CN101976009B

CN101976009B - Thin-film coatings, electro-optic elements and assemblies incorporating these elements

Info

Publication number: CN101976009B
Application number: CN201010298163.4A
Authority: CN
Inventors: J·S·安德森; J·A·福尔杰特; G·A·诺曼; G·J·多泽曼; D·J·卡蒙加; H·A·卢藤; G·B·波; N·F·布鲁梅尔; L·M·佩龙; W·L·汤纳
Original assignee: Gentex Corp
Current assignee: Gentex Corp
Priority date: 2006-03-03
Filing date: 2007-03-02
Publication date: 2015-07-22
Anticipated expiration: 2027-03-02
Also published as: CN101976009A; KR101278371B1; WO2007100921A2; KR20120035222A; CN103838050B; KR20080106963A; MX2008011009A; EP2035886A4; EP2035886A2; CA2644218C; WO2007100921A3; KR101275450B1; CA2644218A1; JP2009529150A; JP5570730B2; JP2014029556A; JP5855623B2; CN103838050A

Abstract

Electro-optic elements are becoming commonplace in a number of vehicular and architectural applications. Various electro-optic element configurations provide variable transmittance and or variable reflectance for windows and mirrors. The present invention relates to various thin-film coatings, electro-optic elements and assemblies incorporating these elements.

Description

Comprise the film coating of improvement and the rearview mirror assemblies of photovalve

The application is the divisional application based on the patented claim that application number is 200780007652.6 (international application no is PCT/US2007/005494), the applying date, to be March 2, denomination of invention in 2007 be " film coating of improvement, photovalve and comprise the assembly of these elements ".

The cross reference of related application

The application requires right of priority according to 35U.S.C. § 119 (e) to following U.S. Provisional Patent Application: at the S/N 60/779369 licensing to the people such as Tonar that on March 3rd, 2006 submits to; At the S/N 60/810921 licensing to the people such as Tonar that on June 5th, 2006 submits to; At the S/N 60/873474 licensing to the people such as Tonar that on Dec 7th, 2006 submits to; With the agency case GEN 10PP-514 that the denomination of invention licensing to Neuman submitted on February 7th, 2007 is ELECTRO-OPTIC ELEMENT WITH IMPROVED TRANSPARENT CONDUCTOR, be incorporated herein the whole of them and disclose as a reference.

The application and following U.S. Patent application about: denomination of invention is the agency case GEN 10-P517 of ELECTRO-OPTICAL ELEMENT INCLUDING IMI COATINGS; With agency case GEN 10P518; Submitted the while of these two patented claims and the application; Be incorporated herein the whole of them to disclose as a reference.

Technical field

The present invention relates to various film coating, photovalve and comprise the assembly of these elements.

Background technology

Photovalve becomes very common in many delivery vehicles and Application in Building.Various photovalve is configured to window and mirror provides variable transmissivity and/or variable reflectivity.

Accompanying drawing explanation

Fig. 1 illustrates the aircraft with variable transmittance windows;

Fig. 2 a and Fig. 2 b illustrates the motorbus and train respectively with variable transmittance windows;

Fig. 3 illustrates the buildings with variable transmittance windows and/or variable reflectivity window;

Fig. 4 illustrates the vehicle with variable transmittance windows and variable reflectivity rearview mirror;

Fig. 5 a-5e illustrates the various views of outside rearview mirror assemblies and relevant variable reflectivity elements;

Fig. 6 a-6d illustrates the various views of inside rear view mirror assembly and relevant variable reflectivity elements;

Fig. 7 illustrates the sectional view of the xsect of variable reflectivity elements;

Fig. 8 a-8d illustrates the sectional view of the xsect of various element;

Fig. 9 a-9j illustrates the various electrical contacts of various element;

Figure 10 illustrates the electric control schematic diagram of multiple element;

Figure 11 a-11c illustrates various electric control schematic diagram;

Figure 12 illustrates the various component warp of argon gas pressure for utilizing in element manufacture process and the graph of a relation of oxygen flow;

Figure 13 illustrates the graph of a relation of film volume resistance (bulk resistance) for the various process gaseous tensions utilized in element manufacture process and oxygen flow;

Figure 14 illustrates the various film thickness of process gaseous tension for utilizing in element manufacture process and the graph of a relation of oxygen flow;

Figure 15 illustrates the graph of a relation of film surface resistance (sheet resistance) for the various process gaseous tensions utilized in element manufacture process and argon flow amount;

Figure 16 illustrates the film volume resistance of various process gaseous tensions for utilizing in element manufacture process and the graph of a relation of argon flow amount;

Figure 17 illustrates the various film absorption of process gaseous tension for utilizing in element manufacture process and the graph of a relation of oxygen flow;

Figure 18 illustrates the various component warp of process gaseous tension for utilizing in element manufacture process and the graph of a relation of oxygen flow;

Figure 19 illustrates the various component warp of process gaseous tension for utilizing in element manufacture process and the graph of a relation of film absorption;

Figure 20 illustrates the various component warp of process gaseous tension for utilizing in element manufacture process and the graph of a relation of film transmission;

Figure 21-32 illustrates various film surface form;

Figure 33 a and Figure 33 b illustrates surfaceness between film peak-peak;

Figure 34 illustrates the graph of a relation of sputtering output for various membraneous material and ion energy;

Figure 35 illustrates the graph of a relation of sputtering output and sputter gas quality/target mass;

Figure 36 and Figure 37 illustrates ion milling (ion-milling) result of amplification;

Figure 38 illustrates the graph of a relation of the inverse of roughness of film and linear velocity;

Figure 39 illustrates the graph of a relation of reflectivity of optical thin film and ion beam current;

Figure 40 illustrates the graph of a relation of the inverse of reflectivity of optical thin film and linear velocity;

Figure 41 illustrates film b ^*with the graph of a relation of the inverse of linear velocity;

Figure 42 illustrates the graph of a relation of reflectivity of optical thin film and ion beam residence time;

Figure 43 illustrates the graph of a relation of reflectivity of optical thin film and thickness;

Figure 44 illustrates the graph of a relation of reflectivity of optical thin film and wavelength;

Figure 45 illustrates the graph of a relation of film transmission and wavelength;

Figure 46 illustrates the graph of a relation of reflectivity of optical thin film and thickness;

Figure 47 illustrates the graph of a relation of film transmission and reflectivity;

Figure 48 a-53c illustrates the various graphs of a relation of reflectivity of optical thin film and/or transmissivity and wavelength; And

Figure 54-62 illustrates the various embodiments of the element of (graded) film coating with mildization.

Figure 63 illustrate according to the present invention before the embodiment of mirror element of state of prior art.

Embodiment

Fig. 1, Fig. 2 a and Fig. 2 b illustrates and uses variable transmittance windows 110, many passengers delivery vehicle 102 of 210a, 210b, 202a, 202b.Many passengers delivery vehicle of use variable transmittance windows 110,210a, 210b comprises such as aircraft 102, motorbus 202a and train 202b.Should be appreciated that other many passengers delivery vehicle also can use variable transmittance windows 110,210a, 210b, describe some in these many passengers delivery vehicles in detail in other places herein.The many passengers delivery vehicle roughly illustrated in Fig. 1, Fig. 2 a and Fig. 2 b also comprises window control system for controlling variable transmittance windows (not shown in Fig. 1-2 b, but be illustrated with reference to Figure 10 and be described).The commonly assigned United States Patent (USP) 6567708 being Variable Transmission Window Systems in the denomination of invention submitted on June 9th, 2006 describes the various details relevant with variable transmittance windows with U.S. Patent application 60/804378, adds full content disclosed in them as a reference at this.

The Another Application of variable transmittance windows shown in Figure 3.The construction window 302 of buildings 301 can advantageously have variable transmissivity function.Should be appreciated that and can comprise these variable transmissivity construction windows in house, commercial and industrial facility.

Fig. 4 illustrates the in check vehicle 400 comprising various variable transmissivity and variable reflectivity elements.As an example, inside rear view mirror assembly 415 is shown, at least one embodiment, assembly 415 comprises variable reflectivity mirror element and automotive vehicle exterior light control systems.The detailed description to this automotive vehicle exterior light control systems is comprised in commonly assigned U.S. Patent No. 5837994,5990469,6008486,6130448,6130421,6049171,6465963,6403942,6587573,6611610,6621616,6631316 and US Pat Appl Ser No.10/208142,09/799310,60/404879,60/394583,10/235476,10/783431,10/777468 and 09/800460; Full content disclosed in them is added as a reference at this.In check vehicle is also shown to include outside rearview mirror assemblies 410a, the outside rearview mirror assemblies 410b of passenger side, center high installation stop light (CHMSL) 445, the A-pillar 450a of driver side, 450b, B-pillar 455a, 455b and C-pillar 460a, 460b; Should be appreciated that in these positions any one can be imageing sensor, multiple imageing sensor or relevant process and/or control assembly provides substituting position.Any or all that should be appreciated that in rearview mirror can be automatic dimmed photoelectricity mirror (that is, variable reflectivity mirror element).In at least one embodiment, in check vehicle can comprise variable transmittance windows 401,402.In check vehicle is shown to include many outer lamps, and these outer lamps comprise headlight 420a, 420b, paillon foil sky gas lamp (foil weather light) 430a, 430b, front side marker light/danger light 435a, 435b, taillight 425a, 425b, rear side marker light 426a, 426b, rear danger light 427a, 427b and backup lamp 440a, 440b.Should be appreciated that such as independent low beam and high beam headlight can be set, the additional outer lamp of the integrated lamp that comprises multipurpose lighting etc.Should also be understood that the steady arm (not shown) of the relevant primary optical axis of the outer lamp that any one had adjustment in outer lamp is given.In at least one embodiment, at least one outer mirror sub-component has the rotating mechanism (pivoting mechanism) allowing to rotate along direction 410a1,410a2,410b1,410b2.Be to be understood that, the in check vehicle of Fig. 4 is generally for illustrative purposes, further, can add as a reference together with the further feature illustrated here and here open in use disclosed in the patent and patented claim that such as add as a reference those suitable automatic dimmed rearview mirror here.

Preferably, in check vehicle comprises the inside rear view mirror of unit enlargement factor.Unit used herein enlargement factor mirror (unit magnification mirror) means the plane or smooth mirror with such reflecting surface, namely, by this reflecting surface, except being no more than the crackle of normal manufacturing tolerance, angle height and the width of the image of object equal angle height when the object in identical distance during direct viewing and width.Here, at least one relevant position provides the prism of unit enlargement factor to adjust rearview mirror round the clock and is regarded as unit enlargement factor mirror.Preferably, the horizontal angle included that mirror provides the viewpoints from projection with at least 20 degree to measure and the visual fields of enough vertical angles, with when in check vehicle by driver and four passengers or when occupying based on (if less) number of occupying of specifying of the averaged occupation person weight of 68kg, provide and extend to the observation to the rear portion of controlled vehicle of the horizontal level road that starts on the point being not more than 61m.Should be appreciated that sight line by the tenant that takes one's seat or may be covered by head constraint portions.The position of the eyes reference point of driver preferably according to the rules or be suitable for any percent 95 the nominal position of male driver.In at least one embodiment, in check vehicle comprises the outside mirror of at least one unit enlargement factor.Preferably, outside mirror to the driver of in check vehicle provide from perpendicular to extending to local horizon at the widest line selecting the fore-and-aft plane tangent with the driver side of in check vehicle, to take seat as rearmost position extend out the observation of the level road of 2.4m from the tangent plane of 10.7m after the eyes of driver.Should be appreciated that sight line may be covered by the rear portion vehicle body of in check vehicle or protective shield outline portion.Preferably, the position of the eyes reference point of driver according to the rules or be suitable for any percent 95 the nominal position of male driver.Preferably, passenger side mirror is not covered by the non-wiping part of corresponding windshield and preferably by tilting from the seated position of driver along horizontal and vertical directions to be adjusted.In at least one embodiment, in check vehicle comprises the convex mirror being arranged on passenger side.Preferably, this mirror is configured to by tilting to be adjusted along horizontal and vertical directions.Preferably, each outer mirror attached bag containing the reflecting surface being not less than 126cm, and is positioned as providing observation below along the associated side driver of in check vehicle.Preferably, according to SAE Recommended Practice J964, the average reflectance of any mirror that OCT84 determines is at least 35% (being 40% for many European countries).Can have in the embodiment of multiple reflectivity levels in mirror element, such as according to photoelectricity mirror element of the present invention, the minimum reflectance level of day mode should be at least 35% (being 40% for Europe uses), further, the minimum reflectance level of night mode should be at least 4%.Should be appreciated that each embodiment of the present invention is equally applicable to motorcycle windscreen and rearview mirror.

Forward now Fig. 5 a and Fig. 5 b of the various parts that outside rearview mirror assemblies 510a, 510b are shown to.As described in detail here, photoelectricity mirror element can comprise the first substrate 521b and the second substrate 522b that are fixed to be formed betwixt chamber by primary seal 523b with the relation of separating.In at least one embodiment, primary seal remain sky at least partially, to form at least one chamber fill port 523b1.In chamber, load photoelectric medium and seal fill port by choke material (plug material) 523b2.Preferably, choke material is epoxy resin or the acryhic material of UV-curable.In at least one embodiment, near the second surface that spectral filter material 545a, 545b are positioned at the first substrate, the periphery of mirror element.Preferably respectively by first adhesive material 526b1,526b2, electric connector 525b1,525b2 are fixed on element.By the second adhesive material 570b, mirror element is fixed on loading plate 575b.Realize from external mirror having indicator light to the electrical connection of other parts of in check vehicle preferably by connector 585b.By steady arm 580b, carrier is fixed on relevant outer casing base (housing mount) 585b.Preferably, outer casing base and shell 515a, 515b meet at least one securing member of merga pass 534b4 and are fixed.Preferably, outer casing base comprises change (swivel) part being configured to engage with change base 533b.Change base is preferably configured to be engaged with vehicle base (vehicle mount) 530b by least one securing member 531b.Other details of these parts, additional parts, their interconnection and operation is provided here.

With further reference to Fig. 5 a and Fig. 5 b, outside rearview mirror assemblies 510a is oriented like this, makes the observation showing the first substrate 521b with the spectral filter material 524b between observer and primary seal material 523b.Can add in rearview mirror assemblies blind-spot indicators 550a, keyhole luminaire 555a, puddle lamp (puddle light) 560a, assisted diversion pilot lamp 540a or 541a, optical sensor 565a, in them any one, their recombinant or their combination, they are positioned at after element relative to observer.Preferably, as discussed in detail in each document of adding as a reference here and here, device 550a, 555a, 560a, 540a or 541a, 565a and mirror element combine and are configured to be hidden at least in part.Other details of these parts, additional parts, their interconnection and operation is provided here.

Forward now Fig. 5 c ~ 5e to, the discussion according to supplementary features of the present invention is provided.Fig. 5 c illustrates the rearview mirror elements 500c observed from the first substrate 502c, wherein makes spectral filter material 596c between observer and primary seal material 578c.First separated region 540c is set substantially to make the first current-carrying part 508c and the second current-carrying part 530c electrical isolation.Circumference material (perimeter material) 560c is applied on the edge of element.Fig. 5 d illustrates the rearview mirror elements 500d observed from the second substrate 512d, wherein, makes primary seal material 578d between observer and spectral filter material 596d.Second separated region 586d is set substantially to make the 3rd current-carrying part 518d and the 4th current-carrying part 587d electrical isolation.Circumference material 560d is applied on the edge of element.Fig. 5 e illustrates the rearview mirror elements 500e observed from profile line Fig. 5 e ~ Fig. 5 e of the arbitrary element Fig. 5 c or Fig. 5 d.First substrate 502e is illustrated as being fixed together with the second substrate 512e with the relation of separating by primary seal material 578e.Spectral filter material (being called as at least one embodiment here " chromium ring (chrome ring) ") 596e is between observer and primary seal material 578e.First and second electrical terminals (electrical clip) 563e, 584e are set respectively to be conducive to the electrical connection with element.Circumference material 560e is applied on the edge of element.Should be appreciated that the means conventional in LCD industry by such as silk screen or distribution apply primary seal material.The U.S. Patent No. 4094058 licensing to the people such as Yasutake describes applicable method, adds full content disclosed in this patent as a reference at this.By using these technology, primary seal material can be applied to determine the shape of substrate on independent otch (cut), or it can be applied on larger substrate as multiple primary seal shape.Then the larger substrate with multiple primary seals of applying can be laminated on another larger substrate, and, can make at least in part primary seal material curing after cut out each mirror shapes from lamination.This repeatedly treatment technology for LCD manufacture be conventional method and sometimes referred to as array processes.Make according to photoelectric device of the present invention by using similar technique.Such as all coatings of transparent conductor, reverberator, spectrum pass filter, and when solid state optoelectronic devices, photonic layer or multiple photonic layer can be applied on larger substrate, and are patterned where necessary.Patterning can be carried out by using many technology to coating, such as applying coating, by optionally applying the soluble layer that is patterned and apply, remove after laser ablation or etching the coating at it and it top in coating below coating by mask.These patterns can comprise for accurately aiming in whole manufacture process or the alignment mark of position substrate or target.Usually such as with using the vision system of pattern recognition techniques to complete this point in an optical manner.Also directly alignment mark or target are applied on glass by such as sandblasting, laser or adamas line if desired.Blank medium for controlling the interval between stacked substrate can be placed in primary seal material, or is applied on substrate before stacked.Blank medium or means can be applied in the lamination area that cuts from the single mirror assembly completed.If device is solution phase photoelectricity mirror element, so can to clog stacked array cutting forming before or after fill port at filling photoelectric material.

Forward now Fig. 6 a and Fig. 6 b to, these illustrate inside rear view mirror assembly 610a, 610b of observing on first substrate 622a, 622b, wherein, make spectral filter material 645a or instrument bezel (bezel) 645b between observer and primary seal material (not shown).Mirror element is illustrated as being positioned at movable housing 675a, 675b, and optionally combines with the static housing 677a on mounting structure 681a (w/ static housing) or 681b (w/o static housing).First indicator 686a, the second indicator 687a, operator interface 691a, 691b and the first optical sensor 696a are positioned at the Jaw part of movable housing.First information display 688a, 688b, the second information display 689a and the second optical sensor 697a are added in assembly, and they are positioned at after element relative to observer.As illustrated about outside rearview mirror assemblies, device 688a, 688b, 689a and 697a is preferably made to be hidden at least in part as described in detail here.In at least one embodiment, inside rear view mirror assembly can comprise on printed circuit board (PCB) 665b at least one or more light fixture 670b, at least one microphone, they recombinant, they combination or combine with other of above-mentioned device.Should be appreciated that and in photoelectricity window or mirror, each aspect of the present invention can be added with multiple combination individually or collectively.

Fig. 6 c illustrates the planimetric map comprising the second substrate 612c of the lamination of material the 3rd, the 4th or third and fourth on the surface.In at least one embodiment, below primary seal material, the substantially opaque layer of the 620c1 at least partially of the lamination of material or at least lamination of material is removed or covers.The 620c2 at least partially of at least one layer of the lamination of material substantially extends to the outer rim of substrate or extends to the region of the electrical connection be conducive between the 3rd surface stack and element driving circuit (not shown in Fig. 6 c).Relevant embodiment provides sealing and/or padding to observe below and/or the inspection of padding solidification from mirror or window element after element assembling.In at least one embodiment, the lamination of material 620c outer rim 620c1 at least partially between the outer rim 678c1 and inner edge 678c2 of primary seal material 678c.In at least one embodiment, below wide at about 2 ~ 8mm, that preferably about 5mm is wide primary seal material, at least substantially opaque layer of a part of 620c1 of the lamination of material or the lamination of material is removed or covers.The 620c2 at least partially of at least one layer of the lamination of material substantially extends to the outer rim of substrate or extends to wide, that preferably about 1mm the is wide region being conducive to the electrical connection between the 3rd surface stack and element driving circuit (not shown) of about 0.5 ~ 5mm.Any one that should be appreciated that in the first, second, third and fourth superficial layer of material or lamination can disclosed in the document that adds as a reference in other place here or here.

Fig. 6 d illustrates the planimetric map of the second substrate 612d of the 3rd surface stack comprising material.In at least one embodiment, the 3rd surface stack of material 620d outer rim 620d1 at least partially between the outer rim 678d1 and inner edge 678d2 of primary seal material 678d.In the embodiment that at least one is relevant, conductive contact sheet part 682d extends from the outer rim of the second substrate inside the outer rim 678d1 of primary seal material 678d.In the embodiment that at least one is relevant, conductive contact sheet part 682d1 below primary seal material 678d with the crossover at least partially of the 3rd surface stack of material.In at least one embodiment, outside the conductive layer (not illustrating separately) of the substantial transparent of the such as conducting metal oxide of the 3rd surface stack of the material outer rim 620d1 extending to the remainder of the 3rd surface stack like that as shown in Figure 8 b to provide the external electrical connections with the 3rd surface.Should be appreciated that can as shown in Fig. 9 c ~ 9i along any one the deposit conductive contact sheet (conductive tab) in its periphery region.In at least one embodiment, conductive contact sheet part comprises chromium.Should be appreciated that compared with conductive electrode, conductive contact sheet part improves conductance; As long as conductive electrode layer has enough conductances, so conductive contact sheet part is optional.In at least one embodiment, conductive electrode layer also gives the color particular characteristics of the hope of corresponding reflection ray except the conductance providing hope.Therefore, when omitting conductive electrode, by subsurface material Authority Contro1 color characteristics.Any one that should be appreciated that in the first, second, third and fourth superficial layer of material or lamination can disclosed in the document that adds as a reference in other place here or here.

Fig. 7 illustrates that enlarged drawing as the element shown in Fig. 5 e is to provide the rearview mirror elements 700 of more details.Element 700 comprises first substrate 702 with first surface 704 and second surface 706.By the first separated region 740, being applied to the first conductive electrode portion 708 on second surface 706 and the second conductive electrode portion 730 is electrically insulated from one another substantially.Can find out, in at least one embodiment, separated region is positioned as making spectral filter material 796 and corresponding Tackifier materials 793 also be electrical isolation substantially, to limit the first and second spectral filter material parts 724,736 respectively and to limit the first and second Tackifier materials parts 727,739 respectively.The part that a part of first separated region 740,540c, 540d, 540e is shown in the primary seal material 778 being positioned at its immediate vicinity extends in parallel.Should be appreciated that this part of separated region 740 is deployable, make observer can not perceive line in spectral filter material easily; Such as, a part for separated region can be aimed at the inside edge 797 of spectral filter material 596 substantially.Should be appreciated that when any part of separated region 740 is positioned at the inner side of primary seal material, as described in detail elsewhere, the uncontinuity that photoelectric material is painted and/or clean can be observed here.This operating characteristic can by the element handling to obtain subjective attractive appearance.

With further reference to Fig. 7, element 700 is shown to include second substrate 712 with the 3rd surface 715 and the 4th surface 714.It should be noted that the first substrate can be larger than the second substrate, offset with the generation at least partially of the circumference along mirror.Third and fourth conductive electrode portion 718,787 is illustrated as the 3rd surface 715 close to being electrically insulated basically by the second separated region 786 respectively.The part that a part of second separated region 786,586c, 586d, 586e is shown in the primary seal material 778 being positioned at its immediate vicinity extends in parallel.Should be appreciated that this part of separated region 786 is deployable, make observer can not perceive line in spectral filter material easily; Such as, a part for separated region can be aimed at the inside edge 797 of spectral filter material 796 substantially.Fig. 7 also illustrates, can apply reflecting material 720 between optional top layer material 722 and the 3rd conductive electrode portion 718.Be to be understood that, commonly assigned United States Patent (USP)/application 6111684 can be used in, 6166848, 6356376, 6441943, 10/115860, 5825527, 6111683, 6193378, 09/602919, 10/260741, any one in these materials disclosed in 60/873474 and 10/430885, to limit the integral surface coating of the hydrophilic coating on such as first surface or to be such as applied to first, second, conductive electrode material on third and fourth surface, spectral filter material, Tackifier materials, reflecting material, the composite laminate of the coating of top layer material, disclosing as a reference of these patents is added at this.Should also be understood that the hydrophobic coating of such as fluorinated alkyl salt or polymkeric substance, the coating of (silicone) that comprises silicones or the surface of specific texture can be applied on first surface.Any one in water wettability or hydrophobic coating will change moisture relative to the glass not having this coating and clash into the contact angle of first surface, and will increase eyesight afterwards when in the presence of moisture.Should be appreciated that the 3rd surface and the 4th surface reflector embodiment all within the scope of the invention.In at least one embodiment, the material be applied on the 3rd surface and/or the 4th surface is configured to the characteristic of the sub reflector/fractional transmission of providing unit at least partially into corresponding surface stack.In at least one embodiment, the material be applied on the 3rd surface is integrated, to provide combined reflector/conductive electrode.Should be appreciated that additional " the 3rd surface " material can extend in the outside of primary seal, in this case, should be appreciated that the material that corresponding separated region runs through additional.Make the surperficial from the 4th at least partially of primary seal, such as fig. 6 c, be conducive to inspection and the UV solidification of choke material.In at least one embodiment, below primary seal material, substantially the opaque layer of at least partially or at least lamination of material of the lamination of material 620c is removed or covers, with provide at least one portion for circumference at least 25% the inspection of primary seal width.The inspection of the primary seal width of 50% of at least one portion provided for circumference is provided.The inspection of the primary seal width of at least 75% of at least one portion for circumference is most preferably provided.Various embodiments of the present invention will comprise the multiple parts with the particular surface of the lamination of coating or coating different from other parts; Such as, light source, information display, optical sensor or their combination " window " above can be formed, with optionally transmission specific wavelength of light band or the wavelength of light band that illustrates in adding as a reference here many documents.

