CN101976009A

CN101976009A - Thin-film coatings, electro-optic elements and assemblies incorporating these elements

Info

Publication number: CN101976009A
Application number: CN2010102981634A
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: 2011-02-16
Anticipated expiration: 2027-03-02
Also published as: EP2035886A2; CN103838050B; EP2035886A4; CN101976009B; CA2644218A1; WO2007100921A3; WO2007100921A2; CN103838050A; KR20120035222A; KR101278371B1; JP2014029556A; JP2009529150A; KR101275450B1; KR20080106963A; JP5570730B2; MX2008011009A; JP5855623B2; CA2644218C

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

Improved film coating, photovalve and comprise the assembly of these elements

It is the dividing an application for the patented claim of " improved film coating, photovalve and comprise the assembly of these elements " that 200780007652.6 (international application no is PCT/US2007/005494), the applying date be on March 2nd, 2007, denomination of invention that the application is based on application number.

The cross reference of related application

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

The application is relevant with following U.S. Patent application: denomination of invention is the case GEN 10-P517 of agency of ELECTRO-OPTICAL ELEMENT INCLUDING IMI COATINGS; With the case GEN 10P518 of agency; These two patented claims and the application are simultaneously submitted; Being incorporated herein the whole of them discloses as a reference.

Technical field

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

Background technology

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

Description of drawings

Fig. 1 illustrates the aircraft with variable transmissivity window;

Fig. 2 a and Fig. 2 b illustrate motorbus and the train that has the variable transmissivity window respectively;

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

Fig. 4 illustrates the vehicle with variable transmissivity window and variable reflectivity rearview mirror;

Fig. 5 a-5e illustrates the various views of external mirror having indicator light assembly and relevant variable reflectivity element;

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

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

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

Fig. 9 a-9j illustrates the various of various elements and electrically contacts;

Figure 10 illustrates the electric control synoptic diagram of a plurality of elements;

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

Figure 12 illustrates for the various argon gas that utilize in the element manufacture process and handles the component warp of gaseous tension and the graph of a relation of oxygen flow;

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

Figure 14 illustrates for the film thickness of the various processing gaseous tensions that utilize in the element manufacture process and the graph of a relation of oxygen flow;

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

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

Figure 17 illustrates for the film absorption of the various processing gaseous tensions that utilize in the element manufacture process and the graph of a relation of oxygen flow;

Figure 18 illustrates for the component warp of the various processing gaseous tensions that utilize in the element manufacture process and the graph of a relation of oxygen flow;

Figure 19 illustrates for the component warp of the various processing gaseous tensions that utilize in the element manufacture process and the graph of a relation of film absorption;

Figure 20 illustrates the graph of a relation for the component warp and the film transmissivity of the various processing gaseous tensions that utilize in the element manufacture process;

Figure 21-32 illustrates various film surface forms;

Figure 33 a and Figure 33 b illustrate surfaceness between the film peak-peak;

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

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

Figure 36 and Figure 37 illustrate 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 ^*Graph of a relation with 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 transmissivity 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 transmissivity 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 embodiment of the element of (graded) film coating with mildization.

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

Embodiment

Fig. 1, Fig. 2 a and Fig. 2 b illustrate and use variable transmissivity window 110, many passengers delivery vehicle 102 of 210a, 210b, 202a, 202b.Use many passengers delivery vehicle of variable transmissivity window 110,210a, 210b to comprise for example aircraft 102, motorbus 202a and train 202b.The many passengers delivery vehicle that should be appreciated that other also can use variable transmissivity window 110,210a, 210b, describes in these many passengers delivery vehicles some in detail in the other places of this paper.The many passengers delivery vehicle that roughly illustrates in Fig. 1, Fig. 2 a and Fig. 2 b also comprises the window control system that is used for controlling the variable transmissivity window (not shown at Fig. 1-2 b, but be illustrated and be described with reference to Figure 10).The denomination of invention of submitting on June 9th, 2006 is that the commonly assigned United States Patent (USP) 6567708 of Variable Transmission Window Systems has been described the various details relevant with the variable transmissivity window with U.S. Patent application 60/804378, at this their disclosed full content of adding as a reference.

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

Fig. 4 illustrates the in check vehicle 400 that comprises various variable transmissivity and variable reflectivity element.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 system.In commonly assigned U.S. Patent No. 5837994,5990469,6008486,6130448,6130421,6049171,6465963,6403942,6587573,6611610,6621616,6631316 and U.S. Patent application series No.10/208142,09/799310,60/404879,60/394583,10/235476,10/783431,10/777468 and 09/800460, comprise detailed description to this automotive vehicle exterior light control system; At this their disclosed full content of adding as a reference.In check vehicle also is shown to include high-order stop light (CHMSL) 445, the A-pillar 450a of installing in external mirror having indicator light assembly 410a, the external mirror having indicator light assembly 410b of passenger side, center of driver side, 450b, B-

pillar

455a, 455b and C-

pillar

460a, 460b; Should be appreciated that in these positions any can be imageing sensor, a plurality of imageing sensor or relevant processing and/or control assembly substituting position is provided.Should be appreciated that in the rearview mirror any or all can be automatic deepening photoelectricity mirror (that is variable reflectivity mirror element).In at least one embodiment, in check vehicle can comprise variable transmissivity window 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, the place ahead 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 and to be provided with such as independent low beam and high beam headlight, to comprise the additional outer lamp of the integrated lamp etc. of multipurpose lighting.Should also be understood that the steady arm (not shown) of the relevant primary optical axis of the outer lamp that any had adjustment in the outer lamp is given.In at least one embodiment, at least one outer mirror sub-component has the rotating mechanism (pivoting mechanism) of permission along direction 410a1,410a2,410b1,410b2 rotation.Be to be understood that, the in check vehicle of Fig. 4 generally is for illustrative purposes, and, can be with further feature that illustrates here and open middle use that here adds such as the suitable automatic deepening rearview mirror of conduct here with reference to those disclosed in patent that adds and the patented claim as reference.

Preferably, in check vehicle comprises the inside rear view mirror of unit enlargement factor.Unit used herein enlargement factor mirror (unit magnification mirror) means plane with such reflecting surface or smooth mirror, promptly, by this reflecting surface, except the crackle that is no more than normal manufacturing tolerance, the angle height and the width of the image of object equals the angle height and the width of the object when direct viewing on identical distance.Here, the prism of at least one the relevant position unit of providing enlargement factor is adjusted the rearview mirror unit of being regarded as enlargement factor mirror round the clock.Preferably, mirror provides the visual field of horizontal angle of measuring from the viewpoints of projection that includes with at least 20 degree and enough vertical angle, with when in check vehicle by driver and four passengers or based on (if still less) of the appointment of average tenant's weight of 68kg when the number of occupying occupies, provide and extend to the observation that the horizontal level road that begins on the point that is being not more than 61m arrives the rear portion of controlled vehicle.Should be appreciated that tenant that sight line may be taken one's seat or covered by the head constraint portions.The optimum seeking site ground of driver's eyes reference point according to the rules or be suitable for any percent 95 male sex driver's nominal position.In at least one embodiment, in check vehicle comprises the outside mirror of at least one unit enlargement factor.Preferably, outside mirror provides from perpendicular to extending to the local horizon at the wideest line of selecting with the tangent fore-and-aft plane of the driver side of in check vehicle, being rearmost position extends out the level road of 2.4m from the tangent plane of driver's eyes back 10.7m observation with the seat to the driver of in check vehicle.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 driver's eyes reference point according to the rules or be suitable for any percent 95 male sex driver's nominal position.Preferably, the passenger side mirror is not partly covered by the not wiping of corresponding windshield and preferably can tilt to be adjusted with vertical both direction along level by the position of taking one's seat from the driver.In at least one embodiment, in check vehicle comprises the convex mirror that is installed in passenger side.Preferably, be configured to can be by tilting to be adjusted with vertical both direction along level for this mirror.Preferably, each outside mirror comprises the reflecting surface that is not less than 126cm, and is positioned as the observation that the back is provided 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% (is 40% for many European countries).Can have among the embodiment of a plurality of reflectivity levels in mirror element, such as photoelectricity mirror element according to the present invention, the minimum reflectance level of day mode should be at least 35% (using for Europe is 40%), and 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 Fig. 5 a and Fig. 5 b of the various parts that external mirror having

indicator light assembly

510a, 510b are shown now to.As describing in detail here, the photoelectricity mirror element can comprise by primary seal 523b and is fixed with the first substrate 521b and the second substrate 522b that forms chamber betwixt with the relation of separating.In at least one embodiment, at least a portion of primary seal remains sky, to form at least one chamber fill port 523b1.The photoelectric medium of packing in chamber also seals fill port by choke material (plug material) 523b2.Preferably, choke material is the epoxy resin or the acryhic material of UV-curable.In at least one embodiment, spectral filter material 545a, 545b be positioned near the second surface of first substrate, near the periphery of mirror element.Preferably by the first adhesive material 526b1,526b2 electric connector 525b1,525b2 are fixed on the element respectively.By the second adhesive material 570b mirror element is fixed on the loading plate 575b.Preferably realize the electrical connection of other parts from external mirror having indicator light in check vehicle by connector 585b.By steady arm 580b carrier is fixed on relevant outer casing base (housing mount) 585b.Preferably, outer casing base engages with

shell

515a, 515b and is fixed by at least one securing member 534b4.Preferably, outer casing base comprises and is configured to change (swivel) part that engages with change base 533b.The change base preferably is configured to engage with vehicle base (vehicle mount) 530b by at 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, external mirror having indicator light assembly 510a is oriented like this, makes to use spectral filter material 524b between observer and primary seal material 523b to show the observation of the first substrate 521b.Can in rearview mirror assemblies, add blind spot indicator 550a, keyhole luminaire 555a, puddle lamp (puddle light) 560a, assisted

diversion pilot lamp

540a or 541a, optical sensor 565a, any in them, their recombinant or their combination, make them be positioned at the element back with respect to the observer.Preferably, as with reference to going through in each document that adds like that,

device

550a, 555a, 560a, 540a or 541a, 565a and mirror element make up and be configured to is hidden at least in part as here and here.Other details of these parts, additional parts, their interconnection and operation is provided here.

Forward Fig. 5 c～5e now to, the discussion according to supplementary features of the present invention is provided.Fig. 5 c illustrates the rearview mirror elements 500c that observes from the first substrate 502c, wherein makes spectral filter material 596c between observer and primary seal material 578c.The first separated region 540c is set to make the first current-carrying part 508c and the second current-carrying part 530c electrical isolation basically.Circumference material (perimeter material) 560c is applied on the edge of element.Fig. 5 d illustrates the rearview mirror elements 500d that observes from the second substrate 512d, wherein, makes primary seal material 578d between observer and spectral filter material 596d.The second separated region 586d is set to make the 3rd current-carrying part 518d and the 4th current-carrying part 587d electrical isolation basically.Circumference material 560d is applied on the edge of element.Fig. 5 e illustrates the rearview mirror elements 500e of profile line Fig. 5 e～Fig. 5 e observation of the element arbitrarily from Fig. 5 c or Fig. 5 d.The first substrate 502e is illustrated as being fixed with the second substrate 512e with the relation of separating by primary seal material 578e.596e is between observer and primary seal material 578e for spectral filter material (being called as " chromium ring (chrome ring) " here at least one embodiment).First and second electrical terminals (electrical clip) 563e, 584e are set to help and being electrically connected of element respectively.Circumference material 560e is applied on the edge of element.Should be appreciated that and to apply the primary seal material by means commonly used in LCD industry such as silk screen or distribution.The U.S. Patent No. 4094058 that licenses to people such as Yasutake has illustrated the method that is suitable for, at this disclosed full content that adds this patent as a reference.By using these technology, the primary seal material can be applied to independent otch (cut) and go up to determine the shape of substrate, and perhaps, it can be used as a plurality of primary seal shapes and is applied on the bigger substrate.Bigger substrate with a plurality of primary seals that apply can be laminated on another bigger substrate then, and, can after making the primary seal material cured at least in part, cut out each mirror shapes from lamination.This repeatedly treatment technology is the method for using always and is called as array processes sometimes for the manufacturing of LCD.Can make according to photoelectric device of the present invention by using similar technology.Such as all coatings of transparent conductor, reverberator, spectrum pass filter, and under the situation of solid-state light electrical part, photonic layer or a plurality of photonic layer can be applied on the bigger substrate, and are patterned where necessary.Can carry out patterning to coating by using many technology, such as apply coating by mask, by below coating, optionally applying the soluble layer that is patterned and applying, remove after laser ablation or the etching coating at it and it top in coating.These patterns can comprise and be used for accurately aiming at or the alignment mark or the target of position substrate in whole manufacturing process.Usually for example finish this point in the mode of optics with the vision system that uses pattern recognition techniques.If desired also can be by directly being applied to alignment mark or target on glass such as sandblast, laser or adamas line.The blank medium that is used for controlling the interval between the stacked substrate can be placed into the primary seal material, perhaps is applied on the substrate before stacked.Blank medium or means can be applied on the lamination area that will cut from the single mirror assembly of finishing.If device is a solution phase photoelectricity mirror element, so can be with stacked array cutting forming before or after filling photoelectric material and clogging fill port.

Forward Fig. 6 a and Fig. 6 b now to, these illustrate inside rear view mirror assembly 610a, the 610b that observes on the 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 can be randomly with mounting structure 681a (w/ static housing) or 681b (w/o static housing) on static housing 677a combination.The 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 the assembly, make them be positioned at the element back with respect to the observer.As about the explanation of external mirror having indicator light assembly, preferably making

device

688a, 688b, 689a and 697a is hidden as describing in detail here at least in part.In at least one embodiment, the inside rear view mirror assembly can comprise at least one or more a plurality of light fixture 670b on the printed circuit board (PCB) 665b, at least one microphone, they recombinant, they combination or with other combination of above-mentioned device.Should be appreciated that and to add each side of the present invention in photoelectricity window or the mirror individually or collectively with multiple being combined in.

Fig. 6 c is illustrated in the planimetric map of the second substrate 612c of the lamination that comprises material on the 3rd, the 4th or third and fourth surface.In at least one embodiment, in the primary seal material underneath, at least a portion 620c1 of the lamination of material or at least the opaque basically layer of the lamination of material be removed or cover.At least a portion 620c2 of at least one layer of the lamination of material extends to the outer rim of substrate basically or extends to the zone that helps the electrical connection between the 3rd surperficial lamination and the element driving circuit (not shown among Fig. 6 c).Relevant embodiment provides the inspection of sealing and/or padding observation and/or padding curing from the back of mirror or window element after the element assembling.In at least one embodiment, at least a portion of the outer rim 620c1 of the lamination of material 620c is between the outer rim 678c1 and inner edge 678c2 of primary seal material 678c.In at least one embodiment,, preferably about 5mm wide primary seal material underneath wide at about 2～8mm, the opaque at least basically layer of a part of 620c1 of the lamination of material or the lamination of material is removed or covers.At least a portion 620c2 of at least one layer of the lamination of material extends to the outer rim of substrate basically or extends to wide, the preferred wide zone that helps the electrical connection between the 3rd surperficial lamination and the element driving circuit (not shown) of about 1mm of about 0.5～5mm.Should be appreciated that the first, second, third and the 4th superficial layer of material or in the lamination any can be as local as disclosed with reference to the document that adds at other or here here.

Fig. 6 d illustrates the planimetric map of the second substrate 612d of the 3rd surperficial lamination that comprises material.In at least one embodiment, at least a portion of the outer rim 620d1 of the 3rd surperficial lamination of material 620d is between the outer rim 678d1 and inner edge 678d2 of primary seal material 678d.In at least one relevant embodiment, conductive contact sheet part 682d extends from the outer rim of second substrate of the outer rim 678d1 inboard of primary seal material 678d.In at least one relevant embodiment, conductive contact sheet part 682d1 below primary seal material 678d with at least a portion crossover of the 3rd surperficial lamination of material.In at least one embodiment, the outer rim 620d1 outside such as the remainder that like that extend to three surperficial lamination of conductive layer (not illustrating separately) shown in Fig. 8 b of the substantial transparent of conducting metal oxide of the 3rd surperficial lamination of material is connected to provide with the external electric on the 3rd surface.Should be appreciated that can be shown in Fig. 9 c～9i like that along any the deposit conductive contact sheet (conductive tab) in the substrate outer peripheral areas.In at least one embodiment, the conductive contact sheet partly comprises chromium.Should be appreciated that with conductive electrode and compare that the conductive contact sheet partly improves conductance; As long as conductive electrode layer has enough conductances, the conductive contact sheet partly is optional so.In at least one embodiment, conductive electrode layer also gives the color particular characteristics of the hope of corresponding reflection ray except the conductance that hope is provided.Therefore, when omitting conductive electrode, by subsurface material standard control color characteristics.Should be appreciated that the first, second, third and the 4th superficial layer of material or in the lamination any can be as local as disclosed with reference to the document that adds at other or here here.

Fig. 7 illustrates the rearview mirror elements 700 of enlarged drawing so that more details to be provided as the element shown in Fig. 5 e.Element 700 comprises first substrate 702 with first surface 704 and second surface 706.By first separated region 740, be applied to the first conductive electrode part 708 on the second surface 706 and the second conductive electrode part 730 and be electrically insulated from one another basically.As can be seen, in at least one embodiment, separated region is positioned as and makes that spectral filter material 796 and corresponding tackify material 793 also are electrical isolation basically, to limit the first and second spectral filter material parts 724,736 respectively and to limit the first and second tackify material parts 727,739 respectively.The part of first separated region 740,540c, 540d, 540e is shown in a part that is positioned near the primary seal material 778 in its center and extends in parallel.This part that should be appreciated that separated region 740 is deployable, makes the observer can not perceive the line in the spectral filter material at an easy rate; For example, the part of separated region can be aimed at the inside edge 797 of spectral filter material 596 basically.Should be appreciated that when any part when separated region 740 is positioned at primary seal material inboard, as describing in detail elsewhere, can observe the painted and/or clean uncontinuity of photoelectric material here.This operating characteristic can be handled to obtain at the attracting element of subjective outward appearance.

With further reference to Fig. 7, element 700 is shown to include second substrate 712 with the 715 and the 4th surface 714, the 3rd surface.Should be noted that first substrate can be bigger than second substrate, produce skew with at least a portion along the circumference of mirror.The third and fourth conductive electrode part 718,787 is illustrated as respectively near passing through second separated region 786 basically by the 3rd surface 715 of electrical isolation.The part of second separated region 786,586c, 586d, 586e is shown in a part that is positioned near the primary seal material 778 in its center and extends in parallel.This part that should be appreciated that separated region 786 is deployable, makes the observer can not perceive the line in the spectral filter material at an easy rate; For example, the part of separated region can be aimed at the inside edge 797 of spectral filter material 796 basically.Fig. 7 also illustrates, and can apply reflecting material 720 between optional top layer material 722 and the 3rd conductive electrode part 718.Be to be understood that, can use in commonly assigned United States Patent (USP)/application 6111684,6166848,6356376,6441943,10/115860,5825527,6111683,6193378,09/602919,10/260741, in 60/873474 and 10/430885 in disclosed these materials any, to limit such as the integral surface coating of the hydrophilic coating on the first surface or such as being applied to first, second, the third and fourth lip-deep conductive electrode material, spectral filter material, the tackify material, reflecting material, the composite laminate of the coating of top layer material adds disclosing as a reference of these patents at this.The surface that should also be understood that the hydrophobic coating such as fluorinated alkyl salt or polymkeric substance, the coating that comprises silicones (silicone) or specific texture can be applied on the first surface.In water wettability or the hydrophobic coating any will change moisture with respect to the contact angle of the glass bump first surface that does not have this coating, and will increase the back eyesight when having moisture.Should be appreciated that the 3rd surface and the 4th surface reflection device embodiment all within the scope of the invention.In at least one embodiment, be applied to the characteristic that the 3rd surface and/or the 4th lip-deep material are configured to provide at least a portion of corresponding surperficial lamination partial reflection/part transmission.In at least one embodiment, be applied to the 3rd lip-deep material by integrated, so that combined reflector/conductive electrode to be provided.Should be appreciated that additional " the 3rd surface " material can extend in the outside of primary seal, in this case, should be appreciated that corresponding separated region runs through additional material.Make primary seal at least a portion from the 4th surface as seen, for example shown in Fig. 6 c, help the inspection and the UV curing of choke material.In at least one embodiment, in the primary seal material underneath, at least a portion of the lamination of material 620c or at least the opaque basically layer of the lamination of material be removed or cover, so that the inspection for the primary seal width of at least 25% around at least one part of circumference to be provided.The inspection that provides for the primary seal width of 50% around at least one part of circumference is provided.Inspection for the primary seal width of at least 75% around at least one part of circumference most preferably is provided.Various embodiments of the present invention will comprise a plurality of parts of the particular surface of the lamination with coating or coating different with other parts; For example, can form " window " of light source, information display, optical sensor or their combination front, with the specific wavelength of light band of transmission optionally or add the wavelength of light band that illustrates in as a reference many documents here.

