JP2009529150A6 - Improved thin film coatings, electro-optic elements, and assemblies incorporating these elements - Google Patents

Abstract

Various thin film coatings, electro-optic elements, and assemblies incorporating these elements are provided.
Electro-optic elements are common in many vehicle and building applications. Various electro-optic element configurations provide variable transmittance and / or variable reflectivity for windows and mirrors. The present invention relates to various thin film coatings, electro-optic elements, and assemblies incorporating these elements.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application 35 USC § 119 (e) below, U.S. Provisional Patent Application Serial No. 60 / 779,369 assigned to Tonar other on March 3, 2006 Application No. 60 / 810,921 granted to Tonar et al. On June 5, 2006, Application No. 60 / 873,474 granted to Tonar et al. On December 7, 2006, and 2007 We claim priority to agent serial number GEN10PP-514 entitled “Electro-Optical Element with Improved Transparent Conductor” granted to Neuman on February 7, the disclosure of which is hereby incorporated by reference in its entirety. The content is incorporated by reference.

  This application relates to agent docket number GEN10-P517 and agent docket number GEN10P518 entitled “Electro-Optical Elements Including IMI Coating”, both of which are filed concurrently with the present disclosure, the disclosure of which is The entire contents of the specification are incorporated by reference.

  Electro-optic elements are becoming common in many vehicle and architectural applications. Various electro-optic element configurations provide variable transmission and / or variable reflectance for windows and mirrors.

U.S. Provisional Application No. 60 / 779,369 U.S. Provisional Application No. 60 / 810,921 U.S. Provisional Application No. 60 / 873,474 US Pat. No. 6,567,708 US Patent Application No. 60 / 804,378 US Pat. No. 5,837,994 US Pat. No. 5,990,469 US Pat. No. 6,008,486 US Pat. No. 6,130,448 US Pat. No. 6,130,421 US Pat. No. 6,049,171 US Pat. No. 6,465,963 US Pat. No. 6,403,942 US Pat. No. 6,587,573 US Pat. No. 6,611,610 US Pat. No. 6,621,616 US Pat. No. 6,631,316 US patent application Ser. No. 10 / 208,142 US patent application Ser. No. 09 / 799,310 US Patent Application Serial No. 60 / 404,879 US patent application Ser. No. 60 / 394,583 US patent application Ser. No. 10 / 235,476 US patent application Ser. No. 10 / 783,431 US patent application Ser. No. 10 / 777,468 US patent application Ser. No. 09 / 800,460 U.S. Pat. No. 4,094,058 US Pat. No. 6,111,684 US Pat. No. 6,166,848 US Pat. No. 6,356,376 US Pat. No. 6,441,943 US patent application Ser. No. 10 / 115,860 US Pat. No. 5,825,527 US Pat. No. 6,111,683 US Pat. No. 6,193,378 US patent application Ser. No. 09 / 602,919 US patent application Ser. No. 10 / 260,741 US Patent Application No. 60 / 873,474 US patent application Ser. No. 10 / 430,885 European Patent EP0728618A2 US Patent Application 20040032638A1 US Pat. No. 5,535,056 US Patent Application 2004022638A1 Canadian Patent No. 1,300,945 US Pat. No. 5,204,778 US Pat. No. 5,451,822 US Patent Application Publication No. 2006/0056003 US Pat. No. 6,700,692 US Patent No. 5,278,693 Zonghe Lai and Johan Liu "Nordic Electronics Packaging Guidelines" Chapter A F. W. Billmeyer and M.M. Saltzman, “Principles of Color Technology”, Second Edition, “J. Wiley and Sons Inc.” (1981)

  The present invention relates to various thin film coatings, electro-optic elements, and assemblies incorporating these elements.

  FIGS. 1, 2a, and 2b show multi-passenger vehicles 102, 202a, 202b using variable transmittance windows 110, 210a, 210b. Examples of multi-passenger vehicles using variable transmittance windows 110, 210a, 210b include aircraft 102, bus 202a, and train 202b. It should be appreciated that other multi-passenger vehicles, some of which are described in more detail elsewhere herein, can use variable transmittance windows 110, 210a, 210b. In addition, the multi-passenger vehicle generally shown in FIGS. 1, 2a, and 2b is a window control system (not shown in FIGS. 1-2b) for controlling a variable transmittance window. Also shown in FIG. 10 and described with reference thereto. US Pat. No. 6,567,708 assigned to the assignee and US patent application 60 / 804,378, filed June 9, 2006, entitled “Variable transmissive window system” Various details regarding windows are described, the disclosure of which is hereby incorporated by reference in its entirety.

  FIG. 3 illustrates another application of the variable transmittance window. The architectural window 302 of the building 301 may advantageously incorporate a variable transmissive function. It should be understood that these variable permeable architectural windows can be included in residential, commercial, and industrial facilities.

  FIG. 4 shows a control vehicle 400 that includes various variable transmittance and variable reflectance elements. As an example, an internal rearview mirror assembly 415 is shown, and in at least one embodiment, the assembly 415 includes a variable reflectance mirror element and a vehicle exterior light automatic control system. A detailed description of such a vehicle exterior light automatic control system can be found in US Pat. Nos. 5,837,994, 5,990,469, 6,008,486, 6, assigned to the present applicant. 130, 448, 6, 130, 421, 6, 049, 171, 6, 465, 963, 6, 403, 942, 6, 587, 573, 6, 611, No. 610, No. 6,621,616, No. 6,631,316, and U.S. Patent Application Nos. 10 / 208,142, 09 / 799,310, No. 60 / 404,879, 60/394, 583, 10/235, 476, 10/783, 431, 10/777, 468, and 09/800, 460, the disclosure of which is The entire contents are cited in this specification. Ri is built-in. In addition, the control vehicle includes a driver-side outer rearview mirror assembly 410a, a passenger-side outer rearview mirror assembly 410b, a stop light (CHMSL) 445 mounted at the center height, A pillars 450a and 450b, B pillars 455a and 455b. , And C pillars 460a, 460b, but any of these positions may alternatively be the position of the image sensor, each image sensor, or associated processing and / or control components. It should be understood that it can. It should be understood that any or all of the rearview mirrors can be self-modulating electro-optic mirrors (ie variable reflectivity mirror elements). In at least one embodiment, the control vehicle can include variable transmittance windows 401, 402. The control vehicle includes front lights 420a and 420b, fog weather lights 430a and 430b, front direction indication / failure indicator lights 435a and 435b, tail lights 425a and 425b, rear direction indicator lights 426a and 426b, rear failure indicator lights 427a and 427b, And a number of external lights, including reverse lights 440a, 440b. It should be understood that additional external lighting such as separate low beam and high beam front lights, integrated lights including multipurpose lighting, etc. can be used. It should further be understood that a positioner (not shown) can be provided on any of the external lights to adjust the associated primary optical axis of a given external light. In at least one embodiment, at least one external mirror assembly is provided that includes a pivoting mechanism so that it can pivot in directions 410a1, 410a2, 410b1, 410b2. The control vehicle of FIG. 4 is generally for purposes of example and is incorporated herein by reference, along with other features described in this specification and the disclosure incorporated herein by reference. It should be understood that suitable self-dimming rearview mirrors such as those disclosed in patents and patent applications can be used.

  The control vehicle preferably includes a unit magnification internal rearview mirror. Unit magnification mirror, as used herein, refers to the elevation angle and width of an object when viewed directly at the same distance, except for scratches where the elevation angle and width of the image of the object passing through it do not exceed normal manufacturing tolerances. Means a flat or flat mirror with a reflective surface equal to. A prismatic day / night adjusting rearview mirror in which unit magnification occurs in at least one relevant position is considered herein to be a unit magnification mirror. Preferably, the mirror has an opening horizontal angle measured from the point of the protruding eye of at least 20 degrees and less than that when the control vehicle is occupied by a driver and four passengers or a designated passenger capacity In some cases, based on an average occupant weight of 68 kg, a field of view of a vertical angle sufficient to provide a field of view of a flat road surface extending to a horizontal line starting at no more than 61 m to the rear of the control vehicle is provided. It should be understood that the line of sight may be partially obscured by a seated passenger or seat pillow. The position of the driver's eye reference point is preferably by convention or a nominal position suitable for all 95th percentile male drivers. In at least one embodiment, the control vehicle includes at least one unit magnification external mirror. Preferably, by means of an external mirror, the driver of the control vehicle is perpendicular to the longitudinal plane tangent to the driver side of the widest point of the control vehicle, with the seat at the rearmost position and 10.7 m of the driver's eyes. A field of view of the flat road surface extending from the line that extends 2.4 m outward from the rear tangential plane to the horizontal line is obtained. It should be understood that the line of sight may be partially obscured by the shape of the control vehicle's platform or mudguard. The position of the driver's eye reference point is preferably by convention or a nominal position suitable for all 95th percentile male drivers. Preferably, the passenger side mirror is not obscured by the portion of the corresponding windshield wiper that does not reach, and is preferably adjustable by tilting both horizontally and vertically from the position the driver is seated. . In at least one of the embodiments, the control vehicle includes a convex mirror provided on the passenger seat side. Preferably, the mirror is configured to adjust by tilting in both horizontal and vertical directions. Each preferred external mirror includes a reflective surface of 126 cm or more and is arranged to provide the driver with a rear view along the side associated with the control vehicle. Preferably, the average reflectivity of any mirror is at least 35 percent (40% in many European countries) as judged according to SAE standard J964, OCT84. In embodiments where the mirror element allows multiple reflectivity levels, such as an electro-optic mirror element according to the present invention, the minimum reflectivity level for daytime mode is at least 35 (40 for European specifications) The minimum reflectance level of the mode is at least 4 percent. It should be understood that the various embodiments of the present invention are equally applicable to motorcycle windshields and rearview mirrors.

  Turning now to FIGS. 5a and 5b, various components of the external rearview mirror assembly 510a, 510b are shown. As described in detail herein, the electro-optic mirror element includes a first substrate 521b that is secured in spaced relation to the second substrate 522b through a primary seal 523b and forms a chamber therebetween. it can. In at least one embodiment, at least a portion of the primary seal leaves an air gap and forms at least one chamber fill port 523b1. An electro-optic medium is enclosed in the chamber and the fill port is hermetically closed through the plug material 523b2. Preferably, the plug material is a UV curable epoxy or acrylic material. In at least one embodiment, the spectral filter material 545a, 545b is disposed near the second surface of the first substrate near the periphery of the mirror element. Electrical connectors 525b1, 525b2 are preferably secured to the elements through first adhesive materials 526b1, 526b2, respectively. The mirror element is fixed to the support plate 575b through the second adhesive material 570b. Electrical connection from the external rearview mirror to the other components of the control vehicle is preferably made through connector 585b. The support plate is attached to the associated housing mount 585b through positioner 580b. Preferably, the housing mount engages the housings 515a, 515b and is secured through at least one fastening device 534b4. Preferably, the housing mount includes a swivel portion configured to engage swivel mount 533b. The swivel mount is preferably configured to engage the vehicle mount 530b through at least one fastening device 531b. Additional details of these components, additional components, their interconnection, and operation are described herein.

  With further reference to FIGS. 5a and 5b, the external rearview mirror assembly 510a is oriented so that the field of view of the first substrate 521b positioned between the viewer and the primary seal material 523b is shown. Placed. Blind spot indicator 550a, keyhole illuminator 555a, paddle light 560a, supplemental directional indicator 540a1 or 541a, light sensor 565a, any of these, a partial combination, or a combination of Can be incorporated into the rearview mirror assembly. Preferably, the devices 550a, 555a, 560a, 540a, or 541a, 565a are at least partially hidden as described in detail in this specification and various references incorporated herein by reference. Configured in combination with mirror elements. Additional details of these components, additional components, their interconnections, and operation are described herein.

  Turning now to FIGS. 5c-5e, additional features according to the present invention are illustrated. FIG. 5c shows the rearview mirror element 500c viewed from the first substrate 502c positioned between the viewer of the spectral filter material 596c and the primary seal material 578c. A first isolation region 540c is provided to substantially electrically isolate the first conductive portion 508c from the second conductive portion 530c. Peripheral material 560c is added to the edge of the element. FIG. 5d shows the rearview mirror element 500d viewed from the second substrate 512d positioned between the viewer of the primary seal material 578d and the spectral filter material 596d. A second isolation region 586d is provided to substantially electrically isolate the third conductive portion 518d from the fourth conductive portion 587d. Peripheral material 560d is added to the edge of the element. FIG. 5e shows a rearview mirror element 500e as seen from cross-sectional views 5e-5e of either the element of FIG. 5c or 5d. The first substrate 502e is shown fixed in a spaced relationship with the second substrate 512e through the primary seal material 578e. A spectral filter material (referred to as a “chrome ring” in at least one of the embodiments herein) 596e is positioned between the viewer and the primary seal material 578e. First and second electrical clips 563e, 584e are each provided to facilitate electrical connection to the element. Peripheral material 560e is added to the edge of the element. It should be understood that the primary seal material can be applied by means commonly used in the LCD industry, such as silk screen or dispensing. U.S. Pat. No. 4,094,058 to Yasutake et al., The disclosure of which is incorporated herein by reference in its entirety, describes a possible method of application. Using these techniques, the primary seal material can be added to individual cuts to form a substrate, and can be added to a large substrate as a plurality of primary seal profiles. A large substrate with a plurality of primary seals can then be laminated to another large substrate, and individual mirror profiles are cut from the laminate after at least partially curing the primary seal material. be able to. This plurality of processing techniques is a commonly used method for manufacturing LCDs and is sometimes referred to as an array process. The electro-optical device according to the present invention can be manufactured using the same process. In the case of transparent conductors, reflectors, spectral filters, and solid state electro-optic devices, all coatings such as electro-optic layers or layers can be applied to a large substrate and patterned as required. it can. The coating can be by adding a coating through the shield, selectively adding a patterned soluble layer under the coating, and removing the coating on and over it after applying the coating, or by laser ablation or etching. Can be patterned using several techniques. These patterns can include alignment marks or targets that are used to accurately align or position during the manufacturing process. This is usually done optically in a vision system, for example using pattern recognition techniques. Further, if necessary, alignment marks or targets can be directly added to the glass by sandblasting, laser, diamond scribing, or the like. A spacing medium for controlling the spacing between the laminated substrates can be placed in the primary seal material and can be added to the substrate prior to lamination. Spacing media or means can be added to the area of the stack that will be detached from the finished split mirror assembly. If the device is a solution phase electro-optic mirror element, the stacked array can be cut into shape before or after filling with electro-optic material and plugging the filling port.

  Referring now to FIGS. 6a and 6b, the spectral filter material 645a or bezel 645b is viewed from the first substrate 622a, 622b positioned between the viewer and the primary seal material (not shown). Internal rearview mirror assemblies 610a, 610b are shown. The mirror elements are positioned within the movable housings 675a, 675b and are optionally shown combined on a mounting structure 681a (with a fixed housing) or 681b (without a fixed housing) of the fixed housing 677a. A first indicator 686a, a second indicator 687a, operator interfaces 691a, 691b, and a first light sensor 696a are positioned on the jaw portion of the movable housing. The first information display 688a, 688b, the second information display 689a, and the second light sensor 697a are incorporated into the assembly to be behind the element relative to the viewer. As described with respect to the external rearview mirror assembly, the devices 688a, 688b, 689a, 697a are preferably at least partially hidden, as will be described in detail herein. In at least one embodiment, the internal rearview mirror assembly includes at least one or more illumination assemblies 670b of the printed circuit board 665b, at least one microphone, a partial combination thereof, a combination thereof, or the apparatus described above. Other combinations can be included. It should be understood that aspects of the present invention can be incorporated into an electro-optic window or mirror individually or collectively in several combinations.

  FIG. 6c shows a plan view of a second substrate 612c comprising material stacked on the third, fourth, or both third and fourth surfaces. In at least one embodiment, at least a portion 620d of the stacked material, or at least a substantially opaque layer of the stacked material, is removed or coated under the primary seal material. At least a portion 620c2 of at least one of the layers of stacked material extends substantially to the outer edge of the substrate or the electrical between the third surface stack and the element drive circuit (not shown in FIG. 6c). Extending to an area to facilitate mechanical contact. In a related embodiment, a seal inspection and / or plug visual inspection and / or plug curing is performed from behind the next mirror or window element of the element assembly. In at least one embodiment, at least a portion of the outer edge 620d of the stacked material 620c is disposed between the outer edge 678c1 and the inner edge 678c2 of the primary seal material 678c. In at least one embodiment, a portion 620c1 of the stacked material, or at least a substantially opaque layer of stacked material, under a primary sealing material between approximately 2 mm and approximately 8 mm wide, preferably approximately 5 mm wide. Is removed or coated. At least a portion 620c2s of the layer of stacked material extends substantially to the outer edge of the substrate or has a third surface stack and a width between approximately 0.5 mm and approximately 5 mm, preferably It extends to an area that facilitates electrical contact between approximately 1 mm of element drive circuitry (not shown). Any of the first, second, third, and fourth surface layers or stacks of materials may be as disclosed in this specification or references cited elsewhere herein. You should understand what you can do.

  FIG. 6d shows a top view of the second substrate 612d including a third surface stack of material. In at least one embodiment, at least a portion of the outer edge 620d1 of the third surface stack 620d of material is disposed between the outer edge 678d1 and the inner edge 678d2 of the primary seal material 678d. In at least one related embodiment, the conductive tab portion 682d extends from the edge of the second substrate inside the outer edge 678d1 of the primary seal material 678d. In at least one related embodiment, the conductive tab portion 682d1 overlaps at least a portion of the third surface stack of material under the primary seal material 678d. In at least one embodiment, a substantially transparent conductive layer (not individually shown), such as a conductive metal oxide of a third surface stack of materials, is formed on the third surface as shown in FIG. 8b. Extends beyond the remaining outer edge 620d1 of the stack and provides an external electrical connection to the third surface. It should be understood that the conductive tabs can be coated along any of the substrate peripheral regions as shown in FIGS. 9c-9i. In at least one embodiment, the conductive tab portion includes chrome. While the conductive tab portion improves the conductivity over the conductive electrode, it should be understood that the conductive tab portion is optional as long as the conductive electrode layer is provided with sufficient conductivity. In at least one embodiment, in addition to providing the desired conductivity, the conductive electrode layer imparts the desired color specific characteristics of the corresponding reflected light. Therefore, when the conductive electrode is omitted, the color characteristics are controlled through the lower layer material standard. Any of the first, second, third, and fourth surface layers or surface stacks of materials can be as disclosed in this specification or references incorporated herein by reference. Should be understood.

  FIG. 7 shows a rearview mirror element 700 and is an enlarged view showing the element shown in FIG. 5e in more detail. Element 700 includes a first substrate 702 having a first surface 704 and a second surface 706. The first conductive electrode portion 708 and the second conductive electrode portion 730 added to the second surface 706 are substantially electrically isolated from each other through the first isolation region 740. As seen here, in at least one of the embodiments, the isolation region forms first and second spectral filter material portions 724, 736, respectively, and first and second coupling promoting material portions 727, 739, respectively. To do so, the spectral filter material 796 and the corresponding coupling promoting material 793 are also arranged to be substantially electrically separated. A portion of the first isolation region 740, 540c, 640d, 540e is shown extending parallel into a portion of the primary seal material 778 located near its center. This portion of the separation region 740 is positioned so that the viewer is not readily aware of the lines in the spectral filter material, eg, a portion of the separation region is substantially positioned with the inner edge 797 of the spectral filter material 596. It should be understood that they can be combined. When any part of the separation region 740 is placed inside the primary seal material, electro-optic material coloring and / or cleanliness discontinuities are observed, as described in more detail elsewhere herein. Should be understood. This actuation characteristic can be skillfully manipulated to lead to subjectively visually attractive elements.

  With further reference to FIG. 7, element 700 is shown to include a second substrate 712 having a third surface 715 and a fourth surface 714. It should be understood that the first substrate can be larger than the second substrate and offset along at least a portion of the periphery of the mirror. Third and fourth conductive electrode portions 718, 787, respectively, are shown near third surface 715 that is substantially electrically isolated through second isolation region 786. A portion of the second isolation region 786, 586c, 586d, 586e is shown extending parallel within a portion of the primary seal material 778 disposed near its center. This portion of the isolation region 786 is positioned so that the viewer is not readily aware of the lines in the spectral filter material, for example, a portion of the isolation region is substantially positioned with the inner edge 797 of the spectral filter material 796. It should be understood that they can be combined. Further, as shown in FIG. 7, a reflective material 720 can be added between the optional over-deposited material 722 and the third conductive electrode portion 718. US Pat. Nos. 6,111,684, 6,166,848, 6,356,376, 6,441, assigned to the Applicant, the disclosure of which is incorporated herein by reference. No. 943, U.S. Patent Application No. 10 / 115,860, U.S. Patent No. 5,825,527, 6,111,683, 6,193,378, U.S. Patent Application No. 09 / 602,919. , 10 / 260,741, 60 / 873,474, and 10 / 430,885, using any of the materials of hydrophilic coating on the first surface Single surface coatings such as, or composites of coatings such as conductive electrode materials, spectral filter materials, bonding promoting materials, reflective materials, over-deposited materials applied to the first, second, third and fourth surfaces Star It should be understood that it is possible to form a click. It should further be appreciated that a hydrophobic coating such as fluorinated alkyl saline or polymer, a silicone-containing coating, or a specially textured surface can be added to the first surface. Either a hydrophilic or hydrophobic coating will change the contact angle of the water impinging on the first surface against glass without such a coating and will improve the rear vision when water is present. . It should be understood that embodiments in which there are reflectors on both the third and fourth surfaces are within the scope of the present invention. In at least one embodiment, the material applied to the third surface and / or the fourth surface is configured to provide partial reflection / partial transmission properties to at least a portion of the corresponding stack of surfaces. In at least one embodiment, the material applied to the third surface is integrated to provide a combined reflector / conductive electrode. It should be understood that the additional “third surface” material can extend outside the primary seal, in which case the corresponding separation region extends through the additional material. . For example, making at least a portion of the primary seal visible from the fourth surface as shown in FIG. 6c facilitates inspection of the plug material and UB curing. In at least one embodiment, at least a portion of the stacked material 620c, or at least a substantially opaque layer of the stacked material, is removed or concealed under the primary seal material, at least at the periphery. Around a portion, at least 25% of the primary seal width is inspected. More preferably, 50% of the primary seal width around at least a portion of the periphery is inspected. Most preferably, at least 75% of the primary seal width around at least a portion of the periphery is inspected. Various embodiments of the present invention will incorporate portions of specific surfaces that have different coatings or stacks of coatings than other portions. For example, a "window" in front of a light source, an information display, a light sensor, or a combination thereof to form a particular band of light wavelength or light in a band as described in many of the references incorporated herein The wavelength can be selectively transmitted.

  Still referring to FIGS. 6 a-6 b and FIG. 7, the first isolation region 740 cooperates with a portion of the primary seal material 775 to form a first conductive electrode portion 708, a first spectral filter material portion. 724 and a second conductive electrode portion 730, a second spectral filter material portion 736, and a second coupling facilitating material portion 739 that are substantially electrically isolated from the first coupling facilitating material portion 727. With this configuration, conductor 748 is positioned so that first electrical clip 763 is in electrical communication with third conductive electrode portion 718, reflective material 720, optional overcoat 722, and electro-optic medium 710. be able to. In particular, in embodiments where a conductor 748 is added to the element prior to placing the first electrical clip 769, it is clear that the conductor can at least partially separate the interfaces 757, 766, 772, 775. It is. Preferably, the third conductive electrode portion 718, the first electrical clip 763, and the material or composition of materials that form the electrical conductor 748 are durable between the material leading to the clip and the electro-optic medium. Selected to facilitate electrical contact. Second isolation region 786 cooperates with a portion of primary seal material 775 to substantially separate third conductive electrode portion 718, reflective layer 720, optional overdeposited material 722, and electro-optic medium 710. A fourth conductive electrode portion 787 is formed which is electrically separated from each other. With this configuration, the second electrical clip 784 is in electrical communication with the first coupling promoting material portion 727, the first spectral filter material portion 724, the first conductive electrode portion 708, and the electro-optic medium 710. A conductor 790 can be disposed. In particular, in embodiments where a conductor 790 is added to the element prior to placing the first electrical clip 784, it is clear that the conductor can at least partially separate the interfaces 785, 788, 789. . Preferably, the material or composition of materials forming the first conductive electrode portion 708, the first electrical clip 784, the coupling facilitating material 793, the spectral filter material 796, and the conductor 790 are in the clip and the electro-optic medium. Selected to promote durable electrical communication between the following materials.