With further reference to Fig. 6 a ~ 6b and Fig. 7, the first separated region 740 cooperates to limit the second conductive electrode portion 730, second spectral filter material part 736 and the second Tackifier materials part 739 substantially with the first conductive electrode portion 708, first spectral filter material part 724 and the first Tackifier materials part 727 electrical isolation with a part for primary seal material 775.This configuration allows to place conductive material 748, and the first electrical terminal 763 is electrically connected with the 3rd conductive electrode portion 718, reflecting material 720, optional external coating 722 and photoelectric medium 710.Obviously, be particularly applied to by conductive material 748 in the embodiment on element before placement first electrical terminal 769,757,766,772,775 points, interface can be opened by conductive material at least in part.Preferably, form the 3rd conductive electrode portion 718, first electrical terminal (electrical clip) 763 and the material of conductive material 748 or the composition of material to be selected as promoting the lasting electrical connection between clip and the material causing photoelectric medium.Second separated region 786 cooperates with a part for primary seal material 775, with limit substantially with the 4th conductive electrode portion 787 of the 3rd conductive electrode portion 718, reflection horizon 720, optional top layer material 722 and photoelectric medium 710 electrical isolation.This configuration allows to place conductive material 790, and the second electrical terminal 784 is electrically connected with the first Tackifier materials part 727, first spectral filter material part 724, first conductive electrode portion 708 and photoelectric medium 710.Obviously, be particularly applied to by conductive material 790 in the embodiment on element before placement first electrical terminal 784,785,788,789 points, interface can be opened by conductive material at least in part.Preferably, form the first conductive electrode portion 708, first electrical terminal 784, Tackifier materials 793, spectral filter material 796 and the material of conductive material 790 or the composition of material to be selected as promoting the lasting electrical connection between clip and the material causing photoelectric medium.

Sometimes wish on reflection horizon 720, arrange one or more optional flash of light external coating 722, make its (not being reflection horizon 720) and electrochromism (electrochromic) medium contact.This flash of light external coating 722 must have stable behavior as electrode, and it must have longer shelf life (shelf life), and it must engage with reflection horizon 720 well, and maintains this joint when containment member 778 engages.If the optical property from layer is below visible, so overlayer is sufficiently thin, makes it not exclusively stop the reflectivity of each layer below 720.According to another embodiment of the present invention; due to flash layer protection reflection horizon, still allow high reflection layer 720 to contribute to the reflection of mirror, therefore simultaneously; when very thin flash of light external coating 722 is placed on the layer of high reflection, reflection horizon 720 can be silver metal or silver alloy.In this case, thin (such as, be less than about 300 dusts, be more preferably less than about 100 dusts) layer of deposit rhodium, ruthenium, palladium, platinum, nickel, tungsten, molybdenum or their alloy on reflection horizon 720.The thickness dependence of flash layer is in selected material.Such as, muddiness in viewing area when hot test stands for the formation of the point defect in processing procedure and element, be coated with few chromium to the flash layer of the ruthenium of 10 dusts under ruthenium, ruthenium under rhodium, the element that builds of three surface coating of rhodium under silver all shows the resistibility of improvement.The initial reflectance with the element of ruthenium flash layer is 70 ~ 72%.When reflection horizon 720 is silver, flash layer 722 also can be the zinc paste of silver alloy or adulterated al.Flash layer or thicker overlayer also can be the transparent conductors of such as transparent metal oxide.Overlayer can be selected as just such as barrier performance especially, the factor of balance etc. and so on of favourable interferometric optical and compression or drawing stress matches (compliment) with other layer.Should be appreciated that and can use above-mentioned flash layer in other embodiment in this paper other places.

When this overlayer by the metal of above-mentioned list or find other the metal/alloy/semimetal compatible with electrochromic system make time, when metal or semimetal layer thicker than 300 dusts time, these overlayers are tending towards allowing each layer below it to have very little optical effect.If think the outward appearance of more wishing metal cladding, so use this thicker overlayer can be favourable.Some explanations of these laminations are provided in the commonly assigned European patent EP 0728618A2 " Dimmable Rearview Mirror for Motor Vehicles " of Bauer etc., add this patent here as a reference.When using the transparency conducting layer of this thicker overlayer and the tin oxide of such as doped indium, the zinc paste of adulterated al or the indium zinc oxide that can combinationally use with cementing layer and flash layer, the conductance benefit with the layer below such as silver, silver alloy, copper, aldary, aluminum or aluminum alloy still can exist.Such as the layer being generally regarded as insulator of titania, silicon dioxide or zinc sulphide etc. also can be used in this overlayer lamination or interlayer, and, as long as their thickness make they still from the layer of highly conductive more through enough electric currents, do not negate just the benefit of the layer of highly conductive more.

Known in electrochromic field, when applying electromotive force to element, mirror or window may be dimmed unevenly.The uneven dimmed local difference being derived from electromotive force along the solid-state EC material flow in EC element or gel.Stride across unit interval between the surface resistance of electromotive force with electrode of element, bus bar configuration, the conductance of EC medium, the concentration of EC medium, electrode or spacing and to bus distance and change.The scheme that this problem is often proposed be make to form the coating of electrode or layer thicker, reduce their surface resistance thus and make element can be more promptly dimmed.As discussed below like that, the unfavorable result of reality that the method that there is this oversimplification of restriction given is dealt with problems.In many cases, unfavorable result makes EC element be unsuitable for given application.In at least one embodiment of the present invention, illustrate solve with the simple thickening produced problem of electrode layer and cause EC element have faster evenly the electrode material of improvement of variable-dark property, the method manufacturing described electrode and bus bar configuration.

In typical internal mirror, bus and length dimension are advanced abreast.This to make the potential drop of the part striden across between electrode minimize.Mirror also generally comprises high surface resistance transparency electrode and low surface resistance reflector electrode.Mirror dimmed is the rapidest near the bus of high surface resistance electrode, and the slowest on some centre positions between two electrodes.Near the bus of low surface resistance electrode, will there is the darkening rate between these two values.When moving between two buses, there is the change of effective electromotive force.When two longer parallel buses have relatively short distance betwixt (distance between bus is less than the half of the length of bus), mirror will be dimmed in the mode of " window-blind (window shade) ".This means that mirror is more promptly dimmed near a bus, and move between two buses dimmed seeming in mode gradually.Usually, measure darkening rate in the middle of part, and when mirror has the ratio of width to height being greater than 2, any unevenness of darkening rate is relatively very little.

Along with the increase of the distance between the increase of the size of mirror and thing followed bus, the relative different striding across the darkening rate of each several part also increases.When designing mirror for applications, may worsen like this.The metal that can tolerate this severe rugged environment generally has than being suitable for and being usually used in the low conductance of the metal of such as silver or the silver alloy in internal mirror application.Therefore the metal electrode of applications can have the surface resistance reaching 6ohm/sq, and internal mirror can have the surface resistance of < 0.5ohm/sq.In other outside mirror application, for various optical requirement, the thickness of transparency electrode may be limited.In modal use, the transparency electrode of such as ITO is often limited to 1/2 wavelength thick (wave thickness).This restriction is the performance due to ITO discussed here, and due to the expense relevant with making thicker ITO coating.In other application, coating be limited to 1/2 wavelength thick 80%.These two thickness limits the surface resistance of transparency electrode is limited to the about 12ohm/sq that is greater than for 1/2 wavelength and be less than for as 1/2 wavelength coating 80% 17 ~ 18ohm/sq of coating.The higher surface resistance of metal and transparency electrode causes more slowly, more uneven dimmed mirror.

Darkening rate can be estimated from the analysis of EC element according to circuit.Following discussion has the coating of uniform plate electrode about striding across element.Electromotive force on any position between parallel pole is the function of the surface resistance of each electrode and the resistance of EC medium.In following table 1, provide the average potential of the element striden across between electrode together with the difference between minimum and maximum electromotive force.This example is used for the element having 10cm interval between parallel bus, have 180 micro unit intervals, have 1.2 volts of driving voltages and 100000Ohm*cm fluid resistivity.Six kinds of combinations of top and bottom electrode surface resistance are compared.

Table 1

Dimmed speed with the electrical contact of highest face temperature resistance electrode on the highest, and relevant with the effective electromotive force on this position.The effective electromotive force of this electrical contact contiguous (or elsewhere) is higher, and the average dimmed of mirror will be faster.When the electromotive force striding across part is high as much as possible, the fastest total dimmed time will be there is.This drives galvanochemistry dimmed by with the speed accelerated.The plate electrode of the coating in top and base substrate is being determined to work in the effective electromotive force between electrode, but as can be seen from the table, high surface resistance electrode plays a part more crucial.In existing electrochemical techniques, the surface resistance almost exclusively by reducing low resistance electrode drives to be improved.This is because the such as use of material of silver provides the benefit of essence and to implement be relatively easy.

In the art, as everyone knows, along with the increase driving electromotive force, general speed can increase, but trend and driving circuit have nothing to do, and will be constant.Current draw (current draw) also under known given voltage affects dimmed homogeneity.Can improve homogeneity by the selection of adjustment unit interval, concentration or EC material, but the improvement of the homogeneity using these to adjust usually has negative impact to dimmed speed, cleaning speed or dimmed and cleaning speed.Such as, increase unit interval and reduce fluid concentrations and reduction Current draw also will be improved homogeneity thus, but cleaning time will increase.Therefore, the surface resistance of layer must suitably be set to obtain dimmed speed and dimmed homogeneity simultaneously.Preferably, the surface resistance of transparency electrode should be less than 11.5ohm/sq, preferably be less than 10.5ohm/sq and be most preferably less than 9.5ohm/sq, and, due to optical requirement discussed below, therefore, in certain embodiments, the thickness of transparency electrode should be less than about half wave optical thickness.Reflector electrode should be less than about 3ohm/sq, preferably be less than about 2ohm/sq be most preferably less than 1ohm/sq.The mirror of such structure or EC element are also relatively uniform dimmed by having, and make the dimmed mistiming the soonest and between the slowest darkening rate be less than the factor 3, be preferably less than the factor 2, be most preferably less than the factor 1.5.The material that can realize the novelty of these quick, even dimmed elements, high-performance, low cost is below discussed.

In other application, it may be unpractiaca for having two opposing parallel buses.This may be because the uneven shape common with outside mirror.When other, may wish that there is the point cantact with low resistance electrode.Point cantact can make it possible to minimize or eliminate the laser strikethrough used in some applications.The use of point cantact simplifies some aspects of mirror structure or is preferred for these aspects, but it makes to be difficult to realize striding across relatively uniform electromotive force partly.The resistance that relatively long bus increases electrode is effectively eliminated along low resistance reflector electrode.Therefore, need the combination of the novelty of bus and coating surface resistance value dimmed rapidly and uniformly to obtain.

As mentioned above, those skilled in the art can expect can need extremely low sheet resistance value to realize point cantact scheme on solid metal reflector electrode.Unexpectedly, find that transparency electrode must have lower surface resistance to improve homogeneity.Table 2 represents the result of homogeneity test.In this experiment, we make the solution phase EC element that about 8 inches wide are multiplied by 6 inches high.The benefit of element design discussed here relates generally to larger element.The larger element minor increment be defined as from the edge of the arbitrfary point the edge of viewing area to geometric center is greater than the element of about 5cm.When this distance is greater than about 7.5cm, lacks dimmed the becoming of homogeneity and be more added with problem, and, when this distance is greater than about 10cm, becomes and be more added with problem.As shown in table 2, the surface resistance change of transparency electrode (ITO) and solid metal reflector.The contact with metal electrode is made with point cantact.Use clip contact (clip contact) of such as so-called J clip to provide the electrical contact with solid metal reflector along in the short length sides of mirror by the Ag paste line of about 1 inch long./ 3rd of a downward distance is continued on two long limits along a limit relative with point cantact and along mirror, makes the electrical contact with transparency electrode by Ag paste.The dimmed time (T5515) is measured in three positions of mirror.The contact of position 1 points of proximity, relative with point cantact on the edge that position 2 is in transparency electrode bus, position 3 is in the center of mirror.The T5515 time (unit is second), to be mirror became from 55% reflectivity the time that 15% reflectivity spends.Maximum reflectivity is the maximum reflectivity of mirror.Δ T5515 is the mistiming between point 1 and point 2 or between point 2 and point 3.This is measuring of the fastest position on mirror and the darkening rate difference between other two positions.Become along with dimmed evenly, these numerical value become closer to.Chronon is the result of the dimmed time on given position divided by the time on the fastest position.It and the absolute speed on any given position independently show the relative conversion of the time between diverse location.As mentioned above, preferably have be less than 3, be preferably less than 2 and be most preferably less than 1.5 chronon.As can be seen from Table 2, for this specific mirror configuration, when ITO surface resistance is 14ohm/sq, we there is no chronon 3.All three examples that ITO has 9 ohms per squares have the chronon being less than 3.The center of mirror reading is the position of departing from the fastest position most.The statistical study carried out for these data is made us unexpectedly disclosing, and ITO surface resistance is to the contributive unique factor of chronon.By Using statistics model, for the present embodiment, need the ITO surface resistance being less than about 11.5ohm/sq with the chronon with 3.0 or less.By using identical statistical model, this mirror being configured, chronon be made to be less than 2.0, ITO and must have the surface resistance being less than 7ohm/sq.Even if chronon does not affect, total darkening rate is also influenced by the surface resistance of the 3rd surface reflector.When the surface resistance of described reverberator be less than or equal to 2ohm/sq and ITO for about 9ohm/sq time, in the darkening rate of this mirror be in the heart less than 8 seconds.This value is generally corresponding with the mirror of the similar size with conventional bus configuration.Therefore, by reducing the surface resistance of ITO, point cantact is realized with relatively high surface resistance reverberator.

Table 2

The unexpected effect of surface resistance in dimmed homogeneity and speed of ITO is described in detail in detail in another group experiment.In these experiments, the length that contacts with the bus of high surfaces resistance electrode in the present example for ITO even extends on the base of mirror to downward-extension further in some cases along the limit of mirror.Table 3 shows the impact of change for homogeneity of bus length.In these trials, except indicating, component shape and to configure with table 2 identical.Contact number percent is that the bus length of ITO contact compares with the number percent of the overall length of circumference.Bus is than being the length contacted relative to the ITO of the little reverberator contact of about 2cm or less.

The bus length that data from table 3 describe increases more high surface resistance electrode can improve homogeneity greatly.For 2ohm/sq reverberator, chronon can be brought up to 1.7 from 2.4 from 40% to 85% length increasing bus contact.For 0.5ohm/sq reverberator, ITO bus length from 40% to 85% same change chronon is brought up to 1.2 from 3.2, and greatly improve darkening rate.It should be noted that the element with lower surface resistance reverberator is generally dimmed than the situation of comparable 2ohm/sq soon, but as shown in chronon, the homogeneity with the situation of the 0.5ohm of shorter ITO contact is in fact poor.It is helpful especially for increasing bus length for the element with 0.5ohm/sq reverberator for ITO.

When contacting number percent and increasing, the fastest and position the most dimmed also can change.In the present example, higher contact number percent improves dimmed time on position 1 and position 3 and corresponding chronon greatly.

Table 3

These experiments show, when using short bus together with low surface resistance electrode, the bus length being increased to comparative electrode is useful to improve homogeneity.Therefore, in the ideal case, for large mirror, the ratio of the length of our preferred bus is greater than 5: 1, be more preferably greater than 9: 1, more preferably greater than 13: 1, be most preferably greater than 20: 1, to obtain the chronon lower than 3.We also find, have nothing to do with the length of less bus, by the length that is increased to the bus of high surfaces resistance electrode with obtain be preferably greater than about 58% and more preferably greater than about 85% contact number percent, homogeneity improves.Typically large EC mirror has the contact number percent being less than 50%.

These discoveries are not only very crucial for the mirror with opaque reverberator, and are also more crucial for the mirror using half-transmitting and half-reflecting sexual reflex device.In order to have the coating of half-transmitting and half-reflecting, metal must be thinned to brocken spectrum.Therefore, thinner metal has higher sheet resistance value.In at least one embodiment of the present invention, photovalve comprise with have the optional point cantact bus bar configuration of instructing here conventional bus bar configuration fast, dimmed equably.The coating being particularly suitable for the half-transmitting and half-reflecting of the novelty of supplementary bus bar configuration described above is below described.

In order to make electrochromism mirror can on its whole region evenly dimmed or first from its center (occurring most headlight high light here) then the outside top towards viewing area and bottom dimmed, also below the lamination of opaque overlayer or opaque layer, patterning can be carried out to conductance.The U.S. Patent application 20040032638A1 " Electrochromic devices with thin bezel-covered edge " adding the people such as Tonar as a reference at this mentions " low surface resistance coating can be arranged in the region around close to relevant electrical contact or perimeter region; and allow surface resistance to increase along with the increase of the distance to electrical contact ", and state " when utilizing point cantact, this is particularly suitable ".When electric driven color-changing part is not applied to the voltage above it, generally can wish to provide in reverberator without any or the contrast in units of ohm of very little visible contrast.

In order to electrochromic device more and obtain enough contrasts between the region of less highly conductive to make some region can be preferentially dimmed, must may comprise nonmetallic material in stacked.This is because opaque layer or the lamination of the metal that reflectivity is stronger and alloy are tending towards enough conductions, with when or not below them supplement more highly conductive pattern in automobile EC mirror, provide acceptable variable-dark property.The example comprising semimetallic this material laminate is the material laminate built similarly with the material laminate illustrated in the United States Patent (USP) 5535056 " Method for making elemental semiconductor mirror for vehicles " added at this as a reference, wherein, opaque silicon layer can be covered, be covered by the silicon of 20 ~ 25nm again, be covered by the tin indium oxide of about 20nm by the tin indium oxide of about quarter-wave optical thickness.This opaque coating stack can have the pattern be positioned at below it has minimum influence adding material to the outward appearance before it.This lamination can also be enough conduct electricity everywhere, not lose the advantage of this patterning.In addition, if find when with the thickness of about 1400 dusts under the condition usually producing about 12ohm/sq during deposit ITO still there is too strong electric conductivity, so reduced than making the electric conductivity of this ITO by change indium tin by adjusting process conditioned disjunction.

Make the element built according to the principle that illustrates in US20040032638A1 of the geometry with Fig. 5 f and Fig. 7 with the 3rd different surface coating laminations and conductive pattern, the point cantact that this element is made along the centre of top, lower limb and left hand edge and edge roughly on the right has conductive epoxy.When mentioning whole 3rd surface, refer to the surface before any laser action, this laser action is for generation of the insulating regions needed for the structure of commonly assigned U.S. Patent application 20040022638A1.

The element making to have 1/2ohm/sq the 3rd surface reflector on whole viewing area with have in the band striding across 1/2 inch of center of the element covered by opaque layer or 1 inch or 2 inches 1/2ohm/sq those compared with, make the conductance that there is 4ohm/sq in the remainder of viewing area, and in bright state, there is the quite uniform outward appearance of element.When making element appearing dark, the center of element with have conductance contrast district edge compared with dimmed trend of delaying reduce a little.

In order to have higher levels of conductance contrast, make the structure of element similar with those in figure above, but, the 3rd on the surface, the ITO being respectively about 12ohm/sq and 40ohm/sq has the conductive strips of the silver of 2 inches of the center placement striding across single-piece, and then this conductive strips is coated with the flash layer (for the treatment of permanance) of transparent conductive oxide.Being made into completely after electrochromic device, element is placed on a silver-plated sheet glass, making, when evaluating variable-dark property, intensity and the similar reverberator of silver bar band can be there is after the region with the ITO of 12ohm/sq and 40ohm/sq of relative transparent.Can find out, when observing under these conditions, with there is 12ohm/sq to compared with the element of 1/2ohm/sq contrast district, the 3rd, there is the 40ohm/sq device to 1/2ohm/sq contrast district on the surface and there is less rainbow effect (iris effect) when dimmed.

Except using except the coating of interpolation on the surface the 3rd, make element according to last paragraph.These coatings comprise: the ITO of the flash layer of the conductive oxide of interpolation (be placed on when there is broken in coating process for the vacuum contained in pack processing carry out bonding), the ITO of the silicon of about 30nm, about 60nm, the silicon of another 20nm and 10nm.Silicon layer may be easy to surface oxidation, and this surface oxidation can form oxide on surface in some EC element, this oxide on surface homogeneity that then overslaugh is dimmed and consistance.The ITO or other TCO or other material that illustrate as flash layer or outer covering layer can be used here to forbid formation or the negative effect of described oxide.When being measured by four-point probe, those elements started with the initiation layer of 40ohm/sq (example according to above) have the 3rd surface conductivity obtained, and this conductance is about 24ohm/squre and is < 1ohm/squre in central area in top and bottom section (according to Fig. 5 f and Fig. 7).In top and bottom section, there is 10 ~ 12ohm/squre with the element that the initial ITO layer of 12ohm/sq starts.According to example above, the element with higher ohm contrast have minimum rainbow effect or maximum center to edge dimmed trend.When using D652 degree observer, these elements also have following optical characteristics under not powering state.

L ^＊a ^＊b ^＊Y

Higher ohm contrast (50ohm basic unit) 76-5 4 50

Lower ohm contrast (12ohm basic unit) 75-3 5 51

Also by the thinner strikethrough (deletion line) in second surface electrically conducting transparent (lamination) or the 3rd surface reflection (lamination) and by the thickness classification to coating as illustrated in other places here, some region of acquisition electrochromic device preferentially dimmed.When using laser to delete as an example, usually, along with the operative wavelength reducing laser, thinner laser rays can be produced.The UV laser being 355nm by use wavelength has made the strikethrough of 15 microns wide.These lines are still recognizable, but distinguish than by use the laser of longer wavelength to make those are much more difficult.More easily obtain along with the more laser of short wavelength continues to become, quite can expect that strikethrough not offensive in appearance in viewing area under the normal condition of motor vehicle mirror will be possible.

When the deletion then making according to existing technique construction element that there is the coating stack on the 3rd surface by becoming element on the multiple line of center instruction striding across Fig. 5 f with Fig. 7 or multiple parts of multiple line exists relatively little contact on an edge of this part and the conductive epoxy resin that uses on other three limits of element, variable-dark property is affected ...

It is as follows that the deletion pattern obtained by laser made by two lines that 1/2ohm/sq reflector electrode represents for the element internal shown in Fig. 5 f and Fig. 7:

1) in the fine rule of position extending to the edge 15cm apart from glass from the edge of glass, there is the deletion completely of coating.

2) the whole width striding across this part 8mm delete and the non-ablation of 2mm repeat patterns fine rule in there is the deletion completely of coating.

3) in the fine rule of position extending to distance edge 14cm from the edge of glass, there is the deletion completely of coating, be then across the deletion of the non-ablation of 5mm of the remainder of this part and the repeat patterns of 5mm deletion.

4) except 2 non-ablation sections of the 0.4mm on about 5cm and 10cm along the line, in the fine rule of position extending to distance edge 15cm from the edge of glass, there is the deletion completely of coating.

When compared with the similar portions without any strikethrough, these elements show some and even substantially little " rainbow effect " when dimmed.In the pattern with strikethrough, the overall appearance of pattern 4 is best and also dimmed.Although all these patterns can need adjustment to obtain acceptable dimmed outward appearance, show the movement of the variable-dark property towards hope.

With reference to Fig. 8 a, the cut-open view of a part for rearview mirror elements is shown, this rearview mirror elements comprises and is fixed to be formed betwixt the first substrate 802a with at least one layer of 808a of the conductive material of the substantial transparent be deposited on second surface of chamber by primary seal material 878a with separated relation and has the second substrate 812a of lamination of the material be deposited on the 3rd surface.In at least one embodiment, photoelectric medium 810a is positioned at described chamber.In at least one embodiment, the 3rd surface stack of material comprises lower floor 818a, conductive electrode layer 820a, metal level 822a and below metal level and primary seal material, has the conductive contact sheet part 882a of overlapped portion 883a.It should be noted that conductive contact sheet part 882a is alternatively deposited on metallic coating 822a to produce overlapped portion.In at least one embodiment, lower floor is titania.In at least one embodiment, lower floor is not used.In at least one embodiment, conductive electrode layer is indium tin oxide.In at least one embodiment, conductive electrode layer is omitted.In at least one embodiment, the thicker layer with the material of some other the substantial transparent of relatively high refractive index (that is, refractive index ratio ITO is high) that conductive electrode layer and lower floor are titania or such as silit is omitted.In at least one embodiment, conductive contact sheet part comprises chromium.Should be appreciated that conductive contact sheet part can comprise to be adhered to well on glass and/or other lamination or epoxy resin according to level sequence and to resist any conductive material of the erosion under automobile-used mirror test condition.Be appreciated that element avoids the problem relevant with the 3rd surface erosion substantially when those layers at least erodible in the 3rd surface stack or lamination of material remain in the region limited by the outer rim of primary seal material.If should be appreciated that the protectiveness external coating or sealant that add such as conductive epoxy resin or external coating, so erodible layer or multiple layer may extend into outside primary seal material.Any one that should be appreciated that in the first, second, third and fourth superficial layer of material or lamination can disclosed in the document that adds as a reference in other place here or here.Should be appreciated that compared with conductive electrode, conductive contact sheet part improves conductance; As long as conductive electrode layer has enough conductances, so conductive contact sheet part is optional.In at least one embodiment, conductive electrode layer also gives the color particular characteristics of the hope of corresponding reflection ray except the conductance providing hope.Therefore, when omitting conductive electrode, by subsurface material Authority Contro1 color characteristics.

Forward Fig. 8 b to, the cut-open view of a part for rearview mirror elements is shown, this rearview mirror elements comprises and is fixed to be formed betwixt the first substrate 802b with at least one layer of 808b of the conductive material of the substantial transparent be deposited on second surface of chamber by primary seal material 878b with separated relation and has the second substrate 812b of lamination of the material be deposited on the 3rd surface.In at least one embodiment, photoelectric medium 810b is positioned at described chamber.In at least one embodiment, the 3rd surface stack of material comprises the conductive contact sheet part below lower floor 818b, conductive electrode layer 820b, metal level 822b and primary seal material.In at least one embodiment, between metal level and conductive contact sheet part, limit cavity area 883c, conductive electrode provides electric continuity betwixt.In at least one embodiment, lower floor is titania.In at least one embodiment, lower floor is not used.In at least one embodiment, conductive electrode layer is indium tin oxide.In at least one embodiment, conductive contact sheet part comprises chromium.Should be appreciated that conductive contact sheet part can comprise to be adhered to well on glass and/or other lamination or epoxy resin according to level sequence and to resist any conductive material of the erosion under automobile-used mirror test condition.Be appreciated that element avoids the problem relevant with the 3rd surface erosion substantially when those layers at least erodible in the 3rd surface stack or lamination of material remain in the region limited by the outer rim of primary seal material.Any one that should be appreciated that in the first, second, third and fourth superficial layer of material or lamination can disclosed in the document that adds as a reference in other place here or here.