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

Sometimes wish on reflection horizon 720, to be provided with one or more optional flash of light external coating 722, make its (not being reflection horizon 720) contact with electrochromism (electrochromic) medium.This flash of light external coating 722 must have stable behavior as electrode, and it must have long shelf life (shelf life), and it must engage with reflection horizon 720 well, and keeps this joint when containment member 778 engages.If the optical property from following layer is visible, overlayer must be enough thin so, makes it not exclusively stop the reflectivity of each layer below 720.According to another embodiment of the present invention; because flash layer protection reflection horizon, still allow high reflection layer 720 to help the reflection of mirror simultaneously, therefore; when extremely thin flash of light external coating 722 be placed in high reflection the layer on the time, reflection horizon 720 can be silver metal or silver alloy.In this case, thin (for example, 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 of flash layer depends on selected material.For example, muddiness in the viewing area when standing hot test for the formation of the point defect in the processing procedure and element, with the chromium of the flash layer that is coated with few ruthenium to 10 dusts under the ruthenium, ruthenium under the rhodium, the element that makes up of three surface coating of rhodium under silver all shows improved resistibility.Initial reflectance with element of ruthenium flash layer is 70～72%.When reflection horizon 720 was 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 such as transparent metal oxide.The factor such as barrier performance, favourable interferometric optical and the balance of compression or drawing stress etc. of overlayer just can being selected as especially match with other layer (compliment).Should be appreciated that and in other embodiment in this paper other places, to use above-mentioned flash layer.

When this overlayer was made by the metal/alloy/semimetal of other compatible with electrochromic system of the metal of above-mentioned tabulation or discovery, when metal or semimetal layer were thicker than 300 dusts, these overlayers were tending towards allowing each layer below it that very little optical effect is arranged.If think the outward appearance of more wishing metal cladding, it can be favourable using this thicker overlayer so.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 this thicker overlayer that can be used in combination with cementing layer and flash layer and during such as the transparency conducting layer of the zinc paste of the tin oxide of doped indium, adulterated al or indium zinc oxide, following layer the conductance benefit that has such as silver, silver alloy, copper, aldary, aluminum or aluminum alloy still can exist.The layer that generally is regarded as insulator such as titania, silicon dioxide or zinc sulphide etc. also can be used in this overlayer lamination or the interlayer, and, as long as their bed thickness makes them still pass enough electric currents from the layer of highly conductive more, just do not negate the benefit of the layer of highly conductive more.

Known in electrochromic field, when when element applies electromotive force, the deepening unevenly of mirror or window.Inhomogeneous deepening is derived from along the local difference of the electromotive force of solid-state EC material fluid in the EC element or gel.Striding across the electromotive force of element changes with the concentration of the conductance of the surface resistance of electrode, bus bar configuration, EC medium, EC medium, unit interval between the electrode or spacing with to the distance of bus.For the normal scheme that proposes of this problem is to make that the coating or the layer that constitute electrode are thicker, reduces their surface resistance thus and makes element deepening more promptly.As following the discussion, the actual unfavorable result that the method for this oversimplification of restriction that existence gives is dealt with problems.Under many situations, unfavorable result makes the EC element be unsuitable for given application.In at least one embodiment of the present invention, illustrate solve the problem that occurs with the simple thickening of electrode layer and cause the EC element have faster, more uniform variable-dark property improved electrode material, make the method and the bus bar configuration of described electrode.

In typical internal mirror, bus and length dimension are advanced abreast.This is that the potential drop that strides across the part between the electrode is minimized.Mirror also generally comprises high surface resistance transparency electrode and low surface resistance reflector electrode.The deepening of mirror 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 have the darkening rate between these two values.When between two buses, when mobile, having the variation of effective electromotive force.Have under the situation of relatively short distance (distance between the bus less than the length of bus half) betwixt at two long parallel buses, mirror will be with the mode deepening of " window-blind (window shade) ".This means near a mirror deepening more promptly bus, and deepening seems mobile between two buses in mode gradually.Usually, darkening rate is measured at the place in the middle of part, and under mirror had situation greater than the ratio of width to height of 2, any unevenness of darkening rate was relatively very little.

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

Can estimate darkening rate from the analysis of EC element according to circuit.Following discussion is about striding across the coating that element has uniform plate electrode.Any locational electromotive force between the parallel pole is the function of the resistance of the surface resistance of each electrode and EC medium.In following table 1, provide the average potential that strides across the element between the electrode together with the difference between the minimum and maximum electromotive force.This example be used between parallel bus, having 10cm at interval, have 180 microns unit intervals, have the element of 1.2 volts of driving voltages and 100000Ohm*cm fluid resistivity.Six kinds of combinations to top and bottom electrode surface resistance compare.

Table 1

The speed of deepening with the electrically contacting of highest face temperature resistance electrode on the highest, and relevant with this locational effective electromotive force.Contiguous this electrically contacts that () effective electromotive force is high more or elsewhere, and the average deepening of mirror will be fast more.When the electromotive force that strides across part is high as much as possible, the fastest total deepening time will appear.This will be with the speed drive galvanochemistry deepening of quickening.The plate electrode of the coating on top and the base substrate works in the effective electromotive force of determining between the electrode, and still, as can be seen from the table, the high surface resistance electrode plays a part more crucial.In existing electrochemical techniques, almost drive by the surface resistance that reduces the low resistance electrode exclusively and improve.This is to be relatively easy because provide the benefit of essence and implement such as the use of the material of silver.

In the art, well-known, along with the increase that drives electromotive force, general speed can increase, but trend and driving circuit are irrelevant, will be constant.Current draw under the also known given voltage (current draw) influences the deepening homogeneity.Can improve homogeneity by the selection of adjustment unit interval, concentration or EC material, but be to use the inhomogeneity improvement of these adjustment usually deepening speed, cleaning speed or deepening and cleaning speed to be had negative influence.For example, increase unit interval and reduce fluid concentrations and will reduce Current draw and will improve homogeneity thus, but cleaning time will increase.Therefore, must suitably set the surface resistance of layer with the speed that obtains deepening simultaneously and the homogeneity of deepening.Preferably, the surface resistance of transparency electrode should be less than 11.5ohm/sq, preferably less than 10.5ohm/sq and most preferably less than 9.5ohm/sq, and, because the optics requirement of discussing 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 less than about 2ohm/sq and most preferably less than 1ohm/sq.Mirror of Gou Jianing or EC element also will have relatively deepening uniformly like this, make between the fast and the slowest darkening rate the deepening mistiming less than the factor 3, preferably less than the factor 2, most preferably less than the factor 1.5.Below discuss can realize these fast, evenly novelties, high-performance, the material cheaply of deepening elements.

In other application, the bus with two opposing parallel may be unpractiaca.This may be because the uneven shape common with outside mirror.In other situation, may wish to have with the point of low resistance electrode and contact.The point contact can make it possible to minimize or eliminate the laser strikethrough that uses in some applications.The use of some contact is simplified some aspects of mirror structure or is preferred for these aspects, but its makes the electromotive force relatively uniformly that is difficult to realize striding across part.Eliminate the resistance that relatively long bus increases electrode effectively along the low resistance reflector electrode.Therefore, need the combination of novelty of bus and coating surface resistance value to obtain deepening rapidly and uniformly.

As mentioned above, those skilled in the art can be expected at can need extremely low sheet resistance value to realize the some contact scheme on the solid metal reflector electrode.Unexpectedly, find that transparency electrode must have lower surface resistance to improve homogeneity.Table 2 expression homogeneity result of experiment.In this test, we make about 8 inches wide solution phase EC elements that multiply by 6 inches high.The benefit of element design discussed here relates generally to bigger element.Bigger element is defined as from the edge of the arbitrfary point on the edge of viewing area the element of the minor increment of geometric center greater than about 5cm.When this distance during, lack the homogeneity deepening problem that more is added with that becomes, and when this distance during greater than about 10cm, the problem that more is added with becomes greater than about 7.5cm.As shown in table 2, the surface resistance of transparency electrode (ITO) and solid metal reflector changes.Make and the contacting of metal electrode with a contact.Use such as the clip contact (clip contact) of so-called J clip to provide and the electrically contacting of solid metal reflector by about 1 inch long Ag paste line along one in the short length sides of mirror.Continue 1/3rd of downward distance along a relative limit and along two long limits of mirror, make and the electrically contacting of transparency electrode by the Ag paste with a contact.On three positions of mirror, measure the deepening time (T5515).The contact of position 1 points of proximity, position 2 are on the edge of transparency electrode bus but relative with a contact, and position 3 is in the center of mirror.The T5515 time (unit is second) is that mirror becomes the time that 15% reflectivity is spent from 55% reflectivity.Maximum reflectivity is the maximum reflectivity of mirror.Δ T5515 is point 1 and puts between 2 or put 2 and put mistiming between 3.This is measuring of the fastest position on the mirror and the darkening rate difference between other two positions.Along with deepening becomes more even, these numerical value become more approaching.Chronon is that deepening time on the given position is divided by the result of the fastest locational time.It irrespectively shows the relative conversion of the time between the diverse location with the absolute speed on any given position.As mentioned above, preferably have less than 3, preferably less than 2 and most preferably less than 1.5 chronon.As can be seen from Table 2, for this specific mirror configuration, when the ITO surface resistance was 14ohm/sq, we did not obtain chronon 3.All three examples that ITO has 9 ohms per squares have the chronon less than 3.The center of mirror reading is to depart from the position of fast position most.Make us unexpectedly disclosing for the statistical study that these data are carried out, the ITO surface resistance is to the contributive unique factor of chronon.By using statistical model, for present embodiment, need be less than the ITO surface resistance of about 11.5ohm/sq to have 3.0 or littler chronon.By using identical statistical model, for this mirror configuration, make chronon less than 2.0, ITO must have the surface resistance less than 7ohm/sq.Even chronon is not influenced by the surface resistance of the 3rd surface reflection device, Zong darkening rate is also influenced.When the surface resistance of described reverberator is less than or equal to 2ohm/sq and ITO for about 9ohm/sq, in the heart the darkening rate of this mirror less than 8 seconds.This value generally mirror with the similar size with conventional bus configuration is corresponding.Therefore, by reducing the surface resistance of ITO, realize the some contact with higher relatively surface resistance reverberator.

Table 2

In another group experiment, the surface resistance of ITO is described in detail in detail in the homogeneity of deepening and the unexpected effect in the speed.In these experiments, with the length that contact for the bus of the high surfaces resistance electrode of ITO in the present example further extension downwards and in some cases even extend on the base of mirror along the limit of mirror.Table 3 shows that the variation of bus length is for inhomogeneity influence.In these trials, except indicating, component shape and configuration are identical with table 2.Contact number percent is the bus length of ITO contact and the number percent comparison of the length overall of circumference.Bus is than being length with respect to the ITO contact of about 2cm or littler little reverberator contact.

From the data description of table 3 increase more that the bus length of high surface resistance electrode can improve homogeneity greatly.For the 2ohm/sq reverberator, from 40% to 85% length that increases the bus contact can bring up to 1.7 from 2.4 with chronon.For the 0.5ohm/sq reverberator, from 40% to 85% same variation of ITO bus length brings up to 1.2 with chronon from 3.2, and improves darkening rate greatly.Should be noted that the element with low surface resistance reverberator generally gets soon than the situation deepening of comparable 2ohm/sq, still, as chronon showed, the homogeneity of situation with 0.5ohm that short ITO contacts was in fact relatively poor.Increasing bus length for ITO is helpful especially for the element with 0.5ohm/sq reverberator.

When contact number percent increased, position the fastest and the slowest deepening also can change.In the present example, higher contact number percent improves deepening time and the corresponding chronon on position 1 and the position 3 greatly.

Table 3

These experiments show that when using short bus with low surface resistance electrode, the bus length that is 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 greater than 5: 1, more preferably greater than 9: 1, more preferably greater than 13: 1, most preferably greater than 20: 1, to obtain to be lower than 3 chronon.We also find, and are irrelevant with the length of less bus, and the length of the bus by being increased to the high surfaces resistance electrode is preferably greater than about 58% and more preferably greater than about 85% contact number percent, homogeneity improves to obtain.Typical big EC mirror has the contact number percent less than 50%.

These discoveries are very crucial for the mirror with opaque reverberator not only, and also are crucial more for the mirror that uses 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, thin metal has high more sheet resistance value.In at least one embodiment of the present invention, photovalve comprise with the conventional bus bar configuration of the optional some contact bus bar configuration that has here instruction fast, deepening equably.The coating of the half-transmitting and half-reflecting of the novelty of the bus bar configuration of explanation more than below explanation is particularly suitable for replenishing.

For make the electrochromism mirror can be on its whole zone evenly deepening or (occur most headlight high light here) at first from its center then outwards towards the top and the bottom deepening of viewing area, also can below the lamination of opaque overlayer or opaque layer, carry out patterning to conductance.Mention at this U.S. Patent application 20040032638A1 " Electrochromic devices with thin bezel-covered edge " that adds people such as Tonar as a reference " low surface resistance coating can be set near relevant electrically contact or perimeter region around the zone in; and allow surface resistance along with increasing to the increase of the distance that electrically contacts ", and statement " when utilizing the some contact, this is a particularly suitable ".When electric driven color-changing part is not applied to voltage above it, generally can wish in reverberator, to provide without any or very little visible contrast be the contrast of unit with ohm.

For electrochromic device obtain enough contrasts more and between the zone of less highly conductive so that the preferentially deepening of some zone, possiblely must in lamination, comprise nonmetallic material.This is because the opaque layer or the lamination of metal that reflectivity is stronger and alloy are tending towards enough conductions, not provide acceptable variable-dark property under the situation of additional highly conductive pattern more in automobile electrochromism mirror below them.An example that comprises semimetallic this material laminate is the material laminate that makes up similarly with the material laminate that illustrates in the United States Patent (USP) 5535056 " Method for making elemental semiconductor mirror for vehicles " that adds at this as a reference, wherein, opaque silicon layer can be covered, be covered, covered by the tin indium oxide of about 20nm by the silicon of 20～25nm again by the tin indium oxide of about quarter-wave optical thickness.This opaque coating stack can have the pattern that is positioned at below it has minimum influence to the outward appearance of its front interpolation material.This lamination can also be enough to 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 that produces about 12ohm/sq usually during deposit ITO still have too strong electric conductivity, so can be by the adjusting process conditioned disjunction by change indium tin than making the electric conductivity reduction of this ITO.

The element that principle that the basis of making the geometry with Fig. 5 f and Fig. 7 with the 3rd different surface coating laminations and conductive pattern illustrates in US20040032638A1 makes up, this element along top, lower limb and left hand edge and roughly on the right the point made of the centre of edge contact and have conductive epoxy.When mentioning whole the 3rd when surface, refer to the surface before any laser action, this laser action is used to produce the required insulating regions of structure according to commonly assigned U.S. Patent application 20040022638A1.

Those that have 1/2ohm/sq in the band of the element that has 1/2ohm/sq the 3rd surface reflection device on the whole viewing area and the center that is striding across the element that is covered by opaque layer 1/2 inch or 1 inch or 2 inches are compared, make the conductance that in the remainder of viewing area, has 4ohm/sq, and in bright state, have the outward appearance quite uniformly of element.When making the element deepening, the center of element is compared the trend that deepening delays and is reduced a little with the edge of the contrast district with conductance.

In order to have higher levels of conductance contrast, make among the figure of the structure of element and front those similar, but, on the 3rd surface, the ITO that is respectively about 12ohm/sq and 40ohm/sq has the conduction band of 2 inches the silver of the center of the single-piece of striding across placing, and this conduction band is coated with the flash layer (being used to handle permanance) of transparent conductive oxide then.After being made into completely electrochromic device, it is on glass that element is placed in silver-plated a slice, make, when estimating variable-dark property, can have intensity and the similar reverberator of silver bar band in the regional back of transparent relatively ITO with 12ohm/sq and 40ohm/sq.As can be seen, when observing under these conditions, with having 12ohm/sq the element of 1/2ohm/sq contrast district is compared, the device of 1/2ohm/sq contrast district is had still less rainbow effect (iris effect) during when deepening having 40ohm/sq on the 3rd surface.

Except using the coating of adding on the 3rd surface, make element according to last paragraph.These coatings comprise: the silicon of ITO, another 20nm of the flash layer of the conductive oxide of interpolation (being placed on the vacuum that is used for comprising in processing there carries out bonding when coating process is broken), the silicon of about 30nm, about 60nm and the ITO of 10nm.Silicon layer may be easy to surface oxidation, and this surface oxidation can form oxide on surface in some EC element, and this oxide on surface is the homogeneity and the consistance of overslaugh deepening then.Can use here ITO or other TCO or of formation or the negative effect of other material to forbid described oxide as flash layer or outer covering layer explanation.When measuring by four-point probe, those elements with the beginning of the initiation layer (according to the example of front) of 40ohm/sq have the 3rd surface conductivity that obtains, this conductance in top and bottom section (according to Fig. 5 f and Fig. 7) for about 24ohm/squre and in the central area be＜1ohm/squre.The element that begins with the initial ITO layer of 12ohm/sq has 10～12ohm/squre in top and bottom section.According to the example of front, the element with higher ohm contrast has the center of minimum rainbow effect or maximum to edge deepening trend.When using D652 degree observer, these elements also do not have following optical characteristics under the 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 can by the thinner strikethrough (deletion line) in second surface electrically conducting transparent (lamination) or the 3rd surface reflection (lamination) and by as other places explanation here to the thickness classification of coating, the preferential deepening in some zone of acquisition electrochromic device.When using the laser deletion, usually,, can produce thinner laser rays along with the operative wavelength that reduces laser as example.By using wavelength to make 15 microns wide strikethroughs as the UV laser of 355nm.These lines are still recognizable, but distinguish than by use that long wavelength's laser more makes those are much more difficult.Along with easier the obtaining of continuing to become of short wavelength's laser more, can expect quite that under the normal condition of motor vehicle mirror not offensive in appearance strikethrough will be possible in viewing area.

When the deletion of the coating stack that has the 3rd surface that will become element on a plurality of parts of a plurality of lines of the center indication that is striding across Fig. 5 f and Fig. 7 or a plurality of lines and make according to existing technique construction element that then variable-dark property is affected when having less relatively the contact on the conductive epoxy resin that uses on edge of this part and other three limits at element ...

It is as follows to make the deletion pattern that obtains by laser for two lines representing at Fig. 5 f and element internal shown in Figure 7 on the 1/2ohm/sq reflector electrode:

1) extending to fine rule apart from the position of the edge 15cm of glass, the edge from glass has the deletion fully of coating.

2) there is the deletion fully of coating in the whole width that strides across this part in the fine rule of the repeat patterns that 8mm deletion and 2mm do not ablate.

3) having the deletion fully of coating the edge from glass extends to fine rule apart from the position of edge 14cm, is that the 5mm that strides across the remainder of this part does not ablate and the deletion of the repeat patterns of 5mm deletion then.

4) except about 5cm along the line and the 0.4mm on the 10cm 2 sections of ablating, extending to fine rule apart from the position of edge 15cm, the edge from glass has the deletion fully of coating.

When comparing without any the similar portions of strikethrough, these elements show some and even seldom " rainbow effect " basically when deepening.In having the pattern of strikethrough, the overall appearance of pattern 4 is best and also deepening.Although all these patterns can need to adjust to obtain acceptable deepening outward appearance, shown moving towards the variable-dark property of hope.

