CN103201676A - Display device - Google Patents
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- CN103201676A CN103201676A CN2011800472806A CN201180047280A CN103201676A CN 103201676 A CN103201676 A CN 103201676A CN 2011800472806 A CN2011800472806 A CN 2011800472806A CN 201180047280 A CN201180047280 A CN 201180047280A CN 103201676 A CN103201676 A CN 103201676A
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Images
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
There is disclosed an electrochromic passive-matrix display (100), wherein each passively addressed pixel cell (111, 112, 113) comprises an electrolyte (113) ionically connecting an electrochromic and electrochemically active polymer (121) and a layer of electrically conducting carbon (122). Thus, each pixel has a pronounced threshold voltage sufficient for reducing cross talk in an electrochromic display.
Description
Invention field
The present invention relates to the organic pixel arrangement of electrochemical activity, and particularly relate to printable electrochemical activity pixel arrangement based on the organic electrochromic material.
Background technology
In the directly address electrochromic display device (ECD), each pixel is connected to the external drive voltage source by independent conductor wire, independent electric control when being conducive in the display all pixels.When the number of pixel in the display is big, connect an independent line or physically impossible to each pixel, or unpractical.For overcoming this problem, usually pixel is arranged as matrix structure, wherein with them by time multiplex technique from matrix edge via the row and column addressing.Be called matrix display and matrix addressing with this display with to their method for addressing.
In Active Matrix Display, each pixel is equipped with at least one transistorized electronic circuit that has separately, wherein each transistorized conduction state control color of pixel state separately.
To there be the independent transistorized matrix display of each pixel to be called passive matrix display.Image element circuit in Active Matrix Display has improved the addressing capability of pixel, yet, to compare with passive matrix display, the manufacturing of Active Matrix Display is more complicated and expensive.On the other hand, several shortcomings such as slow response time, image blurring and crosstalk limits the practical application of passive matrix addressing electrochromic device.Image blurringly can classify as crosstalk effect in a broad sense.It is between the pixel by the interactional phenomenon of electrolyte, and neighbor slightly painted on the row and column that causes selecting.This unfavorable painted along with the distance with selected pixel increases and weakens.The technology of minimizing image blurring effect commonly used is the physical isolation each other of independent display pixel.
Another source of crosstalking is via the interaction of the electrode that is connected with matrix between the pixel.That is, not only the pixel of locating in a pair of row and the capable point of crossing of institute's addressing changes its color, and other adjacent pixels also change its color.The reason that takes place of crosstalking is that also there is voltage difference in the electrolyte of crossing in the pixel pixel on every side that centers on institute's addressing.In addition, compare with the not charged pixel that empties, coloured display pixel that electricity is isolated is crossed over its electrode and is had different voltage usually.When two pixels being charged as different color states and linking together, painted pixel trends towards driving or the painted pixel that empties by capacitor discharge.
An example of electrochromism passive matrix display has been described among the WO 2004/114008.Pixel comprises and is clipped in two electrolyte between the organic layer, and each organic layer comprises electrochromic polymeric compounds.In addition, this pixel is clipped between two electrodes.And passive matrix display forms by the layer with diode characteristic between in the electrode and the organic layer.In other words, before pixel can change its color, must surpass threshold voltage.The amount of therefore, crosstalking in the display reduces.Except in pixel, introducing the layer with diode function, this application also proposes to obtain by the careful combination of pixel material can passive addressed pixel, but about should how to select these materials not provide any information or example fully to obtain this effect.
Summary of the invention
The objective of the invention is to propose a kind of combination of materials, described combination of materials provide a kind of in pixel, do not need independent diode layer can passive addressed pixel.
These and other purposes have been realized by the theme that in independent claims, provides.The preferred embodiments of the invention in independent claims, have been provided.
According to its first aspect, the present invention relates to a kind of passive matrix display device, described display device comprises:
One group of pixel cell that is arranged as matrix,
Wherein each pixel cell comprises:
First pixel layer, but described first pixel layer is included in the different visually electrochromism of electro-chemical conversion and the organic polymer material of electrochemical activity between the perceptible color state,
Second pixel layer, described second pixel layer in the face of described first pixel layer and
Electrolytical the 3rd pixel layer that solidifies, described the 3rd pixel layer spatially is placed between described first pixel layer and described second pixel layer, and contacts with the described second pixel layer ion with described first pixel layer, and
Wherein described second pixel layer of 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 comprises:
One group of pixel cell that is arranged as matrix,
Wherein each pixel cell comprises:
First pixel layer, but described first pixel layer is included in the different visually electrochromism of electro-chemical conversion and the organic polymer material of electrochemical activity between the perceptible color state,
Second pixel layer, described second pixel layer in the face of described first pixel layer and
Electrolytical the 3rd pixel layer that solidifies, described the 3rd pixel layer spatially is placed between described first pixel layer and described second pixel layer, and contacts with the described second pixel layer ion with described first pixel layer, and
Wherein described second pixel layer of each pixel cell is arranged as conductive carbon, thereby provides at least response to cross over the threshold voltage of the voltage that described electrolyte applies.
Each color of pixel is provided by the change on the redox state of the organic polymer material of described electrochromism and electrochemical activity.In other words, electrolyte does not have colorant such as pH dyestuff usually, and namely response environment pH changes the dyestuff of color.Again in other words, in the color of pixel transfer process, electrolytical color remains unchanged usually or is constant basically.
Usually, second pixel layer is arranged as the effect of playing in the electrochemical process to electrode, wherein first pixel layer forms the active photochromic layer of pixel arrangement.The layer of pixel arrangement is settled basically in parallel with each other.According to an embodiment, the layer in the described first pixel layer front, for example described first insulation course and described first electrode be preferably transparent or semitransparent so that can visually discover the variable color of pixel arrangement.
In other words, second pixel layer is electronic conductivity.And second pixel layer comprises carbon, perhaps is arranged as the electronic conductivity material that comprises carbon.
According to a third aspect of the invention we, provide one group of pixel cell to be used for providing response at least to cross over the purposes of the threshold voltage of the voltage that described pixel cell applies, described pixel cell comprises separately:
-the first pixel layer, but described first pixel layer is included in the different visually electrochromism of electro-chemical conversion and the organic polymer material of electrochemical activity between the perceptible color state,
-the second pixel layer, described second pixel layer in the face of described first pixel layer and
Electrolytical the 3rd pixel layer of-curing, described the 3rd pixel layer spatially is placed between described first pixel layer and described second pixel layer, and contacts with the described second pixel layer ion with described first pixel layer, wherein,
Described electrolyte does not have the PH dyestuff basically, and
Described second pixel layer of each pixel cell is arranged as the material that comprises conductive carbon.
By settling the device of describing about described first, second or the third aspect, provide a kind of pixel that is enough to reduce the significant threshold voltage of crosstalking in the electrochromic display device (ECD) that has.Although chemistry and the Physical Mechanism of the threshold value character of control electrochrome pixel device still remain to be disclosed, can utilize resulting voltage threshold behavior to minimize the crosstalk effect in the matrix display, as electric current and the color contrast variation of the relative non-linear to voltage that applies.
According to an embodiment, this display device also comprises one group of first electrode and one group of second electrode, and they are electrically isolated from one, and with certain pattern settle so that:
-each described first electrode only intersects a point of crossing with each described second electrode,
-each described second electrode only intersects a point of crossing with each described first electrode, and
-each described pixel cell is placed in place, the described point of crossing of separately one, and described point of crossing is formed by separately first electrode and second electrode separately, wherein:
Described first pixel layer of-each described pixel cell is a part of consistent with described first electrode separately, perhaps contacts with the described first electrode electronics separately, and
Described second pixel layer of-each described pixel cell is a part of consistent with described second electrode separately, perhaps contacts with the described second electrode electronics separately.
With pixel layer and the uniformly correlated benefit of electrode layer be, need print steps still less, that is, can obtain more efficient manufacture method.