Forward Fig. 8 c to, the cut-open view of a part for rearview mirror elements is shown, this rearview mirror elements comprises and is fixed to be formed betwixt the first substrate 802c with at least one layer of 808c of the conductive material of the substantial transparent be deposited on second surface of chamber by primary seal material 878c with separated relation and has the second substrate 812c of lamination of the material be deposited on the 3rd surface.In at least one embodiment, photoelectric medium 810c is positioned at described chamber.In at least one embodiment, substantially at the whole 3rd deposit the first metal layer 818c on the surface.In at least one embodiment, on the first metal layer, deposit second metal level 820c, makes the outer rim of the second metal level be positioned at the region limited by the outer rim of primary seal material 878c.In at least one embodiment, the first metal layer comprises chromium.In at least one embodiment, the second metal level comprises silver or silver alloy.Any one that should be appreciated that in the first, second, third and fourth superficial layer of material or lamination can disclosed in the document that adds as a reference in other place here or here.

Forward Fig. 8 d to, the second substrate 812d of the lamination of the material with aperture (eyehole) 822d1 be substantially in before optical sensor or information display is shown.In at least one embodiment, the first metal layer 818d has cavity area in orifice region.In at least one embodiment, the second metal level 820d has cavity area in orifice region.In at least one embodiment, the 3rd metal level 822d is set.In at least one embodiment, a deposit the 3rd metal level in orifice region.In at least one embodiment, the first metal layer comprises chromium.In at least one embodiment, the second metal level comprises silver or silver alloy.In at least one embodiment, the 3rd metal level comprises thin silver, chromium or silver alloy.Any one that should be appreciated that in the first, second, third and fourth superficial layer of material or lamination can disclosed in the document that adds as a reference in other place here or here.

Forwarding Fig. 9 a ~ 9k to, illustrating for optionally contacting second and the 3rd various option of specific part of surface conductive electrode part 922,908.Be appreciated that the configuration of Fig. 7 cause in conductive material contacts second and the 3rd surface conductive electrode part each at least partially.Should be appreciated that shown contact configuration can rotate relative to element in any manner.

Element shown in Fig. 9 a constructs the second substrate 912a of the first substrate 902a comprising the second surface lamination with material 908a and the 3rd surface stack with material 922a.3rd surface stack of material is shown to have area of isolation 983a, and the remainder of the part contacted with conductive epoxy resin 948a of the 3rd surface stack of material and the 3rd surface stack of material is separated.First and second substrates are kept with relation spaced apart from each other by primary seal material 978a.Should be appreciated that the opposite side of element can have for providing the similar area of isolation relevant with the second surface lamination of material to the contact of the 3rd surface stack of material in viewing area.Should be appreciated that second or the 3rd of material any one in surface stack can be the monolayer material illustrated in other local and document of adding as a reference here here.

Element shown in Fig. 9 b constructs the second substrate 912b of the first substrate 902b comprising the second surface lamination with material 908b and the 3rd surface stack with material 922b.First and second substrates are kept with relation spaced apart from each other by primary seal material 978b.Conductive epoxy resin 948b contacts with the 3rd surface stack of material and passes through the second surface lamination electrical isolation of insulating material 983b and material.Should be appreciated that the opposite side of element can have for providing the similar area of isolation relevant with the second surface lamination of material to the contact of the 3rd surface stack of material in viewing area.Should be appreciated that second or the 3rd of material any one in surface stack can be the monolayer material illustrated in other local and document of adding as a reference here here.

Element shown in Fig. 9 c constructs the second substrate 912c of the first substrate 902c comprising the second surface lamination with material 908c and the 3rd surface stack with material 922c.First and second substrates are kept with relation spaced apart from each other by primary seal material 978c.The second surface lamination of material extends to outside primary seal material towards the edge of the first substrate, makes it and the first conductive epoxy resin or the first solder 948c1 electrical contact.3rd surface stack of material extends to outside primary seal material towards the edge of the second substrate, makes it and the second conductive epoxy resin or the second solder 948c2 electrical contact.Should be appreciated that the opposite side of element can have for providing the similar area of isolation relevant with the second surface lamination of material to the contact of the 3rd surface stack of material in viewing area.Should be appreciated that second or the 3rd of material any one in surface stack can be the monolayer material illustrated in other local and document of adding as a reference here here.

Fig. 9 d illustrates the second surface electrical contact 948d1 made on the side relative with the 3rd electrical surface contact 948d2 of element.Fig. 9 e illustrates the second surface electrical contact 948e1 made in the side of element and the 3rd electrical surface contact made in one end of element.Fig. 9 f illustrate in side and the second surface electrical contact 948f1 made with one end of element continuously with in relative side and continuously with the 3rd electrical surface contact 948f2 that the opposite side of element is made.Fig. 9 g illustrates the second surface electrical contact 948g1 made in the relative both sides of element and the 3rd electrical surface contact 948g2 made on one end of element.Fig. 9 h illustrates the second surface electrical contact 948h1 made in the relative both sides of element and the 3rd electrical surface contact 948h2 made on the relative two ends of element.Fig. 9 i illustrates the second surface electrical contact 948i1 made on the relative two ends and side of element continuously and the 3rd electrical surface contact 948i2 made in the side of element.Fig. 9 j illustrate continuously relative two ends, fully in side and on the second side at least partially on the second surface electrical contact 948j1 that makes and the 3rd electrical surface contact 948j2 made in the side of element.Should be appreciated that at least one embodiment, longer electrical contact is corresponding with the surface of the highest face temperature resistance lamination with material.Should be appreciated that electrical contact is by conductive epoxy resin, solder or electroconductive binder.

Element shown in Fig. 9 k comprises the first substrate 902k of the second surface lamination with material 908k and has the second substrate 912k of the 3rd surface stack of material 922k.First and second substrates are kept with relation spaced apart from each other by circumference first and second primary seal 948k1,948k2.First primary seal is provided for the second surface lamination electrical contact with material, and the second primary seal is provided for the 3rd surface stack electrical contact with material.First and second primary seals keep the first and second substrates with separated relation, and preferably two primary seals are in the outside at the edge of each substrate all substantially.

By Solid-phase welding process for setting up with the electrode of photovalve or the contact clip of such as J clip or L clip the another kind of method be electrically connected.It is in the electronics industry for setting up the welding process of interconnection reliably between electronic unit (normally IC chip and chip carrier) that wire engages.Wire bond process is described in Zonghe Lai in Nordic Electronics Packaging Guidelines and the Chapter A of Johan Liu.The electrical interconnection be joined to by wire uses the combination of plain conductor or belt and heat, pressure and/or ultrasonic energy wire or belt to be welded on relevant metal surface.Usually, by using special sphenoid or kapillary joining tool welding lead or belt.Typical engaging process uses heat and/or ultrasonic energy, and is generally included into three main classifications: hot compression engages, ultrasonic joint and hot sound engage.Engaged wire can stop on joint, or, multiple joint can be made with continuous print wire.The wire of common form engages and comprises ball bond, wedge bond and stitch bond.The wire be made up of many different metals and alloy and belt can be engaged by wire, comprise aluminium, gold, silver, copper and their alloy.These wires can engage with the many metals or substrate being coated with metal level, and these metal levels are including but not limited to gold, silver, nickel, aluminium and the metal level by these metal alloys.When the electrode engagement with photovalve, preferred substrate is glass, and preferred Metal deposition process is the physical vapor deposition process by such as magnetron sputtering (magnetron sputtering).(one or more) cementing layer of such as chromium, molybdenum, nichrome or nickel is applied, to obtain acceptable adhesiveness between the metal level that can engage at wire and glass.The metal layer thickness of deposit can be 5 dust ~ 1000 micron.More preferably metal layer thickness is 100 dust ~ 1 micron, and most preferred metal layer thickness is 200 ~ 1000 dusts.Diameter of wire or band thickness can be 10 ~ 250 microns, preferably the diameter of 25 ~ 100 microns or thickness, most preferably the diameter of 50 ~ 70 microns or thickness.In at least one embodiment, continuous print wire can along the periphery of substrate by wedge shape or stitch bond on the chromium ring on the second surface of such as electrochromism mirror.By wire or belt being welded to clip and then goblet circle being welded on relevant electrode to substrate, wire or belt bus are electrically connected on the clip of such as nickel J or L clip.Wire or belt can start from metal holder, and advance along EC electrode, or start doubling-up to clip along EC electrode and get back to electrode.In at least one embodiment, in order to the reliability of device and painted uniformly, preferably have to relevant electrode and/or being welded to connect from EC electrode to the redundancy of relevant electrical contact folder.The multiple connections of welding with substrate can be made with the interval of 0.005 ~ 10 inch, preferably 0.040 ~ 2 inch, most preferably 0.100 ~ 0.50 inch.The wire of welding or belt bus can be made from damage by packaging conductive wire and weld seam in the encapsulant.Preferred method is the splice protection bus by packaging conductive wire/belt and welding in the perimeter seal of related elements.Preferably at chemically compatible with the EC medium of the bus (in perimeter seal) surrounded in device plain conductor/paillon foil.Wire bus also can be used to the conductance of the related electrode increased in element.Diameter is 75 microns or less wire is be not easily distinguishable for human eye.Due to be room temperature or chilling process, do not need Post RDBMS or post-processing operation, the technology set up well is proved to be has reliability and promptly can set up joint (each joint about 100 milliseconds), therefore, from the viewpoint manufactured, it is attractive that the wire of welding engages.

Wire engages and also can be used to electronic unit is electrically connected with the substrate surface of element.Such as, many metals are stable when the negative electrode be used as in element instead of anode in galvanochemistry.Wish such as to provide protection by diode, (to discuss this point in detail referring to Figure 11 a ~ 11c in the operation of the contrary limit EC device of polarity.) the electric parts of such as diode with surface mounting engage by wire and to be fixed on substrate or bus clip and to be electrically connected with substrate and/or clip.In another embodiment, as to signal or the light emitting diode (LED) of a part of warning system can such as be fixed on relevant substrate with the form of chip, and with by etching, cover (masking) or laser ablation is connected the circuit that metallic coating carries out on the substrate of patterning formation.These LED of one, two, three or four or other electric parts can be installed on the element on substrate surface or in element.In order to compensate the increase of the rate of propagation of electrochromism species and maintain the good dimmed performance of device in wider temperature range, usually wish the driving voltage be applied to along with the rising increase of temperature on solution-phase electrochromic device.Thermistor required for the variable voltage drive circuit of temperature modulation and electronic unit can be installed on relevant substrate surface and to be engaged by wire and be electrically connected with the metallic coating on substrate.Example: aluminum steel engages as follows with the metallic coating in glass substrate:

Glass is cleaned and is coated with the thick layer of about 400 dusts that comprise following layer by vacuum sputtering: the ground floor of chromium and the second layer (CN) of nickel; The ground floor of chromium and the second layer (CR) of ruthenium; The third layer (CRN) of the ground floor of chromium, the second layer of ruthenium and nickel.By being set using Westbond Model 454647E wire bonding machine with following, be that the aluminium alloy conductor (extensibility is 1 ~ 4%, and tensile strength is 19 ~ 21 grams) of 0.00125 inch joins in the glass substrate of plating by the diameter of the silicon comprising 1%:

Arrange the first joint second to engage

" CN " powder 175 150

Time 30 milliseconds 30 milliseconds

Power 26 grams 26 grams

" CRN " powder 175 150

Time 30 milliseconds 30 milliseconds

Power 26 grams 26 grams

" CR " powder 150 125

Time 75 milliseconds 100 milliseconds

Power 26 grams 26 grams

By after splicing and expose to the open air at 300 DEG C after 1 hour and pull off wire and ergometry, evaluate the bond strength of wire.

Wire engages average pull strength:

After splicing after 300C cures

" CN " 14.51 grams 9.02 grams

" CRN " 19.13 grams 8.2 grams

" CR " 12.42 grams 8.7 grams

Dominant failure after joint is the wire fracture in the engagement end portion of the first welding.After baking, for " CN " and " CRN " group, dominant failure (main failure) is the wire fracture on span centre, and for " CR " group, dominant failure is the wire fracture on the end of the first joint.This example shows, can make multiple reliable solder joints for the typical splash-proofing sputtering metal layer on glass.

Figure 10 generally illustrates the variable transmittance windows 1010 that can use together with window control system 1008 in many coachs, and this window control system 1008 and variable transmittance windows 1010 electric coupling are for controlling the transmission states of variable transmittance windows 1010.Window control system 1008 comprises the window control 1009 be coupled for controlling the transmissivity of each in variable transmittance windows 1010 with each in variable transmittance windows 1010.Each window control 1009 comprises the slave control circuitry 1070 of the transmission states for controlling the variable transmittance windows 1010 of being correlated with.Each window control 1009 is also shown to have and is coupled for providing to slave control circuitry 1070 user to input user's input mechanism 1060 of the transmission states changing relevant variable transmittance windows 1010 to slave control circuitry 1070.Each window control 1009 be also illustrated as with for providing the power of electric power and ground wire 1011 to be coupled to slave control circuitry 1070, user's input mechanism 1060 and variable transmittance windows 1010.As shown in the figure, electric power is provided by slave control circuitry 1070 to variable transmittance windows 1010 from power and ground wire 1011.

Each window control 1009 is also illustrated as being coupled with window control system bus 1013.Same other device be coupled with window control system bus 1013 comprises governor circuit 1090 and other electron device 1092.Governor circuit 1090 is configured to monitor the signal that provided in window control system bus 1013 by each in window control 1009 and the control signal in bus is supplied to each in window control 1009.Governor circuit 1090 comprise comprise logic treatment circuit, storer and bus interface circuit to allow governor circuit 1090 to produce, send, receive the signal in window control system bus 1013 and decode to these signals.The slave control circuitry 1070 comprised in each in window control 1009 is configured to receive the window transmission states the state providing electric signal to be asked by user's input mechanism 1060 the transmission states of variable transmittance windows 1010 to be changed over user to variable transmittance windows 1010 of wishing from user's input mechanism 1060.Slave control circuitry 1070 is also configured to the various characteristics monitoring variable transmittance windows 1010, comprises the transmission states of electric power and the variable transmittance windows 1010 consumed by variable transmittance windows 1010.Slave control circuitry 1070 also comprises the circuit for receiving/send signal from/to window control system bus 1013.

When compared with the transparent conductive oxide of such as indium oxide tin film, some metal film is unstable when being configured to anode.Can work as by the demetalization that gets on from anode, by the chemical change in the metal surface that is such as oxidized or the surface circulation time proof this point in electrochromic device by becoming the movable metallic atom of more rough surface to fog from reprovision.Some metals and metallic film lamination and the pellicular cascade that comprises metal level are by than other these effects of more tolerance.However, still may wish to take steps to ensure that the 3rd surface reflector electrode is negative electrode.

Preferably material may be added in certain embodiments being used as in positive tetchy second surface transparency electrode.In this case, in order to protect second surface electrode, may preferably the 3rd surface electrode be driven as anode be negative electrode by second surface electrode drive.

For the EC mirror of outside vehicle, the power supply directly do not connected to the associated driver circuitry being arranged in relevant internal mirror may be there is, this can make the 3rd surface reflector electrode be the risk minimization (that is, given outside mirror can comprise independently driving circuit) of the anode on this mirror to a certain extent.But, be common by the electric power of internal mirror supply (one or more) outside mirror.Several connection is usually there is between internal mirror and corresponding outside mirror.When relevant reverberator/electrode is used as anode with being not enough to persistence, from internal mirror to the reversal of poles of the electric power of outside mirror thus to make the 3rd surface reflector electrode of device be the risk of anode can be unacceptable.

With reference to Figure 11 a, the circuit 1101a with the diode be connected in series with outer mirror sub-element 1102a prevents from having the current flowing of opposite polarity and prevents electrochromism function.Device can have compromise performance when operating under correct polarity, and this compromise performance is, when apply common voltage and short circuit on clean internal mirror circuit time, mirror is by dimmed.Therefore, outer mirror sub-element will mainly positively charged and electronegative species in solution mutually in and time electric discharge, when they are discharged into the conductive surface of device then not.This can cause the cleaning speed of device greatly slack-off.

Circuit 1100b shown in Figure 11 b comprises the diode 1101b of the lead-in wire parallel connection striden across near outer mirror sub-element 1102b.If to the reversal of poles of the electric current that this part of circuit provides, so will short circuit be caused.Then electric current will flow through diode instead of electric driven color-changing part.Detect short-circuit conditions by internal mirror circuit 1103b, and voltage is switched off automatically.Therefore, even if allow the proper handling of mirror when polarity is correct, if polarity is contrary, this circuit also forbids the electrochromism function of mirror completely.

But, when diode 1101c with do not stop at first when excess current (short circuit) makes voltage reversal executing alive circuit 1100c be coupled time, mirror element 1102c keeps operation, and suitable polarity is transferred to element, and reflector electrode is automatically reconnected automatically as negative electrode.In this circuit 1100c, when excess current being detected, two solid-state switches 1104c1,1104c2 are reconfigured automatically with the sense of current changed along contrary direction by element 1102c.Just in case excess current detected in the configuration, so, because some other fault may cause excess current to be drawn (excessive current draw), therefore solid-state switch is reset and driving for element is disconnected.

Figure 11 d illustrates the alternate configuration of the photoelectricity driving circuit contrary polarity being provided to auto-compensation.Diode 1101d1,1101d2,1101d3,1101d4 limit the rectifier bridge providing double-current path.Actual path current flowing is by the orientation of the hope of the anode and negative electrode always with photovalve 1102d.

Circuit 1100a, 1100b, 1100c and 1100d of Figure 11 a ~ 11d are illustrated as single outside mirror.If wish incessantly to protect single outside mirror, the circuit of so wishing can be reequiped by adaptability like this.

With the photovalve shown in Fig. 7 similar have in the photovalve of the 4th surface reflector (not shown), when there is not electric potential difference between transparent conductor 708 and 718, electrochromic media in chamber 710 is colourless substantially or is almost colourless, further, the light (I entered _o) entered by front element 702, the electrochromic media through in clear coat 708, chamber 710, clear coat 718, rear element 712, and, reflect away from this layer and pass device and advance backward and leave front element 702.Should be appreciated that the above-mentioned each aspect of the present invention for variable transmittance windows can not comprise reflection horizon.In other embodiments, three surface reflector/electrode can be used.Usually, the reflected image (I of electric potential difference is not had _r) size be incident intensity (I _o) about 45 ~ 85%.Definite value depends on many variablees of following general introduction, such as, such as, from before the element of front residual reflection (I ' _r) and from the secondary reflection at front element 702 and front transparency electrode 708, front transparency electrode 708 and electrochromic media, electrochromic media and the interface between the second transparency electrode 718, second transparency electrode 718 and rear element 712.These are reflected in known in the art, and are the differences due to refractive index between the two when light crosses between a kind of material and another kind interface.When front element and rear element not parallel time, residual reflection (I ' _r) or other secondary reflection by not with the reflected image (I from minute surface _r) overlapping, and, dual imaging (in this case, observer can see that the quantity of in esse object in reflected image looks like dual or triple) will be there is.

Be positioned at outside vehicle or vehicle according to electrochromism mirror, there is the minimum requirement of the intensity size for reflected light.Such as, according to the current demand of most of automaker, internal mirror preferably has the minimum high end reflectivity of at least 40%, and outside mirror must have the minimum high end reflectivity of at least 35%.

Electrode layer 708 is connected the electronic circuit that electrochromic media is powered with the effective of such as Figure 10 ~ 11d with 718, thus when striding across conductor 708 and 718 and applying electromotive force, the electrochromic media in chamber 710 is dimmed, makes incident light (I _o) along with passing towards reverberator and passing backward after being reflected along with it and decay.By the electric potential difference between adjustment transparency electrode, preferred device is used as " gray level " device of the transmissivity over a wide range with continuous variable.For solution-phase electrochromic system, the electric potential difference between electrode be removed or back to zero time, device spontaneously returns identical, zero potential, the balanced color and transmissivity that have with device before applying electromotive force.Manufacture electrochromic device is also said that other material is available, and should be appreciated that and no matter use which kind of photoelectric technology, each aspect of the present invention is all applicable.Such as, photoelectric medium can comprise the material of the hybrid combination as solid metal oxide, redox-active polymers and solution phase and solid metal oxide or redox-active polymers; But, the great majority of the electrochromic device of the above-mentioned current use of solution phase design liaison.

In order to provide the photovalve having and there is the second surface transparent conductive oxide of relatively low surface resistance while keeping low absorption, carry out various trial.At above-mentioned electrochromism mirror and in general electrochromic window or photoelectric device, transparency conducting layer 708,718 is often made up of tin indium oxide.Other trial concentrates on the inherent strain reducing the ITO layer be applied in relevant glass substrate and minimizes to make the bending of substrate or warpage.Other trial is by adjustment 1/4th of ITO layer or the optical property of half-wavelength thickness optimization such as reflectivity, or makes the minimize weight of population characteristic valuve assembly.But due to the physical restriction recognized in the past, the effort therefore optimizing above-mentioned all optics and physical property rarely has successfully simultaneously.

The method of the optical property of the given electrochromic window assemblies of optimization before a kind of is like this composition of the electrode controlled wherein.Specifically, some optical property can be obtained by the reflectivity of the reflecting electrode adjusting assembly.More specifically, by controlling the material composition comprising the lamination of reflecting electrode, its reflectivity can be increased, offset the relative absorbance of relevant transparency electrode thus.But the reflectivity increasing reflecting electrode generally needs the metal of the addition used for constructing it, such as rhodium, ruthenium, chromium and silver etc.Because the many metals in these metals are relatively expensive, its addition therefore for electric driven color-changing part makes us unacceptably increasing its cost.Further, many low cost metals, although improve good reflecting properties, with the black box of manufacture process and/or such as outer mirror sub-component and outside window assembly by incompatible for the severe environmental conditions stood.

Other method of ITO electrode is utilized to need the balance of unreciprocal several optics and physical parameter.Such as, as discussed in detail below, the thickness increasing transparent ITO conductive layer with realize low surface resistance can adversely affect the absorption relevant with this layer, 1/4th and/or half-wavelength point position and be applied with substrate bending of ITO layer.

Be known in the art, the surface resistance of ITO layer can be reduced by the thickness increasing ITO layer.But the increase realizing the thickness of ITO layer is attended by the undesirable increase of the light absorption of this layer.Further, the increase of the thickness of ITO layer is generally limited to the integral multiple of the half-wavelength of setted wavelength scope (generally centered by about 550nm), minimizes to make the relative reflectance of the outside surface from ITO layer.Further, the thickness increasing ITO layer can increase the bending of the substrate being applied with ITO layer.As everyone knows, ITO layer comprises the internal stress be applied on substrate, and this internal stress, when being applied on some thinner substrates, can cause the bending of this substrate.In many applications, substrate comprises relatively thin glass to reduce the absorption of glass and to reduce relative weight, and the thickness increase along with ITO layer is occurred, and this is unacceptable bending.In the larger application such as the large window of the window in aircraft or buildings, this is general especially.Distance between bending two electrodes that can affect in black box of associated substrate, affect cleaning speed, color, assembly thus along the relatively uniform darkness on the difference on its surface or brightness, and even optical distortion is caused to the point of the multiple reflected image produced instead of single image.The method of the inherent strain of reduction ITO layer in the past concentrates on the method for the manufacture of electric driven color-changing part.Known in the prior art for a kind of method ITO layer is applied on relevant substrate comprise magnetic sputtering.Up to now, due to several shortcoming, these attempt be only appropriateness successfully, one of shortcoming is the intrinsic physical restriction of method, and its example is the destruction of the lay of ITO layer when increasing pressure, and this causes the cluster of ITO.The ITO layer of this cluster shows surface resistance, the fuzzy and increase that absorbs.

In at least one embodiment, a kind of photovalve is provided, this photovalve utilizes the ITO layer with the surface resistance reduced, the absorptivity reduced and low stress, obtain even darkness or the brightness of black box simultaneously, reduce the weight of black box simultaneously, and realize any recombinant or the combination of these aspects.

In at least one embodiment, a kind of photovalve is provided, this photovalve have the surface resistance relatively reduced provide simultaneously relatively reduce absorptivity, relatively reduce be applied with the bending of the associated substrate of relevant ITO layer, and provide relatively uniform darkness or the brightness of black box while reducing its general assembly (TW).

Although utilize general mirror assembly so that many details of the present invention to be described, it should be noted that, as other places are discussed, embodiments of the invention are equally applicable to the structure of photoelectricity window here here.The light sensing electronic circuit of the type that the internal mirror assembly of Fig. 6 a ~ 6d and the outside rearview mirror assemblies of Fig. 5 a ~ 5f can be included in shown in Canadian Patent No.1300945, U.S. Patent No. 5204778 or U.S. Patent No. 5451822 and to illustrate and high light and surround lighting can be sensed and to other circuit of electric driven color-changing part supply driving voltage; The full content of these patents is added as a reference at this.

As mentioned above, high performance photovalve (mirror or window) requires that the electrode on the 3rd surface and/or reverberator and transparency conductive electrode 708 provide from appropriateness to higher conductance, to provide uniform totally painted, the painted and cleaning speed etc. that adds.Although achieved the improvement of mirror element by use three surface reflector/electrode, wish the improvement about transparency electrode 708,718.As mentioned above, improving the general thickness that increases ito transparent electrode 708,718 while conductance simply, for other optics of electric driven color-changing part and physical property, there are injurious effects by reducing surface resistance.Table 4 illustrates that the reflectivity of EC element has the ITO thickness of three kinds of ITO coatings of different optical constant along with change and reduces.Different ITO coating in this example has different empty refractive indexes (imaginary refractive index).Exemplary elements structure comprises the glass of 1.7mm, the Ru of Cr, 20nm of 50nm, the EC fluid of 140 microns, the glass of different ITO and 1.7mm.The thickness of different I TO layer is shown in table 4.In many side mirror application, customer specifications requires that reflectivity is greater than 55%.According to the performance of ITO, thickness is limited, and therefore feasible surface resistance can be limited.In typical manufacture process, always can operating process under minimum absorption level.Therefore, by upper thickness and the lower limit tables surface resistance of the change constraint reality in manufacture process.In addition, the general surface resistance undesiredly with higher of ITO with low absorption is corresponding.ITO that is thicker, low absorption also can be corresponding with higher surface resistance, limits the benefit of thicker coating thus.

