is the apparatus structure identical with first embodiment, be in place of difference
Use another type of carbon to starch (PF-407A is produced by Acheson), deposited to described second pixel layer replacement
7102 carbon slurries.
Prepare the 3rd embodiment of pixel arrangement, there is the apparatus structure identical with first embodiment, be in place of difference
Use the PET paper tinsel of the PEDOT:PSS (Orgacon El-350, AGFA production) comprising pre-coating as described first pixel
Layer.
Prepare the first reference sample of pixel arrangement, there is the apparatus structure identical with first embodiment, being in of difference
In carbon to be replaced with the electrode comprising PEDOT:PSS to electrode.
Prepare the second reference sample of pixel arrangement, there is the apparatus structure identical with first embodiment, but wherein by carbon
Electrode is replaced with ag paste electrode (Ag 5000, DuPont production).
Measure electrochemical appliance character
By electrochrome pixel device being connected to Semiconductor Parameter Analyzer (Hewlett Packard/Agilent
4155B) measure their I-V characteristic.By providing according to the matrix display disposed described in Fig. 1 a and 1b, and by each sample
Pixel separates with other detailed descriptions in this matrix display, thus prepares sample pixel.Electromotive force is connected to the second pixel layer, with
Time by the first pixel layer ground connection.Electromotive force starts from negative value (by the first pixel layer oxidation) and is swept on the occasion of (by the first pixel layer also
Former), and turn again to negative value, such as-2V afterwards to 2V to-2V.The every 20ms of electromotive force applied increases 10mV.In other words, as
Element electrode layer to its blue reduction-state and converts back transparent Indium state from the conversion of its initial transparent oxidation state afterwards, and passes through
Parameter analyzer records the electric current by pixel arrangement continuously.
Test result
The first of pixel arrangement is with reference to sample, first, second, and third embodiment and the I-V curve of the second reference sample
Or I-V characteristic is given in Fig. 5,6,7,8 and 9.Lack carbon and the most do not show voltage threshold to two of electrode with reference to sample drawing 5 and 9
Value behavior, because electric current raise/lower is more or less with the electromotive force applied linearly.Sample in Fig. 5 and 9 comprises respectively
PEDOT:PSS and silver are as to electrode.On the other hand, pixel arrangement embodiment in figures 6,7 and 8 shows about 0.5-
The voltage threshold electromotive force of 1.0V.This voltage threshold electricity can be utilized in the matrix display driven by passive matrix addressing
Gesture.
Figure 11-14 shows I-V curve or the I-V of the embodiment sample of the pixel arrangement comprising different electrolyte 113
Characteristic.The sampling device that its I-V curve is shown in Figure 11-14 disposes according to described in Fig. 1 a and 1b, wherein by matrix display
In each sample pixel from other pixel separation.Make additionally, the first pixel layer 111 of each pixel 110 comprises PEDOT:PSS
For electrochromic material, and the second pixel layer 112 comprises carbon.Its I-V curve illustrates the sample of pixel arrangement in fig. 11
Electrolyte used is poly-(diallyldimethylammonium chloride), a kind of polycation electrolyte aqueous solution.This pixel arrangement
Show the threshold voltage of about ± 1.0V.Additionally, the embodiment of this embodiment has Low dark curient electric current when 0V.Therefore, this
Plant the matrix display that pixel arrangement can be used for being driven by passive matrix addressing.
Figure 12 illustrates the I-V curve of two different embodiments of sample.The orientation represented by square refers to comprise second
The copolymer of vinyl pyrrolidone and quaternized vinyl imidazole (Thered is provided as an aqueous solution by BASF) make
Sample for polycation electrolyte.The curve represented by circle refer to comprise kayexalate salt (M.W.～70,
000, Alfa Aesar provide) aqueous solution as the sample of polyanion electrolyte.Corresponding to the figure in Figure 12 two
Embodiment device is all shown to be about ± threshold voltage of 1.0V and the Low dark curient electric current when 0V.Therefore, this pixel arrangement is also
Can be used for the matrix display driven by passive matrix addressing.
