CN101421666A - Photovoltaic element comprising a metal film and method for the application thereof - Google Patents

Abstract

A method for manufacturing an electrochromic element includes: providing a first substrate having first and second surfaces and a first edge surface, providing a second substrate having third and fourth surfaces and a second edge surface, the third surface facing the second surface, providing an electrochromic medium between the first and second substrates, the medium having a light transmittance that is variable when an electric field is applied thereto; coating a conductive layer on a portion of at least one of the surfaces, wherein the coating of the conductive layer is accomplished at substantially atmospheric pressure and at least one of metal particles, organometallic, metallorganic, and combinations thereof is applied, wherein the conductive layer has a bulk resistivity greater than or equal to 150 micro-ohm-cm. The conductive layer may be applied via spray coating, ultrasonic spray coating, screw pump spray coating, or jet pump spray coating.

Description

Photoelectric element including metal film and method of application thereof

Cross References to Related Applications

This application claims U.S. Provisional Application Nos. 60/779,369, filed March 3, 2006, entitled IMPROVEDCOATINGS AND REARVIEW ELEMENTS INCORPORATING THE COATINGS, and filed June 5, 2006, entitled ELECTROCHROMIC REARVIEW MIRRORASSEMBLY INCORPORATING A DISPLAY/SIGNAL LIGH 60/810,921 of US Provisional Application No. 60/810,921, all of which are hereby incorporated by reference, and filed June 8, 2004, entitled REARVIEW MIRROR ELEMENTHAVING A CIRCUIT MOUNTED TO THE REAR SURFACE OFTHE ELEMENT Continuation-in-Part of US Patent Application No. 10/863,638.

technical field

The present invention relates to electrochromic elements as used in rear view mirror assemblies for motor vehicles and in window assemblies, and more particularly to improved electrochromic elements for use in such assemblies. More specifically, the invention relates to electrochromic elements comprising a conductive layer deposited at atmospheric pressure without compromising the relative bulk conductivity value.

Background technique

)。已提出了对于电磁辐射可逆可变透射的器件作为可变透射滤光器、可变反射镜和显示器中的可变透射元件，其在传送信息时采用了这样的滤光器或反射镜。Heretofore, various rearview mirrors for motor vehicles have been proposed, which are changed from a total reflection mode (daytime) to a partial reflection mode (night) for preventing the light from headlights of vehicles approaching from behind from being dazzled. Similarly, variable transmission filters have been proposed for architectural windows, sunroofs, interior windows, sunroofs and rear view mirrors of automobiles, as well as for windows or other vehicles such as aircraft portholes. Devices are those in which the transmittance is altered by thermochromic, photochromic, or optoelectronic devices (e.g. liquid crystals, dipole suspensions, electrophoresis, electrochromism, etc.) and the variable transmission properties affect at least part of the electromagnetic spectrum in the visible spectrum. Radiation (wavelength from approx. to appointment

). Devices of reversibly variable transmission for electromagnetic radiation have been proposed as variable transmission filters, variable mirrors and variable transmission elements in displays which employ such filters or mirrors when transmitting information.

For example, "Electrochromic and Electrochemichromic Materials and Phenomena" by Chang in Non-emissive Electrooptic Displays, A. Kmetz and K. von Willisen, eds. Plenum Press, NewYork, NY 1976, pp. 155-196 (1976) and P.M.S. Monk, R.J.Mortimer, D.R.Rosseinsky, VCH Publishers, Inc., New York, New York (1995), in various parts of Electrochromism, describe devices for reversibly variable transmission of electromagnetic radiation in which the transmittance is varied by an electrochromic device . Numerous electrochromic devices are known in the art. See, eg, Manos, U.S. Patent No. 3,451,741; Bredfeldt et al., U.S. Patent No. 4,090,358; Clecak et al., U.S. Patent No. 4,139,276; Kissa et al., U.S. Patent No. 3,453,038; Rogers, U.S. Patent Nos. 3,652,149, 3,774,988, and 3,873,185; Jones et al., US Patent Nos. 3,282,157, 3,282,158, 3,282,160, and 3,283,656. In addition to these devices, there are commercially available electrochromic devices and associated circuits, as described in H.J. Byker, February 20, 1990, entitled "SINGLE-COMPARTMENT, SELF-ERASING, SOLUTION-PHASEELECTROCHROMIC DEVICES SOLUTIONS FOR USE THEREIN, AND USES THEREOF" U.S. Patent No. 4,902,108; J.H. Bechtel et al. published on May 19, 1992, entitled "AUTOMATIC REARVIEW MIRROR SYSTEM FOR AUTOMOTIVE VEHICLES" Canadian Patent No. 1,300,945; H.J.Byker in July 1992 U.S. Patent No. 5,128,799, titled "VARIABLE REFLECTANCE MOTOR VEHICLE MIRROR," published on 7th; U.S. Patent No. 5,202,787, titled "ELECTRO-OPTIC DEVICE," published by H.J. Byker et al. on April 13, 1993; U.S. Patent No. 5,204,778, J.H. Bechtel, published April 20, 1993, entitled "CONTROL SYSTEM FORAUTOMATIC REARVIEW MIRRORS"; U.S. Patent No. 5,278,693 of "; U.S. Patent No. 5,280,380 of H.J. Byker published on January 18, 1994, entitled "UV-STABILIZED COMPOSITIONS AND METHODS"; U.S. Patent No. 5,282,077 for "VARIABLE REFLECTANCE MIRROR"; U.S. Patent No. 5,294,376 issued to H.J. Byker on March 15, 1994, entitled "BIPYRIDINIUM SALTSOLUTIONS"; U.S. Patent No. 5,336,448 entitled "ELECTROCHROMIC DEVICES WITHBIPYRIDINIUM SALT SOLUTIONS"; F.T. Bauer et al., published January 18, 1995, entitled "AUT OMATICREARVIEW MIRROR INCORPORATING LIGHT PIPE" U.S. Patent No. 5,434,407; W.L. Tonar published on September 5, 1995, entitled "OUTSIDE AUTOMATIC REARVIEW MIRROR FORAUTOMOTIVEVE HICLES" U.S. Patent No. 5,448,397; and J.H.Bechtel et al. Disclosed in US Patent No. 5,451,822, issued September 19, entitled "ELECTRONIC CONTROL SYSTEM." Each of these patents collectively specifies the present invention and is hereby incorporated by reference in its entirety, including the disclosure of each contained herein. These electrochromic devices can be used in fully integrated interior/exterior mirror systems or as separate interior or exterior mirror systems and/or variable transmission windows.

