CN101438205B - Electro-optical element including IMI coatings - Google Patents
Electro-optical element including IMI coatings Download PDFInfo
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- CN101438205B CN101438205B CN2007800160013A CN200780016001A CN101438205B CN 101438205 B CN101438205 B CN 101438205B CN 2007800160013 A CN2007800160013 A CN 2007800160013A CN 200780016001 A CN200780016001 A CN 200780016001A CN 101438205 B CN101438205 B CN 101438205B
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Abstract
An electrochromic element comprises a first substrate having a first surface and a second surface opposite the first surface, a second substrate in spaced-apart relationship to the first substrate and having a third surface facing the second surface and a fourth surface opposite the third surface, and an electrochromic medium located between the first and second substrates, wherein the medium has a light transmittance that is variable upon application of an electric field thereto. The element further comprises a transparent electrode layer covering at least a portion of at least a select one of the first surface, the second surface, the third surface, and the fourth surface, wherein the transparent electrode layer comprises an insulator/metal/insulator stack.; The materials utilized to construct the insulator/metal/insulator stack are selected to optimize optical and physical properties of the element such as reflectivity, color, electrical switch stability, and environmental durability.
Description
The application requires the U.S. Provisional Application No.60/779 that is entitled as " IMPROVEDCOATINGS AND REARVIEW ELEMENTSINCORPORATING THECOATINGS " of submission on March 3rd, 2006, the U.S. Provisional Application No.60/810 that is entitled as " ELECTROCHROMIC REARVIEW MIRROR ASSEMBLY INCORPORATINGADISPLAY/SIGNALLIGHT " that on June 5th, 369 and 2006 submitted to, 921 rights and interests, the two merges to herein in full with them by reference.
Background of invention
The present invention relates in the motor vehicles rearview mirror assemblies and the electric driven color-changing part that uses in the window assembly, more particularly, relate to the improved electric driven color-changing part that uses in these assemblies.More specifically, the present invention relates to comprise the electric driven color-changing part of transparent electrode layer, described electrode layer comprises insulator/metal/insulator lamination.
So far, proposed to change over from total reflection pattern (daytime) the various motor vehicle rearview mirrors of partial reflection pattern (night), purpose is the light that is used for the headlight emission of the approaching from behind vehicle of dazzle protection.Similarly, buildings window, skylight, interior window (withinwindow), sun proof and automobile rearview mirror and various window or be used for for example variable transmissivity light filter of aircraft window of other vehicles have been proposed to be used for.In these devices, the change of transmissivity be by means of thermochromism, photochromic or electro-optical device (for example, liquid crystal, dipole suspends, electrophoresis, electrochromism, or the like), and the variable transmissivity properties influence is at least partially in (wavelength is from about 3800 in the visible spectrum
To about 7800
) electromagnetic radiation.People advise utilizing the reversible variation transmissivity of device have to(for) electromagnetic radiation as variable transmissivity light filter, variable reflectivity mirror with adopt this light filter or mirror transmits variable transmissivity element in the display equipment of information.
The device that has reversible variation transmissivity for electromagnetic radiation, wherein transmissivity changes by electrochromism, by following document description, for example, Chang, " Electrochromic and Electrochemichromic Material sandPhenomena ", Non-emissive Electrooptic Displays, A.Kmetz and K.von Willisen, eds.Plenum Press, New York, NY1976, the various piece among 155-196 page or leaf (1976) and the Electrochromism, P.M.S.Monk, R.J.Mortimer, D.R.Rosseinsky, VCH Publishers, Inc., New York, NewYork (1995).Multiple electrochromic device is well known in the art.See for example Manos, U.S. Patent No. 3,451,741; Bredfeldt etc., U.S. Patent No. 4,090,358; Clecak etc., U.S. Patent No. 4,139,276; Kissa etc., U.S. Patent No. 3,453,038; Rogers, U.S. Patent No. 3,652,149,3,774,988 and 3,873,185; With Jones etc., U.S. Patent No. 3,282,157,3,282,158,3,282,160 and 3,283,656.Except these devices, also there are commercially available electrochromic device and interlock circuit, they for example are disclosed in the following patented claim: U.S. Patent No. 4,902,108, title is " SINGLE-COMPARTMENT; SELF-ERASING, SOLUTION-PHASE ELECTROCHROMIC DEVICES SOLUTIONS FOR USETHEREIN, AND USES THEREOF ", authorize February 20 nineteen ninety, H.J.Byker; Canadian Patent No.1,300,945, title is " AUTOMATIC REARVIEW MIRRORSYSTEM FOR AUTOMOTIVE VEHICLES ", on May 19th, 1992 authorized, J.H.Bechtel etc.; U.S. Patent No. 5,128,799, title are " VARIABLE REFLECTANCEMOTOR VEHICLE MIRROR ", and on July 7th, 1992 authorized, H.J.Byker; U.S. Patent No. 5,202,787, title are " ELECTRO-OPTIC DEVICE ", and on April 13rd, 1993 authorized, H.J.Byker etc.; U.S. Patent No. 5,204,778, title are " CONTROLSYSTEM FOR AUTOMATIC REARVIEW MIRRORS ", and on April 20th, 1993 authorized, J.H.Bechtel; U.S. Patent No. 5,278,693, title are " TINTED SOLUTION-PHASEELECTROCHROMIC MIRRORS ", and on January 11st, 1994 authorized, D.A.Theiste etc.; U.S. Patent No. 5,280,380, title are " UV-STABILIZED COMPOSITIONSAND METHODS ", and on January 18th, 1994 authorized, H.J.Byker; U.S. Patent No. 5,282,077, title are " VARIABLE REFLECTANCE MIRROR ", and on January 25th, 1994 authorized, H.J.Byker; U.S. Patent No. 5,294,376, title are " BIPYRIDINIUM SALT SOLUTIONS ", and on March 15th, 1994 authorized, H.J.Byker; U.S. Patent No. 5,336,448, title are " ELECTROCHROMIC DEVI CES WITHBIPYRIDINIUM SALT SOLUTIONS ", and on August 9th, 1994 authorized, H.J.Byker; U.S. Patent No. 5,434,407, title are " AUTOMATIC REARVIEW MIRRORI NCORPORATING LIGHT PIPE ", and authorize January 18 nineteen ninety-five, F.T.Bauer etc.; U.S. Patent No. 5,448,397, title are " OUTSIDE AUTOMATIC REARVIEWMIRROR FOR AUTOMOTIVE VEHICLES ", and authorize September 5 nineteen ninety-five, W.L.Tonar; With U.S. Patent No. 5,451,822, title is " ELECTRONIC CONTROL SYSTEM ", and authorize September 19 nineteen ninety-five, J.H.Bechtel etc.In these patents each is commonly assigned with the present invention, and by reference the disclosure (comprising wherein contained list of references) of each is merged to herein in full with this.These electrochromic devices can be used in the fully-integrated inner/outer rear-view mirror system or are used as independent inside or external mirror having indicator light system, and/or are used in the variable transmissivity window.
Fig. 1 has shown the xsect of the typical EC mirror device 10 with frontal plane substrate 12 and back plane substrate, and the overall arrangement of described lens device is known.Transparent conducting coating 14 is provided on the rear surface of preceding element 12, and another transparent conducting coating 18 is provided on the front surface of back element 16.Reflecting body 20 places on the rear surface of back element 16, and described reflecting body typically comprises the silver metal layer 20a that protection copper metal layer 20b covers, and one or more layers protective paint 20c.In order clearly to describe such structure, the front surface 12a of front glass element 12 is called first surface sometimes, and the inside surface 12b of front glass element 12 is called second surface sometimes, the inside surface 16a of back glass elements 16 is called the 3rd surface sometimes, and the rear surface 16b of back glass elements 16 is called the 4th surface sometimes.In the illustrated embodiment, the front glass element also comprises edge surface 12c, and then glass elements comprises edge surface 16c.Make preceding element 12 and back element 16 keeping parallelisms and space spaced relationship by seal 22, thereby produce chamber 26.Electrochromic media 24 is included in space or the chamber 26.Transparent electrode layer that electrochromic media 24 and electromagnetic radiation are therefrom passed 14 directly contacts with 18, by applying variable voltage or electromotive force to electrode layer 14 and 18, in device, reversibly modulate the intensity of described electromagnetic radiation via clip contact and circuit (not shown).
Place the electrochromism electricity matter 24 of chamber 26 can comprise electrode position type or solution facies pattern electrochromic material and the combination thereof that the surface limits.In all solution phase mediums, any other component that can exist in the electrochemical properties of solvent, optional indifferent electrolyte, anode material, cathode material and the solution, make preferably and under the electric potential difference of cathode material reduction significant galvanochemistry do not take place or other change making the anode material oxidation and make that oneself wipes the reaction between the cathode material of the anode material of the electrochemical reduction of the electrochemical oxidation of anode material, cathode material and oxidised form and reduction form.
In most of situations, between transparent conductor 14 and 18, there is not electric potential difference, the electrochromic media 24 in the chamber 26 is colourless or approximate colourless basically, incident light (I
o) enter by preceding element 12, pass electrochromism dielectric 24 in clear coat 14, the chamber 26, clear coat 18, back element 16 and from layer 20a reflection, return by this device and in the past element 12 come out.Typically, the reflected image (I that does not have electric potential difference
R) intensity is about incident intensity (I
o) about 45% to about 85%.Accurate values depends on a plurality of variablees that outline below, for example, from the residual reflection of the front surface of preceding element (I '
R), and from the secondary reflection at following interface: the interface between the interface between the interface between the interface between preceding element 12 and the preceding transparency electrode 14, preceding transparency electrode 14 and the electrochromic media 24, electrochromic media 24 and second transparency electrode 18 and second transparency electrode 18 and the back element 16.These be reflected in known in the art and since light when passing through two kinds of material interfaces owing to material between the refractive index difference cause.If preceding element is uneven with the back element, then residual reflection (I '
R) or other secondary reflection will be not and image (I from the 20a reflection of mirror surface
R) overlapping, and afterimage (wherein the observer can see the image of dual (or triple) number of in esse object in the reflected image seemingly) will appear.
Depend on that EC mirror places vehicle inside or outside, have minimum requirements reflected image intensity.For example, according to current requirement from most of automakers, internal mirror preferably has and is at least 40% high-end reflectivity, and outside mirror must have and is at least 35% high-end reflectivity.
Even the 4th surface reflection body EC mirror the sort of can being purchased shown in Fig. 1 for example in the past, each group of research electrochromic device has discussed reflecting body has been moved to the 3rd surface from the 4th surface.The advantage of this design is, it should be easy to make in theory because need will be less layer be built in the device, that is, under the situation of existence the 3rd surface reflection body/electrode, the 3rd surface transparent electrode is not to be necessary.Though this notion just was discussed as far back as 1966, there is not group to make its successfully commercialization, this is because comprise the desired strict standard of feasible automatic deepening catoptron of the 3rd surface reflection body.The title that authorize the 25 days October in 1966 of J.F.Donnelly etc. is the U.S. Patent No. 3 of " OPTICALLY VARIABLE ONE-WAYMI RROR ", 280,701 couples of use pH bring out change color and come the 3rd used in the system of attenuate light surface reflection device that one of discussion is the earliest arranged.
The title that authorize the 19 days November in 1991 of N.R.Lynam etc. is the U.S. Patent No. 5 of " PERIMETER COATED; ELECTRO-OPTICMIRROR ", 066,112, instructed the electro-optical glass with conductive coating, described conductive coating is applied to the periphery of the front and back glass elements that is used for hiding seal.Though the 3rd surface reflection body wherein has been discussed, but the defective that effective material of listing as the 3rd surface reflection body suffers is: do not have the enough reflectivity as inner mirror, and/or be unsettled with comprising at least a solution when the solution phase electrochromic media of electrochromic material contacts mutually.
Other people have proposed the problem at the reflecting body/electrode of the middle part of all solid-state version devices placement.For example, the U.S. Patent No. 4,762 of Baucke etc., 401,4,973,141 and 5,069,535 has instructed the EC mirror with following structure: glass elements, transparent indium-tin-oxide electrode, the tungsten oxide electrochromic layer, solid ion conducting stratum, individual layer hydrogen ion permeability reflecting body, the solid ion conducting stratum, hydrogen ion stores layer, Catalytic Layer, back metal level and back of the body element (representing the 3rd conventional surface and the 4th surface).Reflecting body is not deposited on the 3rd surface and goes up and directly do not contact with electrochromic material, certainly also not with at least a solution mutually electrochromic material contact with associated media.Therefore, need provide improved high reflectance electrochromism rearview mirror, it has and the solution that contains at least a electrochromic material the 3rd surface reflection body/electrode of electrochromic media contact mutually.The electrochromic that is proposed typically comprises with similar shown in Fig. 1 but do not have the electric driven color-changing part of a layer 20a, 20b and 20c.
Though the correction of reflectivity the 3rd surperficial electrochromic device helps to solve many problems, in these elements, still there are many defectives.Having carried out various trials provides the electric driven color-changing part with second surface transparent conductive oxide, and its cost is low relatively and do not sacrifice optics or physical characteristics for example reflectivity, color, TURP change stability and environment durability.Though previous method concentrates on indium tin oxide layer, these attempt effectively not solving above mentioned many problems.Particularly, some problems have been supported the development to the transparent conductor substitute of indium tin oxide.For example, switch electrochromic device fast and on the both sides of relevant elements, need low sheet resistance material.Big electric driven color-changing part is responsive especially to sheet resistance, and high sheet resistance conductor causes the remarkable electromotive force on the whole conductive surface to reduce.These space potentials reduce the color change that has reduced local current densities and slowed down involved area, thereby cause for example giving birth to dizzy effect.This paper has stated other intrinsic difficulty and the deficiency relevant with previous electrochromic system.
Therefore be desirable to provide the electric driven color-changing part that comprises transparency electrode, its parts reduce the total cost of electric driven color-changing part and do not sacrifice optics or physical characteristics for example reflectivity, color, TURP change stability and environment durability etc.
Summary of the invention
One aspect of the present invention is the electric driven color-changing part that comprises first substrate, second substrate and the electrochromic media between described first and second substrates, described first substrate have first surface and with described this first surface opposing second surface, described second substrate and described first substrate be the space separate relation and have towards the 3rd surface of described second surface and with the 4th relative surface of the 3rd surface, wherein said electrochromic media has transformable transmittance when it applies electric field.This electric driven color-changing part also comprises transparent electrode layer, this electrode layer covers at least one at least a portion that is selected from second surface and the 3rd surface, wherein transparent electrode layer comprises first insulator layer, at least one metal level and second insulator layer, and wherein this electric driven color-changing part demonstrates colour rendering index more than or equal to 80.
Another aspect of the present invention comprises such electric driven color-changing part, this element comprises first substrate, second substrate and the electrochromic media between described first and second substrates, described first substrate have first surface and with this first surface opposing second surface, described second substrate and described first substrate be the space separate relation and have towards the 3rd surface of described second surface and with the 4th relative surface of the 3rd surface, wherein said electrochromic media has transformable transmittance when it applies electric field.This electric driven color-changing part also comprises transparent electrode layer, this electrode layer covers at least one at least a portion that is selected from second surface and the 3rd surface, wherein transparent electrode layer comprises first insulator layer, at least one metal level and second insulator layer, and wherein be selected from first insulator layer and second insulator layer at least one comprise be selected from following at least a: indium tin oxide, indium-zinc oxide, aluminium zinc oxide, titanium dioxide, CeO
x, tin ash, silicon nitride, silicon dioxide, ZnS, chromium oxide, niobium oxide, ZrO
x, WO
3, nickel oxide, IrO
2And combination.
Another aspect of the present invention comprises such electric driven color-changing part, this element comprises first substrate, second substrate and the electrochromic media between described first and second substrates, described first substrate have first surface and with described first surface opposing second surface, described second substrate and described first substrate be the space separate relation and have towards the 3rd surface of described second surface and with the 4th relative surface of described the 3rd surface, wherein said electrochromic media has transformable transmittance when it applies electric field.This electric driven color-changing part also comprises transparent electrode layer, this electrode layer covers at least one at least a portion that is selected from second surface and the 3rd surface, wherein transparent electrode layer comprises first insulator layer, metal level and second insulator layer, and wherein at least one side in first insulator layer and second insulator layer and at least one restraining barrier be between insulator layer and metal level, wherein the restraining barrier comprise be selected from following at least a: gold, ruthenium, rhodium (rodium), palladium, cadmium, copper, nickel, platinum, iridium and combination thereof.
Of the present invention is to comprise such electric driven color-changing part more on the one hand, this element comprises first substrate, second substrate and the electrochromic media between described first and second substrates, described first substrate have first surface and with described first surface opposing second surface, described second substrate and described first substrate be the space separate relation and have towards relative the 3rd surface of described second surface and with the 4th relative surface of described the 3rd surface, wherein said electrochromic media has transformable transmittance when it applies electric field.This electric driven color-changing part also comprises transparent electrode layer, this electrode layer covers at least one at least a portion that is selected from second surface and the 3rd surface, wherein transparent electrode layer comprises first insulator layer, metal level and second insulator layer, and wherein metal level comprises that at least one side comprises indium tin oxide, indium-zinc oxide, aluminium zinc oxide, titanium dioxide, CeO in silver and first insulator layer and second insulator layer
x, tin ash, silicon nitride, silicon dioxide, ZnS, chromium oxide, niobium oxide, ZrO
x, WO
3, nickel oxide, IrO
2And combination.
Of the present invention also is the method for making electric driven color-changing part on the one hand, wherein this method comprises: provide to have first surface and first substrate relative with this first surface opposing second surface, provide have towards the 3rd surface of described second surface and with second substrate on relative the 4th surface, the 3rd surface, in being selected from second surface and the 3rd surface at least one applies transparent electrode layer, and wherein transparent electrode layer comprises first insulator layer, metal level and second insulator layer.This method comprises that also in being selected from second surface and the 3rd surface at least one applies epoxy resin, and by applying infrared radiation to this epoxy resin first substrate is sealed to second substrate, and the minimum wavelength of its intermediate infrared radiation is 2.5 μ m.
Electric driven color-changing part of the present invention comprises transparency electrode, and its parts reduce the total cost of electric driven color-changing part and do not sacrifice optics or physical characteristics, and for example reflectivity, color, TURP change stability and environment durability etc.In addition, electric driven color-changing part of the present invention is easy to make relatively, help the manufacture method that provides sane, provide multifunctionality in the selection of the parts that in making up insulator/metal/insulator lamination, utilized, and allowed its custom build to obtain specific optics and physical property.