Table 4

Another kind of is have lower reflectivity in dark state for desired design attributes EC element.This causes mirror element to have higher contrast ratio.Table 5 illustrates the dark attitudinal reflexes rate value of the EC mirror with ITO variation in thickness.In the present example, EC stream is not set as is opaque substantially.If EC fluid is not completely opaque, so from the reflectivity that the reflected light of mirror coating will increase in table 5.As shown, when design wavelength is 550nm, dark attitudinal reflexes rate reaches minimum value on about 140 ~ 150nm or 1/2 wavelength coating.Along with thickness departs from this half-wavelength thickness, dark attitudinal reflexes rate rises and the deterioration of contrast ratio.Therefore, in order to obtain given sheet resistance value, ITO thickness can not be set to arbitrary thickness.Absorption and the dark attitudinal reflexes rate demand of coating all limit ITO thickness.

Table 5

In at least one embodiment, photovalve comprises at least one ito transparent electrode 128 with the volume resistance reduced, and improves conductance thus while the relevant optics of not sacrificing other and physical property.Especially, under relatively high pressure and relatively high oxygen gas flow rate, photovalve is built by sputter procedure.Up to now, some maximum pressure is limited to for sputter procedure ITO layer being applied to the routine that substrate utilizes.Exceed these pressure in the past and cause the second-rate of ITO layer, or, specifically, cause the uneven deposit of the cluster showing poor electricity and optical property.

In at least one embodiment, the sputtering coating machine of vertical, in-line arrangement manufactures ITO coating.Negative electrode is about 72 inches long, and uses two or four negative electrode to manufacture coating.The ceramic ITO tile that negative electrode is equipped with industry conventional.Adjust conveyer speed as required with the coating of manufacturing objective thickness.Unless otherwise noted, the power be applied on negative electrode is 5 kilowatts.Each workshop section has two anticathodes in the configuration faced by aiming at.Unless otherwise instructed, the oxygen flow represented here is the workshop section for comprising four negative electrodes.When Liang Ge workshop section is operated, assuming that by the oxygen feed of equivalent in two rooms, and the total amount of oxygen is the twice for the amount of four negative electrodes in a process chamber.Glass substrate is preheating to about 300 DEG C.Sputter gas is adjusted to obtain given pressure, and oxygen is using the flow velocity of regulation or be introduced into as the number percent of the total gas being fed to system.But should understand, owing to those skilled in the art will know that different rooms has different suction configurations, gas access and manifold, negative electrode and power and difference during the course measured their pressure, therefore, the invention is not restricted to above-mentioned definite flow velocity and number percent.On the contrary, those skilled in the art understand for generation of coating and the novelty of method of their performance obtained comprising volume resistance, stress and form, and can when not testing easily for the adjustment of different sputtering systems or adaptive change instruction here.Although the major part of the work illustrated here is carried out with the glass substrate temperature of 300C, but, even if there is no the absolute value illustrated at different temperature here, trend and discovery still can be applicable to higher and lower temperature and will produce the improvement being better than standard conditions.

In at least one embodiment of the present invention, by the increase of oxygen flow, the increase of pressure process is offset.As described, the particular kind of relationship of pressure and oxygen gas flow rate depends on several factor, is included in the specific inert gas used in sputter procedure.Here two kinds of inert gas Kryptons and argon gas is discussed in detail, but, other gas can be utilized by the details of other gas of extrapolating from data-oriented.

About Krypton, preferably have the pressure being more than or equal to 1 millitorr (mT) of the oxygen concentration of 5%, more preferably have 4% oxygen concentration the pressure being more than or equal to 2mT, be more preferably the oxygen concentration with 3% the pressure being more than or equal to 3mT, most preferably have 2% the pressure being more than or equal to 4.5mT of oxygen gas flow rate.

About argon gas, preferably have the pressure being more than or equal to 2mT of the oxygen concentration of 4%, more preferably have 3% oxygen concentration the pressure being more than or equal to 3mT, be more preferably the oxygen concentration with 2% the pressure being more than or equal to 4.5mT, most preferably have 1% the pressure being more than or equal to 6mT of oxygen concentration.

As mentioned above, other gas can also be utilized.Such as, can use have preferably greater than or equal to 3mT, more preferably greater than or equal the neon of higher pressure of expectation of 7 ~ 8mT.Further, compared with Krypton, xenon allows to use relatively low pressure.Those skilled in the art also can recognize, preferred oxygen concentration can change along with the details of sputter equipment.Number percent listed above is meant to be indicative and nonrestrictive.The total flow obtaining the oxygen needed for best of breed of material property generally increases with pressure and increases.Under the flow velocity identical with sputter gas, the requirement of oxygen does not increase, and therefore, the number percent of oxygen reduces with the increase of pressure.

Usually, ITO under low pressure-run at below 2mT.But low-pressure is tending towards causing ITO coating to have compression stress.Particularly when the thickness of glass is less, the stress in ITO can be enough high to make glass bending.When the thickness of reduction glass is to manufacture EC element ignition device, due to the deflection increase of the glass that ITO stress causes.When mirror element or window size larger time, the deflection of glass can be several millimeters.For the manufacture process in enormous quantities of routine, along with the thickness of ITO increases, the deflection of substrate generally increases.

The deflection of glass can be expressed in every way.A kind of mode considers that the deflection of glass is in lens.Times magnification numerical value thus directly relevant with the deflection of glass, and have nothing to do with the size of glass.Times magnification numerical value relates to the radius-of-curvature using following formula: radius-of-curvature=(3124mm)/(1-1/ enlargement factor).The completely smooth glass of a slice will have the times magnification numerical value of 1.0.For the coating glass observed from coated side, when coating is among compression stress, glass is protruding by becoming in coated side.If coating is in drawing stress, so glass will be recessed in coated side.Compression coating causes the warpage or the times magnification numerical value that are less than 1, and on the contrary, if coating stretches, so enlargement factor or warp value will be greater than 1.The warp value of the magnitude of 0.85 is from smooth and glass height warpage.Because the reflection from the first and second surfaces can not crossover, therefore the warp value of this magnitude will produce EC mirror or the window can with dual imaging.In addition, be difficult to the feasible sealing of the glass manufacture with unacceptable warpage.The glass had up to the warp value of 0.97 can go wrong in the mill or about dual imaging.

With reference to the Figure 12 indicating " argon pressure test ", for the ITO Coating measurement warp value on 1.6mm glass.When applying ITO or other band stress coat, thickness of glass plays an important role in deflection and warpage.Deflection is general on the contrary with cube the changing of thickness (assuming that along with the inherent strain in the variation in thickness coating of coating be constant) of glass.Therefore, thinner glass is by relative to thicker glass warpage in a non-linear fashion.When with thicker glassy phase than time, there is the thinner glass of thinner ITO coating generally by warpage.Amount of warpage is along with the thickness linear change of coating.In fig. 12, the thickness of coating is about 50nm.In order to calculate the warpage on other one-tenth-value thickness 1/10, following formula can be used: new warpage=[1-(1-warp value) thickness that * is new/old thickness].This formula is applied to the value of 0.98 in Figure 12, the warp value of 0.94 of the thick ITO coating of 150nm and the warp value of 0.74 of 650nm thick coating can be obtained.If glass is thinner, so these values can depart from flat conditions more greatly.

Figure 12 illustrates the discovery of several key.First, in oxygen gas flow rate scope (x axle) in this experiment, the warp value in the ITO manufactured under 2.1mT or stress (y-axis) do not change greatly.Over this range, ITO is through minimal surface resistance and volumetric resistivity value.May conclude improperly and can not optimize electrically and stress performance simultaneously, say nothing of other required optical property.Under very high oxygen gas flow rate, warp value starts greatly to depart from flat conditions more.

Under higher pressure (4.0mT), there is a kind of trend.Under lower oxygen gas flow rate, the stress in ITO coating reduces.But at a higher pressure, this changes into the lower oxygen concentration in overall sputtering environment.In sputtering technology, generally while adjustment pressure, keep oxygen concentration constant.Therefore, when using conventional experiment, do not find this trend and the discovery that cause one embodiment of the present of invention.Compared with line 1201, under the higher argon pressure with the 4mT shown in line 1202, there is the trend of the very strong minimise stress under lower oxygen flow in ITO.Lower stress is microstructure due to the uniqueness in ITO coating in the following detailed description of or form.Under higher oxygen gas flow rate, warp value departs from flat conditions, but under any specific oxygen gas flow rate, warp value keeps higher than the warp value under low pressure obtained.For the pressure more taller than pressure shown in Figure 12, be still this trend.More than under the pressure of 7mT, these benefits continue.Also can obtain other improvement under high pressures, but the restriction of specific sputtering chamber can limit the experiment under the pressure exceeding this value.

Figure 13 illustrates that the relative increase of argon pressure and oxygen flow is on the impact of volume resistance.Carry out this by utilizing argon gas as sputter gas specifically to test.400sccm argon gas situation (line 1301) produces the pressure of 3.7mT, and 550sccm (line 1302) produces 5mT, 700sccm (line 1303) and produces 6.2mT, 850sccm (line 1304) generation 7.4mT.Oxygen gas flow rate unit in x-axis is sccm.Note, along with argon pressure and oxygen flow increase, specific insulation obtains and improves greatly.In addition, relative to higher pressure condition, lower argon pressure situation is tending towards having minimum value on higher volumetric resistivity value.As a reference, the suitable coating made under the pressure of 2mT comprises the volumetric resistivity value of about 180 ~ 200 μ Ω cm.In disclosed patented claim recently, the current state that another manufacturer of electrochromic device have submitted the prior art of the ITO coating in EC application is corresponding with the volume resistance of 200 μ Ω cm.This represents applies for EC the ITO coating that the benefit of feasible ITO and performance do not consider improvement of the present invention in advance.Here the more high pressure situation illustrated does not obtain their minimum value on the oxygen level of test.

Figure 14 illustrates that higher pressure causes the relatively thin ITO coating on substrate further.This point also contributes to explaining the reason that there is no the present embodiment of the present invention in the past.As shown, when oxygen flow and argon pressure increase, the thickness of ITO coating reduces.The intrinsic volume resistance measured as the quality of the electrical property of ITO is the product of surface resistance and thickness.But, generally only measured surface resistance, but, when coating is not by detailed characterizations, much information dropout.Because the change coating along with process gas is thinning, therefore, surface resistance does not defer to the trend identical with volume resistance.The benefit of the continuity for volume resistance using higher argon pressure (relative to line 1401,1402,1403, line 1404 represents the highest) and oxygen flow to obtain shown in the comparable analysis of surface resistance.If only look-up table surface resistance, so can conclude that 3.7mT situation is best and obtains preferred performance under relatively low oxygen gas flow rate.Another benefit with lower volume resistance is that the real part of refractive index reduces.There is the half-wavelength coating of lower refractive index physically than the half-wavelength thick coating with higher refractive index, thus cause lower surface resistance.

The diagram of Figure 15 illustrates that the argon pressure that combination is higher and higher oxygen flow utilize the effect of argon gas, and the diagram of Figure 16 illustrates the ITO half-wavelength volume resistance of realization.In order to obtain 1/2 wavelength coating, use two process chambers.200sccm situation represents the standard in the existing ITO coating in EC technology.The half-wavelength coating of prior art has the surface resistance higher than 12.5ohm/sq, and obtains according to the more high pressure situation of at least one embodiment of the present invention the value being less than 12ohm/sq, and some are even lower than 11ohm/sq.Essence in figure 16 exemplified with the volume resistance obtained at a higher pressure is improved.In this case, oxygen is not optimised at a higher pressure, and when argon flow amount is 400 ~ 800SCCM, volume resistance seems to keep relative constancy.

The volume resistance of ITO is very important, but as other places are mentioned here, surface resistance is the principal element of the dimmed speed affected in EC element.For half-wavelength coating, the volume resistance of 200 μ Ω cm amounts to into the surface resistance of 13.7ohm/sq, and the volume resistance of 180 amounts to into the surface resistance of 12.4ohm/sq, and the volume resistance of 140 amounts to into the surface resistance of 9.6ohm/sq.Compared with the situation of 13.7ohm/sq, 9.6ohm/sq reduces 30%, and causes the essence of dimmed time to be improved, and can realize the bus configuration of the novelty that other places here illustrate, this bus configuration also improves element appearing dark homogeneity.

In next example, in different coating machines, manufacture coating.This coating machine has about 27 inches of long negative electrodes.Test with the argon gas under the pressure of 2.73 millitorrs and Krypton.Coating is made in through two passages of negative electrode.Oxygen is changed as illustrated in relevant accompanying drawing and form.The thickness of the ITO coating obtained is about 600nm.In fig. 17, the relation of absorption (y-axis) in coating and oxygen gas flow rate (x-axis) is drawn.Can find out, compared with the sample using argon gas (line 1702) to make as sputter gas, under given oxygen gas flow rate, the absorption of the sample made by Krypton (line 1701) is higher.

In figure 18, the relation of warpage (y-axis) as the function of oxygen gas flow rate (x-axis) of glass is drawn.Can find out to have the warp value closer to 1 with the sample that Krypton (line 1801) is made, this represents that the glass that the glass of the coating ITO that Krypton is made is made than argon gas (line 1802) is smooth.Figure 18 illustrates the data more early provided, and wherein, warpage is illustrated as increasing with the increase of oxygen gas flow rate.

In Figure 19, draw the warpage (y-axis) of glass and the relation absorbing (x-axis).The sample (line 1901) that Krypton is made when more absorbing time corresponding with oxygen gas flow rate, but, when for absorptance comparatively warpage time, the sample (line 1902) that the sample that Krypton is made is made than argon gas is smooth.

Figure 20 illustrates for Krypton (line 2001) and the warpage (y-axis) of argon gas (line 2002) and the relation of transmissivity (x-axis).For given higher transmittance values, obtain more smooth glass.At a higher pressure, by using Krypton or xenon or even argon gas, it is possible for further improving.Higher pressure makes it possible to realize lower stress, higher transparency and lower surface resistance simultaneously.

Form or the surface characteristics of ITO coating also change with pressure and oxygen gas flow rate.There is interaction effect between these values, wherein, when pressure change, under different oxygen gas flow rates, obtain different forms.Make in the coating machine with 72 inch cathode at the ITO coating sample shown in Figure 21 ~ 23.All samples are all make under the linear velocity of 2.1mT, each target 5kw, 1 process chamber (2, every side target) and 32ipm.For the sample in Figure 21, Figure 22 and Figure 23, oxygen gas flow rate is respectively 2,8 and 17sccm.The sample of Figure 21 and Figure 23 illustrates the extreme case of form.The sample of Figure 21 has so-called plethora 2101 form, and the sample of Figure 23 has platelet 2302 form.Inspection for the sample of Figure 21 discloses background platelet 2102 structure.The sample of Figure 21 is considered to the form how much with mixing.The sample of Figure 22 has considerably less tubercle 2201 and overall leading platelet 2202 form under middle oxygen flow.Platelet form is relevant to the higher stress in coating, and occurs plethora form in the coating with little stress.According to given process gaseous tension, the transformation between these two kinds of different shapes is unexpected or gradually.The feature of hypoxemia plethora form is roughness between larger peak valley (as described in detail about Figure 33 a and Figure 33 b).Tubercle occurs substantially on the surface of coating, produces roughness between larger peak valley thus.Along with tubercle is transformed into platelet microstructure, the roughness on surface reduces.When tubercle just disappears from surface, roughness is in minimum value.At that point, we have and have more shallow " steep cliff " 2103,2203,2303 or the platelet microstructure in region between platelets.Along with oxygen flow increases further, the height of the steep cliff between platelet increases, thus increases the roughness on surface undesiredly.

The sample of Figure 24 ~ 26 makes under the oxygen under the power suitable with Figure 21 ~ 23 and linear velocity and all at 2sccm.Process gaseous tension is respectively 3.7,2.1 and 1.6 millitorrs.Along with pressure increases, form is dominated by plethora form more and more.At a higher pressure, plethora 2401, transformation between 2501,2601 and platelet form relax more, allow thus to carry out thinner adjustment between the optics of hope in the coating and mechanical property.Platelet 2402 form is still present in the background of 3.7 millitorr samples, but measures considerably less.Along with pressure reduces further, tubercle composition is finally eliminated, thus only leaves platelet form.

Use Krypton or other heavier sputter process gas in some respects with run at a higher pressure similar.As shown in Figure 27 ~ 29, will be with Krypton process gas and compare with three SEM images of 1/2 wavelength ITO sample that the oxygen gas flow rate of change is made.These samples are illustrated in greater detail with reference to table 6.Also these samples are made by use two process chambers (four, every side negative electrode) under the linear velocity and 6.2kw of 40ipm.Thickness of glass is 1.1mm.For the sample in Figure 27, Figure 28 and Figure 29, oxygen gas flow rate is respectively 8,12 and 16sccm.Oxygen gas flow rate is according to process chamber.The surface of the sample made under 8sccm oxygen shown in Figure 17 does not have in fact platelet composition, and is extremely stressless; The surface mainly tubercle 2701 of this sample.Sample shown in Figure 27 and there is the warp value being essentially 1 from the 1/2 other wavelength sample of table 6.The surface structure of the sample shown in Figure 28 generally comprises tubercle 2801 and has considerably less platelet 2802 form with small steep cliff 2803.The sample of Figure 29 is platelet 2902 surface structure with the steep cliff 2903 limited well substantially.Sample has the low-down volumetric resistivity value of about 150 μ Ω cm.Absorption for these coatings of situation of 12sccm is quite low, thus has the best of breed of planarization, resistivity and absorption.The low stress values of these coatings shows, even some platelet forms, when by the higher pressure of use or when manufacturing with heavier sputter gas, also can successfully be utilized.

Sample D, E and F shown in Figure 30 ~ 32 is the 2 wavelength ITO situations listed for table 7 respectively, and corresponding with 8,12 and 16sccm flow velocity respectively.Be 7ipm for these sample wire speed, otherwise treatment conditions are identical with table 6.Thicker than their half-wavelength homologue about 5 times of these coatings.The form of the coating on these samples is how many different from plethora 3001,3101,3201 form of thinner sample, provides structure (sample D, Figure 30) more in pelletized form.Between the particle shown in Figure 30, there is cavity, this causes adversely higher fuzzy and deteriorated conductance; The relatively high volumetric resistivity value of 200 μ Ω cm of this sample illustrates this point.The sample E made with the oxygen of 12sccm has low-down volume resistance (131 μ Ω cm) and thinner particle microstructure.16sccm situation has similar microstructure, but in this case, owing to being in thinner coating, therefore there is not platelet form.The stress level of the coating that these Kryptons are made is relatively low.The scope of warp value is from being essentially the value of 1 to 0.956 in most high oxygen situation low oxygen situation.These samples make than the 1.1mm glass being easier to warpage with the 1.6mm glassy phase illustrated above.Warp value still closely 1.It has the coating of 50nm thick coating more than 10 times than starting to discuss on 1.6mm glass.These coatings not only have extremely low stress, and they also have better volumetric resistivity value and acceptable absorption value.

Between the peak valley of these coatings, surfaceness (peak-to-valley surface roughness) (defining with reference in the discussion of Figure 33 a and Figure 33 b below) is preferably less than or equal to be more preferably less than be more preferably and be less than or equal to about even be more preferably and be less than or equal to about most preferably be less than or equal to about

In order to explain further feature and the advantage of the electrochromism mirror built according at least one embodiment of the present invention, in table 3 and table 4, provide the summary of experimental result below.In these are summed up, mention the spectrum property of the element of the electrochromism mirror built according to the parameter specified in each example.When discussing color, (be commonly referred to as L with reference to Commission Internationale de I ' Eclairage ' s (CIE) 1976 CIELAB Chromaticity Diagram ^*a ^*b ^*chart) be useful.The technology of color is relative complex, but, F.W.Billmeyer and M.Saltzman at Principles of Color Technology, 2 ^ndgive in Edition, J.Wiley and Sons Inc. (1981) and quite comprehensively discuss, and the disclosure is owing to relating to color technology and therefore term generally defers to this discussion.At L ^*a ^*b ^*in chart, L ^*definition brightness, a ^*represent red/value of green, b ^*represent Huang/blue value.Each in electrochromic media has under each specific voltage can be transformed into three quantity instructions i.e. their L ^*a ^*b ^*the absorption spectrum of value.In order to calculate such as L from spectral transmission or reflection ^*a ^*b ^*one group of chromaticity coordinates of value, needs two add-inses.One is the spectral power distributions of light source or working flare.The disclosure uses CIE standard illuminants A with the light of simulation from automobile headlamp, and uses CIE standard illuminants D ₆₅with solar simulated.Required Section 2 is the spectral response of observer.The disclosure uses 2 degree of CIE standard observers.Be generally used for working flare/observer's combination of mirror thus be expressed as A/2 degree, and the combination being generally used for window is expressed as D ₆₅/ 2 degree.Many examples in following example mention the value Y from 1931 CIE standards, because it compares L ^*closer corresponding with spectral reflectivity.The C also illustrated below ^*value equals (a ^*) ²+ (bw ^*) ²square root, be provided for measuring of quantized color neutrality thus.

Table 3 and table 4 summarize the experimental result of the element built according to the present invention.Especially, be sputter gas with Krypton and under the pressure of 3mTorr, for half-wavelength and two wavelength, two kinds of thickness, test in the scope of the oxygen flow of 8 ~ 16sccm.Table 6 summarizes the result being slightly less than half-wavelength ITO thickness, and table 7 summarizes the result less times greater than two wavelength ITO thickness, and half-wavelength thickness is applicable to such as mirror application, and two wavelength thicknesses are applicable to such as window applications.Further, it should be noted that the result of element that these tables comprise individual layer simultaneously and are made up of bilayer.

Table 8 illustrates volume resistance, inside dependence between electron mobility and electron carrier density.Note there is the continuum of carrier concentration and the mobility combination producing given volume resistance.

Table 8

Volume resistance	cc	mu	RI n	RI k
					160	1.15E+21	34.0	1.776	0.0145
160	6.88E+20	56.7	1.8845	0.0054
					160	4.91E+20	79.4	1.9295	0.0031

					140	1.31E+21	34.0	1.7349	0.0168
140	7.86E+20	56.7	1.8616	0.0062
					140	5.61E+20	79.4	1.9135	0.0034

					120	1.53E+21	34.0	1.6791	0.0202
120	9.17E+20	56.7	1.8306	0.0072
					120	6.55E+20	79.4	1.892	0.0039

Electron carrier density is preferably greater than or equal to 40e ²⁰electronics/cc, and mobility is preferably greater than or equal to 25cm^2/-s.Carrier concentration given here and electron mobility, thickness and surfaceness obtain from the ellipsometry analysis of coating.Electron concentration and mobility can from the value changes using Hall characterizing method determine, and, it will be understood by those skilled in the art that can there is deviation between measuring method.As mentioned above, existence can obtain the carrier concentration of given volume resistance and the continuum of mobility value.In the embodiment of preferred low-refraction, adjustment deposition process will be preferred to produce higher carrier concentration.In the other embodiment of preferred low absorption, adjustment deposition process will be preferred to produce higher electron mobility.In other embodiments, the by-level of carrier concentration and mobility may be wished.

In at least one embodiment, photovalve comprises and shows lower volume resistance, the absorption reduced simultaneously, reduces and be applied with the bending of the associated substrate of ITO or warpage, the even darkness of maintenance black box and brightness and the ITO layer reducing the improvement of its weight.

In the non-microscale electrical applications relating to metallic coating, surface topology, form and roughness are generally unessential.When metal is used in optical application, surface topology is particular importance.When surfaceness becomes too large, coating will have noticeable non-mirror reflection or fuzzy.For this roughness, because it can may not have negative effect for function for visual appearance, therefore usually first to be concerned in most application.When the optical application of the many optical application such as illustrated, harmful be fuzzyly regarded as the worst situation here.Under the roughness levels much smaller than the fuzzy roughness levels causing being harmful to, surfaceness can have other negative result.In different optical application, the acceptable form of the metal film that level of surface roughness definition allows metal film to work satisfactorily.Owing to usually needing the higher metal of a large amount of prices with higher reflectivity to overcome the problem relevant with unsuitable configuration of surface, be therefore usually increase cost with the loss of unsatisfactory ground control surface morphologic correlation.The form of varying level or the effect of surfaceness that use thin-skin model technology are analyzed.These technology are accepted and have been proved to be and accurately describe actual film or coat system in the field of thin film technique, and therefore can be used to predict the impact of different changes for coating.A large amount of showing that the sample required for effect can be expensive and time-consuming owing to manufacturing or making, is therefore favourable like this.In this case, use supplied by Software Spectra.Inc. be called that the commercial membrane process of TFCalc is to perform calculating.

Roughness used herein is defined in average peak valley spacing.Figure 33 a and Figure 33 B illustrates two kinds of different roughness scenario.Figure 33 a represents larger crystallite 3302a.Figure 33 B represents less crystallite 3302B.In both cases, peak valley spacing 3301a, 3301b are described to be identical.In addition, two examples have identical empty block ratio (void to bulk ratio).Should be appreciated that each paddy and each peak may not be in identical height.Measure between average peak valley and therefore more representational quantized value is provided.

When layer is thinner, can be similar to it with the single conforming layer with uniform refractive index.There is the mode of the refractive index of several approximate mixolimnion.There is so-called effective intermediate approximation (EMA).Various different EMA has its strong point and shortcoming.In these examples, use Bruggeman EMA method.When thickness becomes large, if use single fixing refractive index, then roughness is not similar to well.In these cases, roughness can be approximately several parts of the different ratio of cavity and block materials to form grading index approximate (graded index approximation).