Different with electrode layer relevant benefits with pixel layer are to use different materials to be used for pixel layer and electrode.By selecting relatively to have the more conductive electrode material of high electrode with pixel layer, more inapparent voltage drop along electrode can be provided, thereby and provide the better conversion of each pixel cell.
According to an embodiment of display device, it does not comprise one group of independent control element that each control element wherein is combined with a described pixel cell separately and is arranged as the transistor function of the color that is provided for the described pixel cell of active control.Relate to the present invention, independent control element is not as the control element of the part of pixel cell.That is, control element is placed in electricity upstream or the downstream of pixel cell.
An embodiment according to display device is placed in it on flexible base, board or the flexible carrier, and preferably comprises substrate or the carrier of paper and/or plastics.The benefit relevant with the use of flexible base, board is that it is conducive to the use for the manufacture of the printing process of display.
An embodiment according to display device is arranged as multilayer with it, and described multilayer has at least one in impressionability and the flexibility.
An embodiment according to display device, described first electrode of described pixel cell and first pixel layer all are arranged as identical materials or are formed by identical materials, and/or described second electrode of described pixel cell and second pixel layer all are arranged as identical materials or are formed by identical materials.About using the benefit of identical materials to be this simplification and to have accelerated the preparation method to several assemblies.
According to an embodiment of display device, described first electrode and first pixel layer of each described pixel cell is the part of identical layer, and/or described second electrode of each described pixel cell and second pixel layer are the parts of identical layer.Benefit about this embodiment is that it provides the structure of simplification usually, thereby brings print steps still less, and cost-efficient production is more arranged.
Alternatively, though described second pixel layer respectively uses different material for second pixel layer with second electrode with in second electrode all is placed in identical plane.Electrode can be arranged as has the more material of high conductivity, thereby makes and can use lower operating voltage and/or provide higher color contrast the switching time of reducing described first pixel layer.The conductivity higher than described first pixel layer that have electrode reduces the voltage drop along electrode.
An embodiment according to display device, described display device comprises insulation course, preferred plastic insulating layer, described insulation course is placed between described second electrode and described second pixel layer in each pixel cell of described one group of pixel cell, and described insulation course also comprises the passage that is mounted with electronic conductor separately, and second pixel layer that described electronic conductor is incited somebody to action pixel cell separately separately is electrically connected with described second electrode.The advantage that this this embodiment is relevant is to make it possible to only use the manufacturing of an intermediate carrier layer.
According to an embodiment of display device, described second pixel layer covers the core of described the 3rd pixel layer in each described pixel cell.In more detail, described second pixel layer and described the 3rd pixel layer can be arranged as and make that the center of layer separately is consistent along the normal orientation of described layer, and described layer has stacked structure, and are arranged to and are parallel to each other.
According to an embodiment of display device, the surface area of second pixel layer in each pixel cell is at least 60% of electrolytical surface area, or at least 75%, or at least 90%, or at least 95%.In other words, described second pixel layer can be placed in described electrolyte behind or be covered by described electrolyte.
According to an embodiment of display device, the electrolyte of curing is polycation electrolyte.According to alternate embodiment, the electrolyte of curing is polyanion electrolyte.
According to an example, electrolyte is arranged as and makes it be divided into less ionic complex and remarkable bigger ionic complex, and wherein less ionic complex has first electric charge and bigger ionic complex has opposite electric charge.Bigger ionic complex preferably comprises long polymer chain or big molecule, and is kation or negative ion.In other words, according to an example, electrolyte is polyelectrolyte or the low polyelectrolyte that comprises bigger cationic complexes.According to alternative example, electrolyte is polyelectrolyte or the low polyelectrolyte that comprises bigger anionic complex.
Basically, to the thickness of described first pixel layer of pixel arrangement without limits or limit, but in one embodiment, mainly for making and flexible viewpoint, it typically can be between 0.1 μ m to the 7 μ m, and wherein selected thickness relies on required device performance; Thinner layer is generally equal to short pixel arrangement switching time, and thicker layer is generally equal to higher color contrast.In addition, the thickness of described second pixel layer of pixel arrangement can be 0.1 μ m to 40 μ m in one embodiment.Should be taken into account the following when selecting the thickness of layer: the second too thin pixel layer can reduce the colorability of described first pixel layer, and too thick layer may reduce resistance to bend(ing) and/or the anti-mechanical pressure of pixel arrangement.In addition, the thickness of described the 3rd pixel layer of pixel arrangement in one embodiment can be between 1 μ m to the 20 μ m, perhaps 1 μ m to 100 μ m not.Usually, layer becomes more thin, and flexibility is more good, but the simultaneous contrast descends.The thickness of each pixel layer is to measure along the direction of observation of each pixel layer normal.According to the optional method that pixel layer is provided, they can be provided by multiple conventional printing technology, are coated with as spin coating, ink jet printing, serigraphy, ion self assembling multilayer, aerosol injection printing or rod.
According to an example, by the mode of laser technology, preferably the mode by laser drill provides the passage in the described insulation course.When the passage made by boring or the mode of laser drill in the insulation course, preferably select enough dystectic materials, make the risk minimization that damages the passage peripheral region.
In one embodiment, the cross-sectional area of the passage of pixel arrangement can be for example 10 μ m
2To 2mm
2According to another example, this area is 100 μ m
2To 0.5mm
2According to another example again, this area is 500 μ m
2To 0.2mm
2According to another example again, this area is 1000 μ m
2To 0.1mm
2Measure cross-sectional area orthogonally with the extension of described passage, that is, if channel formation is the conventional hollow cylinder with base radius r, the cross-sectional area of passage is pi*r
2The benefit of big relatively passage rank street area is that it provides higher levels of conductivity.Yet too big cross-sectional area can cause the problem in the manufacture process, passes the leakage of passage as the 3rd pixel layer.
For some technologies of preparing, be arranged on the inboard that electric conductor in the described passage only is placed in described passage, this means that described electric conductor has hollow or tubular form, have interior girth and outer perimeter, wherein at least outer perimeter corresponding to the girth of described passage.Other arrangements of electric conductor are possible in the described passage, and condition is this conductor provides electronics to be connected between described conduction alignment and described second pixel layer.
Usually, device according to the present invention is operated in the following manner: apply first electromotive force to described first pixel layer, and apply second electromotive force different with described first electromotive force to described second pixel layer, make and set up electric field in the electrolyte of described curing.As long as electromotive force keep long enough, electric field causes the redox reaction of described pixel layer, described reaction causes the color change of described electrochromic material.
The switching time or the color change that should be appreciated that pixel arrangement for example depend on usually:
Ion mobility in the-electrolyte, mobility are more high, and switching time is more short;
The size of the gas current the in-electrolyte, this is determined by the ion mobility in the electrolyte and electrolyte volume;
The selection of-electrochemical activity and/or electrochromic material;
-for the electrochemical activity of the required reaction of color that changes electrochromic material and/or the volume of electrochromic material;
The amplitude of-the voltage that applies; Voltage is more short more high switching time, and vice versa.
Can provide the display with several individually addressable pixels by settling a plurality of aforesaid electrochrome pixel devices.Useful is that pixel arrangement is arranged as the matrix that allows the passive matrix addressing concept and arranges.
That be fit to, the conventional or known scheme of any addressing for passive matrix display can be used for this device of operation.For example, settle the electrode embark on journey to provide electrochrome pixel element or first pixel layer, and the electrode that is positioned to row provide second pixel layer of matrix display.Each row and column separately is connected to the output lead of digital integrated circuit, and it preferably drives by applying voltage.The image storage that hope can be shown by display is in programmable circuit, and it is by once or repeatedly upgrading whole display output image.Matrix display upgrades usually line by line, even be other possible addressing replacement schemes by column scan or single picture element scan.In lining by line scan, allow output activation signal to go accordingly, so that required pixel can be upgraded by voltage being applied to corresponding alignment.The un-activation row and not the output of addressed column forbid.Afterwards, the output lead of the row that upgraded is set at output forbids, and by identical method renewal row subsequently.In such addressing scheme, threshold voltage is in conjunction with allowing passive matrix display in the renewal that has under the very for a short time situation of crosstalking with the not addressing row and column of forbidding.
