CN101421666A - Electro-optical element including metallic films and methods for applying the same - Google Patents
Electro-optical element including metallic films and methods for applying the same Download PDFInfo
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- CN101421666A CN101421666A CNA2007800137159A CN200780013715A CN101421666A CN 101421666 A CN101421666 A CN 101421666A CN A2007800137159 A CNA2007800137159 A CN A2007800137159A CN 200780013715 A CN200780013715 A CN 200780013715A CN 101421666 A CN101421666 A CN 101421666A
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Abstract
A method for manufacturing electrochromism element comprises: providing a first base plate having a first and second surface and a first edge surface; providing a second base plate having a third and fourth surface and a second edge surface with the third surface facing to the second surface; providing an electrochromism medium, which has a variable light transmittance while applied with a electric field, between the first and the second base plate; coating conductive layer at least a part of one of the surfaces under basic atmospheric pressure applying at least one of metal particulate, organic metal, metallorganics and their combination, in which, the conductive layer has a volume resistivity not less than 150 gemmbo.cm. The conductive layer can be coated by spray painting, ultrasonic spray painting, screw pump spray painting or jet pump spray painting.
Description
The cross reference of related application
The application requires on March 3rd, 2006 to submit to, exercise question is the U.S. Provisional Application No.60/779 of IMPROVEDCOATINGS AND REARVIEW ELEMENTS INCORPORATINGTHE COATINGS, on June 5th, 369 and 2006 submitted to, exercise question is the U.S. Provisional Application No.60/810 of ELECTROCHROMIC REARVIEW MIRRORASSEMBLY INCORPORATING A DISPLAY/SIGNAL LIGHT, 921 rights and interests, it is all collected and by reference in this, and be to submit on June 8th, 2004, exercise question is the U.S. Patent application No.10/863 of REARVIEW MIRROR ELEMENTHAVING A CIRCUIT MOUNTED TO THE REAR SURFACE OFTHE ELEMENT, 638 part continuation application.
Technical field
The present invention relates to as being used in the rearview mirror assemblies that is used for motor vehicle and the electric driven color-changing part in the window assembly, more specifically, relate to the improved electric driven color-changing part that is used in this assembly.More specifically, the present invention relates to be included in the conductive layer of atmospheric pressure deposit and the electric driven color-changing part that do not damage relevant bulk conductivity value.
Background technology
So far, proposed to be used for the various rearview mirrors of motor vehicle, it changes to partial reflection pattern (evening) from total reflection pattern (daytime), is used to prevent that the light that the headlight of the vehicle approaching from the rear portion sends is dazzling.Similarly, propose the variable transmission light filter, be used to build the rearview mirror of window, skylight, interior window, sun proof and automobile, and be used for window or other vehicles such as aircraft porthole.Device is such, and wherein transmissivity changes by thermochromism, photochromic or electrooptical device (for example liquid crystal, dipole suspension, electrophoresis, electrochromism etc.) and variable transmission property can influence that (wavelength is from approximately at least partially in the electromagnetic radiation in the visible spectrum
To about
).Proposed device for the reversible variable transmission of electromagnetic radiation as the variable transmission element in variable transmission light filter, variable mirror and the display, it has adopted such light filter or catoptron when the information of transmission.
For example, by " the Electrochromic and Electrochemichromic Materials andPhenomena " of Chang in Non-emissive Electrooptic Displays, A.Kmetz and K.von Willisen, eds.Plenum Press, NewYork, NY1976,155-196 page or leaf (1976) and P.M.S.Monk, R.J.Mortimer, D.R.Rosseinsky, VCH Publishers, Inc., New York, New York (1995), described in a plurality of parts of Electrochromism, for the device of the reversible variable transmission of electromagnetic radiation, wherein transmissivity changes by electrochromic device.Be known in the art numerous electrochromic devices.For example referring to 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, having can commercial electrochromic device and the interlock circuit that obtains, publish in February 20 nineteen ninety as H.J.Byker, exercise question is the U.S. Patent No. 4,902,108 of " SINGLE-COMPARTMENT; SELF-ERASING; SOLUTION-PHASEELECTROCHROMIC DEVICES SOLUTIONS FOR USE THEREIN; AND USES THEREOF "; J.H.Bechtel etc. published on May 19th, 1992, exercise question is the Canadian Patent No.1 of " AUTOMATIC REARVIEWMIRROR SYSTEM FOR AUTOMOTIVE VEHICLES ", 300,945; H.J.Byker published on July 7th, 1992, exercise question is the U.S. Patent No. 5,128,799 of " VARIABLE REFLECTANCE MOTOR VEHICLE MIRROR "; People such as H.J.Byker published on April 13rd, 1993, exercise question is the U.S. Patent No. 5,202,787 of " ELECTRO-OPTIC DEVICE "; J.H.Bechtel published on April 20th, 1993, exercise question is the U.S. Patent No. 5,204,778 of " CONTROL SYSTEM FORAUTOMATIC REARVIEW MIRRORS "; People such as D.A.Theiste published on January 11st, 1994, exercise question is the U.S. Patent No. 5,278,693 of " TINTEDSOLUTION-PHASE ELECTROCHROMIC MIRRORS "; H.J.Byker published on January 18th, 1994, exercise question is the U.S. Patent No. 5,280,380 of " UV-STABILIZED COMPOSITIONS AND METHODS "; H.J.Byker published on January 25th, 1994, exercise question is the U.S. Patent No. 5,282,077 of " VARIABLE REFLECTANCE MIRROR "; H.J.Byker published on March 15th, 1994, exercise question is the U.S. Patent No. 5,294,376 of " BIPYRIDINIUM SALTSOLUTIONS "; H.J.Byker published on August 9th, 1994, exercise question is the U.S. Patent No. 5,336,448 of " ELECTROCHROMIC DEVICES WITHBIPYRIDINIUM SALT SOLUTIONS "; F.T.Bauer etc. published in January 18 nineteen ninety-five, exercise question is the U.S. Patent No. 5,434,407 of " AUTOMATICREARVIEW MIRROR INCORPORATING LIGHT PIPE "; W.L.Tonar published in September 5 nineteen ninety-five, exercise question is the U.S. Patent No. 5,448,397 of " OUTSIDE AUTOMATIC REARVIEW MIRROR FORAUTOMOTIVEVE HICLES "; Publish in September 19 nineteen ninety-five with people such as J.H.Bechtel, exercise question is disclosed in the U.S. Patent No. 5,451,822 of " ELECTRONICCONTROL SYSTEM ".In these patents each all specified the present invention jointly, and will comprise by reference that each that comprise is open here and all incorporate into herein.These electrochromic devices can be used in all integrated inner/outer rear-view mirror system or conduct separates inside or external mirror having indicator light system and/or variable transmission window.
Fig. 1 shows has the sectional view that frontal plane shape substrate 12 and back plane shape substrate 16 and layout commonly used are known typical EC mirror devices 10.On the rear surface of prebasal plate 12, dispose transparent conducting coating 14, on the front surface of metacoxal plate 16, dispose another transparent conducting coating 18.Reverberator 20 is arranged on the rear surface of metacoxal plate 16, and this reverberator 20 generally includes silver metal layer 20a and one or more layers protective coating 20c that protected copper metal layer 20b covers.For this structure of clear description, sometimes the front surface 12a of prebasal plate 12 is called first surface, and sometimes interior (or back) surperficial 12b of prebasal plate 12 is called second surface, sometimes the inside surface 16a of metacoxal plate 16 is called the 3rd surface, and sometimes the rear surface 16b of metacoxal plate 16 is called the 4th surface.Shown in example in, prebasal plate also comprises edge surface 12c, and metacoxal plate comprises edge surface 16c.Forward and backward substrate 12,16 is fixed with parallel and spaced apart relation by sealant 22, has set up chamber 26 thus.Electrochromic media 24 is included in interval or the chamber 26.Electrochromic media 24 and transparent electrode layer 14 directly contact with 18, pass electromagnetic radiation by it, in this device, be applied to the reversibly intensity of modulated electromagnetic radiation of the variable voltage of electrode layer 14 and 18 or current potential by folder formula contact and electronic circuit (not shown).