Fig. 1 shows a cross-sectional view of a typical electrochromic mirror device 10 having a front planar substrate 12 and a rear planar substrate 16 and a common layout is known. A transparent conductive coating 14 is disposed on the rear surface of the front substrate 12 , and another transparent conductive coating 18 is disposed on the front surface of the rear substrate 16 . Disposed on the rear surface of the rear substrate 16 is a reflector 20 that generally includes a silver metal layer 20a covered by a protective copper metal layer 20b and one or more layers of protective paint 20c. To describe this structure clearly, sometimes the front surface 12a of the front substrate 12 is referred to as the first surface, and the inner (or rear) surface 12b of the front substrate 12 is sometimes referred to as the second surface, and the inner surface of the rear substrate 16 is sometimes referred to as the second surface. 16a is referred to as a third surface, and the rear surface 16b of the rear substrate 16 is sometimes referred to as a fourth surface. In the example shown, the front substrate also includes an edge surface 12c, while the rear substrate includes an edge surface 16c. The front and rear substrates 12 , 16 are held in parallel and spaced apart relationship by an encapsulant 22 , thereby creating a chamber 26 . The electrochromic medium 24 is contained in a compartment or chamber 26 . The electrochromic medium 24 is in direct contact with the transparent electrode layers 14 and 18, through which electromagnetic radiation passes, and in this device a variable voltage is applied to the electrode layers 14 and 18 through clip contacts and electronic circuitry (not shown) Or potential reversibly modulates the intensity of electromagnetic radiation.

The electrochromic medium 24 disposed in the chamber 26 may include surface-confined, electrode-site-type or solution-phase-type electrochromic materials and combinations thereof. In all liquid media, the electrochemical properties of the solvent, optional inert electrolyte, anode material, cathode material and any other components that may be present in solution are preferably such that no significant electrochemical or Other variations, the potential difference oxidizes the anode material and reduces the cathode material, rather than electrochemical oxidation of the anode material, electrochemical reduction of the cathode material, and self-erasing between the oxidized form of the anode material and the reduced form of the cathode material reaction.

In most cases, when there is no potential difference between transparent conductors 14 and 18, electrochromic medium 24 in chamber 26 is substantially colorless or nearly colorless, and incident light (I ₀ ) enters and passes through front substrate 12, through through clear coat 14 , electrochromic medium 24 in chamber 26 , clear coat 18 , rear substrate 16 , and reflect off layer 20 a and back through the device and out of front substrate 12 . Typically, the magnitude of the reflected image (I _R ) without potential difference is about 45% to about 85% of the incident light intensity (I ₀ ). The exact value depends on a number of variables outlined below, such as the absorptivity of the various components, the residual reflection (I' _R ) from the front of the front substrate, and the Secondary reflection of the electrochromic medium 24 , the electrochromic medium 24 and the second transparent electrode 18 , and the interface between the second transparent electrode 18 and the rear substrate 16 . These reflections are well known in the art and are due to the difference in refractive index between one material and another as light passes through the interface between the two materials. If the front substrate and back element are not parallel, residual reflections (I' _R ) or other secondary reflections will not coincide with the reflected image (I _R ) from mirror surface 20a, and ghosting will occur (the observer will see double (or triple) the number of objects that are actually present in the reflected image).

There are minimum requirements on the magnitude of the reflected image, depending on whether the electrochromic mirror is placed inside or outside the vehicle. For example, according to the current requirements of most automobile manufacturers, the inner mirror preferably has a high-end reflectivity of at least 70%, and the outer mirror must have a high-end reflectivity of at least 35%.

Electrode layers 14 and 18 are connected to electronic circuitry that effectively electrically activates the electrochromic medium so that when a potential is applied across conductors 14 and 18, the electrochromic medium in chamber 26 turns black such that when light is directed toward mirror 20a The incident light (I ₀ ) is attenuated as it propagates and passes back after being reflected. By adjusting the potential difference between the transparent electrodes, this device can be used as a "gray scale" device with a wide range of continuously variable transmittance. For liquid-phase electrochromic systems, when the potential between the electrodes is removed or returned to zero, the device spontaneously returns to the same, zero potential, balanced color and transmittance that the device had before the potential was applied. For making electrochromic devices, other electrochromic materials can be utilized. For example, an electrochromic medium may include an electrochromic material that is a solid metal oxide, a redox-active polymer, and a mixed combination of a liquid phase and a solid metal oxide or a redox-active polymer; however, the liquid phase The design is typical of most electrochromic devices in use today.

Even before fourth surface reflector electrochromic mirrors such as the one shown in Figure 1 were commercially available, various groups working on electrochromic devices had discussed moving the reflector from the fourth surface to the third surface. This design has the advantage that in theory it should be easier to manufacture since fewer layers are packed into the device, ie a third surface transparent electrode is not necessary when a third surface reflector/electrode is present. Although the concept was described as early as 1996, no team has achieved commercial success because the de facto standard calls for a working auto-dimming mirror with an integrated third-surface reflector. U.S. Patent No. 3,280,701, J.F. Donnelly et al., entitled "OPTICALLY VARIABLE ONE-WAY MIRROR," issued October 25, 1966, has a third surface for a system for attenuating light with pH-induced color changes One of the earliest discussions of reflectors.

U.S. Patent No. 5,066,112, issued November 19, 1991, to N.R. Lynam et al., entitled "PERIMETER COATED, ELECTRO-OPTIC MIRROR," teaches a Photoelectric mirror with conductive coating around the component. Although third surface reflectors are discussed here, the materials listed as useful for third surface reflectors suffer from defects of insufficient reflectivity for endoscopes, and/or when combined with at least A liquid-phase electrochromic material is affected by defects that are unstable when in contact with the liquid-phase electrochromic medium.

Others have proposed articles with reflectors/electrodes placed in the middle of all solid state types of devices. For example, U.S. Patent Nos. 4,762,401, 4,973,141, and 5,069,535 to Baucke et al. teach electrochromic mirrors having the following structure: glass element, transparent indium tin oxide electrode, tungsten oxide electrochromic layer, solid ion conducting layer, single layer hydrogen Ion permeable reflector, solid state ion conducting layer, hydrogen ion storage layer, catalytic layer, rear metal layer and back element (representing conventional third and fourth surfaces). The reflector is not deposited on the third surface and is not in direct contact with the electrochromic material, and certainly not in contact with at least one liquid-phase electrochromic material and associated medium. Accordingly, it would be desirable to provide an improved high reflectivity electrochromic rearview mirror having a third surface reflector/electrode in contact with a liquid-phase electrochromic medium comprising at least one electrochromic material. Proposed electrochromic windows generally comprise electrochromic cells similar to those shown in Figure 1, but without layers 20a, 20b and 20c.

Whether deposited on the first, second, third, fourth, or edge surfaces of the substrate, metals comprising films or layers that are conductive, reflective, or both are important in the construction of electrochromic optoelectronic devices and integrated electronics encapsulated therewith. are very useful in chromic devices. In general, as conductance increases; as adhesion properties increase; as layer pattern complexity increases; as reflectivity increases while maintaining neutral color reflection; as chemical and electrochemical stability increases; and as ease of coating increases; The versatility and utility of metal films or multilayer metal films increases.