In another example, utilize threshold voltage and only have the combination of simulating the external circuit of exporting.Here, suppose in a pixel cell, painted fully by applying voltage V realization.So, addressed row is arranged the general of voltage for this reason, and addressed column is also arranged half of voltage for this reason, but polarity is opposite.Therefore, the total voltage of leap pixel cell is V.The addressing row and column is not set to ground connection.Addressed row and not the point of crossing place of addressed column pixel cell or experience half that upgrade voltage V at the pixel cell at the place, point of crossing of addressed row and addressed column not.Thus, as long as being about as much as, threshold voltage upgrades the general of voltage V, thus the threshold voltage minimise cross talk in the pixel cell separately.
About the present invention, described one group of first electrode and described one group of second electrode are the example explanation with column electrode and row electrode sometimes.The content of stating about column electrode and row electrode also can be used for described one group of first electrode and described one group of second electrode, even these electrodes do not have arranged parallel or orthogonal arrangement.
Definition
Layer: according to an embodiment, pixel arrangement has rhythmo structure, and is made of " layer " of different materials.These layers can be continuous and/or patternings, and can put on each other (self-supporting device) or be applied to supporter or carrier (bracing or strutting arrangement).These terms " self-supporting/support " also can be used for independent layer.The self-supporting layer be can operate with himself and, for example be mounted in the printing machine under the situation of extra supporting layer not damaging and do not need.In addition, term " layer " can comprise all identical materials in the identical plane, interrupts with this patterns of materialization or in the mode that forms discontinuous " island " in the plane no matter be.
Insulation course: insulation course preferably comprises plastics, is perhaps formed by layer, plastic insulating layer, plastic foil or the plastic foil such as the polyester foil that comprise plastics.For plastic insulating layer or comprise the insulation course of plastics, it can comprise for example film, foam films or its laminated film, comprises, for example: polyolefin such as tygon, polypropylene etc.; Polyester such as polyethylene terephthalate, PEN, polybutylene terephthalate etc.; Polyvinylchloride, polystyrene, polyurethane, polycarbonate, polyamide, polyimide, polymethylmethacrylate, polybutylene, polybutadiene, polymethylpentene, vinyl-vinyl acetate copolymer, ethene (methyl) acrylic copolymer, ethene (methyl) acrylate copolymer, ABS resin, ionomer resin etc., but be not limited to these examples.And, for layer, can use commercial membranes, and also can use the film that utilizes process materials to form by cast film process.
In addition, the display with several pixels can comprise the successive layers of insulating material, and it forms at least some described insulation course of described a plurality of electrochrome pixel devices.In other words, the insulation course of several pixels can each independent part of a continuous insulation layer naturally.
Electrochromic layer: " electrochromic layer " that the present invention relates to is the continuous geometry body, and it can be patterned as different shapes, and constituting by a kind of material or multiple material.Described one or more materials can be organic or inorganic, low molecular or high molecular.This electrochromic layer, be to be constituted or irrelevant more than a kind of integral body of material by a kind of material with it, made up following character: at least a material conducts electricity at least one oxidation state, and at least a material is electrochromic, and namely the result as the electrochemical redox reaction in the material represents color change.Randomly, electrochromic layer can comprise electrochemical active material.
Electrochemical activity: be the material that a slice has the electronic conductivity that can change by the redox state galvanochemistry that changes described material according to " electrochemical activity " of the present invention layer.Usually, at least a portion of electrochemically active element contacts with electrolyte ion, and electrochemically active element can also be integrated with the electrode that is made of identical or different material.Electrode can also be placed in the top of described electrochemical active material.
Electrochromic display device (ECD): " electrochromic display device (ECD) " that the present invention relates to is the device that comprises at least one electrochrome pixel layer, settles described device so that the color change of electrochromic layer is visually discernable in reflection and/or transmission.
Color change: when mentioning " color change ", this also means the change that comprises on optical density (OD) or the reflectivity so that " color change " for example also consider from Lan Zhihong, blue to colourless, colourless to blue, dark green to light green, ash to white or dark-grey change to light gray etc.
Passive matrix: in Active Matrix Display, each pixel is equipped with has the electronic circuit that at least one provides the control element of transistor function.In other words, passive matrix display device is the display device with one group of independent control element that each control element wherein links to each other with separately a pixel cell.Control element further is arranged as the transistor function that the color that can control described pixel cell is provided.The example of control element is field effect transistor and electrochemical transistor." independent " means electricity upstream or the downstream that key-course is placed in described pixel cell.
Pixel layer: " pixel layer " that the present invention relates to defined by the interface between electrolyte and the conductive layer.In more detail, pixel layer is the volume of the electronic conductive layer that covered by electrolyte in the one side.When pixel layer was electrochromic layer, the variable color of layer may not correspond to the interface between electrolyte and the electrochromic layer, the i.e. scope of defined pixel layer.Color change may for example extend to outside the interface between electrolyte and the electrochromic layer, and passes electrochromic layer to the opposite side of a side that is covered by electrolyte.
According to an example, electrolyte be clipped in the electrode layer that comprises carbon and comprise electrochromism and the electrode layer of the organic polymer of electrochemical activity between, described electrode layer intersects each other or intersects at a point.As described above, pixel layer is by the corresponding interface definition between electrode and the electrolyte.In other words, pixel layer is consistent with the appropriate section of electrode.
In the optional embodiment of pixel arrangement, electronic conductor can comprise: electrically conductive material as, electrically conductive polymer such as PEDOT:PSS (poly-(3, the 4-ethene dioxythiophene) poly-(styrene sulfonate)), carbon, inert metal or galvanochemistry inert metal such as gold, other conductive materials that perhaps are suitable for contacting with the electrochemical activity layer, the perhaps combination of these electrically conductive materials.Usually, the conductive material that is suitable for contacting with the electrochemical activity layer is inertia, so that they do not cause the electrochemical reaction of essence.These materials can for example provide as the ink or the slurries that are placed in the passage in preparation process or prefabricated process.
Electrode: electrode can comprise any electrically conductive material, as the combination of conducting polymer, metal, conductive carbon, titanium, platinum, graphite, Graphene, noble metal and inert metal or these electrically conductive materials.Electrode can also comprise the galvanochemistry inert metal and be suitable for the conductive material that contacts with the electrochemical activity layer as gold or other.Usually, the conductive material that is suitable for contacting with the electrochemical activity layer is inertia, so that they do not cause the electrochemical reaction of essence.These materials can for example provide as the ink or the slurries that are placed on the described dielectric film in preparation process or prefabricated process.
Electrode is preferably elongation, and can be band shape, or is arranged as line or linear.Electrode can for example be arranged as the layer of conducting polymer or be arranged as tinsel or line.According to an embodiment, first group of electrode is placed in first plane in parallel with each other.Second group of electrode is placed in second plane in parallel with each other, and described second plane is different with described first plane, and wherein said first plane and described second plane are arranged as parallel to each other.Preferably, first and second planes only separate little distance, and described distance equals electrolytical height at least.In addition, described first and second groups of electrodes are arranged as usually and are perpendicular to one another.According to another embodiment, the electrode of described first and/or second group of electrode is not arranged as parallel to each other, and perhaps first and second planes are not arranged as parallel to each other.In addition, electrode can be settled with straight line, but also can be curve or have irregularly shaped.In other words, the pixel cell that is arranged as matrix must not be placed in the straight row and column, but can settle in more irregular mode, condition be in described first group of electrode each electrode only with described second group of electrode in each electrode only intersect a point of crossing.