Be arranged on electrochromic media 24 in the chamber 26 and can comprise electrochromic material and combination thereof surface-limited, electrode position type or liquid phase type (solution-phase-type).In all liquid phase mediums, the electrochemical properties of the solvent that can exist in solution, optional indifferent electrolyte, anode material, cathode material and any other composition preferably makes and significant galvanochemistry or other variation can not occur at following potential difference (PD) place, described potential difference (PD) can the oxidation anode material and the cathode material that reduces, rather than wipes reaction certainly between the reduction form of the oxidised form of the electrochemical reduction of the electrochemical oxidation of anode material, cathode material and anode material and cathode material.
As a rule, when not having potential difference (PD) between transparent conductor 14 and 18, the electrochromic media 24 in the chamber 26 is colourless substantially or approaching colourless, incident light (I
0) enter and pass prebasal plate 12, pass electrochromic media 24, clear coat 18, metacoxal plate 16 in clear coat 14, the chamber 26, and reflection is left layer 20a and is returned and pass this device and leave prebasal plate 12.Usually, the reflected image (I that does not have potential difference (PD)
R) amplitude be incident intensity (I
0) about 45% to about 85%.This exact value depends on the many variablees that outline below, for example, the absorptivity of each parts, from the residual reflection of the front of prebasal plate (I '
R) and from prebasal plate 12 and preceding transparency electrode 14, preceding transparency electrode 14 and electrochromic media 24, electrochromic media 24 and second transparency electrode 18, and second transparency electrode 18 and metacoxal plate 16 between the secondary reflection at interface.These reflections are well-known in the art, and be since light when passing interface between a kind of material and another material refringence between the two cause.If prebasal plate and back of the body element are not parallel, then residual reflection (I '
R) or other secondary reflection will be not can with the reflected image (I from mirror surface 20a
R) superimposed, and afterimage (observer can see the twice (or three times) of the object number that actually exists in the reflected image) will appear.
Amplitude to reflected image has minimum requirement, and this depends on that EC mirror is placed on the inside or the outside of the vehicles.For example, according to the current demand of most automobile factorys, scope preferably has at least 70% high-end reflectivity, and epi mirror must have at least 35% high-end reflectivity.
Even before commerce can obtain the 4th surface reflection device EC mirror for example shown in Figure 1, each team of research electrochromic device had discussed this reverberator has been moved to the 3rd surface from the 4th surface.This design has following advantage, in theory should easier manufacturing, because there is layer still less to be put in the device, that is, the 3rd surface transparent electrode is not necessarily when having the 3rd surface reflection device/electrode.Although just described this notion as far back as 1996, there is not team to obtain business success, this is because the mirror with an automatic light meter of working of actual integrated the 3rd surface reflection device of standard-required.That published on October 25th, 1966, people such as J.F.Donnelly, exercise question is the U.S. Patent No. 3 of " OPTICALLY VARIABLE ONE-WAY MIRROR ", 280,701, have one of argumentation the earliest that the color that is used to utilize pH to cause changes the 3rd surface reflection device of the system that comes attenuate light.
That published on November 19th, 1991, people such as N.R.Lynam, exercise question is the U.S. Patent No. 5 of " PERIMETER COATED; ELECTRO-OPTIC MIRROR ", 066,112, instructed to have the photoelectricity mirror that is used for hiding conductive coating sealant, that be coated to forward and backward glass elements periphery.Although discussed the 3rd surface reflection device here, but list concerning useful this material of the 3rd surface reflection device for the scope, can be subjected to not having the defect influence of enough reflectivity, and/or when contacting with the liquid phase electrochromic media that comprises at least a liquid phase electrochromic material unsettled defect influence.
Other people has proposed to be arranged on the article of the middle reverberator/electrode of all solid-state type devices.For example, people's such as Baucke U.S. Patent No. 4,762,401,4,973,141 and 5,069,535 have instructed the EC mirror with following structure: glass elements, transparent indium tin oxide electrode, tungsten oxide electrochromic layer, solid ionic conductive layer, individual layer hydrogen ion permeability reverberator, solid ionic conductive layer, hydrogen ion store layer, Catalytic Layer, back metal level and back element (third and fourth surface that expression is conventional).Reverberator is not deposited on the 3rd surface and goes up and directly do not contact with electrochromic material, does not contact with relevant medium with at least a liquid phase electrochromic material certainly yet.Therefore, be desirable to provide a kind of improved high reflectance electrochromism rearview mirror, this rearview mirror has the 3rd surface reflection device/electrode that contacts with the liquid phase electrochromic media that comprises at least a electrochromic material.The electrochromic that has proposed generally comprises and similar electrochromic cells shown in Figure 1, but does not have a layer 20a, 20b and 20c.
No matter whether be deposited on first, second, third, fourth or the edge surface of substrate, comprise conduction, reflection or the film of the two or layer metal in the structure of electrochromism photoelectric device and integrated electrochromic device, all be very useful with its encapsulation.Usually, when electricity is led increase; When sticking property increases; When the complicacy of layer pattern increases; The reflectivity increase keeps the muted color reflex time simultaneously; When chemistry and electrochemical stability increase; And the easiness that applies is when increasing; The multifunctionality of metal film or metal multilayer film and effectiveness can increase.
On the surface of the substrate relevant,, electric driven color-changing part carried out various trials aspect the conductive layer for providing with aforesaid electric driven color-changing part.Such method comprises utilizes the resin that is loaded with metallic particles, and the epoxy resin of silver-colored thin slice for example is housed.Yet the electric conductivity of this system can be subjected to making the restriction that is connected of a large amount of particles of being used for conduction current and particle.Each particle can increase resistance with being connected of particle, has limited the validity of the resin that is loaded with metallic particles thus.Current, can not obtain the mirror image light reflection of mirror-quality from these films, this is because the random orientation of big relatively metallic particles can be impelled diffuse reflection.For fear of these restrictions, wish the tightr metal film of deposition near the body metallic character.But for the tightr metal film near the body metallic character that adheres well to conduction on the application substrate and reflection is that chemistry and galvanochemistry are durable, and can utilize vacuum technology for example sputter or evaporate deposit.Yet, based on the equipment of vacuum technology buy, very expensive aspect the operation and maintenance.Utilization is very difficult based on the process deposits pattern film of vacuum.A kind of method of patterning vacuum covering metal film need be passed through the mask metallizing between depositional stage.This mask is expensive and very difficult the maintenance for machining.The another kind of method of patterning vacuum covering metal film need for example laser ablation or chemical etching remove metal by other treatment step after deposition.Except that the complicacy that has increased whole manufacturing process, aforementioned sputter or evaporation technology neither be efficiently when using metal or metal precursor.Particularly, during application of vacuum, the metal of q.s is deposited on mask and on the structure, rather than on desirable device, and its waste recovery will be expensive and expend time in.
Therefore wish in approaching atmospheric condition, specifically under atmospheric pressure, in electrochromism or other photoelectric device, make metal film, and provide enough conductions, bonding and reflectivity properties, keep muted color reflection, enough chemistry and electrochemical stability simultaneously, allow to apply the increase of control simultaneously.
Summary of the invention
One aspect of the present invention comprises a kind of method of making electric driven color-changing part, this method comprise provide have first surface, with first substrate of first surface opposing second surface and first edge surface; The 3rd surface that has towards second surface, four surface relative with the 3rd surface and second substrate of second edge surface are provided; Provide electrochromic media between first and second substrates, wherein electrochromic media has when transmittance variable when it applies electric field.This method further is included in coated with conductive layer at least a portion of one selecting at least of first surface, second surface, first edge surface, the 3rd surface, the 4th surface and second edge surface, wherein the coating of conductive layer is of that finish and selection that comprise applied metal particle, organic metal, metallorganics and combination thereof under basic atmospheric pressure, and wherein conductive layer has the body resistivity more than or equal to 150 μ Ω cm.
A kind of the inventive method that is used to make electric driven color-changing part comprises on the other hand: provide have first surface, with first substrate of the first surface opposing second surface and first edge surface; The 3rd surface that has towards second surface, four surface relative with the 3rd surface and second substrate of second edge surface are provided; And between first and second substrates, provide electrochromic media, wherein electrochromic media has when transmittance variable when it applies electric field.This method further is included in ink jet printing conductive layer at least a portion of one selecting at least of described surface, second surface, first edge surface, the 3rd surface, the 4th surface and second edge surface.