With reference to the following description, claims and accompanying drawing, those skilled in the art will be further understood that and recognize these and other feature of the present invention, advantage and purpose.
Brief Description Of Drawings
In the accompanying drawings:
Fig. 1 is the amplification cross-sectional view that comprises the prior art electrochromism mirror assembly of the 4th surface emitter;
Fig. 2 is the front elevation that schematically illustrates the inner/outer electrochromism rear-view mirror system of motor vehicles;
Fig. 3 is the amplification cross-sectional view of the EC mirror that comprises the 3rd surface reflection body/electrode of getting along Fig. 2 III-III line selection;
Fig. 4 is the further amplification cross-sectional view of the transparency electrode of area I V among Fig. 3;
Fig. 5 is the coordinate diagram of the reflectance/transmittance of ITO on glass in incident (incident) medium of air or electrochromism fluid with respect to wavelength;
Fig. 6 A-6C is the coordinate diagram of transmission difference when using air and EC fluid as incident medium in the 3-layer IMI lamination for the combination of different layers thickness and between the IMI;
Fig. 7 is the coordinate diagram of the transmissivity of 5 layers of IMI lamination with respect to the change of soaking time (soak time);
Fig. 8 is the coordinate diagram of the resistance of 5 layers of IMI lamination with respect to the change of soaking time;
Fig. 9 is the sheet resistance of two-layer IMI lamination and the transmissivity coordinate diagram with respect to oxygen number percent;
Figure 10 is that the oxygen number percent of two-layer IMI lamination is with respect to extinction coefficient with respect to the coordinate diagram of percentage roughness; With
Figure 11 be for DOE2 sample 7,8 and 13 wavelength with respect to the coordinate diagram of reflectivity.
Detailed description of the preferred embodiments
This paper for purposes of illustration, term " on ", D score, " right side ", " left side ", " back ", " preceding ", " vertically ", " level " and their derivative will be referred to the invention that is orientated as in Fig. 1 and 3.Yet should be understood that the present invention can take various alternative orientation and sequence of steps except obvious opposite regulation.Should also be understood that in the accompanying drawings explanation and the concrete apparatus and method of describing in the explanation below only are the exemplary of the notion of the present invention that limits in the appended claims.Therefore, relate to the concrete size of embodiment disclosed herein and other physical characteristics do not think restrictive, unless claims clearly indicate in addition.
Fig. 2 has shown the anterior elevational view that schematically illustrates vehicle mirror system 100, described system comprises inner mirror assembly 110 and is respectively applied for two the external mirror having indicator light assembly 111a and the 111b of driver side and passenger side, all these assemblies are suitable for being installed in a conventional manner on the motor vehicles, wherein mirror is towards the rear portion of vehicle, and can be watched to provide the back to the visual field by the vehicle driver.Though this paper uses mirror assembly to explain the present invention usually, it should be noted that the present invention is applicable to the structure of electrochromic with being equal to.Inner mirror assembly 110 and external mirror having indicator light assembly 111a and 111b can comprise with the Canadian Patent No.1 of institute's reference above, 300,945, U.S. Patent No. 5,204,778 or U.S. Patent No. 5, the photosensitive circuit of 451,822 explanations and description type, and can respond to dazzle and surround lighting and driving voltage other circuit to electric driven color-changing part is provided.In the illustrated embodiment, connecting circuit 150 and allow control to be applied to the electromotive force of reflecting body/electrode 120 and transparency electrode 128, but make electrochromic media 126 deepenings and therefore the decay various amounts of therefrom advancing light and change the reflectivity of the mirror that contains electrochromic media 126 thus.Mirror assembly 110,111a is similar with 111b, because same numbers can be discerned the element in the inside and outside mirror.These parts are textural can be slightly different, but it works in essentially identical mode, and acquisition and the essentially identical result of identical numbered block.For example, the front glass component shape of inner mirror 110 is compared usually long and narrower with outer mirror 111a, 111b.Compare with outer mirror 111a, 111b, inner mirror 110 also is applied with some different performance standards.For example, when bright fully, inner mirror 110 generally should have about 50% to about 85% or higher reflectance value, and outer mirror has about 50% to about 65% reflectivity usually.In addition, the U.S. (providing as the automaker), passenger side mirror 111b is spherical curve or convex normally, and driver side mirror 111a and inner mirror 110 must be smooth at present.In Europe, driver side mirror 111a is plane or aspheric surface normally, and passenger side mirror 111b is a convex.In Japan, two outer mirror 111a, 111b all are convexs.Following description generally is applicable to all mirror assemblies of the present invention, and general notion is applicable to the structure of electrochromic with being equal to.
Fig. 3 has shown the cross-sectional view of the mirror assembly 111a with preceding transparent substrates 112 and back substrate 114, and described preceding transparent substrates 112 has front surface 112a and rear surface 112b, and back substrate 114 has front surface 114a and rear surface 114b.In order clearly to describe this structure, the mark below will adopting hereinafter.The front surface 112a of preceding substrate can be called first surface 112a, and the rear surface 112b of preceding substrate can be called second surface 112b.The front surface 114a of back substrate can be called the 3rd surperficial 114a, and the rear surface 114b of back substrate can be called the 4th surperficial 114b.Preceding substrate 112 also comprises edge surface 112c, and back substrate 114 also comprises edge surface 114c.Chamber 125 is limited by transparent conductor layer 128 (being carried on the second surface 112b), reflecting body/electrode 120 (placing on the 3rd surperficial 114a) and the inside peripheral wall 132 of seal element 116.Electrochromic media 126 is included in the chamber 125.
As being extensive use of and describing herein, " carrying " or the electrode or the layer that are applied on the element surface be meant, directly places on the element surface or place electrode or layer on the other coating, directly places the single or multiple lift on the element surface.In addition, it should be noted, only for illustration purposes mirror assembly 111a is described, and can arrange concrete parts and element therein, structure for example illustrated in fig. 1 and those known structures of electrochromic.
Preceding transparent substrates 112 can be any transparent material, and has the sufficient intensity that can work under various conditions, transformation temperature and pressure that described condition for example can run under automotive environment usually.Before substrate 112 can comprise borosilicate glass, soda-lime glass, the float glass of any kind, or comprise for example transparent polymkeric substance or plastics in the visible region of electromagnetic wave spectrum of any other material.Preceding substrate 112 is glass sheet preferably.Back substrate 114 must satisfy above-mentioned condition of work, and different is, it need all not be transparent in all are used, thereby can comprise polymkeric substance, metal, glass, pottery, and glass sheet preferably.
The coating of the 3rd surperficial 114a separates with parallel relation with the space by seal element 116 and is sealingly attached on the coating of second surface 112b, and described seal element 116 is arranged near the two the circumferential perimeter of second surface 112b and the 3rd surperficial 114a.Seal element 116 can be anyly coating on the second surface 112b adhesively can be attached to coating on the 3rd surperficial 114a with the material of seal perimeter, makes electrochromic material 126 can not leak from chamber 125.Randomly, on the part (be not entire portion, otherwise driving voltage can not be added on these two coatings) of placing seal element 116, can remove the layer 120 of transparent conducting coating 128 and reflecting body/electrode.In this case, seal 116 must be firmly bonded on glass.
The performance requirement of employed peripheral seal element 116 in the electrochromic device is similar to performance requirement for employed perimeter seal in the liquid-crystal apparatus (LCD), and this is known in the art.Seal 116 must have good tack to glass, metal and metal oxide; Must have low perviousness to oxygen, moist steam and other harmful steam and indium; And must not be intended to contain and electrochromic material or the liquid crystal material reaction protected or impair these materials with it.Can apply perimeter seal 116 by method commonly used in the LCD industry, described method is serigraphy or spreading (dispense) for example.Can use vacuum seal material completely for example to make with frit or solder glass, but the high temperature (usually near 450 ℃) that relates in handling this type sealing can cause many problems, for example the oxidation and the deterioration of the variation of glass substrate warpage, transparency conductive electrode character and reflecting body.Because their lower Li Wendu, the organic sealing resin of thermoplasticity, thermosetting or ultra-violet curing is preferred.In U.S. Patent No. 4,297, this organic resin sealing system that is used for LCD has been described in 401,4,418,102,4,695,490,5,596,023 and 5,596,024.Because they are to the excellent adhesion of glass, low oxygen permeability and good solvent resistance, the organic sealing resin of epoxy radicals is preferred.These epoxy sealing bodies can be ultra-violet curings, and for example U.S. Patent No. 4,297, described in 401, or Thermocurable, the potpourri of liquid-state epoxy resin and liquid polyamide or dicyandiamide for example, or they can be equal polymerizations.Epoxy resin can contain and reduces the filler or the thickening agent that flow and shrink, for example aerosil, silicon dioxide, mica, clay, lime carbonate, aluminium oxide etc. and/or add the pigment of color.It is preferred carrying out pretreated filler with hydrophobic or silane surface treatment.Can be by using the potpourri of simple function, difunctionality and polyfunctional epoxy resin and hardening agent, control cured resin cross-linking density.The hydrolytic stability of improving sealing such as the adjuvant of silane or metatitanic acid fat (titanate) be can use, final seal thickness and substrate spacing can be used for controlling such as the spacer of beaded glass or glass bar.The suitable epoxy that is used for perimeter seal 116 includes but not limited to: " EPON RESIN " 813,825,826,828,830,834,862,1001F, 1002F, 2012, DPS-155,164,1031,1074,58005,58006,58034,58901,871,872 and DPL-862, can be from Shell Chemical Co., Houston, Texas obtains; " ARALITE " GY6010, GY6020, CY9579, GT7071, XU248, EPN1139, EPN1138, PY307, ECN1235, ECN1273, ECN1280, MT0163, MY720, MY0500, MY0510 and PT810, can be from Ciba Geigy, Hawthorne, New York obtains; " D.E.R. " 331,317,361,383,661,662,667,732,736, " D.E.N. " 431,438,439 and 444 can be from DowChemical Co., and Midl and Michigan obtains.Suitable epoxy hardener comprises: V-15, V-25 and V-40 polyamide, from ShellChemical Co.; " AJICURE " PN-23, PN-34 and VDH can be from Ajinomoto Co., Tokyo, and Japan obtains; " CUREZOL " AMZ, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 2IZ and 2P4MZ can be from ShikokuFine Chemicals, Tokyo, and Japan obtains; " ERISYS " DDA or the DDA that promotes with U-405,24EMI, U-410 and U-415 can be from CVC Specialty Chemicals, Maple Shade, and New Jersey obtains; " AMICURE " PACM, 352, CG, CG-325, and CG-1200 can be from Air Products, Allentown, Pennsylvania obtains.Appropriate filler comprises: aerosil, and for example " CAB-O-SIL " L-90, LM-130, LM-5, PTG, M-5, MS-7, MS-55, TS-720, HS-5 and EH-5 can be from CabotCorporation, Tuscola, Illinois obtains; " AEROSIL " R972, R974, R805, R812, R812S, R202, US204 and US206 can be from Degussa, Akron, and Ohio obtains.Suitable clay filler comprises: BUCA, CATALPO, ASP NC, SATINTONE5, SATINTONESP-33, TRANSLINK37, TRANSLINK77, TRANSLINK445 and TRANSLINK555, can be from Engelhard Corporation, Edison, NewJersey obtains.Suitable silica filler is SILCRON G-130, G-300, G-100-T and G-100, can be from SCM Chemicals, and Baltimore, Maryland obtains.The suitable qualitatively silane coupling agent of hydrolysis temperature that improves sealing is Z-6020, Z-6030, Z-6032, Z-6040, Z-6075 and Z-6076, can be from Dow Corning Corporation, and Midland, Michigan obtains.Can be from Duke Scientific, Palo Alto, California buys the suitable accurate glass microballoon spacer of various sizes.
Electrochromic media 126 can make the optical attenuation of therefrom advancing, and have at least a solution that directly contacts with reflecting body/electrode 120 electrochromic material and at least a other electroactive material mutually, this electroactive material can be that solution phase, surface limit, and be a kind of lip-deep material that precipitate into simultaneously.Yet at present preferred medium is the redox electrochromic material of solution phase, those disclosed in for example following patent: U.S. Patent No. 4,902,108; 5,128,799; 5,278,693; 5,280,380; 5,282,077; 5,294,376; With 5,336,448.Title is the U.S. Patent No. 6 of " AN IMPROVED ELECTRO-CHROMICMEDIUM CAPABLE OF PRODUCING A PRESELECTED COLOR; DISCLOSESELECTRO-CHROMIC MEDIUM THAT ARE PERCEIVED TO BE GREY THROUGHTHEIR NORMAL RANGE OF OPERATION ", 020,987.By reference this full patent texts is merged to herein thus.If utilize the electrochromic media of solution phase, can via sealable filling mouthfuls 142 it be joined in the chamber 125 by known technology.
In the electrochromism field, be known that when when element applies electromotive force the deepening equably of mirror and window.Inhomogeneous deepening is that the local difference by the electromotive force on solid-state electrochromic material, fluid or the gel in the electric driven color-changing part causes.Electromotive force on the whole element changes with the concentration of the conductivity of the sheet resistance of electrode, bus structure, electrochromic media, electrochromic media, element spacing between the electrode or distance with apart from the distance of bus.Usually the solution of this problem that proposes is to make the coating or the layer that constitute electrode thicker, thereby reduces their sheet resistance and can realize the element of very fast deepening.As hereinafter will discussing, exist give with the actual performance deterioration, this mis-behave has limited this oversimplification method of dealing with problems.In many situations, described mis-behave makes electric driven color-changing part be not suitable for given application.In at least one embodiment of the present invention, described the improvement electrode material that solves the problem that produces along with simple thickening electrode layer, the method for making described electrode and bus structure, and generation has electric driven color-changing part faster, more uniform variable-dark property.
In typical internal mirror, bus is parallel to the length direction process.This is that the reduction of the electromotive force on the parts minimizes between the entire electrode in order to make.This mirror also typically is made of high sheet resistance transparency electrode and low sheet resistance reflecting body electrode.Nearby with deepening full out, and some centre positions between two electrodes are the slowest at the bus that is used for higher sheet resistance electrode for this mirror.Be used for than the darkening rate that will have near the bus that hangs down the sheet resistance electrode between these two values.Between two buses, when mobile, there is the variation of effective electromotive force.Have relatively short distance (distance between bus less than bus length half) for two long parallel buses between them, mirror will be with the deepening of " window shutter " mode.This means as if mirror deepening near a bus is very fast and deepening is mobile between two buses with progressive mode.Typically, record darkening rate, and in mirror had situation greater than the ratio of width to height of 2, any unevenness of darkening rate was less relatively at the middle part of parts.
When the distance between increase of mirror size and bus increased with it, the relative different of the darkening rate of whole parts also increased.This can obtain aggravation when mirror design is used for applications.For example silver or silver alloy have lower conductivity than being fit to and being usually used in metal that internal mirror uses can to stand the overcritical metal typical ground of this environment.Be used for the metal electrode of applications thereby can have the sheet resistance of 6ohm/sq at the most, and internal mirror can have＜sheet resistance of 0.5ohm/sq.In other outside mirror was used, for various optics requirements, the thickness of transparency electrode can be restricted.As by reference this patent being merged to the U.S. Patent application No.60/888 that is entitled as ELECTRO-OPTICAL ELEMENT WITH IMPROVED TRANSPARENT CONDUCTOR herein, described in 686, in the most common use, transparency electrode for example ITO is limited to 1/2 wavelength thickness (wave thickness) usually.This restriction is because the character of ITO discussed in this article, but also because with make the thicker relevant expense of ITO coating.In other was used, coating was limited to 80% of 1/2 wavelength thickness.The sheet resistance that these two kinds of thickness all retrain transparency electrode is restricted to as follows: for 1/2 wavelength, for greater than about 12ohm/sq with for 80% the coating that is 1/2 wavelength coating, be 17-18ohm/sq at the most.The higher sheet resistance of metal and transparency electrode causes more slowly, the mirror of more inhomogeneous deepening.
Can estimate darkening rate by the analysis of electric driven color-changing part according to circuit.Following discussion relates to the coating of the even sheet resistance that has on whole element.The electromotive force of any position only is the function of the resistance of the sheet resistance of each electrode and electrochromic media between the parallel pole.In following table 1, the average potential between the entire electrode on the element provides with the difference between the minimum and maximum electromotive force.This embodiment is for such element, and this element has the interval between the parallel bus of 10cm, 180 microns unit interval, 1.2 volts driving voltage and 100, the fluid resistivity of 0000hm*cm.Contrasted the combination of 6 kinds of tops and bottom electrode sheet resistance.
Table 1
Deepening speed is the fastest with the electrical contacts of the highest sheet resistance electrode and relate to effective electromotive force in this position.The effective electromotive force of contiguous this electrical contacts (or other place) is high more, and the average deepening of mirror will be fast more.When the electromotive force on the whole parts is high as far as possible, the fastest total deepening time will be produced.This will drive galvanochemistry and deepening with the speed that strengthens.The sheet resistance of coating all plays the effect of effective electromotive force between determining electrode on top and the base substrate, but from what this table can be found out is, high sheet resistance electrode plays more important role.In the electrochromism technology in the past, almost be to promote to improve by the sheet resistance that reduces the low resistance electrode bar none, this is because such as the use of the material of silver, this use provides a large amount of benefits and easy to implement relatively.
When improve driving electromotive force, can increase total speed, but trend will not rely on driving voltage and be constant.In addition, the current sinking under the given voltage (current draw) influences the deepening homogeneity.Can be by unit interval, concentration or electrochromic material be selected to adjust improve homogeneity, but the homogeneity when using these to adjust improve usually can to deepening speed, the speed that brightens (clearing speed) or deepening and brighten speed the two have negative effect.For example, the raising unit interval also reduces fluid concentrations and can reduce maximum current, and therefore can improve homogeneity, yet the time of brightening will increase.Therefore, the sheet resistance of layer suitably must be provided with not only to obtain deepening speed but also obtain the deepening homogeneity.Preferably, the sheet resistance of transparency electrode should be less than 11.5ohm/sq, preferably less than 10.5ohm/sq be more preferably less than 9.5ohm/sq, and because following optics requirement, in some embodiments, the thickness of transparency electrode should be less than about half-wavelength (half wave) optical thickness.Scheme as an alternative, transparency electrode can comprise IMI type coating.The reflecting body electrode should be less than about 3ohm/sq, preferably less than about 2ohm/sq with most preferably less than 1ohm/sq.So mirror that makes up or electric driven color-changing part also will have deepening relatively uniformly, make between the fast and the slowest deepening state deepening temporal differences less than 3 times, preferably less than 2 times with most preferably less than 1.5 times.Discussed the material of novel, high-performance, low expense below, these materials allow to realize described fast, the even element of deepening.