Directly electrically contact: allow electric charge by the contact of the direct physical between the two-phase (for example electrochemical activity organic material and electrolyte) of interface exchange (public interface).Charge exchange by the interface can comprise: electronics shifts between the ionic conduction phase at transfer between the conductive phase, ion, perhaps between for example to element and electrolyte or between electrolyte and the electric driven color-changing part at the interface, by electrochemical mode, perhaps by the appearance owing to the capacitance current of the charging of helmholtz layer on this interface, the conversion between electronic current and gas current.
Can provide two ion contacts between the element at the material of transmission ion between two elements by at least a.The electrolyte that directly contacts (public interface) with the first and second electrochemical activity layers is the example that the material of two ion contacts between the electrochemical activity layer can be provided.Therefore can claim this electrolyte to contact with two electrochemical activity leafing.
Two kinds of materials can be for example via the mutual electronics contact of the 3rd material.Electronics contact between two elements can provide by the material of transmission electronic between two elements by at least a.Be the example that the material of electronics contact can be provided between two-layer with carbon-coating that the first and second electrochemical activity layers directly contact (public interface).Therefore carbon-coating can be called electronic conductor, or electronic conduction.
Direct electron contact: the direct physical contact (public interface) between two electronic conductors.
The electrochrome pixel device can comprise at least polymkeric substance an oxidation state conduction as electrochromic material and/or electrochemical active material, and randomly also comprises polyanionic compound.
The electrochromic polymeric compounds that is used for using at electrochrome pixel device of the present invention for example is selected from the group of being made up of the following: electrochromism polythiophene, electrochromism polypyrrole, electrochromism polyaniline, the poly-different sulphur naphthalene of electrochromism, electrochromism p-phenylene vinylene, and their multipolymer.In one embodiment, electrochromic polymeric compounds is homopolymer or the multipolymer of 3,4-dialkoxythiophene, and wherein said two alkoxys can be identical or different, perhaps represents randomly substituted oxygen base-alkylidene-oxygen Ji Qiao together.In a further embodiment, electrochromic polymeric compounds is to be selected from 3 of the group be made up of the following, the homopolymer of 4-dialkoxythiophene or multipolymer: poly-(3,4-methylene dioxy thiophene), poly-(3,4-methylene dioxy thiophene) derivant, poly-(3,4-ethylidene dioxy thiophene), poly-(3,4-ethylidene dioxy thiophene) derivant, poly-(3,4-propylidene dioxy thiophene), poly-(3,4-propylidene dioxy thiophene) derivant, poly-(3,4-butylidene dioxy thiophene), poly-(3,4-butylidene dioxy thiophene) derivant and their multipolymer.Polyanionic compound then is preferably poly styrene sulfonate.
Understand easily as the technician, in alternative embodiment of the present invention, electrochromic material comprises the combination of any non-polymer material, different non-polymer material, the perhaps combination of polymeric material and non-polymer material, they represent conduction and electrochromism behavior at least one oxidation state.For example, people can use the compound substance of conductive material and electrochromic material, as have conducting particles such as tin oxide, ITO or the ATO particle of polymkeric substance or non-polymer electrochromic material such as polyaniline, polypyrrole, polythiophene, nickel oxide, tygon ferrocene, poly-viologen, tungsten oxide, yttrium oxide, molybdena and Prussian blue (ferric ferrocyanide).As the limiting examples of the electric driven color-changing part that is used for device of the present invention, that can mention has: a slice conduction and electrochromic PEDOT-PSS; A slice has Fe
2+/ SCN
-Conduction and electrochromic PEDOT-PSS, and Fe
2+/ SCN
-As additional electrochromism component (vide infra); The sheet that the contiguous network by the electroconductive ITO particle in the insulating polymer matrix that directly electrically contacts with electrochromism WO3 coating constitutes; The sheet that the contiguous network by the electroconductive ITO particle in the insulating polymer matrix that contacts with electrochromism component in being dissolved in electrolyte constitutes.As mentioned above, the electrochrome pixel device can comprise for other electrochromic materials of realizing having more than a kind of display of color.These other electrochromic materials can be arranged in the electrochrome pixel element or in the electrolyte that solidifies, so for example it comprises the electrochromism redox system, Yi Bian as being colourless Fe
2+With the redox couple of SCN-ion, another side is red Fe
3+(SCN) (H2O)
5Complex.Mode by other non-limiting examples, such material can be selected from different azophenlyene classes, as DMPA-5,10-dihydro-5,10-dimethyl azophenlyene, DEPA-5,10-dihydro-5,10-diethyl azophenlyene and DOPA-5,10-dihydro-5,10-dioctyl azophenlyene is selected from TMPD-N, N, N ', N '-tetramethylbenzene diamines, TMBZ-N, N, N ', N '-tetramethyl benzidine, TTF-tetrathiafulvalene, phenanthroline-iron complex, erioglaucine A, diphenylamine, right-the ethoxy chrysol, methylene blue, different indigo-blue and phenosafraine, and their potpourri.
The electrolyte that solidifies: for the purposes of the present invention, a kind of like this electrolyte of " electrolyte of curing " expression, this electrolyte is enough rigidity in its serviceability temperature, make at the particle/thin slice of its body in mutually basically by electrolytical high viscosity/rigidly fix, and its does not flow or leaks.In preferred situation, this electrolyte has suitable rheological properties, allowing this material, for example, by conventional print process, is coated on the supporter with the form of full wafer or pattern.After deposition, electrolyte preparations should solidify after the evaporation of solvent or because of chemical crosslink reaction, described chemical crosslink reaction by additional chemical reagent or by physical influence as by ultraviolet, infrared or microwave radiation irradiation, cooling or the effect any other are brought.The electrolyte that solidifies can for example comprise moisture or contain the gel of organic solvent, as gelatin or polymeric gel.Yet the solid polymerization electrolyte is also expected, and is dropped in the scope of the present invention.In addition, this definition also comprises by suitable matrix material, as paper, fiber or porous polymer leaching or the liquid electrolyte that keeps in any other mode.In some embodiments of the present invention, this material is actually the stilt of settling electrochromic device, so that above support forms the global facility of the operation of electrochromic device.
The electrolyte that solidifies can comprise bonding agent.Preferably this bonding agent has gelling.Bonding agent can be selected from the group of being made up of the following: gelatin, gelatine derivative, polyacrylic acid, polymethylacrylic acid, poly-(vinyl pyrrolidone), polysaccharide, polyacrylamide, polyurethane, polypropyleneoxide, polyethylene oxide, poly-(styrene sulfonic acid) and poly-(vinyl alcohol), and their salt and multipolymer; And can randomly be crosslinked.Electrolyte can be by two or more being combined to form of a kind of or these materials in the above listed material.
In a word, construct the manufacture method that allows to comprise the traditional printing technology according to material selection and the vertical stratification of pixel arrangement of the present invention.This traditional printing technology can comprise that rod is coated with, serigraphy, spin coating, ink jet printing, aerosol injection printing, perhaps any other such manufacturing course.The structure of pixel arrangement also allows to use and can be amplified to the more manufacturing course of large scale manufacturing simply, and this allows faster thereupon and makes at a low price.For example, comprise according to the display array of a plurality of pixel arrangements of the present invention and can in roller-right-roller manufacturing course, make.
In an embodiment of pixel arrangement, electronic conductor, second pixel layer, the 3rd pixel layer and first pixel layer in conduction alignment, the described passage can be settled by the mode of printing technology.Therefore, but the electronic conductor that provides the electronics between described second pixel layer and the conduction alignment to link can preferably be settled the material that comprises printing material in order to be conducive to make, namely in order to print the material with suitable rheological properties.But the China ink that comprises conducting polymer or conductive carbon is the example of this printing material.In the manufacture process of pixel arrangement, electrically conductive material can be placed in the described passage in the following manner: by multiple different printing technology such as rod is coated with, serigraphy, ink jet printing, aerosol injection printing, spin coating etc., perhaps by material being coated on the passage place and it being pressed into described passage by for example crossing over the dilatory squeegee of described passage.It will also be appreciated that the insulation course with the passage that is mounted with electronic conductor can be preassembled or part is preassembled.For example, can in the preprocessing process, be coated with or settle passage and electronic conductor.