With reference to Fig. 8 a, the cut-open view of the part of rearview mirror elements is shown, this rearview mirror elements comprise by primary seal material 878a with separated relation be fixed with form betwixt having of chamber be deposited on the substantial transparent on the second surface conductive material at least one layer 808a the first substrate 802a and have the second substrate 812a of the lamination that is deposited on the 3rd lip-deep material.In at least one embodiment, photoelectric medium 810a is positioned at described chamber.In at least one embodiment, the 3rd of material the surperficial lamination comprises the 818a of lower floor, conductive electrode layer 820a, metal level 822a and has the conductive contact sheet part 882a of crossover part 883a in metal level and primary seal material underneath.Should be noted that conductive contact sheet part 882a alternatively is deposited on the metallic coating 822a to produce the crossover part.In at least one embodiment, lower floor is a titania.In at least one embodiment, do not use lower floor.In at least one embodiment, conductive electrode layer is an indium tin oxide.In at least one embodiment, omit conductive electrode layer.In at least one embodiment, omitting conductive electrode layer and lower floor is titania or such as the thicker layer of the material of some other the substantial transparent with higher relatively refractive index (that is refractive index ratio ITO height) of silit.In at least one embodiment, the conductive contact sheet partly comprises chromium.Should be appreciated that conductive contact sheet part can comprise according to the level preface is adhered on glass and/or other lamination or the epoxy resin well and resists any conductive material of the erosion under the automobile-used mirror test condition.When being appreciated that in the 3rd surperficial lamination of material or erodible at least those layers in the lamination remain on the zone that the outer rim by the primary seal material limits, element avoids the problem relevant with the 3rd surface erosion basically.If should be appreciated that the protectiveness external coating or the sealant that add such as conductive epoxy resin or external coating, so erodible layer or a plurality of layer may extend into primary seal material outside.Should be appreciated that the first, second, third and the 4th superficial layer of material or in the lamination any can be as local as disclosed with reference to the document that adds at other or here here.Should be appreciated that with conductive electrode and compare that the conductive contact sheet partly improves conductance; As long as conductive electrode layer has enough conductances, the conductive contact sheet partly is optional so.In at least one embodiment, conductive electrode layer also gives the color particular characteristics of the hope of corresponding reflection ray except the conductance that hope is provided.Therefore, when omitting conductive electrode, by subsurface material standard control color characteristics.

Forward Fig. 8 b to, the cut-open view of the part of rearview mirror elements is shown, this rearview mirror elements comprise by primary seal material 878b with separated relation be fixed with form betwixt having of chamber be deposited on the substantial transparent on the second surface conductive material at least one layer 808b the first substrate 802b and have the second substrate 812b of the lamination that is deposited on the 3rd lip-deep material.In at least one embodiment, photoelectric medium 810b is positioned at described chamber.In at least one embodiment, the 3rd of material the surperficial lamination comprises the conductive contact sheet part of the 818b of lower floor, conductive electrode layer 820b, metal level 822b and primary seal material underneath.In at least one embodiment, limit cavity area 883c between metal level and conductive contact sheet part, conductive electrode provides electric continuity betwixt.In at least one embodiment, lower floor is a titania.In at least one embodiment, do not use lower floor.In at least one embodiment, conductive electrode layer is an indium tin oxide.In at least one embodiment, the conductive contact sheet partly comprises chromium.Should be appreciated that conductive contact sheet part can comprise according to the level preface is adhered on glass and/or other lamination or the epoxy resin well and resists any conductive material of the erosion under the automobile-used mirror test condition.When being appreciated that in the 3rd surperficial lamination of material or erodible at least those layers in the lamination remain on the zone that the outer rim by the primary seal material limits, element avoids the problem relevant with the 3rd surface erosion basically.Should be appreciated that the first, second, third and the 4th superficial layer of material or in the lamination any can be as local as disclosed with reference to the document that adds at other or here here.

Forward Fig. 8 c to, the cut-open view of the part of rearview mirror elements is shown, this rearview mirror elements comprise by primary seal material 878c with separated relation be fixed with form betwixt having of chamber be deposited on the substantial transparent on the second surface conductive material at least one layer 808c the first substrate 802c and have the second substrate 812c of the lamination that is deposited on the 3rd lip-deep material.In at least one embodiment, photoelectric medium 810c is positioned at described chamber.In at least one embodiment, deposit the first metal layer 818c on whole the 3rd surface basically.In at least one embodiment, the deposit second metal level 820c on the first metal layer makes the outer rim of second metal level be positioned at the zone that the outer rim by primary seal material 878c limits.In at least one embodiment, the first metal layer comprises chromium.In at least one embodiment, second metal level comprises silver or silver alloy.Should be appreciated that the first, second, third and the 4th superficial layer of material or in the lamination any can be as local as disclosed with reference to the document that adds at other or here here.

Forward Fig. 8 d to, the second substrate 812d of lamination of the material of aperture (eyehole) 822d1 with the front that is in optical sensor or information display basically 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, second metal level comprises silver or silver alloy.In at least one embodiment, the 3rd metal level comprises thin silver, chromium or silver alloy.Should be appreciated that the first, second, third and the 4th superficial layer of material or in the lamination any can be as local as disclosed with reference to the document that adds at other or here here.

Forward Fig. 9 a～9k to, the variety of option of the specific part that is used for optionally contacting the second and the 3rd surface conduction electrode part 922,908 is shown.The configuration that is appreciated that Fig. 7 causes each at least a portion in conductive material contact the second and the 3rd surface conduction electrode part.Contact configuration shown in should be appreciated that can be rotated with respect to element in any manner.

Component construction shown in Fig. 9 a comprises the first substrate 902a of the second surface lamination with material 908a and has the second substrate 912a of the 3rd surperficial lamination of material 922a.The 3rd surperficial lamination of material is shown to have area of isolation 983a, makes the remainder of the 3rd surperficial lamination of the part that contacts with conductive epoxy resin 948a of the 3rd surperficial lamination of material and material separate.First and second substrates are held with relation spaced apart from each other by primary seal material 978a.The relevant similar area of isolation of second surface lamination contact and material that is used for providing in viewing area with the 3rd surperficial lamination of material can be provided the opposite side that should be appreciated that element.Should be appreciated that in the second or the 3rd surperficial lamination of material any can be that other is local and here as with reference to the monolayer material that illustrates in the document that adds here.

Component construction shown in Fig. 9 b comprises the first substrate 902b of the second surface lamination with material 908b and has the second substrate 912b of the 3rd surperficial lamination of material 922b.First and second substrates are held with relation spaced apart from each other by primary seal material 978b.Conductive epoxy resin 948b contacts and passes through the second surface lamination electrical isolation of insulating material 983b and material with the 3rd surperficial lamination of material.The relevant similar area of isolation of second surface lamination contact and material that is used for providing in viewing area with the 3rd surperficial lamination of material can be provided the opposite side that should be appreciated that element.Should be appreciated that in the second or the 3rd surperficial lamination of material any can be that other is local and here as with reference to the monolayer material that illustrates in the document that adds here.

Component construction shown in Fig. 9 c comprises the first substrate 902c of the second surface lamination with material 908c and has the second substrate 912c of the 3rd surperficial lamination of material 922c.First and second substrates are held with relation spaced apart from each other by primary seal material 978c.The second surface lamination of material extends to primary seal material outside towards the edge of first substrate, makes it and first conductive epoxy resin or the first scolder 948c1 electrically contact.The 3rd surperficial lamination of material extends to primary seal material outside towards the edge of second substrate, makes it and second conductive epoxy resin or the second scolder 948c2 electrically contact.The relevant similar area of isolation of second surface lamination contact and material that is used for providing in viewing area with the 3rd surperficial lamination of material can be provided the opposite side that should be appreciated that element.Should be appreciated that in the second or the 3rd surperficial lamination of material any can be that other is local and here as with reference to the monolayer material that illustrates in the document that adds here.

Fig. 9 d is illustrated in the second surface of making on the side relative with the 3rd surface electrical contact 948d2 of element and electrically contacts 948d1.Fig. 9 e is illustrated in second surface that a side of element makes and electrically contacts 948e1 and contact with the 3rd surface electrical of making at an end of element.Fig. 9 f is illustrated in a side and the second surface made with an end of element continuously electrically contacts 948f1 and contact 948f2 in a relative side and the 3rd surface electrical made with a relative end of element continuously.Fig. 9 g is illustrated in the second surface of the relative both sides of element making and electrically contacts 948g1 contact 948g2 with the 3rd surface electrical of making on an end of element.Fig. 9 h is illustrated in the second surface of the relative both sides of element making and electrically contacts 948h1 contact 948h2 with the 3rd surface electrical of making on the relative two ends of element.Fig. 9 i illustrates continuously the second surface of making and electrically contacts 948i1 and contact 948i2 with the 3rd surface electrical of making in a side of element on the relative two ends of element and a side.Fig. 9 j illustrates continuously at relative two ends, fully electrically contact 948j1 at a side and the second surface made at least a portion on second side contacts 948j2 with the 3rd surface electrical of making in a side of element.Should be appreciated that at least one embodiment, long electrically contact surperficial corresponding with highest face temperature resistance lamination with material.Should be appreciated that to electrically contact and to pass through conductive epoxy resin, scolder 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 surperficial lamination of material 922k.First and second substrates are held with relation spaced apart from each other by the circumference first and second primary seal 948k1,948k2.First primary seal is used for making that the second surface lamination with material electrically contacts, and second primary seal is used for making that the 3rd surperficial lamination with material electrically contacts.First and second primary seals keep first and second substrates with separated relation, and preferred two primary seals all are in the outside at the edge of each substrate basically.

Be used for the electrode of photovalve or to set up the another kind of method that is electrically connected such as the contact clip of J clip or L clip be by the Solid-phase welding process.It is to be used for setting up between electronic unit (normally IC chip and chip carrier) welding process of interconnection reliably in electronics industry that lead engages.Among Zonghe Lai in Nordic Electronics Packaging Guidelines and the Chapter A of Johan Liu wire bond process has been described.Engaging the electrical interconnection of making by lead uses the combination of plain conductor or belt and heat, pressure and/or ultrasonic energy so that lead or belt are welded on the 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 generally is included into three main classifications: hot compression joint, ultrasonic joint and heat sound engage.Engaged lead can stop on engaging, and perhaps, can make a plurality of joints with continuous lead.The lead of common form engages and comprises ball bond, wedge bond and stitch bond.Lead and the belt made by many different metals and alloy can be engaged by lead, comprise aluminium, gold, silver, copper and their alloy.These leads can engage with the many metals or the substrate that are coated with metal level, and these metal levels are including but not limited to gold, silver, nickel, aluminium with by the metal level of these metal alloys.With the situation of the electrode engagement of photovalve under, preferred substrate is a glass, and preferred metal deposition process is by the physical vapor deposition process such as magnetron sputtering (magnetron sputtering).Can between metal level that lead engages and glass, apply (one or more) cementing layer, to obtain acceptable adhesiveness such as chromium, molybdenum, nichrome or nickel.The metals deposited layer thickness can be 5 dusts～1000 micron.More preferably metal layer thickness is 100 dusts～1 micron, and the most preferred metal layer thickness is 200～1000 dusts.Diameter of wire or belt thickness can be 10～250 microns, preferred 25～100 microns diameter or thickness, most preferably 50～70 microns diameter or thickness.In at least one embodiment, continuous lead can be along the periphery of substrate by wedge shape or stitch bond to such as on the chromium ring on the second surface of electrochromism mirror.Can be by lead or belt being welded to clip and then the goblet circle being welded on the relevant electrode to substrate and with it, lead or belt bus are electrically connected on the clip such as nickel J or L clip.Lead or belt can start from the metal holder, and advance along the EC electrode, perhaps begin doubling-up to clip and get back to electrode along the EC electrode.In at least one embodiment, for the reliability of device and painted uniformly, preferably have to relevant electrode and/or from EC electrode being welded to connect to the relevant redundancy that electrically contacts folder.Can with 0.005～10 inch, preferred 0.040～2 inch, most preferably make and being connected of a plurality of welding of substrate at 0.100～0.50 inch interval.Can make the lead of welding or belt bus avoid damage by packaging conductive wire in sealant and weld seam.Preferable methods is the splice protection bus by packaging conductive wire/belt and welding in the circumference sealing of related elements.Preferably chemically with the compatible plain conductor/paillon foil of EC medium that surrounds the bus (in the circumference sealing) in the device.The lead bus also can be used to increase the conductance of the related electrode in the element.Diameter is that 75 microns or littler lead are not to be easily distinguishable for human eye.Because be room temperature or chilling process, do not need back curing or post-processing operation, the technology set up well is proved to be has reliability and can promptly set up joint (each engages about 100 milliseconds), therefore, from the viewpoint of making, it is attractive that the lead of welding engages.

Lead engages and also can be used to make electronic unit to be electrically connected with the substrate surface of element.For example, many metals are stable on galvanochemistry as negative electrode in the element rather than anode the time.Hope is such as providing protection by diode, (followingly to go through this point with reference to Figure 11 a～11c in the operation of polarity phase inverse time lag system EC device.) can engage be fixed on substrate or the bus clip and with substrate and/or clip by lead such as the electric parts of mounted on surface diode and be electrically connected.In another embodiment, as signaling or the light emitting diode (LED) of the part of warning system can be for example be fixed on the relevant substrate with the form of chip, and with by etching, cover (masking) or laser ablation the circuit that metallic coating carries out on the substrate that patterning forms be connected.One, two, three or four s' these LED or other electric parts can be installed on the element on the substrate surface or in the element.For the increase of the rate of propagation that compensates the electrochromism species and on wider temperature range, keep good device deepening performance, usually wish that rising increase along with temperature is applied to the driving voltage on the solution phase electrochromic device.The needed thermistor of the variable voltage drive circuit of temperature modulation and electronic unit can be installed on the relevant substrate surface and engage with metallic coating on the substrate by lead and be electrically connected.Example: aluminum steel engages as follows with metallic coating on the glass substrate:

Glass is cleaned and is coated with the thick layer of about 400 dusts of comprising following each layer by vacuum sputtering: the ground floor of chromium and the second layer of nickel (CN); The ground floor of chromium and the second layer of ruthenium (CR); The 3rd layer (CRN) of the ground floor of chromium, the second layer of ruthenium and nickel.By use Westbond Model 454647E lead jointing machine with following being provided with, the diameter that will comprise 1% silicon is that 0.00125 inch aluminium alloy conductor (extensibility is 1～4%, and tensile strength is 19～21 grams) joins on the glass substrate of plating:

Be provided with first and engage second joint

" CN " powder 175 150

30 milliseconds 30 milliseconds of times

Power 26 grams 26 grams

" CRN " powder 175 150

30 milliseconds 30 milliseconds of times

Power 26 grams 26 grams

" CR " powder 150 125

75 milliseconds 100 milliseconds of times

Power 26 grams 26 grams

By after engaging and after under 300 ℃, exposing 1 hour to the open air, pulling off lead and ergometry, estimate the bond strength of lead.

Lead engages average pull strength:

After engaging after 300C cures

" CN " 14.51 grams 9.02 grams

" CRN " 19.13 grams 8.2 grams

" CR " 12.42 grams 8.7 grams

Main inefficacy after engaging is the wire fracture on first engagement end portion of welding.After curing, organize for " CN " and " CRN ", main lost efficacy (main failure) is the wire fracture on the span centre, for " CR " group, main inefficacy is the wire fracture on first end that engages.This example shows, can make a plurality of reliable solder joints for typical splash-proofing sputtering metal layer on glass.

Figure 10 generally illustrates the variable transmissivity window 1010 that can use with window control system 1008 in many passengers vehicle, this

window control system

1008 and 1010 electric coupling of variable transmissivity window are used to control the transmissivity state of variable transmissivity window 1010.Window control system 1008 comprise with variable transmissivity window 1010 in each coupling be used for controlling each the window control module 1009 of transmissivity of variable transmissivity window 1010.Each window control module 1009 comprises the subordinate control circuit 1070 of the transmissivity state that is used to control relevant variable transmissivity window 1010.Each window control module 1009 also is shown to have with subordinate control circuit 1070 coupling and is used for providing the user to import user's input mechanism 1060 with the transmissivity state that changes relevant variable transmissivity window 1010 to subordinate control circuit 1070.Each window control module 1009 also is illustrated as and the power and ground wire 1011 couplings that are used for providing to subordinate control circuit 1070, user's input mechanism 1060 and variable transmissivity window 1010 electric power.As shown in the figure, provide electric power by subordinate control circuit 1070 to variable transmissivity window 1010 from power and ground wire 1011.

Each window control module 1009 also is illustrated as and 1013 couplings of window control system bus.Other devices same and 1013 couplings of window control system bus comprise governor circuit 1090 and other electron device 1092.Governor circuit 1090 is configured to monitor by each signal that provides on window control system bus 1013 in the window control module 1009 and with the control signal on the bus and offers in the window control module 1009 each.Governor circuit 1090 comprises that the treatment circuit, storer and the bus interface circuit that comprise logic is to allow governor circuit 1090 and produce, send, receive the signal on the window control system bus 1013 and these signals are decoded.The subordinate control circuit 1070 that comprises in window control module 1009 each is configured to receive the window transmissivity state of hope and provide electric signal to change over the state of user by 1060 requests of user's input mechanism with the transmissivity state with variable transmissivity window 1010 to variable transmissivity window 1010 from user's input mechanism 1060.Subordinate control circuit 1070 also is configured to monitor the various characteristics of variable transmissivity window 1010, comprises by the electric power of variable transmissivity window 1010 consumption and the transmissivity state of variable transmissivity window 1010.Subordinate control circuit 1070 also comprise be used for from/to the circuit of window control system bus 1013 reception/transmission signals.

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

May preferably material be added being used as in the second surface transparency electrode of anode sensitivity in certain embodiments.In this case, in order to protect the second surface electrode, may preferably drive the 3rd surface electrode for anode and with the second surface electrode drive be negative electrode.

EC mirror for outside vehicle, may there be the not direct power supply that connects with the associated driver circuitry that is arranged in relevant internal mirror, this can make the 3rd surface reflection device electrode be the risk minimization of the anode on this mirror (that is, given outside mirror can comprise independent driving circuits) to a certain extent.But the electric power of supplying with (one or more) outside mirror by internal mirror is common.Between internal mirror and corresponding outside mirror, usually there are several connections.When relevant reverberator/electrode is not enough to persistence ground as anode, thereby mirror makes that to the reversal of poles of the electric power of outside mirror the 3rd surface reflection device electrode of device is that the risk of anode can be unacceptable internally.

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

Circuit 1100b shown in Figure 11 b comprises near the lead-in wire diode connected in parallel 1101b that strides across the outer mirror sub-element 1102b.If the reversal of poles of the electric current that provides to this part of circuit will cause short circuit so.Electric current will flow through diode rather than electric driven color-changing part then.Detect short-circuit conditions by internal mirror circuit 1103b, and voltage is by automatic cutout.Therefore, even allow the proper handling of mirror when polarity is correct, if polarity is opposite, this circuit is also forbidden the electrochromism function of mirror fully.

But, as diode 1101c and when excess current (short circuit) does not stop when making voltage reversal applying the circuit 1100c coupling of voltage at first, mirror element 1102c keeps operation, and suitable polarity is transferred to element, makes reflector electrode be reconnected automatically and is negative electrode.In this circuit 1100c, when detecting excess current, two solid-state switch 1104c1,1104c2 are reconfigured automatically to change the sense of current by element 1102c along opposite direction.Just in case detect excess current in this configuration, so, because some other fault may cause excess current to draw (excessive current draw), so solid-state switch is reset and be disconnected for the driving of element.

Figure 11 d illustrates the alternate configuration that opposite polarity is provided the photoelectricity driving circuit of automatic compensation.Diode 1101d1,1101d2,1101d3,1101d4 limit the rectifier bridge that the double-current path is provided.The flow orientation of hope of the anode will always have photovalve 1102d and negative electrode of Actual path electric current.