Various attempts have been made to provide an electrochromic element with a conductive layer on the surface of a substrate associated with the electrochromic element as described above. One such approach involves the use of resins loaded with metal particles, such as epoxy resins loaded with silver flakes. However, the conductivity of such systems can be limited by the large number of particle-to-particle connections that must be made to conduct electrical current. Each particle-to-particle connection increases electrical resistance, thereby limiting the effectiveness of the metal particle-loaded resin. Currently, specular-quality mirror light reflections cannot be obtained from these films because the random orientation of the relatively large metal particles promotes diffuse reflection. To avoid these limitations, it is desirable to deposit metal films that more closely approximate the properties of bulk metals. Conductive and reflective metal films that closely approximate the properties of bulk metals are chemically and electrochemically robust to adhere well to applicable substrates and can be deposited using vacuum processes such as sputtering or evaporation. However, equipment based on vacuum processes is expensive to purchase, operate and maintain. Depositing patterned films using vacuum-based processes is difficult. One method of patterning vacuum-coated metal films requires the metal to be applied through a mask during deposition. Such masks are expensive to machine and difficult to maintain. Another method of patterning vacuum-coated metal films requires removal of the metal after deposition by additional processing steps such as laser ablation or chemical etching. Besides adding to the complexity of the overall manufacturing process, the aforementioned sputtering or evaporation processes are not efficient when using metals or metal precursors. Specifically, during vacuum processing, sufficient amounts of metal are deposited on the mask and surrounding structures, rather than on the desired device, whose scrap recycling would be costly and time consuming.

It is therefore desirable to fabricate metallic films within electrochromic or other optoelectronic devices at conditions near atmospheric pressure, specifically at atmospheric pressure, and to provide sufficient electrical conductivity, adhesion, and reflective properties while maintaining neutral color reflection, sufficient Chemical and electrochemical stability while allowing for increased coating control.

Contents of the invention

One aspect of the present invention includes a method of manufacturing an electrochromic element, the method comprising providing a first substrate having a first surface, a second surface opposite the first surface, and a first edge surface; A third surface of the surface, a fourth surface opposite to the third surface, and a second substrate of the second edge surface; an electrochromic medium is provided between the first and second substrates, wherein the electrochromic medium has Variable light transmittance when an electric field is applied. The method further includes coating a conductive layer on at least a portion of at least a selected one of the first surface, the second surface, the first edge surface, the third surface, the fourth surface, and the second edge surface, wherein the coating of the conductive layer is done at substantially atmospheric pressure and includes the use of selected ones of metallic particles, organometallics, metal organics, and combinations thereof, wherein the conductive layer has a volume resistivity greater than or equal to 150 μΩ·cm.

Another aspect of the inventive method for manufacturing an electrochromic element comprises: providing a first substrate having a first surface, a second surface opposite to the first surface, and a first edge surface; The third surface of the two surfaces, the fourth surface opposite to the third surface, and the second substrate of the second edge surface; and providing an electrochromic medium between the first and second substrates, wherein the electrochromic medium has when Variable light transmittance when an electric field is applied to it. The method further includes inkjet printing a conductive layer on at least a portion of at least a selected one of the surface, the second surface, the first edge surface, the third surface, the fourth surface, and the second edge surface.

Another aspect of the method of the present invention includes: providing a first substrate having a first surface, a second surface opposite the first surface, and a first edge surface; providing a third surface facing the second surface, and the third surface an opposite fourth surface, and a second substrate of the second edge surface; and providing an electrochromic medium between the first and second substrates, wherein the electrochromic medium has a light transmittance that is variable when an electric field is applied thereto . The method further includes ultrasonically spraying the conductive layer on at least a portion of at least a selected one of the first surface, the second surface, the first edge surface, the third surface, the fourth surface, and the second edge surface.

Another aspect of the method of the present invention includes: providing a first substrate having a first surface, a second surface opposite to the first surface, and a first edge surface; providing a third surface facing the second surface, and a third a fourth surface opposite to the surface, and a second substrate of the second edge surface; and providing an electrochromic medium between the first and second substrates, wherein the electrochromic medium has variable light transmission when an electric field is applied thereto Rate. The method further includes applying a conductive layer to at least a portion of at least a selected one of the first surface, the second surface, the first edge surface, the third surface, the fourth surface, and the second edge surface, wherein applying the conductive layer includes At least one selected from screw pump spraying and jet pump spraying.

Another aspect of the inventive method for manufacturing an electrochromic element comprises: providing a first substrate having a first surface, a second surface opposite to the first surface, and a first edge surface; The third surface of the two surfaces, the fourth surface opposite to the third surface, and the second substrate of the second edge surface; and providing an electrochromic medium between the first and second substrates, wherein the electrochromic medium has when Variable light transmittance when an electric field is applied to it. The method further includes applying a conductive layer to at least a portion of at least a selected one of the first surface, the second surface, the first edge surface, the third surface, the fourth surface, and the second edge surface, wherein applying the conductive layer includes At least one selected from combustion chemical vapor deposition, flame spray deposition, and laser sintering.

These and other features, advantages and objects of the present invention will be better understood and appreciated by those skilled in the art by referring to the following specification, claims and drawings.

Description of drawings

In the picture:

Figure 1 is an enlarged cross-sectional view of a prior art electrochromic mirror assembly incorporating a fourth surface reflector;

2 is a front view schematically showing an interior/exterior electrochromic rearview mirror system for a motor vehicle;

Figure 3 is an enlarged cross-sectional view of an electrochromic mirror incorporating a third surface reflector/electrode along line III-III of Figure 2;

Figure 4 is a flow chart illustrating the sequence of the method of the present invention;

Figure 5 is a schematic cross-sectional view of a substrate and bulk metal coating with a larger crystal structure;

Figure 6 is a schematic cross-sectional view of a substrate and bulk metal coating with a small crystal structure; and

7 is a graph of wavelength versus reflectance for Example 7. FIG.

Detailed ways

For purposes of illustration herein, the terms "upper", "lower", "right", "left", "rear", "front", "vertical", "horizontal" and their derivatives refer to the invention oriented as in Figure 2 . However, it is to be understood that the invention may assume various alternative orientations and step sequences, unless expressly stated to the contrary. It is also to be understood that the specific devices and processes shown in the drawings and described in the following description are exemplary embodiments of the invention, unless otherwise stated in the appended claims. Accordingly, specific dimensions and other physical characteristics relating to the embodiments disclosed herein are not to be considered as limiting, unless the claims expressly state otherwise.