Usually, other targets of the present invention, feature and benefit will manifest from following detailed description, dependent claims and accompanying drawing.To embodiment of the present invention be described with reference to the drawings by the mode of embodiment now.Should be appreciated that accompanying drawing not in true ratio, and easy to understand to those skilled in the art, in scope of the present invention, the size different with the size shown in the accompanying drawing is same possible.
The accompanying drawing summary
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 of the described arrangement of Fig. 1 a.
Fig. 2 a schematically shows the decomposition diagram of passive matrix display, and wherein first pixel layer is consistent with first electrode.
Fig. 2 b schematically shows the sectional view according to the pixel in the pixel arrangement of the described arrangement of Fig. 2 a.
Fig. 3 a schematically shows the decomposition diagram of passive matrix display, and it comprises channelled insulation course.
Fig. 3 b schematically shows the sectional view according to the pixel in the pixel arrangement of the described arrangement of Fig. 3 a.
Fig. 4 shows the parameter for the fill factor of calculation display.
Fig. 5-9 shows the I-V characteristic of the different samples of settling according to the present invention.
Figure 10 a is the photo of display device.
Figure 10 b is based on the diagram of the photo of Figure 10 a, and has reflected the part of display device.
Figure 11-14 shows the I-V characteristic that comprises different electrolytical different samples of settling according to the present invention.
Describe in detail
In Fig. 1 a and 1b, schematically show an example according to passive matrix display of the present invention.Fig. 1 a is the decomposition diagram of passive matrix display, and wherein pixel layer is consistent with electrode.First electrode 121 of one group of electrochromic material is set, and one group of second electrode 122 that comprises carbon.Each electrode all forms the element of linear extension.First electrode 121, namely the electrode in described one group of first electrode is placed in the first common plane in parallel with each other.Second electrode 122, namely the electrode in described one group of second electrode is placed in the second common plane in parallel with each other.In addition, settle two arrays of electrodes 121,122, so that each described first electrode only intersects a point of crossing with each described second electrode interrelatedly.In Fig. 1, first electrode and described second electrode are settled orthogonally, and namely electrode is each other with 90 angular cross of spending.Alternatively, electrode can for example, be settled with the angle in 10 ° to 170 ° interval mutually across enough to depart from almost any angle of 0 and 180 degree.
There is the layer that is placed in electrolyte 113 between two electrodes on the space in each infall between described first and second electrodes.In other words, electrolyte 113 is clipped between the second electrode 122a of first an electrode 121a of described one group of first electrode and described one group of second electrode.In addition, first pixel layer 111 is by the scope definition at the interface between electrolyte 113 and the first electrode 121a.Second pixel layer 112 is by the scope definition at the interface between electrolyte 113 and the second electrode 122a.In other words, described first pixel layer 111 and the described first electrode 121a's is a part of consistent; And described second pixel layer 112 is a part of consistent with the described second electrode 122a's.In more detail, described first pixel layer 111 and described second pixel layer 112 have constituted whole volumes of a described 121a and the 2nd 122a electrode respectively.
According to an embodiment, described one group of first electrode arrangement is on first carrier layer 116, and described one group of second electrode arrangement is on second carrier layer 117.First and second carriers preferably are arranged as insulating material.When making pixel arrangement, electrolyte can be placed on one of electrode of their electrode crossings places separately or both.Afterwards, carrier is lumped together, so that can provide ion to connect in the place, point of crossing between first and second electrodes separately.
Fig. 1 b shows the amplification according to the schematic sectional view of a pixel in the pixel arrangement of the described arrangement of Fig. 1 a.The layer of pixel has vertical or stacked arrangement.In more detail, electrolyte 113 is clipped in first pixel layer 111 that comprises electrochromic material and comprises between second pixel layer 112 of carbon.In addition, first pixel layer spatially is placed between first substrate 116 and the electrolyte 113; And second pixel layer spatially is placed between second substrate 117 and the electrolyte.The direction of observing described pixel is the normal direction of described first carrier layer, and points out by arrow 130.
Fig. 2 a schematically shows the decomposition diagram of passive matrix display.According to Fig. 1 a and the described arrangement of 1b, difference is that described second pixel layer and described second electrode are inconsistent at the pixel arrangement 200 shown in Fig. 2 a.Generation be that described second pixel layer 212 is the independent layers that comprise conductive carbon, spatially is placed between the electrolyte of locating the point of crossing between the second electrode 222a and the described first and second electrode 221a, the 222a 213.And second pixel layer is arranged as with described second electrode 222 and directly electrically contacts.Second electrode can be arranged as and the described second pixel layer identical materials, perhaps has material such as the silver of higher electronic conductivity.In more detail, each place, point of crossing between the first electrode 221a and the second electrode 222a, the layer of electrolyte 213 separately and second pixel layer 212 of material with carbon element are laminated to each other, and are placed between the described first and second electrode 221a, the 222a; So that described pixel layer 212 contacts with the described second electrode 222a direct electron, and described electrolyte 213 contacts with described first pixel layer, 211 both ions of the electrochromic material of described second pixel layer 212 and the described first electrode 221a.
In more detail, and according to an embodiment, described one group of first electrode 221 is placed on first carrier layer 216, and described one group of second electrode 222 is placed on second carrier layer 217.First and second carrier layer 216,217 preferably are arranged as insulating material.In addition, second pixel layer 212 of carbon is placed on the described second electrode 222a at each point of crossing between described first and second electrodes 221,222 or place, some point of crossing.In addition, the layer of electrolyte 213 can be placed in first and second electrodes at the first and second electrode crossings places separately one or both.Afterwards, carrier is lumped together, so that between first and second pixel layer 211,212 at place, the point of crossing between the first and second electrode 221a, the 222a separately, provide ion to connect.
Fig. 2 b is the amplification according to the schematic sectional view of a pixel in the pixel arrangement of the described arrangement of Fig. 2 a.The layer of pixel has vertical or stacked arrangement.In more detail, electrolyte 213 is clipped in first pixel layer 211 that comprises electrochromic material and comprises between second pixel layer 212 of carbon.In addition, first pixel layer 211 spatially is placed between first substrate 216 and the electrolyte 213; And second pixel layer 212 spatially is placed between second electrode 222 and the electrolyte 213.In addition, second electrode spatially is placed between second pixel layer and second carrier layer 217.The direction of observing described pixel is the normal direction of described first carrier layer, and points out by arrow 230.
Fig. 3 a schematically shows the decomposition diagram of passive matrix display.Pixel arrangement 300 shown in Fig. 3 a is according to Fig. 2 a and the described arrangement of 2b, and difference is that described second pixel layer 312 does not contact with described second electrode, 322 direct electron.The generation be that the insulation course 318 that comprises passage 319 is placed between described second pixel layer 312 and described second electrode 322.Electronic conductor 320 is placed in each described passage 319.In addition, settle insulation course so that each electronic conductor 320 is connected second electrode 322 with second pixel layer, 312 electronics.