In other was used, the bus with two opposing parallel was unpractical.This may be because follow the irregularly shaped of outside mirror usually.In other environment, can wish to have with the point of low resistance electrode and contact.Employed laser ablation line (laser deletion line) minimized or with its elimination during the contact of this point can make it possible to some are used.For some aspects that mirror makes up, the application of some contact makes to become to be simplified or preferential, but this makes and is difficult to obtain electromotive force on the uniform relatively whole parts.Effectively improved the resistance of electrode along the elimination of long bus relatively of low resistance reflecting body electrode.Therefore, need quick to obtain, the uniform deepening of new combination of bus and coating sheet resistance value.
As noted above, what those skilled in the art were contemplated to is can require extremely low sheet resistance value to the chaff electrode, to realize electrically contacting scheme.Yet transparency electrode must have lower sheet resistance and improve homogeneity.Table 2 has shown the homogeneity result of experiment.In this test, made about 8 inches wide * 6 inch high solution phase electric driven color-changing part.The benefit of element design discussed in this article relates generally to big element.Big element is defined as minor increment from the seamed edge of any position on the edge, visible region to geometric center greater than the element of about 5cm.Evenly the shortage of deepening becomes even bigger problem during greater than about 7.5cm in described distance, and becomes even bigger problem during greater than about 10cm in described distance.By the sheet resistance that changes transparency electrode (ITO) and chaff described in the table 2.Contact with metal electrode with a contact.For about 1 " long Ag sticks with paste (paste) line, uses clip to contact for example so-called J clevis, thus provide and the electrically contacting of chaff along a short length side of mirror.By along sticking with paste, obtain and the electrically contacting of transparency electrode with respect to a side of a contact with along the Ag that two long sides of mirror continue downward 1/3rd distances.Three positions on mirror record the deepening time (T5515).The contact of position 1 points of proximity, position 2 is at the edge with respect to the transparency electrode bus of a contact, and position 3 is at the center of mirror.The T5515 time (in second) is that mirror proceeds to the time that 15% reflectivity is spent from 55% reflectivity.Maximum reflectivity is the maximum reflectivity of mirror.Δ T5515 (delta T5515) is the mistiming between position 1 and position 2 or position 2 and the position 3.This is the measuring of darkening rate difference between the fastest position and other two positions on the mirror.When deepening became more even, these numerals became more near together.Time coefficient (timing factor) is that deepening time of given position is divided by time of fast position.This has shown the relative time ratio (scaling) between the diverse location, and this ratio does not rely on the absolute speed of any given position.As noted above, preferably have less than 3 with preferably less than 2 and most preferably less than 1.5 time coefficient.As seen from Table 2 be that for this specific mirror structure, when the ITO sheet resistance was 14ohm/sq, not have acquisition was 3 time coefficient.All three examples with ITO (having 9ohm/sq) all have the time coefficient less than 3.The center of mirror reading (mirror reading) is to depart from the position of fast position most.These data are carried out statistical study, and it unexpectedly discloses the ITO sheet resistance is to the contributive unique factor of time coefficient.When using statistical model,, need have 3.0 or littler time coefficient less than the ITO sheet resistance of about 11.5ohm/sq for this embodiment.When using same statistical model, for this mirror structure, for making time coefficient less than 2.0, ITO must have the sheet resistance less than 7ohm/sq.Even time coefficient is not subjected to the influence of the sheet resistance of the 3rd surface reflection body, Zong but darkening rate be affected.When the sheet resistance of described reflecting body is less than or equal to 2ohm/sq and ITO and is in about 9ohm/sq, this mirror in the darkening rate at center less than 8 seconds.The about mirror of this value corresponding to similar size with conventional busbar arrangement.Therefore, by reducing the sheet resistance of ITO, the reflecting body of can be enough high relatively sheet resistance is realized the some contact.
Table 2
| Reflecting body ohm/sq | ITOohm/sq | The measuring position | Maximum reflectivity | T5515 | ΔT5515 | Calibration coefficient |
| 0.5 | 9 | 1 | 55.3 | 3.7 | 1.3 | 1.6 |
| 0.5 | 9 | 2 | 55.5 | 2.3 | ||
| 0.5 | 9 | 3 | 55.3 | 6.0 | 3.7 | 2.6 |
| 1 | 9 | 1 | 56.0 | 5.4 | 2.3 | 1.7 |
| 1 | 9 | 2 | 56.0 | 3.1 | ||
| 1 | 9 | 3 | 56.0 | 7.2 | 4.1 | 2.3 |
| 2 | 9 | 1 | 55.8 | 5.0 | 1.9 | 1.6 |
| 2 | 9 | 2 | 55.9 | 3.1 | ||
| 2 | 9 | 3 | 55.9 | 7.8 | 4.6 | 2.5 |
| 0.5 | 14 | 1 | 56.5 | 5.6 | 2.8 | 2.0 |
| 0.5 | 14 | 2 | 56.6 | 2.9 | ||
| 0.5 | 14 | 3 | 56.5 | 10.2 | 7.3 | 3.6 |
| 1 | 14 | 1 | 57.6 | 6.8 | 3.4 | 2.0 |
| 1 | 14 | 2 | 57.6 | 3.4 | ||
| 1 | 14 | 3 | 57.5 | 12.2 | 8.8 | 3.6 |
| 2 | 14 | 1 | 57.3 | 8.4 | 4.4 | 2.1 |
| 2 | 14 | 2 | 57.5 | 4.0 | ||
| 2 | 14 | 3 | 57.4 | 14.0 | 9.9 | 3.5 |
In another group experiment, the ITO sheet resistance has been described in detail in detail in the homogeneity of deepening and the unexpected effect in the speed.In these experiments, the bus contact site further extends downwardly into the side of mirror to the length of higher sheet resistance electrode (in this example be ITO), and in some cases even extend on the bottom margin of mirror.Table 3 has illustrated that the change of bus length is to inhomogeneity influence.In these tests, except that indicating part, component shape is identical with last table B with structure.Contact percentage is that the percentage that the bus length of ITO contact site is compared with peripheral total length compares.Bus is than being ITO contact site length with respect to about 2cm or littler little reflecting body contact site.
Table 3 data presentation, the bus length that improves higher sheet resistance electrode significantly improves homogeneity.For the 2ohm/sq reflecting body, the length of bus contact site is brought up to 85% from 40%, make time coefficient be improved to 1.7 from 2.4.For the 0.5ohm/sq reflecting body, the ITO bus length changes to 85% from 40% equally, makes time coefficient be improved to 1.2 from 3.2, and significantly improves darkening rate.It should be noted that the element with low sheet resistance reflecting body usually than the suitable faster deepening of 2ohm/sq situation, yet illustrated as time coefficient, the homogeneity of 0.5ohm situation with shorter ITO contact site is in fact relatively poor.The bus length that increases ITO helps to have the element of 0.5ohm/sq reflecting body especially.
When improving contact percentage, position the fastest and the slowest deepening also can change.In this example, higher contact percentage significantly improves in the position the 1 and 3 liang of deepening times located and corresponding time coefficient.
Table 3
| Contact percentage | The bus ratio | Reflecting body ohm/sq | ITOohm/sq | The measuring position | Maximum reflectivity | T5515 | ΔT5515 | Calibration coefficient |
| 85 | 20 | 2 | 9 | 1 | 57.0 | 2.9 | ||
| 85 | 20 | 2 | 9 | 2 | 57.0 | 3.7 | 0.8 | 1.3 |
| 85 | 20 | 2 | 9 | 3 | 57.3 | 4.8 | 1.9 | 1.7 |
| 58 | 13 | 2 | 9 | 1 | 56.6 | 3.4 | ||
| 58 | 13 | 2 | 9 | 2 | 57.2 | 3.5 | 2.2 | 1.0 |
| 58 | 13 | 2 | 9 | 3 | 57.5 | 5.6 | 2.2 | 1.6 |
| 40 | 9 | 2 | 9 | 1 | 56.9 | 8 | 4.6 | 2.4 |
| 40 | 9 | 2 | 9 | 2 | 57.3 | 3.4 | ||
| 40 | 9 | 2 | 9 | 3 | 57.4 | 8.2 | 4.8 | 2.4 |
| 85 | 20 | 0.5 | 9 | 1 | 56.0 | 3 | ||
| 85 | 20 | 0.5 | 9 | 2 | 56.2 | 3 | ||
| 85 | 20 | 0.5 | 9 | 3 | 56.1 | 3.5 | 0.5 | 1.2 |
| 58 | 13 | 0.5 | 9 | 1 | 55.8 | 4 | 1.5 | 1.6 |
| 58 | 13 | 0.5 | 9 | 2 | 56.1 | 2.5 | ||
| 58 | 13 | 0.5 | 9 | 3 | 56.0 | 3.5 | 1 | 1.4 |
| 40 | 9 | 0.5 | 9 | 1 | 55.5 | 8.2 | 5.6 | 3.2 |
| 40 | 9 | 0.5 | 9 | 2 | 55.8 | 2.6 | ||
| 40 | 9 | 0.5 | 9 | 3 | 56.0 | 4.9 | 2.3 | 1.9 |
These description of tests, when using the weak point bus for low sheet resistance electrode, it is useful to improving homogeneity that bus length is increased to electrode of opposite.Ideally, therefore for large mirror, the ratio of preferred bus length greater than 5:1, be preferably greater than 9:1 even more preferably greater than 13:1 with most preferably greater than 20:1, to obtain to be lower than 3 time coefficient.Also find, do not rely on the length of less bus, by the length with bus be increased to higher sheet resistance electrode with obtain to be preferably greater than about 58% with more preferably greater than about 85% the percentage that contacts, homogeneity is improved.Typical big EC mirror has the contact percentage less than 50%.Above-mentioned example uses ITO as transparency electrode.Scheme as an alternative can be used IMI coating as herein described and has comparable speed and homogeneity result.
Reflecting body/combination of electrodes 120 places the 3rd surperficial 114a to go up and comprises at least one layer of reflective material 121, this layer is as the specularly reflected layer and form overall electrode, and this electrode contacts and chemistry and the electrochemical stability relation of being with any component in the electrochromic media.As mentioned above, the conventional method that makes up electrochromic device is to include transparent conductive material in as electrode on the 3rd surface, and reflecting body is placed on the 4th surface.By " reflecting body " and " electrode " made up and all be placed on the 3rd surface, produce some advantages, these advantages not only make the device manufacturing not too complicated, and make this device with superior performance work.For example, the reflecting body/electrode 120 that makes up on the 3rd surperficial 114a has higher electric conductivity than conventional transparency electrode and the previous reflecting body/electrode that uses usually, and this allows bigger design flexibility.The composition that perhaps second surface 112b can be gone up transparency conductive electrode 128 changes to the composition that has than low conductivity (cheap and be easy to produce and make), and it is approaching with the obtainable speed of the 4th surface reflection body device to keep painted speed simultaneously, and basic simultaneously the reduction total expenses and the time of producing electrochromic device.Yet, if the performance of particular design is extremely important, can on second surface, use medium transparency electrode to high conductivity, ITO for example, IMI, or the like.High conductivity on the 3rd surperficial 114a is (promptly less than 250hm/sq, preferably less than 15Ohm/sq) combination of high-conductivity transparent electrode 128 on reflecting body/electrode 120 and the second surface 112b not only can produce has more even overall painted electrochromic device, and can allow to improve painted and the speed that brightens.In addition, the 4th surface reflection somascope assembly comprises two transparency electrodes with relative low conductivity, and in the 3rd surface reflection somascope of former use, there are transparency electrode and reflecting body/electrode with relative low conductivity, therefore, need on the element in preceding element and back make the electric current turnover long bus to guarantee enough painted speed.
Transparent conductive material layer 128 deposits to second surface 112b and goes up to serve as electrode.Transparent conductive material 128 can be the material of any good combination to preceding element 112, opposing is to the corrosion of any material in the electrochromic device, the corrosion of opposing atmosphere has minimum diffuse reflection or direct reflection, high transmittance, approaching neutral color and good electrical conductivity.
In this example, transparent conductive material 128 comprises insulator 131, metal level 133 that is right after second surface 112b and the insulator layer 135 that is right after electrochromic media 126, their collaborative insulator/metal/insulator (IMI) laminations 139 that forms.If desired, can between transparent conductive material 128 and second surface 112b, deposit one or more optional colors and suppress material layer 130, to suppress any reflection that does not need part in the electromagnetic spectrum.In addition, as mentioned below, can also include restraining barrier 137 in.Select making up the material that insulator/the metal/insulator lamination is utilized so that the optics of electric driven color-changing part and physical property for example reflectivity, color, TURP change stability and environment durability optimization.
Though in U.S. Patent No. 5,239,406,5,523,877,5,724,187,5,818,625 and 5, disclose in 864,419 in EC mirror is used and utilized the general notion of insulator/metal/insulator lamination, but failed to instruct concrete lamination explanation to obtain various desired properties so that utilize insulator/metal/insulator transparency electrode to produce functional and permanance electrochromic device.
The description details of this paper produce effective IMI lamination 139 necessary requirement and performances of the present invention.The particular configuration of IMI lamination 139 of the present invention has overcome previous many shortcomings relevant with utilize the IMI lamination in electric driven color-changing part and problem.Particularly, fixed is that when considering transmission of visible light, the IMI coating is compared with single-layer and transparent conductive oxide (TCO) and showed differently in electric driven color-changing part.The reflectivity of mirror or the transmissivity of window directly depend on the absorption of the glass that is coated with transparency electrode, and when transparency electrode showed a large amount of absorption, the reflectivity of mirror or window was reduced.If the transmissivity of transparency electrode is lower because of reflection loss, then the window made from such transparency electrode will have low transmissivity and potential unacceptable reflectivity.When being placed to when contacting with the electrochromic media with the refractive index that is higher than air, the transmissivity of TCO will increase, thereby keep the decline that also causes reflectivity when coated glass has approximately identical absorption.Consequently, if use TCO in window, with respect to airborne parts, the gained reflectivity will descend and transmissivity will increase.Yet the IMI coating does not show as this mode usually.Compare when contacting with air with the IMI coating, when being placed to when contacting with electrochromic media, it is identical that the transmissivity of IMI can increase, reduces or keep.Therefore, can not summarize suitable IMI coating structure, and can not calculate, and this can accomplish for the TCO coating the corelation behaviour in the electrochromic applications.Electric driven color-changing part of the present invention has been included the IMI coating that is suitable for relative high-transmission rate of showing of electrochromic applications and low sheet resistance in.Especially, and in air, compare, carry out especially well in the behavior of coating described in the electrochromic cells, because in fact before described all prior art IMI type coatings.
As an example, Fig. 5 has illustrated the different transmissivities of ITO on glass when incident medium is air or electrochromism fluid.In this case, the electrochromism fluid mainly is made of the carbonic allyl ester that has 1.44 refractive indexes at 550nm.The main cause that transmissivity changes is reducing because of reflectivity.Compare with the situation of air, in fact the situation of this electrochromism fluid has higher slightly absorption (0.2%).Yet the change of comparing transmissivity between air and the electrochromism fluid is not directly significantly.Carried out the analysis of IMI lamination, described IMI lamination is made of glass, the dielectric with 2.0 refractive indexes (index), silver layer and the top layer that has 2.0 refractive indexes equally, changes the thickness of each dielectric layer and silver layer.Calculate the change (the electrochromism fluid deducts air) of transmissivity between air and the electrochromism fluid, and the result is carried out statistical study to determine trend.Fig. 6 has illustrated as simple relatively three layers of existing complex relationship of IMI lamination.In each isogram shown in Figure 6, two layers change and other layer keeps constant.
Because usually the refractive index with dielectric layer keeps high as far as possible, the specific components that is used for making up IMI lamination 139 of the present invention helps to improve the transmissivity of lamination.High relatively refractive index helps to improve the transmissivity of the lamination 139 with suitably thick silver or ag alloy layer.When the IMI coating is right after the electrochromism fluid placement of relative high index of refraction, to compare when being right after the air placement with this same coating, dielectric is even more important to the needs of high index.Higher refractive index also helps to obtain a series of colors under high relatively level of transmittance.Preferably, the refractive index of dielectric layer is greater than 1.7, more preferably greater than 2.0 with most preferably greater than 2.5.
Table 4 has been listed the transmissivity of many laminations, and the transmissivity of the IMI lamination with different dielectric refractive indexes and silver-colored thickness has been described.With can be from Port1and, the Software Spectrum of Oregon, Inc., the film computer program (TFCalc) of acquisition calculates value.As pointed in the table 4, carry out optimization so that the transmissivity maximization with silver-colored fixed thickness and to dielectric.The thickness in table 2 middle level is in dust.Particularly, in model, use the dielectric show four kinds of different refractivities, comprise titanium dioxide, (having two kinds of different refractivities) indium-zinc oxide (IZO) and mixed with titanium Si oxide (ixoide) layer.Can mix to titania and improve bulk resistor.Shown transmissivity to be positioned at the air and the electrochromism fluid that are right after the IMI lamination.It should be noted that higher refractive index provides the high transmittance value, and be worth keeping, thereby under lower sheet resistance value, allow high relatively transparency in the window or the high reflectance in the mirror for these high-transmission rates of thicker silver layer.Consequently, obtained switching time faster for relevant electric driven color-changing part.Obtain the ability that the high index dielectric keeps in wide silver thickness scope high-transmission rate, also be expressed as other attribute for example reflection or transmitted colors and leeway that layer is regulated.When refractive index was higher, dielectric thickness can also be thinner, thereby be converted into the more cost effective product and the lamination of versatility more.Preferably, transmissivity greater than about 50%, more preferably greater than about 60% even more preferably greater than 70% even more preferably greater than 80% with most preferably greater than 90%.If high-transmission rate is primary design standards, then silver thickness preferably less than 300 dusts, be more preferably less than 200 dusts even be more preferably less than 150 dusts and most preferably less than 100 dusts.
Table 4: the transmittance values of different I MI lamination
Except that the real part of dielectric refractive index, also be absorbed in the imaginary part of dielectric refractive index.The imaginary part of refractive index influences the absorption of light in the dielectric layer.The dielectric layer of IMI lamination plays the minimized effect of resident (standing) electric field that makes light in the metal level, thereby strengthens the electric field in the dielectric layer.Therefore appreciable with respect to institute in the dielectric layer in substrate separately, the absorption intensity that is caused by the imaginary part of refractive index is improved.Consequently, the uptake in the dielectric layer is minimized, thereby make the transmissivity maximization of transparency electrode.On the contrary, the absorption in the dielectric layer can be used to the transmissivity of the suitable IMI of accent lamination and need not to adjust metal level, and this metal level can and be fixed for other optics or electricity requirement.