  One or more optional flash protection layers 722 covering the reflective layer 720 may be provided such that the flash protection layer 722 (but not the reflective layer 720) contacts the electrochromic medium. Sometimes desirable. This flash protection layer 722 needs to behave as an electrode, has a good shelf life, is well bonded to the reflective layer 720, and maintains its bonding when the seal member 778 is bonded to it. Should. If the optical property from the lower layer is that the cover layer is visible, it must be sufficiently thin so as not to completely block the reflectivity of the lower layer 720. According to another embodiment of the present invention, when a very thin flash protection film 722 is disposed over the highly reflective layer, the highly reflective layer 720 still contributes to the reflectivity of the mirror while the flash layer is To protect the reflective layer, the reflective layer 720 can be silver metal or a silver alloy. In such a case, a thin (eg, less than about 300 angstrom, more preferably less than about 100 angstrom) layer of rhodium, ruthenium, palladium, platinum, nickel, tungsten, molybdenum, or an alloy thereof covers the reflective layer 720. It is covered. The thickness of the flash layer depends on the material selected. For example, a third surface coating of rhodium under silver, ruthenium underneath, and chromium underneath with a flash layer of ruthenium as thin as 10 angstroms is compared to an element without a flash layer. , Showing improved resistance to both spot defects during processing and the formation of haze in the visible region of the element during high temperature testing. The initial reflectivity of the element comprising the ruthenium flash layer was 70-72%. If the reflective layer 720 is silver, the flash layer 722 can also be a silver alloy or aluminum-doped zinc oxide. Further, the flash layer or thicker cover layer can be a transparent conductor such as a transparent metal oxide. More specifically, the cover layer can be selected to match factors such as barrier properties, advantageous interferometric optical elements, balance of compression or tensile stress to other layers. It should be understood that a flash layer as described above can be used in other embodiments described elsewhere herein.

  Such cover layers are made of the metals listed above or other metals / alloys / metalloids found to be compatible with electrochromic systems, where the metal or metalloid layer is thicker than 300 Angstroms. , There is a tendency to hardly receive optical influence from the layer below. It may be advantageous to use such a thick cover layer if it is considered that the appearance of the metal cover layer is more preferable. Some description of such a stack is given in the European patent EP 0 728 618 A2 assigned to the present applicant entitled “Darkerable Rearview Mirror for Automobiles” granted to Bauer et al. Is incorporated herein by reference. Such a thick cover layer can be used in combination with a bonding layer and a flash layer, and a transparent conductive layer such as indium doped tin oxide, aluminum doped zinc oxide, or indium zinc oxide is used. It is done. The conductivity advantage of having a lower layer such as silver, silver alloy, copper, copper alloy, aluminum, or aluminum alloy will still exist. Further, such a cover layer stack or intermediate layer can be a layer typically considered as an insulator, such as titanium dioxide, silicon dioxide, zinc sulfide, etc., which layer has a higher thickness. As long as it still allows sufficient current to pass from the conductive layer, it does not negate the benefits of the higher conductive layer.

  It is well known in electrochromic technology that when a potential is applied to an element, the mirror or window may not be uniformly darkened. Non-uniform darkening is due to the locally different potential across the solid state EC material, fluid, or gel of the EC element. The potential across the element varies with electrode sheet resistance, bus bar configuration, EC media conductivity, EC media concentration, battery spacing or distance between electrodes, and distance from the bus bar. A generally proposed solution to this problem is to thicken the coating or layer that makes up the electrode, thereby reducing the sheet resistance and allowing the element to darken quickly. As explained below, this simplified method has the practical disadvantage of being limited to solving this problem. In many cases, this drawback makes EC elements unsuitable for certain applications. In at least one of the embodiments of the present invention, improved electrode materials, electrodes and busbars that solve the problems arising from simply thickening the electrode layer and that the EC element has the property of darkening more quickly and uniformly A method of manufacturing the configuration will be described.

  In a typical internal mirror, the bus bar extends parallel to the long direction. This is to minimize the potential drop across each part between the electrodes. Furthermore, the mirror typically consists of a high sheet resistance transparent electrode and a low sheet resistance reflector electrode. The mirror will darken most rapidly near the bus bar of the high sheet resistance electrode and will be slowest at some intermediate position between the two electrodes. Near the bus bar of the low sheet resistance electrode will have a darkening rate between these two values. When one moves between two bus bars, the effective potential varies. If the distance between two long parallel busbars is relatively short (the distance between the busbars is less than half the length of the busbar), the mirror will be darkened in a “window shade” fashion. This means that the mirror darkens quickly near one bus and this darkening appears to move gradually between the two busbars. Typically, the darkening rate is measured in the middle of this part, and for a mirror with a width to height ratio greater than 2, any nonuniformity in the darkening rate is relatively small.

  In addition, as the size of the mirror and the distance between the bus bars increases accordingly, the relative difference in the darkening speed across each portion also increases. This can be exacerbated when the mirror is designed for external use. Metals that can withstand harsh conditions such as the environment are typically less conductive than metals such as silver or silver alloys that are suitable for and often used in internal mirror applications. Thus, the sheet resistance of the metal electrode for external use can be up to 6 ohm / square, and the sheet resistance of the internal mirror can be <0.5 ohm / square. In other external mirror applications, the thickness of the transparent electrode can be limited for various optical requirements. Transparent electrodes such as ITO are often limited to 1/2 wave thickness in the most common usage. This limitation is due to the properties of ITO described herein, but also due to the cost associated with thickening the ITO coating. In other applications, the coating is limited to 80% of the 1/2 wave thickness. Both of these thickness constraints cause the sheet resistance of the transparent electrode to be greater than about 12 ohms / square for 1/2 wave and from 17 to 18 ohm / cm for a coating that is 80% of the 1/2 wave coating. limit. If the metal and the transparent electrode have high sheet resistance, the darkening is slow and the mirror becomes less uniform.

The darkening rate can be estimated from an analysis of EC elements for the electrical circuit. The following discussion relates to a coating having a uniform sheet resistance across the element. The potential at any position between the parallel electrodes is simply a function of the sheet resistance of each electrode and the resistance of the EC medium. In Table 1 below, the average potential across the elements between the electrodes is shown along with the difference between the maximum and minimum potential. This example is for elements with 10 cm spacing between parallel busbars, 180 micron battery spacing, 1.2 volt drive voltage, and 100,000 ohm ^* cm fluid resistance. Compare the six combinations of top and bottom electrode sheet resistance.

(Table 1)

  The speed of darkening is fast at the point of electrical contact with the high sheet resistance electrode and is related to the effective potential at this location. As the effective potential adjacent to this electrically contact point (or elsewhere) increases, the average darkening of the mirror increases. The fastest overall darkening time will occur when the potential is as high as possible over that portion. This will promote electrochemistry and darken at an accelerated rate. The sheet resistance of the coating on both the top and bottom substrates serves to determine the effective potential between the electrodes, but as can be seen in the table, the high sheet resistance electrode plays a more important role. In previous electrochromic techniques, improvements were made almost exclusively by lowering the sheet resistance of low resistance electrodes. This was because using a material such as silver produced substantial benefits and was relatively easy to implement.

  It is known in the art that increasing the drive potential can increase the overall speed, but the trend will be constant regardless of the drive voltage. It is also known that current draw at a given voltage affects the darkness uniformity. Uniformity can be improved by adjusting battery spacing, concentration, or EC material selection, but using these adjustments to improve uniformity often results in darkening, lightening speeds. Or both darkening and lightening speeds can be adversely affected. For example, increasing battery spacing and reducing fluid concentration will reduce current draw, thereby improving uniformity, but increasing cleaning time. Therefore, the sheet resistance of the layer should be set appropriately to obtain both darkening speed and darkening uniformity. Preferably, the sheet resistance of the transparent electrode should be less than 11.5 ohm / sq, preferably less than 10.5 ohm / sq, more preferably less than 9.5 ohm / sq, as described below. Due to requirements, in some embodiments, the thickness of the transparent electrode should be less than about half-wave optical thickness. The reflector electrode should be less than about 3 ohms / square, preferably less than about 2 ohms / square, and most preferably less than 1 ohm / square. Furthermore, a mirror or EC element constructed in this way will also have a relatively uniform darkening, and the difference in darkening time between the highest and lowest darkening speed is less than a factor of 3, preferably less than a factor of 2. Most preferably, the factor is less than 1.5. A new high performance low cost material that enables such a fast and uniform darkening element is described below.

  In other applications, having two relatively parallel bus bars may not be practical. This is believed to be due to the uneven shape common to the external mirror. In other situations, it may be desirable to have a point in contact with the low resistance electrode. Point contact can minimize or eliminate the laser deletion line used in some embodiments. Using point contact is simplified or preferred in some mirror construction aspects, but it is difficult to achieve a relatively uniform potential across that portion. Eliminating the relatively long bus along the low resistance reflector electrode substantially increases the resistance of the electrode. Therefore, a new combination of bus bar and coating sheet resistance is required to darken quickly and uniformly.

  As mentioned above, those skilled in the art are expected to require extremely low sheet resistance values for the metal reflector electrode in order to enable point contact systems. Unexpectedly, it has been found that transparent electrodes need to have low sheet resistance to improve uniformity. Table 2 shows the results of the uniformity experiment. In this test, a solution phase EC element approximately 8 inches wide by 6 inches high was made. The advantages of the element design described herein primarily relate to large elements. Large elements are defined as having a minimum distance from the edge of any point to the geometric center of the edge of the visible region that exceeds approximately 5 cm. Without uniform darkening, the problem becomes even greater when the distance exceeds approximately 7.5 cm, and the problem becomes even greater when the distance exceeds approximately 10 cm. The sheet resistance and metal reflector of the transparent electrode (ITO) changed as shown in Table 2. The metal electrode was brought into contact with the point contact portion. A clip contact, such as a so-called J clip, was used with an approximately 1 "long Ag paste line to make electrical contact with the metal reflector along one of the short length sides of the mirror. Through the Ag paste, along one side opposite to the point contact, and continuously in electrical contact over a third of the distance along both long sides of the mirror.Darking time (T5515) Was measured at three positions on the mirror, where position 1 is near the point contact, position 2 is the edge of the transparent electrode bus opposite the point contact, and position 3 is the center of the mirror. The time T5515 (seconds) is the time it takes for the mirror to change from 55% reflectivity to 15% reflectivity, and the maximum reflectivity is the maximum reflectivity of the mirror. Or the time difference between point 2 and point 3. This is a measure of the difference in darkening speed between the fastest position of the mirror and the other two positions, the higher the darkness uniformity, these numbers are closer to each other. Is divided by the time at the fastest position, which shows the relative scaling of the time between different positions, regardless of the absolute velocity at any given position. Thus, preferably, the timing factor is less than 3, preferably less than 2, and most preferably less than 1.5.If the ITO sheet resistance is 14 ohms / square for this particular mirror configuration, the timing factor is The inability to obtain a factor of 3 can be seen in Table 2. The timing factor for all three examples where ITO is 9 ohms / square is less than 3. The center of the mirror read is the fastest position When statistical analysis was performed on this data, it was unexpectedly found that ITO sheet resistance was the only factor contributing to the timing factor. The ITO sheet resistance in this embodiment needs to be less than about 11.5 ohms / square in order to have a timing factor of 3.0 or less, using the same statistical model, the ITO sheet resistance is In this mirror configuration, it should be less than 7 ohms / square for a timing factor of less than 2.0, but the timing factor is not affected by the sheet resistance of the third surface reflector, but overall The darkening rate is affected: if the sheet resistance of the reflector is 2 ohms / square or less and the ITO is approximately 9 ohms / square, the darkening rate for this mirror is 8 at the center. It is less than. This value corresponds roughly to a mirror of the same size in a conventional bus arrangement. Therefore, by reducing the sheet resistance of ITO, point contact is possible with a relatively high sheet resistance reflector.

(Table 2)

  The unexpected role of ITO sheet resistance at uniformity and darkening rates has been extended to another set of experiments. In these experiments, the length of the bus bar contact to the high sheet resistance electrode, in this example ITO, was extended to the side of the mirror and possibly further to the bottom edge of the mirror. Table 3 reveals the effect on uniformity when the bus length changes. In these tests, the shape and configuration of the elements are the same as in Table 2 except as described. The contact percentage is a percentage comparison of the bus bar length of the ITO contact compared to the total length of the periphery. The bus bar ratio is the length of the ITO contact to a small reflector contact of approximately 2 cm or less.

  The data from Table 3 shows that the uniformity improves significantly as the bus length of the high sheet resistance electrode increases. For a 2 ohm / square reflector, the timing factor improves from 2.4 to 1.7 as the bus length increases from 40% to 85%. For a 0.5 ohm / square reflector, if the ITO bus length also varies from 40 to 85%, the timing factor improves from 3.2 to 1.2 and the darkening speed improves significantly. Low sheet resistance reflector elements are typically faster to darken than the comparable 2 ohm / sq, but when the ITO contact is short and the uniformity is 0.5 ohm, the timing factor reveals Note that it becomes bad. Increasing the bus length for ITO is particularly useful with 0.5 ohm / square reflector elements.

  As the contact percentage increases, the fastest and slowest darkening positions can also change. In this example, at high contact percentage, the darkening times and corresponding timing factors for both positions 1 and 3 are significantly improved.

(Table 3)

  These experiments show that when using a short bus with low sheet resistance electrodes, it is advantageous to increase the bus length relative to the opposite electrode to improve uniformity. Thus, ideally, for large mirrors, the bus bar length ratio is greater than 5: 1, preferably greater than 9: 1, more preferably greater than 13: 1, most preferably greater than 20: 1. However, it is preferable to make the timing coefficient smaller than 3. Furthermore, regardless of the length of the small bus, it improves uniformity by increasing the bus length for high sheet resistance electrodes and the contact percentage is preferably greater than about 58%, more preferably greater than about 85%. I also found. Typically, the contact percentage for large EC mirrors is less than 50%.

  These findings are not only significant for mirrors with opaque reflectors, but are even more significant for mirrors that use transflective reflectors. In order to have a transflective coating, the metal should be thin to the point where it becomes transparent. Thus, the thin metal has a high sheet resistance value. In at least one embodiment of the present invention, the electro-optic element is a conventional bus bar arrangement comprising the optical point contact bus arrangement taught herein, including fast and uniform darkening. A new transflective coating is described below which is particularly well suited to supplement the above described bus arrangement.

  Also, darken the electrochromic mirror more uniformly across its entire area, or initially darken outwardly from its center (where most front light glare appears) towards the top and bottom of the visible area. The conductivity can be patterned under an opaque cover layer or a stack of opaque layers. U.S. Patent Application 20040032638 A1 entitled "Electrochromic device with thin film bezel cover edge", granted to Tonar et al., Incorporated herein by reference, describes "low sheet resistance coatings in close proximity to associated electrical contacts. The sheet resistance can be increased as the distance from the electrical contact increases, "and this is particularly useful when using point contacts. It is possible. " Typically, if no voltage is applied to the electrochromic element, it will be desirable to have no or very little visible contrast in the reflector to produce contrast in the ohmic.

  Including a non-metallic stack material to obtain sufficient contrast between the high and low electroconductive areas of the electrochromic device so that certain areas can be preferentially darkened May be necessary. This is because opaque layers or stacked highly reflective metals and alloys are sufficiently conductive to provide acceptable darkening characteristics for automotive electrochromic mirrors without the need for additional high conductivity patterns beneath them. This is because there is a tendency to be. An example of such a stack of materials comprising a semimetal is that described in US Pat. No. 5,535,056 entitled “Method of Making Elemental Semiconductor Mirrors for Vehicles” incorporated herein by reference. The opaque silicon layer is covered with approximately 1/4 wave optical thickness of indium tin oxide, which is covered with 20-25 nanometers of silicon, which is approximately It is thought that it is covered with 20 nm of indium tin oxide. Such a stack of coatings is opaque and allows additional material to be placed underneath in a pattern with minimal impact on the appearance from the front. Furthermore, the stack will be fully conductive throughout without compromising this patterning advantage. In addition, if ITO is found to be still too conductive when coated under conditions of approximately 12 ohms / square at a thickness of approximately 1400 angstroms, the process conditions should be adjusted. Or by changing the indium to tin ratio, the conductivity can be made low.

  Elements constructed in accordance with the principles described in US Pat. No. US20040032638A1 with the geometry of FIGS. 5f and 7 have a conductive epoxy along the top, bottom, and left edges, and the point joint is the right edge. , Which is made of a different third surface coating stack and conductive pattern. When referring to the entire third surface, this will mean the surface prior to laser processing and creating the insulation region necessary for construction according to US Patent Application No. 20040226638 A1 assigned to the present applicant.

  An element with a third surface reflector of 1/2 ohm / square over the visible region is ½ ohm / square over a 1/2 "or 1" or 2 "strip across the center of the element covered by the opaque layer. Contrast with what the rest of the visible region has a conductivity of 4 ohms / square and the appearance of the element is relatively uniform in the bright state. However, there was a slight reduction in the tendency for darkening to be delayed compared to edges with contrasting regions of conductivity.

  In order to have a high degree of conductive contrast, the element has a third surface ITO, which is approximately 12 ohms and 40 ohms / square, respectively, with a 2 "silver conductive strip disposed across the center of the unit, Made for the same construction as in the previous paragraph, except that it was covered with a transparent conductive oxide flash layer (for process durability). The element is placed over the silver-coated part of the glass and has the same strength as the silver strip on the back of the area with relatively transparent 12 ohm / square and 40 ohm / square ITO when darkening properties are evaluated. A device with a contrast area of 40 ohms / square vs. 1/2 ohm sq on the third surface when viewed under these conditions when darkened. It was seen from the throttle effect is small element comprising a 12 ohm / square versus 1/2 ohms / sq contrasting regions.

  The element was made according to the previous paragraph except that an additional coating was used on the third surface. This coating consists of an additional flash layer of conductive oxide (put in for bonding because the process using vacuum is interrupted in the deposition process), approximately 300 nm silicon, approximately 60 nm ITO, another 20 nm silicon, then 10 nm ITO Consists of. Silicon layers can be susceptible to surface oxidation, which can cause surface oxides in certain EC elements, which impairs darkening uniformity and consistency. Other materials described herein as ITO or other TCO or flash layer or cover layer can be used to prevent the formation or adverse effects of the oxides described above. These elements, starting with a 40 ohm / square initial layer (according to the previous example), have a top and bottom area (according to FIGS. 5f and 7) of about 24 ohm / square and a central area < A third surface conductivity of 1 ohm / square was obtained. Elements starting with an initial ITO layer of 12 ohms / square had 10-12 ohms / square in the top and bottom regions. According to the previous example, an element with a large ohmic contrast has the lowest aperture effect or the largest gradient of darkening from the center to the edge. Furthermore, these elements also had the following optical characteristics when no power was applied using the “D65 2” angle observation device.

  Also, preferential darkening of certain areas of the electrochromic device is described by the thin deletion lines of the transparent conductor (stack) on the second surface or the third surface reflection (stack) as well as elsewhere in this specification. It can be obtained by gradually changing the thickness of the coating. Illustratively, using laser ablation, in general, thin laser lines can be generated by reducing the operating wavelength of the laser. A 15 micron wide deletion line was generated using a UV laser with a wavelength of 355 nm. These lines are still identifiable, but are much less distinguishable than those produced by using a long wavelength laser. As even shorter wavelength lasers become available continuously, it can be reasonably expected that deletion lines that are not aesthetically rejected in the visible region will be possible under normal conditions for automotive mirrors.

  There is a deleted portion of the coating stack that will become the third surface of the element at the line or part of the line shown across the center of FIGS. 5f and 7 and then the element is at the edge of the part. The darkening properties are affected when configured according to conventional techniques such that there is a relatively small contact portion in one and conductive epoxy is used on the other three sides of the element. . . .

A laser deletion pattern is created for both lines shown inside the elements as shown in FIGS. 5f and 7 on the 1/2 ohm / square reflector electrode as follows.
1) The coating was completely removed with a thin line extending from the edge of the glass to 15 cm from the edge of the glass.
2) The coating was completely removed with thin lines in a repeating pattern of 8 mm deletion and 2 mm non-ablated across the entire width of the part.
3) The coating was completely removed with a thin line extending from the edge of the glass to 14 cm from the edge, and then removed with a repeating pattern of 5 mm non-excised and 5 mm removed over the remainder of the part.
4) The coating was completely removed with a thin line extending from the edge of the glass to 15 cm from the edge except for two uncut segments of 0.4 mm at approximately 5 and 10 cm along the line.

  Compared to similar parts where there is no deletion line, these elements show a “squeezing effect” from somewhat to substantially less when darkened. Pattern 4 is the best deletion pattern among the overall aesthetics and darkening. Nevertheless, all of these patterns will require adjustment for acceptable darkening aesthetics, but movement towards the desired darkening properties has been shown.

  Referring to FIG. 8a, a first substrate 802a having at least one layer 808a of a substantially transparent conductor coated on a second surface and through a primary seal material 878a so as to form a chamber therebetween. Shown is a side view of a portion of a rearview mirror element including a second substrate 812a having a stacked material coated on a third surface fixed in spaced relation to each other. In at least one embodiment, an electro-optic medium 810a is disposed in the chamber. In at least one embodiment, the third surface stack of material comprises a lower layer 818a, a conductive electrode layer 820a, a metal layer 822a, and a conductive tab portion having a portion 883a overlying the metal layer and the primary seal material. 882a. Note that alternatively, the conductive tab portion 882a can be coated over the metal coating 822a to create an overlapping portion. In at least one embodiment, the lower layer is titanium dioxide. In at least one embodiment, no lower layer is used. In at least one embodiment, the conductive electrode layer is indium tin oxide. In at least one of the embodiments, the conductive electrode layer is omitted. In at least one embodiment, the conductive electrode layer is omitted and the underlying layer is a thick layer of titanium dioxide or some other substance that has a relatively high refractive index such as silicon carbide (ie, a higher refractive index than ITO). One of the transparent materials. In at least one embodiment, the conductive tab portion includes chrome. It is understood that the conductive tab portion can include any conductor that bonds well to glass and / or other layer stacks or epoxies and is resistant to corrosion under vehicle mirror test conditions depending on the layer arrangement. Should. As will be appreciated, if a third surface stack of erodible material or at least a layer in the stack is held in an area defined by the outer edge of the primary seal material, the element is Substantially avoid problems associated with surface corrosion. It should be understood that the layer or layers that are susceptible to corrosion can extend beyond the primary seal material if a protective overcoat or sealant, such as a conductive epoxy or overcoat layer, is incorporated. It is. Any of the first, second, third, and fourth surface or surface material stacks shall be as disclosed in this specification or references incorporated elsewhere herein by reference. It should be understood that It should be understood that the conductive tab portion improves the conductivity over the conductive electrode. That is, the conductive tab portion is optional as long as sufficient conductivity is provided to the conductive electrode layer. In at least one embodiment, the conductive electrode layer imparts the desired color specific properties to the corresponding reflected light in addition to the desired conductivity. Therefore, when the conductive electrode is omitted, the color characteristics are controlled through the specifications of the lower layer material.

  Turning to FIG. 8b, a primary substrate 802b having at least one layer 808b of a substantially transparent conductor coated on a second surface and a primary seal material 878b so as to form a chamber therebetween. Shown is a side view of a portion of a rearview mirror element that includes a second substrate 812b having a stacked material coated on a third surface that is secured in spaced relation to each other through. In at least one embodiment, an electro-optic medium 810b is disposed in the chamber. In at least one embodiment, the third surface stack of material includes a lower layer 818b, a conductive electrode layer 820b, a metal layer 822b, and a conductive tab portion under the primary seal material. In at least one of the embodiments, a void region 883c is formed between the metal layer and the conductive tab portion, and the conductive electrode makes electrical connection therebetween. In at least one embodiment, the lower layer is titanium dioxide. In at least one embodiment, no lower layer is used. In at least one embodiment, the conductive electrode layer is indium tin oxide. In at least one embodiment, the conductive tab portion includes chrome. It is understood that the conductive tab portion can include any conductor that bonds well to glass and / or other layer stacks or epoxies and is resistant to corrosion under vehicle mirror test conditions depending on the layer arrangement. Should. As will be appreciated, if the third surface stack of erodible material or at least the layer in the stack is held in the region formed by the outer edge of the primary seal material, the element is 3 substantially eliminates the problems associated with surface corrosion. Any of the first, second, third, and fourth surface or surface material stacks shall be as disclosed in this specification or references incorporated elsewhere herein by reference. It should be understood that

  Referring to FIG. 8c, a primary substrate 802c having at least one layer 808c of a substantially transparent conductor coated on a second surface and a primary seal material 878a so as to form a chamber therebetween. Shown is a side view of a portion of a rearview mirror element including a second substrate 812a having a stacked material coated on a third surface that is secured in spaced relation to each other through. In at least one embodiment, an electro-optic medium 810c is disposed in the chamber. In at least one embodiment, the first metal layer 818c is coated over substantially the entire third surface. In at least one embodiment, the second metal layer 820c is disposed such that the outer edge of the second metal layer is disposed in a region formed by the outer edge of the primary seal material 878c. Covered over the metal layer. In at least one embodiment, the first metal layer includes chromium. In at least one embodiment, the second metal layer comprises silver or a silver alloy. Any of the first, second, third, and fourth surface or surface material stacks shall be as disclosed in this specification or references incorporated elsewhere herein by reference. It should be understood that

  Turning to FIG. 8d, a second substrate 812d is shown that includes a stacked material that has a small hole 822d1 substantially in front of the light sensor or information display. In at least one of the embodiments, the first metal layer 818d is provided with a void area in the small hole area. In at least one of the embodiments, the second metal layer 820d is provided with a void region in the small hole region. In at least one embodiment, a third metal layer 822d is provided. In at least one embodiment, only the third metal layer is coated on the eyelet area. In at least one embodiment, the first metal layer includes chromium. In at least one embodiment, the second metal layer comprises silver or a silver alloy. In at least one embodiment, the third metal layer comprises thin silver, chromium or a silver alloy. Any of the first, second, third, and fourth surface or surface material stacks shall be as disclosed in this specification or references incorporated elsewhere herein by reference. It should be understood that

  Turning to FIGS. 9a-9k, various options for selectively contacting specific portions of the second and third surface conductive electrode portions 922, 908 are shown. As will be appreciated, the configuration of FIG. 7 results in an electrically conductive material that contacts at least a portion of each second and third surface conductive electrode portion. It should be understood that a contact arrangement as shown here can be rotated around the element in any manner.