Here by several metal pattern to provide surfaceness to the representational example of the optical effect of reflectivity.Table 6, table 7 and table 8 represent the impact of uneven surface thickness (roughness thickness) for the reflectivity on the surface of Ag, Cr and Rh respectively.The unit of thickness is nanometer, and the representative of Cap Y value is from the reflectivity of coated surfaces.For each in these metals, reflectivity declines gradually along with the thickness increase of roughness.According to application, the amount of acceptable roughness will change.Roughness should be less than 20nm average peak valley, be preferably less than 15nm, be more preferably less than 10nm, be more preferably and be less than 5nm, be most preferably less than 2.5nm.As mentioned above, these preferred scopes depend on application.Such as, in one embodiment, the thickness of flash layer, overlayer, restraining barrier or adhesive phase (that is, functional layer) may need to change with the roughness of bottom surface.The thickness of the functional layer that the roughness of bottom surface is required can cause undesirable effect, the change of the optical property of the lamination such as obtained, higher cost or other counter productive.The means being used for making surface smoothing before deposition of functional layer are below described.Should be appreciated that may exist increase surfaceness can be favourable some embodiments, such as produce effectively large surf zone for bonding with encapsulant better.

Table 6, table 7 and table 8 also comprise the value being designated as " % of theoretical maximum ".The reflectance match on the reflectivity that this measure definitions has a coating of rough surface how near-earth and desirable completely level and smooth surface.The coating with the a% of the theoretical maximum of 100% can have the obtainable in theory maximum reflectivity of this material.If the % of theoretical maximum is 85%, the reflectivity so obtained can be only 85% of the value of theoretical smooth finish or have 0.85 times of reflectivity of coating of 0 roughness.

The reflectivity of metal or alloy coating depends on many attributes of the coating of coating or even relative smooth.The density of coating, the existence of interior void are whether, how stress level etc. all work close to some ideal maximum value about reflectivity.Here the theoretical maximum reflectivity defined is not the ideal reflectivity about desired coating, but about the reflectance value of level and smooth real coating.In practice, theoretical maximum is obtained by the combination of optical analysis and thin-skin model.By the real coating using the optical technology analysis of such as variable-angle spectral ellipsometry (Variable angel Spectroscopic Ellipsometry) to have surfaceness, the relation of refractive index and wavelength and surfaceness can be obtained.Then the relation of refractive index and wavelength can be inputted in the thin-skin model program of such as TFCalc or Essential Macleod, and can reflectivity be calculated.Use this reflectivity of calculating of refractive index data of measuring from but from the theoretical maximum reflectivity value of this specific film or coating.

Preferably, the reflectivity of coating be greater than theoretical maximum 85%, more preferably greater than theoretical maximum 90%, be most preferably greater than 95% of theoretical maximum.

Table 9: uneven surface thickness is on the impact of the reflectivity of Ag coating

Table 10: uneven surface thickness is on the impact of the reflectivity of chrome coating

Table 11: uneven surface thickness is on the impact of the reflectivity of rhodium coatings

In some applications, wish to have higher second surface reflectivity, wherein, when being observed by glass, metal level is left in this reflection.In this case, except surfaceness, the cavity imbedded also is related.The amount (% relative to volume) in cavity can change, and the thickness of empty layer also can change.The general rule illustrated for surfaceness above is here also suitable for.

Invariably, when metal level comprises low surface resistance surface, roughness is related especially.Metal or other conductive material have the internal performance being called specific insulation.By by the surface resistance of volume resistance number divided by the thickness determination coating of coating.In principle, as long as coating is enough thick, so any sheet resistance value can be obtained from any conductive material.When also needing other attribute except surface resistance or conductance, low surface resistance is challenging or restricted implementing.

As explained above, along with the thickness of coating increases, surfaceness generally also increases, and this causes the reduction of specular reflectance.Very thick coating usually has the reflectivity levels of the reflectivity being significantly less than complete smooth surface.Coating will with many factors vary by the amount of the roughness of development.The performance of material itself is main driving force, but in border, deposition process parameters (using together with deposition process) can change the surface property of coating.

Due to other consideration, the material of best surface roughness always can not be had for given application choice.Other factor also works.Such as adhesiveness and cost are the key issues that impact enters the selection of the material of coating stack.Single material usually can not be selected to meet all demands; Therefore, laminated coating is used.Such as some platinum group metal of rhodium, ruthenium, iridium etc. has higher reflectivity but very expensive.Therefore, can be that cost is too high by the whole coating with low surface resistance that these materials are made.When needing with glass or other material splendid bonding, also can find that these materials have the bond strength poorer than other material.Based on the coating of silver inadequate as stability during anode, and, according to coating stack, be also problematic viewed from bonding viewpoint.Other Metal Phase of the metal and some of such as chromium than being that relative cost is lower, and knownly has extraordinary cementability.Therefore, chromium can be used as adhesive phase, and can be built into enough thickness to obtain the electrical property of wishing.

Unfortunately, chromium is reactive very high, and this causes being tending towards the inherence tendency of relatively large surface roughness value.Higher reactivity is very important, this is because when such as by using magnetron sputtered vacuum deposit (MSVD) deposit coating, chromium atom will be tending towards adhering to the position of their first implantations.Engage the speed that formed quickly, and this restriction atom finds the ability of energy position along surface diffusion.Usually, the low-yield settling position in coating is the position making himself to be suitable for less surfaceness.This trend less than low-energy state also contributes to the deterioration of the volume resistance of coating.Therefore, need thicker layer to obtain targeted sheet resistance, and surfaceness is tending towards further deterioration.Due to these emulative effects, be therefore difficult to the target simultaneously obtaining low surface resistance and high reflectance.

As everyone knows, by placing the thin layer of the metal of higher reflectivity on low-reflectivity metal, the reflectivity of this low-reflectivity metal can be increased.Such as, the above-mentioned metal of such as rhodium or ruthenium can be used.It will be the direct result of surfaceness of bottom layers of chrome that these metals obtain the necessary thickness of given reflectivity levels.Can be used as other metal of conductive layer including but not limited to aluminium, cadmium, chromium, cobalt, copper, gold, iridium, iron, magnesium, molybdenum, nickel, osmium, palladium, platinum, rhodium, ruthenium, silver, tin, tungsten and zinc.These metals mutual or be possible with the alloy of other metal.The suitability of these materials in given application will depend on whole demands.Such as, ruthenium may be expensive metal in one application, but in Another Application, it may be relatively cheap relative to another metal of such as rhodium, therefore can fall into spirit of the present invention.In other nonrestrictive embodiment, given metal or alloy may not be compatible with other compositions all in application.In this case, responsive metal can be buried or in addition with have that reciprocation limits become to separate.Usually patterning is carried out by the roughness of bottom at each layer of the deposited on top of chromium.Therefore, the thin layer of high reflectance metal does not have its desirable reflectivity by due to the layer below it yet.As a rule, preferred embodiment is the embodiment of the high reflectance metal had towards observer's orientation.Many metals in high conductivity metal listed above also have higher reflectivity.It is metallic alloying to have enough chemistry, environment or physical property that these metals may need with other.Metal or alloy thus unacceptable color or tone can be had.Total reflectivity intensity may be inadequate for the application of hope, but if the color of reflection does not satisfy the demands, so this metal or alloy is inappropriate.In this case, similar with above explanation, metal or alloy can be embedded in below the layer of color that there is lower inherent reflectivity and there is preferred reflection.

Prepare authentic specimen to allow to evaluate the balance between the reflectivity of chromium-ruthenium duplex coating lamination and surface resistance.In these samples, apply chromium to obtain targeted sheet resistance value.Then sample is by the ruthenium of outer painting different-thickness.Use following process conditions:

All coatings are processed under 3.0mTorr

Cr@4.0kw@(130)=about 1000 dust

Cr@4.0kw@(130) × 9=.7 Ohms sq

Cr@4.0kw@(130) × 3=1.5 Ohms sq

Cr@4.0kw@(87) × 1=3 Ohms sq

Cr@4.0kw@(170) × 1=6 Ohms sq

Ru@1.7kw@(130)=400 dust

Ru@.85kw@(130)=200 dust

Ru@.43kw@(130)=100 dust

Ru@.43kw@(260)=50 dust

Ru@.43kw@(520)=25 dust

Chromium sample is deposit under 4kw all.Change linear velocity (in parenthesis-arbitrary unit) and road sub-quantity (such as, × 9) to adjust the thickness of coating to realize surface resistance target.Layer of ruthenium is made to obtain target thickness level by change linear velocity and power.List matrix result in table 12.Reflectivity generally reduces along with the increase of thickness and the reduction of surface resistance.The target prepared is that several samples of 3ohm/sq do not meet these trend.This is because they are made under the linear velocity different from other chrome coating.When linear velocity reduces, substrate moves with slower speed.In linear process, this means that the angle of elevation deposition materials of main sputtering forms initial stratum nucleare.As mentioned in explanation below, angle of elevation deposit causes poor material property.Usually use fender to eliminate this angle of elevation deposit.3ohm/sq chromium situation in this research well shows how the angle of elevation can make the example of the optical performance degradation of coating.

Table 12: the double-deck result of chromium ruthenium

Test	Ruthenium	Ohms	Y	a ^＊	b ^＊	Fuzzy (not comprising minute surface)
							#1 .7	0	0.6	50.0	-0.9	0.0	0.13
#2 1.5	0	1.5	55.3	-0.7	-0.2	0.04
							#3 3	0	2.9	54.4	-0.5	0.5	0.02
#6 6	0	5.1	60.9	-0.9	-0.2	0.02
							#1 .7 25	25	0.6	50.7	-0.9	1.0	0.11
#2 1.5 25	25	1.6	54.2	-0.6	0.8	0.03
							#3 3 25	25	3	53.0	-0.5	1.1	0.02
#4 6 25	25	5.9	58.8	-0.7	1.0	0.02
							#1 .7 50	50	0.6	51.0	-0.9	1.6	0.12
#2 1.5 50	50	1.5	55.0	-0.6	1.2	0.03
							#3 3 50	50	2.9	54.1	-0.5	1.2	0.03
#6 6 50	50	5.6	59.6	-0.6	1.2	0.02
							#1 .7 100	100	0.6	52.7	-0.7	2.4	0.13
#2 1.5 100	100	1.5	56.6	-0.5	1.6	0.04
							#3 3 100	100	2.8	56.7	-0.4	1.3	0.03
#6 6 100	100	5	62.5	-0.4	1.2	0.02
							#1 .7 200	200	0.5	54.7	-0.2	2.7	0.14
#2 1.5 200	200	1.4	60.1	-0.1	1.6	0.04
							#3 3 200	200	2.5	63.1	0.0	1.3	0.03
#6 6 200	200	4.2	67.4	-0.1	0.9	0.03
							#1 .7 400	400	0.6	56.5	0.2	2.6	0.15
#2 1.5 400	400	1.3	64.1	0.1	1.4	0.05
							#3 3 400	400	2	67.5	0.0	1.2	0.03
#6 6 400	400	3	69.8	-0.1	0.8	0.03

As can be seen from Table 12, even if simple chrome coating also has relatively low reflectance value in 6ohm/sq situation.For this sample, reflectivity is only about 61%.The chromium made by other means or process conditions should be able to obtain the value more than 65%.Therefore, even if in the sheet resistance value that this is moderate, chromium reflectivity also affects adversely.

When wishing 3ohm/sq coating, need the ruthenium of 100 of chromium top and 200 dusts to obtain more moderate reflectance value.In the ideal case, ruthenium coating should be able to obtain the reflectivity more than 72%.Even if 400 dusts at 6ohm/sq chromium top are also low than theoretical optimal value by 2%.Low ohm sample is not even close to obtainable in theory reflectance value.Therefore, when needing low surface resistance and high reflectance at the same time, the chromium ruthenium bilayer of standard does not meet the demands.Other means must be used to solve this problem.

Deposition process parameters can be adjusted minimize to make surfaceness in coating forming procedure.In case of a metal, as the following detailed description of, can by under low pressure implementing process and preferably by use neon or argon gas-neon combination gas as sputter gas, reducing surfaceness and also increase reflectivity.These parameters contribute to suitable momentum in deposition process and energy trasfer, thus the surface causing roughness lower and lower specific insulation.

Table 13 illustrates how surfaceness, reflectivity and electric property change when adjusting process parameter.There is provided 3mT situation as benchmark.The thickness of coating is about 600 dusts.This thickness is very important, because coating is almost opaque at which level and surface resistance is relatively low.Can find out, reduce pressure and roughness can be made to reduce about 17%, and realize reflectivity increase about 2%.Reduce pressure and carry out sputtering with 50: 50 combination gass of argon gas and neon and cause further improvement.The situation of roughness ratio benchmark is low by about 20%, and reflectivity height about 2.7%.Last situation adopts the sputter gas of more neon-Yue 70% to be neon.Luminance factor base case height about 3.5%, and roughness reduces about 24%.Thickness and roughness value is determined by using variable-angle spectral ellipsometry (variable angle spectroscopic ellipsometry).

Table 13: the relation between chromium performance and technique are arranged

Can by reducing pressure and improving result further by the neon content increased in sputter gas.In addition, increase underlayer temperature and also contribute to more smooth coating.Higher underlayer temperature causes the higher surface mobility of deposit atom, thus causes more even curface.

Table 13 also comprises the volumetric resistivity value of chrome coating.The theoretical minimum volume resistance value of chromium is about 13 μ Ω cm.The base case obtained under the argon gas typical pressure of 3mT has the volumetric resistivity value of 6 times that are greater than theoretical volume resistance.By improving deposit performance, the volumetric resistivity value of 5 times that are less than theoretical minimum value can be obtained.Preferably, volume resistance be less than 5 times of theoretical minimum value, be preferably less than 4 times of theoretical minimum value, be more preferably less than 3 times of theoretical minimum value, be most preferably less than 2 times of theoretical minimum value.

From the viewpoint of surfaceness, there is oxygen (or water) in systems in which and be harmful to especially.Chromium is very easy to react with oxygen and be tending towards immediate response.This causes the roughness of adding in the coating.Therefore, the coating with less oxygen is recommended.Table 14 illustrates the impact of oxygen for roughness.Oxygen level in table 14 refers to the number percent in sputter gas.Pressure unit of force is mT, and the unit of thickness is dust.The amount of the acceptable oxygen in coating is less than 5at.%, is preferably less than 2at.%, is less than 1at.% in the ideal case.

Table 14: the oxygen number percent in sputtering atmosphere is for the impact of the roughness of chrome coating

Oxygen level	Pressure	Thickness	Roughness
				1	2.00	493	105
5	2.00	438	130
				10	2.00	370	162

The amount of acceptable roughness depends on application.When the reflectance value that hope is higher, also wish less roughness.When reflectivity demand is so not urgent, higher roughness can be acceptable.Usually, roughness should be less than about 200 dusts, is preferably less than 100 dusts, is more preferably less than 50 dusts, is more preferably and is less than 25 dusts, is most preferably less than 15 dusts.Here the roughness used as term refers to the average peak valley distance by using ellipsometry or atomic force microscope to determine.

Can individually or mutually together or use other means to minimize to make surfaceness together with above-mentioned method.Such as, negative electrode conductively-closed can be penetrated (height) angle deposit minimize to make to plunder.Other method for obtaining more level and smooth surface comprises other means of the surface mobility using ion assisted sputtering or ion assisted deposition, plasma asistance sputtering or increase atom.Cathode type can be selected to be conducive to more level and smooth coating, such as, use " twin magnetic (twin mag) ", unbalanced magnetron, radio frequency superposition DC power, microwave radiation technology sputtering, high power pulse deposit, exchange sputtering or other this means.

Although use chromium as conductive layer in the example above, other metal of the explanation in the document that can be used in here in spirit of the present invention or add here, alloy or laminated coating material.Other material may need other process conditions to obtain smooth surface.Such as ITO may not have smooth surface under for the preferred condition of metal.When ITO, change configuration of surface by many state-variables.Compared with the situation of metal, the situation of the surface property of control ITO is more challenging.ITO not to resemble metal always electric conductivity, and, can cause some technique of level and smooth coating that the coating that may not cause highly conductive with ITO is set for metal.Therefore, be quite challenging according to other Properties Control form of material.Usually, high temperature coated on glass or other vitreous substrate, can arrange the coating of lower acquisition relative smooth above as illustrated in this document at high pressure and relatively high oxygen.Other material of multilayer that also can will be used for making the change application of the technological parameter of coating smoothing in the TiO2 such as instructed in half-transmitting and half-reflecting coatings applications or such as TiO2 and ITO.

As mentioned above, roughness is generally along with the thickness of coating increases.Above-mentioned technique arranges the coating being usually not enough to cause having acceptable roughness levels.Like this situation needing extremely low sheet resistance value is exactly.In this case, substituting means are needed to have to obtain the coating that relatively low surfaceness has lower sheet resistance value simultaneously.

In commonly assigned U.S. Patent Application Publication No.2006/0056003, the substrate of coating introducing ion beam as the means for making the coating in regional area thinning, adding the whole of this patent at this and disclosing as a reference.As discussed in detail, ion beam also can be used to make rough coatings (as shown in figure 37) smoothing (as shown in Figure 33 a and Figure 33 B) here.Other method of instructing individually or can be combined here and use ion beam, to reduce the roughness of coating and to increase reflectivity thus.Ion beam source changes on Design and Features.For the object of discussion here, can be suitable with any design of the energy range illustrated here transmission ion current.

Ion beam is one group of energetic positive ions or the negative ion of collimation relatively.The energy of ion becomes with the operation electromotive force of ion beam.The flowing of ion or ion current are become with the background pressure in operation electromotive force and the amount of gas be fed to by ion beam and room.Wish that ion has enough energy with etching, grinds off and/or smoothing coating material.The example of Related Phenomena is the example of billiard ball.The ion entered is considered as mother bulb and coating is considered as the tripod of ball of playing when starting.If mother bulb hits tripod with low-down energy, so tripod does not scatter.On the contrary, if mother bulb is with the impact of higher energy, so tripod can scatter fiercely.

Figure 34 illustrates the sputtering output become with argon ion energy for various material.There is the threshold energy not occurring sputtering or occur minimum sputtering.Along with energy increases, sputtering output increases.Ionized atom also may affect sputtering rate.The preferred mass with the plasma sputter of maximum sputtering output changes with the energy of plasma sputter and the quality of the atom that will be sputtered.Figure 35 illustrates the sputtering output become with the plasma sputter under 500eV ion energy and sputtered atom quality.Be called that the computer simulator of " Stopping and Range of Ions in Matter (SRIM) " produces the data shown in Figure 35 by using.Shown here will produce the scope of the best sputter gas mass of ion of acceptable sputtering output for given target atom quality.Usually, along with beam energy increases, the best in quality of ion increases to make sputtering maximum production.To a certain extent, preferred ion will depend on the quality of sputtered atom.Obtain best energy and momentum, the transfer of atom should have relatively comparable quality.Figure 34 illustrates that threshold energy depends on the material of sputtering.The more energy of other material consumption of the release ratio of some materials.The diagram of Figure 34 also illustrates, on the relatively high energy of ion, sputtering output tends to be platform.On the energy that these are relatively high, process starts to enter in the region of ion implantation instead of ion sputtering.Sputtered efficiently or etched, ion energy should higher than 100 electron-volts, preferably higher than 500 electron-volts, most preferably higher than 1000 electron-volts.

With reference to Figure 36 and Figure 37, smoothing effect is shown.In Figure 36, ionic bombardment is on smooth surface.When ion hits surface, energy is transferred in the mode parallel with vertical with surface simultaneously.Can cause vertical with some in the energy that surface is shifted abreast and leave the component on surface, this component causes the injection of atom.In Figure 37, same ionic bombardment is on rough surface.Be appreciated that ion more may be penetrated from coating.Major part in the energy vertically guided with surface may cause the injection of atom; There is surf zone and the direction that more can discharge atom.Along with ion milling process continues, coating becomes more and more level and smooth.In the example of these and other, ion beam comprises single atom.In practice, the group variety of ions/atoms can be used to replace each single ion.Also can use the known method for generation of group variety in this case.

Similarly, the ion beam struck at an angle on surface can have obviously higher sputtering yield and smoothing effect.In this case, angled ion beam can have higher transversely by probability that material penetrates for coating surface.

As described below, the roughness restriction in the reflectivity of specific half-transmitting and half-reflecting coating, transmissivity, absorption and surface resistance performance tegillum.A kind of relevant coating is the glass/ITO/Si/Ru referred to herein as " option 4 ".ITO is preferably respectively 3/4 or 5/4 wavelength coating of 2100 or 3600 dusts.Si layer is about 220 dusts, and layer of ruthenium is about 70 dusts.Same such as discussed below, the different variants of this lamination are possible.The reflectivity of this lamination and transmissivity depend on surface and interface roughness especially.When considering to comprise the such as option 4 of dielectric, semiconductor layer, transparent conductive oxide and metal multilayer laminated, the roughness on interface roughness and surface so must be considered.

Table 15 illustrates the ion milling effect on the surface of in the ITO-bottom used in option 4 lamination.By using ellipsometry determination data with characterizing coating.Table 15 also illustrates the initial performance of ITO coating.The initial roughness of 3/4 and 5/4 wavelength coating is respectively 7.4 and 11.5nm.These values are relatively high.The Dan Shu (38cm long shot bundle) run under 270mA electric current and 3000 volts when being used in the argon gas be fed under being used in 20sccm carries out ion milling to sample, and the on-stream pressure in room is 2.5mT.Ion beam is the design of closed drift Hall effect anode stratotype.The linear velocity of 2B (two beams suitable on 30ipm) situation is the linear velocity of 15ipm, 4B (four beams suitable on 30ipm) situation is 7.5ipm.The direction of ion beam is vertical with the surface of coating glass.Ion beam removes about 17nm/ beam suitable on 30ipm for 3/4 wavelength ITO, and removes about 11.1nm/ beam suitable on 30ipm.Surfaceness all sharply declines in both cases, makes 3/4 wavelength ITO become almost Perfect ground smoothly.But 5/4 wavelength ITO does not become level and smooth like this, because it is from much coarse original state, therefore it can need slower linear velocity or additional ion beam to obtain minimum roughness value.

Table 15: the ITO performance of ion milling

The crucial reflectivity that proves increases greatly with ion milling process.In table 16a, the ITO coating illustrated in fig .15 is coated with the Ru of Si and 7nm of the 22nm that has an appointment outward.Due to the higher reflectivity of these coatings, therefore transmissivity generally reduces with ion milling.The more important thing is, be quite low by the absorption of the ITO sample of ion milling.This causes the light source of being correlated with to pass the higher light output of coating in identical reflectivity levels.When all these coatings are normalized to identical reflectivity levels, difference is just more obvious.In order to obtain identical reflectivity levels for nonionic milling part, greatly increase the thickness of layer of ruthenium.This reduces transmissivity further again and increases absorption, and this is undesirable in some applications.

The goods (lite) of these coatings listed by table 16a are added in the photoelectricity mirror element of table shown in 16B, to evaluate the optics in actual EC element.Make many 2 inches × 5 inch cell and measure transmissivity and reflectivity (minute surface and non-specular surface).The increase of the reflectivity of the element of assembling is relevant to the result of observing in each individual data.Although the color of reflection is quite neutral, the color of transmission be partial to very much amber.This means this design ruddiness that tranmittance blue light is many due to the structured material of its uniqueness.When red display is such as positioned at after mirror element, this can be particularly advantageous.

Table 16B also illustrates that the minute surface for sample element gets rid of reflectivity (Spec Ex) data.Ion milling makes surface smoothing, and this reduces scattered light substantially.Because the amount of scattered light is little, the image therefore obtained is clearly with distinct.

Many motor corporations have regulation must higher than the specification of 55% for outside mirror application reflectivity.This specification of the discontented foot of initial raw tolerance on the ITO of nonionic milling sample.The sample of ion milling, even if 5/4 wavelength ITO part, also meets this specification.The switching speed of mirror element particularly dimmed speed dependent in the surface resistance of coating.By using the ITO of 5/4 wavelength ITO or thicker, ion beam milling allows while meeting reflectivity requirements, have switching time faster.In addition, some in 3/4 wavelength elements have the reflectance value substantially exceeding minimum requirement.Can by reducing ruthenium or adjust these coatings as the thickness of other high-reflectivity metal of top layer, to make them, there is higher transmittance values, now overall design demand is benefited from this change.If do not have ion beam smoothing method, the usable range of reflectivity and transmissivity option can be restricted.

Table 16a

Table 16B: the cell data of reference ion milling partial properties

Sample ID	Reflectivity	a ^＊	b ^＊	Transmissivity	a ^＊	b ^＊	Spec Ex
								3/4 wavelength	54.2	-1.5	2.3	11.5	2.9	21.7	0.7
3/4 wavelength 2B	57.6	-0.2	3.1	10.4	0.9	21.6	0.2
								3/4 wavelength 4B	59.3	-0.7	4.4	10.0	1.0	19.1	0.3
3/4 wavelength 4B	58.5	-0.4	3.6	10.3	0.7	20.5	0.3

5/4 wavelength	50.1	-2.0	4.0	10.8	3.9	18.2	1.1
								5/4 wavelength 2B	52.9	-0.6	3.6	11.0	2.1	19.8	0.8
5/4 wavelength 2B	52.1	-0.6	3.6	11.5	2.0	19.7	0.8
								5/4 wavelength 4B	55.6	-0.3	3.9	10.0	0.1	20.4	0.5
5/4 wavelength 4B	55.3	0.0	3.2	10.2	0.6	20.8	0.6

In Another Application, use ion milling to be used in the ITO smoothing of non-half-transmitting and half-reflecting application.In this case, coating is glass/ITO/Cr/Ru.Chromium in epoxy sealing and ruthenium are covered, and ITO is used to transmit electric current from electrode to EC element internal.ITO has the roughness to a certain degree reduced by Ion Beam Treatment.Figure 38 represents that roughness is along with the reduction of linear velocity inverse on fixing feam column.In another example, the linear velocity through the glass of coating machine is 30 feet per minute (ipm).Use single ion beam, and adjust electric current to change ion milling speed.Figure 39 illustrates the increase of reflectivity and the relation of feam column.Namely the reflectivity using the ion milling condition of this appropriateness also to obtain 0.5% increases.In these examples, ITO coating maintains its initial roughness may be conducive to the cementability of the epoxy resin increased in ITO and sealing area, carries out milling with the optical property be improved to the ITO in viewing area simultaneously.