Circuit 1100a, 1100b, 1100c and the 1100d of Figure 11 a～11d is illustrated as single outside mirror.If wish the single outside mirror of more than protection, the circuit of Xi Wanging can be reequiped by adaptability so so.

Similarly have in the photovalve of the 4th surface reflection device (not shown) with photovalve shown in Figure 7, when between transparent conductor 708 and 718, not having electric potential difference, electrochromic media in the chamber 710 is colourless basically or almost is colourless, and, the light (I that enters _o) enter, pass electrochromic media, clear coat 718, rear element 712 in clear coat 708, the chamber 710 by the place ahead element 702, and, reflect away and pass device from this layer and advance backward and leave the place ahead element 702.Should be appreciated that the above-mentioned each side of the present invention at the variable transmissivity window can not comprise the reflection horizon.In other embodiments, can use the 3rd surface reflection device/electrode.Usually, the reflected image (I that does not have electric potential difference _R) size be incident intensity (I _o) about 45～85%.Definite value depends on many variablees of following general introduction, such as, for example, from the residual reflection of the front of the place ahead element (I ' _R) and from the secondary reflection at the interface between the place ahead element 702 and the place ahead transparency electrode 708, the place ahead transparency electrode 708 and electrochromic media, electrochromic media and second transparency electrode 718, second transparency electrode 718 and the rear element 712.These are reflected in known in the art, and are because light between the two refractive index poor when crossing interface between a kind of material and the another kind.When the place ahead element and rear element are not parallel, residual reflection (I ' _R) or other secondary reflection will be not and reflected image (I from minute surface _R) overlapping, and, dual imaging (observer can see that in the reflected image quantity of in esse object looks like dual or triple) in this case, will appear.

Be positioned at outside vehicle or the vehicle according to the electrochromism mirror, have minimum requirement for catoptrical intensity size.For example, according to most of automakers' current demand, internal mirror preferably has at least 40% minimum high-end reflectivity, and outside mirror must have at least 35% minimum high-end reflectivity.

Electrode layer 708 with 718 with effectively the electronic circuit of electrochromic media power supply being connected of for example Figure 10～11d, thereby when striding across

conductor

708 and 718 and apply electromotive force, the electrochromic media deepening in the chamber 710 makes incident light (I _o) along with passing towards reverberator and along with it passes backward after being reflected and decays.By adjusting the electric potential difference between the transparency electrode, preferred devices is as " gray level " device of the transmissivity that has continuous variable on the scope of broad.For solution phase electrochromic system, when the electric potential difference between the electrode was removed or return zero, device spontaneously returned identical, zero potential, balanced color and the transmissivity that has with device before applying electromotive force.Say also that for making electrochromic device other material is available, and, should be appreciated that no matter use which kind of photoelectric technology everyway of the present invention is suitable for.For example, photoelectric medium can comprise the material as the hybrid combination of 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.

To have the photovalve that when keeping low the absorption, has the second surface transparent conductive oxide of relatively low surface resistance in order providing, to have carried out various trials.At above-mentioned electrochromism mirror and in general electrochromic window or photoelectric device, transparency conducting layer 708,718 is often made by tin indium oxide.Other trial concentrates on the inherent strain that reduces the ITO layer that is applied on the relevant glass substrate so that the bending of substrate or warpage minimize.Other trial is the optical property by 1/4th or half-wavelength thickness optimization such as the reflectivity of adjusting the ITO layer, or makes the minimize weight of population characteristic valuve assembly.But, because the physical restriction recognized in the past, therefore optimize above-mentioned all optics simultaneously and the effort of physical property rarely has success.

The method of the optical property of the given electrochromic window assemblies of optimization before a kind of like this is to control the composition of electrode wherein.The reflectivity of reflecting electrode that particularly, can be by adjusting assembly obtains some optical property.More specifically, comprise the material composition of the lamination of reflecting electrode, can increase its reflectivity, offset the relative absorption of relevant transparency electrode thus by control.But the reflectivity that increases reflecting electrode generally need use the metal of the addition that is used to construct it, such as rhodium, ruthenium, chromium and silver etc.Because the many metals in these metals are relatively more expensive, therefore its addition for electric driven color-changing part makes us increasing its cost with accepting.And, many low-cost metals, though improve good reflecting properties, the severe environmental conditions that will stand with manufacture process and/or such as the black box of outer mirror sub-component and outside window assembly is incompatible.

Utilize other method of ITO electrode to need the unreciprocal several optics and the balance of physical parameter.For example, as discussed in more detail below, the thickness that increases transparent ITO conductive layer can influence the absorption relevant with this layer, 1/4th and/or the position of half-wavelength point and the bending that has applied the substrate of ITO layer unfriendly to realize low surface resistance.

Be known in the art, can reduce the surface resistance of ITO layer by the thickness that increases the ITO layer.But, realize that the increase of the thickness of ITO layer is attended by the undesirable increase of the light absorption of this layer.And the increase of the thickness of ITO layer is generally limited to the integral multiple of the half-wavelength of setted wavelength scope (being the center with about 550nm generally), so that minimize from the relative reflectance of the outside surface of ITO layer.And the thickness that increases the ITO layer can increase the bending of the substrate that has applied the ITO layer.As everyone knows, the ITO layer comprises the internal stress that is applied on the substrate, and this internal stress can cause the bending of this substrate on being applied to some thin substrates the time.In a lot of the application, substrate comprises relatively thin glass with the absorption that reduces glass and reduce relative weight, makes thickness along with the ITO layer increase and this unacceptable bending occurs.In the bigger application such as the big window of the window that is used for aircraft or buildings, this is general especially.The bending of associated substrate can influence two distance between electrodes in the black box, influence relatively evenly darkness or the brightness on the difference surperficial of cleaning speed, color, assembly thus, and even a plurality of reflected images that produce rather than the point of single image are caused optical distortion along it.The method of the inherent strain of reduction ITO layer in the past concentrates on the method that is used to make electric driven color-changing part.Known in the prior art being used for comprises the magnetic sputter with a kind of method that the ITO layer is applied on the relevant substrate.Up to now, because several shortcomings, these are attempted only is that appropriateness is successful, and one of shortcoming is the intrinsic physical restriction of method, and its example is the destruction of the lay of the ITO layer when pressure boost, and this causes the cluster of ITO.The increase that the ITO layer of this cluster shows surface resistance, blurs and absorb.

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

In at least one embodiment, a kind of photovalve is provided, this photovalve has that the relative surface resistance that has reduced provides the relative absorptivity that has reduced simultaneously, the bending of the associated substrate that has applied relevant ITO layer that reduced relatively, and the relatively evenly darkness or the brightness of black box are provided when reducing its general assembly (TW).

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

As mentioned above, high performance photovalve (mirror or window) requires the 3rd lip-deep electrode and/or reverberator and transparency conductive electrode 708 to provide from appropriateness to higher conductance, with the painted and cleaning speed that provides totally painted uniformly, increased etc.Though, wish improvement about transparency electrode 708,718 by using the 3rd surface reflection device/electrode to realize the improvement of mirror element.As mentioned above, have injurious effects by reducing the general thickness that increases ito transparent electrode 708,718 when surface resistance improves conductance simply for other optics and the physical property of electric driven color-changing part.The reflectivity that table 4 illustrates the EC element have along with change the different optical constant three kinds of ITO coatings ITO thickness and reduce.Different ITO coating in this example has different empty refractive index (imaginary refractive index).The exemplary elements structure comprises Ru, 140 microns EC fluid, different ITO and the glass of 1.7mm of Cr, 20nm of glass, the 50nm of 1.7mm.Thickness at the TO of different I shown in the table 4 layer.In many side mirrors were used, client's code requirement reflectivity was 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 actual upper thickness and the lower limit surface resistance of the constraint of the variation in the manufacture process.In addition, it is general corresponding with higher surface resistance undesiredly to have a low ITO that absorbs.ITO thicker, low absorption also can be corresponding with higher surface resistance, limits the benefit of thicker coating thus.

Table 4

Another kind desirable design attributes for the EC element is to have lower reflectivity in dark state.This causes mirror element to have higher contrast ratio.Table 5 illustrates the dark attitudinal reflexes rate value with the EC mirror of ITO variation in thickness.In the present example, not to be set as be opaque basically for EC stream.If the EC fluid is not opaque fully, will increase reflectivity in the table 5 from the reflected light of mirror coating so.What go out as shown is such, and when design wavelength was 550nm, dark attitudinal reflexes rate reached 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 contrast compares deterioration.Therefore, in order to obtain given sheet resistance value, ITO thickness can not be made as thickness arbitrarily.The absorption of coating and dark attitudinal reflexes rate demand all limit ITO thickness.

Table 5

In at least one embodiment, photovalve comprises at least one ito transparent electrode 128 with the volume resistance that has reduced, and improves conductance thus in relevant optics of not sacrificing other and physical property.Especially, under higher relatively pressure and relative higher oxygen gas flow rate, make up photovalve by sputter procedure.Up to now, the sputter procedure for the routine that is applied to the ITO layer on the substrate to be utilized is limited to some maximum pressure.Surpass these pressure in the past and caused the second-rate of ITO layer, perhaps, particularly, cause showing the uneven deposit of the cluster of relatively poor electricity and optical property.

In at least one embodiment, on the sputter coating machine of vertical, in-line arrangement, make the ITO coating.Negative electrode is about 72 inches long, and uses two or four negative electrodes to make coating.Negative electrode is equipped with industry ceramic ITO tile commonly used.Adjust the coating of conveyer speed as required with manufacturing objective thickness.Unless indicate in addition, the power that is applied on the negative electrode is 5 kilowatts.Each workshop section has two anticathodes in the configuration of facing of aiming at.Unless otherwise instructed, the oxygen flow of expression is the workshop section that is used to comprise four negative electrodes here.When two workshop sections are operated, suppose in oxygen feed to two chamber with equivalent, and the total amount of oxygen is for being used for the twice of the amount of four negative electrodes in a process chamber.Glass substrate is preheating to about 300 ℃.Sputter gas is adjusted obtaining given pressure, and oxygen is introduced into the flow velocity of regulation or as the number percent of total gas of the system of being fed to.But should understand, has the pressure of measuring them on different suction configuration, gas access and manifold, negative electrode and power and the difference during the course owing to those skilled in the art will know that different chambers, therefore, the invention is not restricted to above-mentioned definite flow velocity and number percent.On the contrary, those skilled in the art understand their novelty of method of the performance that obtains be used to producing coating and comprise volume resistance, stress and form, and can be at an easy rate for different sputtering system adjustment or adaptive change the instruction here under the situation of not doing experiment.Though the major part of Shuo Ming work is to carry out with the glass substrate temperature of 300C here, but, even there is not to obtain the absolute value of explanation here under different temperature, trend and discovery still can be applicable to higher and lower temperature and generation be better than the improvement of standard conditions.

In at least one embodiment of the present invention, make the increase skew of pressure process by the increase of oxygen flow.As described, the particular kind of relationship of pressure and oxygen gas flow rate depends on several factors, is included in the specific inert gas that uses in the sputter procedure.Here go through two kinds of inert gas krypton gas and argon gas, still, can be by utilizing other gas from details to other gas of given data extrapolation.

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

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

As mentioned above, also can utilize other gas.For example, can use have be preferably greater than or equal 3mT, more preferably greater than or equal the neon of higher pressure of the expectation of 7～8mT.And with krypton gas phase ratio, xenon allows to use relatively low pressure.Those skilled in the art can recognize that also preferred oxygen concentration can change along with the details of sputter equipment.Number percent listed above means it is indicative and nonrestrictive.The total flow of the oxygen that the best of breed of acquisition material property is required generally increases with pressure.The requirement of oxygen does not increase under the flow velocity identical with sputter gas, and therefore, the number percent of oxygen reduces with the increase of pressure.

Usually, ITO under low pressure-below 2mT, move.But low-pressure is tending towards causing the ITO coating to have compression stress.Particularly when the thickness of glass hour, the stress among the ITO enough height so that glass bending.When the thickness that reduces glass when making EC element lighter, because the deflection of the glass that ITO stress causes increases.When mirror element or window size were big, the deflection of glass can be several millimeters.Manufacturing in enormous quantities for routine is handled, and along with the thickness increase of ITO, the deflection of substrate generally increases.

Can express the deflection of glass in every way.A kind of mode is to consider that the deflection of glass is aspect lens.Thereby times magnification numerical value is directly relevant with the deflection of glass, and irrelevant with the size of glass.Times magnification numerical value relates to the radius-of-curvature of using following formula: radius-of-curvature=(3124mm)/(1-1/ enlargement factor).The complete smooth glass of a slice will have 1.0 times magnification numerical value.For the coating glass of observing from coated side, in the time of among coating is in compression stress, glass will become projection in coated side.If coating is in the drawing stress, glass will be recessed in coated side so.The compression coating causes warpage or the times magnification numerical value less than 1, and on the contrary, if coating stretches, enlargement factor or warp value will be greater than 1 so.0.85 the warp value of magnitude from smooth and glass height warpage.Because can crossover from the reflection on first and second surfaces, so the warp value of this magnitude will produce the EC mirror or the window that can have dual imaging.In addition, be difficult to make feasible sealing with glass with unacceptable warpage.The glass that has up to 0.97 warp value can go wrong in the mill or about dual imaging.

With reference to the Figure 12 that indicates " argon pressure test ", measure warp value for the ITO coating that 1.6mm is on glass.When applying ITO or other band stress coating, thickness of glass plays an important role in deflection and warpage.Deflection is general on the contrary with cube change (supposition is along with the inherent strain in the variation in thickness coating of coating is constant) of the thickness of glass.Therefore, thin glass will be with respect to thicker glass with nonlinear mode warpage.When with thicker glassy phase than the time, the thin glass with thin ITO coating is generally with warpage.Amount of warpage is along with the thickness linear change of coating.In Figure 12, the thickness of coating is about 50nm.In order to calculate the warpage on other one-tenth-value thickness 1/10, can use following formula: new warpage=[1-(1-warp value) thickness that * is new/old thickness].This formula is applied to the value of 0.98 among Figure 12, can obtains 0.74 warp value of 0.94 warp value of the thick ITO coating of 150nm and 650nm thick coating.If glass is thinner, these values can depart from smooth situation more greatly so.

Figure 12 illustrates the discovery of several keys.At first, on the oxygen gas flow rate scope in this experiment (x axle), warp value among the ITO that makes under 2.1mT or stress (y axle) do not change greatly.On this scope, ITO passes minimal surface resistance and volume resistance value.May conclude improperly and can not optimize electric simultaneously and stress performance, say nothing of other needed optical property.Under very high oxygen gas flow rate, warp value begins to depart from greatly more smooth situation.

Under higher pressure (4.0mT), a kind of trend appears.Under lower oxygen gas flow rate, the stress in the ITO coating reduces.But under higher pressure, this changes into the lower oxygen concentration in the whole sputter environment.In sputtering technology, generally when adjusting pressure, keep oxygen concentration constant.Therefore, when using conventional experiment, do not find to cause this trend and the discovery of one embodiment of the present of invention.Compare with line 1201, under higher argon pressure with the 4mT shown in the line 1202, occur very strong under lower oxygen flow the trend of the minimise stress among the ITO.Lower stress is because the microstructure or the form of the uniqueness in the ITO coating in the following detailed description of.Under higher oxygen gas flow rate, warp value departs from smooth situation, still, under any specific oxygen gas flow rate, the warp value height that warp value keeps ratio under low pressure to obtain.Pressure for more taller than pressure shown in Figure 12 is still this trend.Surpassing under the pressure of 7mT, these benefits continue.Also can obtain other improvement under high pressure more, still, the restriction of specific sputtering chamber can limit above the experiment under the pressure of this value.

Figure 13 illustrates the influence of the relative increase of argon pressure and oxygen flow to volume resistance.By utilizing argon gas to carry out this specific test as sputter gas.400sccm argon gas situation (line 1301) produces the pressure of 3.7mT, and 550sccm (line 1302) produces 5mT, and 700sccm (line 1303) produces 6.2mT, and 850sccm (line 1304) produces 7.4mT.Oxygen gas flow rate unit on the x axle is sccm.Notice that along with argon pressure and oxygen flow increase, specific insulation obtains to improve greatly.In addition, with respect to higher pressure condition, lower argon pressure situation is tending towards having minimum value on higher volume resistance value.As a reference, the suitable coating of making under the pressure of 2mT comprises the volume resistance value of about 180～200 μ Ω cm.In nearest disclosed patented claim, another manufacturer of electrochromic device has submitted to the current state of prior art of the ITO coating of EC in using with the volume resistance of 200 μ Ω cm corresponding.This expression is not considered improved ITO coating of the present invention in advance for benefit and performance that EC uses feasible ITO.Here Shuo Ming more high pressure situation does not obtain their minimum value on the oxygen scope of test.

Figure 14 illustrates higher pressure and further causes relatively thin ITO coating on the substrate.Before also helping to explain, this point do not obtain the reason of present embodiment of the present invention.As shown, when oxygen flow and argon pressure increase, the thickness of ITO coating reduces.As the intrinsic volume resistance of measuring of the quality of the electrical property of the ITO product that is surface resistance and thickness.But, general surface measurements resistance only, still, when coating is not characterized in detail, many information dropouts.Because along with the variation coating attenuation of process gas, therefore, surface resistance is not deferred to the trend identical with volume resistance.Shown in the comparable analysis of surface resistance with the benefit for the continuity of volume resistance of higher argon pressure (with respect to line 1401,1402,1403, line 1404 representative is the highest) and oxygen flow acquisition.If only check surface resistance, can conclude that so under relatively low oxygen gas flow rate 3.7mT situation is best and obtains preferred performance.Follow another benefit of lower volume resistance to be that the real part of refractive index reduces.Half-wavelength coating with lower refractive index is physically than the half-wavelength thick coating with higher refractive index, thereby causes lower surface resistance.

The diagrammatic sketch of Figure 15 illustrates the effect of utilizing argon gas in conjunction with higher argon pressure and higher oxygen flow, and the diagrammatic sketch of Figure 16 illustrates the ITO half-wavelength volume resistance of realization.In order to obtain 1/2 wavelength coating, use two process chambers.The 200sccm situation is represented the standard in the existing ITO coating in the EC technology.The half-wavelength coating of prior art has the surface resistance that is higher than 12.5ohm/sq, and obtains value less than 12ohm/sq according to the more high pressure situation of at least one embodiment of the present invention, some in addition be lower than 11ohm/sq.In Figure 16 illustration the essence of the volume resistance that under higher pressure, obtains improve.In this case, oxygen is not optimised under higher pressure, and when argon flow amount was 400～800SCCM, it is constant relatively that volume resistance seems to keep.

The volume resistance of ITO is crucial, and still, as other places were mentioned here, surface resistance was the principal element that influences the deepening speed in the EC element.For the half-wavelength coating, the surface resistance that the volume resistance of 200 μ Ω cm is amounted to into 13.7ohm/sq, 180 volume resistance is amounted to into the surface resistance of 12.4ohm/sq, and 140 volume resistance is amounted to into the surface resistance of 9.6ohm/sq.Compare with the situation of 13.7ohm/sq, 9.6ohm/sq reduces 30%, and causes the essence of deepening time to be improved, and can realize the bus configuration of the novelty of other places explanation here, and this bus configuration is also improved element deepening homogeneity.

In next example, in different coating machines, make coating.This coating machine has about 27 inches long negative electrodes.Experimentize with argon gas under the pressure of 2.73 millitorrs and krypton gas.In passing two passages of negative electrode, make coating.As illustrating, relevant accompanying drawing and form change oxygen.The thickness of the ITO coating that obtains is about 600nm.In Figure 17, the relation of absorption in the coating of drawing (y axle) and oxygen gas flow rate (x axle).As can be seen, compare with the sample that uses argon gas (line 1702) to make as sputter gas, under given oxygen gas flow rate, the absorption of the sample made from krypton gas (line 1701) is higher.

In Figure 18, the warpage of the glass that draws (y axle) is as the relation of the function of oxygen gas flow rate (x axle).As can be seen, the sample made from krypton gas (line 1801) has more the warp value near 1, and the glass that the glass of the coating ITO that this expression krypton gas is made is made than argon gas (line 1802) is smooth.Figure 18 illustrates the data that more early provide, and wherein, warpage is illustrated as increasing with the increase of oxygen gas flow rate.