Table 5 has shown that the absorption in the IMI electrolyte is to the influence of available transmissivity for fixing dielectric refractive index.For IMI lamination with different dielectric layers, reuse thin-skin model and calculate transmissivity and reflectivity, described dielectric layer has approximately identical true refractive index n.During transmissivity is optimized with silver-colored fixed thickness at 100 dusts and allow the dielectric layer activity.Maximum transmission rate is highly related with the k value in dielectric.These data and linearity curve match are produced the equation that the transmissivity in the dielectric and k value are connect.Be displayed in Table 6 based on this equational transmissivity and k value.In order to obtain transmissivity greater than 50%, the k value preferably less than about 0.2, be more preferably less than 0.1 even be more preferably less than 0.04 even be more preferably less than 0.01 and most preferably less than 0.005.In most preferred level and following, transmissivity does not almost change with the k value that changes.Utilize 2.0 fixing true refractive index (index) to determine these preferred range for each layer.When using other true refractive index, preferred k value can be mobile a little.
Table 5:, absorb (k) can get transmissivity and minimum absorption to maximum influence for fixing n value.
| Dielectric | n | k | R | T | A |
| ITO cold (cold) | 2.025 | 8.61E-04 | 7.70 | 88.06 | 4.24 |
| |
2.026 | 1.18E-03 | 7.61 | 88.12 | 4.27 |
| AZO | 1.975 | 5.41E-03 | 8.81 | 85.64 | 5.55 |
| IZO | 2.016 | 1.04E-02 | 7.95 | 85.62 | 6.43 |
| |
2.120 | 1.30E-02 | 6.01 | 87.32 | 6.67 |
| |
2.000 | 2.30E-02 | 8.26 | 82.84 | 8.90 |
| |
2.000 | 2.82E-02 | 8.30 | 81.99 | 9.71 |
| |
2.000 | 3.89E-02 | 8.51 | 80.16 | 11.33 |
| |
2.000 | 4.97E-02 | 9.01 | 78.34 | 12.65 |
Table 6: transmissivity is with respect to the k value when using the equation based on table 4 value.
| k | The transmissivity of evaluation | k | The transmissivity of evaluation |
| 1.00E-05 | 88.0 | 7.00E-02 | 74.0 |
| 5.00E-05 | 88.0 | 8.00E-02 | 72.0 |
| 1.00B-04 | 88.0 | 9.00E-02 | 70.0 |
| 5.00E-04 | 87.9 | 1.00E-01 | 68.0 |
| 1.00E-03 | 87.8 | 1.10E-01 | 66.0 |
| 2.00E-03 | 87.6 | 1.20E-01 | 64.0 |
| 3.00E-03 | 87.4 | 1.30E-01 | 62.0 |
| 4.00E-03 | 87.2 | 1.40E-01 | 60.0 |
| 5.00E-03 | 87.0 | 1.50E-01 | 58.0 |
| 1.00E-02 | 86.0 | 1.60E-01 | 56.0 |
| 2.00E-02 | 84.0 | 1.70E-01 | 54.0 |
| 3.00E-02 | 82.0 | 1.80E-01 | 52.0 |
| 4.00E-02 | 80.0 | 1.90E-01 | 50.0 |
| 5.00E-02 | 78.0 | 2.00E-01 | 48.0 |
| 6.00E-02 | 76.0 |
Should note in some applications, only to show high index of refraction can be favourable to the part dielectric layer, thereby the acquisition optical benefits, for example reflection or transmitted colors are suitable transfers, and this suitable accent can have benefited from refractive index (indecis) combination or the graded index (index) in the dielectric layer.
Maximized another method of transmissivity that makes silver layer in the IMI lamination 139 is to produce the silver layer with alap refractive index (real part).Can obtain this low relatively refractive index by several means.Silver layer is deposited on can helps to produce the silver with relative antiradar reflectivity on the zinc paste, this is because the crystal coupling between zinc paste and the silver.Particularly, silver is false to be intended ground (pseudo) epitaxial growth and has compact texture, and zinc oxide film typically has crystalline structure when depositing by sputter.Therefore zinc oxide film has the tendency that produces rough surface owing to its crystalline state character.Therefore must control the thickness of zinc oxide film in the lamination, make usually constant too much with the roughness of thickness increase.In addition, the deposition parameter that is used for zinc paste can be used for the key-course form and the thickness under the various gross thickness levels is minimized.
The refractive index of silver is also relevant with its electrical property.For given silver coating, preferred layer will have low bulk resistor, thereby produce the high transmittance value.Make the bulk resistor that reduces coating in two ways, comprise and improve electronic carrier concentration and improve electron mobility.Because the raising gained IM lamination of electron mobility has high transmittance.
Except that the electrical property of silver layer, the charged sub-transition of d also influences the performance of silver layer.In silver, as for most of transition metal, electronics can be excited to higher energy level, wherein in the d of metal band or d track generation transition.These transition influence the refractive index of metal significantly.By adjusting the electron concentration in the metal, change can begin to take place to absorb residing frequency.This is achieved by following: be with transition to be transferred to upper frequency d, thereby reduce relevant silver layer in visibility region refractive index and therefore improve transmissivity.Preferably, at least a portion of the visible spectrum of 380-780nm, the real part of Ag refractive index should less than about 0.12, be more preferably less than about 0.10 even be more preferably less than about 0.08 and most preferably less than about 0.06.
Interface between silver and the adjacent material influences the final transmissivity (and sheet resistance) of IMI lamination significantly.When the rough interface degree reduces, the low absorption taken place in the IMI lamination, perhaps when layer be atom level when smooth, the mixing between silver and the dielectric increases, absorption is in maximum.IMI lamination material therefor and deposition are selected, so that smooth layer and interface to be provided.In addition, when the rough interface degree increased, the optical constant of silver particularly electron mobility reduced, and therefore influences transmissivity in negative mode.Preferably, the surperficial peak-paddy roughness of the layer below Ag or metal level should be less than about 50 dusts, be more preferably less than about 30 dusts even be more preferably less than about 15 dusts and most preferably less than about 10 dusts.Ideally, by changing deposition process setting and method, can be adjusted at the used process setting of each layer of Ag or metal level below.When also infeasible in one embodiment, available ion beam technology makes layer smooth, thereby required surfaceness is provided for this.
Carry out other consideration about the selection that is right after the material that silver layer places.Even for the smooth interface of optics, also there is the interfacial state that is called surface plasmon.Surface plasmon serves as normal direction layer (normal layer), and influences the reflecting properties of lamination indistinctively, yet influences intensity in transmission significantly.The frequency of plasman or peak absorbance are the dielectric function of adjacent material and relevant with the plasma frequency of silver layer.Therefore, select to obtain benefit by suitable material, and the significant performance that does not rely in the thin-skin model to be seen.Ideally, the plasma frequency of silver layer should be high as far as possible, has selected specific inductive capacity in abutting connection with the residing layer of silver layer, makes the frequency of surface plasmon not cause the obvious absorption in the coating.
In some applications, need lower transmissivity in EC mirror or the window, and keep acceptable color, reflectivity and low sheet resistance simultaneously.As an example, when using metal such as silver for reflecting body, the transmissivity that might regulate the IMI coating to be reducing the reflectivity of mirror, thereby satisfies market demands.In these cases, material being introduced the IMI lamination produces surface plasma oscillator layer can cause controlled absorbed in the visible region.By this way, the transmissivity of IMI coating is regulated and simultaneously in the preferred performance of other zone maintenance.Can use other method for example restraining barrier or inculating crystal layer (seed layer) to be set in abutting connection with silver layer.By this way, can cause lower transmittance values in abutting connection with silver-colored thin metal layer, and can be used for the auxiliary adjustment transmitted colors.
Can utilize other method to improve the transmissivity of IMI type coating.As noted above, the refractive index of silver layer or metal level is important for obtaining the high-transmission rate value.The back deposition anneal of coating is to improve the another kind of method of transmissivity.By under the temperature that improves sample being heated the given time period, the transmissivity that can improve coating also reduces the sheet resistance of coating simultaneously.
Five layers of IMI lamination have been carried out time-temperature studies.Described lamination is made of glass/IZO/AZO/Ag/AZO/IZO, and wherein IZO is the indium-zinc oxide with about 1% to 99% zinc percentage, and AZO is that the doped level of wherein aluminium is about Al-Doped ZnO of 0.25% to 10%.The AZO layer is that about 50 dusts are thick, and silver-colored thickness to be about 80 dusts thick and the IZO layer is about 440 dusts.Described lamination of heating and lasting different time under three kinds of different temperature.Fig. 7 has illustrated the result that transmissivity changes with heating condition, and Fig. 8 has illustrated the variation for the sheet resistance of same heating condition.As described, produce the IMI lamination that improves with the back deposition heat treatment.Certainly available other metal replaces silver, and preferred metal should have low-refraction, to allow to take place the suitable admittance coupling of metal.Preferred metals is drawn together silver, gold, copper, aluminium zinc, magnesium, beryllium, cadmium, zirconium and vanadium.Preferably, at about 150-450C, more preferably 200-400C and 250-350C heating coating most preferably.Preferably, should be 5-40 minute heat time heating time, more preferably 5-20 minute and most preferably 10-20 minute.
The color of electrochromic or mirror is important aesthetic performance, preferred color of choice neutrality in many application.For example, the modern architecture window is designed to have high " colour rendering index " (CRI), wherein the color of object does not change because of seeing through the transparency observation, 100 colour rendering index is a perfect condition, it is acceptable being higher than 80 value, it is preferred being higher than 90 value, and to be higher than 95 value be preferred.Defined colour rendering index in the list of references below: " CIEPublication13.3.Method of measuring ﹠amp; Specifying colourrendering properties of light sources.CIE, 1995 ".When mirror was converted to the deepening state, the reflection colour of mirror changed.When the complete deepening of mirror, color that observes and reflectivity belong to first and second surfaces of top surface of glass basically.The title that on November 9th, 2004 authorized is the U.S. Patent No. 6 of ELECTROCHROMIC MIRROR HAVING A SELF-CLEANINGHYDROPHILIC COATING, 816, the title that on February 1st, 297 and 2000 authorized is the U.S. Patent No. 6 of ELECTROCHROMIC MEDIUM CAPABLE OF PRODUCING APRESELECTED COLOR, 020,987, transfer the possession of and merge to by reference herein with the present invention is common respectively, how coating and fluid color on described patent has described in detail from bright state (not deepening state) to complete deepening state glass first surface influence the color outward appearance.
When mirror is in complete deepening state, there is not light to arrive the observer from the reflecting body on the 3rd surface or the 4th surface, the outward appearance of mirror is to be caused by the combination from the light on first and second surfaces of first substrate.When not having coating on first surface, obtain about 4% reflectivity from uncoated glass interface, any dyeing is to be caused by the thin film interference effects from the transparency electrode on the second surface.The color of transparent conductive oxide mainly belongs to layer thickness.When improving the thickness of TCO, color changes by predictable mode.Can further change color by above or below TCO, adding additional layer.Above the patent of reference has been instructed the method that the color that makes TCO and other coating is desalinated most.The reflectivity of mirror also is subjected to whether to exist in the thickness of TCO and the coating stack influence of other layer in the dark state.As the quite low result of absorption among ITO or other TCO, the change color that in the bright state of mirror, does not almost have because of layer thickness variation.Similarly, in window, ITO does not have contribution substantially to transmitted colors, carries out color adaptation to transmitted colors yet not contribution by regulating the ITO options.
For the inherent colour of the reflective metal layer that do not influence EC mirror, the IMI transparency electrode must have greater than 80, be preferably greater than 90 and most preferably greater than 95 transmission colour rendering index.Different with window, the light that drops on the mirror must pass coating twice, for the first time is at light during near reflecting body, be for the second time at light when reflecting body reflects.If the colour rendering index of IMI coated glass is low excessively, then the color of reflecting body is changed.In many EC mirror were used, mirror must be suitable neutral color.Low excitation level is preferred, and the tone of image is not changed by mirror substantially thus.It should be noted that not all IMI lamination has sufficiently high colour rendering index inherently.The refractive index of dielectric layer and the thickness of all layers concur, thereby produce final transmitted colors, color change when changing described layer.In many situations,, depart from neutrality because cause transmitted spectrum to move, thereby cause coloured transmissivity the optimization of high-transmission rate to need conflicting mutually of acceptable transmitted colors with needs to maximum transmission rate.Particularly, as use term a
*And b
*The a that can obtain to bear with relative high-transmission rate coating is discussed
*, this is because of the preference response of eye to green glow.In order to obtain positive a
*, must keep the lower upper limit (cap) Y for identical average reflectance level, not preferred in most applications.Application has negative a for high-transmission rate
*The result be, main color distortion is certain moving, it is b that expection should be moved
*Move.Therefore tone moves between Huang skew and blue skew.Consequently, to carrying out appropriate designs, make color not move out IMI with regard to b
*Particular range.Preferably, the gamut of reflecting body is less than about 10C
*Unit, wherein C
*Equal (a
*)
2+ (b
*)
2Square root, be more preferably less than about 5, most preferably less than about 2.5.Scheme as an alternative, preferably, the gamut of reflecting body is less than about 10b
*Unit is more preferably less than about 5b
*Unit and most preferably less than about 2.5b
*Unit.In many application, the colour cast that reflecting body shows makes us unhappy, therefore uses for expection and impels the deviser to abandon specific reflecting body.Because regulate the new ability of the transmitted colors of IMI coating, the deficiency by the color of adjusting the IMI coating is come the compensatory reflex body can make the final color of mirror be accepted.By this way, improved the scope of the acceptable material that is used for reflecting body, this brings other benefit can for final mirror assembly.For example, the common issue with of following various reflecting bodys is yellow skew, and this causes the yellow appearance of image in the final mirror assembly.Yet, for the IMI coating being designed, can make final mirror color become more blue by changing the IMI coating to produce preferential blue transmission color, this is the less relatively yellow of transmissive therefore.The amount of blue shift is based on by the relative transmittance of the blue light of IMI and gold-tinted and can b
*Colour is approximate.Preferably, utilize the reflecting body color correction of IMI coating greater than about 2.5C
*Unit, more preferably greater than about 5, most preferably greater than about 10.Scheme as an alternative, preferably, the gamut of reflecting body is greater than about 2.5b
*Unit, more preferably greater than about 5b
*Unit and most preferably greater than about 10b
*Unit.
As mentioned above, application also is important to reflection colour for EC mirror.In the deepening state, the color that the observer sees mainly is the color of transparency electrode on the second surface, the final color that the thickness of layer and refractive index influence product.Except that layer thickness, can regulate color by being chosen in the dielectric that different-waveband has absorption.Typically, common dielectric can have absorption at the blue portion of spectrum, and other dielectric can have absorption at other wave band of visible spectrum.Can select them according to the absorptive character of dielectric substance, to produce the required final color performance of IMI lamination and final mirror.Also can regulate color by making dielectric substance in the lamination have different refractive indexes.Can use the variations in refractive index of dielectric layer to help obtain the various combination of reflectivity, transmissivity and color, can not obtain described combination with the IMI coating that only constitutes by the dielectric layer of fixed refraction.
The color of middle deepening state also is important in EC mirror usually.Color change when the mirror deepening is also referred to as color offset.Usually deepening state in the middle of mirror being set to, and the color of reflection is fluid color, reflecting body color and transparency electrode color combinations.In middle deepening state, the IMI coating should produce acceptable color.Preferably, the color of dark state reflection have less than about 35, preferably less than about 20, be more preferably less than about 10 and most preferably less than about 5 C
*Value.
In many application, be vital in the color of looking side ways angle.Especially, use, must under all or most of visual angle, have the color of pleasant usually for window.Need special layer, thickness and refractive index to realize this target.Some IMI laminations are more responsive with the variation of angle to color than other lamination.The thickness and the dielectric layer thickness that have shown silver layer can be important for the acceptability in the electric driven color-changing part.The thickness of silver layer should be preferably about 50 dusts-500 dust, more preferably from about about 250 dusts of 75-and 100-150 dust most preferably from about.The gross thickness of top and bottom dielectric layer can be about 100 dusts-700 dust.Specific if desired color target can be used thicker layer sometimes.As described below, the dielectric layer thickness above or below the metal level can be adhered to separately and be that many different dielectric substances, these dielectric substances can be added into lamination so that specific chemistry, physics and/or environment durability requirement to be provided.Preferably, from the gamut of the reflection of normal incidence to 45 degree less than about 20C
*Unit, be more preferably less than 10 and most preferably less than 5.
In many situations,, be difficult to satisfy all esthetic requirements, electricity requirement and environmental requirement for the IMI lamination that only contains single metal layer.This is overcome by the IMI lamination that design is made of a plurality of metal levels.Have the lamination of two or more metal levels by manufacturing, allow bigger degree of freedom for more combinations of transmissivity and reflection colour and intensity.For the IMI coating, many metal levels also allow lower sheet resistance, and this is converted into the very fast switching time of electrochromic or mirror.Typically, two metal level laminations can have the basic unit, metal level of relative thin, the top dielectric layer of thick relatively interlayer dielectric, second metal level and relative thin.Dielectric layer thickness is with respect to other dielectric layer.Metal level is typically thin than dielectric layer.Dielectric layer can comprise different materials and be similar to regard to described some design object of monometallic IMI coating with acquisition.The selection of dielectric substance and metal and their thickness is based on specific design object.For example, if high transmittance is important, then metal level tend to thinner, and if low sheet resistance is an important design goal, then metal level can be thicker.In the IMI coating, use a plurality of metal levels can help usually under given sheet resistance level, to obtain high transmittance.In addition, many metal levels can provide uniform color in the stravismus angle with respect to monometallic IMI lamination.
As known in the art, the protection of ultraviolet shielding and sunlight is the requirement of electrochromic.Typically, these windows use complicated P series glass plate and coating to obtain suitable covering.Yet, go out in the previous trial of electrochromic of necessary screening performance the open IMI coating of failing use therein in design expression.On the contrary, the trial in past is taught in the other coating of utilizing on glass, and these coatings are stacked on the electrochromism glass windows.Although these other layers are functional, must increase the weight and the expense thereof of associated window assembly.
By the material selection of lamination and the combination of optical design, in the IMI transparency electrode, can obtain ultraviolet shielding or blocking-up.For example, can select to demonstrate the dielectric substance of uv absorption property.Particularly, TiO
2, CeO
2With zinc paste be effective ultraviolet absorber.These materials demonstrate uv absorption typically because their optical band gap.Can increase the UV Absorption of these materials by the optical design of coating.For example, but IMI lamination reflecting part ultraviolet light, thus further reduce total ultraviolet transmission rate.