In more detail, according to an embodiment, first carrier layer 316 of insulating material is set, settles one group of first electrode 321 thereon.In addition, the intermediate carrier layer 318 of insulating material is set, and settles one group of passage 319 therein.First side at described intermediate carrier layer 318 is settled one group of second electrode 322, and in described passage 319 electronic conductor 320 is set.And, opposition side at described intermediate carrier layer 318 arranges one group of second pixel layer 312 that comprises conductive carbon, and each described second pixel layer 312 is arranged as with separately described electronic conductor 320 electronics and contacts, so that each electronic conductor 320 is connected second pixel layer 312a separately with its second electrode 322a electronics separately.In all embodiments, second pixel layer is all settled with being isolated from each other.The 3rd pixel layer that comprises electrolyte 313 is placed on each of described second pixel layer 312.Afterwards, first carrier and intermediate carrier 316,318 are lumped together, so that each described first electrode 321 only intersects a point of crossing with each described second electrode 322.As follows first carrier and intermediate carrier 316,318 are lumped together: make the point of crossing between the first electrode 321a and 322a locate, between the described first electrode 321a and described second a pixel layer 312a separately separately, via separately described the 3rd pixel layer 313 ion is set and connects.Organizing the 3rd pixel layer 313 at this contacts with ion between first electrode 321 one group of first pixel layer 311 is provided as mentioned above.
Additionally, or alternatively, before first carrier layer and intermediate carrier layer 316,318 are lumped together, can the 3rd pixel layer be set to corresponding to separately described first and second electrodes 321,322 between the position of predetermined point of crossing contact with described first electrode, 321 ions.Afterwards, in the following manner first carrier and intermediate carrier 316,318 are lumped together: make and locate in separately first electrode and the point of crossing between the second electrode 321a, the 322a, between described first electrode 321a and described second a pixel layer 312a separately separately, via separately described the 3rd pixel layer 313 ion is set and connects.
Fig. 3 b is the amplification according to the schematic sectional view of a pixel in the pixel arrangement of the described arrangement of Fig. 3 a.The layer of pixel has vertical or stacked arrangement.In more detail, electrolyte 313 is clipped in first pixel layer 311 that comprises electrochromic material and comprises between second pixel layer 312 of carbon.In addition, first pixel layer 311 spatially is placed between first insulation course 316 and the 3rd pixel layer 313.And, second insulation course 318 that comprises passage 319 is placed between described second pixel layer 312 and described second electrode 322, and electronic conductor 320 is placed in the described passage 319, and described electronic conductor is connected described second pixel layer 312 with described second electrode, 322 electronics.Randomly, second pixel layer 312 can be placed in described second insulation course and not between the other insulation course shown in Fig. 3 a and the 3b.
Fig. 4 schematically shows and comprises one group according to Fig. 1 a and the described display that is arranged as the pixel cell of matrix of 1b.A plurality of pixel portion are placed in the matrix structure, and wherein each pixel portion limits one according to the described pixel arrangement of Fig. 1 b.The common property of measuring display relates to fill factor.The useful area of fill factor and each pixel is more relevant with the given area of whole display.Fill factor can from shown in size A and B obtain.Distance A is corresponding to the distance between two pixel portion of separating, and is that two pixels are placed how closely, the great indication of the invalid that perhaps exists in display.Apart from B the typical sizes of pixel portion is shown, it is corresponding to the cross-sectional area of pixel element.Usually, the relative minimizing of distance A means the increase of fill factor, and the relative increase of area B means the increase of fill factor.In one embodiment, based on 1 * 1mm
2Single pixel portion area, the fill factor that comprises according to the display of pixel arrangement of the present invention can be 90%.
Preparation with passive matrix addressed displays of insulation course
Provide and comprise the thick polyethylene terephthalate of 50 μ m (being called PET hereinafter) film (Melinex454, produced by DuPont Teijin film) insulation course, wherein shine by laser, net-like pattern with 20 * 20 is set up passage, and wherein the distance between two adjacent passages is 1cm.The inlet diameter of passage is～30 μ m in first side of described insulation course, and is～70 μ m at the opposite side of described insulation course.By using squeegee, conductive carbon paste (7102 serigraphy carbon slurry is produced by DuPont) is deposited in the passage.Carbon slurry is to repeat one time the carbon deposition process step, to guarantee the electronic conduction by passage after 120 ℃ of dryings 3 minutes.On first side of described insulation course, 20 parallel lines (Ag5000 serigraphy silver slurries by brush depositing silver slurries, produced by DuPont), wherein every line be～2-3mm wide and＞200mm grows, so that every line is electrically connected 20 passages in the described insulation course.Afterwards with silver-colored line thermal treatment; 120 ℃, continue 5 minutes.In second side of described insulation course, depositing electrically conductive carbon slurry (7102) has～4-5mm separately to form in described channel roof
2The square of area.To in the electrochrome pixel device, serve as the carbon square of electrode member 120 ℃ of dryings 3 minutes.20 * 20 electrolyte drops (Luviquat Excellence is produced by BASF, comprises the TiO2 powder (Kronos2300 is produced by KRONOS) of 10 weight %) are deposited on the carbon square, and 60 ℃ of dryings 1 minute.Luviquat is vinyl pyrrolidone in the aqueous solution and the multipolymer of quaternised vinyl imidazole.In order to make electrolyte opaque use TiO fully
2The PET paper tinsel that has applied PEDOT:PSS (Orgacon EL-350 is produced by AGFA) in advance is provided.The PEDOT:PSS layer is patterned as 20 rectangles by the pocket knife drawing instrument, and each rectangle has 23 * 1cm
2Area.In resulting matrix display, the PEDOT:PSS rectangle serves as first electrode and first pixel layer.According to net-like pattern deposition 20 * 20 droplet electrolyte drops identical with electrolyte drop on second electrode, and 60 ℃ of dryings 1 minute.As final treatment step, second electrode and first pixel layer is stacked together so that described layer in vertical stratification toward each other, and conductive silver wire and conductive PEDOT: the PSS rectangle is orientated in the mode of quadrature.The latter guarantees that matrix display comprises row and column.
The preparation of embodiment device and comparable device
Can make the electrochrome pixel device by using with the material identical materials that is used for above-mentioned matrix display (carbon slurry, PEDOT:PSS and electrolyte) and substrate (PET paper tinsel).In single pixel arrangement, do not need to comprise the conductor wire of silver.
According to first embodiment of pixel arrangement, serigraphy is on PET foil substrate separately carbon to be starched (7102, produced by DuPont) and PEDOT:PSS slurries (Clevios S V3 serigraphy slurries are provided by H.C.Starck), and each sedimentary deposit has 35x35mm
2Area, and afterwards 110 ℃ dry 5 and 2 minutes respectively.Afterwards, will have 2x2mm
2The dielectric substrate of area be deposited on the corner of the substrate of pre-coating separately, to a kind of electrolyte pattern of each substrate.With dielectric layer after 60 ℃ of dryings 1 minute, finish pixel arrangement by being stacked as vertical stratification layer by layer, the electrolyte that wherein is clipped in the middle guarantees that the ion between first and second pixel layer connects.
Second embodiment of preparation pixel arrangement has the apparatus structure identical with first embodiment, and the difference part is to adopt the carbon slurry (PF-407A is produced by Acheson) of another kind of type, it is deposited into replace 7102 carbon slurry on described second pixel layer.
The 3rd embodiment of preparation pixel arrangement has the apparatus structure identical with first embodiment, and the difference part is to adopt the PET paper tinsel of the PEDOT:PSS (Orgacon El-350 is produced by AGFA) that comprises pre-coating as described first pixel layer.
The preparation pixel arrangement first with reference to sample, have the apparatus structure identical with first embodiment, the difference part is carbon is replaced with the electrode that comprises PEDOT:PSS to electrode.
The preparation pixel arrangement second with reference to sample, have the apparatus structure identical with first embodiment, but wherein carbon replaced with ag paste electrode (Ag5000 is produced by DuPont) to electrode.