Comprising on the other hand of the inventive method: provide have first surface, with first substrate of first surface opposing second surface and first edge surface; The 3rd surface that has towards second surface, four surface relative with the 3rd surface and second substrate of second edge surface are provided; And between first and second substrates, provide electrochromic media, wherein electrochromic media has when transmittance variable when it applies electric field.This method further is included in ultrasonic spray conductive layer at least a portion of one selecting at least of first surface, second surface, first edge surface, the 3rd surface, the 4th surface and second edge surface.
The inventive method comprises on the other hand: provide have first surface, with first substrate of first surface opposing second surface and first edge surface; The 3rd surface that has towards second surface, four surface relative with the 3rd surface and second substrate of second edge surface are provided; And between first and second substrates, provide electrochromic media, wherein electrochromic media has when transmittance variable when it applies electric field.This method further is included in coated with conductive layer at least a portion of one selecting at least of first surface, second surface, first edge surface, the 3rd surface, the 4th surface and second edge surface, and wherein the coated with conductive layer comprises in helicoidal pump spraying and the jetting pump spraying one of selection at least.
A kind of the inventive method that is used to make electric driven color-changing part comprises on the other hand: provide have first surface, with first substrate of the first surface opposing second surface and first edge surface; The 3rd surface that has towards second surface, four surface relative with the 3rd surface and second substrate of second edge surface are provided; And between first and second substrates, provide electrochromic media, wherein electrochromic media has when transmittance variable when it applies electric field.This method further is included in coated with conductive layer at least a portion of one selecting at least of first surface, second surface, first edge surface, the 3rd surface, the 4th surface and second edge surface, wherein the coated with conductive layer comprise combustion chemical vapor deposition, flame spraying deposition and laser sintered in select at least one.
By the following instructions of reference, claims and accompanying drawing, those skilled in the art are understanding and cognition these and other feature of the present invention, advantage and purpose more.
Description of drawings
In the drawings:
Fig. 1 is the amplification sectional view in conjunction with the prior art electrochromism mirror assembly of the 4th surface reflection device;
Fig. 2 is the schematically illustrated front elevation that is used for the inside/outside electrochromism rear-view mirror system of motor vehicle;
Fig. 3 is the amplification sectional view of combination along the EC mirror of the 3rd surface reflection device/electrode of the line III-III of Fig. 2;
Fig. 4 is the process flow diagram that the order of the inventive method is shown;
Fig. 5 has than the substrate of megacryst structure and the schematic cross-section of body metallic coating;
Fig. 6 has the substrate of small crystals structure and the schematic cross-section of body metallic coating; With
Fig. 7 is used for the wavelength of example 7 and the curve map of reflectivity.
Embodiment
Here in order to illustrate, term " on ", D score, " right side ", " left side ", " back ", " preceding ", " vertical ", " level " and derivative thereof relate to as invention directed among Fig. 2.Yet, understand that the present invention can suppose each optional orientation and sequence of steps, except clearly stipulating on the contrary.Also to understand shown in the accompanying drawing with following description in concrete device and the technology described be one exemplary embodiment of the present invention, unless regulation is arranged in the appended claims.Therefore, relate to the concrete size of embodiment disclosed herein and other physical characteristics do not think restrictive, unless claim clear and definite regulation in addition.
Fig. 3 shows the sectional view of the mirror assembly 111a with preceding transparency carrier 112 and metacoxal plate space 114, and preceding transparency carrier 112 has front surface 112a and rear surface 112b, and metacoxal plate space 114 has front surface 114a and rear surface 114b.For this structure of clear description, will use following title hereinafter.To call first surface 112a to the front surface 112a of prebasal plate, the rear surface 112b of prebasal plate will be called second surface 112b.To call the 3rd surperficial 114a to the front surface 114a of metacoxal plate, and the rear surface 114b of metacoxal plate will be called the 4th surperficial 114b.Prebasal plate 112 further comprises edge surface 112c, and metacoxal plate 114 further comprises edge surface 114c.Internal perisporium 132 delimit chamber 125 by layer of transparent conductor 128 (in second surface 125 upper supports), reverberator/electrode 120 (being arranged on the 3rd surperficial 114a) and seal assembly 116.Electrochromic media 126 is included in the chamber 125.
As being extensive use of here and describing, " supports " or be applied to electrode or layer on the element surface, refer to be set directly on the element surface or be arranged on another coating electrode or layer, be set directly on the element surface one or more layers.And, notice and only described mirror assembly 111a for illustrative purposes, and can rearrange concrete parts and element here, for example those known structures of structure shown in Fig. 1 and electrochromic.
Preceding transparency carrier 112 can be any material, and it is transparent and has enough intensity working in automotive environment under the condition of transformation temperature that for example finds jointly and pressure.Prebasal plate 112 can comprise borosilicate glass, soda-lime glass, float glass or any other material of any kind, and for example polymkeric substance or plastics are transparent in the visible range of electromagnetic spectrum promptly.Prebasal plate 112 is glass sheet preferably.Except needn't be in all are used all transparent, metacoxal plate 114 must satisfy the condition of work of above-mentioned general introduction, therefore can comprise polymkeric substance, metal, glass, pottery, and glass sheet preferably.
By near the seal assembly 116 the neighboring that is arranged on second surface 112b and the 3rd surperficial 114a, the coating of the 3rd surperficial 114a can be joined on the coating on the second surface 112b hermetically with spaced apart and parallel relation.Seal assembly 116 can be the coating adhesively attached on the second surface 112b can be incorporated into coating on the 3rd surperficial 114a to seal any material that this periphery makes that electrochromic material 126 can 125 internal leakages from the chamber.Alternatively, can above the part that seal assembly 116 is set, remove the layer of transparent conducting coating 128 and the layer of reverberator/electrode 120 (be not entire portion, can not be applied on two coatings) otherwise drive current potential.In this case, seal assembly 116 must join on glass well.
Similar with the periphery sealing of using in LCD (LCD) for the performance requirement of the peripheral seal assembly 116 that uses in electrochromic device, it is well-known in the art.Sealing 116 must have the good adhesion with glass, metal and metal oxide; Must have low permeability for oxygen, wet steam and other harmful steam and indium; And must be interact with electrochromism or liquid crystal material or poison electrochromism or liquid crystal material, it means and comprises and protect.Periphery sealing 116 can for example apply by serigraphy or dispersion by the mode that generally is used in the LCD industry.Can use air-locked sealing generally, the gas tight seal for preparing with glass dust or solder glass for example, but the high temperature that relates in the sealing of handling (usually near 450 ℃) the type can cause many problems, and for example the character of glass substrate warpage, transparency conductive electrode changes and the oxidation or the degeneration of reverberator.Since their reduction process temperature, organic sealing resin that preferred thermoplastic, thermosetting or UV solidify.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.Since the good adhesiveness of they and glass, low oxygen permeability and good anti-dissolubility, organic sealing resin of preferred epoxy base.These epoxy encapsulants can be that UV solidifies, as in U.S. Patent No. 4,297, describe in 401, and perhaps heat curing, as have the potpourri of the liquid epoxies of liquid polyamide or dicyandiamide, perhaps they can be equal polymerizations.Epoxy resin can comprise filler or thickening agent to reduce flow velocity and amount of contraction, as fumed silica, monox, mica, clay, lime carbonate, aluminium oxide etc. and/or add the pigment of color.Preferably with hydrophobicity or the pretreated filler of silane surface treatment.Can control the cured resin cross-linking density by using single function, potpourri difunctional and multi-functional epoxy resin and hardening agent.Can use adjuvant such as silane or titanate to improve the hydrolytic stability of sealing, and can use sept such as beaded glass or glass bar to control final seal thickness and substrate spacing.The epoxy resin that is fit to that is used for peripheral containment member 116 comprises, but be not limited to: from Houston, " the EPON RESIN " 813,825,826,828,830,834,862 that Texas, ShellChemical company obtain, 1001F, 1002F, 2012, DPS-155,164,1031,1074,58005,58006,58034,58901,871,872 and DPL-862; Can be from New York, Hawthorne, Ciba Geigy " ARALITE " GY 6010, the GY 6020, CY 9579, GT 7071, XU 248, EPN 1139, EPN 1138, PY 307, ECN 1235, ECN 1273, ECN 1280, MT 0163, MY 720, MY 0500, MY 0510 and the PT 810 that obtain; With from the state of Michigan, Midland, " D.E.R. " 331,317,361,383,661,662,667,732,736, " D.E.N. " 431,438,439 and 444 that Dow Chemical company obtains.The epoxy curing agent that is fit to comprises V-15, V-25 and the V-40 polyamide of Shell Chemical company; " AJICURE " PN-23, PN-34 and VDH from the acquisition of Tokyo Ajinomoto company; " CUREZOL " AMZ, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 2IZ and the 2P4MZ that obtain from the Shikoku Fine Chemicals of Tokyo; From New Jersey, " ERISYS " DDA or DDA that Maple Shade, CVC Specialty Chemicals obtain with U-405,24EMI, U-410 and U-415 catalysis (accelerate); With " AMICURE " PACM, 352, CG, CG-325 and the CG-1200 that obtain from Pennsylvania, Allentown, Air Products.Appropriate filler comprises fumed silica, as from the Illinois, Tuscola, Cabot company " CAB-O-SIL " L-90, LM-130, LM-5, PTG, M-5, M-7, MS-55, TS-720, HS-5 and the EH-5 that obtain; From the Ohio, Akron, " AEROSIL " R972, R974, R805, R812, R812 S, R202, US204 and US206 that Degussa obtains.Suitable clay filler comprises from the New Jersey, the Engelhard company of Edison obtains BUCA, CATALPO, ASP NC, SATINTONE 5, SATINTONE SP-33, TRANSLINK 37, TRANSLINK77, TRANSLINK 445 and TRANSLIKN 555.Suitable cilicon oxide filler be from the Maryland State, the SCM Chemicals of Baltimore SILCRON G-130, the G-300, G-100-T and the G-100 that obtain.The suitable silane coupling agent that improves the hydrolytic stability of sealing be from the state of Michigan, the Dow Corning company of Midland Z-6020, the Z-6030, Z-6032, Z-6040, Z-6075 and the Z-6076 that obtain.From California, the DuckScientific of Palo Alto can obtain the glass microballoon sept by the suitable accuracy of size classes.