Figure 2 shows a front view schematically showing the interior mirror assembly 110 and two exterior rear view mirror assemblies 111a and 111b for the driver's side and passenger side respectively, all of which are suitable for use in conventional The way and said mirror are mounted on the motor vehicle facing the rear of the vehicle and can be seen by the driver of the vehicle to provide a rear view. Although the invention is generally described herein in terms of mirror assemblies, it is noted that the invention is equally applicable to the construction of electrochromic windows. The inner mirror assembly 110 and the exterior rearview mirror assemblies 111a, 111b may incorporate light sensing electronics of the type shown and described in the aforementioned Canadian Patent No. 1,300,945, U.S. Patent No. 5,204,778, or U.S. Patent No. Dazzle light and ambient light and supply driving voltage to other circuits of the electrochromic element. In the example shown, electronics 150 connect and allow control of the potential applied across reflector/electrode 120 and transparent electrode 128 such that electrochromic medium 126 darkens and thereby attenuates varying amounts of light traveling therethrough , and thereby change the reflectivity of the mirror comprising the electrochromic medium 126 . The mirror assemblies 110, 111a, 111b are similar in that like reference numerals designate parts of the inner and outer mirrors. These components may have slightly different structures, but function substantially the same and achieve substantially the same results as similarly labeled components. For example, the shape of the front glass element of the inner mirror 110 is generally longer and narrower than that of the outer mirrors 111a, 111b. There are also some different performance criteria set on the inner mirror 110 compared to the outer mirrors 111a, 111b. For example, when fully cleaned, the inner mirror 110 should generally have a reflectance value of about 70% to about 85% or higher, while the outer mirror generally has a reflectance of about 50% to about 65%. Also, in the US (as supplied by the car manufacturer), the passenger side mirror 111b generally has a spherically curved or convex shape, while the driver's side mirror 111a and inner mirror 110 must currently be flat. In Europe, the driver's side mirror 111a is generally flat or aspherical, while the passenger's side mirror 111b has a convex shape. In Japan, the outer mirrors 111a, 111b both have a convex shape. The following description generally applies to all mirror assemblies of the present invention, while the general concepts apply equally to the construction of electrochromic windows.

3 shows a cross-sectional view of a mirror assembly 111a having a front transparent substrate 112 having a front surface 112a and a rear surface 112b and a rear substrate space 114 having a front surface 114a and a rear surface 114b. In order to describe this structure clearly, the following names will be used hereinafter. The front surface 112a of the front substrate will be referred to as a first surface 112a, and the rear surface 112b of the front substrate will be referred to as a second surface 112b. The front surface 114a of the rear substrate will be referred to as a third surface 114a, and the rear surface 114b of the rear substrate will be referred to as a fourth surface 114b. The front substrate 112 further includes an edge surface 112c, and the rear substrate 114 further includes an edge surface 114c. Chamber 125 is defined by a layer of transparent conductor 128 (supported on second surface 125 ), reflector/electrode 120 (disposed on third surface 114 a ), and inner peripheral wall 132 of seal assembly 116 . An electrochromic medium 126 is contained within chamber 125 .

As broadly used and described herein, an electrode or layer "supported" on or applied to a surface of a component refers to an electrode or layer disposed directly on the surface of the component or disposed on another coating, disposed directly on the surface of the component one or more layers above. Also, note that mirror assembly 111a is described for illustrative purposes only, and that particular components and elements may be rearranged herein, such as the structure shown in FIG. 1 , and those known for electrochromic windows.

The front transparent substrate 112 may be any material that is transparent and has sufficient strength to be able to perform under conditions of varying temperature and pressure such as are commonly found in an automotive environment. The front substrate 112 may comprise any type of borosilicate glass, soda lime glass, float glass or any other material, such as a polymer or plastic, that is transparent in the visible region of the electromagnetic spectrum. The front substrate 112 is preferably a glass sheet. Besides not necessarily being transparent in all applications, the rear substrate 114 must meet the operating conditions outlined above and thus may comprise polymers, metals, glass, ceramics, and preferably a glass sheet.

The coating on the third surface 114a is sealably bonded in spaced apart and parallel relationship to the coating on the second surface 112b by a seal assembly 116 disposed about the outer perimeters of the second surface 112b and the third surface 114a. . Sealing component 116 may be any material capable of adhesively bonding the coating on second surface 112b to the coating on third surface 114a to seal the perimeter so that electrochromic material 126 does not leak from within chamber 125 . Optionally, the layer of transparent conductive coating 128 and the layer of reflector/electrode 120 may be removed over the portion where sealing assembly 116 is located (not the entire portion, otherwise the drive potential cannot be applied to both coatings). In this case, the seal assembly 116 must bond well to the glass.

Performance requirements for perimeter seal assemblies 116 used in electrochromic devices are similar to perimeter seals used in liquid crystal displays (LCDs), and are well known in the art. The seal 116 must have good adhesion to glass, metals, and metal oxides; must have low permeability to oxygen, moisture and other harmful vapors, and indium; and must not interact with electrochromic or liquid crystal materials or Toxic electrochromic or liquid crystal materials, which are meant to contain and protect. Perimeter seal 116 may be applied by means commonly used in the LCD industry, such as by screen printing or dispensing. It is generally possible to use hermetic seals, for example prepared with glass frit or glass for soldering, but the high temperatures involved in handling (typically close to 450°C) this type of seal cause many problems, e.g. glass substrates warping, changes in the properties of the transparent conductive electrodes, and oxidation or degradation of the reflector. Because of their low processing temperatures, thermoplastic, thermosetting or UV-curing organic sealing resins are preferred. Such organic resin sealing systems for LCDs are described in US Pat. Epoxy-based organic sealing resins are preferred because of their excellent adhesion to glass, low oxygen permeability, and good solvent resistance. These epoxy sealants may be UV cured, as described in U.S. Patent No. 4,297,401, or heat cured, such as a mixture of liquid epoxy resins with liquid polyamide resins or dicyandiamide, or they may be homopolymeric of. Epoxy resins may contain fillers or thickeners to reduce flow rate and shrinkage, such as fumed silica, silica, mica, clay, calcium carbonate, alumina, etc. and/or pigments to add color. Pretreated fillers are preferably treated with a hydrophobic or silane surface treatment. Cured resin crosslink density can be controlled by using mixtures of monofunctional, bifunctional and multifunctional epoxy resins and curing agents. Additives such as silanes or titanates can be used to increase the hydrolytic stability of the seal, and spacers such as glass beads or glass rods can be used to control the final seal thickness and substrate spacing. Suitable epoxy resins for the perimeter seal member 116 include, but are not limited to: "EPON RESIN" 813, 825, 826, 828, 830, 834, 862, 1001F, 1002F, 2012 available from Shell Chemical Company of Houston, Texas , DPS-155, 164, 1031, 1074, 58005, 58006, 58034, 58901, 871, 872, and DPL-862; "ARALITE" GY 6010, GY 6020, CY 9579, GT available from New York, Hawthorne, Ciba Geigy 7071, XU 248, EPN 1139, EPN 1138, PY 307, ECN 1235, ECN 1273, ECN 1280, MT 0163, MY 720, MY 0500, MY 0510, and PT 810; and from Dow Chemical Company, Midland, Michigan "D.E.R." 331, 317, 361, 383, 661, 662, 667, 732, 736, "D.E.N." 431, 438, 439, and 444. Suitable epoxy curing agents include V-15, V-25, and V-40 polyamides from Shell Chemical; "AJICURE" PN-23, PN-34, and VDH from Ajinomoto, Tokyo, Japan; "CUREZOL" AMZ, 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 2IZ and 2P4MZ obtained from Shikoku Fine Chemicals; U-405, 24EMI, U-410 and U-415 obtained from New Jersey, Maple Shade, CVC Specialty Chemicals Accelerate "ERISYS" DDA or DDA; and "AMICURE" PACM, 352, CG, CG-325 and CG-1200 available from Air Products, Allentown, PA. Suitable fillers include fumed silica such as "CAB-O-SIL" L-90, LM-130, LM-5, PTG, M-5, M-7 available from Tuscola, Cabot Company, IL , MS-55, TS-720, HS-5, and EH-5; "AEROSIL" R972, R974, R805, R812, R812 S, R202, US204, and US206 obtained from Akron, Degussa, Ohio. Suitable clay fillers include BUCA, CATALPO, ASP NC, SATINTONE 5, SATINTONE SP-33, TRANSLINK 37, TRANSLINK 77, TRANSLINK 445 and TRANSLIKN 555 available from Engelhard Company of Edison, NJ. Suitable silica fillers are SILCRON G-130, G-300, G-100-T and G-100 available from SCM Chemicals of Baltimore, Maryland. Suitable silane couplants to improve the hydrolytic stability of the seal are Z-6020, Z-6030, Z-6032, Z-6040, Z-6075 and Z-6076 available from Dow Corning, Midland, Michigan. Glass bead spacers are available in suitable precision by size at Duck Scientific from Palo Alto, CA.