In Figure 19, warpage of the glass that draws (y axle) and the relation that absorbs (x axle).The sample that krypton gas is made (line 1901) when with oxygen gas flow rate to having more absorption at once, still, when at absorptance during than warpage, the sample that the sample that krypton gas is made is made than argon gas (line 1902) is smooth.

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

The form of ITO coating or surface characteristics also change with pressure and oxygen gas flow rate.Between these values, there is interaction effect, wherein, when pressure change, under different oxygen gas flow rates, obtains different forms.At the ITO coating sample shown in Figure 21～23 is to have in the coating machine of 72 inches negative electrodes to make.All samples all are to make under the linear velocity of 2.1mT, each target 5kw, 1 process chamber (2 targets of every side) and 32ipm.For the sample among 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 forms, and the sample of Figure 23 has platelet 2302 forms.Inspection for the sample of Figure 21 discloses background platelet 2102 structures.The sample of Figure 21 is considered to how much have the form of mixing.The sample of Figure 22 has considerably less tubercle 2201 and overall leading platelet 2202 forms under middle oxygen flow.The platelet form is relevant with higher stress in the coating, and occurs the plethora form in the coating with stress seldom.According to given processing gaseous tension, the transformation between these two kinds of different shapes is suddenly or gradually.Hypoxemia plethora form is characterised in that roughness between bigger peak valley (as about Figure 33 a and Figure 33 b detailed description).Tubercle occurs on the surface of coating basically, produces roughness between bigger peak valley thus.Along with tubercle is transformed into the platelet microstructure, the roughness on surface reduces.When tubercle just disappeared from the surface, roughness was in minimum value.At that point, we have the platelet microstructure that has more shallow " steep cliff " 2103,2203,2303 or zone between platelet.Along with oxygen flow further increases, the height of the steep cliff between the platelet increases, thereby increases the roughness on surface undesiredly.

The sample of Figure 24～26 is under power suitable with Figure 21～23 and linear velocity and all makes under the oxygen at 2sccm.Handle gaseous tension and be respectively 3.7,2.1 and 1.6 millitorrs.Along with pressure increases, form is dominated by the plethora form more and more.Under higher pressure, the transformation between

plethora

2401,2501,2601 and the platelet form relaxes more, allows thus to carry out thinner adjustment between the optics of the hope in coating and the mechanical property.Platelet 2402 forms still are present in the background of 3.7 millitorr samples, but measure considerably less.Along with pressure further reduces, the tubercle composition finally is eliminated, thereby only stays the platelet form.

Use krypton gas or other heavier sputter process gas similar with operation under higher pressure in some respects.Shown in Figure 27～29, will serve as to handle gas and three SEM images of the 1/2 wavelength ITO sample made with the oxygen gas flow rate of change are compared with krypton gas.Illustrate in greater detail these samples with reference to table 6.Under the linear velocity of 40ipm and 6.2kw and by two process chambers of use (four negative electrodes of every side), make these samples.Thickness of glass is 1.1mm.For the sample among 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 of making under 8sccm oxygen shown in Figure 17 does not have the platelet composition in fact, and is extremely stressless; The surface of this sample mainly is a tubercle 2701.Sample shown in Figure 27 and have from the 1/2 other wavelength sample of table 6 and to be essentially 1 warp value.The surface structure of sample shown in Figure 28 generally comprises tubercle 2801 and has considerably less 2802 forms of the platelet with small steep cliff 2803.The sample of Figure 29 is platelet 2902 surface structures with the steep cliff 2903 that limits well basically.Sample has the low-down volume resistance value of about 150 μ Ω cm.Absorption for these coatings of situation of 12sccm is quite low, thereby has the best of breed of planarization, resistivity and absorption.The low stress values of these coatings shows, even some platelet forms, when by using higher pressure or during with heavier sputter gas manufacturing, also can successfully being utilized.

Sample D, E shown in Figure 30～32 and F are respectively the 2 wavelength ITO situations of listing for table 7, and corresponding with 8,12 and 16sccm flow velocity respectively.For these sample wire speed is 7ipm, otherwise treatment conditions are identical with table 6.Thick about 5 times of these coatings than their half-wavelength homologue.What are different with plethora 3001,3101,3201 forms of thin sample for the form of the coating on these samples, provide more in pelletized form structure (sample D, Figure 30).Have the cavity between particle shown in Figure 30, this causes the conductance of higher unfriendly fuzzy and deterioration; The higher relatively volume resistance value illustration of 200 μ Ω cm of this sample this point.The sample E that makes with the oxygen of 12sccm has low-down volume resistance (131 μ Ω cm) and thinner particle microstructure.The 16sccm situation has similar microstructure, but in this case, owing to be in the thin coating, does not therefore have the platelet form.The stress level of the coating that these krypton gas are made is relatively low.The scope of warp value under the low oxygen situation be essentially 1 value under the maximum oxygen gas situation 0.956.These samples are to use with the 1.6mm glassy phase that illustrates previously to make than the 1.1mm glass that is easier to warpage.Warp value is still very near 1.It has than beginning in the coating of the 50nm of 1.6mm discussion on glass thick coating above 10 times.These coatings not only have extremely low stress, and they also have better volume resistance value and acceptable absorption value.

Surfaceness between the peak valley of these coatings (peak-to-valley surface roughness) (defining in the discussion with reference to Figure 33 a and Figure 33 b below) preferably is less than or equal to

Be more preferably less than Be more preferably and be less than or equal to approximately

Even be more preferably and be less than or equal to approximately

Most preferably be less than or equal to approximately

In order to explain the further feature and the advantage of the electrochromism mirror that at least one embodiment according to the present invention makes up, 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 that makes up according to predetermined parameter in each example.When color is discussed, (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 a relative complex, and still, F.W.Billmeyer and M.Saltzman are in Principles of Color Technology, 2 ^NdEdition has provided among the J.Wiley and Sons Inc. (1981) quite comprehensively and has discussed, and therefore the disclosure generally defers to this discussion owing to relating to color technology and term.At L ^*a ^*b ^*In the chart, L ^*Definition brightness, a ^*Represent red/green value, b ^*Expression Huang/indigo plant value.In the electrochromic media each has under each specific voltage, and can be transformed into the indication of three quantity be 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 second is observer's spectral response.The disclosure is used 2 degree CIE standard observers.Be expressed as the A/2 degree thereby generally be used for the working flare of mirror/observer's combination, and the combination table that generally is used for window is shown D ₆₅/ 2 degree.Many examples in the following example are mentioned the value Y from 1931 CIE standards, because it compares L ^*Closer corresponding with spectral reflectivity.The C that the back also illustrates ^*Value equals (a ^*) ²+ (bw ^*) ²Square root, be provided for measuring of quantized color neutrality thus.

Table 3 and table 4 have been summed up the experimental result of the element that makes up according to the present invention.Especially, be sputter gas with krypton gas and under the pressure of 3mTorr,, experimentize for half-wavelength and two kinds of thickness of two wavelength, scope at the oxygen flow of 8～16sccm.Table 6 has been summed up the result who is slightly less than half-wavelength ITO thickness, and table 7 has been summed up less times greater than the result of two wavelength ITO thickness, and half-wavelength thickness is applicable to that for example mirror is used, and two wavelength thicknesses are applicable to for example window applications.And, should be noted that these tables comprise individual layer simultaneously and the result of the element that is made of bilayer.

Table 8 illustrates the inside dependence between volume resistance, electron mobility and the electronic carrier concentration.Note, have the carrier concentration of the given volume resistance of generation and the continuum of mobility combination.

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

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

In at least one embodiment, photovalve comprises the absorption that shows lower volume resistance simultaneously, reduced, reduces bending or warpage, the even darkness of keeping black box and the brightness of the associated substrate that has applied ITO and reduces the improved ITO layer of its weight.

In relating to the non-microscale electrical applications of metallic coating, surface topology, form and roughness generally are unessential.When metal was used in the optical application, surface topology was a particular importance.When surfaceness becomes too big, coating will have noticeable non-mirror reflection or fuzzy.For this roughness,, therefore in most application, usually at first to be paid close attention to because it can be for visual appearance but may not have negative effect for function.Under the situation of optical application such as many optical application of explanation here, harmful fuzzy the worst situation that is regarded as.Under the roughness levels of the fuzzy roughness levels that causes 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 permission metal film works satisfactorily.Because usually need the higher metal of a large amount of prices with higher reflectivity to overcome the problem relevant with unsuitable configuration of surface, therefore the loss with unsatisfactory ground control surface morphologic correlation is usually to increase cost.The form of the varying level that uses the thin-skin model technology or the effect of surfaceness have been analyzed.These technology are accepted in the field of thin film technique and have been proved to be accurately describes actual film or coat system, and therefore can be used to predict the influence of different variations for coating.Because it can be expensive and time-consuming making or make a large amount of needed samples of effect that shows, is favourable so therefore.In this case, use the commercial film program of supplying with by Software Spectra.Inc. that is called TFCalc to calculate to carry out.

Average peak valley spacing from aspect define roughness used herein.Figure 33 a illustrates two kinds of different roughness situations with Figure 33 B.The crystallite 3302a that Figure 33 a representative is bigger.The crystallite 3302B that Figure 33 B representative is less.In both cases, it is identical being described to apart from 3301a, 3301b between peak valley.In addition, two examples have identical empty block than (void to bulk ratio).Should be appreciated that each paddy may not be in identical height with each peak.Therefore average peak valley measurements provides more representational quantized value.

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

Here with several metal patternizations so that the representational example of the optical effect of surfaceness to reflectivity to be provided.Table 6, table 7 and table 8 are represented the influence of uneven surface thickness (roughness thickness) for the reflectivity on the surface of Ag, Cr and Rh respectively.The unit of bed thickness is a nanometer, and the representative of Cap Y value is from the reflectivity of coated surfaces.For in these metals each, reflectivity increases along with the thickness of roughness and descends gradually.According to application, the amount of acceptable roughness will change.Roughness should less than the average peak valley of 20nm, preferably less than 15nm, be more preferably less than 10nm, be more preferably less than 5nm, most preferably less than 2.5nm.As mentioned above, these preferred range depend on application.For example, in one embodiment, the thickness of flash layer, overlayer, restraining barrier or adhesive phase (that is functional layer) may change with the roughness of bottom surface.The thickness of the functional layer that the roughness of bottom surface is essential can cause undesirable effect, such as variation, higher cost or other the counter productive of the optical property of the lamination that obtains.Below explanation is used for making the means of surface smoothing before the deposition of functional layer.Should be appreciated that to exist increases some embodiment that surfaceness can be favourable, is used for bonding with encapsulant better such as producing big effectively surf zone.

Table 6, table 7 and table 8 also comprise the value that is designated as " % of theoretical maximum ".The definition of this tolerance have rough surface coating reflectivity how the reflectivity on near-earth and desirable complete level and smooth surface mate.Coating with a% of 100% theoretical maximum can have the obtainable in theory maximum reflectivity of this material.If the % of theoretical maximum is 85%, the reflectivity of Huo Deing can be only be 85% or 0.85 times of reflectivity with coating of 0 roughness of the value of theoretical smooth finish so.

The reflectivity of metal or alloy coating depends on many attributes of coating or even level and smooth relatively coating.The density of coating, the existence of interior void are whether, how stress level etc. all work near some ideal maximum value about reflectivity.Here Ding Yi theoretical maximum reflectivity is not the ideal reflectivity about desired coating, but about the reflectance value of level and smooth real coating.In practice, the combination by optical analysis and thin-skin modelization obtains theoretical maximum.By using the real coating that has surfaceness such as the optical technology analysis of variable-angle spectrum ellipsometry (Variable angel Spectroscopic Ellipsometry), can obtain the relation of refractive index and wavelength and surfaceness.The relation of refractive index and wavelength can be imported then in the thin-skin model program such as TFCalc or Essential Macleod, and can calculate reflectivity.This reflectivity that the refractive index data of use measuring are calculated from but from the theoretical maximum reflectivity value of this specific film or coating.

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

Table 9: uneven surface thickness is to the influence of the reflectivity of Ag coating

Table 10: uneven surface thickness is to the influence of the reflectivity of chrome coating

Table 11: uneven surface thickness is to the influence of the reflectivity of rhodium coatings

In some applications, wish to have higher second surface reflectivity, wherein, this reflection is to leave metal level when observing by glass.In this case, except surfaceness, the cavity of imbedding also is related.The amount (with respect to the % of volume) in cavity can change, and the thickness of cavity layer also can change.More than here also be suitable for for the general rule of surfaceness explanation.

Invariably, roughness is related especially when metal level comprises low surface resistance surface.Metal or other conductive material have the internal performance that is called specific insulation.By the volume resistance number is determined the surface resistance of coating divided by the thickness of coating.On principle,, can obtain any sheet resistance value from any conductive material so as long as coating is enough thick.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 increase of coating, surfaceness generally also increases, and this causes the reduction of specular reflectance.Very thick coating usually has the reflectivity levels of the reflectivity that is significantly less than complete smooth surface.Coating will be with many factors vary with the amount of the roughness of development.The performance of material itself is main driving force, and still, in the border, deposition process parameters (using with deposition process) can change the surface property of coating.

Since other consideration, the material that can not always have the best surface roughness for given application choice.Other factor also works.For example adhesiveness and cost are the key issues that influences the selection of the material that enters coating stack.Usually can not select single material to satisfy all demands; Therefore, use laminated coating.Has higher reflectivity but very expensive such as some platinums group metal of rhodium, ruthenium, iridium etc.Therefore, the whole coating made from these materials with low surface resistance can be that cost is too high.In the time may needing, can find that also these materials have the bond strength than other material difference with glass or other material splendid bonding.Coating stability as anode time the based on silver is not enough, and, according to coating stack, see it also is problematic from bonding viewpoint.Comparing such as other metal of the metal and some of chromium is that relative cost is lower, and knownly has an extraordinary cementability.Therefore, chromium can be used as adhesive phase, and can be built into the electrical property of enough thickness to obtain wishing.

Unfortunately, chromium is reactive very high, the inherence tendency of the surface roughness value that this causes being tending towards relatively large.Higher reactivity is crucial, and this is because when for example by use magnetron sputtering vacuum deposition (MSVD) deposit coating, chromium atom will be tending towards adhering to their at first positions of implantation.The speed that engage to form is very fast, and this restriction atom is along surface diffusion and find the ability of energy position.Usually, the low-yield settling position on the coating is to make the position that himself is suitable for littler surfaceness.This deterioration that also helps the volume resistance of coating less than the trend of low-energy state.Therefore, need thicker layer with the acquisition targeted sheet resistance, and surfaceness is tending towards further deterioration.Since these emulative effects, the target that therefore is difficult to obtain simultaneously to hang down surface resistance and high reflectance.

As everyone knows, by on low-reflectivity metal, placing the thin layer of the metal of higher reflectivity, can increase the reflectivity of this low-reflectivity metal.For example, can use above-mentioned metal such as rhodium or ruthenium.It will be the direct result of the surfaceness of bottom chromium layer that these metals obtain the given necessary thickness of reflectivity levels.Other metal that can be used as conductive layer is 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 with the alloy of other metal be possible.The suitability of these materials in given application will depend on whole demands.For example, ruthenium may be expensive metal in an application, but it may be relatively cheap with respect to another metal such as rhodium in Another Application, therefore can fall into spirit of the present invention.In other non-restrictive example, given metal or alloy may be not with use in all other compositions compatible.In this case, Min Gan metal can by embedding or in addition with exist interaction constraints become to separate.Each layer in the deposited on top of chromium will carry out patterning to the roughness of bottom usually.Therefore, the thin layer of high reflectance metal will not have its desirable reflectivity owing to the layer below it yet.As a rule, preferred embodiment is the embodiment that has towards the high reflectance metal of observer's orientation.Many metals in the high conductivity metal of listing above also have higher reflectivity.These metals may need with other metal alloyization to have enough chemistry, environment or physical property.Thereby metal or alloy can have unacceptable color or tone.Total reflectivity intensity may be not enough for the application of hope, and still, if the color of reflection does not satisfy the demands, this metal or alloy is inappropriate so.In this case, similar with above explanation, metal or alloy can be embedded in have lower inherent reflectivity and have preferred reflection color the layer below.

The preparation authentic specimen is to allow to estimate chromium-reflectivity of ruthenium duplex coating lamination and the balance between the surface resistance.In these samples, apply chromium to obtain the targeted sheet resistance value.Sample is coated with the ruthenium of different-thickness outward then.Use following process conditions:

All coatings are processed under 3.0mTorr

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

Cr@4.0kw@ (130) * 9=.7 ohm square

Cr@4.0kw@ (130) * 3=1.5 ohm square

Cr@4.0kw@ (87) * 1=3 ohm square

Cr@4.0kw@ (170) * 1=6 ohm square

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

The chromium sample is deposit under 4kw all.Change linear velocity (in parenthesis-arbitrary unit) and road sub-quantity (for example, * 9) with the thickness of adjusting coating with realization surface resistance target.Make the ruthenium layer to obtain the target thickness level by changing linear velocity and power.In table 12, list the matrix result.Reflectivity is generally along with the increase of thickness and reducing of surface resistance and reduce.The target of preparation is that several samples of 3ohm/sq do not meet these trend.This is because they are to make under the linear velocity different with other chrome coating.When linear velocity reduced, substrate moved with slower speed.In linear process, this means that main angle of elevation deposition materials with sputter forms initial forming core layer.As following explanation was mentioned, angle of elevation deposit caused relatively poor material property.Usually use fender to eliminate this angle of elevation deposit.3ohm/sq chromium situation in this research is to show well 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 simple chrome coating also has relatively low reflectance value under the 6ohm/sq situation.For this sample, reflectivity only is about 61%.Means or the chromium made of process conditions by other should be able to obtain to surpass 65% value.Therefore, even on this moderate sheet resistance value, the chromium reflectivity also affects adversely.

When wishing the 3ohm/sq coating, the ruthenium of 100 and 200 dusts that needs the chromium top is to obtain more moderate reflectance value.In the ideal case, ruthenium coating should be able to obtain to surpass 72% reflectivity.Even 400 dusts at 6ohm/sq chromium top are also than theoretical optimal value low 2%.Low ohm sample is not even near obtainable in theory reflectance value.Therefore, need at the same time under the situation of low surface resistance and high reflectance, the chromium ruthenium bilayer of standard does not meet the demands.The means that must use other are to address this problem.

Can adjust deposition process parameters minimizes to make surfaceness in coating forming procedure.Under the situation of metal, as following detailed description the in detail, can be also preferred by using neon or argon gas-neon combination gas as sputter gas by under low pressure implementing to handle, reduce surfaceness and increase reflectivity.These parameters help suitable momentum and the energy in the deposition process to shift, thereby cause roughness lower surface and lower specific insulation.

Table 13 illustrates how surfaceness, reflectivity and electric property change when the adjusting process parameter.Provide the 3mT situation as benchmark.The thickness of coating is about 600 dusts.This thickness is crucial, because coating is almost opaque under this level and surface resistance is relatively low.As can be seen, reducing pressure, that roughness is reduced is about 17%, and realizes that reflectivity increases about 2%.Reduce pressure and carry out sputter and cause further improvement with 50: 50 combination gass of argon gas and neon.The situation of roughness ratio benchmark is low about 20%, and reflectivity high about 2.7%.It is neon that last situation adopts the sputter gas of more neon-Yue 70%.The luminance factor base case is high about 3.5%, and roughness reduces about 24%.Determine thickness and roughness value by using variable-angle spectrum ellipsometry (variable angle spectroscopic ellipsometry).

Table 13: the relation between chromium performance and technology are provided with

Can be by reducing pressure and further improving the result by the neon content that increases in the sputter gas.In addition, increase underlayer temperature and also help more smooth coating.Higher underlayer temperature causes the higher surface mobility of deposit atom, thereby causes more even curface.