This layer of deposition transparent conductive material 128 is to be used as electrode on second surface 112b.Transparent conductive material 128 can be following any material, this material joins on the prebasal plate 112 well, any material tolerance burn into tolerance atmospheric corrosion in the electrochromic device has minimum diffusion or specular reflectance, high light transmission, nearly neutral colored and good electricity and leads.Transparent conductive material 128 can be as by Germany, Alzenau, the J.Stollenwerk of LEYBOLD AG, B.Ocker, K.H.Kretschmer is disclosed tin oxide, the zinc paste of doping, the indium zinc oxide (Zn that mixes fluorine in " Transparent ConductiveMultilayer-Systems for FPD Applications "
3In
2O
6), tin indium oxide (ITO), ITO/ metal/ITO (IMI), in above-mentioned U.S. Patent No. 5, the material of describing in 202,787, as can be from the Ohio, the Libbey Owens-Ford company of the Toledo TEC 20 or TEC 15 or other transparent conductor that obtain.Usually, the electricity of transparent conductive material 128 is led thickness and the composition that depends on it.If desired, can between transparent conductive material 128 and second surface 112b, deposit optionally one or more layers colored material 130 that suppresses, to suppress any reflection of not wishing part of electromagnetic spectrum.
Combined reflector/electrode 120 is arranged on the 3rd surperficial 114a and comprises one deck reflecting material 121 at least, and this reflecting material is used as the mirror reflection layer and also forms the overall electrode that contacts and have chemistry and electrochemical stability relation with the composition in the electrochromic media.As mentioned above, the conventional method of setting up electrochromic device be on the 3rd surface in conjunction with transparent conductive material as electrode, and on the 4th surface, place reverberator.The two is placed on the 3rd surface by combination " reverberator " and " electrode " and with them, several advantages can occur, and it makes that not only the device manufacturing is simpler, and allows this device with higher performance work.For example, the reverberator/electrode 120 of the combination on the 3rd surperficial 114a has usually than the transparency electrode of routine and the previous high electricity of reverberator/electrode that uses leads, and it makes design flexibility bigger.The composition of the transparency conductive electrode on the second surface 112b 128 can be changed over and have the more composition of low conductivity (production and manufacturing are more cheap and easier), keep simultaneously with the obtainable similar painted speed of the 4th surface reflection device device, the while has been reduced the overall cost and the time of manufacturing electrochromic device fully.Yet, if the performance of particular design is most important, can on second surface, use the transparency electrode of high conductivity, for example, such as ITO, IMI etc.High conductivity on the 3rd surperficial 114a (promptly, less than 250 ohm/side) the reverberator/electrode 120 and the combination of the high-conductivity transparent electrode 128 on the second surface 112b not only can obtain more even overall painted electrochromic device, increase painted speed and cleaning but also taken into account.In addition, in the 4th surface reflection device mirror assembly, two transparency electrodes with relative low conductivity are arranged, and formerly in the 3rd surface reflection device mirror of Shi Yonging, transparency electrode and the reverberator/electrode with relative low conductivity are arranged, similarly, make the long bus-bar on the preceding and metacoxal plate of electric current turnover must guarantee enough painted speed.
Shown in example in, on the 4th glass surface 114b, be provided with electric resistance heater 138. Power spring folder 134a, 134b are arranged on the glass sheet 112,114 of coating, with transparent conducting coating 128 expose zone (intermediate plate 134b) and the 3rd surface reflection device/electrode 120 (intermediate plate 134a) electrically contacts.Suitable electric conductor (not shown) can weld or otherwise be connected to spring clamp 134a, 134b so that from suitable power supply desirable voltage is applied on this device.
The technology of the present invention (Fig. 4) that is used to make as electric driven color-changing part described herein comprises the steps: to provide (200) aforesaid substrate, cleaning (202) substrate will the coated with conductive layer the surface, the surface of pre-service alternatively (204) substrate, pattern with definition applies (206) conductive layer on substrate surface, and solidifies (208) conductive layer alternatively after it applies.
The available any known cleaning glass technology of the cleaning of substrate surface (202) is finished, and comprises chemical cleaner, polishing, etching etc.Alternatively, the substrate surface of pre-service (204) coated with conductive layer causes the hydrophilic and/or hydrophobic reactant of metal level when applying metal in solution.
The institute's favored area that conductive layer is coated to (206) substrate can be finished via several different methods and technology.Particularly, can by ink-jet (inkjet) technology, ultrasonic spray, helicoidal pump spraying (pumping) or jetting pump spraying or similarly dispersion method conductive metal layer is coated to the surface of substrate, under atmospheric conditions, finish, do not use vacuum particularly.These methods comprise metallizing particle (preferable alloy nano particle), organic metal, metallorganics and combination thereof.For example by the relevant substrate of pre-service, but original position (in sito) is solidified every kind of material of (208) deposition, and/or solidifies subsequently to form final metal conducting layer.
The example of metallizing film or metal multilayer film includes, but not limited to electronics bus-bar conductor in the electrochromic device of using via the technology of the present invention; Electric resistance heater film and/or bus-bar system; Metal wire, bar, grid or pattern; The conductive trace that is used for electronic circuit; The basic unit of the solder of enhancing is provided; Reflection or the specular metal film of half reflection; With the metal zona.Electronics bus-bar conductor dbus is normally placed near the periphery of relevant electrochromic device.Technology of the present invention allows the bus-bar conductor to be set following on any one: the edge of any in surface one, surface two, surface three, surface four and/or the substrate.And, can use this technology that bus-bar is coated in the substrate edge of any and can overlap and be electrically connected to the conduction region on surface one, two, three or four.And; because the metal bus-bar film that applies by the technology of the present invention demonstrates the adhesiveness that improves with substrate; therefore it can be arranged on below the electrochromic device sealing; sealing can be crossed and apply and protect the metal bus-bar not corroded, and can be in conjunction with sealed region occupied to minimize its overall combination area occupied.In this example, the resistance of wishing bus-bar is more preferably less than 5 ohm of every linear foots less than 10 ohm of every linear foots, most preferably less than 1 ohm of every linear foot.
The electric resistance heater film and/or the bus-bar system that apply via the technology of the present invention are suitable for heating equably and/or electrochromic device being removed frost.Since these metal films must with device substrate thermo-contact well, so this metal film of preferred patternization and this metal film directly being coated on one of surface of the electrochromic device that provides by the inventive method.