In the Another Application using ion milling, color and the reflectivity of the ring-like coating of so-called chromium are studied.In this application, multiple layer metal coating is applied at the top being in the ITO coating on glass.In the ring of component ambient to the glass of coating ITO carry out ion etching with in this position by thinning for ITO coating with the color improving chromium ring lamination and reflectivity, realize the lower surface resistance of thicker ITO at the center of this part simultaneously.Figure 40 illustrates the reflectivity of the different condition when observing through glass.The reflectivity of ion milling is not had to be illustrated as thick line.The reflectivity with several different linear velocity is also illustrated.Along with speed reduces, the residence time under beam increases and roughness reduces.This causes the increase of reflectivity.Reflectivity appears as platform, but there are some arc discharges of beam in these trials, this may have adverse effect to result.It is crucial as a result, by ion milling, even if when there is arc discharge, reflectivity also increases.Figure 38 shows the change of the ITO roughness in these tests and the relation of the linear velocity under the condition not having an arc discharge.

Another battery of tests inspection in same coating machine has the color of the chromium ring of ion milling.Linear velocity is adjusted to change ITO removal amount.ITO starts with 1/2 wavelength, and target thickness is reduced to about 80% of 1/2 wavelength to be namely reduced to about 115nm from about 145nm.Figure 41 illustrates the b of the reflection of the chromium ring with linear velocity adjustment ^*.As illustrated in the priority document that here adds as a reference, the b of reflection ^*directly relevant to the thickness of ITO.The b of 1/2 wavelength ITO coating ^*for about 16.Along with linear velocity reduces, the amount of etching material reduces.In at least one embodiment, the b mating namely about 2.5 with center viewing area desirable is wished ^*.Therefore, linear velocity should be about 12.5ipm.When needs faster linear velocity time, more ion beam can be used.

Reduce in another example of sheet resistance value in hope, research ion milling is for the impact of reflectivity and materials'use.As mentioned above, coating roughness with thickness increase and reflectivity reduce with thickness.In the present example, the coating with 1.5ohm/sq of the Rotating fields with glass/chromium/ruthenium is wished.Chromium thickness is set as about 2500 dusts to provide most contribution to surface resistance.Ruthenium is starting to be set as 400 dusts.When surface is completely level and smooth, obtain maximum reflectivity by with the little ruthenium to 180 ~ 200 dusts.Use the level of 400 dusts to ensure that ruthenium is enough thick in the rough surface how much compensating chromium.Additional ruthenium increases reflectivity but too increases cost.

Figure 42 illustrates the reflectivity of Ion Beam Treatment for the layers of chrome applied before layer of ruthenium and the relation of linear velocity inverse.Feam column is set as about 250mA.Under the linear velocity of about 4 inch per minute clocks, coating obtains its maximum reflectivity of almost 70.5%.The further reduction of linear velocity does not cause the extra increase of reflectivity.If wish linear velocity faster, the beam of interpolation so can be used.

Figure 43 illustrates the ruthenium that how may use the amount decreased due to the smoothing effect of ion beam in coating process.Linear velocity is about 2.1ipm, and the result in feam column and Figure 42 is suitable.The little ruthenium to 160 dusts can be used to obtain maximum reflectivity.Relative to using extra ruthenium to compensate the baseline case of the thickness of initiation layer, this causes cost greatly to reduce.In addition, when not having ion beam smoothing, the 1.5ohm/sq coating of the chromium and ruthenium with relatively high reflectivity may be even unpractiaca.

Usually, in the roughness without any the coating made when making the special effort of smooth finish by about 10 ~ 20% of the gross thickness for coating.Table 17 illustrates the thickness of the chromium/ruthenium lamination obtained required for various sheet resistance value.The volume resistance of layers of chrome changes to obtain different sheet resistance value with the thickness demonstrating layers of chrome by how changing to change along with volume resistance.Can used as the example of chromium volume resistance performance change, or can be regarded as and prove when by the means occurring what situation when there is the material substitution chromium of volumetric resistivity value of difference or change.

The scope of roughness is calculated as 10% and 20% of ulking thickness in fig. 17.Ruthenium is set as 200 dusts, and this thickness has just been a bit larger tham the thickness required for the maximum reflectivity obtaining this material in desirable application.If layers of chrome is level and smooth, or by ion beam by smoothing, the reflectance behavior that so demonstration of this thickness is best.Result of calculation when table 17 to illustrate the thickness of ruthenium compared with gross thickness.The contribution of roughness is regarded as 10 and 20% mean value of situation.As the number percent of the lamination of ruthenium with the targeted sheet resistance of lamination and the volume resistance with chromium or basic unit change.If surface resistance is more than or equal to 6ohm/sq, so wish that ruthenium or other high-reflectivity metal are less than 50% of gross thickness.If the surface resistance of lamination is about 2ohm/sq, so ruthenium thickness should be less than about 25% of gross thickness.The percentage thickness of high refractive index layer also changes with the volume reflection rate of this metal and reflectivity target.The suitable high reflectance number percent of the gross thickness surface resistance with the reflectivity of the hope of lamination, the hope of lamination and the volume resistance for the different material that builds lamination and become.The number percent of highly reflective material should be less than gross thickness 50%, be preferably less than gross thickness 25%, be more preferably less than gross thickness 15%, be more preferably be less than gross thickness 10%, be most preferably less than 7.5% of gross thickness.In the present example, chromium and ruthenium are used to the benefit proving one embodiment of the present of invention.As the most means providing surface resistance, other metal can be used to replace layers of chrome.So-called high-reflectivity metal is defined as the metal relative to the most layer of contribution statement surface resistance with higher reflectivity.In the present example, the effect that we discuss most top layer has higher reflectivity relative to conductive layer.In other embodiments, (one or more) conductive layer may have unacceptable color or tone.Reflectivity intensity may be acceptable, but the color of reflection may be considered to unsatisfactory.In the present embodiment, the high refractive index layer of top may in fact be not used in increases reflectivity and is to provide acceptable color.In one example in which, conductive layer can be highly colored, and the color of preferred neutral reflection.In this case, so-called high refractive index layer is used in and makes color more neutral.

In another embodiment, conductive layer can have neutral reflection color, and the reflection that preferred heights is painted.Here, the high-reflectivity metal at top can be selected to provide the outward appearance of non-neutral.In another embodiment, can applying multilayer laminated on conductive layer, while making to be stacked in the dirigibility had by adjusting the multilayer laminated adjustment color be placed on conductive layer, obtaining lower surface resistance.In the present example, multilayer laminatedly metal, dielectric layer and/or semiconductor layer is comprised.Comprise the material of lamination, they thickness, relative to the selection of the orientation of conductive layer and adjacent medium, the design criteria by given application is determined.

Table 17: sheet resistance analysis

Owing to reducing for various application surface resistance, therefore thickness must increase and surfaceness increases and reflectance reduction thus.The reflectivity of coating thus the low value that will be reduced to relative to theoretical maximum.Sheet resistance value as desired value is lower, and the number percent of the theoretical maximum reflectivity value so obtained is lower.For the coating of surface resistance with about 6ohm/sq or less, the technology illustrated here by allow to obtain be greater than theoretical maximum 90% and be preferably greater than the reflectivity of about 95% of theoretical maximum.For the coating of surface resistance with about 3ohm/sq or less, the technology illustrated here by allow to obtain be greater than theoretical maximum 80%, be preferably greater than theoretical maximum about 85%, more preferably greater than theoretical maximum about 90%, be most preferably greater than theoretical maximum about 95% reflectivity.For the coating of surface resistance with about 1.5ohm/sq or less, the technology illustrated here by allow to obtain be greater than theoretical maximum 75%, be preferably greater than theoretical maximum about 85%, more preferably greater than theoretical maximum about 90%, be most preferably greater than theoretical maximum about 95% reflectivity.For the coating of surface resistance with about 0.5ohm/sq or less, the technology illustrated here by allow to obtain be greater than theoretical maximum 70%, be preferably greater than theoretical maximum about 80%, more preferably greater than theoretical maximum about 90%, be most preferably greater than theoretical maximum about 95% reflectivity.

In commonly assigned U.S. Patent Application Publication No.2006/0056003, discuss various metal laminated for " chromium ring " mirror element, add the full content of this patent as a reference at this.Thin chromium adhesive phase is deposited on ITO, and the metal level with higher inborn reflex rate is deposited in layers of chrome.Discuss various high reflectance metal.Describe and when observing coating from glass side outward appearance not contributed but to be applied to the second layer chromium of the transmissivity minimizing visible ray and UV light.Reducing visible ray is to hide encapsulant, and reduces UV and only will protect encapsulant when being exposed under daylight.Chromium is regarded as the low cost means of the transmissivity for reducing light in the present example, no matter this only UV light or visible ray.Other low cost metal can provide identical function, as long as they have good with sealing with the adhesiveness of high reflectance metal.

Also can increase the thickness of high-reflectivity metal simply to reduce light transmission simultaneously, but high-reflectivity metal is usually relatively costly, and is used alone these materials and can causes higher coating price.

ITO layer can be arbitrary transparent conductive oxide or other transparency electrode.Transparent conductive oxide or transparency electrode can comprise single or multiple lift.Each layer in multilayer can be selected as the color or the outward appearance that change reflection, makes " ring " have suitable optical property.A kind of such multilayer can comprise the color suppression layer (color suppression layer) between glass substrate and transparent conductive oxide.This layer is used to cause this ring when adjusting ITO layer and being thick to have more color selecting.

Adhesive phase can be the chromium of various composition, Ni, NiCr, Ti, Si or silicon alloy or other suitable adhesion enhancement layers." high-reflectivity metal " is selected from the metal and alloy with the volumetric resistivity value higher than chromium.Illustrative metal comprises the alloy of aluminium, ruthenium, rhodium, iridium, palladium, platinum, cadmium, copper, cobalt, silver, gold and these materials.Except alloy, these metals potpourri each other or the potpourri with other metal can also be used.Also multilayer can be used to replace the illustrated individual layer for high-reflectivity metal.Similarly, UV restraining barrier can comprise homogenous material, alloy, multilayer or cause suitably reducing other combination of transmissivity.

Adhesiveness also by using the Ion Beam Treatment illustrated to improve material, layer or coating here.Such as, by using argon gas and then passing through to use the combination gas of argon gas and oxygen to perform the Ion Beam Treatment on ITO surface.By these tests compared with nonionic milling surface.By epoxide resin material, sample is attached on test glass sheet to form the chamber of sealing.Hole at the top (top lite) of glass, and to chamber pressurization to determine the force value needed for chamber inefficacy.Failure mode can comprise adhesion failure in epoxy resin, epoxy resin is bonding with coating, and the fracture of glass or coating can cause losing viscosity with substrate, or can there is adhesion failure in coating.

ITO passes through on surface argon gas, argon gas/oxygen mixture by Ion Beam Treatment, or through process.Then use the thinner layers of chrome that about 50 dusts are thick and then pass through thick layer of ruthenium (the so-called Beta ring) coated surfaces of about 500 dusts.The glass of coating is engaged with another sheet glass by the epoxy resin used general in EC element, and then epoxy resin be cured.Force value when table 18 illustrates inefficacy and the metal-stripping amount from ITO coating.Control section has the metal-stripping of trace.Argon gas beam portion has obvious metal-stripping (metal lift), but pressure when losing efficacy is substantially the same.Use oxygen to have similar failure pressure value equally, but metal is eliminated from the stripping of ITO.Oxygen improves the adhesiveness of chromium and ITO.Ion beam is preferably as the sputtering oxygen of adhering composition contributing to chromium.The situation of argon gas is only had to cause minimizing of critical oxygen and poor joint.Can believe, oxygen is added to " healing " ITO surface in beam, strengthening engages and makes metal-stripping minimized thus.Because glass ruptures in test, force value when therefore losing efficacy does not show correlativity.This fracture determines that force value when losing efficacy also arranges test thus.In the present example, oxygen is required, but can exist can the situation of preferred other gas, or simple argon gas may be better selection.

Ruthenium is directly being deposited in another example on ITO, the change of sharply change and the failure mode of force value when observing inefficacy.When not using Ion Beam Treatment, force value during inefficacy is quite low, is about 6 ~ 7psi, and coating stripping is failure mode; Glass does not rupture.When with comprise oxygen beam treatment ITO surface and then from the teeth outwards deposit ruthenium time, the factor that force value increase during inefficacy is greater than 2, and glass breakage is main failure mode.Coating is still peeled off from ITO, but adhesion strength increases greatly.

Table 18: force value during inefficacy and the metal-stripping amount from ITO coating

A-Beta ring controls

B-adopts the Beta ring of argon gas ion milling

C-adopts the Beta ring of argon gas/oxygen ion milling

The top layer used in some applications can be conductive stable formed material.Its effect provides good conduction between ring metal and bus or silver-colored paste.Material can be selected from the platinum group metal of such as iridium, osmium, palladium, platinum, rhodium and ruthenium.Can use these metals potpourri each other or alloy or with the potpourri of other suitable metal or alloy.

As instructed in the patented claim of reference, thickness and the selection of the material in layer are preferably selected as providing suitable color and reflectivity intensity.The thickness of each layer also should be selected as obtaining required transmissivity performance.Transmission of visible light should be set up, and makes epoxy sealing when visualized be sightless.Transmission of visible light should be less than 5%, is preferably less than 2.5%, is more preferably less than 1%, is most preferably less than about 0.5%.UV transmissivity can or cannot be relevant definitely to transmission of visible light.When UV transmissivity, the outward appearance of ring is not problem, and the protection of sealing is major concern.This supposes that the sealing selected is for UV photaesthesia certainly.How responsive it is for UV light that the amount of admissible UV light depends on sealing.In the ideal case, coating should be designed so that ring coating is opaque for UV light, but unfortunately, the UV transmissivity of this level can be that cost is too high.In addition, if gross thickness becomes too large, the adhesiveness of so each layer can affect adversely.The stress that can exist in layer can cause straining enough large to cause each layer to be peeled off from other layer of glass or coating.For this reason, the UV transmissivity considering limited amount is needed.UV transmissivity should be less than about 1%, is preferably less than 0.5%, is more preferably less than 0.1%, is most preferably less than 0.05%.

Just changing to the feature that a popular feature/region is the half-open warning of car door (door ajar warning) using outside mirror to be ready opening with the Pedestrians and vehicles car door showing such as blinker, well heater ON/OFF indicator, warning contact.Mirror or mirror shell are also used to hold puddle lamp (puddle lighting) or approach signal lamp.

When with compared with the mirror outside vehicle time, these require for distinctive internal mirror.In at least one embodiment, the specular reflectance of internal mirror is preferably 60% or higher, and preferred mask in front of the display has enough transmissivities to make the light of q.s through relevant mirror element.Further, internal mirror need not tolerate the severe chemistry and environment challenge that run in outside mirror application.A kind of challenge be balance meet for the automobile specification of rearview mirror needs and comprise the hope of information center of aesthetic pleasant.Higher mirror element light transmission is provided to be a kind of means compensating limited light output display technique.Invariably, higher transmissivity causes mirror element circuit below and other hardware to be visible.Shading oxidant layer can be applied on the surface to tackle this problem the 4th of mirror element.

The blinker supplemented shown in Fig. 5 a is an example of the indicating characteristic of wishing in outside mirror assembly.A kind of mode adding signal characteristic after electrochromism mirror element is that some from element in laser ablation reflecting material are passed through to allow light.The motivation desirably using half-transmitting and half-reflecting mirror element technology of substituting style and design is provided.The half-transmitting and half-reflecting method of some embodiments of the present invention allows the feature in mirror to have more " secret " (hidden) outward appearance.Secret makes light to pass half-transmitting and half-reflecting element while the observation stopping light source.Secret or can also mean to there is minimum contrast alternatively between viewing area and principal reflection region.In some cases, it is desirable to clearly to indicate display or feature to provide framework (framing) effect by the contrast of color or reflectivity, make observer have the clearly instruction of the information where finding hope.The material of the routine utilized in outside mirror application generally has lower reflectivity and/or the higher surface resistance relevant to realizing noticeable level of transmittance.

Such as, ruthenium is often used to due to its relatively high reflectivity and environment durability in outside EC application.23nm Ru coating as the reverberator in EC element can have the reflectivity of about 57.5%, and this level can meet most business specularly reflected rate specification.This coating can have the surface resistance of about 20ohm/sq, and EC element can have the transmissivity of about 2.5%.Transmissivity and surface resistance are all infeasible for the application of reality.Other environment durability metal can have slightly different reflectivity, transmissivity and sheet resistance value, but does not all have the performance of the demand met in EC application.

Lower reflectivity requirements for OEC element makes it possible to more easily to meet preferred reflectivity, permanance and electrochromic property and idiocratically uses the difference of material to configure, and comprises for the silver of relevant reflection and/or semi-transmissive semi-reflective layer lamination, silver alloy, chromium, rhodium, ruthenium, rhenium, palladium, platinum, iridium, silicon, semiconductor, molybdenum, nickel, nickel-chromium, gold and alloy combination.Some in these materials have the advantage being better than silver or silver alloy, and reason is that silver and silver alloy are easy to impaired in outside mirror environment.In view of manufacture option and more durable final products, use harder metal for mirror element permanance be favourable.Also can make reflection and/or half-transmitting and half-reflecting lamination with the dielectric substance for the sufficiently high reflectivity levels of the generation in OEC element.

In visible ray intermediate range, reflectivity often reduces one of percentage, the transmissivity that the material based on Ag will generally obtain about 1%.The advantage relevant to increasing transmissivity is the light source that can utilize more low cost, lower light output, such as display or LED.Outside mirror is generally used for indicator type display, and these indicator type displays generally use the LED be customized with very high light output.Here the novel designs using the half-transmitting and half-reflecting coating based on Ag in inside and outside mirror application is openly made it possible to.The optical property of design uniqueness that protection obtains from Ag layer while solution uses the restriction based on the material of Ag in applications of these novelties and benefit.When low transmissivity be use have and do not have the design criteria of the lamination of the layer based on Ag a part of time, different coating options can be considered.The advantage that of low transmissivity is very large reduces or eliminates the demand for shading oxidant layer.

In much market, the size of mirror is increasing to allow larger visual field.The dimmed time of larger mirror is a kind of challenge and is the important consideration item in design option.The general larger mirror relevant to outside mirror needs conductance that is that add or that improve to maintain acceptable dimmed and cleaning speed.The above-mentioned former restriction for single thin metallic coating is solved by using transparent conductive oxide (TCO) innovatively in stacked.TCO is provided for the means realizing good conductance while the transmissivity maintaining higher level.Several examples below illustrate, can realize the transmissivity of the gratifying level being used for outside mirror with relatively thick tin indium oxide (ITO).ITO is a specific examples of wider TCO class material.Other TCO material comprises: ZnO, IZO etc. of F:SnO2, Sb:SnO2, doping.The metallic coating or multiple layer metal coating that can comprise single metal or alloy is scribbled outside tco layer.Such as, in order to be conducive to the adhesiveness between different materials, need to use multiple metal level.In another embodiment, can in addition or alternative metals layer add semiconductor layer.Semiconductor layer provides the performance of some uniquenesses be discussed later.When the thickness of ITO/TCO layer increases to improve conductance, need the impact considering coating roughness.The roughness added can cause lower reflectivity, and this needs again the metal thickness added, and the metal thickness added can reduce transmissivity.As illustrated in other places, the roughness added also can cause unacceptable fuzzy.By changing the deposition process of ITO and/or realized ion beam smoothing before the deposit of each layer subsequently after ITO deposit, roughness problem can be solved.Two kinds of methods are all discussed in detail above.In addition, the ITO material of above-mentioned improvement can be used in the present embodiment to reduce the surface resistance of overall half-transmitting and half-reflecting coating.

Semiconductor layer can comprise the silicon of silicon or doping.A small amount of (one or more) additional elements can be added to change the physics of silicon or optical property to be conducive to its use in different embodiments.The benefit of semiconductor layer is, with Metal Phase ratio, it improves reflectivity with less absorption.Another benefit of many semiconductor materials is that they have relatively low band gap.This equates the indigo plant of visible light to the noticeable uptake in green wavelength.The preferential absorption of one or more light belt makes coating have relatively pure transmitted colors.The transmittance values that high transmitted colors purity is equal to some part of visible ray or near infrared spectrum is greater than 1.5 times of the transmissivity of low regional transmission.More preferably, the transmissivity in high regional transmission is greater than 2 times of transmissivity in low regional transmission, is most preferably greater than 4 times of transmissivity in low regional transmission.Alternatively, the transmitted colors of half-transmitting and half-reflecting lamination should have the C being greater than about 8, being preferably greater than about 12, being most preferably greater than about 16 ^*value [sqrt (a ^{* 2}+ b ^{* 2})].Other semiconductor material causing half-transmitting and half-reflecting coating to have relatively high-purity transmitted colors comprises SiGe, InSb, InP, InGa, InAlAs, InAl, InGaAs, HgTe, Ge, GaSb, AlSb, GaAs and AlGaAs.Other feasible semiconductor material has those of the band-gap energy that is less than or equal to about 3.5eV.Wishing confidential nature and using in the application of danger signal, can the material of preferred such as Ge or SiGe potpourri.Ge has the band gap less than Si, and this causes the larger wavelength coverage with relatively low level of transmittance.Owing to being more effective from the lower transmissivity on the different wavelength of display for any feature after hiding mirror, therefore this is preferred.If need uniform transmissivity, the semiconductor material with relatively high band gap is so selected to be favourable.

Viewing area can be secret in itself, make display be activated or by backlight before observer can not perceive mirror there is display.When the reflectivity of viewing area is relatively similar with remaining viewing area and color or shade contrast's degree are minimum, realize secret.Because viewing area does not reduce the viewing area of mirror as discussed above, therefore this feature is very favorable.

A small amount of transmitted light can make the mirror of such as circuit board, LED array, guard shield and heater terminals feature below be visible.Light blocking (opaque) layer can be used to avoid this problem.Opaque layer is applied on the surface at the 4th of mirror often through using the various materials of such as pigment, ink, plastics, foam, metal or metal forming.In outside mirror, the task of applying this layer is complicated.Most outside mirror has projection or aspherical shape, and this makes the applying of film or coating become more difficult.

Opaque layer can be added in the 3rd surface stack of element.Half-transmitting and half-reflecting region can be covered, further, the such as ruthenium of suitable reflectivity and color (opacity), rhodium or other single or multilayer laminated (metal, metal/dielectric and/or dielectric) can be provided to provide on residual surface.When maintaining the color and reflectance match or mismatch of wishing, realize secret outward appearance.In a preferred embodiment, the viewing area of mirror element and main viewing area are visually undistinguishables.In other embodiments, may wish that half-transmitting and half-reflecting region has different colors with the contrast of pleasant aesthetically.

Another option in a part of visible light, maintains higher level of transmittance to obtain secret outward appearance with lower total transmittance.Also narrow spectral bandpass filters can be used to obtain secret effect.

When or not using coating or belt or other opaque material on the rear surface of element or except this service condition, the 3rd surface coating lamination relatively opaque layer (no matter whether its material is identical with the material in adjacent layer) being inserted other half-transmitting and half-reflecting may contribute to the electron device after hiding mirror element.Add this layer and can affect the reflectivity inserted in its region.Thus the reflectivity adjusted by selection material and their thickness in this region, make the viewing area of mirror element and the difference relatively between zone of opacity be very incognizable, the unification of the outward appearance of holding device thus.

Even if the reflectivity of intentional skew viewing area and/or tone also may be favourable to provide about will being in visual cues where when being presented at activation and providing some instructions also comprising Presentation Function when showing and closing in mirror.When using conductive material to increase opacity, the conductance of the relative opaque section of display is now larger, and, stride across and provide the major part of the viewing area of colouring speeds faster to there is correspondingly less voltage drop.(one or more) additional opaque layer can make reflectivity after from this region substantially lower than the situation not having (one or more) opaque layer, thus reduce can in addition from the effect of the multipath reflection of parasitic light appearance.Prove that a kind of such device of above-mentioned principle comprises the TiO of about 400 dusts ₂, be then 200 dusts substantially on whole 3rd surface ITO, be then about 90 dusts except the region roughly on display chromium, be then the 3rd surface coating lamination of 7% gold medal 93% silver alloy of about 320 dusts substantially on whole 3rd surface.

For with some spectrophotometer measurement reflectivity based on ball, the opening of the display on the interior automotive mirror of this particular model is too little, therefore, in order to be conducive to the measurement of the reflectivity of the different piece of lamination, make element by the different piece of lamination on the surface in their whole observation.Transmissivity and albedo measurement is carried out from the both sides, front and back of element.

Together with the table 19 of Figure 44 and Figure 45 and table 20, the measurement result obtained is shown respectively.

Table 19

Table 20

Can find out, for this specific example, chromium be added for lamination and adds opacity and reduce from the reflectivity after element.If increase the thickness of silver alloy in non-display area to realize opacity, the reflectivity do not reduced after from element so can be found out from this example, but, if omit chromium, the relatively high reflectivity of the back side from element so can be increased further.Also can find out, even if be enough for being used as half-transmitting and half-reflecting device transmission in viewing area, the viewing area of this design also has relatively little tonal difference and luminance difference when compared with having the region of the layers of chrome comprised.

It should be noted that in example above, by increasing or reduce the thickness of the ag alloy layer in half-transmitting and half-reflecting region, greater or lesser " blue biased (bias) " will be obtained respectively in the transmissison characteristic of this viewing area.After this region, use rgb video to show be benefited to maintain better color reproduction by the relative intensity adjusting redness, green and BLUE EMITTER.Such as, when transmission for the blue region of spectrum comparatively large and less for red area, may wish to reduce the intensity of BLUE EMITTER and increase the intensity of red emitters.Spectrum regardless of transmission is biased slight gradient or has the gradient of more obvious transmission bands, and such adjustment can be all suitable in the design of this half-transmitting and half-reflecting and the design of other half-transmitting and half-reflecting.