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

From the viewpoint of surfaceness, it is harmful especially having oxygen (or water) in system.Chromium is very easy to the oxygen reaction and is tending towards immediate response.This causes the roughness of adding in coating.Therefore, recommend to have the coating of less oxygen.Table 14 illustrates the influence of oxygen for roughness.Oxygen level in the table 14 refers to the number percent in sputter gas.The unit of pressure is mT, and the unit of thickness is a dust.The amount of the acceptable oxygen in the coating is less than 5at.%, preferably less than 2at.%, in the ideal case less than 1at.%.

Table 14: the oxygen number percent in the sputtering atmosphere is for the influence 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 higher reflectance value of hope, also wish less roughness.When the reflectivity demand was so not urgent, higher roughness can be acceptable.Usually, roughness should less than about 200 dusts, preferably less than 100 dusts, be more preferably less than 50 dusts, be more preferably less than 25 dusts, most preferably less than 15 dusts.Here the roughness of using as term refers to the average peak valley distance by using ellipsometry or atomic force microscope to determine.

Can be individually or mutually together or with above-mentioned method use other means so that surfaceness minimize.For example, negative electrode can conductively-closed so that plunder and penetrate (height) angle deposit and minimize.Other method that is used to obtain more level and smooth surface comprises other means of using the auxiliary sputter of ion or ion assisted deposition, the auxiliary sputter of plasma or increasing the surface mobility of atom.Can select cathode type helping more level and smooth coating, such as, use " twin magnetic (twin mag) ", unbalanced magnetron, radio frequency stack DC power, microwave-assisted sputter, high power pulse deposit, exchange sputter or other this means.

Though in above example, use chromium as conductive layer,, can in spirit of the present invention, use here or the document of adding here in other metal, alloy or the laminated coating material of explanation.Other material may need other process conditions to obtain smooth surface.For example ITO may not have smooth surface under the preferred condition for metal.Under the situation of ITO, change configuration of surface by many state-variables.Compare with the situation of metal, the situation of the surface property of control ITO is more challenging.ITO does not resemble the metal electric conductivity always, and, for metal, can cause some technology settings of level and smooth coating may not cause the coating of highly conductive with ITO.Therefore, other Properties Control form according to material is quite challenging.Usually, high temperature coated on glass or other vitreous substrate can be provided with at high pressure and relative higher oxygen illustrating in the presents as the front and obtain level and smooth relatively coating down.Also can will be used for making the change application of technological parameter of coating smoothing in such as the TiO2 that instructs in the half-transmitting and half-reflecting coatings applications or such as other material of the multilayer of TiO2 and ITO.

As mentioned above, roughness is generally along with the thickness of coating increases.Above-mentioned technology setting usually is not enough to cause having the coating of acceptable roughness levels.Need the situation of extremely low sheet resistance value to come to this.In this case, need substituting means to obtain to have the coating that relatively low surfaceness has lower sheet resistance value simultaneously.

In commonly assigned U.S. Patent Application Publication No.2006/0056003, the means as the coating attenuate that is used for making regional area on the substrate of coating are introduced ion beam, add the whole of this patent at this and disclose as a reference.As going through, also ion beam can be used here so that rough coatings (as shown in figure 37) smoothing (shown in Figure 33 a and Figure 33 B).Can use ion beam individually or in conjunction with other method of instruction here, also increase reflectivity thus with the roughness that reduces coating.Ion beam source changes on Design and Features.For the purpose of the discussion here, can be suitable with any design of the energy range transmission ion flow of explanation here.

Ion beam is the one group of high energy positive ion or the negative ion of relatively collimation.Energy of ions becomes with the operation electromotive force of ion beam.Ion flow or the amount of the gas that ion flow is presented with the operation electromotive force with by ion beam and the background pressure in the chamber become.Wish ion have enough energy with etching, grind off and/or the smoothing coating material.The example of relevant phenomenon is the example of billiard ball.The ion that enters is considered as mother bulb and the tripod of ball when coating is considered as playing beginning.If mother bulb hits tripod with low-down energy, tripod does not scatter so.On the contrary, if mother bulb impacts with higher energy, tripod can scatter fiercely so.

Figure 34 illustrates the sputter output that becomes with the argon ion energy for various materials.There is the threshold energy that sputter do not occur or minimum sputter occurs.Along with energy increases, sputter output increases.Ionized atom also may influence sputtering rate.Preferred mass with plasma sputter of maximum sputter output will and will be changed by the quality of the atom of sputter with the energy of plasma sputter.Figure 35 illustrates the sputter output that becomes with plasma sputter under the 500eV ion energy and sputtered atom quality.The computer simulator that is called " Stopping and Range of Ions in Matter (SRIM) " by use produces data shown in Figure 35.What illustrate here is the scope that will produce the best sputter gas mass of ion of acceptable sputter output for given target atom quality.Usually, along with beam energy increases, the best in quality of ion increases so that the sputter 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 comparable relatively quality.Figure 34 illustrates the material that threshold energy depends on sputter.Other material of the release ratio of some materials expends more energy.The diagrammatic sketch of Figure 34 also illustrates, and on the higher relatively energy of ion, sputter output tends to be platform.On these higher relatively energy, process begins to enter the zone of ion injection rather than ion sputtering.Obtain sputter efficiently or etching, ion energy should be higher than 100 electron-volts, preferably be higher than 500 electron-volts, most preferably be higher than 1000 electron-volts.

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

Similarly, strike lip-deep ion beam at an angle and can have obviously higher sputtering yield and smoothing effect.In this case, angled ion beam can have the probability that higher edge is laterally penetrated material for coating surface.

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

Table 15 is illustrated in the ion milling effect on one surface in the ITO-bottom that uses in option 4 laminations.By using the ellipsometry specified 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 higher relatively.The Dan Shu (38cm long shot bundle) that is used under the situation of the argon gas that use presents operation under 270mA electric current and 3000 volts under 20sccm carries out ion milling to sample, and the on-stream pressure in the chamber is 2.5mT.Ion beam is the design of closed drift Hall effect anode stratotype.The linear velocity of 2B (on 30ipm suitable two beams) situation is 15ipm, and the linear velocity of 4B (on 30ipm suitable four beams) situation is 7.5ipm.The direction of ion beam and the Surface Vertical that applies glass.Ion beam is removed about 17nm/ suitable beam on 30ipm for 3/4 wavelength ITO, and the about 11.1nm/ of removal suitable beam on 30ipm.Surfaceness all sharply descends in both cases, makes 3/4 wavelength ITO become intimate ideally level and smooth.But 5/4 wavelength ITO does not become level and smooth like this, because it is from much coarse original state, so 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 the ion milling process.In table 16a, outside ITO coating illustrated in fig. 15, be coated with the Si of the 22nm that has an appointment and the Ru of 7nm.Because the higher reflectivity of these coatings, so 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 light source that causes being correlated with on identical reflectivity levels passes the higher light output of coating.When all these coatings were normalized to identical reflectivity levels, difference was just more obvious.In order partly to obtain identical reflectivity levels, increase the thickness of ruthenium layer greatly for the nonionic milling.This further reduces transmissivity again and increases absorption, and this is undesirable in some applications.

The goods (lite) of these coatings that table 16a is listed are added in the photoelectricity mirror element shown in the table 16B, to estimate the optics in the actual EC element.Make many 2 inches * 5 inches unit and measure transmissivity and reflectivity (minute surface and non-specular surface).The increase of the reflectivity of the element of assembling is relevant with the result who observes 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 because the many ruddiness of its particular structure material and tranmittance blue light.When red display for example was positioned at the mirror element back, this can be particularly advantageous.

Table 16B also illustrates the minute surface that is used for sample element and gets rid of reflectivity (Spec Ex) data.Ion milling makes surface smoothingization, and this reduces scattered light basically.Because the amount of scattered light seldom, therefore the image that obtains is clear and distinct more.

Many motor corporations have regulation must be higher than 55% standard for outside mirror application reflectivity.This standard of the discontented foot of initial coarse tolerance on the ITO of nonionic milling sample.The sample of ion milling is even 5/4 wavelength ITO part also satisfies this standard.The particularly deepening speed dependent of switching speed of mirror element is in the surface resistance of coating.By using 5/4 wavelength ITO or thicker ITO, ion beam milling allows to have switching time faster when satisfying the reflectivity requirement.In addition, some in 3/4 wavelength elements have the reflectance value that substantially exceeds minimum requirement.Can be by reducing ruthenium or adjust these coatings so that they have higher transmittance values as the thickness of other high-reflectivity metal of top layer, overall design this moment demand changes from this is benefited.If there is not the 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 that non-half-transmitting and half-reflecting is used.In this case, coating is glass/ITO/Cr/Ru.Chromium and ruthenium in the epoxy sealing are covered, and ITO is used to transmit electric current from electrode to the EC element internal.ITO has the roughness to a certain degree that reduces by Ion Beam Treatment.Figure 38 is illustrated on the fixing feam column roughness to be reduced along with linear velocity is reciprocal.In another example, the linear velocity of passing the glass of coating machine is 30 inches per minutes (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.Promptly use this appropriate ion milling condition also to obtain 0.5% reflectivity increase.In these examples, the ITO coating is kept its initial roughness and is beneficial to the cementability that increases the epoxy resin in ITO and the sealing area to have, and simultaneously the ITO in the viewing area is carried out the optical property of milling to be improved.

In the Another Application of using ion milling, the color and the reflectivity of the ring-like coating of so-called chromium are studied.In this is used, apply the multiple layer metal coating at the top that is in ITO coating on glass.In the ring of component ambient to the glass of coating ITO carry out ion etching with in this position with ITO coating attenuate improving the color and the reflectivity of chromium ring lamination, realize the lower surface resistance of thicker ITO simultaneously at the center of this part.Figure 40 illustrates the reflectivity of the different condition when passing the glass observation.There is not the reflectivity of ion milling to be illustrated as thick line.Reflectivity with several different linear velocities also is illustrated.Along with speed reduces, the residence time under the beam increases and roughness reduces.This causes the increase of reflectivity.Reflectivity appears as platform, still, has some arc discharges of beam in these trials, and this may have adverse effect to the result.Crucial result is that by ion milling, even exist under the situation of arc discharge, reflectivity also increases.Figure 38 shows the variation and the relation that does not have the linear velocity under the condition of arc discharge of the ITO roughness in these tests.

Another group test check in the same coating machine has the color of the chromium ring of ion milling.Linear velocity is adjusted to change the ITO removal amount.ITO begins with 1/2 wavelength, and target is thickness to be reduced to about 80% of 1/2 wavelength promptly be reduced to about 115nm from about 145nm.Figure 41 illustrates the b of the reflection of the chromium ring of adjusting with linear velocity ^*As explanation in the priority document that conduct reference here adds, the b of reflection ^*Directly relevant with the thickness of ITO.The b of 1/2 wavelength ITO coating ^*Be about 16.Along with linear velocity reduces, the amount of etching material reduces.In at least one embodiment, the b of the ideal matching promptly about 2.5 of hope and center viewing area ^*Therefore, linear velocity should be about 12.5ipm.When needs faster during linear velocity, can use more ion beam.

Reduce in another example of sheet resistance value in hope, the research ion milling is for the influence of reflectivity and material use.As mentioned above, the roughness of coating reduces with thickness with thickness increase and reflectivity.In the present example, hope has the coating with 1.5ohm/sq of the layer structure of glass/chromium/ruthenium.Chromium thickness is set as about 2500 dusts so that most contribution to be provided to surface resistance.Ruthenium is beginning to be set as 400 dusts.Under the level and smooth fully situation in surface, will obtain maximum reflectivity with little ruthenium to 180～200 dusts.The level of using 400 dusts is to guarantee the enough thick rough surface with how much compensation chromium of ruthenium.Additional ruthenium increases reflectivity but has also increased cost.

Figure 42 illustrates for the reflectivity of the Ion Beam Treatment that applies ruthenium layer chromium layer before 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 almost its maximum reflectivity of 70.5%.The further reduction of linear velocity does not cause the extra increase of reflectivity.If wish linear velocity faster, can use the beam of interpolation so.

Figure 43 illustrates because the ruthenium of the amount that the smoothing effect of ion beam and how may using in coating process has reduced.Linear velocity is about 2.1ipm, and the result among feam column and Figure 42 is suitable.Can use little ruthenium to 160 dusts to obtain maximum reflectivity.With respect to the baseline case of using extra ruthenium with the thickness of compensation initiation layer, this causes cost to reduce greatly.In addition, under the situation that does not have the ion beam smoothing, have the 1.5ohm/sq coating of the chromium of higher relatively reflectivity and ruthenium even may be unpractiaca.

Usually, the roughness of the coating of making under the situation without any the special effort of making smooth finish will be about 10～20% of the gross thickness of coating.Table 17 illustrates the thickness that obtains the needed chromium of various sheet resistance value/ruthenium lamination.How the thickness that the volume resistance of chromium layer changes with demonstration chromium layer will change to obtain different sheet resistance value along with the volume resistance change.Can be used as the example of chromium volume resistance performance change, perhaps it can be considered as proving the means that what situation when with the material substitution chromium of volume resistance value, occurs with difference or change.

The scope of roughness is calculated as 10% and 20% of ulking thickness in Figure 17.Ruthenium is set as 200 dusts, and this thickness just has been a bit larger tham the needed thickness of maximum reflectivity that obtains this material in desirable application.If the chromium layer is level and smooth, perhaps by smoothedization of ion beam, this thickness is demonstrated best reflectivity situation so.Result of calculation when table 17 illustrates the thickness of ruthenium compared with gross thickness.The contribution of roughness is regarded as the mean value of 10 and 20% situation.Change with the targeted sheet resistance of lamination and with the volume resistance of chromium or basic unit as the number percent of the lamination of ruthenium.If surface resistance, wishes so that ruthenium or other high-reflectivity metal are less than 50% of gross thickness more than or equal to 6ohm/sq.If the surface resistance of lamination is about 2ohm/sq, ruthenium thickness should be less than about 25% of gross thickness so.The thickness number percent of high refractive index layer also will change with the volume reflection rate and the reflectivity target of this metal.The suitable high reflectance number percent of gross thickness becomes with the surface resistance of the hope of the reflectivity of the hope of lamination, the lamination volume resistance with the different material that is used to make up lamination.The number percent of highly reflective material should less than gross thickness 50%, preferably less than gross thickness 25%, be more preferably less than gross thickness 15%, be more preferably less than gross thickness 10%, most preferably less than 7.5% of gross thickness.In the present example, chromium and ruthenium are used to prove the benefit of one embodiment of the present of invention.As the most means that surface resistance is provided, can use other metal to replace the chromium layer.So-called high-reflectivity metal is defined as having with respect to the most layer of contribution surface resistance the metal of higher reflectivity.In the present example, our effect of discussing top layer is to have higher reflectivity with respect 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 the increase reflectivity and provide acceptable color.In an example, conductive layer can be by highly colored, and the color of sexual reflex in preferred.In this case, so-called high refractive index layer is used in and makes color neutral more.

In another embodiment, conductive layer can have neutral reflection colour, and the painted reflection of preferred heights.Here, can select the high-reflectivity metal at top so that the outward appearance of non-neutral to be provided.In another embodiment, can on conductive layer, apply multilayer laminatedly, make to be stacked in to have to obtain lower surface resistance when being placed on the dirigibility of the multilayer laminated adjustment color on the conductive layer by adjustment.In the present example, multilayer laminated metal, dielectric layer and/or the semiconductor layer of comprising.Comprise lamination material, they thickness, will determine by the design criteria of given application with respect to the selection of the orientation of conductive layer and adjacent medium.

Table 17: sheet resistance analysis

Owing to reduce for various application surface resistance, so thickness must increase and surfaceness increase and reflectivity reduction thus.Thereby the reflectivity of coating will be reduced to the low value with respect to theoretical maximum.Sheet resistance value as desired value is low more, and the number percent of the theoretical maximum reflectivity value of Huo Deing is low more so.For coating with about 6ohm/sq or littler surface resistance, here Shuo Ming technology will allow to obtain greater than theoretical maximum 90% and be preferably greater than about 95% reflectivity of theoretical maximum.For coating with about 3ohm/sq or littler surface resistance, here Shuo Ming technology will allow to obtain greater than theoretical maximum 80%, be preferably greater than theoretical maximum about 85%, more preferably greater than theoretical maximum about 90%, most preferably greater than about 95% reflectivity of theoretical maximum.For coating with about 1.5ohm/sq or littler surface resistance, here Shuo Ming technology will allow to obtain greater than theoretical maximum 75%, be preferably greater than theoretical maximum about 85%, more preferably greater than theoretical maximum about 90%, most preferably greater than about 95% reflectivity of theoretical maximum.For coating with about 0.5ohm/sq or littler surface resistance, here Shuo Ming technology will allow to obtain greater than theoretical maximum 70%, be preferably greater than theoretical maximum about 80%, more preferably greater than theoretical maximum about 90%, most preferably greater than about 95% reflectivity of theoretical maximum.

In commonly assigned U.S. Patent Application Publication No.2006/0056003, discussed for " chromium ring " mirror element various metal laminated, at this full content that adds this patent as a reference.Thin chromium adhesive phase is deposited on the ITO, and the metal level with higher inborn reflex rate is deposited on the chromium layer.Various high reflectance metals have been discussed.Having illustrated not have to contribute to outward appearance when observing coating from glass side but is applied to the second layer chromium that minimizes visible light and UV optical transmission rate.Reducing visible light is to hide encapsulant, only will be exposed to daylight protection of following time encapsulant and reduce UV.Chromium is regarded as being used to reduce the low-cost means of optical transmission rate in the present example, no matter this only UV light or visible light.Other low-cost metal can provide identical functions, as long as they have good and adhesiveness sealing and high reflectance metal.

The thickness that also can increase high-reflectivity metal simply is reducing light transmission simultaneously, but high-reflectivity metal usually is relatively costly, and uses these materials can cause higher coating price separately.

The ITO layer can be transparent conductive oxide or other transparency electrode arbitrarily.Transparent conductive oxide or transparency electrode can comprise single or multiple lift.In the multilayer each layer can be selected as changing the color or the outward appearance of reflection, makes " ring " have suitable optical property.The color that a kind of such multilayer can comprise between glass substrate and transparent conductive oxide suppresses layer (color suppression layer).Use this layer to cause that this ring has more color to select when adjusting the ITO bed thickness.

Adhesive phase can be chromium, Ni, NiCr, Ti, Si or silicon alloy or other suitable adhesion enhancement layer of various compositions." high-reflectivity metal " is selected from metal and the alloy with volume resistance 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, can also use these metals each other potpourri or with the potpourri of other metal.Also can use multilayer to replace the illustrated individual layer that is used for high-reflectivity metal.Similarly, the UV restraining barrier can comprise homogenous material, alloy, multilayer or cause suitably reducing other combination of transmissivity.

Also can improve the adhesiveness of material, layer or coating by the Ion Beam Treatment of using explanation here.For example, by using argon gas and carrying out the Ion Beam Treatment on ITO surface then by the combination gas that uses argon gas and oxygen.These tests are compared with nonionic milling surface.By epoxide resin material sample is attached on the test glass sheet to form the chamber of sealing.Hole at the top of glass (top lite), and chamber is pressurizeed to determine the required force value of chamber inefficacy.Failure mode can comprise the bonding of epoxy resin interior viscosity inefficacy, epoxy resin and coating, and the fracture of glass or coating can cause losing viscosity with substrate, perhaps can have viscosity inefficacy in the coating.

By Ion Beam Treatment, perhaps process is not handled by argon gas, argon gas/oxygen mixture on the ITO surface.Then with the thick thin chromium layer of about 50 dusts, and then by the thick ruthenium layer of about 500 dusts (so-called Beta ring) coated surfaces.The glass of coating engages with another sheet glass by the general epoxy resin that uses in the EC element, and epoxy resin is cured then.Force value when table 18 illustrates and lost efficacy and from the metal-stripping amount of ITO coating.Control section has the metal-stripping of trace.The argon gas beam partly has tangible metal-stripping (metal lift), but the pressure when losing efficacy is substantially the same.Use oxygen to have similar failure pressure value equally, but metal is eliminated from peeling off of ITO.Oxygen improves the adhesiveness of chromium and ITO.Ion beam is preferably as the sputter oxygen that helps the adhering composition of chromium.Only there is the situation of argon gas to cause minimizing of critical oxygen and relatively poor joint.Can believe, add oxygen in the beam " healing " ITO surface, strengthen joint thus and make metal-stripping minimized.Because glass ruptures in test, the force value when therefore losing efficacy does not show correlativity.Force value when this fracture is determined to lose efficacy and domination test thus.In the present example, oxygen is essential, but can have the preferably situation of other gas, and perhaps simple argon gas may be a better choice.