The Another Application of method disclosed herein comprises provides metal wire, bar, grid or the pattern conductance with the relevant surfaces in intensifier electrode 120 and 128 one or both of.The enhancing conductivity that provides by metal helps the painted of relevant electrochromic device and cleaning.By using the inventive method, the zone that makes electrochromic device by the pattern of regulating depositing metallic films than other comparison domain optionally or painted quickly or clean.This method has proved for strengthening more particularly useful than the electric conductivity of most of metals transparent conductive oxide (TCO) that poorly conductive is a lot inherently.For minimize on the TCO surface or under the visibility of pattern metal, wish to have wide pattern characteristics less than 5mm, preferably wide and to be more preferably less than 0.5mm wide less than 1mm.Also can below the reflectance coating or above metallizing line, bar, grid and/or pattern to strengthen or optionally to change relevant conductivity and performance as electrode.
The Another Application of the inventive method provides patternable and is used as the metal film of the conductive trace of electronic circuit.Electronic circuit can be applied directly on electrochromism substrate or other substrate (such as substrate conventional in printed circuit board industry, for example epocel glass stack, polyimide film or polyester film).These metal films at first can be deposited on the substrate with electronic components associated therewith, and these electronic units can be adhered on the substrate subsequently and be electrically connected on the metal film conductive trace.Alternatively, on the substrate that electronic unit can at first be installed to, the electrical traces pattern is applied on the substrate with the interconnection electronic unit subsequently.Electrical connection between parts and the metal film can be undertaken by for example welding of routine techniques, wire-bonded, Elastic Contact or conductive adhesion.And, be electrically connected and also can directly finish by metal film, wherein can three-D pattern metallizing film in case metal film from substrate continuously to electronic unit.By this way, electronic unit at first can be mounted substrate, and can in a metal film pattern step, finish electronic circuit and with being electrically connected of parts.Notice that further the pattern metal film that applies via the technology of the present invention can make up to form conductor/insulation body/conductor circuit with the pattern dielectric film, allows to realize higher current densities thus or apply a plurality of electrochromism electrode converging bars on same substrate.
Another Application comprises that the metallizing film is as the basic unit that strengthens solder wettability or substrate weldability.Use the metal film weld layer to strengthen conductivity, provide with the electric connection and/or the mechanical engagement of parts to be connected, and/or gas-tight seal is provided.For example, each edge of the substrate relevant with electrochromic device can be coated with metal film.Fix this substrate by substrate and the uniform gap between it then, the edge of substrate is welded together subsequently.Notice that scolder in this example can form bubble-tight tight edge sealing and protect the electrochromic media that is included between the substrate.This is to allowing to be welded direct to the scolder of glass, pottery and conducting metal oxide and the improvement of solder technology, because can provide poor solder joints owing to process variability sometimes in preceding known technology.Another example of the serviceability of the technology of the present invention is by applying the edge with metal film and allow the filler opening soldered cut-out relevant with electric driven color-changing part after filling this device with electrochromic material or electrolyte, filling the port edge of electric driven color-changing part thus.Have, this is the improvement to the past technology again, because the technology of the present invention provides the easier execution and the technology of robustness more.
The Another Application of technology of the present invention is to apply reflection or the specular metal film of half reflection on one of at least in second, third and the 4th surface of relevant electrochromic device.This metal film can be coated to whole surface or be patterned coated portion with target surface optionally to provide transparent, half reflection or to reflect specular part.Can be used as electrode if these layers are arranged on the surface three, replenish bus-bar if perhaps be arranged on the surface four then can be used as electrode.And these films can be made enough thickly so that only need point, short-term or small size to electrically contact.Preferably, be more preferably less than 1 ohm of every side,, and can easily realize via the technology of the present invention most preferably less than 0.5 ohm of every side less than 10 ohm of every sides' sheet resistance.
Near the reflective metals zona of the patterning periphery that the Another Application of the technology of the present invention one of provides in related substrate, wherein becket will be used for hiding relevant seal area and the mirror surface on the mirror surface on will additional second substrate will be provided.This metal film will be provided between 1mm and the wide ring of 8mm, and it will cover the periphery of first substrate and overlap onto on its edge.This metal film can be used as the electronics bus-bar of electric bus-bar or additional second surface transparency conductive electrode.And, be arranged on metal film on the second surface can be coated in below the transparency conductive electrode, on the transparency conductive electrode top or be clipped between the transparency conducting layer.And light grey or dusk metal level can be used for hiding seal area and can be used as electric bus-bar and the reverberator on additional second substrate of aesthetic.
As arriving in prerequisite, a kind of method with high-resolution patterned film is ink jet printing.10 μ m or following printing details can realize with ink jet printing, and the China ink amount of deposition can closely be controlled and accurately be regulated during each passes through.Print film thickness can change through the number of pass times of surface to be printed by controlling frequency that each ink drop size, ink droplet produce, speed that ink gun crosses substrate and ink gun.Notice, be mounted with the ink jet printing effectively of oarse-grained China ink, this is because bulky grain can hinder ink gun and be easy to from solution deposition, if especially this solution viscosity is low.As a result, the China ink of loading nano particle metal is preferred.Particularly, can be that the metallic China ink that ink jet printing and generation have near the metal film of body metalline is the black solution that comprises nano particles such as silver, nickel, copper, gold, silver-copper, silver-palladium, palladium-Jin.The transparent conductive oxide coating also can be formed by the China ink of the nano particle that comprises the transparent oxide material, and described transparent oxide material for example is the tin oxide (ATO) of tin indium oxide (ITO), antimony dopant, the zinc paste (AZO) of adulterated al, the zinc paste (IZO) or the similar metal oxide system of doped indium.Notice that these black metal particle size must be enough little of to form the specular film of mirror reflection when carrier solvent evaporates.
Can use ink-jet imaging to come the mode of depositing metallic films to utilize two-phase UV to solidify China ink, wherein spray to the two-phase China ink on the substrate and carry out UV and solidify to make solid-state two-phase polymer matrix.A kind of polymer phase is optionally to become solvate from this matrix, and remaining polymer phase forms honeycomb and comprises the metal deposited catalyst.Utilize alms giver's fluid that metallizes that metal is deposited on the catalyzer that comprises the polymkeric substance honeycomb then.Has satisfactory electrical conductivity and adhering copper, silver, gold, nickel and cobalt can utilize this deposition techniques.
Can utilize the another way of ink jet printing depositing metallic films to relate to the thermal decomposition of Organometallic precursor to form metal.Make these Organometallic precursors become solvate with organic metal solution and spray to (100 to 250 ℃) on the hot substrate.Heated substrates meeting this solvent of flashing off (flash-off) and organometallics can resolve into the metal that deposits on the substrate.If the metal pair oxidation-sensitive, then this coating/decomposition technique can carry out in air, inert gas or reducing atmosphere.Organometallic precursor also can make the nano particle sintering together with help with the nano particle combination when solidifying.
Can optionally apply solution or the China ink that comprises nanoparticle based, Organometallic precursor base or metal ion-based by the method except ink-jet.Other technology comprises the solution that utilizes nano steam spraying and/or ultrasonic spray technology to come coated copper, tungsten, silver, gold etc., has and the similar metal film of the quality of vacuum technology with manufacturing.Fujimori TechnicalLaboratory Ltd. by Japan adopts this technology to make the money base mirror.Also can utilize ultrasonic spray technology applying liquid coating accurately on various substrates, for example fluid, photoresist and conductive ink, for example by Haverhill, the Sono-Tek company of the Ultrasonic Systems company of MA and New York, Milton adopts.And, can utilize the minor spiral pump that is connected to XYZ motion control able to programme and solenoid pump with pattern, line or put accurately dispersing fluid, those systems that adopt as Asymtek by Canada, Carlsbad.These systems can control by image surveillance and the servo-drive controlling pump that is connected to accurate motion control apparatus, with 3D shape and pattern dispersed electro-conductive and non-conducting material exactly.