The electrochromic medium 126 is capable of attenuating light traveling therethrough and has at least one liquid phase electrochromic material in intimate contact with the reflector/electrode 120 and may be liquid phase, surface defined, plateable onto a surface at least one additional electroactive material. However, the presently preferred media are redox electrochromics in the liquid phase, as disclosed in US Patent Nos. 4,902,108, 5,128,799, 5,278,693, 5,280,380, 5,282,077, 5,294,376, and 5,336,448. U.S. Patent No. 6,020,987, entitled "AN IMPROVEDELECTRO-CHROMIC MEDIUM CAPABLE OF PRODUCTING APRESELECTED COLOR, DISCLOSES ELECTRO-CHROMIC MEDIUM THAT ARE PERCEIVED TO BE GRAY THROUGHTHEIR NORMAL RANGE OF OPERATION.". The entire disclosure of this patent is incorporated herein by reference. If a liquid phase electrochromic medium is utilized, it can be inserted into chamber 125 through sealable fill port 142 by known techniques.

The layer of transparent conductive material 128 is deposited on the second surface 112b to serve as an electrode. The transparent conductive material 128 may be any material that bonds well to the front substrate 112, is resistant to corrosion of any material within the electrochromic device, is resistant to atmospheric corrosion, has minimal diffuse or specular reflectivity, High light transmission, near-neutral coloration and good electrical conductivity. The transparent conductive material 128 may be fluorine-doped tin oxide, doped zinc oxide, Indium Zinc (Zn ₃ In ₂ O ₆ ), Indium Tin Oxide (ITO), ITO/Metal/ITO (IMI), materials described in the aforementioned U.S. Patent No. 5,202,787, as available from Libbey Owens- TEC 20 or TEC 15 available from Ford, or other transparent conductors. In general, the conductance of transparent conductive material 128 depends on its thickness and composition. If desired, an optional layer or layers of color suppressing material 130 may be deposited between transparent conductive material 128 and second surface 112b to suppress reflection of any undesired portions of the electromagnetic spectrum.

The combined reflector/electrode 120 is disposed on the third surface 114a and includes at least one layer of reflective material 121 that acts as a specularly reflective layer and also forms contact with components in the electrochromic medium and is in a chemically and electrochemically stable relationship the overall electrode. As mentioned above, a conventional approach to build an electrochromic device is to incorporate a transparent conductive material as an electrode on the third surface and place a reflector on the fourth surface. By combining the "reflector" and "electrode" and placing them both on the third surface, several advantages arise which not only make the device manufacturing simpler, but also allow the device to operate with higher performance. For example, the combined reflector/electrode 120 on the third surface 114a generally has a higher conductance than conventional transparent electrodes and previously used reflectors/electrodes, which allows greater design flexibility. The composition of the transparent conductive electrode 128 on the second surface 112b can be changed to a composition with lower conductivity (cheaper and easier to produce and manufacture) while maintaining similar coloration as achievable with the fourth surface reflector device speed while substantially reducing the overall cost and time to fabricate electrochromic devices. However, if the performance of a particular design is paramount, a high conductivity transparent electrode such as, for example, ITO, IMI, etc. can be used on the second surface. The combination of a high conductivity (i.e., less than 250 ohm/square) reflector/electrode 120 on the third surface 114a and a high conductivity transparent electrode 128 on the second surface 112b will not only result in a more uniform overall colored electrochromic devices, but also allows for increased coloring speed and cleaning. Furthermore, in the fourth surface reflector mirror assembly, there are two transparent electrodes with relatively low conductivity, and in the previously used third surface reflector mirror, there are transparent electrodes and a reflector/ The electrodes, likewise, and the long bus bars on the front and rear substrates that bring the current in and out must ensure adequate coloring speed.

In the example shown, a resistive heater 138 is disposed on the fourth glass surface 114b. Conductive spring clips 134a, 134b are disposed on coated glass sheets 112, 114 to make electrical contact with exposed areas of transparent conductive coating 128 (clip 134b) and third surface reflector/electrode 120 (clip 134a). Suitable electrical conductors (not shown) may be soldered or otherwise connected to the spring clips 134a, 134b to apply the desired voltage to the device from a suitable power source.

The inventive process ( FIG. 4 ) for manufacturing an electrochromic element as described herein comprises the steps of providing ( 200 ) a substrate as described above, cleaning ( 202 ) the surface of the substrate to be coated with a conductive layer, optionally The surface of the substrate is pretreated (204), coated (206) with a conductive layer in a defined pattern on the substrate surface, and optionally cured (208) after its coating.

Cleaning (202) of the substrate surface can be accomplished with any known glass cleaning technique, including chemical cleaners, polishing, etching, and the like. Optionally, the conductive layer-coated substrate surface is pretreated (204) to cause a hydrophilic and/or hydrophobic reaction of the metal layer when the metal is applied in solution.

Applying (206) the conductive layer to selected areas of the substrate can be accomplished via a variety of methods and techniques. Specifically, the conductive metal layer can be applied to the surface of the substrate by inkjet process, ultrasonic spray coating, screw pump spray coating (pumping) or jet pump spray coating, or similar dispersion methods, which can be done under atmospheric conditions, specifically No vacuum was applied. These methods include coating metal particles (preferably metal nanoparticles), organometallics, metal organics, and combinations thereof. Each deposited material may be cured (208) in situ, for example by pre-treating the relevant substrate, and/or subsequently cured to form the final metallic conductive layer.