Figure 13 and 14 illustrate comprise vinyl pyrrolidone and quaternized vinyl imidazole copolymer (Thered is provided as an aqueous solution by BASF) as the I-V curve of sample of polycation electrolyte.But, each
The electrolyte of pixel arrangement comprises different additives.Additive in the electrolyte of the pixel arrangement of the curve in generation Figure 13
Purpose be able to that there is impressionability and curability.The curve represented by square refers to have Luviquat: DL-
The ratio of lactic acid is the sample of the electrolyte of 100: 18.5 weight ratios.The orientation represented by circle refers to have Luviquat:
DL-LACTIC ACID: glycerol 1, the sample of the electrolyte that ratio is 100: 18.5: 2.7 weight ratios of 3-bis-glycerol alkyd diacrylate.
The figure represented by triangle refers to have Luviquat: glycerol 1, and the ratio of 3-bis-glycerol alkyd diacrylate is 100: 10 weights
The sample of the electrolyte of amount ratio.Therefore, it is possible to use additive such as DL-LACTIC ACID and glycerol 1,3-bis-glycerol alkyd diacrylate
As the additive to Luviquat, it is used for obtaining curability and impressionability, remains able to show at passive matrix simultaneously
Device has the threshold voltage needed for addressability.
For producing the pixel arrangement of the I-V curve in Figure 14, additive is glycerol 1,3-bis-glycerol alkyd diacrylate
Ester (purchased from Sigma-Aldrich), DL-LACTIC ACID (purchased from Sigma-Aldrich), Irgacure2959 (2-hydroxyl-4'-(2-hydroxyl
Base oxethyl)-2-methyl phenyl ketone 98%, purchased from Sigma Aldrich), TPO (diphenyl (2,4,6-trimethylbenzoyl
Base) phosphine oxide, Lucirin TPO, BASF provide), TiO2 and water.The figure represented by square refers to have Luviquat:
Glycerol 1,3-bis-glycerol alkyd diacrylate: the ratio of DL-LACTIC ACID: Irgacure 2959: TPO: TiO2 is by weight
The sample of the electrolyte of 100: 3: 1.9: 0.21.0.17.10.The figure represented by circle refers to have Luviquat: glycerol 1,
3-bis-glycerol alkyd diacrylate: DL-LACTIC ACID: Irgacure2959: TPO: TiO2: the ratio of water is 100 by weight:
The sample of the electrolyte of 10.8: 18.5: 0.77: 0.62: 92: 19.2.Irgacure 2959 and TPO is light trigger, so that electric
Solve matter layer can solidify by UV, and the turbidity layer that TiO2 particle can serve as under reflective-mode in the pixel of operation.These charts
Bright, it is possible to use these additives and do not weaken threshold voltage.
Figure 10 a is the photo of the passive matrix addressed displays manufactured according to above-mentioned 3rd embodiment, and according to chessboard
Pattern updates.This specific matrix display includes 20 × 20 electrochrome pixel devices, and there is no that crosstalk can
To observe, i.e. corresponding pixel is dark or bright.Figure 10 b is the sketch of the part reflecting display, corresponding in Figure 10 a
Content in broken circle.Comparing with Figure 10 a, the sketch of Figure 10 b has slight turning clockwise.In photo, Ag-electrode exists
Each row pixel element lower horizontal stretches.In the sketch of Figure 10 b, Ag-electrode being drawn as rectangle, it is when observing from right to left
It is to tilt (owing to turning clockwise).Electrode is arranged on the insulated substrate comprising the through hole with carbon electrode.Absolutely
The opposite side of edge substrate, arranges the pixel layer comprising carbon.Additionally, white electrolyte drop is provided in each pixel comprising carbon
On the top of layer.Finally, it is provided that comprise translucent of conducting polymer, and be arranged as so that it cover all electrolyte, i.e.