When show to use when mirror element is dimmed time, intensity adjustment can be carried out biased with any spectrum of the electrochromic media of compensating coating and activation.Intensity adjustment can become with the operating voltage of device and/or other feedback mechanism, suitably to mate relative RGB intensity for set point in the color displacement of electric driven color-changing part.Even if when using those the dyestuff that such as also can be used for generation " blue mirror " when electrochromism species are not activity, the intensity of emitter is adjustable to the color reproduction with improvement.Along with the reflectance reduction of mirror element, first and/or any spectrum of second surface coating is biased will become more factor; The degree of compensation of the intensity of the different colours of display can correspondingly be adjusted.UV absorbing agent and also can affect the visible absorption of element for other adjuvant of EC medium, can comprise intensity adjustment with the color reproduction improving relevant display.

It can be favourable for designing half-transmitting and half-reflecting coating for display and signal or the application of other indicator.When signal or when indicating required high output, the transmitted spectrum of half-transmitting and half-reflecting device can be biased to emphasize the transmission in this region.Have after all equicohesive RGB is presented at through semi-transmissive semi-reflective layer (and other parts of mirror element) in the redness of spectrum, green and blue portion and can have different intensity.Then the output by adjusting each single RGB color correspondingly compensates the skew of this intensity, to obtain suitable color reproduction.

The situation of more wishing the reflectance match between opaque and viewing area than the example in table 19 and table 20 may be there is.In addition, the benefit that reflectivity is mated in the scope of different reflectivity value may be there is.Like this, the transmissivity of viewing area can be adjusted when not damaging the reflectance match between opaque viewing area and viewing area.Another purpose of design is that color is mated in observation and viewing area, or makes them different in the mode making people joyful aesthetically.When hope exists minimum noticeable difference between the two regions, color-match can be useful.In other cases, there is reflectance match but have color mismatch with help by observer, the position be directed to residing for display can be useful.

Other means can be used with the reflectivity in independently reducing when observing the other way around zone of opacity further with first surface reflectivity.Another aspect of the present invention relates to the perceiveing of viewing area relative to opaque or viewing area.Observer only will see reflected light in viewing area, and observer sees the combination of reflected light and transmitted light in viewing area.Even if interpolation transmitted light can make the reflectivity in two regions be identical viewing area in this region is also apparent.Therefore, reflectivity in viewing area can be reduced to compensate the transmitted light added.

It should be noted that, in example above, the reflectance match between zone of opacity and viewing area becomes with the thickness of each layer.The thickness of chromium and AgAu7x is optimised, makes reflectance match be relatively close, still has relatively low transmissivity simultaneously.The reflectivity become with chromium and AgAu7x thickness shown in table 21 and the change of transmissivity.Data in table 21 are modeled data of the electric driven color-changing part of the top board of the ITO coating comprising the lamination of identification, the EC fluid of 0.14 micron and have 1/2 wavelength on a second surface.When layers of chrome is relatively constantly thin, and/or when AgAu7x layer is relatively thick, the reflectivity difference between opaque and viewing area is less.The method provides the means made and have and have the zone of opacity of goodish coupling and the mirror of display in some transmissivity and reflectivity range.

Table 21: the optical property calculating the lamination of gained when having and do not have opaque layers of chrome

Half-transmitting and half-reflecting example

Wish the means obtaining reflectance match while maintaining the high transmittance in the opaque and viewing area in viewing area in the wider scope of the reflectance value of hope.This point is realized at least one embodiment by adding extra play to the lamination illustrated in the example of table 21.This preferred 3rd surface stack is TiO2/ITO/AgAu7x/Cr/AgAu7x.By sputtering AgAu7x, obtain and in wider strength range, realize reflectance match and the ability with the transmissivity simultaneously controlling the lamination in zone of opacity.For the value that AgAu7x lamination illustrates before transmissivity in viewing area is limited to.

Layers of chrome is covered in the region of display, and other layer substantially can be present on whole surface or at least be present in the region of display.This example uses TiO2/ITO remainder quarter-wave bilayer (so-called GTR3 basic unit) to neutralize the silver of the half-transmitting and half-reflecting in the region of display or the color of ag alloy layer.Can be replaced in viewing area with layer in other half-transmitting and half-reflecting color, and in the scope of the present embodiment.Separately the layers of chrome of AgAu7x layer has in this application and is not only lamination and provides opaque characteristic and optically by novel performance that bottom and top AgAu7x layer are isolated.Figure 46 represents that how reflectivity changes with the thickness of layers of chrome.Can find out, on the thickness being a bit larger tham 5nm, thinner layers of chrome prevents the silver-colored gold alloy layer in bottom from having contribution to reflectivity effectively.This isolation is derived from the thin layer of this chromium, and the thin layer of this chromium allows chromium thickness to be adjustable to the transmittance values obtaining a certain scope, and the total reflectivity simultaneously for lamination affects without any noticeable (applicable).

A benefit of this method expands to viewing area.Owing to only needing thinner layers of chrome to have contribution to prevent bottom AgAu7x layer to reflectivity, therefore the thickness of bottom AgAu7x can be changed the design object obtaining other.Such as, the hope in zone of opacity and in viewing area as expressed with reflectance match can be realized above.Have in the example in the region of relatively high transmissivity and lower transmissivity in half-transmitting and half-reflecting mirror element, term " opaque " means that instruction level of transmittance is enough low with the outward appearance hiding parts when or not adding opaque material on the surface the 4th after the 4th surface.In certain embodiments, transmissivity should be less than 5%, is preferably less than 2.5%, is more preferably less than 1% and is most preferably less than 0.5%.Because AgAu7x is spaced in zone of opacity, thickness therefore can be adjusted as required to obtain the reflectivity of hope in viewing area.AgAu7x top layer will have higher reflectivity when being deposited to Cr above to TiO2/ITO (being present in viewing area).Bottom AgAu7x thickness can be set up, and makes the reflectance match of viewing area and zone of opacity.The reflectance value of mirror element can be low as the reflectance value of simple layers of chrome, and can reach the reflectivity of thick AgAu7x layer.Reflectivity can be adjusted to the value of any hope over this range, and transmissivity also can be adjusted.The reflectance match of the hope between viewing area and viewing area is also obtainable.

The layer of argentiferous can be the combination of other alloy except 7%Au93%Ag or alloy.Such as, it can be favourable that the alloy under these layers of alloy ratio on opaque layer has more gold.This may be due to the reason obtaining more durable interface between opaque layer and the upper strata of argentiferous, color is wished or the permanance of upper strata in processing procedure or when contacting with electrochromic media of argentiferous is relevant.If two Ag containing layers comprise the easy material spread in silver of such as gold, platinum, palladium, copper or the indium etc. of different levels, the half-transmitting and half-reflecting region that so silver layer no longer has an opaque layer that one or more is got involved may become average weighted alloy as upper and lower alloy after process or certain hour.Such as, if silver-palladium alloy is used as the upper strata of argentiferous and silver-billon is used as lower floor, so half-transmitting and half-reflecting region may become Yin-Jin-palladium ternary alloy layer.Similarly, if the silver of gold using the silver comprising the gold of 7% of same thickness and comprise 13% is as two Ag containing layers, the layer in the half-transmitting and half-reflecting region so obtained may be have the equally distributed layer comprising the silver of the gold of 10% substantially.

Opaque layer can be each the independent layer combined in half-transmitting and half-reflecting region, and wherein, one or two or all layers can not comprise silver.Such as, among many possible combinations, the structure of silver alloy on silicon or the structure of ruthenium on silicon can be used in half-transmitting and half-reflecting region.

Can also will add in above-mentioned design at the flash of light outer covering layer adding the material mentioned in its full content United States Patent (USP) 6700692 as a reference at this, these flash of light outer covering layers are useful for flash layer, and they comprise tin indium oxide, other conductive oxide, platinum group metal and their alloy, nickel, molybdenum and their alloy and other material.According to thickness and the optical property of the material selected for flash layer, may need to adjust to maintain similar coupling or mismatch between relative zone of opacity and half-transmitting and half-reflecting region to bottom laminate layer.

As mentioned above, the transmissivity that can obtain in " opaque " region depends on based on the layer of silver and chromium or " opaque " layer.Layers of chrome is thicker, then the transmissivity under given reflectivity levels is lower.Layers of chrome can be thinned to the level of hope with the transmissivity close to viewing area.If need higher level of transmittance, be so usually difficult to the thickness controlling very thin layer.If metal opaque layer is partially oxidized, so thicker layer can be used.Thicker layer may be needed to obtain the higher transmissivity relative to thinner pure metal layer.Figure 47 illustrate from table 21 above lamination and use CrOx layer as the relation between the transmissivity of the situation of opaque layer and reflectivity.Figure 47 illustrates for different opaque layer and the transmissivity of thickness and the relation of reflectivity.The AgAu7x layer of the symbology different-thickness in figure.Thicker layer on the right, thinner layer on the left side.

Can find out, when the thickness of AgAu7x layer is thinned, reflectivity is close to the value of chromium or opaque layer.The thickness of opaque layer will affect the low side reflectivity of mirror element.Such as, when Cr layer be 10nm thick time, low side reflectivity is 41.7%, when Cr layer be 20nm thick time, it is 50.5%, when Cr layer be 30nm thick time, it is 52.7%.Along with the thickness of opaque layer increases, low side reflectivity close to steady state value, but, for thinner layer, when layer is too thin, will the decline of reflectivity be there is.According to the design criteria for given application, this may be favourable or disadvantageous.By replacing layers of chrome with different materials completely or by adding additional layer, overcome for the restriction between the reflectivity of layers of chrome and transmissivity.

To teach on including ag layers with reference to United States Patent (USP) 6700692 or on there is different metals, semiconductor, nitride or oxide.Select these layers and material to provide the improvement for lamination.Teaching can for the basic unit under the reverberator of conducting metal, metal oxide, metal nitride or alloy.Also can there is middle layer between basic unit and reflecting material.These metals and material can being selected, making not exist between the layers electricity reaction (galvanic reaction) and/or for improving and substrate and the adhesiveness with reverberator or other layer.Can on substrate these layers of deposit, or the extra play of the characteristic of the hope providing additional can be there is under above-mentioned basic unit.Such as, the dielectric pair comprising TiO2 and ITO with effective odd number quarter-wave optical thickness (effective odd quarter optical thickness) can be there is.The thickness of TiO2 and ITO layer can be adjusted as required to meet specific conductance and optical requirement.

When below Ag containing layer during deposited metal, the alloy of the self-contained chromium of this metal layer optional, stainless steel, silicon, titanium, nickel, molybdenum and chromium/molybdenum/nickel, nickel/chromium, molybdenum, nickel-base alloy, inconel, indium, palladium, osmium, tungsten, rhenium, iridium, molybdenum, rhodium, ruthenium, stainless steel, silicon, tantalum, titanium, copper, nickel, gold, platinum and composition are mainly the alloy of above-mentioned material, other platinum group metal any and the group of their potpourri.In addition, the layer below reflector layer can be oxide or the metal oxide layer of such as chromium oxide and zinc paste.

The group of the self-contained rhodium of optional metal layer optional, ruthenium, palladium, platinum, nickel, tungsten, tantalum, stainless steel, gold, molybdenum and their alloy on Ag containing layer.

The disclosure divides imagination opaque layer in conjunction with the transflective portion of mirror or optical element.This to make new advances or the design criteria that increases, the impact of this design criteria is for reducing the selection of the metal of the transmissivity in some region of element or mirror.Table 22 below represents reflectivity and the color of various suitable basic unit on the TiO2/ITO dielectric layer in EC unit or opaque layer metal.The thickness of all metal levels is 30nm.Thickness with metal level changes by color and reflectivity.Table 22 illustrates the various suitable color of metal opaque layer when the relatively thick and AgAu7x of opaque metal or other do not exist containing Ag top layer, on the reflectivity of lower end and the relative different of reflectivity.As is well known in the art, these metals each other or will different optical properties be had from the alloy of other metal.In some cases, the behavior of alloy is by the potpourri as each single metal, but in other cases, alloy does not have simply as the reflecting properties of the interpolation of each single metal.Metal or alloy can be selected as required for their electrical property, reflectivity, color or other performance.

Containing in argentum reflecting layer, when being deposited on these different metal or alloy, the reflectivity of lamination and color will change.Table 23 illustrates the metallic lamination of the bag of the AgAu7x at top with 20nm.By being used as color and the reflectivity of the including ag layers lamination of the performance change 20nm of the metal of opaque layer.The transmissivity of different lamination is also shown.What as above regard to that chromium represents is such, can change transmissivity, reflectivity and color by the thickness changing opaque metal.Can be clear that very much from these examples, the performance by changing (one or more) opaque metal layer obtains color, transmissivity and the reflectivity of wishing.

Table 22: the reflectivity and the color that are in the various metals in the EC unit at the top of TiO2/ITO substrate system

Lamination	RCapY	a ^＊	b ^＊
				Glass/45nm TiO2/18nm ITO/30nm Mo/0nm AgAu7x	45.9	-2.2	1.6
Glass/45nm TiO2/18nm ITO/30nm Au/0nm AgAu7x	50.8	1.3	16.6
				Glass/45nm TiO2/18nm ITO/30nm NiCr (80/20)/0nm AgAu7x	52.8	-2.1	4.4
Glass/45nm TiO2/18nm ITO/30nm Si/0nm AgAu7x	36.9	-0.8	-3.4
				Glass/45nm TiO2/18nm ITO/30nm Pd/0nm AgAu7x	55.8	-2.2	4.0
Glass/45nm TiO2/18nm ITO/30nm Os/0nm AgAu7x	37.4	-0.9	-9.8
				Glass/45nm TiO2/18nm ITO/30nm W/0nm AgAu7x	39.3	-0.2	4.8
Glass/45nm TiO2/18nm ITO/30nm Rh/0nm AgAu7x	63.9	-1.3	2.2
				Glass/45nm TiO2/18nm ITO/30nm Ru/0nm AgAu7x	60.3	-2.3	1.1
Glass/45nm TiO2/18nm ITO/30nm Ir/0nm AgAu7x	56.0	-2.9	3.7
				Glass/45nm TiO2/18nm ITO/30nm Cu/0nm AgAu7x	48.4	-2.1	7.4
Glass/45nm TiO2/18nm ITO/30nm Pt/0nm AgAu7x	51.2	-1.8	5.4

table 23: the reflectivity and the color that are in various metal in the EC unit at the top of TiO2/ITO substrate system and AgAu7x

Table 23

Lamination	RCapY	a ^＊	b ^＊	Transmissivity
					Glass/45nm TiO2/18nm ITO/30nm Mo/20nm AgAu7x	73.2	-2.8	3.8	2.1
Glass/45nm TiO2/18nm ITO/30nm Au/20nm AgAu7x	78.4	-3.0	8.4	6.3
					Glass/45nm TiO2/18nm ITO/30nm NiCr (80/20)/20nm AgAu7x	77.3	-3.1	4.2	1.9
Glass/45nm TiO2/18nm ITO/30nm Si/20nm AgAu7x	62.7	-2.0	0.5	15.8
					Glass/45nm TiO2/18nm ITO/30nm Pd/20nm AgAu7x	78.8	-3.0	3.9	2.1
Glass/45nm TiO2/18nm ITO/30nm Os/20nm AgAu7x	66.6	-1.0	-0.5	7.3
					Glass/45nm TiO2/18nm ITO/30nm W/20nm AgAu7x	70.4	-2.5	6.1	3.8
Glass/45nm TiO2/18nm ITO/30nm Rh/20nm AgAu7x	80.9	-2.6	2.9	0.9
					Glass/45nm TiO2/18nm ITO/30nm Ru/20nm AgAu7x	78.5	-3.0	2.6	0.4
Glass/45nm TiO2/18nm ITO/30nm Ir/20nm AgAu7x	78.3	-3.2	3.8	1.4
					Glass/45nm TiO2/18nm ITO/30nm Cu/20nm AgAu7x	76.4	-3.2	5.5	3.1
Glass/45nm TiO2/18nm ITO/30nm Pt/20nm AgAu7x	76.8	-3.0	4.7	2.2
					Glass/45nm TiO2/18nm ITO/30nm Cr/20nm AgAu7x	76.6	-3.0	2.4	1.4

By metal opaque layer and the dielectric illustrated in United States Patent (USP) 6700692 are in addition combined, the color increasing further or strengthen in viewing area and reflectivity adjustment capability.Dielectric layer can change color and reflectivity, and this change is usually significantly do not affect for the absorption of lamination.

In order to the color in viewing area and reflectance match, the double-deck basic unit containing illustrating before below argentum reflecting layer can be used.Table 24 illustrates how AgAu7x layer, reflectivity and the color for fixing changes with the change of ITO and TiO2 thickness.Can find out, double-deck thickness not only affects reflectivity, and color also can be adjusted.Thus these layers can be adjusted as required to obtain reflectivity and the color of hope simultaneously.By adjustment AgAu7x or the thickness containing argentum reflecting layer, further expand the adjustable of color and reflectivity.By adding additional dielectric or metal level as a part for display lamination or the refractive index by changing dielectric layer on or below Ag containing layer, additional color and reflectivity change can be obtained.

Table 24: for fixing argentiferous thickness with viewing area in color and reflectivity change with the change of TiO2 and the ITO thickness of basic unit

Table 24

Such as, when the color in viewing area is by the selection of the metal under argentum reflecting layer or due to argentum reflecting layer self or when being biased by yellow, blueness, green or redness by the combination of each layer, color and/or reflectance match can be realized by each layer in adjustment viewing area.A benefit of the method is, substantially each layer can be applied on whole surface, but, due to the optics shielding performance of the uniqueness of opaque layer, therefore these bottoms are for observe or reflectivity in zone of opacity and color are not contributed, but worked completely by the viewing area of covering in opaque layer.The layer that the invention is not restricted to make to work in viewing area covers whole part.This is specially adapted to the layer under opaque layer.If manufacture process permits the method, so can as required only display general area in these layers of deposit.

In some cases, it may be favourable for making reverberator and/or half-transmitting and half-reflecting device be bluish in the tone of reflection.Combine the zone of opacity blue reflector region in identity element and be with blue half-transmitting and half-reflecting region also can be favourable for the outward appearance of secret.

It is known for manufacturing blue color electrochromic element, uses dyestuff like that, even if this blue color electrochromic element also has blue color when not being applied to the electromotive force on them by the United States Patent (USP) 5278693 such as added as a reference at this.Also there is use the 3rd surface coating lamination to make the practical methods of this device of the exemplary requirement of satisfied outside automobile electrochromic device.These technology also may be combined use.This device must have the reflectance value higher than 35% of the U.S. and 40% of Europe at present.Preferably, at least one embodiment, preferably higher than 50% or 55% reflectivity.No matter utilize what the 3rd surface stack, all need in electrochromic device chemistry and physics and electric on there is permanance.

Can obtain bluish electrochromic device by following steps: deposit one deck chromium on dense glass substantially, then on its top, deposit is about the ITO of 900A, then completes the structure of electrochromic device.The coating stack made by this way and use has the reflectance spectrum shown in the color value shown in table 25 and Figure 53.Value when table 25 and Figure 53 represent that coating is on the glass of single-piece and after adding in EC element.

When by the coating on the glass measured in atmosphere compared with the reflectivity of the device completed time, will exist obvious reflectivity decline.In order to compensate, except there is the layers of chrome of similar top layer or alternatively, it is contemplated that the opaque layer that can use silver or silver alloy.But the optics of silver makes more to be difficult to obtain the blue coating of high reflectance band on silver-based material.This part is because the slightly yellow spectrum of silver is biased, and due to a kind of so true, namely, due to reflectivity on visible spectrum very close to 100%, therefore can do for interference capability increase the silver in any part of spectrum reflectivity be little to give the work of its obvious color.

But, if between chromium silver or the semitransparent layer of silver alloy put in superincumbent lamination and ITO, so still reflectivity can be increased significantly, maintain bluish color and increase the conductance of the 3rd surface reflector electrode.

According to the instruction comprised in this document, when there is the semitransparent layer of silver, by adding in color and bottom also " separate " region that the silver-colored and opening covered in chromium makes half-transmitting and half-reflecting.

Such as, the silver of ITO, 14nm of TiO2,20nm of about 40nm, the chromium of 50nm, the silver of 10nm are modeled as hue and luminance with the reflective stacks of the ITO of 90nm and do not have the identical lamination of layers of chrome similar.When not having layers of chrome, the transmissivity of lamination is calculated as being used as display or optical sensor region is enough.Therefore, chromium can be covered in the deposit of this layer, and in the opaque of device and transflective portion are divided, make the electric driven color-changing part with similar band blue color and brightness (namely secret) simultaneously.

Also by insert between chromium and ITO low-index layer or by multiple hi-lo index layer of replacing increase chromium the reflectivity of ITO lamination.But most have enough thickness to have the low index oxide of suitable optical effect and fluoride materials also will be electrical insulator.But silver itself is low index material, this section explains its benefit when being placed between chromium and ITO.

Table 25

Another beneficial aspects in the region of display window and half-transmitting and half-reflecting coating is for rightabout antireflection feature.Invariably, the parasitic light that display translation is significantly measured, this parasitic light launching below or scattering finally leave the region of display along mirror element.Relatively low from rightabout reflectivity by making element have, this parasitic light can reduce.Do not having on the surface when extra play, to obtain the benefit reduced costs that lower reflectivity has increase the 4th.

While there is TiO2/ITO/AgAu7x/AgAu7x in viewing area, Cr/TiO2/ITO/AgAu7x/Cr/AgAu7x is set in opaque or viewing area.First layers of chrome is thinner, is about that 2 ~ 15nm is thick, to be preferably about 5 ~ 10nm thick and covered in viewing area.Second chromium is also covered in viewing area, and its thickness is adjusted in viewing area, obtain the transmissivity of wishing.TiO2/ITO bilayer covers whole surface and is adjusted to obtain for rightabout anti-reflection effect in viewing area, provides suitable color before this part viewing area simultaneously.

Table 26 illustrates from reverse direction or the reflectivity from the 4th surface.The first situation is base case.It is the above-mentioned lamination for the opaque of mirror element or viewing area.Can find out, quite high from reflectivity below, be about 61%.In the latter case, below dielectric layer, add thin layers of chrome (~ 5nm).In viewing area, add this thin layer by reflectance reduction to about 6%, intensity about 10 times can be reduced.Like this, the scattering of any parasitic light will be reduced.Thickness by layers of chrome and dielectric layer adjusts this reflectance value and color thereof.About 4% of 6.2% reflectivity is increased from the 4th surface of the uncoated of glass.If wish to reduce reflectivity further, the anti-reflecting layer of additional routine so can be added.The reflectance value of 6.2% can be reduced to the value lower than 2.5%.

Table 26: when having and do not have anti-reflecting layer in viewing area from the reflectivity on reverse direction (the 4th surface).There is the component value of combination.

Lamination	RCapY
		Glass/35nm TiO2/18nm ITO/14nm AgAu7x/25nm Cr/8.5nm AgAu7x	61.4
Glass/5Cr/35nm TiO2/18nm ITO/14nm AgAu7x/25nm Cr/8.5nm AgAu7x	6.2

Reflectivity reduction and absolute value thereof depend on the performance of the first Ag containing layer and layers of chrome subsequently.As mentioned above, these layers are by the reflectivity adjusting not only to adjust transmissivity but also adjust towards observer.Along with these layers are adjusted to meet different design objects or object, dielectric layer and/or basic unit's layers of chrome can be adjusted to realize best anti-reflection effect.

Other metal beyond chromium or absorption layer can be used as anti-reflecting layer.Such as the material of tungsten, chromium, tantalum, zirconium, vanadium and other similar metal also will provide antireflective property widely.Other metal can cause reflectivity that is higher, polychrome more.In addition, chromium or other metal level can with a small amount of oxygen or N doping to change the optical property of metal to adjust antireflective property.

The serviceability of one group of high low-index layer replaced or many these layers of group has been mentioned in the other places of presents.The material being generally regarded as having low-refraction as metal oxide, nitride, oxynitride, fluoride tends to be poor conductor.Usually, the refringence between adjacent materials is larger, and so optical effect is larger.This is the reason of material as low index material of the refractive index usually using about 1.6 or less.But, when the material be coupled with TCO has sufficiently high refractive index and causes hi-lo index pair, obtain useful effect with the material with higher-index of such as transparent conductive oxide.Especially, when using titania as the relatively high index material be coupled with the tin indium oxide as relatively low index material, benefit can be obtained on optics and electricity.Especially, titania is relatively high-index material, and this material is not enough good insulator on optical thickness, to be separated in the face that is located thereon of such as ITO, another TCO or metal or semimetal layer or more conductive film below.When applying T as optical thin film between the layer that the electric conductivity of such as tin indium oxide is higher _io ₂time, T _io ₂will not make the ITO layer mutually insulated in electric driven color-changing part, and realize the optical effect of the hope of the high lamination of height.In other words, the major part of the accumulation conduction benefit of the gross thickness of the ITO in film is retained, and obtains the optical benefits of high index layer and low-index layer simultaneously.Following example will generally explain the benefit of this principle particularly these materials.Basic unit's (n is about 1.5 in the visible spectrum) that deposit is all with measurement on soda-lime glass.

Basic unit A=is about the half-wavelength optical thickness ITO (manufacturing under the condition of the ideal conditions lower than conductance) of 145nm physical thickness and 23ohm/sq surface resistance.Basic unit B=has the titania of the about 40nm below the ITO of the about 20nm of the surface resistance of about 110 ~ 150ohm/sq.Basic unit C=have about 16ohm/sq surface resistance (lower than the surface resistance expected may be due to compared with simple layer A in vacuum breaking and cover ITO layer A before cooling and may enhance conductance) A+ basic unit of basic unit B.Basic unit D=has the titania of about 42.5nm, the titania of ITO, 42.5nm of 42.5nm, the ITO of 42.5nm of the surface resistance of about 40ohm/sq.Figure 54 a illustrates the aerial reflectance spectrum of these basic units (do not have additional coating, and be before being assembled into electric driven color-changing part) on glass.

As the sample (attention of laying from same coating of the sample of Figure 54 a, even if also there are some changes in once laying) be given the additional coatings of 6%Au94%Ag (the being called 6x) alloy of about 25nm, and be assembled in electric driven color-changing part according to the principle summarized in the other places of presents.The half-wavelength optical thickness ITO with about 12ohm/sq on glass is used as the second surface coating of these elements.Then metric measurement is carried out as shown in Figure 54 b and Figure 54 c.Result is listed in table 27.