Examples of coated metal films or multilayer metal films in electrochromic devices applied via the present technology include, but are not limited to, electrical bus bar conductors; resistive heater films and/or bus bar systems; metal wires, bars, Grids or patterns; conductive traces for electronic circuits; substrates that provide enhanced solder wetting; reflective or semi-mirror-like metallic films; and metallic film rings. Electronic bus bar conductors are typically disposed near the perimeter of the associated electrochromic device. The technique of the present invention allows bus bar conductors to be placed on any of: surface one, surface two, surface three, surface four, and/or the edge of any of the substrates. Furthermore, this technique can be used to apply bus bars to the edge of any of the substrates and can overlap and electrically connect to conductive regions of surfaces one, two, three or four. Also, since the metal bus bar film coated by the present technology exhibits improved adhesion to the substrate, it can be placed under an electrochromic device seal that overcoats and protects the metal bus bar from corrosion , and can combine the area occupied by the seal to minimize its overall combined footprint. In this example, it is desirable for the bus bar to have a resistance of less than 10 ohms per length, more preferably less than 5 ohms per length, and most preferably less than 1 ohms per length.

Resistive heater films and/or bus bar systems coated via the present technology are suitable for uniform heating and/or defrosting of electrochromic devices. Since these metal films must be in good thermal contact with the device substrate, it is preferred to pattern and apply the metal film directly onto one of the surfaces of the electrochromic device provided by the method of the invention.

Another application of the methods disclosed herein includes providing metal lines, strips, grids or patterns to enhance the conductivity of the associated surfaces of either or both electrodes 120 and 128 . The enhanced electrical conductivity provided by the metal aids in the coloring and cleaning of related electrochromic devices. By applying the method of the invention, regions of an electrochromic device are colored or cleaned selectively or faster than other comparative regions by adjusting the pattern of the deposited metal film. This approach has proven particularly useful for enhancing the conductivity of transparent conductive oxides (TCOs), which are inherently much less conductive than most metals. In order to minimize the visibility of the pattern metal on or under the TCO surface, it is desirable to have pattern features less than 5 mm wide, preferably less than 1 mm wide and more preferably less than 0.5 mm wide. Metal lines, strips, grids and/or patterns can also be coated under or over the reflective film to enhance or selectively alter the relative conductivity and performance as an electrode.

Another application of the method of the present invention is to provide metal films that can be patterned and used as conductive traces for electronic circuits. The electronics can be applied directly to the electrochromic substrate or to other substrates such as those conventional in the printed circuit board industry, eg epoxy fiberglass laminates, polyimide films or polyester films. These metal films may first be deposited on a substrate with associated electronic components that are then adhered to the substrate and electrically connected to the metal film conductive traces. Alternatively, electronic components may be first mounted on a substrate, and then a pattern of electronic traces is applied to the substrate to interconnect the electronic components. Electrical connections between components and metal films can be made by conventional techniques such as soldering, wire bonding, spring contacts or conductive bonding. Furthermore, the electrical connection can also be made directly through the metal film, which can be coated in a three-dimensional pattern so that the metal film is continuous from the substrate to the electronic component. In this way, electronic components can be mounted to the substrate first, and electronic circuits and electrical connections to the components can be completed in one metal film patterning step. Note further that patterned metallic films coated via the present technique can be combined with patterned insulating films to form conductor/insulator/conductor circuits, thereby allowing higher circuit densities or coating of multiple electrochromic electrodes on the same substrate bus bar.

Another application includes coating metal films as a base layer to enhance solder wettability or substrate solderability. Metal film solder layers are used to enhance electrical conductivity, provide electrical and/or mechanical bonding connections to components, and/or provide a hermetic seal. For example, the edges of each of the substrates associated with the electrochromic device may be coated with a metal film. The substrates are then secured with a uniform gap between them, and the edges of the substrates are then welded together. Note that the solder in this example will form a tight edge seal that is hermetic and protects the electrochromic medium contained between the substrates. This is an improvement over solder and soldering techniques that allow direct soldering to glass, ceramics and conductive metal oxides, as previously known techniques sometimes provided poor solder joints due to process variability. Another example of the usefulness of the technique of the present invention is to fill electrochromic components by coating the edges with a metal film and allowing the filled holes associated with electrochromic elements to be cut off by soldering after filling the device with electrochromic material or electrolyte, thereby filling electrochromic components. Port edge of color changing element. Again, this is an improvement over past techniques, as the present technique provides an easier to perform and more robust process.

Another application of the inventive process is the coating of reflective or semi-reflective mirror-like metal films on at least one of the second, third and fourth surfaces of an associated electrochromic device. The metal film can be applied to the entire surface or patterned to selectively target coated portions of the surface to provide transparent, semi-reflective or mirror-like portions. These layers can be used as electrodes if provided on surface three, or as electrode supplementary bus bars if provided on surface four. Also, these films can be made thick enough that only point, short wire or small area electrical contacts are required. A sheet resistance of less than 10 ohms per square is preferred, more preferably less than 1 ohms per square, most preferably less than 0.5 ohms per square, and is readily achievable via the present technique.

Another application of the present technology is to provide a ring of reflective metal film patterned near the perimeter of one of the associated substrates, where the metal ring will serve to hide the associated sealing area and provide a mirror that will complement the mirror surface on the second substrate. surface. The metal film will be provided between a 1mm and 8mm wide ring which will cover the perimeter of the first substrate and also overlap onto its edge. The metal film can be used as an electrical bus bar or an electronic bus bar that complements the second surface transparent conductive electrode. Also, the metal film disposed on the second surface may be coated under the transparent conductive electrode, on top of the transparent conductive electrode, or sandwiched between transparent conductive layers. Also, a light gray or slightly black metal layer can be used to hide the sealing area and can act as an electrical bus bar and aesthetically complement the reflector on the second substrate.

As mentioned before, one method of patterning films with high resolution is inkjet printing. Printing details of 10 μm or less can be achieved with inkjet printing, while the amount of ink deposited during each pass can be tightly controlled and precisely adjusted. Printed film thickness can be varied by controlling the individual ink droplet sizes, the frequency at which ink droplets are generated, the velocity of the inkjet head across the substrate, and the number of passes of the inkjet head over the surface to be printed. It was noted that inks loaded with large particles could not be inkjet printed efficiently because large particles would hinder the inkjet head and tend to deposit from solution, especially if the solution was low in viscosity. As a result, nanoparticulate metal loaded inks are preferred. Specifically, metal-containing inks that can be inkjet printed and produce metal films with near-bulk metallic properties are ink solutions containing nanoparticles of silver, nickel, copper, gold, silver-copper, silver-palladium, palladium-gold, etc. . Transparent conductive oxide coatings can also be formed from inks containing nanoparticles of transparent oxide materials such as indium tin oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped Zinc oxide (AZO), indium-doped zinc oxide (IZO), or similar metal oxide systems. Note that the metal particle size of these inks must be small enough to form a specular mirror-like film upon evaporation of the carrier solvent.