  The element configuration shown in FIG. 9a includes a first substrate 902a having a second surface stack 908a of material and a second substrate 912a having a third surface stack 922a of material. The third surface stack of material has an isolation region 983a, and a portion of the third surface stack of material in contact with the conductive epoxy 948a is isolated from the rest of the third surface stack of material. As shown. The first and second substrates are held in spaced relation through the primary seal material 978a. It should be understood that another side of the element can have a similar isolation region associated with the second surface stack of material in contact with the third surface stack of material within the visible region. It is. As described elsewhere in this specification and references incorporated herein by reference, either the second or third surface stack of material can be a single layer of material. Should be understood.

  The element configuration shown in FIG. 9b includes a first substrate 902b having a second surface stack 908b of material and a second substrate 912b having a third surface stack 922b of material. The first and second substrates are held in spaced relation through the primary seal material 978b. The conductive epoxy 948b contacts the third surface stack of material and is electrically isolated from the second surface stack of material through the insulator material 983b. It should be understood that another side of the element can have a similar isolation region associated with the second surface stack of material in contact with the third surface stack of material within the visible region. It is. As described elsewhere in this specification and references incorporated herein by reference, either the second or third surface stack of material can be a single layer of material. Should be understood.

  The elements of FIG. 9c include a first substrate 902c having a second surface stack 908c of material and a second substrate 912c having a third surface stack 922c of material. The first and second substrates are held in spaced relation through the primary seal material 978c. The second surface stack of material extends beyond the primary seal material and toward the edge of the first substrate to be in electrical contact with the first conductive epoxy or first solder 948c1. Yes. The third surface stack of material extends beyond the primary seal material and toward the edge of the second substrate so as to be in electrical contact with the second conductive epoxy, or the second solder 948c2. Yes. It should be understood that another side of the element can have a similar isolation region associated with the second surface stack of material in contact with the third surface stack of material within the visible region. It is. As described elsewhere in this specification and references incorporated herein by reference, either the second or third surface stack of material can be a single layer of material. Should be understood.

  FIG. 9d shows a second surface electrical contact 948d1 made on one side opposite from the third surface electrical contact 948d2 of the element. FIG. 9e shows a second surface electrical contact 948e1 made on one side of the element and a third surface electrical contact made on one end of the element. FIG. 9f is made at one side of the element and a second surface electrical contact 948f1 made continuously at one end and one opposite side of the element and one continuously opposite end. A third surface electrical contact 948f2 is shown. FIG. 9g shows a second surface electrical contact 948g1 made on opposite sides of the element and a third surface electrical contact 948g2 made on one end of the element. FIG. 9h shows a second surface electrical contact 948h1 made on opposite sides of the element and a third surface electrical contact 948h2 made on opposite ends of the element. FIG. 9i shows a second surface electrical contact 948i1 made continuously on opposite ends and one side of the element and a third surface electrical contact made on one side of the element. 948i2 is shown. FIG. 9j shows a second surface electrical contact 948J1 made continuously on both ends, the entire side, and at least a portion of the second side, and a third made on one side of the element. The surface electrical contact portion 948J2 is shown. It should be understood that in at least one of the embodiments, the long electrical contact will coincide with the surface having the highest sheet resistance stack of materials. It should be understood that the electrical contact can be through conductive epoxy, solder, or conductive adhesive.

  FIG. 9k shows an element including a first substrate 902k having a second surface stack 908k of material and a second substrate 912k having a third surface stack 922k of material. The first and second bases are held in a spaced relationship from each other through the peripheral first and second primary seals 948k1, 948k2. The first primary seal serves to make electrical contact to the second surface stack of material, and the second primary seal so as to make electrical contact to the third surface stack of material. work. The first and second primary seals hold the first and second substrates in spaced relation to each other, and preferably both primary seals are substantially outside the edges of each substrate.

  Another method for establishing an electrical connection to a contact clip, such as a J clip or an L clip of an electrode or electro-optic element, is by solid phase welding. Wire bonding is a welding method used in the electronics industry to establish a reliable interconnection between electronic components (usually IC chips and chip carriers). The wire bonding method is described in Chapter A, “Nordic Electronics Packaging Guidelines” by Zonghe Lai and Johan Liu. Electrical interconnects created by wire bonding use a combination of metal wire or ribbon and heat, pressure, and / or ultrasonic energy to weld the wire or ribbon to the associated metal surface. Typically, the wire or ribbon is welded using a special wedge or capillary coupling tool. Typical bonding processes use thermal and / or ultrasonic energy and are generally classified into three main categories. That is, thermocompression bonding, ultrasonic bonding, and thermosonic bonding. Wires to be joined can be terminated at the joint and multiple joints can be made on the continuous wire. Common forms of wire bonding include ball bonding, wedge bonding, and stitch bonding. Wires and ribbons made of many different metals and alloys, including aluminum, gold, silver, copper, and alloys thereof can be wire bonded. These wires bond to a substrate coated with a metal layer, including, but not limited to, metal layers of gold, silver, nickel, aluminum, and alloys made of these metals Can be made. For bonding to the electrode of the electro-optic element, the preferred substrate is glass and the preferred metal deposition process is by a physical vapor deposition process such as magnetron sputtering. One or more glue layers, such as chromium, molybdenum, nichrome, or nickel, can be added between the wire bonded metal layer and the glass to obtain an acceptable adhesive bond. The thickness of the coating metal layer can be between 5 Angstroms and 1000 microns. More preferably, the metal layer thickness is between 100 angstroms and 1 micron, and most preferably the metal layer thickness is between 200 and 1000 angstroms. The wire diameter or ribbon thickness can be between 10 and 250 microns, with a diameter or thickness between 25 and 100 microns being preferred, and a diameter or thickness between 50 and 75 microns being most preferred. In at least one embodiment, the continuous wire can be wedged or stitched along the periphery of the substrate, such as a chrome ring on the second surface of the electrochromic mirror. A wire or ribbon bath is electrically connected to a clip, such as a nickel J or L clip, by welding the wire or ribbon to the clip, and then annularly connecting the cup to the substrate and welding it to the associated electrode. Can be connected. The wire or ribbon can start at the metal clip and travel along the EC electrode, can start along the EC electrode, can be annularly connected to the clip, and can return to the electrode. In at least one embodiment, it is preferred to have a weld connection that overlaps to the relevant electrode and / or from the EC electrode to the relevant electrically contacting clip in order to reliably and uniformly color the device. Multiple weld connections to the substrate can be made at intervals of 0.005 inches to 10 inches, with a spacing of 0.040 inches to 2 inches being preferred, with a spacing between 0.100 and 0.50 inches. Most preferred. The welding wire or ribbon bath can be protected from damage by encapsulating the wire and weld in a seal. The preferred method is to protect the bus by encapsulating the wire / ribbon and weld joint in the peripheral seal of the associated element. The metal wire / foil is preferably chemically compatible with the EC media that encapsulates the bath within the device (inside the peripheral seal). In addition, a wire bus can be used to supplement the conductivity of the associated electrode within the element. Wires with lineages of 75 microns or less are not readily apparent to the human eye. Welding wire bonding is a room temperature or low temperature process and does not require post-curing or post-processing, and this technique has been established with proven reliability and is capable of rapid bonding (approximately 100 milliseconds / bonding). It is attractive from a manufacturing point of view because it can be established.

  Also, wire bonding can be used to electrically connect the electronic component to the substrate surface of the element. For example, many metals are electrochemically stable when used as an element cathode, but are not stable when used as an anode. It is desirable to protect with a diode or the like that limits the operation of the EC device when the polarity is reversed. (This is described in detail below with reference to FIGS. 11a-11c.) Electrical components such as surface mounted diodes are attached to the substrate or bus clip and electrically connected to the substrate and / or clip by wire bonding. Can be connected. In another embodiment, a light emitting diode (LED) that is part of a signaling or warning system is attached to the associated substrate in the form of a chip, for example, by patterning a metal coating by etching, masking, or laser ablation. It can be electrically connected to the circuit of the substrate. These LEDs or other electrical components can be mounted on or within the elements of the substrate surface 1, 2, 3, or 4. In many cases, increasing the temperature increases the drive voltage applied to the solution phase electrochromic device to compensate for the increased diffusion rate of the electrochromic species and maintain good device darkening characteristics over a wide temperature range. It is desirable. The thermistor and electronic components required for the temperature modulated variable voltage drive circuit can be mounted on the associated substrate surface and electrically connected to the metal coating on the substrate by wire bonding. Example: An aluminum wire is bonded to a metal coating on a glass substrate as follows.

Glass is cleaned, first layer chromium and second layer nickel (CN), first layer chromium and second layer ruthenium (CR), first layer chromium, second layer Vacuum sputter coat with a layer of approximately 400 Angstroms thick, including a ruthenium and a third layer of nickel (CRN). 0.00125 "diameter aluminum alloy wire containing 1% silicon (1-4% elongation, 19-21 gram tensile strength) metallized glass substrate using" Westbond Model 454647E "wire bonder with the following settings To wire.
Set value, first coupling, second coupling “CN” power, 175, 150
Time, 30 ms, 30 ms force, 26 grams, 26 grams “CRN” power, 175, 150
Time, 30 ms, 30 ms force, 26 grams, 26 grams “CR” power, 150, 125
Time, 75 ms, 100 ms force, 26 grams, 26 grams The bond strength of the wire was evaluated by pulling the wire apart after bonding and after exposure to 300 degrees Celsius for 1 hour and measuring the force.
Wire bond average tensile strength:
After bonding, after firing at 300C “CN”, 14.51 grams, 9.02 grams “CRN”, 19.13 grams, 8.2 grams “CR”, 12.42 grams, 8.7 grams

  The main breakage after the bond was a wire break at the end of the first weld bond. After firing, the main breaks were the wire break at the center of the span for the “CN” and “CRN” groups and the wire break at the end of the first bond for the “CR” group. It was. This example demonstrates that multiple reliable weld joints can be made in a typical sputtered metal layer on glass.

  FIG. 10 is generally electrically coupled to the variable transmittance window 1010 to control the transmittance state of the variable transmittance window 1010 in addition to the variable transmittance window 1010 that can be used in multi-passenger vehicles. A window control system 1008 is shown. The window control system 1008 includes a window control unit 1009 coupled to each variable transmittance window 1010 to control the transmittance of each variable transmittance window 1010. Each window control unit 1009 includes a slave control circuit 1070 for controlling the transmittance state of the associated variable transmittance window 1010. Further, each window control unit 1009 provides a user input mechanism 1060 coupled to the slave control circuit 1070 for providing user input to the slave control circuit 1070 to change the state of transmission of the associated variable transmittance window 1010. Is also shown to have. Further, each window control unit 1009 is also shown connected to a power source and ground line 1011 for supplying power to the slave control circuit 1070, a user input mechanism 1060, and a variable transmittance window 1010. . As shown, power is supplied from the power and ground line 1011 to the variable transmittance window 1010 through the slave control circuit 1070.

  Each window control unit 1009 is also shown connected to a window control system bus 1013. In addition, other devices coupled to the window control system bus 1013 include a master control circuit 1090 and other electronic devices 1092. The master control circuit 1090 is configured to monitor a signal supplied to the window control system bus 1013 by each window control unit 1009 and supply a control signal regarding the bus to each window control unit 1009. The master control circuit 1090 includes processing circuitry including logic, memory, and bus interface circuits, allowing the master control circuit 1090 to generate, transmit, receive, and decode signals related to the window control system bus 1013. The slave control circuit 1070 included in each window control unit 1009 receives a desired window transmittance state from the user input mechanism 1060 and supplies an electric signal to the variable transmittance window 1010 to transmit the variable transmittance window 1010. The rate state is configured to change to the state requested by the user through the user input mechanism 1060. Further, the slave control circuit 1070 is also configured to monitor various characteristics of the variable transmittance window 1010 including the power consumed by the variable transmittance window 1010 and the state of the transmittance of the variable transmittance window 1010. In addition, slave control circuit 1070 includes circuitry for receiving signals from window control system bus 1013 and transmitting signals thereto.

  Certain metal films, when configured as anodes, may not be as stable as transparent conductive oxides such as indium tin oxide films. This may be due to metal plating annihilation from the anode, due to chemical changes in the metal surface such as oxidation, or due to the surface becoming hazy due to rearrangement of mobile metal atoms to a rough surface, thereby circulating in the electrochromic device. Sometimes it becomes obvious. Some metal and metal thin film stacks and thin film stacks containing metal layers will be more resistant to these effects than others. Nevertheless, it may be desirable to take measures to ensure that the third surface reflector electrode is a cathode.

  In certain embodiments, it may be considered preferable to incorporate a material sensitive to use as the anode into the transparent electrode on the second surface. In this case, it would be preferable to drive the third surface electrode as an anode and the second surface electrode as a cathode to protect the second surface electrode.

  For electrochromic mirrors outside the vehicle, there can be a power source that is not directly connected to the associated drive circuit located in the associated internal mirror, whereby the third surface reflector electrode is The risk of being an anode at that mirror can be reduced to some extent (ie, a given external mirror can include an independent drive circuit). However, the power of the external mirror (or a plurality of mirrors) is generally supplied through the internal mirror. In many cases, there are several connections between an inner mirror and a corresponding outer mirror. The danger of reversing the polarity of power from the inner mirror to the outer mirror and creating the reflector electrode and anode on the third surface of the device is not durable enough that the associated reflector / electrode functions as an anode. The case may be unacceptable.

  Referring to FIG. 11a, circuit 1101a having a diode in parallel with external mirror element 1102a prevents reverse polarity current as well as electrochromic functionality. The device will be darkened when a normal voltage is applied to the mirror, but if the circuit is shorted by the internal mirror circuit for lightening, the external mirror cannot be discharged through its path In that respect, performance may be degraded when operating with the correct polarity. Thus, the external mirror element will primarily discharge when positively and negatively charged species are neutralized together in solution, but will not discharge when discharged to the conductive surface of the device. This substantially slows down the lightening speed of the device.

  The circuit 1100b shown in FIG. 11b includes a diode 1101b in parallel between the conductors near the external mirror element 1102b. A reversal of the polarity of the current supplied to that part of the circuit will cause a short circuit. The current will then flow through the diode but not through the electrochromic element. When a short circuit is detected by the internal mirror circuit 1103b, the voltage is automatically disconnected. Thus, even if the mirror can operate properly when the polarity is correct, this circuit completely disables the mirror's electrochromic function when the polarity is reversed.

  However, when diode 1101c is initially coupled to a circuit 1100c that is overcurrent (short circuit) but does not interrupt the application of voltage when in reverse voltage, mirror element 1102c remains operable and has the proper polarity. Is delivered to the element and the reflector electrode is automatically reconnected as the cathode. In this circuit 1100c, when an excess current is detected, the two solid state switches 1104c1, 1104c2 are automatically configured to redirect power back through the element 1102c. If excessive current is detected in this configuration, the solid state switch is reset and the drive mechanism to the element is discontinued because some other fault is likely causing excessive current draw.

  FIG. 11d shows another configuration for an electro-optic drive circuit that automatically compensates for reverse polarity. The diodes 1101d1, 1101d2, 1101d3, and 1101d4 form a rectifier bridge that provides a double current path. The actual path current flow will always have the desired direction of the anode and cathode of the electro-optic element 1102d.

  The circuits 1100a, 1100b, 1100c, 1100d of FIGS. 11a-11d are shown for a single external mirror. If it is desired to protect more mirrors than a single external mirror, the desired circuitry can be adapted to it.

  In an electro-optic element similar to that shown in FIG. 7 having a fourth surface reflector (not shown), if there is no potential difference between the transparent conductors 708 and 718, the in-chamber electrochromic medium 710 is , Essentially colorless or nearly colorless, and incident light (I0) enters through the front element 702, passes through the transparent coating 708, the in-chamber electrochromic medium 710, the transparent coating 718, the rear element 712, and the layers Back through the device and out of the front element 702. It should be understood that aspects of the present invention relating to variable transmittance windows as described above may not incorporate a reflective layer. In other embodiments, a third surface reflector / electrode can be used. Typically, the magnitude of the reflected image (IR) with no potential difference is about 45 percent to about 85 percent of the incident light intensity (I 0). Exact values include, for example, residual reflection (IR) from the front surface of the front element, and secondary reflection from the interface between the front element 702 and the front transparent electrode 708, the front transparent electrode 708 and the electrochromic It depends on a number of variables outlined below, such as the medium, the electrochromic medium and the second transparent electrode 718 and the second transparent electrode 718 and the rear element 712. These reflections are well known in the art and are due to the difference in the refractive index between one material and another when light crosses the interface between the two materials. If the front and back elements are not parallel, the residual reflectivity (I'R) or other secondary reflections will not overlap the reflected image (IR) from the mirror surface and a double image will appear. (The observer will see what appears double or triple, ie, the number of objects actually present in the reflected image).

  There is a minimum requirement for the magnitude of the intensity of the reflected light, depending on whether the electrochromic mirror is located inside or outside the vehicle. For example, according to current requirements for most automobile manufacturers, the minimum high-end reflectivity of the inner mirror is preferably at least 40 percent, and the minimum high-end reflectivity of the outer mirror is at least 35 percent. Should.

The electrode layers 708 and 718 are connected to, for example, the electronic circuitry of FIGS. 10-11d, which provides electrical energy to the electrochromic medium, and when a potential is applied across the conductors 708 and 718, The electrochromic medium 710 is darkened, which is effective to attenuate the incident light (l ₀ ) when the light passes toward the reflector and is reflected back. By adjusting the potential difference between the transparent electrodes, the preferred device functions as a “grayscale” device with continuous variable transmission over a wide range. For solution phase electrochromic systems, when the potential between the electrodes is removed or returned to zero, the device will spontaneously become the same zero potential that the device had before the potential was applied. , Return to equilibrium color, and transmittance. It should be understood that other materials can be used to make the electrochromic device, and embodiments of the present invention can be applied whether or not electro-optic technology is used. For example, the electro-optic medium can include a solid metal oxide, a redox active polymer, and a material that is a hybrid combination of a solution phase and a solid metal oxide, or a redox active polymer, but the solution phase design described above. Are typical of most electrochromic devices in use today.

  Various attempts have been made to provide the electro-optic element with a second surface transparent conductive oxide having a relatively low sheet resistance while maintaining low absorption. In the electrochromic mirrors described above, as well as electrochromic windows or generally electro-optic devices, the transparent conductive layers 708, 718 are often made of indium oxide. Other attempts have focused on reducing the intrinsic stress of the ITO layer when applied to the associated glass substrate and minimizing substrate bending or warping. Yet another attempt is to optimize optical properties such as reflectivity by adjusting the quarter and / or half wave thickness of the ITO layer, or to minimize the associated overall assembly weight. Was done. However, due to the above physical limitations, efforts to optimize all of the above optical and physical properties at the same time have been almost unsuccessful.

  One such previous method of optimizing the optical properties of a given electrochromic assembly has been to manipulate the composition of the electrode. More specifically, specific optical properties can be obtained by adjusting the reflectivity of the reflective electrode of the assembly. More specifically, by manipulating the material composition of the stacked layer containing the reflective electrode, its reflectivity can be increased, thereby eliminating the relative absorption of the associated transparent electrode. However, in order to increase the reflectivity of the reflective electrode, it is typically necessary to use additional amounts of metal used to make it such as rhodium, ruthenium, chromium, silver. . Many of these metals are relatively expensive, so adding that additional amount to the electrochromic element results in an unacceptably high cost. Furthermore, many low cost metals have good reflective properties, but are incompatible with the manufacturing process and / or harsh environmental conditions that the overall assembly, such as the external mirror assembly and the external window assembly, will experience. .

  Other methods using ITO electrodes required balancing some optical and physical parameters that were not compatible with each other. For example, increasing the thickness of a transparent ITO conductive layer to achieve low sheet resistance, as described in detail below, the absorption associated with that layer, the location of quarter and / or half wave points, and ITO The bending of the substrate to which the layer is added can be adversely affected.

  As is known in the art, the sheet resistance of the ITO layer can be reduced by increasing the thickness of the layer. However, increasing the thickness of the ITO layer is accompanied by an undesired increase in light absorption of the layer. In addition, increasing the thickness of the ITO layer typically reduces the relative reflectivity from the outer surface of the ITO layer, typically in a given wavelength range (typically centered around 550 nm). Limited to the amount of half-wave. Furthermore, when the thickness of the ITO layer is increased, the bending of the substrate to which the ITO layer is added may increase. As is known, ITO layers contain internal stresses that are exerted on a substrate, which can cause such substrates to bend when applied to several thin substrates. In many applications, the substrate includes a relatively thin glass to reduce glass absorption and its associated weight, so that unacceptable bending occurs as the thickness of the ITO layer increases. This is particularly common in large applications such as large windows as used in aircraft or buildings. Bending of the associated substrate affects the distance between the two electrodes in the overall assembly, thereby causing the lightening speed, color, relatively uniform darkness of the assembly at various points across its surface, or It affects brightness and can also cause optical distortion at the points of the multiple reflected images generated rather than a single image. Previous approaches to reducing the internal stress of the ITO layer have focused on the method used to produce the electrochromic element. One method known in the art for applying an ITO layer to an associated substrate includes magnetic sputtering. Traditionally, these attempts have been only moderately successful due to a number of drawbacks, one of which is the physical limitations inherent in this method, examples of which include pressure Increasing it destroys the stack of ITO layers and clusters the ITO. Such clustered ITO layers show increased sheet resistance, haze, and absorption.

  In at least one embodiment, the sheet resistance is reduced, the absorbency is reduced, the stress is reduced, and at the same time the overall assembly, any partial combination or combination thereof is reduced in weight while reducing the weight of the entire assembly. An electro-optic element using an ITO layer that provides darkness or brightness is provided.

  In at least one embodiment, an electro-optic element is provided in which the sheet resistance is relatively reduced while at the same time the absorbency is relatively reduced and the associated substrate bending to which the associated ITO layer is added is relatively reduced. This provides a relatively uniform darkness and brightness for the overall assembly while reducing its total weight.

  Although mirror assemblies are generally used herein to describe many details of the present invention, embodiments of the present invention are not limited to electro-optic window configurations as described elsewhere herein. Note that is equally applicable. The inner mirror assembly of FIGS. 6a-6d and the outer rearview mirror assembly of FIGS. 5a-5f are described in Canadian Patent 1,300,945, US Pat. No. 5,204,778, or US Pat. No. 5,451. These patents can incorporate light sensing electronics of the type shown and described in US Pat. No. 822, and other circuits that can detect glare and ambient light and provide a drive voltage to the electrochromic element. The entire disclosure of which is incorporated herein by reference.

  As noted above, high performance electro-optic elements (either mirrors or windows) have a third surface electrode and / or reflector and transparent conductive electrode 708 medium to high conductivity, and overall coloration; It is necessary to obtain an increase in coloring and light color speed. Although improvements in the mirror element are achieved by using a third surface reflector / electrode, improvements with respect to the transparent electrodes 708, 718 are desirable. Again, as described above, simply increasing the overall thickness of the ITO transparent electrodes 708, 718 while improving the conductivity to reduce the sheet resistance will result in other optical and physical properties of the electrochromic element. Adversely affect. Table 4 shows the decrease in reflectivity of EC elements when changing the ITO thickness for three ITO coatings with different optical constants. The different ITO coatings in this example have different imaginary refractive indices. An example element configuration consists of 1.7 mm glass, 50 nm Cr, 20 nm Ru, 140 micron EC fluid, various ITO, and 1.7 mm glass. The thicknesses of the different ITO layers are shown in Table 4. For many side mirror applications, customer specifications require a reflectivity greater than 55%. The thickness is limited by the properties of the ITO, and therefore the workable sheet resistance is also limited. With a suitable manufacturing process, it is not always possible to operate the process at the lowest absorption level. Therefore, practical upper thickness and low sheet resistance limitations are constrained by manufacturing process variations. Furthermore, it is common for low absorption ITO to accommodate high sheet resistance, which is undesirable. In addition, thick and low absorption ITO can also support high sheet resistance, thereby limiting the benefits of thick coatings.