The metal level of IMI lamination 139 also can have ultraviolet blocking-up performance.For example, silver has absorption in ultraviolet spectrum, and this is because electronics is with to d from more low-yield band optical transition.These so-called d band transition cause a large amount of UV Absorption.For silver, the transition of d band takes place under high relatively energy in the ultraviolet portion of spectrum.Other metal for example gold and copper has d and is with transition under lower energy state.For these metals, the transition of d band causes the significantly painted of metal, yet these metals demonstrate better ultraviolet blocking-up than silver.By carrying out alloying with the metal that demonstrates higher uv absorption, can increase the described performance of silver or other metal, cause and the not absorption relevant if particularly absorb with crystal structure by atomic absorption.Preferably, the ultraviolet transmission rate less than about 75%, be more preferably less than 50% even be more preferably less than 25% and most preferably less than 15%.
Metal and other conductive material reflective infrared and solar irradiation.Catoptrical intensity is directly proportional with conductivity of electrolyte materials and layer thickness.When improving the thickness of layer or coating, reflectivity is progressively near maximal value, and this maximal value is pressed once (to first order) and depended on conductivity of electrolyte materials.The higher material of conductance has higher infrared reflectivity.In addition, when improving the conductance of material, increase at the shorter wavelength reflectivity.As mentioned above, the cause of conductivity influences the transmissivity and the reflectivity of coating.Conductivity of electrolyte materials is the combination of electron density and electron mobility.In these attributes each influences infrared reflectivity by different way, and when conductivity is when being caused by high electron density rather than high electron mobility, infrared reflectivity is maximized.
Also can adjust sunlight transmissivity and reflectivity by the optical design of IMI coating.For example, the comparable single metal layer lamination of many metal levels lamination has higher sunlight rejection rate.If add other layer to the first and the 4th surface, can further regulate the sunlight barrier property of electrochromic.These other coatings can provide low radiation (low e) benefit and/or other sunlight shielding properties can be provided.In addition, electrochromic and other one or more glass plates can be combined into the insulating glass configuration.Described other glass plate can be uncoated, or with the layer apply so that specific ultraviolet or sunlight barrier property to be provided.Minimize for making sunlight heat obtain coefficient (SHGC), electrochromic should be placed to make the glass blocks of winning (lite) outside and low-emissivity coating place on the 4th surface.In the needs aesthetic with when functional, can on the surface of glass plate, add other layer.Usually, compare with transparent conductive oxide, the use of IMI layer can intercept significantly more solar irradiation in the electrochromic under given ohm/sq.In addition, the IMI layer can be realized this by much lower cost.Under bright state, SHGC preferably less than about 0.7, be more preferably less than about 0.5, most preferably less than 0.3.Under dark state, SHGC less than about 0.5, be more preferably less than about 0.3 and most preferably less than about 0.15.
Traditionally, the dielectric layer in the IMI coating belongs to two diverse classifications.In the building window was used, dielectric layer was nonconducting typically, and in the past, avoids transparent conductive oxide, and this is because with the high Master Cost of these material canonical correlations with make complicacy.Usually need high temperature or obtain the best transmittance and the conductivity of described layer through the processing of meticulous control.If can use the IMI coating as transparency electrode, dielectric layer is transparent conductive oxide normally, utilizes needed transparent conductive oxide to allow the conductivity perpendicular to coating surface.The strict restriction of previous method is used for the classification of the viable material of the used IMI coating of electrochromic applications.
The purpose of transparency electrode is to provide electric current to electrochromic cells, and provides enough transparencies for given application simultaneously.Yet, can obtain other benefit by the conductivity of different relevant layers is carried out optimization.Electrochromic cells can be handled as one group of parallel resistor device, first resistor is as the high conductivity metal layer.The high conductivity of this layer allows more electric current to arrive the center of associated components, rather than advances perpendicular to the clad plate near cell edges, this so that cause parts deepening more equably.What suppose is, does not have tangible voltage drop in the direction perpendicular to metallic coating, and when using TCO as transparency electrode this typically situation.
When adding other layer the top of metal level to, for example in the situation of IMI lamination, then must put into effect other design standards, this standard can suitably be adjusted with regard to the other benefit in the electrochromic cells.By placing the TCO of relative high conductivity, do not introduce obvious voltage drop perpendicular to metal level at the top of metal level.Yet, if TCO or other dielectric layer have low relatively conductivity, extra voltage drop occurs, thereby the restriction electric current flows perpendicular to the metal surface.Compare with the center of visible region, this extra voltage drop makes perpendicular to the voltage drop on surface, edge-of-part place even.Quantitative benefit is for example functions of the relative conductivity of unit interval, fluid property, unit size and different materials of many variablees.Actual result is, can obtain more uniform deepening by the layer of introducing relative low conductivity between higher metal level of conductivity and electrochromic media in some applications.
The necessary electrical conductivity problems and the location of the concrete level of conductivity are important for the IMI coating that is made up by a plurality of metal levels.If in all parts of IMI lamination, do not need for example ITO of expensive material, then can significantly reduce the cost of many metals IMI coating.For example, in two silver layer laminations, the thickness of interlayer dielectric is often up to 700 dusts or bigger, and top and bottom-dielectric can surpass 350 dusts, and the total amount of ITO is about 1400 dusts in the lamination, thereby has brought great expense to product.By substituting some or all of ITO with the conductivity materials with smaller, the overall performance of coating does not suffer damage, but expense is able to remarkable minimizing.
Directly the material that contacts with electrochromic media is important for the performance of electrochromic device.For example, the material reaction in some materials and seal or the fluid, and passivation all or part surface, this causes the difference of the deepening performance of electrochromic device.Having certain desired properties by the top layer of guaranteeing IMI can make passivation minimize.A kind of such performance is the ability of described layer conduction current.By making top layer have the conductivity of about 10MOhm, then reduced the possibility of passivation significantly.Can make the general low conductivity layer can be as the top layer that is right after electrochromic media by change forming, the change of described composition be by mixing or stechiometry is introduced the conductivity of the certain level that is enough to reduce passivation.It is feasible to use other chemical method by the surface chemical property that changes layer inconsistent material to be become.The suitable application of chemistry part or composition (moiety) can be enough to change surface property, thereby but makes the potential energy minimization of passivation.
Dielectric layer below metal level can be TCO, yet it is optional.If basic unit is not TCO, then the total conductivity of IMI lamination is not fully improved, and this is because high a lot of conductivity of metal level.Other preferred material that the conductivity that improves because of metal level is used for dielectric layer comprises: ITO, IZO, AZO, ZnO, TiO
x, CeO
x, SnO
2, SiN, SiO
2, ZnS, NiO
x, CrO
x, NbO
xAnd ZrO
xDescribed material can be pure, stoichiometry or part are stoichiometric, mixes or mixes so that intermediate performance to be provided with another kind of material.Preferably, if make the transmissivity optimization, should avoid demonstrating the material of obvious absorption.If material has high relatively refractive index, and the absorption of layer increases the reflectivity and the transmissivity of film interference optical devices, and is created in attribute actual unavailable when not absorbing, then preferred absorbent material.Sometimes a part that also can be used as the IMI lamination as other conductive oxide of electroluminescence layer (these layers not obviously deepening when covering) with other layer.These layers can be acceptable and can cover, even described layer is with the slow deepening of the electric field that applies.Such as WO
3, NiO or IrO
2Material belong to this kind.
Be important for the overall performance of IMI lamination directly at the layer below metal level above the metal level or more importantly.As mentioned above, some material can have influence to the transmissivity and the electrical property of lamination.The layer of contiguous metal layer also influences metal level adhering to dielectric layer.The effect that the protection metal level is not influenced by the deposition process with rear dielectric layer also can be played in the restraining barrier of metal level top.Therefore, regard top barrier as sacrifice layer usually, changed by subsequently deposition step because it becomes usually.
If do not use suitable basic unit or top layer, the structural intergrity of IMI lamination can suffer damage.If in electrochromic device, the IMI coating is installed between substrate (for example glass) and the epoxy encapsulant (or other encapsulating method) the IMI lamination that then may need to have good structural integrity.Therefore the IMI lamination need have good tack and have good interior tack glass and epoxy resin.If the adhesion failure between any of these zone, this application floating coat can become invalid.The common failure position is normally between the material of metal level and vicinity in the IMI coating.If should not have enough tacks in the zone, then electrochromic device can suffer sudden failure and stop to play a role.The material that well plays a role as promoting to accept the restraining barrier of tack comprises Ru, Ni, NiCr, NiCrO
x, ZnO (or mix ZnO), Cu, Ti, Nb, NbO
x, Ni, Pd and Pt.The thickness that can adjust these layers is to obtain necessary protection and adhesion property.Typically, the metal layer thickness of using with this ability can be to change between greater than 20 dusts or 40 dusts on several dusts and the thick side at thickness on the thin side.Preferably, the thickness of metal barrier is about 1-40 dust, more preferably from about 2-20 dust and 3-10 dust most preferably from about.It is a lot of to have the low comparable corresponding metal bed thickness of oxide, nitride or other material that absorbs, and thickness preferably is less than or equal to about 150 dusts, is more preferably less than or equals about 100 dusts and most preferably is less than or equal to about 50 dusts.
TURP change or " circulation (cycling) " during the layer of next-door neighbour's metal level also can influence the performance of metal level.Metal can decompose (break down) or enter the residing electromotive force of solution is the function of electrochromic cells performance.The material of next-door neighbour IMI lamination metal had the greatest impact before coating is damaged and can obtain electric potential difference.Typically, as the noble metal of adjacent material can help metal for example silver apply to switch under the electromotive force in higher institute and exist, and preferably include Au, Ru, Rh, Pd, Cd, Cu, Ni, Pt and Ir.Electricity cycle period barrier material also can change the generation decomposition or remove plating (de-plate) residing electromotive force.Preferably, adjacent material or electric resistant strata can improve the feasible electromotive force that effectively applies of the other metal of silver or the feasible alternative thing as Ag described herein, improve about 0.05 volt, more preferably it can improve effective electromotive force 0.10 volt even more preferably from about 0.20 volt even most preferably be higher than about 0.30 volt.The suitable selection of adjacent material can improve the feasible electromotive force that is applied to the unit.If use IMI as negative electrode or anode, the required feasible electromotive force of IMI will change.
Can be used for further stablizing the IMI coating and comprise, carry out alloying with itself holding out against the higher metal to metal layer that applies voltage to hold out against the higher another kind of method that applies voltage.For example, available silver is mixed or alloying to gold, holds out against the higher voltage that applies to allow silver.Other spendable material comprises other noble metal, and preferably includes Pd, Si, Ge, Mg, Au, optisils, Ti or Cu.
Except that for higher apply exist under the voltage, the IMI coating also needs to hold out against cut or other damage, and damage is not in time or electric cycle development.This can be achieved by comprise adjuvant in metal, defective that described adjuvant " is cured (heal) ".For example, indium in the silver metal layer or titanium doped causing to crystal boundary or to the migration at the interface of silver layer, thus prevent from that silver is coalescent or become further to be damaged.By silver being mixed, can obtain these healing abilities with the element or the compound of moving to crystal boundary of material naturally or moving to the interface.
IMI lamination, the particularly stability of money base IMI lamination depend on the performance of metal level.Typically, under the environment harsh conditions, (typically be accelerated weathering test), decompose or deterioration in the coating of metal level.Ideally, the IMI lamination can provide the free of pinholes coating, yet may make perfect coating hardly aborning.Consequently, need other method to stablize or protect the IMI coating, thereby these coatings can not decomposed during the expected service life cycle.
The common deterioration mechanism of money base IMI coating is because silver layer is tending towards crystallization again or coalescent and form big low-yield structure.Thermodynamics drives and causes this agglomeration process, and it is because silver layer is tending towards being positioned at low-energy state that described thermodynamics drives.By eliminating the one or more intermediate steps in total deterioration mechanism, make described process interruption and can slow down or stop deterioration mechanism.For example, whether for no matter taking place coalescent or formation speed, the zero energy state of silver layer is a key factor.If silver layer deposits or enter stable thermodynamic state by aftertreatment after deposition, the IMI coating can resist coalescent when being exposed to outside stimulus (stimuli) subsequently, because do not have significant energy drives for silver layer.Can silver be entered than low-energy state by some diverse ways.At first be to be that lamination selects suitable restraining barrier or base material, make that silver is absorbed in its low-energy state naturally during the deposition process.Zinc paste as basic unit is suitable for this task especially well.Other material also has benefit and is preferred, for example Sb.
Next is the use of ion beam assisted depositing, and is to comprise such as plasman, metastable species options such as (metastables) once more.Before the deposition of succeeding layer, but also improved surface and therefore promote the nucleation of improving and/or adhere to of the processing at basic unit and/or metal level top.The silver layer that also can use chemical method allow will to deposit enters than low-energy state or with silver layer and is attached to restraining barrier or basic unit, thus the agglutinating power of restriction silver layer.Preferred metal barrier thing comprises NiCr and other Ni alloy and noble metal.The contiguous material of dielectric layer or metal barrier thing or other with sulfocompound for example disulfide carry out pre-service and can improve the combination of nucleation and silver metal layer fully basic unit.The nucleation of the enhancing that is produced by described processing and the combination of improvement can improve the stability of silver or metal level fully, thereby increase the service life.Can use and introduce a small amount of sulphur in the correct position of other method in the IMI lamination.For example, can in deposition process, add a small amount of sulfurous gas (H for example
2S or SO
2).In addition, can make given target be doped with the sulphur of proper level wittingly.The additional benefits that this method has is the height reactant gas not to be incorporated into deposition chambers, and to make the amount of sulphur be easy to be controlled simultaneously.Available a small amount of sulphur mixes to zinc paste restraining barrier mentioned above, strengthens silver layer adhering to the restraining barrier helping.
Except the useful life of improving parts, these devices help also to comprise that (intra-stack) adheres in the lamination of layer of IMI coating.The improvement of adhering in the lamination allows to use this lamination in more application, and does not need elaborate sheltering to protect this lamination and be not subjected to epoxy encapsulant or other similar stress inducement (stressor) applied force.
Also can be by adding the stability that adulterant strengthens silver or metal level to metal level.For silver, interior fast about 100 times along silver atoms diffusion ratio main body (bulk) metal grain of surperficial crystal boundary.Therefore expection produce coalescent main path be because silver atoms along the surface or the crystal boundary diffusion.When silver brain clip during, can reduce the possibility that whole lip-deep diffusion will occur at interlayer.The suitable material of the adjacent material of contiguous metal layer is selected or chemical treatment is selected further to reduce and surperficial relevant diffusion and coalescent possibility.Crystal boundary then becomes the coalescent main path of silver layer.By silver being mixed with element or compound, can stop diffusion along crystal boundary, described element or compound have limited dissolubility and to crystal boundary migration in silver-colored crystal grain.These adulterants have limited silver atoms and have spread along crystal boundary, and preferably include Pd, Cu, In, Zn or Ti.
Another coalescent factor of influence silver and other metal is adhering to of metal pair adjacent metal.Though preferred metal and material above have been discussed, some application can make these previous acceptable metals become and not be accepted.Some element that runs in the glass substrate for example Na, Mg, Ca or other component can cause attachment issue between silver or other metal level and the adjacent material.Therefore these elements influence adhering to of silver layer, and make and prevent from or stabilize one of coalescent concatenator of silver layer to weaken.These elements are spreading from substrate under high temperature and the high humidity or during the thermal treatment in coated glass usually, and can spread more lentamente from substrate in normal working conditions, thereby cause so-called incipient fault.
The element hydrogen or the proton that can be subjected to exist the coating stack from the amount of the sodium of substrate diffusion influence.Sodium is as positive ion in the glass, and in order to keep neutral charge, counter ion counterionsl gegenions must move in the glass matrix.Proton works with this ability.Therefore, the hydrogen in the coating is minimized.This can by so that in the relevant processing equipment hydrogen or the minimized mode of liquid water content operate deposition process and be achieved.Water is minimized with hydrogen, and this is because in fact water is easy to decompose in plasma, thereby discharges hydrogen.By suitable selection pump in the described method and use hydroextractor for example cold-trap (polycolds) water and hydrogen are minimized.Careful leak detection and elimination also are important.
Make sodium and other glass ingredient comprise the use restraining barrier to the minimized another kind of method of influence of IMI coating damage.Typically, because the tight coupling of refractive index, the restraining barrier mainly is made of silicon dioxide and directly deposits on the glass substrate.Usually in the silicon dioxide restraining barrier, add the transfer that adulterant helps promote to stop element.Also can use phosphorus doped silica and aluminum phosphate.
Importantly, the restraining barrier is being amorphous state character.The crystalline state layer is not too effective in the transfer that stops little element owing to their many crystal boundaries.In addition, the restraining barrier does not need directly to deposit on glass, as function or optical layers and be attached in the IMI lamination and play barrier function simultaneously.Silicon nitride and zinc stannate are effective especially barrier materials.By making silicon nitride be rich in the composition that silicon changes silicon nitride slightly, improve the efficient that silicon nitride stops Elements Diffusion, thereby strengthen the sodium barrier properties of described layer.
In the benefit of using amorphous layer below the metal also applicable to the layer above the metal.Can design top dielectric, make some or all of layers constitute by amorphous layer.Amorphous layer restriction ambient moisture or gas chemistry are diffused in the IMI lamination, therefore prolong its serviceable life.
Stress level in dielectric and/or metal or the silver layer also influences the life-span of IMI lamination, because the stress in the material produces dissimilar power on metal level.For example, if the layer of silver layer top is in the compression stress, then it applies vertical orientated power on metal.This power can promote or strengthen any intrinsic driving force that makes metal coalescent then.From the stress viewpoint, preferred state is metal and dielectric layer when being in suitable stress state, described stress or be tension force or be force of compression.How the driving intensity of force index stress that stress is applied on the metal becomes significant problem to life-span of IMI lamination.The preferred absolute stress level of dielectric (dialetric) layer is lower than 3GPa, more preferably less than 1.5 with most preferably be lower than 0.5.Stress in the material changes with material property usually, but also depends on the technological parameter that is used to deposit each layer.If use the MSVD technology to deposit each layer, then pressure is the significant variable that is used for adjusting the coating stress level.High stress level promotes the tension stress state, and low-pressure promotes compression stress.The atom of sputter also works in the final stress of coating with the ratio of sputter gas atomic mass.The higher quality of sputter gas can promote bigger tension stress, and lower quality can promote bigger compression stress.Also can use adulterant or low-level adjuvant to help suitably adjust stress level in each layer.Advantageously obtain necessary stress level with different sputter gas or the one or more layers of pressure deposition.Can use ion beam assisted depositing or other to the method that system provides energy, help suitably adjust the stress level in the different layers.