Two-phase UV curable inks can be utilized for depositing metal films using inkjet imaging, where the two-phase ink is sprayed onto a substrate and UV-cured to produce a solid two-phase polymer matrix. One polymer phase is selectively solvated from the matrix, while the remaining polymer phase forms a honeycomb structure and contains the metal deposition catalyst. The metal is then deposited onto the catalyst comprising the polymer honeycomb using a donor metallization fluid. Copper, silver, gold, nickel and cobalt with good electrical conductivity and adhesion can be deposited using this technique.

Another way that inkjet printing can be used to deposit metal films involves the thermal decomposition of organometallic precursors to form metals. These organometallic precursors were solvated with organometallic solutions and sprayed onto hot substrates (100 to 250°C). Heating the substrate flash-offs the solvent and the organometallic compound decomposes into metals that deposit on the substrate. If the metal is sensitive to oxidation, the coating/decomposition process can be carried out in air, inert gas or reducing atmosphere. Organometallic precursors can also be combined with nanoparticles to help sinter the nanoparticles together upon curing.

Solutions or inks comprising a nanoparticle-based, organometallic precursor-based, or metal ion-based can be selectively applied by methods other than inkjet. Other techniques include coating solutions of copper, tungsten molybdenum, silver, gold, etc. using nano-vapor spraying and/or ultrasonic spraying techniques to produce metal films with a quality similar to vacuum processes. This technique has been adopted by Fujimori Technical Laboratory Ltd. of Japan to manufacture silver-based mirrors. Ultrasonic spraying techniques can also be used to precisely apply liquid coatings, such as fluids, photoresists, and conductive inks, on a variety of substrates, such as are employed by Ultrasonic Systems, Inc. of Haverhill, MA, and Sono-Tek, Inc. of Milton, New York. of. Also, small screw and solenoid pumps connected to programmable XYZ motion controls can be used to precisely disperse fluid in patterns, lines or points, such as those systems employed by Asymtek of Carlsbad, Canada. These systems can be controlled by image monitoring and servo-drive controlled pumps connected to precise motion control equipment to accurately dispense conductive and non-conductive materials in three-dimensional shapes and patterns.

Furthermore, the application of conductive and non-conductive materials can be accomplished by spraying heated powder directly onto the surface of the patterned structure through the holes. Furthermore, laser techniques may also be used, including direct transfer of the material onto the substrate by irradiating a ribbon coated with the material to be deposited with a pulsed laser beam. Material is evaporated from the ribbon held close to the substrate by a laser beam and transferred onto the substrate. The deposited material is patterned by moving the substrate under a laser beam/belt mechanism with precise XY motion control. This deposition can be accomplished in air or in an inert, reducing or oxidizing atmosphere, if desired. Conductive and insulating materials can also be deposited by a plasma spray process, which involves projecting thermal material towards the substrate to be coated, where the projected spray is converging. In one approach, the powdered material is fed to a hot flame, melted, and then directed towards the substrate by combustion gas or a combination of combustion gas and inert gas, where the hot particles converge on the substrate to be coated. In another mode, the material is fed in thread form into a head that melts the material with an electrical discharge. The material is then directed towards the substrate by an inert gas vapor. In each approach, the deposited material can be patterned by spraying the material through a mask or aperture while moving the deposition head or substrate with precise motion control. Another technique is an electroless metal deposition process involving sensitization of glass surfaces with palladium chloride or tin chloride solutions. A silver solution, typically consisting of silver nitrate dissolved in ammonia, is applied to the substrate along with an organic reducing agent. Silver ions are reduced to silver metal by an organic reducing agent and deposited on the substrate as a metal film. By selectively applying a silver solution, the deposited silver film can be patterned.

Surface topography, morphology or roughness is usually not very important in dealing with most electrical applications of metal coatings, however, surface topography becomes critical when coatings are used in optical applications. Specifically, if the surface roughness becomes too large, the coating will have a perceivable non-specular reflectivity or be hazy. In most applications, roughness is generally addressed first when addressing haze-related issues, since it can have a negative appearance and is not necessarily a functional issue, such as with conductivity. In the case of optical applications such as many described here, the presence of objectionable blurring is considered to be the worst case scenario. Also, roughness may have other negative consequences to a much lesser degree than that of creating an objectionable blur. Previous attempts to account for problems related to blur include utilizing higher priced metals that exhibit higher reflectivity. The effect of varying morphology or degree of surface roughness as discussed in this application has been calculated using thin film modeling techniques. Specifically, calculations regarding morphology or surface roughness as included herein are calculated using a commercially available thin film program known as TFCalc as obtained from Software Spectra, Inc., Portland, Oregon.

In this example, roughness is defined as the average peak-to-valley distance. Figure 5 shows a first roughness case where a substrate 300a is coated with a bulk metal coating 302a exhibiting a first roughness 304a with large grains, while Figure 6 shows a second roughness case where the substrate 300b is coated with a bulk metal coating 302b exhibiting a second roughness 304b having relatively small grains. Note that each example shows similar peak-to-valley distances 306a, 306b. Additionally, both instances have the same void to bulk ratio. A relatively thin layer approximation can be made by considering the layer as a single homogeneous layer with uniform refractive index, however, this approximation does not work well for mixed layers. Specifically, if the thickness of the metal layer becomes too large, the roughness cannot be well approximated by a single fixed index of refraction, and in those cases the roughness is approximated as several sheets with different void-to-volume ratios. This example utilizes the Bruggeman EMA method, which is used to calculate the effective medium approximation of the refractive index of the mixed layer.

Tables 1-3 show the effect of roughness thickness on reflectivity (Y) for silver, chrome and rhodium surfaces, respectively. Note that the reflectivity decreases gradually with increasing roughness for each of these metals. Depending on the application, the amount of acceptable roughness will vary, however, the roughness should preferably be less than 60 nm, more preferably less than 40 nm, even more preferably less than 20 nm, even more preferably less than 10 nm and most preferably less than 5 nm. As noted above, these preferred ranges depend on the particular application involved. Surface roughness is critical to first surface reflectivity.

Table 1: Effect of roughness thickness on the reflectivity of Ag coatings

silver

Body thickness (nm) Roughness (nm) Reflectance (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: Effect of roughness thickness on the reflectivity of chrome coatings

chromium

Body thickness (nm) Roughness (nm) Reflectance (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: Effect of roughness thickness on the reflectivity of rhodium coatings

rhodium

Body thickness (nm) Roughness (nm) Reflectance (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 the process and method of the present invention to provide preferably following conductive layer, it has less than or equal to 150μΩ·cm, more preferably less than or equal to 100μΩ·cm and more preferably less than or equal to 50μΩ·cm volume resistivity; Less than or equal to 20nm, preferably Peak-to-valley roughness of 10 nm or less and more preferably 5 nm or less; reflectance of preferably 35% or more, more preferably 55% or more, and still more preferably 70% or more, and exhibits an image retained therein spectral reflectance.