(Table 4)

  Another design attribute desirable for EC elements is having low reflectivity in the dark. This results in a high contrast of the mirror element. Table 5 shows the dark reflectance values for the EC mirror as a function of ITO thickness. In this example, the EC fluid is set to be substantially opaque. If the EC fluid is not completely opaque, the reflected light from the mirror coating will be added to the reflectivity in Table 5. As shown. The dark state reflectance reaches a half-wave coating at a minimum of about 140-150 nm or a design wavelength of 550 nm. When the thickness deviates from this half-wave thickness, the dark reflectance increases and the contrast ratio decreases. Therefore, the ITO thickness cannot be set to an arbitrary thickness in order to obtain a predetermined sheet resistance value. ITO thickness is constrained by both the absorption and dark state reflectance requirements of the coating.

(Table 5)

  In at least one embodiment, the electro-optic element comprises at least one ITO transparent electrode 128 that has improved conductivity by reducing bulk resistance without compromising other associated optical and physical properties at the same time. Including. More particularly, the electro-optic element is constructed through a sputtering process at a relatively high pressure and a relatively high oxygen flow rate. Traditionally, the conventional sputtering process used to apply an ITO layer to a substrate is limited to a certain maximum pressure. Exceeding these pressures previously resulted in a poor quality layer of ITO, more specifically a clustered, non-uniform coating, resulting in poor electrical and physical properties.

  In at least one embodiment, the ITO coating was generated with a vertical in-line sputtering coating apparatus. The cathode was approximately 72 "in length and the coating was produced using either two or four cathodes. The cathode was equipped with ceramic ITO tiles commonly used in the industry. Conveyor speed depends on the target thickness. The power applied to the cathodes was 5 kilowatts unless otherwise noted Each treatment compartment has two pairs of cathodes in an aligned facing configuration. The oxygen gas flow shown here is for a treatment compartment consisting of four cathodes unless otherwise indicated, and when two treatment compartments are operated, an equivalent amount of oxygen is supplied to both chambers. And the total amount of oxygen is thought to be twice that used for the four cathodes in one processing chamber.The glass substrate is preheated to approximately 300 degrees Celsius. The sputtering gas was adjusted to reach a predetermined pressure and oxygen was introduced as a specified flow rate or as a percentage of the total gas supplied to the system, but the present invention does not have the exact flow rate described herein. As will be appreciated by those skilled in the art, different chambers have different pumping configurations, gas inlets and manifolds, cathodes and power sources to measure pressure at different points in the process. On the contrary, those skilled in the art will understand the novelty of the properties, including the bulk resistance, stress, and morphology obtained by the method used to produce the coating, and the present specification without canceling the experiment. Can be easily scaled or adapted to different sputtering systems and is described herein. Most of the work to be done was done at a glass substrate temperature of 300C, but the trends and findings are applicable to higher and lower temperatures, and the absolute values described here are not obtained at different temperatures. Even better than the standard condition.

  In at least one embodiment of the present invention, the increase in process pressure is offset by increasing the oxygen flow rate. As described herein, the specific relationship of pressure to oxygen flow depends on several factors including the particular noble gas used during the sputtering process. Two noble gases, krypton and argon are described in detail herein, but other gases can be used with extrapolation of details for other gases from predetermined data.

  For krypton, a pressure equal to or greater than 1 millitorr (mT) at 5% oxygen is preferred, a pressure equal to or greater than 2 mT at 4% oxygen is more preferred, and a oxygen percentage of 3%. A pressure equal to or greater than 3 mT is more preferred, and a pressure equal to or greater than 4.5 mT at 2% oxygen flow is most preferred.

  For argon, a pressure equal to or greater than 2 mT at 4% oxygen percent is preferred, a pressure equal to or greater than 3 mT at 3% oxygen is more preferred, and 4.5 mT at 2% oxygen. A pressure equal to or greater than is more preferred, and a pressure equal to or greater than 6 mT at 1% oxygen percentage is most preferred.

  As described above, other gases can be used. For example, neon can be used, the expected high pressure, preferably equal to or greater than 3 mT, more preferably equal to or greater than 7 or 8 mT. Furthermore, xenon can use relatively low pressure compared to krypton. Furthermore, those skilled in the art will appreciate that the preferred oxygen percentage may vary with the details of the sputtering apparatus. The percentages listed above are meant to be illustrative and non-limiting. The total oxygen flow required to obtain the optimal combination of material properties will generally increase with increasing pressure. Since the required amount of oxygen does not increase the sputtering gas at the same rate, the oxygen percentage decreases as the pressure increases.

  Typically, ITO is operated at low pressure, ie 2 mT or less. However, at low pressures, there is a tendency to have an ITO coating with compressive stress. The stress of ITO can be high enough to bend the glass, especially when the glass thickness decreases. As the thickness of the glass decreases and the EC element becomes lighter, the deflection of the glass due to ITO stress increases. If the size of the mirror element or window is large, the deflection of the glass can be several millimeters. In conventional mass production processes, as the thickness of the ITO decreases, the deflection of the substrate typically decreases.

  Glass deflection can be expressed in various ways. One way is to think that the glass deflection is lens related. The magnification value is then directly related to the glass deflection and is independent of the glass dimensions. The magnification value is related to the radius of curvature using the following formula: radius of curvature = (3124 mm) / (1-1 / magnification). The magnification value of a completely flat glass piece is 1.0. When the coating glass viewed from the coating side is subjected to compressive stress, the glass has a convex surface on the coating side. When the coating is under tensile stress, the glass is concave on the coating side. In a compression coating, distortion occurs or the magnification value is less than 1; conversely, if the coating is under tension, the magnification or distortion value will be greater than 1. A strain value of about 0.85 is highly distorted from flat glass. With this degree of distortion value, the reflectivity from the first and third surfaces cannot overlap, resulting in an EC mirror or window that may have a double image. Furthermore, it is difficult to produce a viable seal with glass having unacceptable strain. Glass with a strain value as high as 0.97 can cause manufacturing or double image problems.

Referring to FIG. 12, labeled “Argon Pressure Test”, the strain values are measured against an ITO coating on 1.6 mm glass. Glass thickness plays a major role in deflection and strain when ITO or other stress coatings are applied. The amount of deflection generally varies inversely with the cube of the thickness of the glass (the intrinsic stress of the coating is considered constant with respect to the thickness of the coating). Therefore, the thin glass is distorted nonlinearly with respect to the thick glass. Thin glass will generally be distorted with thin ITO coatings compared to thick glass. The amount of strain is linearly proportional to the coating thickness. In FIG. 12, all coatings were approximately 50 nm thick. To calculate the strain at other thickness values, the following equation can be used: New strain = [1− (1−strain value) ^* new thickness / old thickness]. Using this equation for the value of 0.98 in FIG. 12 would lead to a strain value of 0.94 for an ITO coating thickness of 150 nm and a strain value of 0.74 for a coating thickness of 650 nm. If the glass is thin, these values will deviate further from being substantially flat.

  FIG. 12 shows some important findings. In this experiment, the first strain value or stress (y axis) of ITO produced at 2.1 mT does not substantially change over the oxygen flow range (x axis). Over this range, ITO passes the minimum sheet resistance and bulk resistance values. This can lead to a false conclusion that it is not possible to optimize both electrical and stress properties simultaneously, let alone other necessary optical properties. At very fast oxygen flow rates, the strain values begin to deviate substantially more than flat.

  At high pressure (4.0 mT), a certain tendency appears. At low oxygen flow rates, the ITO coating stress is reduced. However, at high pressure this translates to the low oxygen percentage of the overall sputtering environment. In the sputtering art, it is common to keep the oxygen percentage constant while adjusting the pressure. Thus, this trend and insight leading to one embodiment of the present invention has not been found when using conventional experiments. At a high argon pressure of 4 mT shown by line 1202, a strong trend appears, thereby minimizing ITO stress at low oxygen flow rates compared to 1201. The low stress is due to the unique microstructure or morphology of the ITO coating described in detail below. At high oxygen flow rates, the strain values deviate from flatness, but at any particular oxygen flow rate, the strain values remain higher than those obtained at low pressures. This tendency continues even at a higher pressure than that shown in FIG. Profits will continue even at pressures above 7mT. Furthermore, improvements may be obtained at higher pressures, but experiments at pressures above this value may be constrained by certain sputtering chamber limitations.

  The graph of FIG. 13 shows the effect of a relative increase in argon pressure and oxygen flow rate on the bulk resistance. This particular test was performed using argon as the sputtering gas. For 400 sccm argon (line 1301), a pressure of 3.7 mT results, 550 sccm (line 1302) yields 5 mT, 700 sccm (line 1303) yields 6.2 mT, and 850 sccm (line 1304) yields 7.4 mT. . The oxygen flow rate on the x-axis is sccm. Note that increasing argon pressure and oxygen flow yields significant improvements in bulk resistance. Further, in the case of low argon pressure, there is a tendency to have a minimum value with a high bulk resistance value as compared with the case of high pressure. As a reference, a comparable coating produced at a pressure of 2 mT includes a bulk resistance value between about 180 and 200 micro ohm cm. In a recently published patent application, another manufacturer of electrochromic devices has shown that the current state of ITO coatings for EC applications corresponds to a bulk resistance of 200 micro ohm cm. This indicates that the improved ITO coating of the present invention is not expected due to the advantages and properties of ITO that are viable for EC applications. For the high pressures described herein, a minimum value is not obtained in the range of oxygen tested.

  The graph of FIG. 14 shows that the high pressure further causes the ITO coating on the substrate to be relatively thin. Furthermore, this fact is the reason why this embodiment of the present invention has not been achieved previously. As shown, as the oxygen flow rate and argon pressure increase, the thickness of the ITO coating decreases. Bulk resistance is an inherent measure of the quality of the electrical properties of ITO, which is multiplied by sheet resistance and thickness. It is common to measure only the sheet resistance, but much information is lost if the coating properties are not detailed. Since the coating becomes thinner with changes in process gas, the sheet resistance does not follow the same trend as the bulk resistance. For comparable analysis of sheet resistance, high argon pressure (line 1404 represents the highest for lines 1401, 1402, and 1403) and oxygen flow will continue to benefit bulk resistance. Show. If only the sheet resistance is examined, it can be concluded that the case of 3.7 mT is the best, and that favorable characteristics are obtained at a relatively low oxygen flow rate. Another advantage that arises with low bulk resistance is that the real part of the refractive index is reduced. The low refractive index half-wave coating is physically thicker than the high refractive index one, resulting in even lower sheet resistance.

  The graph in FIG. 15 shows the effect of using argon gas in combination with increased argon pressure and increased oxygen flow, and the graph in FIG. 16 shows the achieved ITO half-wave bulk resistance. Two processing chambers were used to obtain a 1/2 wave coating. The 200 sccm represents the prior art ITO coating standard in the EC technical field. The sheet resistance of the prior art half wave coating exceeded 12.5 ohms / square, but at higher pressures according to at least one embodiment of the present invention, the sheet resistance is less than 12 ohms / square and 11 ohms / square. Values less than square were also obtained. A substantially improved bulk resistance obtained at high pressure is illustrated in FIG. In this case, oxygen is not optimized at high pressure and the bulk resistance appears to be relatively constant at an argon flow rate of 400-800 SCCM.

  While the bulk resistance of ITO is important, as described elsewhere herein, sheet resistance is a major factor affecting the darkening rate of EC elements. A bulk resistance of 200 micro ohm cm is equivalent to a sheet resistance of 13.7 ohm / square for a half wave coating, a bulk resistance of 180 is equivalent to a sheet resistance of 12.4 ohm / square, and a bulk resistance of 140 is 9 Equivalent to a sheet resistance of 6 ohm / square. 9.6 ohm / square is a 30% reduction compared to the 13.7 ohm / square case, which will substantially improve the darkening time, as described elsewhere herein. New bus configurations will be possible, which also improves the uniformity of element darkening.

  In the following examples, the coatings were produced with different coating equipment. The coating apparatus has a cathode that is approximately 27 inches long. Experiments were performed on both argon and krypton at a pressure of 2.73 millitorr. The coating was done in two passes past the cathode. The oxygen was varied as shown in the accompanying figures and tables. The resulting ITO coating is approximately 600 nm thick. In FIG. 17, the absorption of the coating (y axis) is plotted as a function of the oxygen flow rate (x axis). As can be seen, the sample made of krypton (line 1701) is more absorbing than the sample (line 1702) produced using argon as the sputtering gas at a given oxygen flow rate.

  In FIG. 18, glass strain (y-axis) is plotted as a function of oxygen flow rate (x-axis). The strain value of the sample produced with krypton (line 1801) is seen to be close to 1, indicating that the krypton produced ITO coated glass is flatter than the argon (line 1802) produced glass. FIG. 18 represents the data presented above showing the strain increasing as the oxygen flow rate increases.

  In FIG. 19, the distortion (y-axis) of the glass is plotted against the absorption (x-axis). The krypton-generated sample (line 1901) has a large absorption when plotted against the oxygen flow rate, but the distortion is absorbed. In comparison, the krypton production sample is flatter than the argon production sample (line 1902).

  FIG. 20 shows strain (y-axis) versus transmittance (x-axis) for krypton (line 2001) and argon (line 2002). A flat glass is obtained with a predetermined increased transmittance value. Additional improvements are possible using krypton or xenon at high pressure or using argon. With high pressure, low stress, high transparency and low sheet resistance can be achieved simultaneously.

  Also, the ITO coating morphology or surface properties change with pressure and oxygen flow rate. There is an interaction between these values, and different forms are achieved at different oxygen flow rates when the pressure is changed. The ITO coated samples shown in FIGS. 21-23 were produced on a coating apparatus with a 72 "cathode. All samples were 2.1 mT, 5 kW / target, 1 processing chamber (2 targets / side), and line speed. The oxygen flow rates were 2, 8, and 17 sccm for the samples of Figures 21, 22, and 23, respectively, which are shown in extreme form. 21 has a so-called nodule 2101 form, but the sample of Figure 23 has a form of platelet 2302. Examining the sample of Figure 21 reveals the structure of the background platelet 2102. Sample of Figure 21 The sample of Fig. 22 at the intermediate oxygen flow rate has very few nodules 2201, and the whole plate 22 is considered to have a slightly mixed form. The platelet morphology correlates with the high stress of the coating, while the nodular morphology occurs in low stress coatings, depending on the given process gas pressure, between these two different configurations. The hypoxic nodular morphology is characterized by a high peak-valley roughness (described in detail with respect to FIGS. 33a and 33b). Bulges above the surface of the coating, thus producing a large peak-valley roughness, as the nodule transitions to the platelet microstructure, the surface roughness decreases. At this point, there is a platelet microstructure with shallow “cliffs” 2103, 2203, 2303, or areas between the platelets. As the oxygen flow rate increases further, the height of the cliff between the platelets increases, and undesirably increases the roughness of the surface.

  The samples of FIGS. 24-26 are made with power and line speed comparable to the samples of FIGS. 21-23, and all at 2 sccm oxygen. Process gas pressures were 3.7, 2.1, and 1.6 millitorr, respectively. The morphology gradually becomes dominant in the nodular morphology as the pressure increases. The transition between the nodular form 2401, 2501, 2601 and the platelet form is more gradual at high pressures and can therefore be finely tuned between the desired optical and mechanical properties of the coating. The platelet 2402 form is still in the background of the 3.7 millitorr sample, but in a much less dominant amount. As the pressure is further reduced, the nodular components are eventually eliminated, leaving only the platelet form.

  The use of krypton or other heavy sputtering process gas is similar to operating at high pressure in some aspects. Compare three SEM images of 1/2 wave ITO samples generated with krypton as process gas at various oxygen flow rates as shown in FIGS. These samples are described in more detail with reference to Table 6. These samples were made using a 40 ipm line speed and 6.2 kw, two processing chambers (four cathodes / sides). The glass thickness was 1.1 mm. The oxygen flow rates are 8, 12 and 16 sccm for the samples of FIGS. 27, 28 and 29, respectively. The oxygen flow rate is per process chamber. The surface of the sample shown in FIG. 27 produced with 8 sccm oxygen is substantially free of platelet components and very stress free. That is, the surface of this sample is dominated by nodules 2701. The distortion value of the sample shown in FIG. 27 and the other half wave sample of Table 6 is essentially 1. The sample surface structure shown in FIG. 28 generally has a very small platelet 2802 configuration consisting of nodules 2801 with few cliffs 2803. The sample of FIG. 29 is the surface structure of a platelet 2902 with essentially all clear cliffs 2903. The sample has a very low bulk resistance of approximately 150 micro ohm cm. The absorption of these coatings is quite low, with 12 sccm being the best combination of flatness, resistance and absorption. The low stress values for these coatings indicate that high pressures or generation with heavy sputtering gases can be successful using the platelet configuration.

  Samples D, E, and F shown in FIGS. 30-32 are for the two-wave ITO listed in Table 7 and correspond to 8, 12, and 16 sccm flow rates, respectively. The line speed was 7 ipm for these samples, otherwise the processing conditions were equivalent to those in Table 6. These coatings are almost 5 times thicker than their half-wave counterparts. The coating morphology is somewhat different for these samples, and the thin sample nodularity 3001, 3101, 3201 morphology results in a fine-grained structure (Sample D, FIG. 30). The presence of voids between the particles shown in FIG. 30, which undesirably results in a high haze and poor conductivity, which is a relatively high bulk resistance value for this sample. Is exemplified by 200 micro ohm cm. Sample E made with 12 sccm of oxygen has a very low bulk resistance (131 micro ohm cm) and a fine grain microstructure. In the case of 16 sccm, it has a similar microstructure, but in this case there is no platelet morphology as with a thin coating. The stress levels of these krypton-generating coatings are relatively low. Strain values range from essentially 1 for the hypoxic case to 0.956 for the highest oxygen. These samples were produced with 1.1 mm glass that is more susceptible to distortion than the thicker 1.6 mm glass described above. Still, the strain value is very close to 1. This comprises a coating that is more than 10 times thicker than the 50 nm coating originally described for 1.6 mm glass. These coatings not only have very low stress, but also have good bulk resistance and acceptable absorption values.

  The peak-valley surface roughness (formed in the discussion below with respect to FIGS. 33a and 33b) for these coatings is preferably 200 Å or less, more preferably less than 150 、, more preferably about 100 Å or less, more preferably Is about 50 cm or less, most preferably about 25 cm or less.

In order to demonstrate additional features and advantages of electrochromic mirrors constructed in accordance with at least one embodiment of the present invention, a summary of experimental results is shown in Tables 3 and 4 below. These summaries refer to the spectral characteristics of the elements of the electrochromic mirror configured according to the parameters specified in each example. When discussing color, it is useful to refer to the International Commission on Lighting (CIE) 1976 CIELAB chromaticity diagram (commonly referred to as the L ^* a ^* b ^* diagram). Although the color technology is relatively complex, F.I. W. Billmeyer and M.M. Saltzman's "Principles of Color Technology", 2nd edition, "J. Wiley and Sons Inc." (1981), is a fairly comprehensive discussion, and the disclosure of the present invention relates to color technology and terminology. In general, follow this consideration. In the L ^* a ^* b ^* chart, L ^* defines lightness, a ^* means red / green value, and b ^* means yellow / blue value. Each electrochromic medium has an absorption spectrum that can be converted to L ^* a ^* b ^* values, which are three numerical representations at each particular voltage. In order to calculate a set of color coordinates, such as L ^* a ^* b ^* values, from spectral transmission or reflectance, two additional items are required. One is the spectral distribution of the source or light source. In the present disclosure, the CIE standard light source A is used to simulate light from an automobile headlamp, and the CIE standard light source D65 is used to simulate daylight. The required second item is the observer's spectral response. The present disclosure uses a CIE standard observer twice. The light source / observer combination commonly used for mirrors is then represented as A / 2 degrees, and this combination commonly used for windows is represented as D65 / 2 degrees. Many of the examples below relate to the value Y from the 1931 CIE standard because it corresponds more closely to spectral reflectance than L ^* . The value C ^{*, which} is also explained below, is equal to the square root of (a ^* ) ² + (b ^* ) ² and is therefore a measure for quantifying the intermediate state of the color.

  Tables 3 and 4 summarize the results of experiments on elements constructed according to the present invention. More specifically, the experiment was conducted using krypton as the sputtering gas and a range of between 8 sccm and 16 sccm oxygen flow for both half-wave and double-wave thicknesses at a pressure of 3 mTorr. Table 6 summarizes the results for ITO thicknesses slightly less than half-wave, and Table 7 summarizes the results for ITO thicknesses slightly greater than two waves, where half-wave thickness is, for example, for mirror applications The two-wave thickness can be applied to window applications, for example. Furthermore, it should be noted that these tables contain results for both single layer and double layer elements.

(Table 6)

(Table 7)

  Table 8 shows the interdependence between bulk resistance, electron mobility, and electron carrier concentration. Note that there are continuous combinations of carrier concentration and mobility that will result in a given bulk resistance.

(Table 8)

The electron carrier concentration is preferably equal to or greater than 40e ²⁰ electrons / cc, and the mobility is preferably equal to or greater than 25 cm ^Λ 2 / V-s. The carrier concentration and electron mobility, thickness and surface roughness indicated herein are derived from the ellipsometry of the coating. The electron concentration and mobility can be different from those determined using Hall characterization methods, and those skilled in the art will recognize that there may be discrepancies between measurement methods. As mentioned above, there are continuously carrier concentrations and mobility values that can achieve a given bulk resistance. In embodiments where a low refractive index is preferred, it may be preferable to tailor the deposition process to provide a high carrier concentration. In other embodiments where low absorption is preferred, it may be preferable to tailor the deposition process to provide high electron mobility. In other embodiments, both carrier concentration and mobility may be desirable at intermediate levels.

  In at least one embodiment, the electro-optic element has reduced bulk resistance, reduced absorption, reduced bending or distortion of the associated substrate to which ITO is added, and uniform darkness and brightness of the overall assembly. Includes an improved ITO layer that simultaneously shows maintenance and reduces its weight.

  Surface topography, morphology, or roughness is typically not important for non-microscale electrical applications dealing with metal coatings. Surface topography is of particular interest when using metals for optical applications. If the surface roughness becomes too great, the coating will have appreciable non-mirror surface reflectivity or haze. This degree of roughness does not necessarily affect functionality in most applications, but is often addressed first because it can adversely affect the appearance. In the case of optical applications, such as the many applications described herein, the presence of undesired haze is considered to be the worst case scenario. The surface roughness can have other negative results at a roughness level that is much smaller than the level at which undesired haze occurs. The surface roughness level forms an acceptable form for the metal film so that it can function properly in different optical applications. The disadvantages associated with not properly controlling the surface morphology are often costly due to the large amount of high reflectivity, expensive metal required to overcome the problems associated with improper surface morphology. To be higher. The effects of different levels of morphology or surface roughness using thin film modeling techniques were analyzed. These techniques have been accepted in the field of thin film technology and have been found to accurately describe real thin films or coating systems and are therefore used to predict the effect of different changes on coatings. be able to. This is advantageous because it can be costly or time consuming to produce or produce the large number of samples needed to show the effect. In this case, calculation is performed using a commercially available thin film program called “TFCalc” supplied from “Software Spectra, Inc.”.

  As used herein, roughness is defined in terms of average peak-valley distance. Figures 33a and 33b show two different roughness scenarios. In FIG. 33a, a large crystallite 3302a is shown. In FIG. 33b, a small crystallite 3302b is shown. In both of these cases, the peak-to-valley distances 3301a, 3301b are shown to be the same. Furthermore, both examples have the same void-to-bulk ratio. It should be understood that the valleys and peaks may not be the same height. Therefore, more representative quantitative values are obtained in the average peak-valley measurement.

  If the layer is thin, it can be approximated by a single homogeneous layer with a uniform refractive index. There are several ways to approximate the refractive index of the mixed layer. These are called effective media approximation (EMA). Each different EMA has its strengths and weaknesses. In these examples, the Bruggeman EMA method was used. As the layer thickness increases, the roughness cannot be reliably approximated using a single fixed index of refraction. In these cases, the roughness can be approximated as several slices of different ratios of voids and bulk material, forming a graded index approximation.