In another example that ruthenium directly is deposited on the ITO, observe the rapid variation of the force value when losing efficacy and the variation of failure mode.When not using Ion Beam Treatment, the force value during inefficacy is quite low, is about 6～7psi, and coating stripping is a failure mode; Glass does not rupture.When with the beam treatment ITO surface that comprises oxygen and then from the teeth outwards during the deposit ruthenium, the force value during inefficacy increases the factor greater than 2, and glass breakage is main failure mode.Coating is still peeled off from ITO, but adhesion strength increases greatly.

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

A-Beta encircles control

B-adopts the Beta ring of argon gas ion milling

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

The top layer of Shi Yonging can be the conduction stabilization material in some applications.Its effect is to provide favorable conductive between ring metal and bus or silver-colored paste.Material can be selected from the platinum group metal such as iridium, osmium, palladium, platinum, rhodium and ruthenium.Can use these metals each other potpourri alloy or with the potpourri or the alloy of other proper metal.

As instructing in the patented claim of reference, the thickness of the material in the layer and select preferably is selected as the color and the reflectivity intensity that provide suitable.The thickness of each layer also should be selected as obtaining essential transmissivity performance.Transmission of visible light should be set up, and makes that epoxy sealing is sightless when observing.Transmission of visible light should be less than 5%, preferably less than 2.5%, be more preferably less than 1%, most preferably less than about 0.5%.The UV transmissivity can or cannot be relevant definitely with transmission of visible light.Under the situation of UV transmissivity, the outward appearance of ring is not a problem, and the protection of sealing is a major concern.This supposes that certainly the sealing of selecting is for the UV photaesthesia.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 the ring coating is opaque for UV light, but unfortunately, the UV transmissivity of this level can be that cost is too high.In addition, too big if gross thickness becomes, the adhesiveness of each layer can affect adversely so.The stress that can exist in layer can cause strain enough greatly to cause each layer to be peeled off from other layer of glass or coating.For this reason, need to consider the UV transmissivity of limited amount.The UV transmissivity should less than about 1%, preferably less than 0.5%, be more preferably less than 0.1%, most preferably less than 0.05%.

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

When comparing with the mirror that is used for the vehicle outside, these requirements are distinctive for internal mirror.In at least one embodiment, the specular reflectance of internal mirror is preferably 60% or higher, and preferably has enough transmissivities so that the light of q.s passes relevant mirror element in the display front.And internal mirror needn't tolerate abominable chemistry and the environment challenge that runs in the externally mirror application.A kind of challenge is the needs and the hope that comprises the information center of aesthetic pleasant that balance satisfies the automobile standard that is used for rearview mirror.It is a kind of means of the limited light output of compensation display technique that higher mirror element light transmission is provided.It is visible that invariably, high transmittance cause the circuit of mirror element back and other hardware.Can on the 4th surface of mirror element, apply the opacifier layer to tackle this problem.

The blinker that replenishes shown in Fig. 5 a is an example of the indicating characteristic of externally wishing in the mirror assembly.A kind of mode that adds signal characteristic in electrochromism mirror element back is that some the laser ablation reflecting material are passed through to allow light from element.Provide the hope of substituting style and design to be to use the motivation of half-transmitting and half-reflecting mirror element technology.The half-transmitting and half-reflecting method of some embodiments of the present invention allows the feature in the mirror to have more " secret " (hidden) outward appearance.Secret makes that in the observation that stops light source light can pass the half-transmitting and half-reflecting element.Secret can also or mean the contrast that has minimum between viewing area and principal reflection zone alternatively.In some cases, wish with the contrast of color or reflectivity clearly indicated number or feature to provide framework (framing) effect, to make the observer have the clearly indication of the information of where seeking hope.The material of the routine of utilizing during externally mirror is used generally have lower reflectivity and/or with realize the relevant higher surface resistance of noticeable level of transmittance.

For example, ruthenium is because its higher relatively reflectivity and environment durability and often be used to during outside EC uses.Can have about 57.5% reflectivity as the 23nm Ru coating of the reverberator in the EC element, this level can satisfy most commercial specularly reflected rate standard.This coating can have the surface resistance of about 20ohm/sq, and the EC element can have about 2.5% transmissivity.Transmissivity and surface resistance all are 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 that satisfies the demand in the EC application.

Lower reflectivity for the OEC element requires to make it possible to easier preferred reflectivity, permanance and the electrochromic property different configurations of materials used idiocratically of satisfying, and comprises the reflection that is used to be correlated with and/or silver, silver alloy, chromium, rhodium, ruthenium, rhenium, palladium, platinum, iridium, silicon, semiconductor, molybdenum, nickel, nickel-chromium, gold and the alloy combination of half-transmitting and half-reflecting layer laminate.In these materials some have the advantage that is better than silver or silver alloy, and it is impaired that reason is that silver and silver alloy externally are easy in the mirror environment.In view of making option and more durable final products, using harder metal is favourable for the permanance of mirror element.Also can make reflection and/or half-transmitting and half-reflecting lamination with the dielectric substance of the sufficiently high reflectivity levels of generation that is used for the OEC element.

One of every reduction percentage of reflectivity in the visible light intermediate range will generally obtain about 1% transmissivity based on the material of Ag.The advantage relevant with increasing transmissivity is to utilize more low-cost, the light source exported of low light more, such as display or LED.Outside mirror generally is used to indicate escope, the general LED that is customized with very high light output that uses of these indicator type displays.Here openly make it possible in inside and outside mirror is used, use novel designs based on the half-transmitting and half-reflecting coating of Ag.The design of these novelties solve use in externally using based on the restriction of the material of Ag in the optical property and the benefit of the uniqueness that obtains from the Ag layer of protection.When low transmissivity is to use and do not have design criteria a part of based on the lamination of the layer of Ag, can consider different coating options.A very big advantage of low transmissivity is the demand that reduces or eliminates for the opacifier layer.

In many markets, the size of mirror is increasing to allow bigger visual field.The deepening time of bigger mirror is a kind of important consideration item of challenging and being in the design option.That the general bigger mirror relevant with outside mirror need increase or the conductance that improved is to keep acceptable deepening and cleaning speed.By in lamination, use innovatively transparent conductive oxide (TCO) solve above-mentioned before for the restriction of single thin metallic coating.TCO is provided for realizing the means of favorable conductive rate when keeping the transmissivity of higher level.Following several examples illustrate, and can be used for the transmissivity of the gratifying level of outside mirror with thicker relatively tin indium oxide (ITO) realization.ITO is a specific examples of the TCO class material of broad.Other TCO material comprises: the ZnO of F:SnO2, Sb:SnO2, doping, IZO etc.Tco layer scribbles the metallic coating or the multiple layer metal coating that can comprise single metal or alloy outward.For example, in order to help the adhesiveness between the different materials, need to use a plurality of metal levels.In another embodiment, can be in addition or the alternative metals layer add semiconductor layer.Semiconductor layer provides some particular performances that are discussed later.When the thickness of ITO/TCO layer increases with the raising conductance, need to consider the influence of coating roughness.The roughness that has increased can cause lower reflectivity, metal thickness that this has needed again to increase, and the metal thickness that has increased can reduce transmissivity.As other places explanations like that, the roughness that has increased also can cause unacceptable bluring.Deposition process that can be by changing ITO and/or the ITO deposit after and before the deposit of each layer subsequently, realize the ion beam smoothing, solution roughness problem.Two kinds of methods are all gone through in the above.In addition, can use the ITO material of above-mentioned improvement to reduce the surface resistance of whole half-transmitting and half-reflecting coating in the present embodiment.

Semiconductor layer can comprise the silicon of silicon or doping.Can add a spot of (one or more) additional elements with the physics that changes silicon or optical property to help its use in different embodiment.The benefit of semiconductor layer is, compares with metal, and it improves reflectivity with absorption still less.Another benefit of many semiconductor materials is that they have relatively low band gap.The noticeable uptake of the indigo plant that this equates visible light in the green wavelength.The preferential absorption of one or more light belt makes coating have purer transmitted colors relatively.High transmitted colors purity is equal to the transmittance values of some part of visible light or near infrared spectrum greater than 1.5 times of the transmissivity of low regional transmission.More preferably, the transmissivity in the high regional transmission greater than 2 times of the transmissivity in the low regional transmission, most preferably greater than 4 times of the transmissivity in the low regional transmission.Alternatively, the transmitted colors of half-transmitting and half-reflecting lamination should have greater than about 8, be preferably greater than about 12, most preferably greater than about 16 C ^*Value [sqrt (a ^{* 2}+ b ^{* 2})].Other semiconductor material that causes the half-transmitting and half-reflecting coating to have relative higher degree transmitted colors comprises SiGe, InSb, InP, InGa, InAlAs, InAl, InGaAs, HgTe, Ge, GaSb, AlSb, GaAs and AlGaAs.Other feasible semiconductor material is to have those of the band-gap energy that is less than or equal to about 3.5eV.In the secret characteristic of hope and use in the application of danger signal, can be preferably such as the material of Ge or SiGe potpourri.Ge has the band gap littler than Si, and this causes having the bigger wavelength coverage of relatively low level of transmittance.Because is more effective with the lower transmissivity on showing different wavelength for any feature of hiding behind the mirror, so this is preferred.Uniform transmissivity if desired, the semiconductor material of selecting to have higher relatively band gap so is favourable.

The viewing area can be secret in itself, makes before demonstration is activated or is illuminated by the back side observer can not perceive mirror and has demonstration.Relatively similar and color or tone contrast realize secret for hour with remaining viewing area when the reflectivity of viewing area.Because the viewing area is not reduced the viewing area of mirror as discussed above like that, so this feature is very favorable.

A spot of transmitted light can make that the mirror latter feature such as circuit board, led array, guard shield and well heater terminal is visible.Can use light blocking (opaque) layer to avoid this problem.Usually by using various materials on the 4th surface of mirror, to apply opaque layer such as pigment, China ink, plastics, foam, metal or metal forming.Externally in the mirror, the task of applying this layer is complicated.Most outside mirror has projection or aspherical shape, and this makes applying of film or coating become difficult more.

Opaque layer can be added in the 3rd surperficial lamination of element.The half-transmitting and half-reflecting zone can be covered, and, can on residual surface, apply the reflectivity that provides suitable and color (opacity) such as ruthenium, rhodium or other single or multilayer laminated (metal, metal/dielectric and/or dielectric).When the color of keeping hope and reflectivity coupling or mismatch, realize secret outward appearance.In a preferred embodiment, the viewing area of mirror element and the subjective zone of examining are undistinguishables visually.In other embodiments, may wish that the half-transmitting and half-reflecting zone has different colors with the contrast of pleasant aesthetically.

Another option is to keep the high transmittance level to obtain secret outward appearance in a part of visible light with lower total transmittance.Also can use narrow band bandpass filter to obtain secret effect.

On rear surface or not, use under the situation of coating or belt or other opaque material or except this operating position element, will opaque relatively layer (no matter whether its material identical with material in the adjacent layer) insert on the 3rd surface coating lamination of other half-transmitting and half-reflecting and have the electron device that helps hide the mirror element back.Add this layer and can influence reflectivity in the zone of inserting it.Thereby can adjust reflectivity in this zone by selecting material and their thickness, make the viewing area of mirror element and relatively the difference between the zone of opacity be difficult to perceive the unification of the outward appearance of holding device thus.

Even deliberately will to be in visual cues where when activating and to provide some indications that also comprise Presentation Function when closing when demonstration in mirror also may be favourable about being presented to provide for the reflectivity of skew viewing area and/or tone.When using conductive material with the increase opacity, the conductance of the relative opaque section of demonstration is bigger now, and striding across provides the correspondingly littler voltage drop of major part existence of the viewing area of painted speed faster.(one or more) additional opaque layer can make the reflectivity from this regional back be lower than the situation that does not have (one or more) opaque layer basically, thus reduce can be in addition from the effect of the multipath reflection of parasitic light appearance.A kind of such device that proves above-mentioned principle comprises the TiO of about 400 dusts ₂, then be basically at the ITO of 200 dusts on whole the 3rd surface, then be except that the chromium of about 90 dusts the zone on showing roughly, be the 3rd surface coating lamination of 7% gold medal, 93% silver alloy of about 320 dusts on whole the 3rd surface basically then.

For with some spectrophotometer measurement reflectivity based on ball, the opening of the demonstration on the interior automotive mirror of this particular model is too little, therefore, for the measurement of the reflectivity of the different piece that helps lamination, on their whole observation surface, make element with the different piece of lamination.Carry out transmissivity and albedo measurement from the both sides, front and back of element.

Table 19 and table 20 together with Figure 44 and Figure 45 illustrate the measurement result that obtains respectively.

Table 19

Table 20

As can be seen, for this specific example, adding chromium for lamination has increased opacity and has reduced reflectivity from the back of element.If in order to realize that opacity increases the thickness of silver alloy in non-display area, from this example, do not reduce reflectivity so as can be seen from the back of element, but,, can further increase the higher relatively reflectivity of observing later so from element if omit chromium.Also can find out, though for as the half-transmitting and half-reflecting device in the viewing area transmission be enough, the viewing area of this design also has relative less tonal difference and luminance difference when comparing with the zone with the chromium layer that comprises.

Should be noted that in the example in front,, will in the transmissison characteristic of this viewing area, obtain greater or lesser " blue biasing (bias) " respectively by increasing or reduce the thickness of the ag alloy layer in the half-transmitting and half-reflecting zone.Using rgb video to show can be benefited to keep the better color reproduction by the relative intensity of adjusting redness, green and blue emission body in this back, zone.For example, big and for red area under the less situation in transmission for the blue region of spectrum, the intensity that may wish to reduce the intensity of blue emission body and increase red emitters.No matter the biasing of the spectrum of transmission is slight gradient or has the gradient of more obvious transmission band, such to be adjusted in design of this half-transmitting and half-reflecting and the design of other half-transmitting and half-reflecting all can be suitable.

Can carry out any spectrum biasing of intensity adjustment when showing when using will be in the mirror element deepening time with the electrochromic media of compensating coating and activation.The 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 when using those the dyestuff that also can be used for generation " blue mirror " when not being active when the electrochromism species, the intensity of emitter is adjustable to have the color reproduction of improvement.Along with the reflectivity of mirror element reduces, first and/or any spectrum biasing of second surface coating will become more factors; The degree of compensation of the intensity of the different colours that shows can correspondingly be adjusted.UV absorbing agent and also can influence the visible absorption of element for other adjuvant of EC medium can comprise the intensity adjustment to improve the color reproduction of relevant demonstration.

For demonstration and signal or other indicator Application Design half-transmitting and half-reflecting coating can be favourable.When the essential high output of signal or indication, the transmitted spectrum of half-transmitting and half-reflecting device can be biased to emphasize the transmission in this zone.The RGB that has equal equal strength in redness, green and the blue portion of spectrum is presented at and passes half-transmitting and half-reflecting layer (and other parts of mirror element) and can have different intensity afterwards.Can correspondingly compensate the skew of this intensity then by the output of adjusting each single RGB color, to obtain suitable color reproduction.

May there be the situation of more wishing the reflectivity coupling between opaque and the viewing area than the example in table 19 and the table 20.In addition, may there be the benefit that reflectivity is mated on the scope of different reflectivity value.Like this, can under the situation of not damaging the reflectivity coupling between opaque viewing area and the viewing area, adjust the transmissivity of viewing area.Another purpose of design is that color is mated in observation and viewing area, or to make the joyful mode of people make its difference aesthetically.When there was minimum noticeable difference in hope between two zones, color-match can be useful.In other cases, having the reflectivity coupling but have color mismatch can be useful to help that the observer is directed to the residing position of demonstration.

The means that can use other are irrespectively further to reduce reflectivity in the zone of opacity when observing the other way around with the first surface reflectivity.Another aspect of the present invention relates to perceiveing with respect to the viewing area of opaque or viewing area.The observer will only see reflected light in viewing area, and the observer sees the combination of reflected light and transmitted light in the viewing area.Can make that the reflectivity in two zones is that identical viewing area also is conspicuous even in this zone, add transmitted light.Therefore, can reduce the transmitted light that the reflectivity in the viewing area adds with compensation.

Should be noted that in the example in front that the reflectivity coupling between zone of opacity and the viewing area becomes with the thickness of each layer.The thickness of chromium and AgAu7x is optimised, makes that the reflectivity coupling is approaching relatively, still has relatively low transmissivity simultaneously.In the reflectivity that becomes with chromium and AgAu7x thickness shown in the table 21 and the variation of transmissivity.Data in the table 21 be the lamination that comprises identification, 0.14 micron the EC fluid and on second surface, have the modelling data of electric driven color-changing part of top board of the ITO coating of 1/2 wavelength.When the chromium layer relatively thin constantly, and/or, when the AgAu7x layer was thicker relatively, the reflectivity difference between the opaque and viewing area was less.This method provides the means of making the mirror with the zone of opacity that has goodish coupling in some transmissivity and reflectivity range and demonstration.

Table 21: the optical property of under the situation that has and do not have opaque chromium layer, calculating the lamination of gained

The half-transmitting and half-reflecting example

On the scope of the broad of the reflectance value of hope, obtain the means of reflectivity coupling in the high transmittance in the opaque and viewing area of hope in keeping viewing area.Add extra play by the lamination that in example, illustrates at least one embodiment and realize this point at table 21.This preferred the 3rd surperficial lamination is TiO2/ITO/AgAu7x/Cr/AgAu7x.By sputter AgAu7x, the ability that obtains on the strength range of broad, to realize the reflectivity coupling and have the transmissivity of controlling the lamination in the zone of opacity simultaneously.Transmissivity in the viewing area is limited to the value of front for the explanation of AgAu7x lamination.

The chromium layer is covered in the zone that shows, and other layer can be present on the whole surface basically or be present at least in the zone of demonstration.This example uses the silver of the half-transmitting and half-reflecting in TiO2/ITO remainder quarter-wave bilayer (the so-called GTR3 basic unit) zone that shows that neutralizes or the color of ag alloy layer.Can be replaced in the viewing area in other the half-transmitting and half-reflecting color with layer, and in the scope of present embodiment.Separately the chromium layer of AgAu7x layer should with in have and not only provide opaque characteristic but also optically with the novel performance of bottom with the isolation of top AgAu7x layer for lamination.Figure 46 represents that how reflectivity changes with the thickness of chromium layer.As can be seen, be a bit larger tham on the thickness of 5nm, thin chromium layer prevents that effectively the silver-colored gold alloy layer in bottom from having contribution to reflectivity.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 obtain the transmittance values of a certain scope, and the total reflectivity for lamination influences without any noticeable (applicable) simultaneously.

A benefit of this method expands to the viewing area.Because only need thin chromium layer to prevent bottom AgAu7x layer reflectivity to be had contribution, therefore the thickness of bottom AgAu7x can be changed to obtain other design object.For example, can realize as express the front, in zone of opacity and in the viewing area, having the hope of reflectivity coupling.Have in the example in zone of relative high transmittance and lower transmissivity in the half-transmitting and half-reflecting mirror element, term " opaque " mean the indication level of transmittance enough low with or not under the situation of adding opaque material on the 4th surface in the 4th surperficial back the outward appearance of hiding parts.In certain embodiments, transmissivity should be less than 5%, preferably less than 2.5%, be more preferably less than 1%, and most preferably less than 0.5%.Because AgAu7x is spaced in zone of opacity, therefore can adjust the reflectivity of thickness as required in the viewing area, to obtain to wish.The AgAu7x top layer will have higher reflectivity when being deposited to Cr to above the TiO2/ITO (being present in the viewing area).Bottom AgAu7x thickness can be set up, and makes the reflectivity of viewing area and zone of opacity mate.The reflectance value of mirror element can be low as the reflectance value of simple chromium layer, and can reach the reflectivity of thick AgAu7x layer.Reflectivity can be adjusted to the value of any hope on this scope, and transmissivity can be adjusted also.The reflectivity coupling of the hope between viewing area and the viewing area also is obtainable.