Several experiments were performed using various coating processes and curing techniques, the details of which are provided below.

Example 1

Inkjet Silver ConductorAG-IJ-G-100-S1 ink from Cabot Printable Electronics and Displays (Albuquerque, NM) was coated with a JetDrive III driver and MJ-AB-01 40 μm inkjet head from MicroFab Technologies (Plano, TX). Cladding to flat, 1.6 mm thick soda lime glass. Printing parameter settings are typical for inkjet printing. After printing the conductive ink, the isolated samples were cured in a convection oven or drying oven at temperatures of 200, 300, 400 and 500° C. for 20 minutes. The thickness of the cured film was measured using a profilometer (Dektek) and the volume resistivity was calculated.

Curing temperature (°C) Curing time (min) Thickness(μm)(avg.of 3) Volume resistivity (μΩ 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

Adhesion between films and substrates was evaluated by tape peel test. After curing, an adhesive tape is applied to the film and removed with a peel action. A rating of 1 indicates that the film was removed through the tape. A rating of 5 indicates that removal by the tape did not affect the film. The median number is specified by how much of the film is removed by band removal.

Curing temperature (°C) Curing time (min) Adhesion (1-5) 200 20 1 300 20 3 400 20 5 500 20 5

Example 2

Silverjet DGH 50LT-25CIA ink from AdvancedNano Products (Seoul, Korea) was applied to flat, 1.6 mm thick soda lime glass using equipment and printing parameter settings similar to Example 1. After printing the conductive ink, the isolated samples were cured in a convection oven or drying oven at temperatures of 250, 350, 450 and 560° C. for 20 minutes. The thickness of the cured film was measured using a profilometer (Dektek) and the volume resistivity was calculated.

Curing temperature (°C) Curing time (min) Thickness(μm)(avg.of 3) Volume resistivity (μΩ 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

Adhesion between films and substrates was evaluated by tape peel test as described in Example 1. A rating of 1 indicates that the film was removed through the tape. A rating of 5 indicates that removal by the tape did not affect the film. How much of the membrane is removed by band removal specifies the median number.

Curing temperature (°C) Curing time (min) Adhesion (1-5) 250 20 1 350 20 1 450 20 5 560 20 5

Example 3

Silverjet DGH 50HT-25CIA ink from AdvancedNano Products (Seoul, Korea) was applied to flat, 1.6 mm thick soda lime glass using equipment and printing parameter settings similar to Example 1. After printing the conductive ink, the isolated samples were cured in a convection oven or drying oven at temperatures of 250, 350, 450 and 560° C. for 20 minutes. The thickness of the cured film was measured using a profilometer (Dektek) and the volume resistivity was calculated.

Curing temperature (°C) Curing time (min) Thickness(μm)(avg.of 3) Volume resistivity (μΩ 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

Adhesion between films and substrates was evaluated by tape peel test as described in Example 1. A rating of 1 indicates that the film was removed through the tape. A rating of 5 indicates that removal by the tape did not affect the film. How much of the membrane is removed by band removal specifies the median number.

Curing temperature (°C) Curing time (min) Adhesion (1-5) 250 20 1 350 20 1 450 20 5 560 20 5

Example 4

Silverjet DGH 50HT-50CIA ink from AdvancedNano Products (Seoul, Korea) was applied to flat, 1.6 mm thick soda lime glass using equipment and printing parameter settings similar to Example 1. After printing the conductive ink, the isolated samples were cured in an oven at 560°C for 20, 40 and 60 minutes. The thickness of the cured film was measured using a profilometer (Dektek) and the volume resistivity was calculated.

Curing temperature (°C) Curing time (min) Thickness(μm)(avg.of 3) Volume resistivity (μΩ cm) (avg.of 3) 560 20 0.72 2.45 560 40 0.60 2.24 560 60 0.78 1.94

Adhesion between films and substrates was evaluated by tape peel test as described in Example 1. A rating of 1 indicates that the film was removed through the tape. A rating of 5 indicates that removal by the tape did not affect the film. How much of the membrane is removed by band removal specifies the median number.

Curing temperature (°C) Curing time (min) Adhesion (1-5) 560 20 5 560 40 5 560 60 5

Example 5

Parmod VLTGXA-100 silver ink from Parelec Corporation (Rocky Hill, NJ) was applied to flat, 1.6 mm thick soda lime glass using a stencil to form 2.54 mm x 7.5 cm traces. The isolated samples were then cured for 20 minutes in a convection oven or drying oven at temperatures of 250, 300 and 350°C. The thickness of the cured film was measured using a micrometer and the volume resistivity was calculated.

Curing temperature (°C) Curing time (min) Thickness(μm)(avg.of 3) Volume resistivity (μΩ cm) (avg.of 3) 250 20 14.00 7.6 300 20 15.70 6.2 350 20 10.00 5.7

Adhesion between films and substrates was evaluated by tape peel test as described in Example 1. A rating of 1 indicates that the film was removed through the tape. A rating of 5 indicates that removal by the tape did not affect the film. How much of the membrane is removed by band removal specifies the median number.

Curing temperature (°C) Curing time (min) Adhesion (1-5) 250 20 3 300 20 5 350 20 5

Example 6

Parmod VLTGXA-100 silver ink from Parelec Corporation (Rocky Hill, NJ) was applied to planar, 1.6 mm thick soda lime glass using a stencil to form 2.54 mm x 7.5 cm traces. The isolated samples were then cured in a convection oven or drying oven at a temperature of 300°C for 10, 20 and 30 minutes. The thickness of the cured film was measured using a micrometer and the volume resistivity was calculated.

Curing temperature (°C) Curing time (min) Thickness(μm)(avg.of 3) Volume resistivity (μΩ cm) (avg.of 3) 300 10 11.67 5.2 300 20 15.67 6.8 300 30 18.33 7.9

Adhesion between films and substrates was evaluated by tape peel test as described in Example 1. A rating of 1 indicates that the film was removed through the tape. A rating of 5 indicates that removal by the tape did not affect the film. How much of the membrane is removed by band removal specifies the median number.

Curing temperature (°C) Curing time (min) Adhesion (1-5) 300 10 5 300 20 5 300 30 5

Example 7

Inkjet Silver ConductorAG-IJ-G-100-S1 ink from Cabot Printable Electronics and Displays (Albuquerque, NM) was coated with a JetDrive III driver and MJ-AB-01 40 μm inkjet head from MicroFab Technologies (Plano, TX). Cladding to flat, 1.6 mm thick soda lime glass. Printing parameter settings are typical for inkjet printing. After printing the conductive ink, the isolated samples were cured in a drying oven at 200° C. for 20 minutes. The reflectance of the cured film was measured using a spectrophotometer (Gretag Macbeth Coloreye 7000A). The reflectance results can be seen in Figure 7.

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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