And the conduction and the coating of non-conducting material can be sprayed directly into the powder that heats on the surface of pattern structure by the hole and finish.And, also can utilize laser technology, comprise the ribbon that is coated with the material that will deposit with pulse laser beam by irradiation, thereby material directly is transferred on the substrate.Material by laser beam from keeping near this ribbon evaporation of substrate and being transferred on the substrate.Come the material of patterned deposition by moving substrate below the banded mechanism of the accurate XY motion control of laser beam/have.If desired, this deposition can be finished in air or inertia, reduction or oxidizing atmosphere.Also can come depositing electrically conductive and insulating material by plasma spray coating technology, it comprises that with hot material emission to substrate that will be coated, wherein Fa She spraying can be converged.In a kind of mode, dusty material is supplied with thermal-flame, fusion is guided substrate into by the combination of burning gases or burning gases and inert gas then, and wherein hot particle converges on substrate that will be coated.In another way, this material is supplied in the head of using the discharge melted material with the wire form.Guide this material into substrate by inert gas steam then.In every kind of mode, this deposition materials can come patterning by mask or hole sprayed on material, controls mobile deposition head or substrate with accurate movement simultaneously.Another technology is the electrodeless metal depositing operation that comprises with palladium bichloride or tin chloride solution sensitization glass surface.The silver-colored solution that the silver nitrate that generally dissolves in ammoniacal liquor is formed is coated on the substrate together with organic reducing agent.Silver ion is reduced to silver metal by organic reducing agent and is deposited on the substrate as metal film.By optionally applying silver-colored solution, silverskin that can patterned deposition.
Surface topography, form or roughness are not very important in the most electric application facet of handling metallic coating usually, yet surface topography becomes very crucial when using coating in optical application.Particularly, too big if surfaceness becomes, then coating will have appreciable non-specular reflectivity or smudgy.In majority is used, when solving, generally at first solve roughness with smudgy relevant problem, this is because can have to bear looks outward appearance and may not be the function problem, and is for example relevant with conductivity.Under the situation of optical application of many descriptions here for example, think exist offensive fuzzy be the situation of worst.And, to compare with forming offensive fuzzy aftermath, roughness can have the aftermath of much lower other of degree.Calculate with the previous trial of bluring relevant problem and comprise the metal that utilizes the higher price that shows high reflectance.Utilized the thin-skin model technique computes as the influence of the degree of the change shape discussed in this application or surfaceness.Particularly, be to utilize as the calculating that comprises here from Portland about form or surfaceness, Oregon, Software Spectra company obtains is called can the commercial film program that obtains calculating of TFCalc.
In this example, roughness is defined as average peak valley distance.Fig. 5 shows the first roughness situation, wherein substrate 300a is coated with the body metallic coating 302a that shows the first roughness 304a with big crystal grain, and Fig. 6 shows the second roughness situation, and wherein substrate 300b is coated with the body metallic coating 302b that shows the second roughness 304b with relatively little crystal grain.Notice that each example has shown that similar peak valley is apart from 306a, 306b.In addition, two examples have identical hole body than (void to bulk ratio).Can carry out the approximate of relative thinner layer by this layer being regarded as single uniform bed, yet this approximate effect for mixolimnion not fine with homogeneous refractive index.Particularly, excessive if metal layer thickness becomes, then roughness can not be approximate well by single fixing refractive index, and under those situations, and roughness is approximately the space body than different some.This example utilizes Bruggeman EMA method, is used to calculate the effective medium approximation value of the refractive index of mixolimnion.
Table 1-3 shows roughness thickness and influence for the reflectivity (Y) on the surface of silver, chromium and rhodium respectively.Note, reflectivity along with for these metals each roughness increase and reduce gradually.According to application, the amount that can accept roughness can change, yet roughness should be more preferably less than 40 nanometers, even be more preferably less than 20 nanometers preferably less than 60 nanometers, even is more preferably less than 10 nanometers and most preferably less than 5 nanometers.As mentioned above, these preferred range depend on the application-specific that relates to.Surfaceness is very crucial for the first surface reflectivity.
Table 1: roughness thickness is to the influence of the reflectivity of Ag coating
Silver
| Body thickness (nm) | Roughness (nm) | Reflectivity (Cap Y) % |
| 350 | 0 | 98.5 |
| 350 | 5 | 95.2 |
| 350 | 10 | 91.3 |
| 350 | 15 | 87.1 |
| 350 | 20 | 82.7 |
| 350 | 25 | 78.4 |
| 350 | 30 | 74.2 |
| 350 | 35 | 70.4 |
| 350 | 40 | 66.8 |
| 350 | 45 | 63.6 |
| 350 | 50 | 60.8 |
| 350 | 55 | 58.3 |
| 350 | 60 | 56.2 |
Table 2: roughness thickness is to the influence of the reflectivity of chrome coating
Chromium
| Body thickness (nm) | Roughness (nm) | Reflectivity (Cap Y) % |
| 40 | 0 | 65.9 |
| 40 | 5 | 64.6 |
| 40 | 10 | 62.2 |
| 40 | 15 | 59.0 |
| 40 | 20 | 55.2 |
| 40 | 25 | 51.3 |
| 40 | 30 | 47.7 |
| 40 | 35 | 44.5 |
| 40 | 40 | 41.9 |
| 40 | 45 | 39.8 |
| 40 | 50 | 38.3 |
| 40 | 55 | 37.2 |
| 40 | 60 | 36.5 |
Table 3: roughness thickness is to the influence of the reflectivity of rhodium coatings
Rhodium
| Body thickness (nm) | Roughness (nm) | Reflectivity (Cap Y) % |
| 40 | 0 | 76.9 |
| 40 | 5 | 74.8 |
| 40 | 10 | 71.6 |
| 40 | 15 | 67.2 |
| 40 | 20 | 62.1 |
| 40 | 25 | 56.4 |
| 40 | 30 | 50.7 |
| 40 | 35 | 45.2 |
| 40 | 40 | 40.3 |
| 40 | 45 | 36.0 |
| 40 | 50 | 32.4 |
| 40 | 55 | 29.6 |
| 40 | 60 | 27.4 |
Utilize technology of the present invention and method to provide and be preferably as follows conductive layer, it has and is less than or equal to 150 μ Ω cm, is more preferably less than or equals 100 μ Ω cm and be more preferably less than or equal 50 μ Ω cm body resistivities; Be less than or equal to 20nm, preferably be less than or equal to 10nm and be more preferably less than or equal the valley roughness of 5nm; Be preferably greater than or equal 35%, more preferably greater than or equal 55% and further more preferably greater than or equal 70% reflectivity, and demonstrate the spectral reflectance that wherein keeps image.
Utilize multiple coating processes and curing technology to carry out some experiments, their details is provided below.
Example 1
Utilization is from MicroFab Technologies (Plano, TX) JetDrive III driver of Huo Deing and MJ-AB-01 40 μ m ink guns, will (Albuquerque, Inkjet Silver ConductorAG-IJ-G-100-S1 China ink NM) be coated to soda-lime glass smooth, that 1.6mm is thick from Cabot Printable Electronicsand Displays.It is typical that printing parameter is set for ink jet printing.After having printed conductive ink, 200,300,400 with 500 ℃ temperature under in convection current baking oven or drying oven to the sample solidifies of separating 20 minutes.Utilize talysurf (Dektek) to measure the thickness of cured film and calculated body resistivity.
| Solidification temperature (℃) | Set time (min) | Thickness (μ m) (avg.of 3) | Body resistivity (μ Ω cm) (avg.of 3) |
| 200 | 20 | 0.87 | 10.63 |
| 300 | 20 | 1.06 | 4.24 |
| 400 | 20 | 0.86 | 2.90 |
| 500 | 20 | 1.00 | 3.11 |
By the adhesiveness between band disbonded test evaluated for film and the substrate.After the curing, splicing tape is applied to this film and it is removed with the effect of peeling off.Rating 1 expression has removed this film by this band.Rating 5 expressions remove by this band and do not influence this film.Thereby removed the mediant of how much having specified of this film by band.
| Solidification temperature (℃) | Set time (min) | Adhesiveness (1-5) |
| 200 | 20 | 1 |
| 300 | 20 | 3 |
| 400 | 20 | 5 |
| 500 | 20 | 5 |
Example 2
Utilize and example 1 similar equipment and printing parameter setting, will (Seoul, Silverjet DGH 50LT-25CIA China ink Korea) be coated to soda-lime glass smooth, that 1.6mm is thick from AdvancedNano Products.After having printed conductive ink, 250,350,450 with 560 ℃ temperature under in convection current baking oven or drying oven to the sample solidifies of separating 20 minutes.Utilize talysurf (Dektek) to measure the thickness and the calculating body resistivity of cured film.