Measure electrochemical appliance character
Measure their I-V characteristic by the electrochrome pixel device being connected to analyzing parameters of semiconductor instrument (Hewlett Packard/Agilent 4155B).By the matrix display according to Fig. 1 a and the described arrangement of 1b is provided, and each sample pixel separated with other detailed descriptions in this matrix display, thus preparation sample pixel.Electromotive force is connected to second pixel layer, simultaneously with the first pixel layer ground connection.Electromotive force starts from negative value (with the first pixel layer oxidation) and is swept on the occasion of (with first pixel layer reduction), and gets back to negative value afterwards again, for example-and 2V to 2V is to-2V.The every 20ms of the electromotive force that applies increases 10mV.In other words, pixel electrode layer is converted to its blueness from its initial transparent oxidation state and goes back ortho states and change back transparent oxidation state afterwards, and by the electric current of parameter analyzer continuous recording by pixel arrangement.
Test result
First of pixel arrangement provides in Fig. 5,6,7,8 and 9 with reference to sample, first, second, and third embodiment and second I-V curve or the I-V characteristic with reference to sample.Lack carbon two of electrode are not shown the voltage threshold behavior with reference to sample Fig. 5 and 9, be linear with the electromotive force that applies more or less because electric current raises/reduces.Sample among Fig. 5 and 9 comprises PEDOT:PSS and silver respectively as to electrode.On the other hand, the pixel arrangement embodiment in Fig. 6,7 and 8 is shown as the voltage threshold electromotive force of about 0.5-1.0V.In the matrix display that drives by passive matrix addressing, can utilize this voltage threshold electromotive force.
Figure 11-14 shows I-V curve or the I-V characteristic of the embodiment sample of the pixel arrangement that comprises different electrolyte 113.Its I-V curve is illustrated in sampling device among Figure 11-14 according to Fig. 1 a and the described arrangement of 1b, wherein with each sample pixel in the matrix display from other pixel separation.In addition, first pixel layer 111 of each pixel 110 comprises PEDOT:PSS as electrochromic material, and second pixel layer 112 comprises carbon.The used electrolyte of sample that its I-V curve is illustrated in the pixel arrangement among Figure 11 is poly-(diallyldimethylammonium chloride), a kind of polycation electrolyte aqueous solution.This pixel arrangement shows and is about ± threshold voltage of 1.0V.In addition, the embodiment of this embodiment has low leakage electrode stream when 0V.Therefore, this pixel arrangement can be used for the matrix display by the passive matrix addressing driving.
Figure 12 illustrates the I-V curve of two different embodiments of sample.The orientation of representing by square refer to comprise vinyl pyrrolidone and quaternised vinyl imidazole multipolymer (
Provided with the aqueous solution form by BASF) as the sample of polycation electrolyte.The curve of representing by circle refers to comprise the aqueous solution of kayexalate salt (M.W.～70,000 are provided by AlfaAesar) as the sample of polyanion electrolyte.All illustrate corresponding to two embodiment device of the figure among Figure 12 and to be about ± threshold voltage and the stream of the low leakage electrode when 0V of 1.0V.Therefore, this pixel arrangement also can be used for the matrix display by the passive matrix addressing driving.
Figure 13 and 14 illustrate the multipolymer that comprises vinyl pyrrolidone and quaternised vinyl imidazole (
Provided with the aqueous solution form by BASF) as the I-V curve of the sample of polycation electrolyte.Yet the electrolyte of each pixel arrangement comprises different adjuvants.The purpose of the additive in electrolyte of the pixel arrangement of the curve among generation Figure 13 is in order to have impressionability and curability.The curve of representing by square refers to have Luviquat: the ratio of DL-lactic acid is the electrolytical sample of 100: 18.5 weight ratios.The orientation of representing by circle refers to have Luviquat: DL-lactic acid: glycerine 1, the ratio of 3-two glycerine alkyd diacrylates is the electrolytical sample of 100: 18.5: 2.7 weight ratios.The figure that represents by triangle refers to have Luviquat: glycerine 1, the ratio of 3-two glycerine alkyd diacrylates is the electrolytical sample of 100: 10 weight ratios.Therefore, can use adjuvant such as DL-lactic acid and glycerine 1,3-two glycerine alkyd diacrylates are used for obtaining curability and impressionability as the adjuvant to Luviquat, keep having the required threshold voltage of addressing capability simultaneously in passive matrix display.
For the pixel arrangement that produces the I-V curve among Figure 14; adjuvant is glycerine 1; 3-two glycerine alkyd diacrylates (available from Sigma-Aldrich), DL-lactic acid (available from Sigma-Aldrich), Irgacure 2959 (2-hydroxyl-4 '-(2-hydroxyl-oxethyl)-2-methyl phenyl ketone 98%; available from Sigma Aldrich), TPO (diphenyl (2; 4; the 6-trimethylbenzoyl) phosphine oxide, Lucirin TPO is provided by BASF), TiO2 and water.The figure that represents by square refers to have Luviquat: glycerine 1,3-two glycerine alkyd diacrylates: the ratio of DL-lactic acid: Irgacure 2959: TPO: TiO2 is 100: 3: 1.9 by weight: the electrolytical sample of 0.21.0.17.10.The figure that represents by circle refers to have Luviquat: glycerine 1,3-two glycerine alkyd diacrylates: DL-lactic acid: Irgacure2959: TPO: TiO2: the ratio of water is 100: 10.8: 18.5 by weight: 0.77: 0.62: 92: 19.2 electrolytical sample.Irgacure2959 and TPO are light triggers, so that dielectric substrate can UV solidify, and the TiO2 particle can be as turbidization in the pixel of operating under the reflective-mode layer.These figure show, can use these adjuvants and do not weaken threshold voltage.
Figure 10 is the photo according to the passive matrix addressed displays of above-mentioned the 3rd embodiment manufacturing, and upgrades according to checkerboard pattern.This specific matrix display comprises 20 * 20 electrochrome pixel devices, and does not crosstalk basically and can observe, and namely corresponding pixel is dark or bright.Figure 10 b is the sketch that has reflected the part of display, corresponding to the content in the broken circle among Figure 10 a.Compare with Figure 10 a, the sketch of Figure 10 b has slight turning clockwise.In photo, the Ag-electrode stretches in each row pixel element lower horizontal.In the sketch of Figure 10 b, the Ag-electrode is drawn as rectangle, it is (owing to turning clockwise) of tilting when observing from right to left.Electrode is arranged on the insulated substrate that comprises the through hole with carbon electrode.At the opposite side of insulated substrate, the pixel layer that comprises carbon is set.In addition, white electrolyte drop is provided on the top of each pixel layer that comprises carbon.At last, provide translucent that comprises conducting polymer, and be arranged as and make it cover all electrolyte, that is, form first pixel layer at described electrolyte and described translucent contact position.Thin straight vertical otch is set in translucent sheet, and with pixel fragment electrical isolation each other, wherein, the pixel in each section is settled to the photo top one by one from the photo bottom.Distance between two vertical otch is 1cm.Pixel in each section is by translucent electronics contact each other.As can in photo, can seeing, each color of pixel, namely translucent color meets basically perfectly square.White material around the pixel be not with translucent electrolyte that contacts, but can see through.In Figure 10 b, be placed in discrete island on the top of Ag-electrode corresponding to electrolyte.In more detail, one group of first electrode settling by row provides electrochrome pixel element or first pixel layer, and one group of second electrode settling by row provides matrix display second pixel layer.Each corresponding row and column is connected to the output lead of digital integrated circuit, and it drives by applying voltage.Will be stored in by the required image that display provides in the programmable circuit, it is by once or repeatedly upgrading whole display output image.Matrix display upgrades line by line, though be other possible addressing replacement schemes by column scan or single picture element scan.In lining by line scan, allow the signal activation of output to go accordingly, so that required pixel can be upgraded by voltage being applied to corresponding alignment.Unactivated row and not the output of addressed column forbid.Afterwards, the output lead of the row that upgraded is forbidden, and upgraded subsequently row by identical method.