  In this specification, several metals are modeled to generate a representative example of the optical effect of surface roughness on reflectivity. Tables 6, 7 and 8 show the influence of roughness thickness on surface reflectivity for Ag, Cr and Rh, respectively. The layer thickness is nanometer and the “Cap Y” value represents the reflectance from the coating surface. The reflectivity decreases as the roughness thickness increases for each of these metals. Depending on the application, the amount of roughness that can be tolerated will vary. The roughness should be less than 20 nm average peak-valley, preferably less than 15 nm, more preferably less than 10 nm, more preferably less than 5 nm, and most preferably less than 2.5 nm. These preferred ranges depend on the application as described above. For example, in one embodiment, it is contemplated that the thickness of the flash layer, cover layer, barrier layer, or adhesive layer (ie, functional layer) need not correspond to the degree of roughness of the underlying surface. The thickness of the functional layer required by the roughness of the underlying surface can cause undesirable effects such as changes in the optical properties of the resulting stack, high cost or other harmful effects. Means for smoothing the surface before coating the functional layer are described below. It should be understood that in some embodiments, increasing surface roughness may have benefits such as substantially increased surface area and better contact with the sealing material.

  Table 6, Table 7, and Table 8 also include a value indicated as “% of theoretical maximum value”. This metric defines how closely the reflectance of a coating with a rough surface matches the reflectance of an ideal perfectly smooth surface. A coating with a theoretical maximum of 100% will have the maximum reflectivity theoretically achievable with the material. If the theoretical maximum% is 85%, then the achieved reflectance will be only 85% of an ideal smooth coating, or 0.85 times the reflectance of a coating with zero roughness. Become.

  The reflectivity of a metal or alloy coating depends on many attributes of the coating, even if it is relatively smooth. The density of the coating, the presence or absence of internal voids, the stress level, etc. all influence how close the reflectance is to some ideal maximum. The theoretical maximum reflectivity defined herein does not relate to this ideal reflectivity of an ideal coating, but to the reflectivity value of a smooth real-world coating. In practice, the theoretical maximum is obtained from a combination of optical analysis and thin film modeling. Such refractive index versus wavelength and surface roughness can be obtained by analyzing a real world coating with surface roughness using optical techniques such as variable angle spectroscopic ellipsometry. The refractive index vs. wavelength can then be input into a thin film modeling program such as “TFCalc” or “Essential Macintosh” and the reflectance can be calculated. This calculated reflectance using measured refractive index data is thus the “theoretical maximum” reflectance value from that particular film or coating.

  Preferably, the reflectance of the coating is greater than 85% of the theoretical maximum, more preferably greater than 90% of the theoretical maximum, and most preferably greater than 95% of the theoretical maximum.

  In some applications, it is desirable that the second surface reflectivity be high if the reflection is away from the metal layer when viewed through the glass. In this case, in addition to the surface roughness, attention is paid to the embedded voids. The amount of voids (% of bulk) can vary and the thickness of the void layer can also vary. The above principles for surface roughness apply here as well.

  Surface roughness is of particular interest in many cases where the metal layer includes low sheet resistance. Metals or other electrically conductive materials have an inherent property known as bulk resistance. The sheet resistance of the coating is determined by dividing the bulk resistance number by the thickness of the coating. In principle, any sheet resistance value can be obtained from any conductor as long as the coating is sufficiently thick. Challenges or limitations in achieving low sheet resistance arise when other attributes are required in addition to sheet resistance or conductivity.

  As the thickness of the coating increases, the surface roughness typically also increases, thereby reducing the mirror surface reflectivity as described above. Very thick coatings often have significantly lower reflectance levels than perfectly smooth surfaces. The amount of roughness that the coating will produce is a function of several factors. While the properties of the material itself are the main driving force, within the boundaries, the deposition process parameters (with which the deposition process is used) can modify the surface characteristics of the coating.

  Due to other considerations, it is not always possible to select a material with the best surface roughness for a given application. Other factors also play a role. For example, bonding and cost are critical issues that affect the selection of materials to be placed in a coating stack. In many cases it is not possible to select a single material to meet all of the requirements. Thus, a multilayer coating is used. Certain platinum group metals such as rhodium, ruthenium and iridium are highly reflective but very expensive. Therefore, it would be prohibitively expensive to produce an entire low sheet resistance coating with these materials. It is known that these materials may have a lower bond strength than other materials, where extreme bonding may be required for glass or other materials. Silver-based coatings may be poorly stable as an anode, and depending on the coating stack, may also be problematic from a bonding perspective. It is known that metals such as chromium are relatively inexpensive compared to some other metals and have very good bonding properties. Thus, chromium can function as an adhesive layer and can be grown to a thickness sufficient to obtain desirable electrical properties.

  Unfortunately, chromium is very reactive, which leads to the inherent property of relatively high surface roughness values. High reactivity is important in that, for example, when depositing a coating using “magnetron sputter vacuum deposition (MSVD)”, the chromium atoms tend to adhere to where they were originally deposited. The bond formation rate is very fast, which limits the ability of atoms to diffuse along the surface and find low energy sites. Typically, low energy stable sites on the coating are sites that help reduce surface roughness. Furthermore, this tendency not to go to a low energy state can also cause the bulk resistance of the coating to deteriorate. Therefore, a thick layer is required to achieve the target sheet resistance, and the surface roughness tends to be further deteriorated. Achieving the objectives of low sheet resistance and high reflectivity at the same time is difficult due to these competitive effects.

  It is known that the reflectivity of low reflectivity metals can be increased by placing a thin layer of high reflectivity metal thereon. For example, the above metals such as rhodium or ruthenium can be used. The thickness required for these metals to achieve a given reflectivity level is a direct result of the surface roughness of the underlying chrome layer. Other metals that can be used as the conductive layer include, but are not limited to, aluminum, cadmium, chromium, cobalt, copper, gold, iridium, iron, magnesium, molybdenum, nickel, osmium, palladium, Platinum, rhodium, ruthenium, silver, tin tungsten, and zinc are included. Alloys of these metals with each other or with other metals or with each metal are possible. The suitability of these materials for a given application will depend on a complete list of requirements. For example, ruthenium may be an expensive metal in one application, but may be less expensive in another application compared to another metal such as rhodium, and thus the present invention. Can be included in the spirit of. In other non-limiting embodiments, a given metal or alloy may not be compatible with all of the other components of the application. In this case, the sensitive metal can be incorporated or otherwise isolated from the component where the interaction is limited. The layer coated on top of chrome will typically be patterned to the roughness of the underlying layer. Thus, a thin layer of high reflectivity metal will not have ideal reflectivity for that layer or for each layer below it. In most cases, the preferred embodiment is one having a high reflectivity metal towards the observer. Furthermore, many of the highly conductive metals listed above have high reflectivity. These metals may need to be alloyed with other metals to have appropriate chemical, environmental, or physical properties. The metal or alloy may then have an unacceptable color or hue. The overall reflectance intensity can be appropriate for the desired application, but if the reflected color does not meet the requirements, this metal or alloy is unsuitable. In this case, similar to the description above, the metal or alloy can be incorporated under a layer having a lower intrinsic reflectivity but a more favorable reflection color.

A reference sample was prepared so that a compromise between reflectivity and sheet resistance for a chromium-ruthenium bilayer coating stack could be evaluated. In these samples, chromium was added to obtain the target sheet resistance value. The samples were then overcoated with different thicknesses of ruthenium. The following processing conditions were used.
All of the coatings were processed at 3.0 mtorr.
Cr @ 4.0Kw @ (130) = approximately 1000 angstroms Cr @ 4.0Kw @ (130) X9 =. 7 ohm square Cr @ 4.0Kw @ (130) X3 = 1.5 ohm square Cr @ 4.0Kw @ (87) X1 = 3 ohm square Cr @ 4.0Kw @ (170) X1 = 6 ohm square Ru @ 1 .7 Kw @ (130) = 400 Angstroms Ru @. 85Kw @ (130) = 200 Angstroms Ru @. 43Kw @ (130) = 100 Angstroms Ru @. 43Kw @ (260) = 50 Angstrom Ru @. 43Kw @ (520) = 25 Angstrom

  All chromium samples were coated with 4 kW. Line speed (arbitrary units in parentheses) and number of passes (eg, X9) were varied to adjust the coating thickness to match the sheet resistance target. The ruthenium layer was generated by varying the line speed and power to achieve the target thickness level. Matrix results are listed in Table 12. The reflectivity generally decreases with increasing thickness and decreasing sheet resistance. Some samples prepared targeting 3 ohm squares do not fit this trend. This is because it was made at a different line speed than other chrome coatings. As the line speed decreases, the substrate moves at a slower speed. In the linear process, this means that the initial nucleation layer is mainly formed of sputtered high angle deposition material. As shown in the following description, high angle deposition results in poor material properties. Shielding is often used to eliminate this high angle deposition. In the case of the 3 ohm square chrome of this test, it is an excellent example of how high angles can degrade the optical properties of the coating.

  As can be seen from Table 12, the chrome coating alone has a relatively low reflectivity value even at 6 ohm square. The reflectivity was only about 61% for this sample. Chromium produced by other means or processing conditions needs to be able to achieve values exceeding 65%. Therefore, the chromium reflectance was inhibited even with this moderate sheet resistance value.

  If a 3 ohm square coating is desired, 100 and 200 Angstroms of ruthenium are needed on top of the chrome to achieve reasonable reflectivity values. Ideally, the ruthenium coating should be able to achieve a reflectivity greater than 72%. Even 400 angstroms above 6 ohm square chrome does not reach 2% of the theoretical optimum. Low ohm samples do not attempt to approach the theoretically achievable reflectance values. Thus, if both low sheet resistance and high reflectivity are desired, the reference chrome-ruthenium bilayer does not meet the requirements. Other means should be used to solve this problem.

  Deposition processing parameters can be adjusted to minimize surface roughness while forming the coating. In the case of metals, the surface roughness can be reduced and the reflectivity increased by performing the process at low pressure, preferably using neon or an argon-neon mixture as the sputtering gas, as described in detail below. it can. These parameters help to transfer momentum and energy properly in the deposition process, resulting in reduced surface roughness and lower bulk resistance.

  Table 13 shows how the surface roughness, reflectivity, and electrical characteristics change as the processing parameters are adjusted. In the case of 3 mT, it is included as a reference. The thickness of the coating is about 600 angstroms. This thickness is important because the coating is almost opaque at this level and the sheet resistance is relatively low. As can be seen, decreasing the pressure reduces the roughness by about 17% and achieves an almost 2% increase in reflectivity. Further improvement is achieved by reducing the pressure and sputtering with a 50:50 mixture of argon and neon. The roughness is about 20% lower than the standard case, and the reflectance is about 2.7% higher. In the last case, a larger amount of neon is used and approximately 70% of the sputtering gas is neon. The reflectivity is about 3.5% higher than the reference case, and the roughness is reduced by about 24%. Thickness and roughness values are determined using variable angle spectroscopic ellipsometry.

  The results can be further improved by reducing the pressure and increasing the neon content of the sputtering gas. Furthermore, increasing the substrate temperature helps to smooth the coating. When the substrate temperature is high, the surface mobility of the coating atoms increases and the surface becomes smooth.

  Table 13 also includes the bulk resistance value for the chromium coating. The theoretical minimum bulk resistance value for chromium is about 13 micro ohm cm. The bulk resistance value for a reference made at 3 mT, a typical pressure in argon, is greater than 6 times the theoretical bulk resistance. By improving the coating properties, the bulk resistance value can be reduced to less than 5 times the theoretical minimum. Preferably, the bulk resistance is less than 5 times the theoretical minimum, more preferably less than 4 times the theoretical minimum, more preferably less than 3 times the theoretical minimum, most preferably the theoretical minimum. Smaller than twice.

  The presence of oxygen (or water) in the system can be particularly detrimental in terms of surface roughness. Chromium is very reactive with oxygen and tends to react immediately. This results in additional roughness of the coating. Therefore, a coating with low oxygen is recommended. Table 14 shows the effect of oxygen on roughness. The oxygen level in Table 14 means percent in sputtering gas. The pressure is expressed in mT and the thickness is expressed in angstroms. The amount of oxygen that can be tolerated in the coating is less than 5 atomic percent, preferably less than 2 atomic percent, and ideally less than 1 atomic percent.

  The amount of roughness that is acceptable depends on the application. If a high reflectivity value is desired, it is also desirable that the roughness be small. If the reflectivity is not strictly necessary, a high roughness may be acceptable. Generally, the roughness should be less than about 200 angstroms, preferably less than 100 angstroms, more preferably less than 50 angstroms, more preferably less than 25 angstroms, and most preferably less than 15 angstroms. Roughness, as used herein, refers to the average peak-to-valley distance determined using ellipsometry or atomic force microscopy mirrors.

  Other means can be used alone or in combination with each other or with the methods described above to minimize surface roughness. For example, the cathode can be shielded to minimize glazing (high) angle deposition. Other methods of smoothing the surface include increasing the surface mobility of atoms using ion-assisted sputtering or ion-assisted deposition, plasma-assisted sputtering, and other means. The type of cathode is “Twin Mags”, unbalanced magnetron, rf superimposed DC power, microwave assisted sputtering, high power pulse deposition, AC sputtering, or other such means to facilitate smooth coating You can choose to

  In the above example, chromium was used as the conductive layer, but within the spirit of the invention, other metals, alloys, or multilayers as described herein and in the references incorporated herein. Deposition materials can also be used. Other materials may require other processing conditions to achieve a smooth surface. For example, ITO does not always have a smooth surface under favorable conditions for metals. In the case of ITO, the surface morphology is modified by several process variables. Controlling the surface properties of ITO is even more difficult than with metals. ITO is not always conductive like metal, and some processing settings that can be a smooth coating in the case of metal may not be a highly conductive coating in ITO. Therefore, it is quite difficult to control the morphology in terms of other properties of the material. In general, high temperature coatings of glass or other vitreous substrates can result in relatively smooth coatings at high pressures and relatively high oxygen settings as described herein above. Variations in processing parameters for smooth coatings can also be applied to other materials such as TiO2, or multilayers such as TiO2 and ITO, as taught in transflective coating applications.

  As mentioned above, roughness generally increases with coating thickness. In many cases, the process settings described above are insufficient to achieve an acceptable roughness level coating. This is the case where extremely low sheet resistance is required. In this scenario, alternative means are required to achieve a relatively low surface roughness coating with a low sheet resistance value at the same time.

  In commonly assigned U.S. Patent Application Publication No. 2006/0056003, the entire disclosure of which is incorporated herein by reference, an ion beam is used as a means for thinning a coating in a localized area on a coated substrate. Has been introduced. As described in detail herein, an ion beam can be used to smooth a rough coating (as shown in FIG. 37) (as shown in FIGS. 33a and 33b). . The ion beam can be used alone and can be used in combination with other methods taught herein to reduce the roughness of the coating and thus increase the reflectivity. The design and function of the ion beam source varies. For this discussion, any design that can deliver ion fluxes in the energy range described herein is suitable.

  An ion beam is a relatively parallel group of positive or negative energy ions. The energy of the ions is a function of the working potential of the ion beam. The current, or ion flux, is a function of the working potential and the amount of gas delivered through the beam and the background pressure of the chamber. Sufficient energy is desirable for the ions to etch, grind and / or smooth the deposited material. An example of a related phenomenon is that of billiards. Think of the incident ions as the ball and the coating as the ball rack at the start of the game. If the cue rack is struck with very low energy, the rack will not fall apart. Conversely, if the cue ball is struck with high energy, the racks can fall apart quite violently.

  FIG. 34 shows the amount of sputtering generated as a function of argon ion energy for various materials. There is a threshold energy at which sputtering does not occur or occurs minimally. As the energy increases, the amount of sputtering generated increases. Furthermore, ionized atoms can also affect the sputtering rate. The preferred mass of sputtering ions that will yield the maximum amount of sputtering will vary depending on the energy of the sputtering ions and the mass of the atoms being sputtered. FIG. 35 shows the amount of sputtering produced as a function of the mass of sputtering ions and sputtered atoms at 500 eV ion energy. The data shown in FIG. 35 was generated using a computer simulation program called “stop and range of ions in a substance (SRIM)”. As shown, there is a range of optical sputter gas ion masses that will result in an acceptable amount of sputtering generation for a given target atomic mass. In general, as the beam energy increases, the optimum mass of ions that maximizes the amount of spatter generated increases. Preferred ions will depend to some extent on the mass of the sputtering atoms. For optimal energy and momentum, the movement of atoms needs to be a relatively comparable mass. FIG. 34 shows that the threshold energy depends on the sputtered material. Some materials require more energy than others to release. Furthermore, the graph of FIG. 34 also shows that for relatively high energy ions, the amount of sputtering generated tends to reach a horizontal state. At these relatively high energies, the process begins to move into the region of ion implantation rather than ion sputtering. For efficient sputtering or etching, the ion energy needs to exceed 100 eV, preferably more than 500 eV, and most preferably more than 1000 eV.

  The smoothing effect is illustrated with reference to FIGS. In FIG. 36, ions are colliding with a smooth surface. When ions strike the surface, energy is transferred both parallel and perpendicular to the surface. Some of the energy transmitted parallel to the surface can be a component perpendicular to and away from the surface, which becomes the emitted atom. In FIG. 37, the same ions collide with a rough surface. As will be appreciated, ions tend to be released from the coating. Most of the energy directed perpendicular to the surface can cause electrons to be emitted. That is, the surface area is large, and there are many directions in which atoms are emitted. As the ion milling process continues, the coating becomes increasingly smooth. In these and other examples, the ion beam consists of a single atom. In practice, ion / atom clusters can be used instead of single ions. In this situation, known methods for generating clusters can also be used.

  Similarly, an ion beam that strikes the surface at an angle can have a substantially higher sputtering efficiency and smoothing effect. In this case, the angled ion beam has a high probability of releasing material laterally onto the coating surface.

  As explained below, the reflectivity, transmittance, absorption, and sheet resistance characteristics of certain transflective coatings are limited by the roughness of the layer. One related coating is glass / ITO / Si / Ru, referred to herein as “Option 4”. ITO is optimally a 3/4 or 5/4 wave coating, 2100 or 3600 angstroms, respectively. The Si layer is about 220 angstroms and the ruthenium layer is about 70 angstroms. Furthermore, different variations of this stack are possible, as will be explained below. The reflectivity and transmittance of this stack is highly dependent on the surface and interface roughness. When considering a multi-layer stack such as option 4 consisting of a dielectric semiconductor layer, a transparent conductive oxide, and a metal, it is necessary to consider the roughness of the interface as well as the roughness of the surface.

  Table 15 shows the effect of ion milling the surface of ITO (one of the bottom layers is used in the Option 4 stack). Data was determined by characterization of the coating using ellipsometry. In addition, Table 15 also shows the initial properties of the ITO coating. The initial roughness of the 3/4 and 5/4 wave coatings is 7.4 and 11.5 nm, respectively. These values are relatively high. The sample was supplied with argon at 20 sccm, the working pressure in the chamber was 2.5 mT, and ion milled with a single beam (38 cm long beam) run at 270 mA current and 3000 volts. The ion beam is a closed drift Hall effect anode layer type design. The line speed for the case of 2B (2 beam equivalents at 30 ipm) was 15 ipm and the line speed for 4B (4 beam equivalents at 30 ipm) was 7.5 ipm. The beam was directed perpendicular to the surface of the coated glass. The ion beam removed about 17 nm / beam equivalent at 30 ipm and about 11.1 nm / beam equivalent at 30 ipm for 3/4 wave ITO. The surface roughness dropped dramatically in both cases, and the 3/4 wave ITO became almost completely smooth. The 5/4 wave ITO did not become as smooth as it started from a rougher initial state, but this may require a slower line speed and additional to achieve the minimum roughness value Sometimes a beam is required.

  The important evidence is that the reflectivity is substantially increased during the ion milling process. In Table 16a, the ITO coating described in Table 15 is overcoated with approximately 22 nm Si and 7 nm Ru. Because these coatings are highly reflective, the transmittance is generally reduced by ion milling. More importantly, the absorption of ion milled ITO samples is appreciably low. This results in a higher light output from the associated light source through the coating with the same reflectivity level. If all these coatings are normalized at the same reflectance level, the difference is much larger. In order to achieve the same reflectivity level for the non-ion milled portion, the thickness of the ruthenium layer is substantially increased. This, in turn, further reduces transmission and increases absorption, which is undesirable for some applications.

  These coated “lites” as listed in Table 16a were incorporated into electro-optic mirror elements as listed in Table 16b to evaluate the optical properties of actual EC elements. Several 2 "x5" cells were made and the transmittance and reflectance (mirror and non-mirror surfaces) were measured. The increase in reflectivity of the assembled element is consistent with the results seen in the single piece of data. The transmitted color is very biased in amber even if the reflected color is completely neutral. This suggests that this design transmits red light rather than blue light because of the specific material that is constructed. This can be particularly advantageous when, for example, the red display is positioned behind the mirror element.

  Table 16b shows mirror surface exclusion reflectance (Spec Ex) data for the sample elements. Ion milling smoothes the surface, thereby substantially reducing scattered light. The resulting image is much clearer and clearer due to the small amount of scattered light.

  Many automobile companies have standards that indicate that the reflectivity needs to exceed 55% for external mirror applications. Non-ion milling samples did not meet this standard with an initial amount of roughness of ITO. The ion milling sample satisfies this standard even in the 5/4 wave ITO part. The switching speed of the mirror element, in particular the darkening speed, depends on the sheet resistance of the coating. By allowing 5/4 wave ITO or thicker to be used, ion beam milling allows faster switching times while at the same time meeting the reflectance requirements. In addition, the reflectance values of some of the 3/4 wave elements significantly exceed the minimum requirements. These coatings have high transmission values by reducing the thickness of ruthenium or other high reflectivity metals used as the top layer, if this variation benefits the overall design requirements. Can be adjusted to have Without the ion beam smoothing method, the useful range of reflectivity and transmittance options would be limited.

(Table 16a)

  In another application, ion milling has been used to smooth ITO in non-transflective applications. In this case, the coating is glass / ITO / Cr / Ru. Chromium and ruthenium are shielded inside the epoxy seal, and ITO is used to transfer current from the electrode to the internal EC element. ITO has some degree of roughness, which decreases when treated with an ion beam. FIG. 38 shows the roughness decreased with reciprocal line speed at a fixed beam current. In another example, the line speed through which the glass passed through the coating apparatus was 30 inches per minute (ipm). A single ion beam was used and the current was adjusted to change the ion milling rate. FIG. 39 shows the increase in reflectivity with respect to the beam current. A 0.5% increase in reflectivity is also achieved with this modest ion milling condition. In these examples, the ITO coating potentially mills the ITO in the visible region to achieve improved optical properties while maintaining the initial roughness and makes it easier for the ITO to bond to the epoxy in the sealed region. Improved.

  In another application using ion milling, the color and reflectivity of so-called chrome ring type coatings were investigated. In this application, a multilayer metal coating is applied on top of the ITO coating on the glass. The ITO coated glass is ion etched into the ring around the element and thins the ITO coating at this site to improve the color and reflectivity of the chrome ring stack, while at the same time lowering the sheet resistance of the thick ITO at the center of the part Made it possible. FIG. 40 shows the reflectance under different conditions when viewed through glass. The reflectance when ion milling is not performed is indicated by a thick line. In addition, the reflectivity for several different line speeds is also shown. As the speed decreases, the residence time under the beam increases and the roughness decreases. This increases the reflectivity. Even though the reflectivity seemed flat, there was some arcing during these tests that could affect the results. The important result is that even if arcing occurs, reflectivity increases when ion milling is performed. FIG. 38 shows the change in ITO roughness in these tests with respect to line speed under conditions without arcing.

In another set of tests on the same coating equipment, the color of the ion milled chrome ring was examined. The line speed was adjusted to vary the amount of ITO removed. The ITO started as a 1/2 wave and the goal was to reduce the thickness to approximately 80% of the 1/2 wave, in other words from approximately 145 nm to approximately 115 nm. FIG. 41 shows the reflected b ^* of a chrome ring with adjusted line speed. The reflection b ^* directly correlates with the thickness of the ITO as described in the priority document incorporated herein by reference. The b ^* for a 1/2 wave ITO coating is about 16. As the line speed decreases, the amount of etching material decreases. In at least one embodiment that ideally corresponds to the central visible region, it is desirable that b ^* be about 2.5. Therefore, the line speed should be about 12.5 ipm. If higher line speeds are required, more ion beams can be used.

  In another example where it is desirable to reduce sheet resistance, the effect of ion milling on reflectivity and material usage was investigated. As described above, the roughness of the coating increases with thickness and the reflectance decreases with roughness. In this example, a 1.5 ohm / square coating with a layer structure of glass / chromium / ruthenium was desirable. The chromium thickness was set at approximately 2500 angstroms to produce the majority of the contribution to sheet resistance. Ruthenium was initially set to 400 angstroms. In situations where the surface is perfectly smooth, maximum reflectivity will be achieved with as little ruthenium as 180-200 angstroms. A level of 400 Angstroms was used to ensure that the ruthenium was thick enough to compensate somewhat for the rough surface of the chromium. Additional ruthenium increases reflectivity but also increases costs.

  FIG. 42 shows the reciprocal of reflectivity versus line speed for ion beam treatment of the chromium layer prior to the addition of the ruthenium layer. The beam current was set to about 250 mA. At a line speed of about 4 ″ / min, the coating achieves its maximum reflectivity of approximately 70.5%. Further reduction of the line speed did not increase the reflectivity. If desired, additional beams can be used.