The first pixel layer is formed in described electrolyte and described translucent contact position.The most straight vertical cutting is set in translucent sheet
Mouthful, with by pixel fragment electrical isolation each other, wherein, pixel in each segment disposes one by one to photo top bottom photo.
Distance between two vertical otch is 1cm.Pixel in each section is by translucent electronics contact each other.As can be at photo
In it can be seen that, the color of each pixel, the color of the most translucent, meet substantially perfect square.Around pixel
White material be not with the translucent electrolyte contacted, but can see through.In figure 10b, the top of Ag-electrode it is placed in
On discrete island corresponding to electrolyte.In more detail, one group of first electrode disposed by row provides electrochrome pixel element
Or first pixel layer, and one group of second electrode disposed by row provides matrix display the second pixel layer.Each corresponding row and
Row are connected to the output lead of digital integrated electronic circuit, and it drives by applying voltage.The required image that display to be passed through is given
Being stored in programmable circuit, it is by once or repeatedly updating whole display output image.Matrix display is the most more
Newly, although scan by column or single picture element scan is other possible addressing replacement schemes.In progressive scan, it is allowed to output
The corresponding row of signal activation, so that required pixel can update by applying a voltage to corresponding alignment.Un-activation
Row and the output of non-addressed column be prohibited from.Afterwards, the output lead of the row being updated over is forbidden, and by identical
Method updates row subsequently.
In the foregoing description, generally described the present invention with reference to the disclosedest many embodiments.But, as
Skilled addressee readily understands that, as in the scope of the present invention that limited in the dependent claims other be different from
Upper disclosed embodiment be also it is also possible that.Such as, the electrochrome pixel layer of the embodiment in Fig. 5-9 is by PEDOT:
PSS is formed.But, other electrochromic materials in addition to the electrochromic material formed by PEDOT:PSS can be used for
Electrochrome pixel layer, and fall within the scope of the present invention.Additionally, other to be different from the disclosed above electromotive force applied big
Little be the most also it is also possible that.
Claims (15)
1. a passive matrix display device (100；200), described display device includes
One group of pixel cell (110 being arranged as matrix；210),
The most each pixel cell includes:
First pixel layer (111；211), described first pixel layer is included between the most perceptible different color state
The electrochromism that can electrochemically convert and the organic polymer material of electro-chemical activity,
Second pixel layer (112；212), described first pixel layer faced by described second pixel layer, and
3rd pixel layer (113 of the electrolyte of solidification；213), described 3rd pixel layer is spatially placed in described first picture
Element layer and described second pixel layer between, and with described first pixel layer and described second pixel layer contacted with ions,
Each pixel cell (110；210) described second pixel layer (112；212) material comprising conductive carbon it is arranged as, and
The electrolyte of wherein said solidification is polycation electrolyte or polyanion electrolyte,
Thus provide at least response to cross over the threshold voltage of the voltage that described pixel cell applies,
And the color of the most each pixel is by the oxidation of described electrochromism and the organic polymer material of electro-chemical activity also
Change on ortho states provides；And in the color conversion processes of described pixel, the color of described electrolyte keeps constant.
Display device the most according to claim 1, described display device also includes one group of first electrode (121；221) and one
Organize the second electrode (122；222), described one group of first electrode and described one group of second electrode electrical isolation each other, and be arranged as
Make:
-each described first electrode (121；221) with each described second electrode (221；222) only intersect in a cross point,
And
-each described pixel cell (110；210) being placed in a respective described intersection, described cross point is by respective
First electrode and respective second electrode (121a, 122a；221a, 222a) formed, wherein:
-each described pixel cell (110；210) described first pixel layer (111；211) with described respective first electrode
(121a；Part 221a) is consistent, and
-each described pixel cell (110；210) described second pixel layer (112；212) with described respective second electrode
(122a；Part 222a) is consistent, or with described respective second electrode (122a；222a) electronics contact.