In the foregoing description, with reference to many clear and definite disclosed embodiments the present invention has been described substantially.Yet, as readily understood by the skilled person, as in the scope of the present invention that limits in the dependent claims other to be different from above disclosed embodiment also be same possible.For example, the electrochrome pixel layer of the embodiment among Fig. 5-9 is formed by PEDOT:PSS.Yet other electrochromic materials except the electrochromic material that is formed by PEDOT:PSS also can be used for the electrochrome pixel layer, and fall within the scope of the present invention.In addition, other to be different from the above-mentioned disclosed electromotive force size that applies also be same possible within the scope of the invention.
Claims (14)
1. passive matrix display device (100; 200), described display device comprises
One group of pixel cell (110 that is arranged as matrix; 210),
Wherein each pixel cell comprises:
First pixel layer (111; 211), but described first pixel layer is included in the different visually electrochromism of electro-chemical conversion and the organic polymer material of electrochemical activity between the perceptible color state,
Second pixel layer (112; 212), described second pixel layer in the face of described first pixel layer and
Electrolytical the 3rd pixel layer (113 that solidifies; 213), described the 3rd pixel layer spatially is placed between described first pixel layer and described second pixel layer, and contacts with the described second pixel layer ion with described first pixel layer, and
Each pixel cell (110 wherein; 210) described second pixel layer (112; 212) be arranged as the material that comprises conductive carbon.
2. passive matrix display device (100; 200), described display device comprises
One group of pixel cell (110 that is arranged as matrix; 210),
Wherein each pixel cell comprises:
First pixel layer (111; 211), but described first pixel layer is included in the different visually electrochromism of electro-chemical conversion and the organic polymer material of electrochemical activity between the perceptible color state,
Second pixel layer (112; 212), described second pixel layer in the face of described first pixel layer and
Electrolytical the 3rd pixel layer (113 that solidifies; 213), described the 3rd pixel layer spatially is placed between described first pixel layer and described second pixel layer, and contacts with the described second pixel layer ion with described first pixel layer, and wherein
Described electrolyte does not have the PH dyestuff basically, and
Each pixel cell (110; 210) described second pixel layer (112; 212) be arranged as the material that comprises conductive carbon, thereby provide at least response to cross over the threshold voltage of the voltage that described pixel cell applies.
3. display device according to claim 1 and 2, described display device also comprises one group of first electrode (121; 221) and one group of second electrode (122; 222), described one group of first electrode and described one group of second electrode be electrical isolation each other, and is arranged as feasible:
-each described first electrode (121; 221) with each described second electrode (221; 222) only intersect a point of crossing, and
-each described pixel cell (110; 210) be placed in place, the described point of crossing of separately one, described point of crossing is by separately first electrode and second electrode (121a, 122a separately; 221a, 222a) form, wherein:
-each described pixel cell (110; 210) described first pixel layer (111; 211) with the described first electrode (121a separately; Part 221a) is consistent, and
-each described pixel cell (110; 210) described second pixel layer (112; 212) with the described second electrode (122a separately; Part 222a) is consistent, perhaps with the described second electrode (122a separately; 222a) electronics contact.
4. display device according to claim 1 and 2, described display device also comprises one group of first electrode (121; 221) and one group of second electrode (122; 222), described one group of first electrode and described one group of second electrode be electrical isolation each other, and is arranged as feasible:
-each described first electrode (121; 221) with each described second electrode (221; 222) only intersect a point of crossing, and
-each described pixel cell (110; 210) be placed in place, the described point of crossing of separately one, described point of crossing is by separately first electrode and second electrode (121a, 122a separately; 221a, 222a) form, wherein:
-each described pixel cell (110; 210) described first pixel layer (111; 211) with the described first electrode (121a separately; 221a) electronics contact, and
-each described pixel cell (110; 210) described second pixel layer (112; 212) with the described second electrode (122a separately; Part 222a) is consistent, perhaps with the described second electrode (122a separately; 222a) electronics contact.
5. according to each the described display device in preceding claim, described display device not wherein each control element be combined with a described pixel cell separately and be arranged as one group of independent control element of the transistor function of the color that is provided for the described pixel cell of active control.
6. according to each the described display device in preceding claim, described display device is placed in flexible base, board (117; 217), and preferably comprise on the flexible base, board of paper and/or plastics.
7. according to each the described display device in preceding claim, described display device is arranged as multilayer, and described multilayer has at least one in impressionability and the flexibility.
8. according to each the described display device among the claim 3-7, wherein said pixel cell (110; 210) described first electrode (121; 221) and first pixel layer (111; 211) all comprise identical materials, and/or
Wherein said pixel cell (110; 210) described second electrode (122; 222) and second pixel layer (112; 212) all be arranged as identical materials.
9. display device according to claim 8, wherein each described pixel cell (110; 210) described first electrode (121; 221) and first pixel layer (111; 211) all be a part in the identical layer, and/or
Each described pixel cell (110 wherein; 210) described second electrode and second pixel layer (112; 212) all be a part in the identical layer.
10. according to each the described display device among the claim 4-8, described display device also comprises insulation course (318), preferred plastic insulating layer, described insulation course is placed between described second electrode (322) and described second pixel layer (312) in each pixel cell (310) of described one group of pixel cell, and described insulation course also comprises the passage (319) that is mounted with electronic conductor (320) separately, and second pixel layer (312) separately of the pixel cell (310) that described electronic conductor will be separately and described second electrode (322) electronics separately are connected.
11. according to each the described display device in preceding claim, wherein in pixel cell separately, described second pixel layer covers the core of described the 3rd pixel layer.
12. according to each the described display device in preceding claim, wherein in pixel cell separately, the surface area of described second pixel layer is at least 60% of described electrolytical surface area, or at least 75%, or at least 90%, or at least 95%.
13. according to each the described display device in preceding claim, the electrolyte of wherein said curing is polycation electrolyte or polyanion electrolyte.
14. one group of pixel cell is used for providing response at least to cross over the purposes of the threshold voltage of the voltage that described pixel cell applies, described pixel cell comprises separately
-the first pixel layer (111; 211), but described first pixel layer is included in the different visually electrochromism of electro-chemical conversion and the organic polymer material of electrochemical activity between the perceptible color state,
-the second pixel layer (112; 212), described second pixel layer in the face of described first pixel layer and
Electrolytical the 3rd pixel layer (113 of-curing; 213), described the 3rd pixel layer spatially is placed between described first pixel layer and described second pixel layer, and contacts with the described second pixel layer ion with described first pixel layer, wherein
Described electrolyte does not have the PH dyestuff basically, and
Each pixel cell (110; 210) described second pixel layer (112; 212) be arranged as the material that comprises conductive carbon.
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| 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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| CN103201676B CN103201676B (en) | 2016-11-16 |
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| CN107342309A (en) * | 2017-07-05 | 2017-11-10 | 固安翌光科技有限公司 | A kind of highly reliable passive organic electroluminescent device and preparation method thereof |
| 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 |
| CN111323979A (en) * | 2020-01-03 | 2020-06-23 | 深圳市光羿科技有限公司 | Electrochromic device and preparation method |
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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 |
| 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 |
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| JP2003315843A (en) * | 2002-04-19 | 2003-11-06 | Fuji Photo Film Co Ltd | Electrochromic display |
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| 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 |
| US20100002282A1 (en) * | 2008-07-03 | 2010-01-07 | Ajjer Llc | Metal coatings, conductive nanoparticles and applications of the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107342309A (en) * | 2017-07-05 | 2017-11-10 | 固安翌光科技有限公司 | A kind of highly reliable passive organic electroluminescent device and preparation method thereof |
| 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 |
| 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 |
| CN111323979A (en) * | 2020-01-03 | 2020-06-23 | 深圳市光羿科技有限公司 | Electrochromic device and preparation method |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5774111B2 (en) | 2015-09-02 |
| CN103201676B (en) | 2016-11-16 |
| WO2012045485A1 (en) | 2012-04-12 |
| JP2013539081A (en) | 2013-10-17 |
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