IMI coating structure with basic neutral stress distribution has the additional benefits that does not make glass or substrate distortion.Internal stress during the deposition process in the coating intrinsic or that caused by thermal expansion coefficient difference applies power on substrate, thereby causes the warpage and the deflection of substrate.In mirror or window application, when smooth and even unit interval was the key character of product, then substrate can become very big problem by the deflection that the stress in the coating causes.IMI coating with the stress through neutralizing helps to make warpage issues to minimize, thereby produces overall good quality production.For saving in weight during, increase for the deflection of given applied stress level with substrate thinning.Therefore, aggravated described problem under these conditions, and the needs of counter stress neutral products are more important.Stress among the IMI should be controlled, and makes application for the IMI coating, the change of glass radius-of-curvature greater than 3000mm, be preferably greater than 5000mm and most preferably greater than about 10,000mm.
As noted above, the performance of IMI coating can change with hot-working.Typically use epoxy resin with two glass capsulations together, have the electrochromic cells that preferred time and temperature-curable distribute with formation, described time and temperature-curable distribute and bring best epoxy resin to distribute.Some existing family of distributions produces the epoxy resin performance of equivalence.The selection of given distribution is then usually based on other standard for example economy, process velocity or other actual item.Typically, the TCO based transparent electrode will significantly not change performance during hot-working, thereby the given furnace temperature that does not need to select to be used for cured epoxy resin distributes.Yet, can use these heat distributions to make the best performanceization of IMI coating.For example, depend on that time-temperature distributes, sheet resistance can be reduced being up to 2-3 ohm, and transmissivity can be improved 1-3%.By this way, the IMI performance improvement is extremely also nonessential by adjusting the state that deposition properties could obtain.Think that the reason of performance improvement is the raising that belongs to the electron mobility of electronics in the metal.As noted above, when electron mobility was big relatively, metal (silver) had lower refractive index, and lower refractive index helps higher transmittance, and higher electron mobility then also helps lower sheet resistance.
If because the restriction of other component of epoxy resin or electrochromic cells, and can not regulating ring epoxy resins cure profile make the abundant optimization of IMI performance, then can in different stoves or baking oven, carry out pre-service to obtain desired properties to the IMI coated glass.The useful performance that the hot-working of IMI also can have is to have lower stress level, thereby keeps the glass opposed flattened.The best of transmissivity improves and the reduction of sheet resistance changes with ambiance usually.Typically, if do not use preferred gas, time or can be damaged in early days in the lower temperature coating.Preferred gas changes with the dielectric layer that is used for the IMI lamination usually.Some materials are effective especially in the diffusion that stops gas with various.For example silicon nitride (amorphous material) stops the diffusion of oxygen especially effectively during the thermal treatment of IMI lamination.Also work at heat of transformation curing action in basic unit and the restraining barrier that is used for improving environment durability discussed above.
In some cases, can select to change the cure profile behavior the method for heating glass.For example, can use the infrared wavelength that passes glass but effectively combine with the IMI coating.Heating glass is similar to from the bottom glass blocks that upwards heating applies by this way.Typically, in convection oven or in conventional IR bake, the electrochromic cells ecto-entad is heated.The outside surface of top and bottom glass piece is exposed to convection gas and/or infrared radiation.If the residing wavelength of the peak value of infrared radiation is greater than about 5 micron wave lengths, then only glass surface is heated.Come heating glass and epoxy resin by in main body, conducting then from the surface.Coating surface is the decline of heating part.When using hot infrared components to heat described parts, then the main body of infrared radiation is at the wavelength than about 2.5 microns weak points.Because glassy phase is when transparent, so radiation is passed and is not absorbed from glass.Energy combines with the IMI coating because of the unique optical properties of IMI coating, the optical property of described uniqueness causes the coating surface ratio in fact more to heat potentially with faster rate near the outside surface of thermal source, thereby reduce set time, make the body temperature that in this process, can reduce glass.Epoxy resin also will heat quickly, because it directly contacts with epoxy resin.
Can use online applicator for example to rotate applicator or streamline list applicator applies the IMI coating.These applicator types can allow coating stratification (laid up) relatively soon after depositing.In these methods each has the different choice item that is used to shelter.Because coating will not be exposed to the time period of any prolongation under the atmosphere, these methods allow to use greater range of materials.Therefore can protect it is not subjected to many harmful environmental stress inducements in the sealing of IMI lamination in the electric driven color-changing part.In some cases, with regard to one group of given standard that not too produces the suitable environment permanance IMI lamination is carried out optimization.As noted above, a method tackling this situation is to shelter the IMI coating with epoxy resin board.This is the feasible method of this problem of reply.Yet some application may not allow to shelter the IMI coating with epoxy resin board.In this case, use the protectiveness edge and for example apply polymer-coated device etc., described coating can be sealed the IMI coating, therefore prevents to contact with any harmful chemicals in the environment.
In other situation, can be advantageously make IMI lamination and store glass so that on the production line that does not have applicator, use later with the large tracts of land applicator.For such fabrication scheme, above discussed about how the IMI lamination has been designed with the optimized method of this lamination with regard to such manufacturing situation.For example, can apply for example PVA of for example low viscous plastic sheet of temporary protection layer material or chemoproection material.Can be after any machining or before washing these materials of physical removal.For using for example situation of PVA of water-soluble chemical protective seam, can utilize scrubber itself as the equipment of removing stripping lacquer.Can use for example Metal Zn of other stripping lacquer.In this case, in first workshop section of scrubber, may remove described layer by weak acid.Other processing as known in the art also is feasible.
Some galvanochemistry mirrors are used can be by applying the screen body that epoxy sealing spare is introduced in the reflection horizon on the top glass piece.In the U.S. Patent Application Publication No.2004/0032638 that is entitled as ELECTROCHROMIC DEVICES WITH THIN BEZEL-COVERED EDGE that submitted on May 6th, 2003, disclose method and the material that is used for these application, by reference this patent has been merged to herein.The IMI coating has been brought some marked changes as the use of transparency electrode in these devices.For example, in some applications, the deposition of reflective metal level is not to be that cost is effective below transparency electrode.This be because the TCO class for example ITO be used as transparency electrode.These material require temperature high depositions obtain enough electrical properties and optical property.Glass with reflective metal layer heats before the TCO deposition.The existence that centers on this high reflection metal of glass edge changes the thermal behavior that adds of glass substantially, and therefore distortion can be brought in the parts.
If use the IMI lamination as transparency electrode, then avoided this problem.The IMI coating does not need high depositing temperature in deposition process.Can before the IMI coating, apply one or more metal levels then and not have the meeting problem relevant with tco layer.If use rotation applicator or other can allow the applicator of a plurality of masks for deposition, then can be in (or a plurality of) station with a mask at the metal level that applies on glass, available then another mask is applied to IMI on the glass remainder.If necessary, then the available epoxy plate is sheltered metal level, and still keeps simultaneously the excellent electric contact with edge-of-part.
Experiment
The first round experiment showed, that the material that is right after the Ag layer influences the aesthetic of the performance of lamination in the shock-testing (blowtest), steam life-span (steam lifetime) and final parts.The steam life-span is the accelerated test of stability (following be described in further detail) of the combination of metering seal, coating or these materials.These test demonstration, and Al-Doped ZnO with regard to tack (AZO) is best (29psi and do not have the inner perk of coating), and with regard to steam with regard to the life-span indium-zinc oxide (IZO) be the best (35 days).Take turns experiment to second and design building on these results, and obtain the steam life-span and adaptive compromise of relatively poor shock-testing result of the first round (lacking coating inside adheres to).Shock-testing is the assessment coating to the method for the tack of seal, substrate and the inner tack of coating (following be described in further detail).Unfilled EC element has boring and chamber is pressurizeed till destroying in glass.Pressure when writing down destruction together in company with this failure mode.Take turns experiment by second, the reflectivity of mirror element brings up to 79% with the lamination of optimizing.When initially having cut or finger-type line, the circulation of the room temperature of second wheel component electricity has demonstrated potential defective.
It should be noted that for IZO basic unit and AZO top layer, obtained maximum transmission rate and minimum interior resistance; The AZO/Ag/AZO lamination provides the inner tack of maximum coating and has not been ripped in shock-testing; Directly the IZO on the Ag top has poor tack; Have being stacked in the steam test of IZO top layer and have good stable, have poor performance in the steam test and have being stacked in of AZO top layer; And outward appearance (cosmetics) improves with the IZO top layer.
In first round experiment, use silver to be used in combination and prepare 3 layers of IMI lamination that are used to estimate with Al-Doped ZnO (AZO) and indium-zinc oxide (IZO).Employed AZO target is for containing 2 weight %Al
2O
3ZnO.Employed IZO target is the In that contains 15 weight %ZnO
2O
3AZO is and the similar transparent conductive oxide of ITO, but has lower a little conductivity.As ITO, AZO needs very high underlayer temperature between depositional stage, so that crystallinity maximization and the best electrical property of generation.AZO has the lattice performance of the uniqueness of mating with Ag.This causes the IMI lamination to have lower sheet resistance and high transmittance.On the contrary, IZO is amorphous material and can deposits in room temperature and do not have the loss of conductivity.The amorphous state character of IZO gives the additional benefits of its smoothness.IZO forms can be from 100% zinc content almost to 100% indium content almost.Selected a kind of In/Zn that is used for this research to form.AZO is owing to its crystalline state character is tending towards forming more coarse film.Excessive roughness can influence the transmissivity and the conductivity of silver layer in the IMI lamination unfriendly, has therefore eliminated the benefit for the Ag layer that is obtained with proper A ZO performance.
The absolute conductivity of dielectric layer does not influence the performance of lamination significantly in the IMI lamination, crosses thin and does not work as insulator because (functional) conductivity that works is obtained from silver layer and dielectric layer.AZO is extremely cheap, and the additional benefits that has is to have well attached to silver.In addition, silver demonstrates when growing on the AZO top and improves the performance that strengthens, and this is because of excellent lattice matching between the described material.Yet the chemoresistance of AZO is not excellent.The main IZO that is made of indium oxide is expensive; Yet it has better conductivity and chemoresistance than AZO.Use the 15%Zn/85%In target to form in the present embodiment, yet can use other potpourri with more or less indium.In at least one embodiment, IZO can be preferably amorphous.
For the sake of simplicity, machinery and chemical durability rather than color or transmissivity are the main concern items of this serial experiment, and dielectric layer thickness is fixed on 350
For these initial experiment, only deposit AZO with argon gas.Do not add oxygen.Use 4%O
2(in argon gas) deposits the IZO layer.
Coatings prepared lamination and their performance in table 7, have been provided.In each lamination, the nominal dielectric layer thickness is 350
And nominal silver thickness is 110
Use these laminations to prepare EC mirror.Be displayed in Table 6 modelling effect with the coating that is right after air and electrochromism fluid.Use has the automotive interior mirror form of high reflection the 3rd surface coating.The IMI coated glass forms transparent roof panels.In table 7, listed the optical property of mirror assembly.Parts " 1173IEC " are meant the reference cell of making as transparency electrode with 1/2 wavelength ITO.Mirror assembly is carried out shock-testing estimate IMI coating tack.With regard to permanance the mirror of filling is carried out the steam test.
Table 7
The transmisivity data that provides in the table 7 is corresponding to the monolithic glass that (does not contrast the EC fluid) measure in air.Sheet resistance in 6-7 ohm scope is equivalent to the long ITO of all-wave roughly.As shown, the transmissivity of the long ITO of 1.6mm all-wave on glass is about 85%.For the element that its epoxy resin makes and solidifies according to the general principle of explaining among US6/95193B1 and the US6963439B2, the IMI lamination demonstrates the raising by the transmissivity due to the hot-working in the epoxy resin cure baking oven.When two coatings all contact with the EC fluid, can only between two transparency electrodes, carry out the direct contrast of transmissivity.This requirement or use thin-skin model calculate, and perhaps use two kinds of Materials Measurement EC unit.Be displayed in Table 8 modelling transmittance values for these options.
Table 8: transmissivity is with the variation (sample lamination model) of adjacent media.
The reflectivity of the unit with IMI top board that makes is markedly inferior to the mirror with 1/2 wavelength ITO top board.In addition, the sheet resistance of IMI top board is half of 1/2 wavelength ITO product that is used for standardized component.Yet, as mentioned above, the IMI lamination from the first round is not carried out optimization with regard to color or transmissivity.The relative reflectance of the unit of listing in the table 9 and single-piece (singles) transmittance values is inconsistent.Unclear why like this.Sample is consistent with heat treated variation with transmissivity between the sample in this group.Yet this variation and attachment level and material optical constant in a way will change with coating parameter and condition on certain level.By the blank cell (element cell) of choosing the curing of carrying out epoxy resin, and with the filler opening jam-pack, about 1/2 inch hole that drills through diameter for about 1.5mm, the edge of the described unit of distance obtains the shock-testing value.With 0.5 or the speed of the 1psi/ second pressure when parts pressurization and record are destroyed.Also write down destructive process (mechanism) for example coating and separating of glass or separating or inner the separating of epoxy resin own of coating stack inside.By the U.S. Patent No. 6,195 that is entitled as SEAL FOR ELECTROCHROMIC DEVICES of authorizing February 27 calendar year 2001, the test procedure described in 193 obtains the steam test value, by reference this patent is merged to herein.
Table 9: mirror element optical property (GMR4 backboard, light state, average data)
| Lamination | ％R | L * | a * | b * |
| Glass | AZO|Ag|AZO | 70.8 | 87.4 | -3.5 | 7.0 |
| Glass | AZO|Ag|IZO | 69.5 | 86.8 | -3.3 | 6.1 |
| Glass | IZO|Ag|AZO | 74.8 | 89.3 | -3.8 | 4.0 |
| Glass | IZO|Ag|IZO | 74.0 | 88.9 | -3.8 | 3.4 |
| The 1173IEC parts | 86.8 | 94.7 | -3.7 | 6.0 |
Usually, for the variation of compensation sealing part width, before carrying out further statistical study, be valuable with data " normalization ".A kind of method of doing like this is that test value be multiply by the nominal seal width, and with its actual seal width divided by each separate part.
The average impact value of AZO|Ag|AZO lamination with equate substantially as the parts of transparency electrode with ITO.For all laminations of being estimated, find that glass/AZO/Ag/AZO equates with ITO, other lamination owing to some lamination interior layers from then numerically hanging down about 20%.On each side of silver, have the AZO layer the strongest attachment level can be provided.For the AZO|Ag|AZO sample, totally there is not perk to increase the HI high impact value in the IMI layer.The number percent of IMI coating perk obviously with silver-colored top on layer interrelated; AZO provides result preferably once more.The strongest trend is in the steam data, has the performance as the enhancing of the lamination of the IZO of top layer.
The steam life test that the lamination of same train is carried out is by average demonstration, and IZO|Ag|IZO is stacked in and shows the most by force in the steam test, and the AZO|Ag|IZO lamination does not far lag behind.Regrettably, being stacked in of showing the most by force in this shock-testing shows the most poorly in the steam test.These strong points of stack-design may command and weakness by innovation.
With variable color equably with the influence of many factors that brighten the element aesthetic feeling relevant and can be subjected to, described factor comprises the selection of material in the selection of material in cure profile, the coating stack and the encapsulant.
At present preferably use as US.6 the material of those described in 195,193 and curing in a large number.Epoxy radicals organic resin sealing system is preferred, this be because they to glass good adhere to, low oxygen permeability and good solvent resistance.These epoxy sealing bodies can be that ultra-violet curing (for example is entitled as LIQUIDCRYSTAL DISPLAY ANDPHOTOPOLYMEZIRABLE SEALANT THEREFOR U.S. Patent No. 4,297, described in 401) or Thermocurable, the potpourri of liquid epoxies and liquid polyamide or dicyandiamide for example, perhaps they can be equal polymerizations.Organic sealing resin can contain and reduces the filler or the thickening agent that flow and shrink, for example aerosil, silicon dioxide, mica, clay, lime carbonate, aluminium oxide etc., and/or contain the pigment that adds color.It is preferred carrying out pretreated filler with hydrophobic or silane surface treatment.Can be by using the potpourri of simple function, difunctionality and polyfunctional epoxy resin and hardening agent, control cured resin cross-linking density.Can use adjuvant to improve the hydrolytic stability of seal, and can use such as the spacer of beaded glass or rod and control final seal thickness and substrate spacing such as silane or metatitanic acid fat (titanate).The suitable epoxy sealing resin that is used for peripheral seal element 116 includes but not limited to: " EPON RESIN " 813,825,826,828,830,834,862,1001F, 1002F, 2012, DPS-155,164,1031,1074,58005,58006,58034,58901,871,872, and DPL-862, can be from ShellChemical Co., Houston, Tex obtains; " ARALITE " GY6010, GY6020, CY9579, GT7071, XU248, EPN1139, EPN1138, PY307, ECN1235, ECN1273, ECN1280, MT0163, MY720, MY0500, MY0510 and PT810 can be from Ciba Geigy, Hawthome, N.Y. obtains; " D.E.R. " 331,317,361,383,661,662,667,732,736, " D.E.N. " 431,438,439 and 444, can be from Dow ChemicalCo., Midland, Mich. obtains, m-xylene diamine, 1,8-diamido-right-methane, isophorone (isophrone) diamines, 1, the two amino methyl cyclohexanes of 3-, 1, the 6-hexane diamine, diethylene triamine, 1,4 diamino-cyclohexane, 1,3 diamino-cyclohexane, 1,2 diamino-cyclohexane, 1,3 pentanediamines and 2-methyl isophthalic acid, 5-pentanediamine (2-methyl pentamethylenediamine).
Suitable epoxy curing agent comprises from the V-15 of Shell Chemical Co., V-25 and V-40 polyamide; From Ajinomoto Co., Tokyo, " AJICURE " PN-23, PN-34 and VDH that Japan obtains; From Shikoku Fine Chemicals, Tokyo, " CUREZOL " AMZ, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 2IZ and 2P4MZ that Japan obtains; From CVC Specialty Chemicals, Maple Shade, " ERISYS " DDA that N.J. obtains or the DDA that quickens with U-405,24EMI, U-410 and U-415; From Air Products, Allentown, " AMICURE " PACM, 2049,352, CG, CG-325 and CG-1200 that Pa obtains.