| Solidification temperature (℃) | Set time (min) | Thickness (μ m) (avg.of 3) | Body resistivity (μ Ω cm) (avg.of 3) |
| 250 | 20 | 3.45 | 11.64 |
| 350 | 20 | 3.06 | 10.69 |
| 450 | 20 | 2.50 | 9.65 |
| 560 | 20 | 1.48 | 3.34 |
Come adhesiveness between evaluated for film and the substrate by the band disbonded test described in example 1.Rating 1 expression has removed this film by this band.Rating 5 expressions remove by this band and do not influence this film.Removed the mediant of how much having specified of this film by band.
| Solidification temperature (℃) | Set time (min) | Adhesiveness (1-5) |
| 250 | 20 | 1 |
| 350 | 20 | 1 |
| 450 | 20 | 5 |
| 560 | 20 | 5 |
Example 3
Utilize and example 1 similar equipment and printing parameter setting, will (Seoul, Silverjet DGH 50HT-25CIA China ink Korea) be coated to soda-lime glass smooth, that 1.6mm is thick from AdvancedNano Products.After having printed conductive ink, 250,350,450 with 560 ℃ temperature under in convection current baking oven or drying oven to the sample solidifies of separating 20 minutes.Utilize talysurf (Dektek) to measure the thickness of cured film and calculated body resistivity.
| Solidification temperature (℃) | Set time (min) | Thickness (μ m) (avg.of 3) | Body resistivity (μ Ω cm) (avg.of 3) |
| 250 | 20 | 5.38 | 18.17 |
| 350 | 20 | 5.29 | 17.23 |
| 450 | 20 | 5.31 | 17.89 |
| 560 | 20 | 3.28 | 7.39 |
Come adhesiveness between evaluated for film and the substrate by the band disbonded test described in example 1.Rating 1 expression has removed this film by this band.Rating 5 expressions remove by this band and do not influence this film.Removed the mediant of how much having specified of this film by band.
| Solidification temperature (℃) | Set time (min) | Adhesiveness (1-5) |
| 250 | 20 | 1 |
| 350 | 20 | 1 |
| 450 | 20 | 5 |
| 560 | 20 | 5 |
Example 4
Utilize and example 1 similar equipment and printing parameter setting, will (Seoul, Silverjet DGH 50HT-50CIA China ink Korea) be coated to soda-lime glass smooth, that 1.6mm is thick from AdvancedNano Products.After having printed conductive ink, 560 ℃ in stove to the sample solidifies of separating 20,40 and 60 minutes.Utilize talysurf (Dektek) to measure the thickness of cured film and calculated body resistivity.
| Solidification temperature (℃) | Set time (min) | Thickness (μ m) (avg.of 3) | Body resistivity (μ Ω cm) (avg.of 3) |
| 560 | 20 | 0.72 | 2.45 |
| 560 | 40 | 0.60 | 2.24 |
| 560 | 60 | 0.78 | 1.94 |
Come adhesiveness between evaluated for film and the substrate by the band disbonded test described in example 1.Rating 1 expression has removed this film by this band.Rating 5 expressions remove by this band and do not influence this film.Removed the mediant of how much having specified of this film by band.
| Solidification temperature (℃) | Set time (min) | Adhesiveness (1-5) |
| 560 | 20 | 5 |
| 560 | 40 | 5 |
| 560 | 60 | 5 |
Example 5
Utilize that masterplate will (Rocky Hill, NJ) Parmod VLTGXA-100 silver China ink be coated to soda-lime glass smooth, that 1.6mm is thick to form 2.54mm * 7.5cm trace from Parelec company.Then 250,300 with 350 ℃ temperature under in convection current baking oven or drying oven to the sample solidifies of separating 20 minutes.Utilize micrometer to measure the thickness of cured film and calculated body resistivity.
| Solidification temperature (℃) | Set time (min) | Thickness (μ m) (avg.of 3) | Body resistivity (μ Ω cm) (avg.of 3) |
| 250 | 20 | 14.00 | 7.6 |
| 300 | 20 | 15.70 | 6.2 |
| 350 | 20 | 10.00 | 5.7 |
Come adhesiveness between evaluated for film and the substrate by the band disbonded test described in example 1.Rating 1 expression has removed this film by this band.Rating 5 expressions remove by this band and do not influence this film.Removed the mediant of how much having specified of this film by band.
| Solidification temperature (℃) | Set time (min) | Adhesiveness (1-5) |
| 250 | 20 | 3 |
| 300 | 20 | 5 |
| 350 | 20 | 5 |
Example 6
Utilize that masterplate will (Rocky Hill, NJ) Parmod VLTGXA-100 silver China ink be coated to the soda-lime glass plane, that 1.6mm is thick to form 2.54mm * 7.5cm trace from Parelec company.Then under 300 ℃ the temperature in convection current baking oven or drying oven to the sample solidifies of separating 10,20 and 30 minutes.Utilize micrometer to measure the thickness of cured film and calculated body resistivity.
| Solidification temperature (℃) | Set time (min) | Thickness (μ m) (avg.of 3) | Body resistivity (μ Ω cm) (avg.of 3) |
| 300 | 10 | 11.67 | 5.2 |
| 300 | 20 | 15.67 | 6.8 |
| 300 | 30 | 18.33 | 7.9 |
Come adhesiveness between evaluated for film and the substrate by the band disbonded test described in example 1.Rating 1 expression has removed this film by this band.Rating 5 expressions remove by this band and do not influence this film.Removed the mediant of how much having specified of this film by band.
| Solidification temperature (℃) | Set time (min) | Adhesiveness (1-5) |
| 300 | 10 | 5 |
| 300 | 20 | 5 |
| 300 | 30 | 5 |
Example 7
Utilization is from MicroFab Technologies (Plano, TX) JetDrive III driver of Huo Deing and MJ-AB-01 40 μ m ink guns, will (Albuquerque, Inkjet Silver ConductorAG-IJ-G-100-S1 China ink NM) be coated to soda-lime glass smooth, that 1.6mm is thick from Cabot Printable Electronicsand Displays.It is typical that printing parameter is set for ink jet printing.After having printed conductive ink, under 200 ℃ in drying oven to the sample solidifies of separating 20 minutes.Utilize spectrophotometer (Gretag MacbethColoreye 7000A) to measure the reflectivity of cured film.Can in Fig. 7, see the reflectivity result.
Claims (59)
1. method that is used to make electric driven color-changing part, this method comprises:
Provide have first surface, with first substrate of first surface opposing second surface and first edge surface;
The 3rd surface that has towards second surface, four surface relative with the 3rd surface and second substrate of second edge surface are provided;
Electrochromic media between first and second substrates is provided, and wherein said electrochromic media has when transmittance variable when it applies electric field; With
Coated with conductive layer at least a portion of one selecting at least of first surface, second surface, first edge surface, the 3rd surface, the 4th surface and second edge surface, wherein the coating of conductive layer be under basic atmospheric pressure, finish and comprise select at least in metallizing particle, organic metal, metallorganics and the combination thereof a kind of, and wherein conductive layer has body resistivity more than or equal to 150 μ Ω cm, and wherein conductive layer is mirror reflection.
2. method according to claim 1, wherein the step of coated with conductive layer provides the conductive layer of body resistivity more than or equal to 100 μ Ω cm.
3. method according to claim 2, wherein the step of coated with conductive layer provides the conductive layer of body resistivity more than or equal to 50 μ Ω cm.
4. method according to claim 1, wherein the step of coated with conductive layer provides valley roughness to be less than or equal to the conductive layer of 20nm.
5. method according to claim 4, wherein the step of coated with conductive layer provides valley roughness to be less than or equal to the conductive layer of 10nm.
6. method according to claim 5, wherein the step of coated with conductive layer provides valley roughness to be less than or equal to the conductive layer of 5nm.
7. method according to claim 1, wherein the step of the coated with conductive layer wavelength place reflectivity that is provided at about 550nm is more than or equal to 35% conductive layer.
8. method according to claim 7, wherein the step of the coated with conductive layer wavelength place reflectivity that is provided at about 550nm is more than or equal to 55% conductive layer.
9. method according to claim 8, wherein the step of the coated with conductive layer wavelength place reflectivity that is provided at about 550nm is more than or equal to 70% conductive layer.