Table 27

As mentioned above, covering silver alloy makes it not be deposited on Chang Youyong's below sealing area for most part.As a result, if select this option, so make the electrical contact with lower floor on the surface the 3rd.In this case, to become situation about being guided in electrical contact by bus or conductive epoxy resin or other means from start to finish than silver or silver alloy more important for the lower surface resistance of lower floor.

Carry out the resistance measurement in described basic unit with four-point probe, if this probe is through insulation course, so this four-point probe can provide the result of misleading about surface conductivity.Therefore, be only that the 3rd surface coating builds element with basic unit, and painted and sanitary characteristics is compared it.The performance of element is consistent with the surface resistance measurement result obtained by four-point probe.

In one embodiment of the invention, the color between viewing area and viewing area and reflectance match may be wished.In some above-mentioned examples, can exist in two regions two different metal laminated, and if identical metal is top layer, so the thickness of this layer can different or other metal can be in or be not in below metal layer at top.As the single-piece before being laid in EC element, the reflectivity in two regions can be adjusted to substantially the same.After deployment, when the medium with Metal Contact becomes the medium of EC fluid from air, reflectivity can be different in two regions.This is because each lamination in a different manner with the medium reciprocation of new incidence.

Such as, the ruthenium as top layer in a design (glass/TiO2 45nm/ITO 18nm/Ru 14nm) and another AgAu7x designed in (glass/TiO2 45nm/ITO 18nm/AgAu7x 19nm) are all adjusted with the reflectivity as single-piece with 70.3%, then, when being assembled in element, Ru side will drop to the reflectivity of 56.6%, and AgAu7x side will drop to 58.3%.

Another example TiO2 40nm/ITO 18nm/Cr 25nm/AgAu7x 9nm as single-piece have 77.5% reflectivity and have when being assembled in element 65.5% reflectivity, and TiO2 40nm/ITO 18nm/AgAu7x 23.4nm as single-piece have 77.5% reflectivity and have when being assembled in element 66% reflectivity.In this case difference is not large as in the previous example above, but, even if it represents that the layer be embedded in also can affect the reflectivity declined from single-piece to element.This will explain may need reflectivity mismatch as single-piece for coating when wishing reflectance match in the component.

For the method obtaining good reflectivity and color-match in two regions of mirror, above-mentioned supposes that the outward appearance in two regions is in fact completely deserved by reflectivity.But observer not only awares reflectivity, and aware transmitted light in viewing area.In observation or zone of opacity, because transmissivity is relatively low, therefore observer only awares reflection.The amount of transmitted light is with after the transmissivity of viewing area and the 4th surface of mirror or the reflectivity of its parts contacted and becoming.The amount of the light that observer perceives increases with the increase of the transmissivity of the coating in viewing area.Similarly, along with the reflectivity of the parts after mirror increases, the light that observer perceives also increases.This can increase the light of significantly amount, and because viewing area is brighter than viewing area, therefore, observer can aware it.Even if this can cause two regions to have identical reflectivity display area and also seem brighter.By manufacture have the parts of antiradar reflectivity element and/or by the transmissivity in viewing area is set to relatively low level, alleviate this effect.If the output brightness of display is relatively limited or lower, so reduces transmissivity and display can be made greatly dimmed.

For another example, the EC element comprising 40nm TiO2/18nm ITO/EC fluid/140nm ITO/ glass has the reflectivity of 8.1%.When the layer of ruthenium of the 4th deposit 5nm is on the surface to simulate the display after mirror (that is, 5nm Ru/ glass/40nm TiO2/18nmITO/EC fluid/ITO/ glass), reflectivity is elevated to 22.4%.The EC element comprising glass/40nmTiO2/18nm ITO/22nm AgAu7x/EC fluid/ITO/ glass has the reflectivity of 61.7%.The lamination with the ruthenium of 5nm has the reflectivity of 63.5%-reflectivity increase about 2%.The amount of this reflectivity is easy to aware for observer.As mentioned above, actual reflectivity increases the reflectivity of parts that depends on after mirror and the transmissivity of EC element.

In order to reduce the luminance difference perceiveed in two regions, relative reflectance can be adjusted to compensate transmitted light component in two regions.Therefore, in order to realize clean 2% more bright area in the display section of mirror, the reflectivity preferably increasing the reflectivity in viewing area or reduce in viewing area.Adjustment amount depends on the specific environment of system.

Example 1a

In the present example, the 3rd surface application of the glass substrate of 2.2mm is had an appointment tiO ₂, be about afterwards iTO, be finally about silver-colored billon silver/7 % by weight of 93 % by weight (gold).Titania and ITO are preferably applied to the edge of glass substantially, and silver alloy is preferably covered in the inner side at least outside of related seals.In at least one embodiment, second surface comprises 1/2 wavelength (HW) layer of ITO.Line 4801a and 4801b in Figure 48 a and Figure 48 b illustrates relevant element reflects rate and transmissivity model respectively.Model reflectivity is about 57% under about 550nm, and transmissivity is about 36.7%.

Example 1b

Except the perimeter region along the 3rd surface sealing below extend there is chromium/metal tab at least partially to improve except the electric conductivity between relevant clip contact area and silver alloy, configuration and the example 1a of this example are similar.Outward appearance keeps identical, but dimmed speed is improved.This feature can be applied to a large amount of following examples to improve the electric conductivity from the 3rd surface to relevant electrical contact.As can be seen from Figure 48 a and Figure 48 b, reflectivity is relevant to the element of example 1a, and the transmissivity of each is different greatly; This represents one in advantage of the present invention.

Example 1c

Configuration and the example 1a of example 1c are similar, but viewing area is covered at first, and after lift off mask, deposit comprises the lamination (that is, causing only having Cr/Ru on glass in viewing area) of Cr/Ru on the whole surface substantially.The opaque lamination of Cr/Ru can be replaced by many combinations.In Figure 48 a and Figure 48 b, by line 4802a and 4802b, reflectivity and transmissivity result are shown respectively.Relative to viewing area, opaque lamination preferably has lower contrast for reflectivity and color.Another advantage of this example is, the edge that the general metal used may extend into glass in opaque layer is with the relevant electrical connection clip of bridge joint and the 3rd surperficial silver-colored billon.Model reflectivity is about 56.9% in viewing area under about 550nm, and be the reflectivity of about 57% in viewing area, in viewing area, transmissivity design object (being applicable to all suitable designs) is preferred < 10%, < 5%, more preferably < 1%, most preferably < 0.1%, and the transmissivity in viewing area is about 36.7%.Should be appreciated that except display or other light source or alternatively, optical sensor can be positioned at after " viewing area ".

Example 2a

In the present example, the 3rd surface application of mirror element is had an appointment iTO, be then about 50% transmissivity chromium, be finally about silver-colored billon.Preferred ITO and chromium are applied to the edge of glass substantially, and silver alloy is covered in the inner side at least outside of sealing.Cr thickness is preferably adjusted, and the transmissivity extending only through rear plate making ITO add Cr layer is 50%.In at least one embodiment, second surface preferably comprises HWITO layer.Reflectivity and the transmissivity of element are shown with line 4901a and 4901b respectively in Figure 49 a ~ 49d.Cr layer can be adjusted (thickening or thinning) to adjust the final transmissivity of half-transmitting and half-reflecting element.Along with Cr layer is thickening, transmissivity will decline.And when Cr is thinning, transmissivity will increase.The advantage of the increase of Cr layer is, for the normal vacuum sputtering deposition process fluctuation in substrate I TO layer, lamination is that relative color is stable.The physical thickness of layers of chrome is preferably about be more preferably most preferably be model reflectivity is about 57% under about 550nm, and transmissivity is about 21.4%.

Example 2b

Coated with beyond the chromium/ruthenium combination stack of the transmissivity of (that is, before adding in mirror element) acquisition 50% when only measuring rear plate except having, example 2b and example 2a is similar.Ru is added on the stability providing improvement in the solidification of epoxy sealing.Ru and chromium Thickness Ratio can be adjusted, and, there are some designs tolerance (design latitude).Chromium add the adhesiveness mainly will improving Ru and ITO.Preferential and Ag or the Ag alloy bond of Ru.As long as maintain suitable material and physical property, other (one or more) metal so can be placed between Cr and Ru layer.In Figure 49 c, with line 4901c and 4902c, reflectivity and transmission characteristics are shown respectively.

Example 2c

Except viewing area is covered and after the removal of the mask substantially except the whole 3rd on the surface deposit Cr/Ru (or other opacifier) layer, example 2c and example 2a and 2b is similar at first.In Figure 49 a and 49b, with line 4902a and 4902b, transmissivity and reflectivity results are shown respectively.Relevant advantage and example 1c's is similar.

Example 3a

In the present example, the 3rd surface application of EC element is had an appointment t _io ₂, be about afterwards iTO, be about afterwards silver, be finally about izo-Tco.

This example is similar with example 1a; TiO2 and ITO is applied to the edge of glass substantially; and silver is covered in the inner side at least outside of sealing, and, on silver, apply the indium oxide layer zinc (IZO) as the protection restraining barrier for EC fluid or other TCO subsequently.As an alternative, IZO/TCO layer can extend to the edge of glass substantially.In at least one embodiment, second surface preferably comprises HWITO layer.Line 5001a and 5001b in Figure 50 a and Figure 50 b illustrates element reflects rate and transmissivity respectively.Model reflectivity is about 57% under about 550nm, and transmissivity is about 36%.

Example 3b

Being covered except viewing area and substantially do not cover deposit on region the 3rd surface whole comprises except the lamination of Cr/Ru, and configuration and the example 3a of example 3b are similar.The opaque lamination of Cr/Ru can be replaced by many combinations of materials.In Figure 50 a and Figure 50 b, by line 5002a and 5002b, reflectivity and transmissivity result are shown respectively.The advantage of this example is, in opaque layer, the general metal used can extend to the edge of glass substantially to provide bridge joint between relevant electrical contact folder and silver alloy.In Figure 50 c, with line 5001c, 5002c, relevant transmissivity and albedo measurement data are shown respectively.

Example 4a

In the present example, the 3rd surface application of EC element is had an appointment iTO, be about afterwards silicon, be finally about ru or Rh.

All each layers all can be applied to the edge of glass substantially.As an alternative, glass the form of sheet can be processed and be cut into the single-piece for adding in mirror element subsequently.Ru or Rh layer can be replaced by the one in the metal or alloy of several high reflector.In at least one embodiment, second surface preferred coated has HWITO.This example illustrates the advantage increasing transmissivity under different wavelength.Substrate I TO layer can be replaced by the layer with different thickness.In certain embodiments, preferred ITO is the odd-multiple of 1/4 wavelength.In these cases, reflectivity will be increased a little by ITO.Along with ITO is thickening, how many this effects is eliminated.The benefit of thicker ITO is generally lower surface resistance, and this causes the element appearing dark time faster.Model reflectivity is about 57% under about 550nm, and transmissivity is about 11.4%.Modeled reflectivity and transmissivity shown in Figure 51 a and 51b respectively.Reflectivity and the transmissivity of measurement are shown with line 5101c, 5102c respectively in Figure 51 c.

Example 5

In the present example, the 3rd surface application of EC element is had an appointment iTO, be about afterwards chromium, be about afterwards ru, last optionally coating have an appointment rh.

All each layers all can be applied to the edge of glass substantially, or glass the form of sheet can be processed and be cut into the single-piece for adding in mirror element subsequently.Ru layer can be replaced by the one in the metal or alloy of several high reflector, or, the adding layers of such as rhodium can be added.Metal level is adjustable to obtain higher or lower reflectance/transmittance balance.In at least one embodiment, second surface preferred coated has HWITO layer.A benefit of thicker ITO is lower surface resistance, and this causes the element appearing dark time faster.Thicker ITO can increase by the 3rd surface stack roughness, and this can cause lower reflectivity.When respectively by the model transmissivity of Figure 52 a with 52b and reflectivity with from test the transmissivity obtained compare with reflectivity (being respectively line 5201c1,5201c2 of Figure 52 c) time, observe this effect.Model reflectivity is about 57% under about 550nm, and transmissivity is about 7.4%.

Shading oxidant layer on example 6a the 3rd surface

In the present example, shading oxidant layer is added in the 3rd surface coating lamination.Will about chromium, be then about the based laminate of ITO be deposited in glass substrate, wherein, or in the deposition process of based laminate, viewing area is covered, or, in viewing area, based laminate laser is deleted subsequently.Subsequently, apply about iTO layer peace treaty silver alloy Ag-X layer (wherein, X represents the option of the alloy for Ag).The method is substantially opaque in viewing area, and is half-transmitting and half-reflecting in viewing area.

Can relatively away from covering alloy hermetically to improve the life-span of element in rugged surroundings.Model reflectivity is about 52% under about 550nm, and transmissivity is about 41%.

Example 6b

Example 6b and example 6a is similar.In the present example, the 3rd surface initially applies and has an appointment beyond viewing area chromium, be then about iTO, be then about tiO ₂, be finally about the based laminate of chromium.Substantially whole 3rd surface applies subsequently and has an appointment t _io ₂, be then about iTO, be finally about silver-colored billon.Model reflectivity is about 54% under about 550nm, and transmissivity is about 41%.

For electrochromism mirror, if wish higher transmissivity (T) level, limited reflectivity (R) so can be had, or, if need higher reflectivity, so limited transmissivity can be had.Assuming that absorb (A) to keep constant, so with relation R+T+A=1, this point can be described.In some displays or optical sensor, mirror application, the transmitted light (or brightness) may wishing to have higher level with observe relevant display satisfactorily or by mirror element through enough light.This usually causes mirror to have the reflectivity of the reflectivity being less than hope.

Discuss the scheme of the restriction described in reply in other example here, wherein, the thickness of metal level in order to reflectivity is enough, and is only thinner on the display region in viewing area.Other example uses layer or the coating laminated of different metal on the display region, to attempt the color and/or the reflectivity that mate zones of different.Invariably, the sudden change of reflectivity or color is that observer institute is unsatisfied.With reference to Figure 55 and Figure 56 a, such as, the border (C) between two regions is sudden change.Region (A) has the transmissivity higher than region (B).Border (C) draws two regions.In Figure 63, the border during beginning of the transition between high low reflectivity regions is also sudden change.When transition between zones, the slope approach infinity of the reflectivity change of per unit distance.

In at least one embodiment, the transition of metal layer thickness is in mode gradually.For human eye, it is more difficult that the detection that gradually changes of the reflectivity in transitional region and/or transmissivity is got up.Two regions still have visibly different reflectivity and transmittance values, but the border between two regions is by mildization (grade).Gentle slope eliminates unexpected uncontinuity and replaces it with transition gradually.When interface is changed gently, human eye is attracted by it no longer like that.Gentle slope can be transition that is linear, curve or other form shown in Figure 56 b ~ 56d.Occur that the distance on gentle slope can change.In at least one embodiment, this distance becomes with the reflection differences between two regions.When reflection differences between two regions is relatively low, the distance on gentle slope can be relatively short.When reflection differences is larger, can wish that larger gentle slope minimizes to make the observability of transition.In at least one embodiment, the length on gentle slope becomes with the purposes, observer, illumination etc. applied and expect.

In at least one embodiment shown in Figure 56 e, transmissivity can be reduced to close to zero in one or more part.In other situation here illustrated, reflectivity can be identical or different." secret " embodiment that other places here can be used to illustrate, to keep reflectivity to be relative constancy, allows in the various piece of mirror element, to adjust transmissivity as desired simultaneously.

The invention is not restricted to two or more regions with constant transmissivity or reflectivity.An embodiment shown in Figure 56 f.Region B have can be zero relatively low transmissivity.If one of design object is the light that region B will be made to stop the object after from the coated substrates being positioned at half-transmitting and half-reflecting, so this can be desired.Coating laminated has transition gradually by slope C from region B.Region A can have another gradient in self.There is the possible benefit be discussed later in this point.

In some applications, enough length may not be obtained to obtain Double tabletop situation.In these cases, stride across as shown in Figure 57 a and wish that the region of half-transmitting and half-reflecting performance uses continuous print gentle slope to be favourable.The change of reflectivity is gradually, and obtains the benefit of high transmittance; The interface do not suddenlyd change between zones.

Various forms can be taked in gentle slope between two regions.In its broadest sense, element can comprise the region of obvious difference and uniform transmissivity and reflectivity.In the example shown in Figure 57 a ~ 57c, there is not constant reflectivity and the region of transmissivity.These situations have and change with continuous print gradually in optical property.The advantage of the method shown in Figure 58.

When the glass substrate viewing display of observer by mirror element or coating, exist comparatively near part about display relative to display compared with the path of distal part and the continuity of angle.According to orientation, the size of element, the distance etc. to observer of mirror element display, incident effective relative angle will change.This causes in the various piece of viewing area, having different transmission amounts through glass.Different transmission amounts causes again the change of the brightness shown.When the constant output of light of hope from all regions of display, half-transmitting and half-reflecting coating can be changed to consider the loss being derived from the transmission of viewing angle and path difference by glass.If effectively viewing angle becomes 60 degree from about 45 degree, so pass the transmissivity of glass by change about 6%.Therefore, how many half-transmitting and half-reflecting coatings having mildization in the region of display can compensate this effect, and edge therefore can be caused to show more impartial to the light intensity perceiveed.

The transitional region of mildization can be used to the display of such as backside photograph device (rear camera) or traditional compass temperature indicator.In some here in " secret " example of discussing of other places, so-called " cut Ag " lamination is set, wherein, opaque layer between two Ag layers, to contribute to the outward appearance between coupling half-transmitting and half-reflecting and the region of opaqueness.In another embodiment of secret display, Ag layer is placed on opaque layer.These two embodiments all can be benefited from the mildization transition between region.Opaque layer or Ag layer or all layers all can be changed gently.In at least one embodiment, opaque layer can be minimized by changing gently to make the emergentness of the transition between region.

In order to change material thickness in (one or more) layer to produce transitional region, can use many methods, these methods include but not limited to: cover; Movement in substrate or paint-on source or velocity variations; Changes of magnetic field in magnetron or the layer thinning technique of ion beam milling such as illustrated here or other suitable means.

Figure 59 illustrates an example of electrochromism mirror structure, and this electrochromism mirror structure has: the rear plate 5914 of glass; Comprise about the layering peace treaty of titania the layer 5972 of layering of ITO; The layer 5978 of 6Au94Ag, wherein, a region has about thickness, another region has about thickness, the 3rd region is between these two regions, and wherein, thickness is transition gradually between; There is the electrochromism fluid/gel 5925 of the thickness of about 140 microns; About the layer 5928 of ITO and the glass plate 5912 of 2.1mm.The variation range of the reflectivity of the element obtained is from about 63% major part of mirror to about 44% in the region shown above.

Build the electrochromic device similar with above-mentioned electrochromic device, wherein, by the combination using the magnetic of concealing technique and deposit source to handle, the thickness of layer 5978 changes in the mode similar with the mode illustrating in Figure 57 c and illustrate.The method selected will depend on the definite feature that needs in final element and what disposal route is available.Figure 60 and Figure 61 illustrates the corresponding reflectivity data become with the position on mirror.In this case, display is positioned at after the region of antiradar reflectivity, high-transmission rate.

The Another Application of the transition of mildization is the electric driven color-changing part of the second surface reverberator with hiding epoxy sealing; The reflectivity between " ring " and the reverberator on the 3rd or the 4th surface and color-match can be realized.Best coupling is when the reflection strength of ring and reflector reflects strength matching.In at least one embodiment, while not changing ring, the reflectivity of reverberator increases further.Due to permanance, manufacture or other consideration, therefore this situation can be there is.When making the reflectivity of reverberator change gently as discussed above, the means for maintaining the coupling between reverberator and ring can be obtained.When there is the change gradually of reflectivity, then the reflectivity of reverberator can be adjusted to the reflectivity mating ring near ring also increases along with away from ring gradually.Like this, as shown in Figure 62, in viewing area, reflectivity is in the heart relatively high.

Similarly, ITO can taper to the center of viewing area to keep the thickness range needed for acceptable color from ring region, allow there is relatively high reflectivity at the center of element simultaneously.Like this, with ITO coating along compared with the thinner situation of elements relative, mirror will be relatively rapidly dimmed.

Identical design can be extended to solid metal reflector electrode.In this case, can mildization be used, the surface resistance of coating is gradually changed with position.The method coordinate various bus configuration and cause faster and evenly dimmed.Figure 63 illustrate according to the present invention before the embodiment of mirror element of state of prior art.

Should be appreciated that the detailed description provided should allow those skilled in the art to propose and use the best mode of each embodiment of the present invention here.These illustrate the scope of the claim that never should be interpreted as appended by restriction.Claim and each independently claim restriction should be interpreted as comprising all equivalents.

Claims

1. a vehicle rearview mirror assembly, comprise the electrochromism EC element with viewing area and zone of opacity, this EC element comprises:

The substrate of substantial transparent;

Lower reflection horizon that be arranged on the types of flexure of substantial transparent, that comprise Ag containing layer, this lower reflection horizon covers zone of opacity and viewing area;

To be arranged on outside viewing area and opaque layer on lower reflection horizon; And

Upper reflection horizon that extend on the viewing area and opaque layer of EC element, that comprise Ag containing layer,

Wherein, opaque layer is upper reflection horizon and lower reflection horizon separately, and utilizes mask viewing area in the forming process of opaque layer, thus in viewing area, does not form opaque layer.

2. rearview mirror assemblies according to claim 1, wherein, upper reflection horizon is changed gently.

3. rearview mirror assemblies according to claim 1, wherein, opaque layer comprises the material in the group being selected from and being made up of chromium, silicon, molybdenum, inconel, palladium, osmium, tungsten, iridium, rhodium, ruthenium, tantalum, copper, gold and platinum.

4. rearview mirror assemblies according to claim 1, also comprises the flash layer of the metal be arranged under Ag containing layer.

5. rearview mirror assemblies according to claim 4, wherein, flash layer comprises at least one in conductive oxide, platinum group metal or its alloy, nickel or its alloy and molybdenum or its alloy.

6. rearview mirror assemblies according to claim 1, also comprises and to be deposited under lower reflection horizon and the basalis of substrate in substantial transparent.

7. rearview mirror assemblies according to claim 6, wherein, basalis comprises the coating comprising the nonmetal bilayer with quarter-wave optical thickness.

8. rearview mirror assemblies according to claim 1, wherein, optics isolation is carried out in lower reflection horizon and upper reflection horizon by opaque layer in zone of opacity.

9. rearview mirror assemblies according to claim 1, wherein, the transmissivity of zone of opacity is no more than 5%.

10. rearview mirror assemblies according to claim 1, wherein, the transmissivity of zone of opacity is no more than 2.5%.

11. rearview mirror assemblies according to claim 1, wherein, the transmissivity of zone of opacity is no more than 0.5%.

12. rearview mirror assemblies according to claim 1, wherein, lower reflection horizon and upper reflection horizon comprise silver or silver alloy.

13., according to the rearview mirror assemblies of any one in Claims 1-4, also comprise at least one device in the group being selected from and being made up of interior illumination assemblies, GPS, exterior light controller, information display, optical sensor, blind-spot indicators, side marker light, operator interface, compass, temperature indicator, microphone, light adjusting circuit and warning system.

14. rearview mirror assemblies according to claim 1, wherein, EC element has the reflectivity more than 50%.

15. rearview mirror assemblies according to claim 1, wherein, lower reflection horizon and upper reflection horizon comprise ruthenium.

16. rearview mirror assemblies according to claim 6, wherein, basalis comprises containing TiO ₂the coating of/ITO bilayer.

17. 1 kinds of vehicle rearview mirror assemblies, comprise the electrochromism EC element with half-transmitting and half-reflecting region and zone of opacity and transitional region between these two regions, this EC element comprises:

The substrate of substantial transparent;

Opaque layer outside the half-transmitting and half-reflecting region being arranged on EC element and on the substrate of substantial transparent; And

The upper reflection horizon extended on the half-transmitting and half-reflecting region and opaque layer of EC element,

Wherein, the thickness of at least one in opaque layer and upper reflection horizon little by little changes corresponding between the first one-tenth-value thickness 1/10 of zone of opacity and the second one-tenth-value thickness 1/10 corresponding to half-transmitting and half-reflecting region in transitional region, thus makes little by little changing between zone of opacity and half-transmitting and half-reflecting region at least one in environment light reflectance and transmissivity of EC element.

18. rearview mirror assemblies according to claim 17, wherein, in zone of opacity, the transmissivity of EC element is no more than 5%.

19. rearview mirror assemblies according to claim 17, wherein, in zone of opacity, the transmissivity of EC element is no more than 2.5%.

20. rearview mirror assemblies according to claim 17, wherein, the transmissivity of zone of opacity is no more than 0.5%.

21. rearview mirror assemblies according to claim 20, wherein, the thickness in upper reflection horizon little by little changes in transitional region between the one-tenth-value thickness 1/10 corresponding to zone of opacity and the one-tenth-value thickness 1/10 corresponding to half-transmitting and half-reflecting region.

22. rearview mirror assemblies according to claim 20, wherein, upper reflection horizon comprises silver.

23. according to the rearview mirror assemblies of any one in claim 17 and 18, wherein, and the surround lighting reflected by zone of opacity and be less than 5C* unit by the colour-difference between the light of half-transmitting and half-reflecting regional reflex.

24. rearview mirror assemblies according to claim 23, wherein, opaque layer comprises the material in the group being selected from and being made up of chromium, stainless steel, silicon, titanium, nickel, molybdenum, inconel, indium, palladium, osmium, tungsten, rhenium, iridium, rhodium, ruthenium, tantalum, copper, gold, platinum and alloy thereof.

25. rearview mirror assemblies according to claim 23, wherein, upper reflection horizon comprises silver or silver alloy.

26., according to the rearview mirror assemblies of any one in claim 17 and 18, also comprise at least one device in the group being selected from and being made up of interior illumination assemblies, GPS, exterior light controller, information display, optical sensor, blind-spot indicators, side marker light, operator interface, compass, temperature indicator, microphone, light adjusting circuit and warning system.

27. rearview mirror assemblies according to claim 17, wherein, the transmittance values of transitional region changes between zone of opacity and half-transmitting and half-reflecting region, and the reflectance value of transitional region keeps identical between zone of opacity and half-transmitting and half-reflecting region.