Optional filler comprises aerosil, for example from CabotCorporation, and Tuscola, " CAB-O-SIL " L-90, LM-130, LM-5, PTG, M-5, MS-7, MS-55, TS-720, HS-5, EH-5 that I11 obtains; From Degussa, Akron, " AEROSIL " R972, R974, R805, R812, R812S, R202, US204 and US206 that Ohio obtains.Suitable clay filler comprises the Corporation from Engelhard, Edison, BUCA, CATALPO, ASP NC, SATINTONE5, SATINTONFSP-33, TRANSLINK37, TRANSLINK77, TRANSLINK445, TRANSLINK555 that N.J. obtains.Suitable silica filler is from SCM Chemicals, Baltimore, SILCRONG-130, G-300, G-100-T and G-100 that Md obtains.Suitable precision glass microballon spacer optional with various sizes from Duke Scientific, Palo Alto, Calif obtains.
Randomly, can introduce the hydrolytic stability that silane coupling agent improves seal, described silane coupling agent comprises the Corporation from Dow Corning, the Z-6020 that Midland, Mich obtain (it is identical or similar with A-1120 from Union Carbide), Z-6030, Z-6032, Z-6040, Z-6075 and Z-6076.
Whether the selection of cross-linked polymer or thickening agent in addition,, in-situ cross-linked method, the selection of plug material and the particular combinations that employed electrochromism kind can influence material produce acceptable appearance results.Yet the trend that exists for the TCO material with better volume conductance is, and is when contiguous electrochromic media is placed, a little not too responsive to various problem of appearance.
The AZO oxidation level has shown the O that adds in optimized experiment therein
2To the glass/conductivity of AZO/Ag lamination and the influence of transmissivity.This forms and will change for different equipment and target, but trend has been indicated the more necessary steps of the such lamination of optimization.The sheet resistance and the transmissivity of glass/AZO/Ag lamination have been optimized by this way.In Fig. 9, shown the O that adds
2Influence to the conductivity and the transmissivity of this lamination.The absolute conductivity of AZO layer itself is unessential, and only it is important to the silver layer Effect on Performance.This is the ultimate principle for the optimization approach of being taked.In the argon gas charging, add 4% O
2Best conductivity and transmissivity have been provided.Figure 10 has shown that the extinction coefficient (absorbability) of AZO and roughness are with the O that adds
2 Variation.Add 6% O
2Than the O that adds 4%
2In time, produces and to have the more AZO of low absorptivity, yet roughness also increases.The roughness that increases is at 6% O among Fig. 9
2The possible cause that the sheet resistance that observes increases.This hint really by sacrifice some conductivity increase slightly lamination transmissivity potential may.
For the AZO sputter that all laminations deposited for preparing in this serial experiment has 4% O
2, IZO also is like this.Table 10 has been listed the lamination that is used to estimate that deposits with DOE-2.In order to contrast, also comprise the transmissivity and the sheet resistance of all-wave length and half-wavelength ITO top board.The ultimate principle that is used for these stack-design is to solve tack and steam life-span.As measured by shock-testing, AZO places on the one or both sides of Ag layer and improves tack.IZO placed helping as top layer solve the steam life-span.Layer thickness is adjusted, transmissivity maximization is regulated and made to lamination with regard to light blue in the deepening state.
The transmissivity of stack-design is 84.5-87.3%.Sheet resistance is 5.0-9.0Ohm/sq.For given Ag thickness, when bottom is made of glass/IZO/AZO/Ag, maximum transmission rate and minimum sheet resistance appear.IZO makes layer keep level and smooth, and AZO improves the microstructure of Ag owing to the lattice matched between AZO and the Ag.This produces conductivity and the tack of improved Ag.Because the AZO layer is a crystalline state, surfaceness increases with layer thickness.Therefore, double-deck IZO/AZO provides required optical thickness, and has suitable contact bed simultaneously so that Ag produces seed crystal.The remarkable higher resistance of sample #11 may be to be caused by the relevant roughness of blocked up AZO basic unit below silver.This also is tangible in sample 7 and 8.The sheet resistance that the roughness relevant with thick AZO basic unit causes observing in the sample 7 is than the sample 8 high 1 Ω/ with level and smooth relatively IZO basic unit.When the attenuation of Ag layer, roughness will have bigger influence to electrical property.
In table 11, provided the optical characteristics data of prepared EC-element.Use has the automotive interior mirror form of high reflection the 3rd surface reflection body electrode, and wherein reflectivity is substantially all from the 7%Au93%Ag alloy.
Table 10: second takes turns stack-design and performance.
The average optical performance of table 11:EC element
| Lamination | ％R | L * | a * | b * |
| 7.G-AZO-Ag-AZO-IZO | 75.8 | 89.8 | -3.5 | 7.4 |
| 8.G-IZO-Ag-AZO-IZO | 77.7 | 90.7 | -4.1 | 4.0 |
| 13.G-IZO-AZO-Ag-AZO-IZO | 79.4 | 91.4 | -3.9 | 4.0 |
| ITO IEC parts | 86.8 | 94.7 | -3.7 | 6.0 |
In second group of experiment, by placing the experiment of IZO layer as top layer in the above, the steam result of AZO/Ag/AZO lamination improves about 50% than previous.On the contrary, along with placing additional thin AZO layer between Ag in the IZO/Ag/IZO lamination and the IZO layer, the steam life-span reduces about 1/3rd.
The reflectivity of IMI base unit is 76-79%, and contrast is that 1173IEC is about 87% and is 69-75% for first round experiment therewith.The reflection colour of IMI base unit is suitable with the reflection colour of product component, and #8 and #13 are slightly shallow yellow than average product component.The #7 lamination produces and reasonably impacts numerical value, but demonstrates high destructive rate in the IMI lamination.Lamination 8 and 13 lost efficacy under low surge pressure and provided very high adhesion failure rate in the IMI lamination.Steam test result quite general (flat) and common.Though the best and the poorest lamination of the first round continues 30 to 15 days respectively, second takes turns sample average lost efficacy at 20 days.Have some differences (except that stack-design changes) between taking turns in the first round and second, these differences may influence impact and steam performance.Second problem of taking turns in the performance of EC-element is their storage.The IMI coated glass was placed (sit) some days and was demonstrated and handles sign before storage.Also change the sequencing in applicator middle level.In the first round, in applicator preparation not only forwards to but also the layer of passing through in backward directions.In second takes turns, the preparation all along forwards to pass through layer.In second takes turns, also make in the AZO layer to have oxygen, and in the first round, do not have oxygen.
Match with identical fluid and good appearance that epoxy resin obtains in the outward appearance of second wheel component and the first round.Carry out the room temperature circulation time under 1.2 volts, parts produce potential defective when having finger-type line, scratch or other defective.
The performance of check (run) sample #13 is used for the deepening that compares with standardized product and the performance that brightens with generation on the final test device.Table 12 has shown some performance statisticses.IMI lamination #13 is than the faster deepening 20% of standardized product.As expected, lower sheet resistance causes higher current sinking.Figure 13 explanation and table 10 have been listed the reflection colour in DOE2 sample No.7,8 and 13 the bright and dark state.
Table 12: the EC performance of handoffs of lamination #13
| Sample | MRH | MRL | Electric current | Peak point current | The 70-15 time | The 10-60 time |
| IMI#13 | 82.3 | 8.13 | 142 | 475.7 | 2.56 | 5.12 |
| ITO | 86.5 | 7.3 | 123 | 300.9 | 3.2 | 4.7 |
The color that reflects in table 13:DOE2 sample No.7,8 and 13 the bright and dark state
| Sample | CapY is bright | a *Bright | b *Bright | Cap Y dark | a *Dark | b *Dark |
| 7 | 76.9 | -3.5 | 8.5 | 8.8 | -1.4 | -3.8 |
| 8 | 79.7 | -4.2 | 4.8 | 9.6 | 1 | -3.6 |
| 13 | 81.7 | -4.1 | 4.8 | 8.2 | -2.9 | -10.4 |
The color of IMI lamination is with suitable as the standardized product of transparency electrode with ITO in the dark state.The dark state reflectivity is in the design object of level crossing.
Be from experimental result and the term of several groups of loose lumps below in the experiment of IMI DOE-3.With two kinds of processing pressure to Al-Doped ZnO (AZO), mix zinc indium oxide (IZO) and argent (Ag) carries out the ply stress analysis.The result represents that AZO has the highest compression stress, can reduce described stress slightly by handling under higher chamber pressure.Based on the minor alteration of stress, determine almost can not obtain to reduce under elevated pressures, handling.According to the result who demonstrates potential correlativity between chamber pressure and the coating perk for certain layer design, this conclusion has problems.
Sedimentary sequence is studied, to determine the susceptibility of IMI lamination the procedure of processing in the applicator.The purpose of these experiments is to determine to realize with the rotation applicator whether the IMI coating exists remarkable risk, and described applicator utilizes stationary substrate to deposit.For different job operations, do not observe the remarkable change of coating performance.
Because the susceptibility of thick AZO layer in steam autoclave exposes, carry out serial experiment bottom determining and the optimum thickness of top AZO cushion with regard to maximized tack and steam stable to destroying.For the top cushion, definite is, with little to 50
AZO obtain to adhere to, and do not obtain to increase by the AZO layer being thickened above this level.For bottom AZO cushion, the result is uncertain.As mentioned above, the stress among the thick AZO is big must to be enough to influence and to adhere to, and may cover any performance change that change caused of bottom buffering thickness fully.
Carry out two groups of thermal treatment tests.First group of demonstration continues down until the thermal treatment of 30 minutes prolongation period does not damage the IMI coating and in fact improved its performance at 300 ℃.Second group of experiment shows, forms for the IZO that is rich in zinc paste, shows better after IZO base IMI is stacked in thermal treatment.
Carry out the optical modelization of IMI lamination.This modelling research dielectric refractive index to the influence of the transmissivity of IMI coating and finally its to the Effect on Performance of EC element.The result shows that high index of refraction (index) layer is as TiO
2Use help to provide the 1/2 wavelength ITO coating institute that is in close proximity to using at present can obtainable performance and color.
Ply stress in the laminated coating lamination can influence adhering to of coating unfriendly.Owing to this reason, importantly examining the dielectric layer that uses in the IMI lamination of being studied is to deposit with reasonable low stress.For each material, move high and the used argon pressure of low deposition, to determine the corresponding slope of each material.The result is displayed in Table 14.The stress that all coatings record is reasonably low, less than 1 gpa (Giga-Pascal).Stress ratio IZO floor height in the AZO layer, however the minor alteration that pressure caused that improves is represented pressure and is regulated and possess limited benefit.Based on deriving from these result of experiment, under 3.0 millitorrs, deposit for remaining DOE.
Table 14. deposition pressure is to the influence of ply stress:
AZO is the very good material that is used for contacting with silver layer, because it provides best tack and thermal stability.Regrettably, AZO is not extremely stable to chemical erosion.Owing to this reason, multilevel method is preferred, and the AZO that this method is used minimum thickness is as against the cushion of silver layer and remaining coating thickness is made of IZO, ITO or other dielectric with enough steam stables.It is two parts that part 3 is broken, respectively research bottom and top AZO cushion.Table 15 has shown employed stack-design of this evaluation and layer thickness.The first half experiment (13-17) research changes the influence of top AZO buffer layer thickness to tack and steam stable.Half experiment of back (18-22) research changes the influence of bottom AZO buffer layer thickness to tack.Use thick AZO top layer because test 18 to 22, with regard to steam stable it is tested, this is owing to the known vulnerability for this test monolithic AZO top layer.Be displayed in Table 16 the test average result.The thick AZO basic unit that uses in the experiment 13 to 17 all provides very good result respectively in shock-testing and steam test, average out to 26psi and 34 days.Exposure has sufficient protection to steam autoclave below silver layer.Experiment 18 to 22 average out to 21.5psi in shock-testing of research AZO underlayer thickness.Thickness for AZO layer above or below the silver layer does not manifest clear and definite trend.Significantly, 50
The AZO cushion is enough to provide good adhering to.Clear and definite trend from this series is, for having 450
The sample of AZO bottom (experiment 13-17) is not observed the coating perk.Experiment 18 to 22 has average 65% coating perk in shock-testing.In addition, glass breakage mainly takes place in the shock-testing from experiment 13 to 17 sample.For the sample from experiment 18 to 22, the mark that destroys because of glass breakage is lower.On the contrary, destroying mainly is the coating perk.Regrettably, because use the such fact of thick AZO top layer, experiment 18-22 may be invalid.Significantly, the strain in these thick-layers is enough high, thereby arranges adhering to of IMI coating.Any interference that change caused of bottom AZO buffer layer thickness may be subjected to cover (swamp) of top layer stress.
Table 15: cushion is studied employed AZO/IZO layer thickness:
Table 16: from the average test result of the sample of part 3:
Use the service condition of experiment 10 to prepare some 11.8 " * 16 " the be of five storeys piece of IMI lamination of coating, described IMI lamination comprises the IZO of 440 dusts, the AZO of 50 dusts, the silver of 80 dusts, the AZO of 50 dusts, the IZO and the glass of 449 dusts.Being cut into measurement size by these pieces is 4 " * 4 " sample.Measure optical transmittance, mist degree and the sheet resistance of each sample then, as baseline.Under the temperature in three following temperature are 200 ℃, 300 ℃ and 400 ℃, each two ground of sample are carried out soaking (soak), continue one of promptly 5 minutes, 10 minutes, 15 minutes four times and 20 minutes.Remeasure then each sample transmissivity, mist degree and sheet resistance and with the contrast of its baseline value.In table 7, provided average data.
For all thermal treatment, the transmissivity of IMI lamination increases, yet for 300 ℃ of samples, observes maximum the variation.400 ℃ of samples demonstrate the transmissivity that reduces with respect to 300 ℃ of samples to be increased.This is changed by significant optical property and causes, described optical property change also causes b
*Displacement.The possible explanation that the uv absorption border that is observed is shifted in visible light is the change that IZO is subjected to high temperature.Second kind of possible explanation is that Ag surface plasmon band is at high temperature owing to being shifted in AZO/Ag chemistry or structural change at the interface.This unlikely is based on the high-temperature response of viewed existing Ag/AZO base low emissivity coatings.
The average IMI performance of table 17. is with heat treated variation
For the purpose of these experiments, mist degree is defined as surface reflectivity (Y
R) the non-specular surface component.At 200 ℃ and 300 ℃, mist degree does not exist can survey variation.For the shortest equal thermal endurance (5 minutes) under 400 ℃ also is like this.Long equal thermal endurance under 400 ℃ produces the mist degree that can survey to be increased; Yet total mist degree still is minimum.
For transmissivity also is like this, and all thermal treatments have reduced sheet resistance.300 ℃ of thermal treatments cause bigger improvement than 200 ℃ of experiments.400 ℃ of experiments provided good result at 5 minutes, this result is suitable with 300 ℃ of results.When surpassing 5 minutes for 400 ℃, the improvement of sheet resistance is lost gradually, makes 20 minutes samples almost be equivalent to conductivity before their heating.If all IMI are stacked in 300 ℃ of heat treated 10-15 minutes, then obtain optkmal characteristics.
These results represent that any thermal treatment or the epoxy resin cure method that may use aborning can be improved the IMI performance, rather than make its deterioration.It can be best for the performance of optimizing the IMI coating that the epoxy resin temperature of oven is increased to 300 ℃, yet it may not be favourable to the epoxy resin performance.
Relate to three layers of IMI laminate samples that are used to estimate below.At National Renewable Energy Laboratory (NREL), these laminations have benefited from making up the sputter ability, and this is because the dielectric layer of each sample forms the component gradient that passes through on the whole sample, thereby allows to estimate simultaneously a plurality of compositions of IZO.IZO is indium oxide (In
2O
3) and the nonspecific combination of zinc paste (ZnO).Usually, for best electrical conductivity, use～20%Zn, however can tend to preferentially make physics and the chemical property optimization of IZO, thus the stability and the tack of IMI lamination improved.The absolute conductivity of dielectric layer is not very important for the performance of IMI lamination.Four groups of (library) indium Zn compositions are applied to 2 " * 2 " glass substrate (1.1mm) goes up as three layers of IMI lamination: matrix dielectric (400
), silver (100
), top dielectric (400
).In various situations, deposition is as far as possible near uniform dielectric and silver-colored thickness.Because the NREL system uses little by 2 " annular magnetic keyholed back plate and stationary substrate, homogeneity more is not best.Owing to this reason and some other reasons, have 3 " set up combined system in the Temescal applicator of annular magnetic keyholed back plate and linear movement, this system can provide better homogeneity and repeatability than the system of NREL.In table 18, listed the compositing range of four groups.
The composition of four groups of table 18.
| Group | Indium mark (atom %) |
| L1 | 4-15％ |
| L2 | 15-50％ |
| L3 | 35-70％ |
| L4 | 70-95％ |
Before thermal treatment, 5 positions on each sample have recorded the baseline value of transmissivity, sheet resistance and mist degree.The epoxy resin cure baking oven (502 line) that sample is passed set up for standard production (200 ℃).Remeasure transmissivity, sheet resistance and mist degree then.The result provides in table 19.Available In/Zn comparison data are classified.The dielectric of low In, high Zn content produces the IMI lamination with high transmittance and low sheet resistance.Mist degree is comparable before the thermal treatment.After thermal treatment, under very high Zn content, exist mist degree to increase, but, have much bigger increase for rich In sample.Big mist degree increase is may the indicating of IZO crystallization during the thermal treatment.Put down in writing this behavior with regard to the composition ultimate value of IZO in the literature.
IMI performance before and after table 19. thermal treatment:
Described experimental result attracts people's attention very much.Usually, deposit IZO with about 20%ZnO content so that the conductivity maximization.The conductivity of IMI lamination is very inresponsive to the absolute conductivity of employed dielectric layer on the either side of silver.The high ZnO content scope (～70%) of combined sample demonstrates best performance in thermal treatment.Even the conductivity of IZO is poor under high zinc content, but the total conductivity of IMI lamination is the highest in this scope.Under high ZnO content, mist degree after the thermal treatment and transmissivity also are best.If～30%In
2O
3Content is sufficiently high for enough steam performances being provided and keeping enough adhering to simultaneously, and then for the IMI stack-design, 3 layers of design may be feasible.
Carry out optical modelization, as the part of the benefit evaluation of optional dielectric layer and so that some patent documentations are proved.Modeled purpose is to quantize the color of IMI lamination and may improving of transmissivity by material substitution.As described in the 2nd IMIDOE report, depend on that the outlet medium is air or carbonic allyl ester (PC) solution, the transmissivity of coated glass can change considerably.On glass be in the situation of 1/2 wavelength ITO, the modelling transmissivity is that 88.0% to bring up to the contrast carbonic allyl ester be 92.4% from the contrast air.In order to simplify, in model, use 3 layer laminate, (table 20).Above or below the Ag layer, add 50
The AZO cushion has minimum influence to the optical property of lamination.