Display device the most according to claim 1, described display device also includes one group of first electrode (121；221) and one
Organize the second electrode (122；222), described one group of first electrode and described one group of second electrode electrical isolation each other, and be arranged as
Make:
-each described first electrode (121；221) with each described second electrode (221；222) only intersect in a cross point,
And
-each described pixel cell (110；210) being placed in a respective described intersection, described cross point is by respective
First electrode and respective second electrode (121a, 122a；221a, 222a) formed, wherein:
-each described pixel cell (110；210) described first pixel layer (111；211) with described respective first electrode
(121a；221a) electronics contact, and
-each described pixel cell (110；210) described second pixel layer (112；212) with described respective second electrode
(122a；Part 222a) is consistent, or with described respective second electrode (122a；222a) electronics contact.
4., according to the display device described in any one in claim 1-3, described display device is the most each controls unit
Part is combined with a respective described pixel cell and is arranged as to provide the color for pixel cell described in Active control
One group of transistor function individually controls element.
5., according to the display device described in any one in claim 1-3, described display device is placed in flexible base board (117；
217)。
Display device the most according to claim 5, wherein said flexible base board (117；217) for comprising paper and/or plastics
Flexible base board.
7., according to the display device described in any one in claim 1-3, described display device is arranged as multilamellar, described multilamellar
There is at least one in impressionability and flexibility.
8. according to the display device described in any one in claim 2-3, wherein said pixel cell (110；210) described
First electrode (121；221) and the first pixel layer (111；211) identical material is all comprised, and/or
Wherein said pixel cell (110；210) described second electrode (122；222) and the second pixel layer (112；212) whole
It is arranged as identical material.
Display device the most according to claim 8, the most each described pixel cell (110；210) described first electrode
(121；221) and the first pixel layer (111；211) it is entirely the part in identical layer, and/or
The most each described pixel cell (110；210) described second electrode and the second pixel layer (112；212) it is entirely phase
The same part in layer.
Display device the most according to claim 3, the most each described pixel cell (110；210) described second picture
Element layer (112；212) with described respective second electrode (122a；222a) electronics contact, and wherein said display device is also wrapped
Including insulating barrier (318), described insulating barrier is placed in described second in each pixel cell (310) of described one group of pixel cell
Between electrode (322) and described second pixel layer (312), and described insulating barrier also includes each being mounted with electronic conductor
(320) passage (319), described electronic conductor is by respective second pixel layer (312) of respective pixel cell (310) and institute
State the second electrode (322) each electronics to connect.
11. according to the display device described in any one in claim 1-3, wherein in respective pixel cell, and described
Two pixel layers cover the core of described 3rd pixel layer.
12. according to the display device described in any one in claim 1-3, wherein in respective pixel cell, and described
The surface area of two pixel layers is at least the 60% of the surface area of described electrolyte, or at least 75%, or at least 90%, or at least
95%.
13. is polycation according to the display device described in any one in claim 1-3, the electrolyte of wherein said solidification
Electrolyte.
14. display devices according to claim 10, wherein said insulating barrier is plastic insulating layer.