10. method according to claim 1, the wherein conductive layer of the step cremasteric reflex of coated with conductive layer.
11. method according to claim 1, wherein the step of coated with conductive layer provides the conductive layer of transmission.
12. method according to claim 1, wherein the step of coated with conductive layer provides the conductive layer of half reflection.
13. method according to claim 1, wherein the step of coated with conductive layer comprises the plated metal nano particle.
14. method according to claim 1, wherein the step of coated with conductive layer further comprises the organic metallic metal precursor of deposition.
15. method according to claim 1, wherein the step of coated with conductive layer comprises select at least in ink jet printing, ultrasonic spray, helicoidal pump spraying, the jetting pump spraying a kind of.
16. method according to claim 1 further comprises:
After the step of coated with conductive layer, solidify this conductive layer.
17. method according to claim 16, wherein curing schedule comprises by using of selecting at least in UV light, microwave and the convective heating and solidifies this conductive layer.
18. method according to claim 1, wherein the step of coated with conductive layer comprises provides conductive layer as being applied to one the electrode of selecting at least in second surface and the 3rd surface.
19. method according to claim 1, wherein the substrate to its coated with conductive layer comprises glass.
20. method according to claim 1, wherein the step of coated with conductive layer further comprise chemical vapor deposition, flame spraying deposition and laser sintered in select at least a kind of.
21. a method that is used to make electric driven color-changing part, this method comprises:
Provide have first surface, with first substrate of first surface opposing second surface and first edge surface;
The 3rd surface that has towards second surface, four surface relative with the 3rd surface and second substrate of second edge surface are provided;
Provide electrochromic media between first and second substrates, wherein this electrochromic media has at transmittance variable when it applies electric field; With
At least ink jet printing conductive layer at least a portion of one selecting in described surface, second surface, first edge surface, the 3rd surface, the 4th surface and second edge surface, wherein conductive layer is mirror reflection.
22. method according to claim 21, wherein the step of ink jet printing comprises select at least in metallizing particle, organic metal, metallorganics and the combination thereof a kind of.
23. method according to claim 22, wherein the step of ink jet printing comprises the coated with nano metallic particles.
24. method according to claim 21, wherein the step of ink jet printing provides the conductive layer as semi-reflective layer.
25. method according to claim 21, wherein the step of ink jet printing further comprises select at least in organic metallic metal precursor of deposition and the metal Organometallic precursor a kind of.
26. method according to claim 21 further comprises:
Curing conductive layer after the ink jet printing step.
27. method according to claim 26, wherein curing schedule comprises select at least in application UV light, microwave and the convective heating a kind of.
28. method according to claim 21 further comprises:
Curing conductive layer in position during the ink jet printing step.
29. method according to claim 21, wherein the step of ink jet printing comprises provides conductive layer as being applied to one the electrode of selecting at least in second surface and the 3rd surface.
30. method according to claim 21, wherein the substrate to its coated with conductive layer comprises glass.
31. a method that is used to make electric driven color-changing part, this method comprises:
Provide have first surface, with first substrate of first surface opposing second surface and first edge surface;
The 3rd surface that has towards second surface, four surface relative with the 3rd surface and second substrate of second edge surface are provided;
Provide electrochromic media between first and second substrates, wherein electrochromic media has when transmittance variable when it applies electric field; With
Ultrasonic spray conductive layer at least a portion of one selecting at least of first surface, second surface, first edge surface, the 3rd surface, the 4th surface and second edge surface, wherein conductive layer is mirror reflection.
32. method according to claim 31, wherein the ultrasonic spray step comprises select at least in metallizing particle, organic metal, metallorganics and the combination thereof a kind of.
33. method according to claim 31, wherein the step of coated with conductive layer provides the conductive layer of half reflection.
34. method according to claim 31, wherein the step of ultrasonic spray comprises one that selects at least in organic metallic metal precursor of deposition and the metal Organometallic precursor.
35. method according to claim 31 further comprises:
Curing conductive layer after the ultrasonic spray step.
36. method according to claim 35, wherein the ultrasonic spray step comprises by using of selecting at least in UV light, microwave and the convective heating and solidifies this conductive layer.
37. method according to claim 35 further comprises:
Curing conductive layer in position during the ultrasonic spray step.
38. method according to claim 31, wherein the step of ultrasonic spray comprises provides conductive layer as being applied to one the electrode of selecting at least in second surface and the 3rd surface.
39. method according to claim 31, wherein the substrate to its coated with conductive layer comprises glass.
40. a method that is used to make electric driven color-changing part, this method comprises:
Provide have first surface, with first substrate of first surface opposing second surface and first edge surface;
The 3rd surface that has towards second surface, four surface relative with the 3rd surface and second substrate of second edge surface are provided;
Provide electrochromic media between first and second substrates, wherein said electrochromic media has when transmittance variable when it applies electric field; With
Coated with conductive layer at least a portion of one in first surface, second surface, first edge surface, the 3rd surface, the 4th surface and second edge surface, selecting at least, wherein the coated with conductive layer comprises select at least in helicoidal pump spraying and the jetting pump spraying a kind of, and wherein conductive layer is mirror reflection.
41. according to the described method of claim 40, wherein the step of coated with conductive layer comprises select at least in metallizing particle, organic metal, metallorganics and the combination thereof a kind of.
42. according to the described method of claim 41, wherein the step of coated with conductive layer comprises the coated with nano metallic particles.
43. according to the described method of claim 40, wherein the step of coated with conductive layer provides the conductive layer of half reflection.
44. according to the described method of claim 40, wherein the step of coated with conductive layer further comprises select at least in organic metallic metal precursor of deposition and the metal Organometallic precursor a kind of.
45., further comprise according to the described method of claim 40:
Curing conductive layer after the step of coated with conductive layer.
46. according to the described method of claim 45, wherein curing schedule comprises one that selects at least in application UV light, microwave and the convective heating.
47., further comprise according to the described method of claim 40:
Curing conductive layer in position during coated with conductive layer step.
48. according to the described method of claim 40, wherein the step of coated with conductive layer comprises provides conductive layer as being applied to one the electrode of selecting at least in second surface and the 3rd surface.
49. according to the described method of claim 40, wherein the substrate to its coated with conductive layer comprises glass.
50. a method that is used to make electric driven color-changing part, this method comprises:
Provide have first surface, with first substrate of first surface opposing second surface and first edge surface;
The 3rd surface that has towards second surface, four surface relative with the 3rd surface and second substrate of second edge surface are provided;
Provide electric driven color-changing part between first and second substrates, wherein electrochromic media has when transmittance variable when it applies electric field; With
Coated with conductive layer at least a portion of one in first surface, second surface, first edge surface, the 3rd surface, the 4th surface and second edge surface, selecting at least, wherein the coated with conductive layer comprise combustion chemical vapor deposition, flame spraying deposition and laser sintered in select at least a kind of, and wherein conductive layer is mirror reflection.
51. according to the described method of claim 50, wherein the step of coated with conductive layer comprises select at least in metallizing particle, organic metal, metallorganics and the combination thereof a kind of.
52. according to the described method of claim 51, wherein the step of coated with conductive layer comprises the coated with nano metallic particles.
53. according to the described method of claim 50, wherein the step of coated with conductive layer provides the conductive layer of half reflection.
54. according to the described method of claim 50, wherein the step of coated with conductive layer further comprises the deposition inorganic metallic precursor.
55., further comprise according to the described method of claim 50:
Curing conductive layer after the step of coated with conductive layer.
56. according to the described method of claim 55, wherein curing schedule comprises one that selects at least in application UV light, microwave and the convective heating.
57., further comprise according to the described method of claim 50:
Curing conductive layer in position during coated with conductive layer step.
58. according to the described method of claim 50, wherein the step of coated with conductive layer comprises provides conductive layer as being applied to one the electrode of selecting at least in second surface and the 3rd surface.
59. according to the described method of claim 50, wherein the substrate to its coated with conductive layer comprises glass.
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| US60/779,369 | 2006-03-03 | ||
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| 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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Also Published As
| Publication number | Publication date |
|---|---|
| CN101438205B (en) | 2011-09-28 |
| CN101395521A (en) | 2009-03-25 |
| CN101395521B (en) | 2010-09-29 |
| CN101438205A (en) | 2009-05-20 |
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