  FIG. 43 shows how much less ruthenium can be used in the coating due to the smoothing effect of the ion beam. The line speed was about 2.1 ipm, and the beam current was equivalent to the result of FIG. Maximum reflectivity can be obtained using as little as 160 Angstroms of ruthenium. This results in a substantial cost reduction compared to a standard that uses extra ruthenium to guarantee the roughness of the initial layer. Furthermore, relatively high reflectivity chromium and ruthenium 1.5 ohm / square coatings may not be practical without ion beam smoothing.

  Typically, the roughness of the coating produced without any special effort to achieve a smooth coating will vary between approximately 10 and 20% of the total thickness of the coating. Table 17 shows the chromium / ruthenium stack thickness required to achieve various sheet resistance values. The bulk resistance of the chromium layer is varied and it is shown how the thickness of the chromium layer varies to achieve different sheet resistance values when the bulk resistance changes. This can be used as an example of variation in chromium bulk resistance properties and can be viewed as a means of revealing what happens when using materials with different or varying bulk resistance values instead of chromium.

  Roughness ranges are calculated in Table 17 as 10 and 20% bulk thickness. Ruthenium is set to 200 angstroms, which is only slightly beyond the thickness required to achieve maximum reflectivity for this material in ideal applications. If the chrome layer is smooth or smoothed with an ion beam, this thickness represents an optimal reflectivity case. Table 17 shows the results of calculations comparing the ruthenium thickness to the total thickness. The roughness contribution is considered to be the average for 10 and 20%. The percentage that the stack is ruthenium varies depending on the target sheet resistance of the stack and the bulk resistance of the chromium or substrate. If the sheet resistance is 6 ohms / square or more, it is desirable that ruthenium or other highly reflective metals be less than 50% of the total thickness. If the sheet resistance of the stack is approximately 2 ohms / square, the ruthenium thickness should be less than about 25% of the total thickness. Furthermore, the thickness percentage of the high reflectivity layer will vary depending on the bulk reflectivity and reflectivity target of the metal. A suitable high reflectivity percentage of the total thickness is a function of the desired reflectivity of the stack, the desired sheet resistance of the stack, and the bulk resistance of the different materials used to construct the stack. The percentage of highly reflective material should be less than 50% of the total thickness, preferably less than 25%, more preferably less than 15%, more preferably less than 10%, and most preferably less than 7.5%. In this example, chromium and ruthenium are used to illustrate the advantages of one embodiment of the present invention. The chromium layer can be replaced with other metals as a means of generating the majority of sheet resistance. So-called high reflectivity metals are defined to be high reflectivity metals compared to layers that contribute the majority of sheet resistance. In this example, the role of the uppermost layer having a higher reflectance than the conductive layer will be described. In other embodiments, the conductive layer or layers may have an unacceptable color or hue. The reflectance intensity can be acceptable, but the reflected color may be considered undesirable. In this embodiment, the top high reflectivity layer can actually function to produce acceptable color without increasing reflectivity. In one example, the conductive layer can be highly colored, but a neutral reflective color is preferred. In this case, the so-called high reflectivity layer will act to make the color more neutral.

  In another embodiment, the conductive layer can have a neutral reflective color, but highly colored reflectance is preferred. In this case, the upper high reflectivity metal can be selected to produce a non-neutral appearance. In yet another embodiment, a multilayer stack is added over the conductive layer, and the stack achieves low sheet resistance while having the flexibility to adjust color through adjustment of the multilayer stack overlying the conductive layer. Can be made possible. In this example, the multilayer stack can be composed of metal, dielectric layers, and / or semiconductor layers. The choice of material, including stack, thickness, orientation with respect to the conductive layer, and adjacent media will be determined by the design criteria of any application.

  As sheet resistance decreases in various applications, it is necessary to increase the thickness, thus increasing the surface roughness and decreasing the reflectivity. Next, the reflectance of the coating will drop to a value lower than the theoretical maximum. As the targeted sheet resistance value is lowered, the percentage of the theoretical maximum reflectance value achieved is lowered. For coatings with a sheet resistance of approximately 6 ohms / square or less, the techniques described herein achieve reflectivities greater than 90% of the theoretical maximum, and preferably greater than about 95% of the theoretical maximum. Will be able to. For coatings with a sheet resistance of approximately 3 ohms / square or less, the techniques described herein exceed 80% of the theoretical maximum, preferably exceed about 85% of the theoretical maximum, and more preferably Will be able to achieve a reflectivity greater than about 90% of the theoretical maximum, and most preferably greater than about 95% of the theoretical maximum. For coatings having a sheet resistance of approximately 1.5 ohms / square or less, the techniques described herein exceed 75% of the theoretical maximum, preferably exceed about 85% of the theoretical maximum, More preferably, a reflectivity greater than about 90% of the theoretical maximum can be achieved, and most preferably greater than about 95% of the theoretical maximum. For coatings having a sheet resistance of approximately 0.5 ohms / square or less, the techniques described herein exceed 70% of the theoretical maximum, preferably exceed about 80% of the theoretical maximum, More preferably, a reflectivity greater than about 90% of the theoretical maximum can be achieved, and most preferably greater than about 95% of the theoretical maximum.

  U.S. Patent Application Publication No. 2006/0056003, assigned to the present applicant, is hereby incorporated by reference in its entirety, in which various metal stacks are made of "chrome ring" mirrors. Described in terms of elements. A thin chrome adhesion layer is deposited on the ITO and a layer of metal with high intrinsic reflectivity is deposited on the chrome layer. Various high reflectivity metals have been described. A second layer of chromium is described that does not contribute to the appearance when the coating is viewed from the glass side, but is added to minimize the transmission of visible and UV light. The reduction in visible light is to hide the sealing material, and the UV light is reduced to protect the sealing material while exposed to sunlight. Chromium is intended in this example as a low-cost means of reducing light transmission whether UV or / and visible. Other low cost metals can perform the same function if well bonded to the seal and high reflectivity metal.

  In addition, the thickness of the high reflectivity metal can be simply increased to reduce the light transmission, but the light reflectivity metal is relatively expensive, and using these materials alone reduces the cost of the coating. Will be higher.

  The ITO layer can be any transparent conductive oxide or other transparent electrode. The transparent conductive oxide or transparent electrode can be composed of a single layer or multiple layers. Multiple layers can be selected to adjust the reflection color or appearance, and the “ring” can have the appropriate optical properties. One such multilayer can include using a color suppression layer disposed between the glass substrate and the transparent conductive oxide. Using this layer increases the color options for the ring as the ITO layer thickness is adjusted.

  The adhesion layer can be various compositions of chromium, Ni, NiCr, Ti, Si, or silicon alloys, or other suitable bond promoting layers. “High reflectivity metals” are selected from metals and alloys that have higher bulk reflectivity values than chromium. Exemplary metals include aluminum, ruthenium, rhodium, iridium, palladium, platinum, cadmium, copper, cobalt, silver, gold, and alloys of these materials. In addition to alloys, mixtures of these metals with each other or with other metals can be used. Furthermore, multiple layers can be used instead of the single layer shown in the schematic diagram of the high reflectivity metal. Similarly, the UV blocking layer can be composed of a single material, alloy, multilayer, or other combination that will adequately reduce transmission.

  Also, adhesion of materials, layers, or coatings can be improved by using the ion beam treatment described herein. For example, the ion beam treatment of the ITO surface was performed using argon and then a mixture of argon and oxygen. These tests were compared to non-ion milling surfaces. The sample was attached to a glass specimen with an epoxy material to form a sealed cavity. A hole is made in the upper left side of the glass, and the pressure value required to break the cavity by pressurizing the cavity is determined. The manner of failure can include cohesive failure within the epoxy, adhesion of the epoxy to the coating, glass cracking, or the coating can debond from the substrate and there is a poor adhesion within the coating. There is also.

  The ITO surface was either ion beam treated or not treated with argon, an argon / oxygen mixture. The surface was then coated with a thin layer of chromium about 50 Å thick and then with a ruthenium layer of about 500 Å thickness (so-called beta ring). The coated glass was bonded to another portion of glass with epoxy typically used for EC elements, after which the epoxy was cured. Table 18 shows the pressure values at break and the amount of metal lift from the ITO coating. The amount of metal lift was tracked in the control part. The part irradiated with the argon beam had a considerable metal lift, but the pressure at break was essentially the same. The use of oxygen was again the same pressure value at the time of failure, but the metal lift from the ITO was eliminated. Oxygen improves the adhesion of chromium to ITO. The ion beam will preferably sputter oxygen, which is a component that aids adhesion of chromium. In the case of argon alone, critical oxygen is minimized and bonding is weakened. It is believed that adding oxygen to the beam “heals” the ITO surface, thereby strengthening the bond and minimizing metal lift. The pressure value at the time of fracture does not show a correlation because the glass is broken during the test. This crack determines the pressure value at failure and is therefore dominant in the test. In this example, oxygen is required, but there may be situations where other gases are preferred or argon alone is a better choice.

  In another example where ruthenium was deposited directly on ITO, dramatic changes in pressure values at failure and changes in the failure mode were observed. When ion beam treatment is not used, the pressure value at break is fairly low, approximately 6-7 psi, the coating lift is in a break mode, and the glass does not break. If the ITO surface is treated with an oxygen-containing beam and then ruthenium is deposited on the surface, the pressure value at break increases beyond a factor of 2 and glass cracking is the dominant break mode. The coating still lifts from the ITO, but the bond strength increases dramatically.

  The top layer that can be used in some applications can be a conductive stabilizing material. Its role is to conduct well between the ring metal and the bus bar or silver paste. The material can be selected from platinum group metals such as iridium, osmium, palladium, platinum, rhodium, and ruthenium. Mixtures or alloys of these metals or other suitable metals can also be used.

  The choice of thickness and layer material is preferably selected to provide the appropriate color and reflectance intensity as taught in the reference patent application. Furthermore, the thickness of the layer should be chosen so as to achieve the required transmission characteristics. The visible light transmittance should be set so that the epoxy seal is not visible. The visible light transmission should be less than 5%, preferably less than 2.5%, more preferably less than 1%, and most preferably less than about 0.5%. The UV light transmittance may or may not be precisely correlated with the visible light transmittance. In the case of UV light transmission, the appearance of the ring is not a problem and protection of the seal is an essential concern. This, of course, assumes that the selected seal is sensitive to UV light. The amount of UV light that can be tolerated depends on how sensitive the seal is to UV light. Ideally, the coating should be designed so that the ring coating is impermeable to UV light, but unfortunately this level of transmission is cost prohibitive. Furthermore, layer adhesion can be hindered if the total thickness becomes too large. The stress that may be present in the layer will be enough strain to cause the layer to delaminate from the glass or other layer of the coating. For this reason, a finite amount of UV transmission should be intended. The UV transmission should be less than about 1%, preferably less than 0.5%, more preferably less than 0.1%, and most preferably less than 0.05%.

  One of the more common features / areas is such as turn signals, heater on / off indicators, half-door warnings, or warnings that doors to oncoming traffic may still open Using an external mirror to display the features. In addition, mirrors or mirror housings are also used to accommodate paddles or proximity illumination.

  Compared to the external mirror of the vehicle, the requirements for the internal mirror are specific. In at least one embodiment, the mirror surface reflectivity of the inner mirror is preferably 60% or higher, preferably at the front of the display to allow an appropriate amount of light to pass through the associated mirror element. It has abundant transmittance. Further, the inner mirror need not withstand the harsh chemical and environmental challenges encountered in outer mirror applications. One difficult problem is balancing the need to meet rearview mirror automotive standards and the desire to incorporate an aesthetically appealing information center. Increasing the mirror element light transmission is one way to ensure display technology with limited light output. In many cases, a high transmittance will reveal the circuitry and other hardware behind the mirror element. An opacifier layer can be added to the fourth surface of the mirror element to address this problem.

  A supplemental turn indicator as shown in FIG. 5a is an example of a desirable display feature for an external mirror assembly. One way to incorporate signal features on the back of an electrochromic mirror element is to laser ablate a portion of the reflective material from the element, allowing light to pass through. Attempting to provide another style and design is the motivation for using transflective mirror element technology. The method using the transflective type of some embodiments of the present invention allows the features in the mirror to have a much more “close” (hidden) appearance. Confidentiality allows light to pass through the transflective element while blocking the light source from being visible. Confidentiality may additionally or alternatively mean that the contrast between the display area and the main reflective area is minimized. In some cases, it may be desirable to contrast the color or reflectivity and provide a framing effect so that the viewer can clearly see where the desired information is obtained, to clearly show the display or feature. Conventional materials used for external mirror applications typically have a low reflectivity and / or a high sheet resistance associated with achieving a perceivable transmission level.

  For example, ruthenium is often used for external EC applications because of its relatively high reflectivity and high environmental durability. The 23 nm Ru coating as a reflector for the EC element will have a reflectivity of approximately 57.5%, a level that meets most commercial mirror reflectivity standards. The sheet resistance of this coating will be approximately 20 ohms / square and the transmission of the EC element will be approximately 2.5%. Neither this transmittance nor sheet resistance is feasible in practical applications. Other environmentally durable metals may have slightly different reflectivity, transmittance, and sheet resistance values, but none have properties that meet the requirements for EC applications.

  The low reflectivity of OEC elements requires the associated reflective and / or transflective layer stacks with little effort to meet favorable reflectivity, durability, and electrochromic performance characteristics. Different configurations of materials can be used, including silver, silver alloys, chromium, rhodium, ruthenium, rhenium, palladium, platinum, indium, silicon, semiconductors, molybdenum, nickel, nickel-chromium, gold, and alloy combinations. Some of these materials have an advantage over silver or silver alloys in that silver and silver alloys are susceptible to damage in an external mirror environment. The use of hard metal is advantageous because it provides the durability of the mirror element and the end product robustness with respect to manufacturing options. Further, the reflective and / or transflective stack can be made of a dielectric that produces a reflectivity level high enough for use in an OEC element.

  Ag-based materials will generally increase transmission by approximately 1% for every 1% decrease in central visible reflectivity. The advantage associated with increased transparency is that low cost, low light output light sources such as displays or LEDs can be used. External mirrors are typically used in display-type displays that typically use LEDs that can indicate with very high light output. Disclosed herein is a new design that can use Ag-based transflective coatings for internal and external mirror applications. These new designs maintain the specific optical properties and benefits from Ag layers, while at the same time addressing the limitations of using Ag-based materials for external applications. If low transmission is part of the design criteria, different coating options can be considered using stacks with and without an Ag base layer. One major advantage over low transmittance is that the need for an opaque layer is reduced or eliminated.

  In many markets, the size of mirrors is increasing more and more so that the field of view can be increased. The darkening time of large mirrors is a difficult issue and is an important consideration in design options. Large mirrors are generally associated with external mirrors and require increased or improved conductivity to maintain acceptable darkening and lightening rates. The previous limitations of a single thin metal coating as described above are solved by innovatively using “transparent conductive oxide (TCO)” in the stack. TCO provides a means to achieve good conductivity while maintaining a high level of transmission. The following few examples show that a satisfactory level of transmission for an external mirror can be achieved with a relatively thick “indium tin oxide (ITO)”. ITO is a specific example of a broad range of TCOs of materials. Other TCO materials include F: SnO2, Sb: SnO2, doped ZnO, IZO, and others. The TCO layer is overcoated with a metal coating or multi-layer metal coating that can be composed of a single metal or alloy. For example, it may be necessary to use multiple metal layers to facilitate adhesion between different materials. In another embodiment, a semiconductor layer can be added in addition to or instead of the metal layer. The semiconductor layer provides some specific properties described below. When increasing the ITO / TCO layer thickness to improve conductivity, the effect of coating roughness should be considered. As the roughness increases, the reflectivity may decrease, requiring an increase in metal thickness, which may reduce the transmittance. In addition, increasing roughness can result in unacceptable haze as described elsewhere. The roughness problem can be solved either by modifying the deposition process for ITO and / or by performing ion beam smoothing after the ITO coating and before depositing the next layer. . Both methods are described in detail above. In addition, the improved ITO material described above can be used in this embodiment to reduce the overall sheet resistance of the transflective coating.

The semiconductor layer can include silicon or doped silicon. A small amount of additional one or more elements can be added to alter the physical or optical properties of the silicon to facilitate its use in different embodiments. The advantage of the semiconductor layer is that the absorptance is smaller than that of metal and the reflectance is improved. Another advantage of many semiconductor materials is that their band gap is relatively small. This is equivalent to an appropriate amount of absorption in the blue to green wavelengths of the visible spectrum. The preferential absorption of one or more bands of light helps the coating to have a relatively pure transmitted color. The purity of the highly transmitted color is equivalent to having a certain portion in the visible or near infrared spectrum where the transmission value is greater than 1.5 times the transmission in the low transmission region. More preferably, the transmittance of the high transmission region will be greater than twice the transmittance of the low transmission region, and most preferably greater than four times the transmittance of the low transmission region. Alternatively, the C ^* value [sqrt (a ^{* 2} + b ^{* 2} )] of the translucent color of the transflective stack should be greater than about 8, preferably greater than about 12, and most preferably greater than about 16. is there. Other semiconductor materials that result in a transflective coating with a relatively high purity transmission color include SiGe, InSb, InP, InGa, InAlAs, InAl, InGaAs, HgTe, Ge, GaSb, AlSb, GaAs, and AlGaAs. It is. Other semiconductor materials considered feasible would be those with a band gap energy of about 3.5 eV or less. For applications where confidential properties are desired and a red signal is used, materials such as Ge or SiGe mixtures may be preferred. Ge has a smaller band gap than Si, thereby increasing the range of wavelengths with relatively low transmittance levels. This may be more preferable because a smaller transmittance at a wavelength different from that of the display is effective in hiding all features on the back of the mirror. If uniform transmission is required, it may be advantageous to select a semiconductor material with a relatively large band gap.

  Because the display area is confidential in nature, the observer may not notice that the mirror has a display until the display is activated or illuminated from behind. Confidentiality is achieved when the reflectance of the display area is relatively similar to the rest of the visible area and the color or hue contrast is minimal. This feature is very advantageous because the display area does not reduce the visible area of the mirror as described above.

  A small amount of transmitted light can reveal mirror back features such as circuit boards, LED strings, covers, and heater terminals. A light blocking (opaque) layer can be used to avoid this problem. The opaque layer is often applied to the fourth surface of the mirror using various materials such as paint, ink, plastic, foam, metal, or metal foil. A difficult problem in adding this layer is the complexity of the external mirror. Most external mirrors have a convex or spherical shape, which makes it more difficult to add a film or coating.

  An opacifying layer can be incorporated into the third surface stack of elements. The transflective regions can be shielded and of ruthenium, rhodium, or other single or multilayer stacks (metals, metals / dielectrics, and / or dielectrics) that provide appropriate reflectivity and color (opacity) A suitable stack such as this can be added over the remaining surface. Confidential appearance is achieved when the desired color and reflectance match or mismatch is maintained. In a preferred embodiment, the display area and the main visible area of the mirror element are virtually indistinguishable. In other embodiments, it may be desirable for the transflective regions to have different colors with an aesthetically attractive contrast.

  Another option is to maintain a high transmission level in the part of the visible spectrum that has a low overall transmission, and to obtain an intimate overview. Confinement effects can be obtained using a narrow spectral bandpass filter.

  Without or in addition to coating or tape or other opacifying material on the rear surface of the element, a relatively opaque layer (regardless of the same material or a different material from the adjacent layer) is otherwise translucent Incorporating insertion into the third surface coating stack of the mold may help to hide the electronics behind the mirror element. The addition of this layer can affect the reflectivity of the inserted area. Secondly, since the reflectivity of this area can be adjusted by the choice of material and its thickness, the difference between the display area and the relatively opaque area of the mirror element is hardly noticeable, and thus the device The integrity of the appearance is maintained.

It also deliberately alters the reflectivity and / or hue of the display area to provide a visual stimulus to where the display is when activated, and to include the display function in the mirror even when the display is off. It may also be advantageous to show. Adding opacity using a conductor increases the conductivity of the relatively opaque portion of the display, correspondingly reducing the voltage drop over the majority of the visible region and increasing the coloration rate. The additional opacifying layer can be such that the reflectivity from the back of the region is substantially less than without the opacifying layer, and therefore less affected by multiple reflections. . One such device that demonstrates the principles described above covers approximately 400 Å of TiO ₂ followed by 200 Å of ITO covering substantially all of the third surface, followed by approximately the display. Approximately 90 Å of chromium, excluding the area, followed by a third surface coating stack of approximately 320 Å of 7% gold 93% silver alloy covering substantially the entire third surface.

  The opening for the display for this particular model of internal car mirror is too small to measure reflectivity with a sphere-based spectrophotometer, thus the element facilitates the measurement of reflectivity on different parts of the stack Made with different parts of the stack covering its entire screen. Transmittance and reflectance measurements were taken from both the front and back of the element.

  Table 19 and Table 20 show the measured values obtained with the graphs of FIGS. 44 and 45, respectively.

(Table 19)

(Table 20)

  In this particular example, it can be seen that adding chrome to the stack increases the opacity and reduces the reflectivity from the back of the element. Increasing the thickness of the silver alloy in the non-display area to achieve opacity would not reduce the reflectivity from the back of the element as seen in this example, but omitted chrome. In some cases, the already relatively high reflectivity seen from the back of the element is further increased. In addition, the display area of this design is relatively small and different in hue, such as the difference in brightness, even though the transparency is sufficient to act as a reflector in the display area compared to the area containing the chrome layer. I understand.

  Further, in the previous example, by increasing or decreasing the thickness of the silver alloy layer in the semi-transmissive region, the “blue bias” of the transmittance characteristic of the display region is increased or decreased, respectively. You should also be careful. Using an RGB video display at the back of this area can benefit from adjusting the relative intensities of the red, green, and blue emitters to maintain good color rendering. For example, if the transmittance is large in the blue region of the spectrum and small in the red region, it may be desirable to reduce the intensity of the blue emitter and increase the intensity of the red emitter. This type of adjustment may be appropriate for this and other transflective designs, regardless of whether the spectral bias of the transmission is a gradual slope or has a distinct band of transparency. .

  If the display is intended to be used when the mirror element is dimmed, intensity adjustments can be made to compensate for any spectral bias from the coating and of the activated electrochromic media. Intensity adjustment can be a function of the device operating voltage and / or other feedback mechanism that matches the relative RGB intensity at approximately a predetermined point in the color range of motion of the electrochromic element. When using a dye that can be used to create a “blue mirror” without electrochromic species being activated, the intensity of the emitter can be adjusted to improve color rendering. As the reflectivity of the mirror element decreases, any spectral bias of the first and / or second surface coating becomes increasingly important. That is, the degree of compensation for the different color intensities of the display can be adjusted accordingly. In addition, UV absorbers and other additives to EC media can also affect elemental intensity-controlled visible light absorption, which can be incorporated to improve the color rendering of related displays.

  It can be advantageous to design transflective coatings for both display and signal or other indicator applications. If the signal or indicator requires high power, the transmissivity spectrum of the reflector may be biased to emphasize the transmissivity in this region. RGB displays with equal intensities in the red, green, and blue portions of the spectrum will have different intensities after passing through the transflective layer (and other components of the mirror element). This offset in intensity can then be compensated accordingly by adjusting the output of the individual RGB colors to obtain a proper color rendering.

  There may be situations where matching reflectivity between the opaque and display areas is more desirable than the examples in Table 19 and Table 20. Furthermore, there may be an advantage of matching the reflectivity in a range of different reflectivity values. Thus, the transmittance of the display area can be adjusted without hindering the reflectance match between the opaque visible area and the display area. Another design objective is to have colors that either match in the visible and display areas or differ in an aesthetically attractive manner. Color matching can be advantageous when a minimal identifiable margin between the two regions is not desired. In other circumstances, it may be advantageous for the colors to match to reflect the reflectivity but to help guide the viewer where the display is located.

  Other means can be used to further reduce the reflectivity of the opaque regions when viewed from the opposite direction regardless of the first surface reflectivity. Another aspect of the invention relates to perceiving the display area relative to the opaque or visible area. The viewer will see only the reflected light in the visible region and the combination of reflected and transmitted light in the display region. Adding transmitted light to this area can make the display area stand out even if both areas have the same reflectivity. Thus, the reflectivity of the display area can be reduced to compensate for the added transmitted light.

  It should be noted that in the previous example, the reflectance match between the opaque and display areas is a function of the layer thickness. The thicknesses of chrome and AgAu7x are optimized so that the reflectivity matches relatively closely but still has a relatively low transmittance. The change in reflectance and transmittance as a function of chromium and AgAu7x thickness is shown in Table 21. The data in Table 21 is model data for an electrochromic element consisting of an identified stack, a 0.14 micron EC fluid, and a top plate with a 1/2 wave ITO coating on the second surface. The difference in reflectance between the opaque and display areas is small when the chrome layer is relatively thin and / or when the AgAu7x layer is relatively thick. This method provides a means of making mirrors with opaque areas and displays that match fairly well over a range of transmittance and reflectance.