15. the followings are for providing the purposes of the pixel cell that can use in one group of pixel cell:
-the first pixel layer (111；211), described first pixel layer color is contained between the most perceptible different color state
The electrochromism that can electrochemically convert and the organic polymer material of electro-chemical activity,
-the second pixel layer (112；212), described second pixel layer is in the face of described first pixel layer, and described second pixel layer is by wrapping
Material containing conductive carbon is formed, and
3rd pixel layer (113 of the electrolyte of-solidification；213), described 3rd pixel layer is spatially placed in described first picture
Element layer and described second pixel layer between, and with described first pixel layer and described second pixel layer contacted with ions,
The electrolyte of wherein said solidification is polycation electrolyte or polyanion electrolyte, when crossing over any described pixel list
One group of pixel cell described in when unit applies voltage each has threshold voltage response,
And the color of the most each pixel is by the oxidation of described electrochromism and the organic polymer material of electro-chemical activity also
Change on ortho states provides；And in the color conversion processes of described pixel, the color of described electrolyte keeps constant.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38976910P | 2010-10-05 | 2010-10-05 | |
| US61/389,769 | 2010-10-05 | ||
| EP10186570A EP2312386A1 (en) | 2009-10-05 | 2010-10-05 | Passive-matrix electrochromic display device |
| EP10186570.7 | 2010-10-05 | ||
| PCT/EP2011/055284 WO2012045485A1 (en) | 2010-10-05 | 2011-04-05 | Display device |
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| Publication Number | Publication Date |
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| CN103201676A CN103201676A (en) | 2013-07-10 |
| CN103201676B true CN103201676B (en) | 2016-11-16 |
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| CN201180047280.6A Active CN103201676B (en) | 2010-10-05 | 2011-04-05 | Display device |
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| JP (1) | JP5774111B2 (en) |
| CN (1) | CN103201676B (en) |
| WO (1) | WO2012045485A1 (en) |
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| EP2607950B1 (en) * | 2011-12-22 | 2014-05-21 | Acreo Swedish ICT AB | Fixed image display device and method of manufacturing the same |
| CN107342309B (en) * | 2017-07-05 | 2020-03-24 | 固安翌光科技有限公司 | High-reliability passive organic electroluminescent device and preparation method thereof |
| CN107895735A (en) * | 2017-11-30 | 2018-04-10 | 深圳市普耐光电科技有限公司 | A kind of flexible display screen |
| CN109256310A (en) * | 2018-10-10 | 2019-01-22 | 中山大学 | Addressable nanometer of cold cathode X-ray plane source of one kind and preparation method thereof |
| CN111323979B (en) * | 2020-01-03 | 2024-06-07 | 深圳市光羿科技有限公司 | Electrochromic device and preparation method thereof |
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| CN1965263A (en) * | 2004-06-11 | 2007-05-16 | Lg化学株式会社 | Display device using printed circuit board as substrate of display panel |
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| JPS61130929A (en) * | 1984-11-30 | 1986-06-18 | Tokuyama Soda Co Ltd | Electrochromic display element |
| JPS60217345A (en) * | 1985-02-14 | 1985-10-30 | Asahi Glass Co Ltd | Electrochromic display element |
| AU643093B2 (en) * | 1990-12-26 | 1993-11-04 | Ppg Industries Ohio, Inc. | Solid-state electrochromic device with protong-conducting polymer electrolyte |
| JP2003315843A (en) * | 2002-04-19 | 2003-11-06 | Fuji Photo Film Co Ltd | Electrochromic display |
| DE10328377A1 (en) | 2003-06-24 | 2005-01-20 | Siemens Ag | Electrochromic display system |
| US9030724B2 (en) * | 2008-07-03 | 2015-05-12 | Chromera, Inc. | Flexible and printable electrooptic devices |
| US8130438B2 (en) * | 2008-07-03 | 2012-03-06 | Ajjer Llc | Metal coatings, conductive nanoparticles and applications of the same |
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- 2011-04-05 JP JP2013532084A patent/JP5774111B2/en active Active
- 2011-04-05 WO PCT/EP2011/055284 patent/WO2012045485A1/en active Application Filing
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1199408A (en) * | 1996-08-20 | 1998-11-18 | 大曹株式会社 | polymer solid electrolyte |
| CN1498357A (en) * | 2001-03-19 | 2004-05-19 | Matrix addressable electrochromic display device | |
| CN1965263A (en) * | 2004-06-11 | 2007-05-16 | Lg化学株式会社 | Display device using printed circuit board as substrate of display panel |
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| JP5774111B2 (en) | 2015-09-02 |
| JP2013539081A (en) | 2013-10-17 |
| CN103201676A (en) | 2013-07-10 |
| WO2012045485A1 (en) | 2012-04-12 |
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