Table 20. is used for the stack-design of part 5
Therefrom to arrive high a series of refractive indexes in order estimating to contain, to select four kinds of dielectric substances.These materials are TiSi
2O
6(1.7), IZO (2.0), cold TiO
2(2.4) and hot TiO
2(2.8).In original research, all lamination is carried out optimization with regard to air and carbonic allyl ester outlet medium.Data given here are fully based on the optimization of being carried out with regard to the carbonic allyl ester situation.For various dielectric substances, estimated several A g thickness.Data provide in table 21.In each embodiment, dielectric substance and silver-colored thickness are selected.Then, use TFCalc, become thickness to revise to provide optimum transmission rate to dielectric.In order to contrast, in various situations, also provide transmissivity with regard to the air out medium.For two low-refractions (index) situation, for thin Ag situation, airborne transmissivity is higher.For contrasting the thicker Ag situation that carbonic allyl ester has high transmittance, described relation is inverted.Two kinds of TiO
2Situation has provided the high transmittance of contrast carbonic allyl ester without exception.For being higher than approximately
Silver-colored thickness, by using high index of refraction (index) dielectric layer such as TiO
2Obtained optimum transmission rate.For obtaining 6 Ω/ IMI, it is about 100 that coating needs thickness
Silver layer.For having 100 of Cr/Ru backreflection body
Ag layer situation calculated color.These data provide in table 22.In order to contrast, use identical OEC element (1/2 wavelength ITO) as calculated.TiSi
2O
6The highlighted attitudinal reflexes rate of situation is misleading.As by shown in the very high dark state reflectivity, the remarkable mark of reflectivity comes from second surface.Reflection colour is green slightly in bright state and is strong bronze colour in dark state.For the IZO situation, the bright state reflectivity is lower and be green slightly.IZO unit dark state reflectivity is only a little more than reference OEC unit, and is very neutral.TiO
2The bright state reflectivity of unit is only low by 1% than reference, and tone is identical with the IZO unit, for green slightly.Dark state has low-down reflectivity and basic neutral color.Hot TiO
2The unit provides higher reflectivity than reference unit and is very neutral color.Dark state has low reflectivity and the tone of purple slightly.
Table 21. from the modeled optical data of IMI lamination (thickness with
Meter):
| TiSI 2 O 6 | Ag | TiSi 2 O 6 | ％T | The %T-air | IZO | Ag | IZO | ％T | The %T-air | |
| 557 | 25 | 504 | 94 | 91.7 | 514 | 25 | 493 | 90.6 | 85.3 | |
| 479 | 50 | 472 | 91 | 92.7 | 429 | 50 | 418 | 91 | 87.5 | |
| 491 | 75 | 488 | 85 | 90.5 | 384 | 75 | 388 | 89.4 | 89.2 | |
| 506 | 100 | 504 | 77 | 85.4 | 397 | 100 | 401 | 85.2 | 88.4 | |
| 519 | 125 | 517 | 68 | 78.1 | 407 | 125 | 410 | 79 | 85 | |
| 530 | 150 | 529 | 58 .9 | 69.7 | 415 | 150 | 418 | 71.6 | 79.6 | |
| TiO 2 | Ag | TiO 2 | ％T | The %T-air | TiO 2 (heat) | Ag | TiO 2 (heat) | ％T | The %T-air | |
| 484 | 50 | 440 | 92.9 | 89.1 | 451 | 50 | 409 | 92 | 87.7 | |
| 434 | 75 | 410 | 92.86 | 89.3 | 410 | 75 | 386 | 92.2 | 88.1 | |
| 383 | 100 | 371 | 92.6 | 89.7 | 371 | 100 | 356 | 92.3 | 88.6 | |
| 340 | 125 | 336 | 91.6 | 90.5 | 330 | 125 | 323 | 92.1 | 89.3 | |
| 326 | 150 | 324 | 88.8 | 90.64 | 302 | 150 | 298 | 90.8 | 90.2 | |
| 323 | 175 | 322 | 84.2 | 88.8 | 292 | 175 | 290 | 87.8 | 89.9 | |
| 323 | 200 | 322 | 78 | 85 | 288 | 200 | 288 | 82.9 | 87.7 |
Table 22. transmissivity is through the element color (100 of optimized lamination
Situation)
*All the unit has 1/2 wavelength ITO top board and same backboard and fluid.
For the Ru of OEC type base mirror, will be confined to about 52.8% reflectivity based on three layers of IMI lamination (100A Ag) of certain combination of AZO, IZO, ITO or these materials.The 1/2 wavelength ITO base unit of close copyization can have about 60.1% reflectivity.For the transmissivity of IMI base unit is brought up to the level that is obtained for 1/2 wavelength ITO at present, need include the TiO that uses in for example described model of high index of refraction (index) layer in
2Five layers of IMI lamination are with TiO
2Including in may be near 59.2% reflectivity.More the material of high index of refraction (index) can allow the unit reflectivity near 60.3%, and this reflectivity is in fact a little more than standard block.Below the IMI lamination, deposit to single TiO on glass
2Layer can provide about 57.8% reflectivity.If the transmissivity of IMI lamination must be high to 1/2 wavelength ITO, then high index of refraction (index) layer will be necessary for the part of lamination.
Electric driven color-changing part of the present invention comprises transparency electrode, and the parts of this transparency electrode reduce the total cost of electric driven color-changing part and do not sacrifice optics or physical characteristics for example reflectivity, color, TURP change stability and environment durability etc.In addition, electric driven color-changing part of the present invention is easy to make relatively, help the manufacture method that provides sane, in the selection that makes up insulator/parts that the metal/insulator lamination is utilized, provide multi-functional, and allow its custom build to obtain specific optics and physical property.
Preferred embodiment is only thought in above-mentioned explanation.But those skilled in the art and the modification of using people of the present invention to invent.Therefore should understand, show in the accompanying drawing and above-described embodiment only for purpose of explanation and be intended within the scope of the present invention, but be not intended to limit scope of the present invention, scope of the present invention is limited by following claims of being understood according to Patent Law principle (comprising doctrine of equivalents).
Claims (44)
1. electric driven color-changing part, it comprises:
First substrate, this first substrate have first surface and with this first surface opposing second surface;
Second substrate, this second substrate and described first substrate be the space separate relation and have towards the 3rd surface of described second surface and with the 4th relative surface of the 3rd surface;
Electrochromic media, this electrochromic media are between described first and second substrates, and wherein this electrochromic media has transformable transmittance when it applies electric field; With
Transparent electrode layer, this transparent electrode layer covers at least one at least a portion that is selected from second surface and the 3rd surface, wherein this transparent electrode layer comprises first insulator layer, at least one metal level and second insulator layer that is right after electrochromic media, wherein electric driven color-changing part demonstrates the colour rendering index more than or equal to 80, and wherein in first insulator layer and second insulator layer at least one side comprise be selected from following at least a: indium-zinc oxide, aluminium zinc oxide, titanium dioxide, conduction TiO
2, CeO
x, tin ash, tin oxide, silicon nitride, silicon dioxide, ZnS, chromium oxide, niobium oxide, ZrO
x, WO
3, nickel oxide, IrO
2And combination.
2. the electric driven color-changing part of claim 1, wherein one of selected insulator layer is between the selected surface that at least one metal level and transparent electrode layer cover.
3. the electric driven color-changing part of claim 1, first insulator layer that wherein contacts with electrochromic media has the resistance of 10MOhm.
4. electric driven color-changing part, it comprises:
First substrate, this first substrate have first surface and with this first surface opposing second surface;
Second substrate, this second substrate and described first substrate be the space separate relation and have towards the 3rd surface of described second surface and with the 4th relative surface of the 3rd surface;
Electrochromic media, this electrochromic media are between described first and second substrates, and wherein this electrochromic media has transformable transmittance when it applies electric field; With
Transparent electrode layer, this transparent electrode layer covers at least one at least a portion that is selected from second surface and the 3rd surface, wherein this transparent electrode layer comprises first insulator layer, at least one metal level and second insulator layer that is right after electrochromic media, wherein electric driven color-changing part demonstrates the colour rendering index more than or equal to 80, and wherein first insulator layer comprises indium tin oxide, and wherein the transmissivity of this transparency electrode more than or equal to 75%.
5. the electric driven color-changing part of claim 4, wherein first insulation course has the resistance of 10MOhm.
6. electric driven color-changing part, it comprises:
First substrate, this first substrate have first surface and with this first surface opposing second surface;
Second substrate, this second substrate and described first substrate be the space separate relation and have towards the 3rd surface of described second surface and with the 4th relative surface of the 3rd surface;
Electrochromic media, this electrochromic media are between described first and second substrates, and wherein this electrochromic media has transformable transmittance when it applies electric field; With
Transparent electrode layer, this transparent electrode layer covers at least one at least a portion that is selected from second surface and the 3rd surface, wherein this transparent electrode layer comprises first insulator layer, metal level and second insulator layer and the electric resistant strata between metal level and arbitrary insulator layer that is right after electrochromic media, wherein electric resistant strata comprise be selected from following at least a: gold, ruthenium, rhodium, palladium, cadmium, copper, nickel, platinum, iridium and combination thereof, wherein electric driven color-changing part demonstrates the colour rendering index more than or equal to 80.
7. the electric driven color-changing part of claim 6, wherein said metal level comprises silver.
8. the electric driven color-changing part of claim 6, wherein electric resistant strata can improve about 0.05 volt with the feasible electromotive force that applies of metal level.
9. the electric driven color-changing part of claim 6, wherein electric resistant strata can improve about 0.10 volt with the feasible electromotive force that applies of metal level.
10. the electric driven color-changing part of claim 6, wherein electric resistant strata can improve about 0.20 volt with the feasible electromotive force that applies of metal level.
11. the electric driven color-changing part of claim 6, wherein electric resistant strata can improve about 0.30 volt with the feasible electromotive force that applies of metal level.
12. the electric driven color-changing part of claim 6, wherein said metal level comprise noble metal and the alloy that is different from the underlying metal of noble metal.
13. electric driven color-changing part, it comprises:
First substrate, this first substrate have first surface and with this first surface opposing second surface;
Second substrate, this second substrate and described first substrate be the space separate relation and have towards the 3rd surface of described second surface and with the 4th relative surface of the 3rd surface;
Electrochromic media, this electrochromic media are between described first and second substrates, and wherein this electrochromic media has transformable transmittance when it applies electric field; With
Transparent electrode layer, this transparent electrode layer covers at least one at least a portion that is selected from second surface and the 3rd surface, wherein this transparent electrode layer comprises first insulator layer that is right after electrochromic media, the metal level and second insulator layer, wherein electric driven color-changing part demonstrates the colour rendering index more than or equal to 80, and place metal level and be selected from second surface and at least one at least a portion on the 3rd surface between the one layer surface of appointing have peak-paddy roughness less than 50 dusts, described metal level comprises silver, and at least one side in first insulator layer and second insulator layer comprises zinc paste or Sb or its combination.
14. the electric driven color-changing part of claim 13, at least one that wherein is selected from the surface that first and second insulator layers and metal level cover is to be in low-energy state.
15. the electric driven color-changing part of claim 13, wherein place metal level and be selected from second surface and at least one at least a portion on the 3rd surface between the method for appointing one layer surface to be to use to comprise Ion Beam Treatment form.
16. the electric driven color-changing part of claim 13, wherein place metal level and be selected from second surface and at least one at least a portion on the 3rd surface between appoint one layer surface to be to use to comprise what chemically treated method formed.
17. the electric driven color-changing part of claim 16, wherein place metal level and be selected from second surface and at least one at least a portion on the 3rd surface between the method for appointing one layer surface to be to use to comprise vulcanizing treatment form.
18. the electric driven color-changing part of claim 16, wherein place metal level and be selected from second surface and at least one at least a portion on the 3rd surface between appoint an one layer surface to be to use to comprise sulfuretted hydrogen or SO
2The method of handling forms.
19. the electric driven color-changing part of claim 6, wherein metal level be doped be selected from following at least a: palladium, copper, indium, titanium and combination thereof.
20. claim 1,4,6 and 13 electric driven color-changing part, wherein said first or second insulator layer has the absolute stress less than 3GPa.
21. the electric driven color-changing part of claim 20, wherein said first or the absolute stress of second insulator layer less than 1.5GPa.
22. the electric driven color-changing part of claim 21, wherein said first or the absolute stress of second insulator layer less than 0.5GPa.
23. the electric driven color-changing part of claim 1, it also comprises:
First restraining barrier that promotion between the selected surface that first insulator layer and transparent electrode layer cover is adhered to, wherein this first restraining barrier comprise select following at least a: ruthenium, NiCr, NiCrO
x, copper, titanium, niobium, nickel, palladium, platinum and combination thereof.
24. each electric driven color-changing part in the claim 1,4,6 and 13, wherein this electric driven color-changing part demonstrates the colour rendering index more than or equal to 90.
25. each electric driven color-changing part in the claim 1,4,6 and 13, wherein this electric driven color-changing part demonstrates the colour rendering index more than or equal to 95.
26. the electric driven color-changing part of claim 1, wherein at least one metal level comprises single metal layer.
27. the electric driven color-changing part of claim 26, wherein said single metal layer comprises silver, and wherein said single metal layer has the thickness of 50 dusts-500 dust.
28. the electric driven color-changing part of claim 27, wherein said single metal layer has the thickness of 75 dusts-250 dust.
29. the electric driven color-changing part of claim 28, wherein said single metal layer has the thickness of 100 dusts-150 dust.
30. the electric driven color-changing part of claim 1, wherein the gross thickness of first insulator layer, at least one metal level and second insulator layer is 100 dusts-700 dusts.
31. each electric driven color-changing part in the claim 1,4,6 and 13, wherein this electric driven color-changing part demonstrates in bright state and is less than or equal to 0.70 sunlight heat and obtains coefficient.
32. the electric driven color-changing part of claim 31, wherein the sunlight heat of this electric driven color-changing part is obtained coefficient and is less than or equal to 0.50.
33. the electric driven color-changing part of claim 32, wherein the sunlight heat of this electric driven color-changing part is obtained coefficient and is less than or equal to 0.30.
34. each electric driven color-changing part in the claim 4,6 and 13, wherein at least one of first insulator layer and second insulator layer comprises and is selected from indium-zinc oxide, indium tin oxide, aluminium zinc oxide, titanium dioxide, zinc paste, conduction TiO
2, CeO
x, tin ash, tin oxide, silicon nitride, silicon dioxide, ZnS, chromium oxide, niobium oxide, ZrO
x, WO
3, nickel oxide, IrO
2, TiSi
2O
6At least a.
35. each electric driven color-changing part in the claim 1,4,6 and 13 also comprises:
Restraining barrier between in being selected from second surface and the 3rd surface at least one and second insulator layer; Described restraining barrier reduce by second insulator layer and be selected from second surface and the 3rd surface at least one between Elements Diffusion; Wherein, described restraining barrier comprise be selected from following at least a: silicon dioxide, doped silica, amorphous state aluminium oxide, aluminum phosphate, SiN, SnZnO
xAnd their combination.
36. the electric driven color-changing part of claim 35, wherein said restraining barrier is an amorphous state.
37. the electric driven color-changing part of claim 23, wherein said first restraining barrier has the thickness that is less than or equal to 150 dusts.
38. the electric driven color-changing part of claim 37, wherein said first restraining barrier has the thickness that is less than or equal to 40 dusts.
39. the electric driven color-changing part of claim 38, the thickness on wherein said first restraining barrier is less than or equal to 20 dusts.
40. each electric driven color-changing part in the claim 1,4,6 and 13, wherein said electric driven color-changing part is configured in the rearview mirror assemblies of vehicle.
41. each electric driven color-changing part in the claim 1,4,6 and 13, wherein said electric driven color-changing part is configured to electrochromic.
42. each electric driven color-changing part in the claim 1,4,6 and 13 also comprises:
Restraining barrier between in being selected from second surface and the 3rd surface at least one and second insulator layer; Described restraining barrier reduce by second insulator layer and be selected from second surface and the 3rd surface at least one between Elements Diffusion; Wherein, described restraining barrier comprises phosphorus doped silica.
43. the electric driven color-changing part of claim 42, wherein said restraining barrier is an amorphous state.
44. electric driven color-changing part, it comprises:
First substrate, this first substrate have first surface and with this first surface opposing second surface;
Second substrate, this second substrate and described first substrate be the space separate relation and have towards the 3rd surface of described second surface and with the 4th relative surface of the 3rd surface;
Electrochromic media, this electrochromic media are between described first and second substrates, and wherein this electrochromic media has transformable transmittance when it applies electric field; With
Transparent electrode layer, this transparent electrode layer covers at least one at least a portion that is selected from second surface and the 3rd surface, wherein this transparent electrode layer comprises first insulator layer, metal level and second insulator layer that is right after electrochromic media, wherein electric driven color-changing part demonstrates the colour rendering index more than or equal to 80, described metal level comprises silver, and at least one side in first insulator layer and second insulator layer comprises zinc paste or Sb or its combination.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110214011.6A CN102253559B (en) | 2006-03-03 | 2007-03-05 | Comprise the electrooptic cell of IMI coating |
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| US77936906P | 2006-03-03 | 2006-03-03 | |
| US60/779,369 | 2006-03-03 | ||
| US81092106P | 2006-06-05 | 2006-06-05 | |
| US60/810,921 | 2006-06-05 | ||
| PCT/US2007/005638 WO2007103342A2 (en) | 2006-03-03 | 2007-03-05 | Electro-optical element including imi coatings |
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| CN201110214011.6A Division CN102253559B (en) | 2006-03-03 | 2007-03-05 | Comprise the electrooptic cell of IMI coating |
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| CN101438205A CN101438205A (en) | 2009-05-20 |
| CN101438205B true CN101438205B (en) | 2011-09-28 |
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| CN2007800160013A Active CN101438205B (en) | 2006-03-03 | 2007-03-05 | Electro-optical element including IMI coatings |
| CNA2007800137159A Pending CN101421666A (en) | 2006-03-03 | 2007-03-05 | Electro-optical element including metallic films and methods for applying the same |
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| CN101421666A (en) | 2009-04-29 |
| CN101395521A (en) | 2009-03-25 |
| CN101438205A (en) | 2009-05-20 |
| CN101395521B (en) | 2010-09-29 |
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