  It is desirable to have a means of achieving reflectance matching over a wide range of desirable reflectance values while maintaining opacity in the visible region and high transmittance in the display region. This is accomplished in at least one embodiment by adding additional layers to the stack as described in the example of Table 21. This preferred third surface stack is TiO2 / ITO / AgAu7x / Cr / AgAu7x. By dividing the AgAu7x, the function of achieving reflectance matching over a wide intensity range and simultaneously the function of controlling the transmittance of a stack of opaque regions is achieved. The transmittance of the display area is limited to the values described above for the AgAu7x stack.

  The chromium layer is shielded in the area of the display and the other layers can be substantially over the entire surface or at least in the area of the display. In this example, the color of the transflective silver or silver alloy layer in the display area is neutralized using two layers of TiO2 / ITO net 1/4 wave (so-called GTR3 base layer). Other transflective color neutralization layers can be substituted in the display area, and this is within the scope of this embodiment. The chromium layer that divides the AgAu7x layer has new properties in this application that not only give the stack an opaque property, but also optically isolate the lower layer from the upper AgAu7x layer. FIG. 46 shows how the reflectivity varies with the thickness of the chromium layer. As can be seen, at a thickness slightly greater than 5 nm, the thin chromium layer is substantially isolated so that the bottom silver-gold alloy layer does not contribute to reflectivity. Such isolation using such a thin layer of chrome allows the chrome thickness to be adjusted to achieve a range of transmittance values without having an effect applicable to the overall reflectivity of the stack.

  One advantage of this approach extends to the display area. Since only a thin chrome layer is required to isolate the bottom AgAu7x layer so that it does not contribute to reflectivity, the thickness of the bottom AgAu7x layer can be varied to achieve other design objectives. For example, as indicated above, the desire to match the reflectance of the opaque and display areas can be achieved. In the example where the transflective mirror element has relatively high and low transmittance regions, the term “opaque” refers to the back component of the fourth surface without adding opacifying material to the fourth surface. This means that the transmittance level is low enough to hide the appearance. In certain embodiments, the transmittance should be less than 5%, preferably less than 2.5%, more preferably less than 1%, and most preferably less than 0.5%. Since AgAu7x is isolated in opaque areas, the thickness can be adjusted as needed to achieve the desired reflectivity for the display area. The AgAu7x upper layer will have a high reflectivity when coated with Cr against TiO2 / ITO (present in the display area). The thickness of the bottom AgAu7x can be set so that the display area matches the reflectance of the opaque area. The reflectivity value of the mirror element can be as low as the reflectivity value of the chrome layer alone to the reflectivity of the thick AgAu7x layer. The reflectivity can be adjusted to any desired value over this range, and the transmittance can also be adjusted. In addition, the desired reflectance match between the display area and the visible area can also be achieved.

  The silver-containing layer can be 7% Au 93% Ag, and other alloys or combinations of alloys. For example, it can be advantageous to have a large amount of gold in the alloy above the layer below the opacifying layer. This is because of the reasons associated with obtaining a durable interface between the opacifying layer and the upper silver support layer, color preference, or durability of the upper silver support layer during processing or in contact with electrochromic media. For that. If the two silver support layers contain different levels of material that diffuses easily through silver, such as gold, platinum, palladium, copper, indium, the silver layer is no longer one or more intervening A semi-transmissive region that does not have an opacifying layer will likely be an alloy having an average weight of the upper and lower alloys after processing time. For example, when a silver palladium alloy is used as the upper silver support layer and a silver gold alloy is used as the lower layer, the semi-transmissive region is likely to be a silver-gold-palladium ternary alloy layer. Similarly, when two equal thicknesses of 7% gold in silver and 13% gold in silver are used as the two silver support layers, the resulting layer in the semi-transmissive region has an essentially uniform distribution of 10% gold in silver. It is highly possible that the layer is provided with

  The opacifying layer may be a separate layer connected to a semi-transmissive region where one, both, or all layers may not contain silver. For example, a silver alloy covering silicon or ruthenium covering silicon among many possible combinations can be used for the semi-transmissive region.

  The flash overcoat layer of material shown in US Pat. No. 6,700,692, the entire contents of which are incorporated herein by reference, is useful as a flash layer, including other Materials are included, but include indium tin oxide, other conductive oxides, platinum group metals and alloys thereof, nickel, molybdenum and alloys thereof, and can be incorporated into the above design. Depending on the thickness and optical properties of the material selected for the flash layer, the underlying stack may need to be adjusted to maintain the same degree of match or mismatch between the relatively opaque and translucent areas There is.

  As mentioned above, the transmittance achievable in the “opaque” region depends on both the silver base layer and the chrome or “opaque” layer. The thicker the chrome layer, the lower the transmittance at a given reflectance level. The chrome layer can be thinned to the desired level to approximate the transmittance of the display area. If high transmission levels are required, it is often difficult to control the thickness of very thin layers. A thick layer can be used if the metal opacifying layer is partially oxidized. In order to achieve high transmission for a thin pure metal layer, a thick layer may be required. FIG. 47 shows the relationship between transmittance and reflectance for the stack in Table 21 above and using a CrOx layer as the opacifying layer. FIG. 47 shows the transmittance versus reflectance for different opacifying layers and thicknesses. The symbols in the figure represent AgAu7x layers with different thicknesses. Thick layers are on the right and thin layers are on the left.

  As can be seen here, as the thickness of the AgAu7x layer is reduced, the reflectivity approaches the value of the chromium or opacifying layer. The thickness of the opacifying layer will affect the lower end reflectivity of the mirror element. For example, when the Cr layer has a thickness of 10 nm, the lower end reflectance is 41.7%, when it is 20 nm, it is 50.5%, and when it is 30 nm, it is 52.7%. When the thickness of the opaque layer increases, the lower end reflectance approaches a constant value. However, in a thin layer, the reflectance decreases as the layer becomes thinner. This can be advantageous or disadvantageous depending on the design criteria for a given application. The limitation between reflectivity and transmissivity for the chrome layer can be overcome by replacing the chrome layer with a completely different material or adding additional layers.

  With reference to US Pat. No. 6,700,692, different metals, semiconductors, nitrides or oxides are taught above or below the Ag-containing layer. These layers and materials are selected to improve the stack. A base layer under the reflector is taught that can be a conductive metal, metal oxide, metal nitride, or alloy. Furthermore, there may be intermediate layers or layers between the base layer and the reflective material. These metals and materials can be selected so that there is no DC electrical reaction between the layers and / or to improve adhesion to the substrate and reflector or other layers. These layers can be deposited on the substrate, or there can be additional layers under the aforementioned base layer that provide additional desirable properties. For example, there can be a dielectric pair comprising TiO2 and ITO with an effective odd quarter wave optical thickness. The thickness of the TiO2 and ITO layers can be adjusted as needed to meet specific conductivity and optical requirements.

  If the metal layer is deposited below the silver-containing layer, it can be chromium, stainless steel, silicon, titanium, nickel, molybdenum, and alloys of chromium / molybdenum / nickel, nickel / chromium, molybdenum, and nickel-based alloys; Inconel, Indium, Palladium, Osmium, Tungsten, Rhenium, Iridium, Molybdenum, Rhodium, Ruthenium, Stainless Steel, Silicon, Tantalum, Titanium, Copper, Nickel, Gold, Platinum, and Alloys whose components are mainly the above materials, any It can be selected from the group consisting of other platinum group metals and mixtures thereof. Furthermore, the layer below the reflector layer can be an oxide or metal oxide layer such as chromium oxide and zinc oxide.

  The optional metal layer covering the silver-containing layer can be selected from the group consisting of rhodium, ruthenium, palladium, platinum, nickel, tungsten, tantalum, stainless steel, gold, molybdenum, or alloys thereof.

  The present disclosure contemplates an opacifying layer in combination with a transflective portion of a mirror or optical element. This indicates that new or additional design criteria are included that affect the choice of metal that serves to reduce the transmission of certain areas of the element or mirror. Table 22 below shows the metal reflectivity and color of various suitable base or opacifying layers on a stack of TiO2 / ITO dielectric layers in an EC cell. The thickness of all metal layers is 30 nm. The color and reflectivity will vary depending on the thickness of the metal layer. Table 22 shows the relative difference in color and reflectivity of various suitable metal opacifier layers versus bottom reflectivity when the opacifier metal is relatively thick and no AgAu7x or other Ag-containing top layer is present. As is known in the art, these metals or alloys with other metals will have different optical properties. The alloy may behave like a mixture of individual metals, but may not have the reflective properties of simply interpolating the individual metals. The metal or alloy can be selected for DC electrical properties, reflectivity, color, or other properties as desired.

  In silver-containing reflective layer stacks, the reflectivity and color will change when deposited on these different metals or alloys. Table 23 shows the metal-containing stack with 20 nm AgAu7x. The color and reflectivity of the 20 nm Ag-containing layer stack varies with the properties of the metal used, as does the opacifying layer. In addition, the transmittance of different stacks is also shown. As shown above for chrome, the transmittance, reflectance, and color can be changed by changing the thickness of the opacifying metal. It is clear from these examples that the desired color, transmission, and reflectance can be achieved by changing the properties of the opacifying metal layer or each layer.

  The ability to adjust the color and reflectivity of the visible region can be further enhanced or enhanced by combining a metal opacifying layer additionally described in US Pat. No. 6,700,692 with a dielectric layer. . The dielectric layer can often modify both color and reflectivity without substantially affecting the absorption of the stack.

  In order to match the color and reflectivity of the display area, the two-layer base layer described above under the silver-containing reflective layer can be used. Table 24 shows how for a fixed AgAu7x layer the reflectivity and color change as the ITO and TiO2 thicknesses change. As can be seen here, the thickness of the two layers not only affects the reflectivity, but can also adjust the color. These layers can then be adjusted as necessary to obtain both the desired reflectivity and color. The tunability of color and reflectivity can be further expanded by adjusting the thickness of the AgAu7x or silver-containing reflective layer. Additional color and reflectance changes may be due to the addition of an additional dielectric or metal layer either above or below the silver-containing layer as part of the display stack, or the refractive index of the dielectric layer. Can be obtained by changing

  For example, if the color in the visible region is yellow, blue, green, or red biased by selecting the metal under the silver reflective layer or by the silver reflective layer itself or by a combination of layers And / or reflectivity matching can be achieved by adjusting the layers of the display area. One advantage of this approach is that layers can be applied over substantially the entire surface, but due to the specific optical shielding properties of the opacifying layers or layers, these lower layers are visible or opaque. It does not contribute to the reflectivity and color of the area and is fully functional in the display area where the opacifying layer or layers are shielded. The present invention is not limited to the layer functioning in the display area covering the entire part. This is particularly applicable to layers below the opacifying layer. These layers can be deposited only in the general area of the display as needed if the manufacturing process guarantees this approach.

  In some circumstances, it may be advantageous for the reflector and / or transflector to be bluish in the reflected hue. Furthermore, it may be advantageous to combine the opaque bluish reflector region and bluish translucent region of the same element for an intimate appearance.

  It is known to make blue electrochromic elements with a blue phase using a dye even when no potential is applied, as in US Pat. No. 5,278,693, incorporated herein by reference. In addition, there is also a practical way of using a third surface coating stack to make such a device that meets the typical requirements for external automotive electrochromic devices. Furthermore, these techniques can be used in combination in some cases. The reflectance values of such devices currently need to exceed 35% in the United States and more than 40% in Europe. Preferably, in at least one of the embodiments, the reflectance value is preferably greater than 50% or 55%. Whatever third surface stack is used, the electrochromic device needs to be chemically and physically and electrically durable.

  A bluish electrochromic device by depositing an essentially opaque layer of chromium on the glass, then depositing approximately 900 A of ITO over the top, and then completing the construction of the electrochromic device. Can be obtained. The coating stack made and used in this way had the color values shown in Table 25 and the reflectance spectrum shown in FIG. Table 25 and FIG. 53 show the values when the coating is on a single “lite” of glass and after being incorporated into an EC element.

  There will be a substantial reflectivity drop when comparing the coating on glass measured in air to the reflectivity of the completed device. To compensate for this, it may be considered that an opaque layer of silver or silver alloy with the top layer or each layer similar may be used instead of or in addition to the chromium layer. However, the optical properties of silver are such that it is more difficult to obtain a highly reflective bluish coating covering the silver base material. This is due in part to the fact that silver is biased to a slightly yellow spectrum and because the reflectivity is already close to 100% across the visible spectrum, the reflectivity of silver is intervening in every part of the spectrum. It is also due to the fact that there is little that can be done to increase and give significant color.

  However, if a semi-transparent layer of silver or silver alloy is placed between the upper stack of chrome and ITO, the third surface reflector electrode still maintains a significant amount of reflectivity and maintains a bluish color. The conductivity of the can be increased.

  If a silver translucent layer is present, the teachings contained in this document can be used to create a translucent region by adding a color neutralization underlayer, “split” the silver, and shield the chrome openings. I will.

  For example, a reflective stack of approximately 40 nm TiO2, 20 nm ITO, 14 nm silver, 50 nm chromium, 10 nm silver, and 90 nm ITO is modeled as similar in hue and brightness to the same stack without the chromium layer. Is done. Without the chrome layer, the transmittance of the stack is calculated as appropriate for use as a display or photosensor area. Thus, while coating the layer, it is possible to shield the chromium and create a similar bluish hue and brightness (ie, tightness) electrochromic element in both the opaque and transflective parts of the device.

  Also, the reflectivity of the chrome / ITO stack can be increased by inserting a low refractive index layer between chrome and ITO or by a plurality of alternating low and high refractive index layers. However, the lowest refractive index oxide and fluoride material with sufficient layer thickness to have an appropriate optical effect will also be an electrical insulator. However, silver itself is a low refractive index material, which partially explains its advantages when located between chromium and ITO.

(Table 25)

  Another property that is advantageous in the area of display windows and transflective coatings is the anti-reflective property from the reverse direction. In many cases, the display generates a significant amount of stray light that bounces or scatters around the back of the mirror element and eventually exits the display area. By making the element have a relatively low reflectivity in the opposite direction, this stray light can be reduced. Achieving low reflectivity without using an additional layer on the fourth surface has the added benefit of reducing costs.

  At the same time having TiO2 / ITO / AgAu7x / AgAu7x in the display area, Cr / TiO2 / ITO / AgAu7x / Cr / AgAu7x is provided in the opaque or visible area. The first chrome layer is thin and has a thickness of about 2-15 nm, preferably about 5-10 nm, and is shielded by the display area. In addition, the second chrome is also shielded by the display area and its thickness is adjusted to obtain the desired transmittance in the visible area. The TiO2 / ITO2 layer covers the entire surface and is adjusted from the front to obtain an antireflection effect from the reverse direction of the visible region while making the display region an appropriate color.

  Table 26 shows the reflectivity from the reverse direction or from the fourth surface. The first case is a reference case. This is the stack described above for the opaque or visible region of the mirror element. As can be seen here, the reflectivity from the back is quite high, about 61%. In the second case, a thin chrome layer (˜5 nm) is added below the dielectric layer. Adding this thin layer in the visible region reduces the reflectivity to approximately 6%, where the intensity is reduced by a factor of 10. Accordingly, any stray light scattering is reduced. This reflectance value and its color can be adjusted by the thickness of the chromium layer and the dielectric layer. Nearly 4% of the 6.2% reflectivity comes from the uncoated fourth surface of the glass. If it is desired to further reduce the reflectivity, a conventional antireflection layer can additionally be added. The reflectance value of 6.2% can be reduced to a value of less than 2.5%.

  The amount of decrease in reflectivity and its absolute value depend on the characteristics of the first silver-containing layer and the subsequent chromium layer. As mentioned above, these layers are adjusted by adjusting not only the transmittance but also the reflectivity towards the viewer. When these layers are adjusted to meet various design objectives or targets, the dielectric layer and / or the base chrome layer can be adjusted to achieve an optimal anti-reflection effect.

  A metal other than chromium or an absorption layer can be used as the antireflection layer. In addition, materials such as tungsten, chromium, tantalum, zirconium, vanadium, and other similar metals will also produce a wide range of anti-reflective properties. Other metals can result in high and more colored reflectivity. In addition, chromium or other metal layers can be doped with a small amount of oxygen or nitrogen to change the optical properties of the metal in order to adjust the antireflection properties.

The usefulness of alternating sets of high and low index layers or multiple sets of such layers to modify the optical properties of a surface or thin film stack is described elsewhere in this document. Materials that are typically considered to have a low refractive index are metal oxides, nitrides, oxynitrides, fluorides, which tend to be poor conductors. Typically, the greater the difference in refractive index between adjacent materials, the greater the optical effect. This is why a material having a refractive index of about 1.6 or less is usually used as the low refractive index material. However, when the material to which the TCO is coupled has a sufficiently high refractive index, resulting in a high-low refractive index pair, an advantageous effect occurs with a high refractive index material such as a transparent conductive oxide. In particular, when titanium dioxide is used as a relatively high refractive index material coupled to indium tin oxide as a relatively low refractive index material, optical and electrical advantages are obtained. In particular, titanium dioxide is optically thick enough to isolate highly conductive thin films such as ITO, another TCO, or one or more metal or metalloid layers disposed thereon or below it. It is a relatively high refractive index material that is not a good insulator. When TiO ₂ is added as an optical thin film between layers with much higher conductivity, such as indium tin oxide, TiO ₂ does not isolate the ITO layers of the electrochromic element from each other, and the high − The desired optical effect of low-high stack is achieved. In other words, most of the cumulative conductivity advantage of the total thickness of the thin film ITO is maintained, while the optical advantages of the high and low index layers are obtained. The following example will generally demonstrate this principle, particularly the advantages of these materials. All base layers were measured deposited on soda lime glass (n is approximately 1.5 in the visible spectrum).

  Base layer A = half-wave optical thickness ITO of approximately 145 nm physical thickness and 23 ohm / square sheet resistance (generated under sub-ideal conditions). Base layer B = approximately 40 nm titanium dioxide under approximately 20 nm ITO with sheet resistance between approximately 110 and 150 ohms / square. Base layer C = Base layer A + base layer B with sheet resistance of approximately 16 ohms / square (below the expected sheet resistance is layer A by capping and cooling the ITO layer of A before breaking vacuum This may be due to the fact that the conductivity may have increased compared to the single case). Base layer D = approximately 42.5 nm titanium dioxide, 42.5 nm ITO, 42.5 nm titanium dioxide, 42.5 nm ITO with a sheet resistance of about 40 ohms / square. FIG. 54a shows the reflectance spectrum of these base layers on glass (without additional coating and before assembly into an electrochromic element) in the air.

  An additional coating of approximately 25 nm of 6% Au 94% Ag (referred to as 6x) alloy was applied to a sample from the same coating operation as the sample in FIG. 54a (note that there is some variation within one operation) The electrochromic element was assembled according to the principles outlined elsewhere in this specification. The second surface coating of these elements was ITO with a half wave optical thickness of approximately 12 ohms / square on glass. Next, spectrophotometric measurements were taken as shown in FIGS. 54b and 54c. The results are listed in Table 29.

(Table 27)

  As mentioned above, it is often useful to shield the silver alloy so that, for the most part, it is not covered under the seal area. If this option is selected, electrical contact to the element is made under the third surface. In such an example, the low sheet resistance of the underlying layer is even more important than if the silver or silver alloy was taken all the way to electrical contact through a bus bar or conductive epoxy or other means.

  The described base layer resistance measurements were made with a four-point probe, which can produce false results with respect to surface conductivity if the probe breaks through the insulating layer. Therefore, the element consisted of only the base layer as a third surface coating and the coloring and lightening properties were compared. Element performance was consistent with sheet resistance measurements made with a four-point probe.

  In one embodiment of the present invention, it may be desirable for the color and reflectance to match between the visible region and the display region. In some examples above, there can be two different metal stacks in the two regions, and if the same metal is the top layer, the layer thickness can be different and under the top metal layer. Other metals may or may not be present. As a single unit, the reflectivity of the two regions can be adjusted to be substantially the same before being deposited into the EC element. If the medium in contact with the metal changes from air to EC fluid medium after deposition, the reflectivity may be different in the two regions. This is because each stack interacts with the new incident medium in a different way.

  For example, ruthenium as the top layer in one of the designs (glass / TiO2, 45 nm / ITO, 18 nm / Ru, 14 nm) and AgAu7x in another design (glass / TiO2, 45 nm / ITO, 18 nm / AgAu7x, 19 nm) Both have a reflectivity of 70.3% as a single unit, and when assembled to an element, the Ru side will decrease to 56.6% and the AgAu7x side will decrease to 58.3%. Adjust to.

  Another example of TiO2, 40nm / ITO, 18nm / Cr, 25nm / AgAu7x, 9nm reflectivity is 77.5% as a single unit and 65.5% when assembled into an element, TiO2, 40nm / ITO, 18nm / The reflectance of AgAu7x, 23.4 nm is 77.5% as a simple substance, and 66% when assembled into an element. Although the difference in this case is not as dramatic as the previous example, it indicates that the buried layer may affect the decrease in reflectance from a single element to an element. This indicates that if the reflectance of the element is desired to be consistent, it may be necessary for the coating itself to have a mismatch in reflectance with respect to the coating.

  In the method described above, which is intended to achieve good reflectivity and color matching in the two areas of the mirror, the appearance of the two areas is assumed to be due to substantially full reflectivity. However, the viewer perceives not only the reflectance but also the transmitted light in the display area. In the visible or opaque regions, the transmittance is relatively low, so only the viewer sees the reflectance. The amount of transmitted light is a function of the transmittance of the display area and the reflectivity of the back of the fourth surface of the mirror or components in contact therewith. The amount of light perceived by the viewer increases as the transmittance of the coating in the display area increases. Similarly, as the reflectivity of the components on the back of the mirror increases, so does the light perceived by the viewer. This can add a significant amount of light and the viewer will know this because the display area is brighter than the visible area. Thereby, the display area can appear brighter even if the two areas have the same reflectivity. This effect may be mitigated by creating an element with components having low reflectivity and / or setting the transmittance in the visible region to a relatively low level. If the output brightness of the display is relatively limited or low, the display can be substantially dimmed by reducing the transmission.

  In yet another example of a 40 nm TiO 2/18 nm ITO / EC fluid / 140 nm ITO / glass EC element with a reflectivity of 8.1%, the fourth surface is coated with a 5 nm ruthenium layer to simulate the display on the back of the mirror (ie, 5 nm Ru / glass / 40 nm TiO 2/18 nm ITO / EC fluid / ITO / glass), the reflectivity increases to 22.4%. The reflectivity of the EC element consisting of glass / 40 nm TiO2 / 18 nm ITO / 22 nm AgAu7x / EC fluid / ITO / glass is 61.7%. The reflectivity of the stack with 5 nm ruthenium is 63.5%, increasing the reflectivity by almost 2%. This amount of reflectivity is completely perceivable by the viewer. As described above, the actual increase in reflectivity will depend on the reflectivity of the components behind the mirror and the transmissivity of the EC element.

  In order to reduce the difference in brightness perceived between the two regions, the relative reflectance of the two regions can be adjusted to compensate for the transmitted light component. Thus, to achieve a net 2 percent bright area in the mirror display section, either the reflectance of the visible area is preferentially increased or the reflectance of the display area is preferentially reduced. The amount of adjustment depends on the particular situation of the system.

Example 1a
In this example, TiO ₂ approximately 400Å of the third surface of 2.2mm glass substrate, followed by approximately ITO of 180 Å, finally approximately 195Å silver - gold alloy (93% silver / 7% gold by weight) Cover. Titanium dioxide and ITO are preferably added substantially to the edge of the glass and the silver alloy is preferably shielded inside at least the outer side of the associated seal. In at least one embodiment, the second surface comprises a 1/2 wave (HW) layer of ITO. The associated element reflectivity and transmittance models are shown as lines 4801a and 4801b in FIGS. 48a and 48b, respectively. The reflection of the model is approximately 57% at approximately 550 nm and the transmittance is approximately 36.7%.

[Example 1b]
This embodiment is the same except for the chromium / metal tabs along at least a portion of the peripheral area of the third surface that extends under the seal to improve electrical conductivity between the associated clip contact area and the silver alloy. The configuration is the same as 1a. The appearance remains the same, but the darkening speed is improved. This feature can be applied to several embodiments below to improve the conductivity from the third surface to the associated electrical contact. As can be seen in FIGS. 48a and 48b, with respect to the reflectivity associated with the elements of Example 1a, each transmissivity is dramatically different, which represents one of the advantages of the present invention.

Example 1c
Example 1c is configured similarly to Example 1a, except that the display area is initially shielded and a stack of Cr / Ru is deposited over substantially the entire surface after removing the mask (ie, the display Only Cr / Ru on the area glass). The Cr / Ru opacifying stack can be replaced in several combinations. The reflectance and transmittance results are shown in FIGS. 48a and 48b by lines 4802a and 4802b, respectively. The opacifying stack is preferably of low contrast for both reflectivity and color compared to the display area. Another advantage of this example is that the metal commonly used in the opacifying layer extends to the edge of the glass and bridges between the associated electrical connection clip and the third surface silver-gold alloy. It can be done. The model reflection is approximately 56.9% at approximately 550 nm in the visible region and approximately 57% reflection in the display region, with a visible region transmittance of <10, preferably <5%, more preferably <1%, most preferred. For design purposes, it is <0.1% (this applies to all comparable designs) and the transmittance of the display area is approximately 36.7%. It should be understood that the light sensor can be placed on the back of the “display area” in addition to or instead of a display or other light source.

Example 2a
In this example, the third surface of the mirror element is coated with approximately 2000 ＩＴＯ ITO, followed by approximately 50% transmissive chromium, and finally with approximately 170 Å silver-gold alloy. Preferably, the ITO and chrome are coated substantially on the edge of the glass and the silver alloy is shielded on the inside at least the exterior side of the seal. The Cr thickness is preferably adjusted to be 50% transmittance when the ITO plus Cr layer is measured only through the back plate. In at least one embodiment, the second surface preferably comprises a HWITO layer. The reflectivity and transmissivity of the elements are shown by lines 4901a and 4901b, respectively, in FIGS. The Cr layer can be adjusted (thickened or thinned) to adjust the final transmission of the transflective element. When the Cr layer is thickened, the transmittance is reduced, and when the Cr layer is thinned, the transmittance is increased. An additional advantage of the Cr layer is that the color of the stack is relatively stable against normal vacuum sputter deposition process variations of the base ITO layer. The physical thickness of the chromium layer is preferably between approximately 5 and 150 inches, more preferably between 20 and 70 inches, and most preferably between 30 and 60 inches. The model reflection is approximately 57% at approximately 550 nm and the transmittance is approximately 21.4%.

[Example 2b]
Example 2b is the same as Example 2a except that the chromium / ruthenium combination stack is coated to give a transmission of 50% when measuring only the backplate (ie before incorporation into the mirror element). It is the same. Adding a Ru layer improves the stability during the epoxy seal. The ratio of Ru and chromium thickness can be adjusted, and there is some design tolerance. Chromium is mainly incorporated to improve the adhesion of Ru to ITO. Ru has favorable binding properties to Ag or an Ag alloy. Other metals or each metal can be placed between the Cr and Ru layers as long as appropriate materials and physical properties are maintained. The reflectance and transmittance characteristics are shown by lines 4901c and 4902c in FIG. 49c, respectively.

Example 2c
Example 2c was performed except that the display area was initially shielded and the Cr / Ru (or other opacifier) layer deposited substantially the entire third surface after removal of the mask. Similar to Example 2a and Example 2b. The transmittance and reflectance results are shown by lines 4902a and 4902b in FIGS. 49a and 49b, respectively. Related advantages are similar to Example 1c.

Example 3a
In this embodiment, the third surface of an EC element is approximately 400Å of TiO _2, followed by approximately 180Å of ITO, followed by approximately 195Å silver, finally, is coated with Izo-Tco of approximately 125 Å.

  This example is similar to Example 1a, where TiO2 and ITO are substantially coated on the edge of the glass, silver is shielded at least inside the exterior side of the seal, and then from the EC fluid. As a protective barrier, an indium-zinc-oxide (IZO) or other layer of TCO is added over the silver. Alternatively, the IZO / TCO layer can extend substantially to the edge of the glass. In at least one embodiment, the second surface preferably comprises a HWITO layer. The reflectivity and transmissivity of the elements are indicated by lines 5001a and 5001b in FIGS. 50a and 50b, respectively. The model reflection is approximately 57% at approximately 550 nm and the transmittance is approximately 36%.

[Example 3b]
Example 3b is configured in the same way as Example 3a, except that the display area is shielded and the Cr / Ru stack is deposited over substantially the entire unshielded area of the third surface. The The Cr / Ru opacifying stack can be replaced with several combinations of materials. The reflectance and transmittance results are shown in FIGS. 50a and 50b by lines 5002a and 5002b, respectively. The advantage of this example is that the metal typically used in the opacifying layer can extend substantially to the edge of the glass and bridge between the associated electrical contact clip and the silver alloy. Data obtained by measuring the associated reflectance and transmittance are shown in FIG. 50c by lines 5001c and 5002c, respectively.

Example 4a
In this example, the third surface of the EC element is coated with approximately 2100 ＩＴＯ ITO, followed by approximately 225 シ リ コ ン silicon, and finally approximately 70 Ｒ Ru or Rh.

  All of the layers can be coated substantially up to the edge of the glass. Alternatively, the glass can be processed into a sheet and then cut into a single piece for incorporation into the mirror element. The Ru or Rh layer can be replaced with one of several highly reflective metals or alloys. In at least one embodiment, the second surface is preferably coated with HWITO. This example shows the advantage of increased transmission at different wavelengths. The base ITO layer can be replaced with a layer of different thickness. In some embodiments, the ITO is preferably an odd multiple of a quarter wave. In these cases, the reflectivity will be slightly enhanced by ITO. This effect decreases somewhat as the ITO becomes thicker. The advantage of thick ITO is generally low sheet resistance, which results in faster element darkening time. The model reflection is approximately 57% at approximately 550 nm, and the transmittance is approximately 11.4%. The model reflectance and transmittance are shown in FIGS. 51a and 51b, respectively. The measured reflectivity and transmissivity are shown in FIG. 51c by lines 5101c and 5102c, respectively.

Example 5
In this example, the third surface of the EC element is coated with approximately 2100 ＩＴＯ ITO, followed by approximately 50 ク ロ ム chromium, followed by approximately 75 Ｒ Ru, and optionally, optionally approximately 77 Ｒ Rh.

  All of the layers can be coated substantially to the edge of the glass, and the glass can be processed into a sheet and then cut into a single piece for incorporation into the mirror element. The Ru layer can be replaced with one of several highly reflective metals or alloys, or additional layers such as rhodium can be added. The metal layer can be adjusted to obtain a high or low reflectivity / transmittance balance. In at least one embodiment, the second surface is preferably coated with a HWITO layer. One advantage of thick ITO is that it generally has a low sheet resistance, which results in faster element darkening times. Thicker ITO can increase the roughness of the third surface stack, thereby reducing the reflectivity. This effect is observed when comparing the model transmittance and reflectance of FIGS. 52a and 52b to experimentally obtained transmittance and reflectance (line 5201c1 and line 5201c2 of FIG. 52c, respectively). The model reflection is approximately 57% at approximately 550 nm and the transmittance is approximately 7.4%.

Example 6a
Opacifier layer on the third surface In this example, the opacifier layer is incorporated into the third surface coating stack. A base layer stack of approximately 600 liters of chromium, followed by approximately 600 liters of ITO, either shields the display area during the deposition process of the base layer stack, or later laser deletes the display area of the base layer stack. Deposited on a glass substrate. Next, a layer of approximately 700 ＩＴＯ ITO and (approximately 180 銀 silver alloy Ag-X, X indicates an Ag alloy option) is added. In this approach, the visible area is substantially opaque and the display area is transflective.

  The alloy can shield relatively far from the seal and improve the life of the element in harsh environments. The model reflection is approximately 52% at approximately 550 nm and the transmittance is approximately 41%.

[Example 6b]
Example 6b is similar to Example 6a. In this example, the third surface is a base layer stack of first approximately 600 liters of chrome, followed by approximately 100 liters of ITO, followed by approximately 500 liters of TiO ₂ , and finally approximately 50 liters of chromium, except for the display area. Covered. In effect, the entire third surface is then substantially TiO ₂ of 150 Å, followed by approximately 500Å of ITO, finally approximately 180Å silver - coated with gold alloy. The model reflection is approximately 54% at approximately 550 nm and the transmittance is approximately 41%.

  The reflectivity (R) of the electrochromic mirror can be limited when a high transmittance (T) level is desired, or the transmittance can be limited when high reflectivity is required. This can be explained by the relationship R + T + A = 1, assuming that the absorption (A) remains constant. In some displays, or light sensor, mirror applications, it may be desirable to have a high level of transmitted light or (brightness) to properly view the associated display or transmit the appropriate light to the mirror element. is there. In many cases, this results in a mirror with a reflectivity that is less than desired.

  Solutions to address the above limitations are described in other examples herein where the thickness of one or more metal layers is appropriate for the reflectivity of the visible region and is thin only in the portion that covers the display region. ing. Other examples use different metal or coating stack layers covering the display area in an attempt to match the color and / or reflectivity of the different areas. In many cases, sudden changes in reflectance or color are undesirable for the observer. For example, referring to FIGS. 55 and 56a, the boundary (C) between the two regions is abrupt. The transmittance of the region (A) is higher than that of the region (B). The boundary (C) delineates the two regions. In FIG. 63, the boundary at which the transition between the high and low reflectivity regions begins is also abrupt. The change in reflectance / inclination of unit distance approaches infinity when transitioning between regions.

  In at least one embodiment, the mode of transition of the metal layer thickness is gradual. If the reflectance and / or transmittance gradually changes in the transition region, it is difficult to detect with the human eye. The two regions still have different reflectance and transmission values, but the boundary between the two regions changes gradually and the gradual transition eliminates the sudden discontinuity and replaces it with a gradual transition. . The human eye cannot be attracted to its interface when it is gradually changed. This grading can be linear, curvilinear, or other forms of transition shown in FIGS. 56b-56d. The distance over which gradual change occurs can be varied. In at least one embodiment, the distance is a function of the reflectance difference between the two regions. If the reflectivity between the two regions is relatively low, the gradual distance can be relatively short. If the reflectivity difference is large, it may be preferable to have a long grading to minimize the visibility of the transition. In at least one embodiment, the grading length is a function of the application and intended usage, observer, illumination, etc.

  In at least one of the embodiments shown in FIG. 56e, the transmittance may decrease to near zero in one or more portions. In other cases described herein, the reflectivity can be the same or different. The “confidentiality” embodiments described elsewhere in this specification can be used to maintain the reflectance relatively constant while adjusting the transmittance in various parts of the mirror element as needed. .

  The present invention is not limited to having two or more regions with constant transmittance or reflectance. One embodiment is shown in FIG. 56f. The transmittance of region B is relatively low and may be zero. This may be desirable if one of the design objectives is to block the light entering from the object located in the region B behind the transflective coated substrate. The coating stack can transition progressively from region B with slope C. Region A can have another slope on its own. This has the potential advantages described below.

  In certain applications, sufficient length may not be available to achieve a double plateau situation. In such a case, it is advantageous to use a continuous slope over the region where semi-transmissive characteristics are desired, as shown in FIG. 57a. The change in reflectivity is gradual, and the advantage of high transmittance is obtained. That is, there is no sudden interface between the regions.

  The slope between the two zones can take various forms. In the broadest sense, an element can include regions of uniform transmission and reflectance that are different from each other. In the example shown in FIGS. 57a to 57c, there is no region of constant reflectance and transmittance. In these cases, the optical properties change gradually and continuously. The advantages of this approach are shown in FIG.

  When a viewer views the display through a mirror element or coated glass substrate, there is a continuity in path length and angle in the portion near the display relative to the distant portion of the display. The effective angle relative to the incident angle varies depending on the direction of the mirror element display, the size of the element, the distance from the observer, and the like. This will result in different amounts of transmission through the glass at various portions of the display area. If the amount of transmittance is different, then the brightness of the display will change. If it is desirable to have constant light output from all areas of the display, the transflective coating can be varied to account for transmission loss resulting from viewing angles and differences in path through the glass. Effective viewing angle. When changing from about 45 degrees to 60 degrees, the transmission through the glass will change by about 6%. Thus, having a gradual transflective coating in the area of the display can compensate for this effect somewhat and thus make the sensed light intensity across the display even more equal.

  For displays such as rear cameras or conventional compass temperature displays, a gradual transition zone can be used. In some examples of “confinement” described elsewhere herein, an opacifying layer is placed between two Ag layers to help match the appearance of regions of transflective and opaque properties. A “split Ag” stack is provided. In another embodiment of the covert display, an Ag layer is placed over the opacifying layer. Both of these embodiments can benefit from a gradual transition between regions. The opacifying layer or Ag layer or all layers can be graded. In at least one embodiment, the opacifying layer can be graded to minimize the abrupt transition between regions.

  To change the material thickness of one or more layers to create a transition region, including but not limited to masking, movement of either the substrate or the coating source or a change in velocity, magnetron Many methods can be used including layer reduction techniques such as magnetic field changes, or ion beam etching or other suitable means as described herein.

  FIG. 59 shows a 6Au94Ag glass backplate 5914, a layer 5972A comprising approximately 440 チ タ ン of titanium dioxide sub-layer and about 200 ＩＴＯ of ITO sub-layer, one region having a thickness of about 140 Å and another region having a thickness of about 235 図. Layer 5978, and a third region between the first two regions where the thickness gradually transitions between the two, an electrochromic fluid / gel 5925 with a thickness of approximately 140 microns, a layer 5928 with an ITO of approximately 1400 inches. , And an example of an electrochromic mirror configuration having a 2.1 mm glass plate 5912. The resulting reflectivity of the element ranges from about 63% for most of the mirrors to about 44% for the front area of the display.

  A combination of the masking technique and the magnetic manipulation of the deposition source was used to construct an electrochromic device similar to that described above that varied the thickness of layer 5978 in a manner similar to that illustrated and shown in FIG. 57c. The method chosen will depend on the exact features required for the finished element and what processing methods are available. 60 and 61 show the corresponding reflectance data as a function of mirror position. In this embodiment, the display is placed on the back of a low reflectance, high transmittance area.

  Another application of the gradual transition is an electrochromic element having a second surface reflector that hides the epoxy seal, and the reflectivity between the “ring” and the reflector positioned on the third or fourth surface. And color matching can be achieved. The best match is when the reflection intensity of the ring matches the reflection intensity of the reflector. In at least one embodiment, the reflectivity of the reflector is further increased while not changing the ring. This can occur due to durability, manufacturability, or other considerations. Means for maintaining coincidence between the reflector and the ring can be obtained when the reflectivity of the reflector is graded as described above. When a gradual change in reflectivity occurs, the reflectivity of the reflector can be adjusted to match the reflectivity of the ring near the ring and then gradually increase away from the ring. Therefore, the reflectivity at the center of the visible region is relatively high as seen in FIG.

  Similarly, ITO can gradually change from the ring region to the center of the visible region, keeping the thickness range required for acceptable colors while keeping the reflectivity at the center of the element relatively high. Thus, the mirror will darken relatively quickly compared to the relatively thin ITO coating across the element.

  The same concept can be extended to metal reflector electrodes. In this case, grading can be used such that the sheet resistance of the coating changes gradually with position. This method complements various bus configurations and results in faster and uniform darkening. FIG. 63 shows an embodiment of a prior art mirror element prior to the present invention.

  It should be understood that the detailed description provided herein is intended to enable one of ordinary skill in the art to make and use the best mode of the various embodiments of the present invention. These descriptions are in no way intended to limit the scope of the claims. The claims, as well as the limitations of each individual claim, should be construed to include all equivalents.

It is a figure which shows the airplane which has a variable transmittance window. It is a figure which shows the bus | bath which has a variable transmittance window. It is a figure which shows the train vehicle which has a variable transmittance window. FIG. 2 shows a building with variable transmittance and / or variable reflectance window. It is a figure which shows the vehicle which has a variable transmittance window and a variable reflectance rearview mirror. FIG. 5 shows an external rearview mirror assembly and associated variable reflectivity element. FIG. 5 shows an external rearview mirror assembly and associated variable reflectivity element. FIG. 5 shows an external rearview mirror assembly and associated variable reflectivity element. FIG. 5 shows an external rearview mirror assembly and associated variable reflectivity element. FIG. 5 shows an external rearview mirror assembly and associated variable reflectivity element. FIG. 6 shows an internal rearview mirror assembly and associated variable reflectivity element. FIG. 6 shows an internal rearview mirror assembly and associated variable reflectivity element. FIG. 6 shows an internal rearview mirror assembly and associated variable reflectivity element. FIG. 6 shows an internal rearview mirror assembly and associated variable reflectivity element. It is sectional drawing which shows the cross section of a variable reflectance element. It is sectional drawing which shows the cross section of an element. It is sectional drawing which shows the cross section of an element. It is sectional drawing which shows the cross section of an element. It is sectional drawing which shows the cross section of an element. FIG. 6 shows electrical connections to elements. FIG. 6 shows electrical connections to elements. FIG. 6 shows electrical connections to elements. FIG. 6 shows electrical connections to elements. FIG. 6 shows electrical connections to elements. FIG. 6 shows electrical connections to elements. FIG. 6 shows electrical connections to elements. FIG. 6 shows electrical connections to elements. FIG. 6 shows electrical connections to elements. FIG. 6 shows electrical connections to elements. It is the schematic which shows the electric control with respect to a some element. It is the schematic which shows electric control. It is the schematic which shows electric control. It is the schematic which shows electric control. It is the schematic which shows electric control. FIG. 5 is a graph showing element strain versus oxygen flow for various argon process gas pressures used in the element manufacturing process. FIG. Figure 6 is a graph showing thin film bulk resistance versus oxygen flow rate for various process gas pressures used in the element manufacturing process. FIG. 5 is a graph showing thin film thickness versus oxygen flow rate for various process gas pressures used in the element manufacturing process. FIG. FIG. 6 is a graph showing thin film sheet resistance versus argon flow for various process gas pressures used in the element manufacturing process. Figure 5 is a graph showing thin film bulk resistance versus argon flow for various process gas pressures used in the element manufacturing process. FIG. 5 is a graph showing thin film absorption versus oxygen flow for various process gas pressures used in the element manufacturing process. FIG. FIG. 6 is a graph showing element strain versus oxygen flow for various process gas pressures used in the element manufacturing process. FIG. FIG. 6 is a graph showing element strain versus thin film absorption for various process gas pressures used in the element manufacturing process. FIG. It is a graph which shows the element distortion with respect to various process gas pressures used for an element manufacturing process with respect to the thin film transmittance. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film surface form. It is a figure which shows a thin film peak-peak surface roughness. It is a figure which shows a thin film peak-peak surface roughness. Figure 5 is a graph showing sputtering yield versus ion energy for various thin film materials. It is a graph which shows sputter | spatter yield versus sputter gas mass / target mass. It is a figure which shows the result of the expanded ion milling. It is a figure which shows the result of the expanded ion milling. It is a graph which shows the reciprocal number of thin film surface roughness versus line speed. It is a graph which shows a thin film reflectance versus ion beam current. It is a graph which shows the reciprocal number of thin film reflectivity versus line speed. It is a graph which shows the reciprocal number of thin film b ^* versus line speed. It is a graph which shows thin film reflectivity versus ion beam residence time. It is a graph which shows thin film reflectance vs. thickness. It is a graph which shows a thin film reflectance with respect to a wavelength. It is a graph which shows a thin film transmittance vs. wavelength. It is a graph which shows thin film reflectance vs. thickness. It is a graph which shows a thin film transmittance | permeability versus a reflectance. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. It is a graph which shows a thin film reflectance and / or transmittance | permeability versus a wavelength. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating. FIG. 5 shows an embodiment of an element having a graded thin film coating.

Explanation of symbols

700 Rearview mirror element 702 First substrate 708 First conductive electrode portion 730 Second conductive electrode portion

Claims (44)

A first comprising a first and second surface, wherein at least one layer of material comprising an average peak-valley surface roughness equal to or less than about 150 Å on at least one of the first and second surfaces; A base of
A second comprising a third and fourth surface, wherein at least one layer of material comprising an average peak-valley surface roughness equal to or less than about 150 Å on at least one of the third and fourth surfaces A base of
An electro-optic element comprising:   The electro-optic element of claim 1, wherein the average peak-valley surface roughness is less than or equal to about 100%.   The electro-optic element of claim 1, wherein the average peak-valley surface roughness is less than or equal to about 50%.   The electro-optic element of claim 1, wherein the average peak-valley surface roughness is less than or equal to about 25%.   The electro-optic element of claim 1, wherein the at least one layer of material comprises an indium-tin-oxide layer.   6. The electro-optic element of claim 5, wherein the indium-tin-oxide layer has a thickness of at least about 1/4 wave.   6. The electro-optic element of claim 5, wherein the indium-tin-oxide layer has a thickness of at least about 1/2 wave.   The electro-optic element of claim 1, wherein the at least one layer of material comprises a bulk resistance of less than 200 μohm-cm.   The electro-optic element of claim 1, wherein the at least one layer of material comprises a layer of chromium.   The electro-optic element of claim 9, wherein the chromium layer has a thickness of at least about 250 mm.   10. The electro-optic element according to claim 9, wherein the upper surface of the at least one layer of chromium is smoothed through ion milling after being deposited.   The electro-optic element of claim 9, wherein the chromium layer comprises a reflectivity of at least about 80% of a theoretically possible value.   The electro-optic element according to claim 1, comprising variable transmittance.   The electro-optic element of claim 1 including a variable reflectivity. A first substrate including first and second surfaces;
Including
The first substrate comprises at least one layer of material comprising an average peak-valley surface roughness equal to or less than about 150 に on at least one of the surfaces;
An electro-optic element characterized by that.   The electro-optic element according to claim 15, wherein the average peak-valley surface roughness is less than or equal to about 100%.   The electro-optic element of claim 15, wherein the average peak-valley surface roughness is less than or equal to about 50%.   The electro-optic element of claim 15, wherein the average peak-valley surface roughness is less than or equal to about 25%.   The electro-optic element of claim 15, wherein the at least one layer of material comprises an indium-tin-oxide layer.   The electro-optic element of claim 19, wherein the indium-tin-oxide layer has a thickness of at least about ¼ wave.   The electro-optic element of claim 19, wherein the indium-tin-oxide layer has a thickness of at least about ½ wave.   The electro-optic element of claim 15, wherein the at least one layer of material comprises a bulk resistance of less than 200 μohm-cm.   The electro-optic element according to claim 15, wherein the at least one layer of material comprises a layer of chromium.   The electro-optic element of claim 23, wherein the chromium layer has a thickness of at least about 250 mm.   24. The electro-optic element according to claim 23, wherein the upper surface of the at least one layer of chromium is smoothed through ion milling after being deposited.   24. The electro-optic element of claim 23, wherein the chromium layer includes a reflectivity of at least about 80% of a theoretically possible value.   The electro-optic element according to claim 15, comprising a variable transmittance.   The electro-optic element according to claim 15, comprising variable reflectivity.   A second substrate comprising a third and fourth surface, the second substrate having an average peak-valley surface less than or equal to about 150 mm on at least one of the third and fourth surfaces; The electro-optic element according to claim 15, comprising at least one layer of material comprising roughness. A first layer comprising at least one layer of indium-tin-oxide comprising a first and second surface and comprising an average peak-valley surface roughness equal to or less than about 150 第 on the second surface; A base of
A second substrate comprising at least one layer of chromium on the third surface including a third and fourth surface and comprising an average peak-valley surface roughness equal to or less than about 150 、;
An electro-optic element comprising:   31. The electro-optic element of claim 30, wherein the indium-tin-oxide layer has a thickness of at least about 1/4 wave.   The electro-optic element of claim 30, wherein the indium-tin-oxide layer has a thickness of at least about ½ wave.   31. The electro-optic element of claim 30, wherein the indium-tin-oxide layer has a thickness of at least about 80% of a half wave.   31. The electro-optic element of claim 30, wherein the indium-tin-oxide comprises a bulk resistance of less than 200 [mu] ohm-cm.   31. The electro-optic element of claim 30, wherein the chromium layer has a thickness of at least about 250 mm.   31. The electro-optic element according to claim 30, wherein the top surface of the chromium layer is smoothed through ion milling after being deposited.   31. The electro-optic element of claim 30, wherein the chromium layer includes a reflectivity of at least about 80% of a theoretically possible value.   31. The electro-optic element according to claim 30, comprising variable reflectivity.   32. The electro-optic element of claim 30, further comprising a second layer of chromium near a peripheral area of the second surface.   40. The electro-optic element of claim 39, wherein the top surface of the second layer of chromium is smoothed through ion milling after being deposited. A first substrate comprising an indium-tin-oxide layer on the second surface comprising a first and second surface and comprising an average peak-valley surface roughness equal to or less than about 150 と,
A second substrate comprising an indium-tin-oxide layer on the third surface comprising a third and a fourth surface and comprising an average peak-valley surface roughness equal to or less than about 150 と,
An electro-optic element comprising:   42. The electro-optic element of claim 41, wherein the indium-tin-oxide layer has a thickness of at least about ½ wave.   42. The electro-optic element of claim 41, wherein the indium-tin-oxide layer includes a bulk resistance of less than 200 [mu] ohm-cm.   42. The electro-optic element according to claim 41, comprising variable transmittance.

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