The layer of argentiferous can be other alloy except that 7%Au93%Ag or the combination of alloy.For example, to have more gold can be favourable to the alloy under these layers of alloy ratio on the opaque layer.This may be owing to obtain between the upper strata of opaque layer and argentiferous that more durable interface, color are wished or the upper strata of argentiferous in processing procedure or the relevant reason of the permanance when contacting with electrochromic media.If two Ag containing layers comprise the material that spreads easily such as gold, platinum, palladium, copper or indium etc. of different levels in silver, so silver layer no longer have one or more intervention opaque layer the half-transmitting and half-reflecting zone may handle or certain hour after become as about the average weighted alloy of alloy.For example, silver-billon is used as lower floor if silver-palladium alloy is used as the upper strata of argentiferous, and the half-transmitting and half-reflecting zone may become Yin-Jin-palladium ternary alloy three-partalloy layer so.Similarly, if the silver that uses the silver that comprises 7% gold of same thickness and comprise 13% gold as two Ag containing layers, the layer in the half-transmitting and half-reflecting zone that obtains so may be to have the equally distributed basically layer that comprises the silver of 10% gold.

Opaque layer can be each the independent layer that makes up in the half-transmitting and half-reflecting zone, and wherein, one or two or all layers can not comprise silver.For example, among many possible combinations, can in the half-transmitting and half-reflecting zone, use silver alloy in structure on the silicon or ruthenium the structure on silicon.

The flash of light outer covering layer of the material mentioned in add its full content United States Patent (USP) 6700692 as a reference at this can also be added in the above-mentioned design, 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 the thickness and the optical property of the material of selecting for flash layer, may need the bottom lamination is adjusted to keep similar coupling or mismatch degree between zone of opacity and the half-transmitting and half-reflecting zone relatively.

As mentioned above, the transmissivity that can obtain in " opaque " zone depends on layer and chromium or " opaque " layer based on silver.The chromium layer is thick more, and the transmissivity under the then given reflectivity levels is low more.The chromium layer can be thinned to the level of hope with the transmissivity near the viewing area.High transmittance level if desired so usually is difficult to control the thickness of extremely thin layer.If the metal opaque layer by partial oxidation, can be used thicker layer so.May need thicker layer to obtain high transmittance with respect to thin simple metal layer.Figure 47 illustrates from the lamination of top table 21 and uses the CrOx layer as the transmissivity of the situation of opaque layer and the relation between the reflectivity.Figure 47 illustrates for the transmissivity of different opaque layers and thickness and the relation of reflectivity.The AgAu7x layer of the symbology different-thickness among the figure.Thicker layer on the right, thin layer on the left side.

As can be seen, when the thickness of AgAu7x layer was thinned, reflectivity was near the value of chromium or opaque layer.The thickness of opaque layer will influence the low side reflectivity of mirror element.For example, when the Cr layer is 10nm when thick, the low side reflectivity is 41.7%, and when the Cr layer is 20nm when thick, it is 50.5%, and when the Cr layer is 30nm when thick, it is 52.7%.Along with the thickness increase of opaque layer, the low side reflectivity is near steady state value, and still, when layer is too thin, will there be the decline of reflectivity in the layer for thin.According to the design criteria for given application, this may be favourable or disadvantageous.Can be by replacing the chromium layer with different materials fully or, overcoming for the reflectivity of chromium layer and the restriction between the transmissivity by adding additional layer.

With reference to United States Patent (USP) 6700692 instructed contain on the Ag layer or on have different metals, semiconductor, nitride or oxide.Select these layers and material so that the improvement for lamination to be provided.Instructed and to be the basic unit under the reverberator of conducting metal, metal oxide, metal nitride or alloy.Also can between basic unit and reflecting material, there be the middle layer.Can select these metals and material, make between each layer, do not exist electricity reaction (galvanic reaction) and/or be used to improve with substrate and with the adhesiveness of reverberator or other layer.Can be on substrate these layers of deposit, perhaps can under above-mentioned basic unit, have the extra play of the characteristic of the hope that provides additional.For example, can exist the dielectric that comprises the have effective odd number quarter-wave optical thickness TiO2 of (effective odd quarter optical thickness) and ITO right.The thickness that can adjust TiO2 and ITO layer as required is to satisfy specific conductance and optics requirement.

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

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

The disclosure is divided the imagination opaque layer in conjunction with the transflective portion of mirror or optical element.This gives the design criteria make new advances or increase, and this design criteria influence is used to reduce the selection of metal of some regional transmissivity of element or mirror.The various suitable basic unit on the TiO2/ITO dielectric layer in the following table 22 expression EC unit or the reflectivity and the color of opaque layer metal.All metal layer thickness are 30nm.Color and reflectivity will change with metal layer thickness.The color of the various proper metal opaque layers when table 22 illustrates containing the Ag top layer and not existing of when opaque metal relatively thicker and AgAu7x or other, on the reflectivity of lower end and the relative different of reflectivity.As being known in the art, these metals each other or will have different optical properties with the alloy of other metal.In some cases, the behavior of alloy will be as the potpourri of each single metal, and still, in other cases, alloy does not have simply the reflecting properties as the interpolation of each single metal.Can select metal or alloy for their electrical property, reflectivity, color or other performance as required.

In containing argentum reflecting layer, in the time of on being deposited to these different metal or alloy, the reflectivity of lamination and color will change.Table 23 is illustrated in the lamination that comprises metal that the top has the AgAu7x of 20nm.By color that contains the Ag layer laminate and reflectivity as the performance change 20nm of the metal of opaque layer.The transmissivity of different laminations also is shown.Regard to as above that chromium represents like that, can change transmissivity, reflectivity and color by the thickness that changes opaque metal.Can be clear that very much from these examples, can obtain color, transmissivity and the reflectivity of wishing by the performance that changes (one or more) opaque metal layer.

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

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: be in various metals in the EC unit at top of system of TiO2/ITO basic unit and reflectivity and the color of 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

Can further increase or strengthen color and reflectivity adjustment capability in the viewing area by with metal opaque layer and the dielectric of explanation combination in United States Patent (USP) 6700692 in addition.Dielectric layer can change color and reflectivity, and this change usually is not influence for the absorption of lamination is tangible.

For with the viewing area in color and reflectivity coupling, can use the double-deck basic unit that illustrates previously that contains below the argentum reflecting layer.Table 24 illustrates for fixing AgAu7x layer, reflectivity and color and how changes with the variation of ITO and TiO2 thickness.As can be seen, double-deck thickness not only influences reflectivity, and color also can be adjusted.Thereby can adjust reflectivity and the color of these layers as required to obtain simultaneously wishing.Can further expand the adjustable of color and reflectivity by adjusting AgAu7x or containing the thickness of argentum reflecting layer.Can by on the Ag containing layer or under add additional dielectric or metal level as a part that shows lamination or by changing the refractive index of dielectric layer, obtain additional color and reflectance varies.

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

Table 24

For example, when the color in the viewing area by the metal under the argentum reflecting layer selection or because argentum reflecting layer self or the combination by each layer during by yellow, blue, green or red biasing, can realize that color and/or reflectivity mate by each layer of adjusting in the viewing area.A benefit of this method is, can on whole surface, apply each layer basically, but, because the optics shielding performance of the uniqueness of opaque layer, therefore these bottoms are not contributed for reflectivity in observation or the zone of opacity and color, but work fully in the concealed viewing area of opaque layer.The invention is not restricted to make the layer that in the viewing area, works to cover entire portion.This is specially adapted to the layer under the opaque layer.If manufacture process is permitted this method, so can be as required these layers of deposit in the general area that shows only.

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

It is known making blue electric driven color-changing part, by using dyestuff like that such as the United States Patent (USP) 5278693 that adds as a reference at this, even this blueness electric driven color-changing part also has blue color when the electromotive force that is not applied on them.Also exist to use the practical methods of the 3rd surface coating lamination with this device of making the exemplary requirement that satisfies outside automobile electrochromic device.The use that also may be combined of these technology.This device must have 40% the reflectance value in 35% and the Europe that are higher than the U.S. at present.Preferably, at least one embodiment, preferably be higher than 50% or 55% reflectivity.No matter utilize what the 3rd surperficial lamination, all need be in electrochromic device chemistry and physics and electric on have permanance.

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

When the coating on glass that will measure in air is compared with the reflectivity of the device of finishing, will exist tangible reflectivity to descend.In order to compensate, except chromium layer or as it, substitute with similar top layer, it is contemplated that the opaque layer that can use silver or silver alloy.But the optics of silver makes and be difficult to obtain the blue coating of high reflectance band more on silver-based material.This part is because the yellow slightly spectrum biasing of silver, and because a kind of like this fact, promptly, since reflectivity on visible spectrum very near 100%, the reflectivity of the silver of any part that is used for interference capability ground increase spectrum that therefore can do is seldom with the work that gives its obvious color.

But, if the semitransparent layer of silver or silver alloy is placed between the chromium and ITO in the top lamination, so still can increase reflectivity significantly, keep bluish color and increase the conductance of the 3rd surface reflection device electrode.

According to the instruction that in presents, comprises, when having the semitransparent layer of silver, can also " separate " silver and cover the zone that the opening in the chromium is made half-transmitting and half-reflecting with bottom by adding in the color.

For example, to be modeled as hue and luminance similar with the identical lamination that does not have the chromium layer for the reflective stacks of the ITO of the silver of the chromium of the silver of the ITO of the TiO2 of about 40nm, 20nm, 14nm, 50nm, 10nm and 90nm.When not having the chromium layer, it is enough that the transmissivity of lamination is calculated as for being used as demonstration or optical sensor zone.Therefore, can in the deposit of this layer, cover chromium, and in the opaque and transflective portion of device is divided, make electric driven color-changing part simultaneously with similar band blue color and brightness (promptly secret).

Also can by between chromium and ITO, insert low index layer or by a plurality of hi-lo index layers that replace increase chromium the reflectivity of ITO lamination.But most to have enough bed thickness also will be electrical insulator with low index oxide and the fluoride materials with suitable optical effect.But silver itself is low index material, and this part has explained its benefit when being placed between chromium and the ITO.

Table 25

Another useful feature in the zone of demonstration window and half-transmitting and half-reflecting coating is at rightabout antireflection feature.Invariably shows the significantly parasitic light of amount of output, and this parasitic light launches along the back of mirror element or scattering and finally leave the zone of demonstration.Relatively low from rightabout reflectivity by element is had, this parasitic light can reduce.Has the benefit that reduces cost of increase at the lower reflectivity of acquisition under the situation that does not have extra play on the 4th surface.

When in the viewing area, having TiO2/ITO/AgAu7x/AgAu7x, in opaque or viewing area, Cr/TiO2/ITO/AgAu7x/Cr/AgAu7x is set.The first chromium layer is thinner, is about that 2～15nm is thick, to be preferably about 5～10nm thick and covered in the viewing area.Second chromium is also covered in the viewing area, and its thickness is adjusted the transmissivity to obtain wishing in viewing area.TiO2/ITO is double-deck to be covered whole surface and is adjusted obtaining in viewing area at rightabout anti-reflection effect, and the front from this part provides suitable color the viewing area simultaneously.

Table 26 illustrates from reverse direction or from the reflectivity on the 4th surface.First kind of situation is base case.It is the above-mentioned lamination that is used for the opaque or viewing area of mirror element.As can be seen, quite high from the reflectivity of back, be about 61%.Under second kind of situation, the thin chromium layer of interpolation below dielectric layer (～5nm).In viewing area, add this thin layer and reflectivity can be reduced to approximately 6%, reduce about 10 times of intensity.Like this, will reduce any spuious scattering of light.Can adjust this reflectance value and color thereof by chromium layer and dielectric layer thickness.Increase by about 4% of 6.2% reflectivity from the 4th surface of the uncoated of glass.If wish further to reduce reflectivity, can add the anti-reflecting layer of additional routine so.6.2% reflectance value can be reduced to and be lower than 2.5% value.

Table 26: under the situation that in viewing area, has and do not have anti-reflecting layer from the reflectivity on reverse direction (the 4th surface).The component value that has 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 first Ag containing layer and chromium layer subsequently.As mentioned above, these layers are adjusted not only to adjust transmissivity but also the adjustment reflectivity towards the observer.Along with these layers are adjusted to satisfy different design objects or purpose, can adjust dielectric layer and/or basic unit's chromium layer to realize best anti-reflection effect.

Can use other metal beyond the chromium or absorption layer as anti-reflecting layer.Material such as tungsten, chromium, tantalum, zirconium, vanadium and other similar metal also will provide antireflective property widely.That other metal can cause is higher, the reflectivity of polychrome more.In addition, chromium or other metal level can mix with the optical property that changes metal to adjust antireflective property with a spot of oxygen or nitrogen.

The serviceability of having mentioned one group of high low-index layer that replaces or having organized these layers more in the other places of presents.The material that generally is regarded as having a low-refraction as metal oxide, nitride, oxynitride, fluoride tends to be relatively poor conductor.Usually, the refringence between the adjacent materials is big more, and optical effect is big more so.This is the reason that the index material is hanged down in use about 1.6 usually or littler refractive index materials conduct.But, when the material with TCO coupling have sufficiently high refractive index and cause hi-lo index to the time, use material to obtain useful effect with higher-index such as transparent conductive oxide.Especially, when using titania, can on optics and electricity, obtain benefit as with the time as the relative higher-index material of the tin indium oxide coupling of relatively low index material.Especially, titania is relative high index material, and this material is not enough good insulator on optical thickness, with will such as ITO, another TCO or metal or semimetal layer be positioned at above it or following more conductive film separates.When between such as the higher layer of the electric conductivity of tin indium oxide, applying T as optical thin film _iO ₂The time, T _iO ₂Will not make the ITO layer mutually insulated in the 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 of the gross thickness of the ITO in film conduction benefit is retained, and obtains the optics benefit of high index layer and low index layer simultaneously.Following example will generally be explained the particularly benefit of these materials of this principle.In soda-lime deposit on glass and all basic unit'ss (n is about 1.5 in visible spectrum) of measurement.

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

The sample that lays from same coating as the sample of Figure 54 a (is noted, even in once laying, also exist some to change) be given the additional coatings of 6%Au94%Ag (the being called 6x) alloy of about 25nm, and be assembled in the electric driven color-changing part according to the principle of summarizing in the other places of presents.Half-wavelength optical thickness ITO with about 12ohm/sq on glass is used as the second surface coating of these elements.Shown in Figure 54 b and Figure 54 c, carry out metric measurement like that then.In table 27, list the result.

Table 27

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

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

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

For example, the AgAu7x as in the ruthenium of top layer and another design (glass/TiO2 45nm/ITO 18nm/AgAu7x 19nm) in the design (glass/TiO2 45nm/ITO 18nm/Ru 14nm) all is adjusted the reflectivity to have 70.3% as single-piece, then, in the time of in being assembled into element, the Ru side will drop to 56.6% reflectivity, and the AgAu7x side will drop to 58.3%.

Another example TiO2 40nm/ITO 18nm/Cr 25nm/AgAu7x 9nm has 77.5% reflectivity as single-piece and has 65.5% reflectivity in being assembled into element the time, and TiO2 40nm/ITO 18nm/AgAu7x 23.4nm has 77.5% reflectivity as single-piece and have 66% reflectivity in being assembled into element the time.Difference in this case is not big as in the previous example above, still, even the layer that its expression is embedded in also can influence the reflectivity that descends from the single-piece to the element.This is will explain when wishing the reflectivity coupling in element to need the reflectivity mismatch for coating as single-piece.

The above-mentioned outward appearance that is used for obtaining in two zones of method supposition of good reflectivity and color-match in two zones of mirror in fact is deserved by reflectivity fully.But the observer not only awares reflectivity, and awares transmitted light in the viewing area.In observation or zone of opacity, because transmissivity is relatively low, so the observer only awares reflection.The amount of transmitted light becomes with transmissivity and the 4th surperficial back of mirror or the reflectivity of its parts that contact of viewing area.The amount of the light that the observer perceives increases with the increase of the transmissivity of the coating in the viewing area.Similarly, along with the reflectivity of the parts of mirror back increases, the light that the observer perceives also increases.This can increase the light of tangible amount, and because the viewing area is brighter than viewing area, therefore, the observer can aware it.Even this can cause two zones to have identical reflectivity display area and also seem brighter.Can by manufacturing have antiradar reflectivity parts element and/or by the transmissivity in the viewing area is made as relatively low level, alleviate this effect.If the output brightness that shows is relatively limited or lower, reduces transmissivity so and can make and show deepening greatly.

For another example, the EC element that comprises 40nm TiO2/18nm ITO/EC fluid/140nm ITO/ glass has 8.1% reflectivity.As the ruthenium layer of deposit 5nm on the 4th surface during with the demonstration of simulation mirror back (, 5nm Ru/ glass/40nm TiO2/18nmITO/EC fluid/ITO/ glass), reflectivity is elevated to 22.4%.The EC element that comprises glass/40nmTiO2/18nm ITO/22nm AgAu7x/EC fluid/ITO/ glass has 61.7% reflectivity.Lamination with ruthenium of 5nm has reflectivity-reflectivity of 63.5% increases about 2%.The amount of this reflectivity is easy to aware for the observer.As mentioned above, Shi Ji reflectivity increase will depend on the reflectivity of parts of mirror back and the transmissivity of EC element.

In order to reduce the luminance difference that perceives in two zones, can in two zones, adjust relative reflectance with compensation transmitted light component.Therefore, in order in the display part of mirror, to realize clean 2% bright area more, preferably increase the reflectivity in the viewing area or reduce reflectivity in the viewing area.Adjustment amount depends on the specific environment of system.

Example 1a

In the present example, the 3rd surface applied of the glass substrate of 2.2mm is had an appointment

TiO ₂, be approximately afterwards ITO, be approximately at last

Silver-colored billon (gold of the silver of 93 weight %/7 weight %).Titania and ITO preferably are applied to the edge of glass basically, and silver alloy is preferably covered in the inboard in the outside at least of related seals.In at least one embodiment, second surface comprises 1/2 wavelength (HW) layer of ITO.Figure 48 a illustrates relevant element reflects rate and transmissivity model with line 4801a among Figure 48 b respectively with 4801b.The model reflectivity is about 57% under about 550nm, and transmissivity is about 36.7%.

Example 1b

Except at least a portion of extending below sealing along the perimeter region on the 3rd surface has chromium/metal tab to improve relevant the folder formula contact area and the electric conductivity between the silver alloy, configuration of this example and example 1a are similar.It is identical that outward appearance keeps, and still, deepening speed is improved.This feature can be applied to a large amount of following examples to improve from the 3rd surface to the relevant electric conductivity that electrically contacts.From Figure 48 a and Figure 48 b as can be seen, reflectivity is relevant with the element of example 1a, and the transmissivity of each is big different; This represents in the advantage of the present invention one.

Example 1c

The configuration of example 1c and example 1a are similar, and still, the viewing area is covered at first, and after lift off mask, and deposit comprises the lamination (that is, causing in the viewing area at the Cr/Ru of having only on glass) of Cr/Ru on whole surface basically.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.With respect to the viewing area, opaque lamination preferably has lower contrast for reflectivity and color.Another advantage of this example is that the general metal that uses may extend into the edge of glass with bridge joint relevant electrical connection clip and the 3rd surperficial silver-colored billon in opaque layer.The model reflectivity is about 56.9% under about 550nm in viewing area, and in the viewing area about 57% reflectivity, transmissivity design object in viewing area (being applicable to all suitable designs) for preferred＜10%,＜5%, more preferably＜1%, most preferably＜0.1%, the transmissivity in the viewing area is about 36.7%.Should be appreciated that except demonstration or other light source or to substitute that optical sensor can be positioned at " viewing area " back as it.

Example 2a

In the present example, the 3rd surface applied of mirror element is had an appointment

ITO, then be the chromium of about 50% transmissivity, be approximately at last

Silver-colored billon.Preferred ITO and chromium are applied to the edge of glass basically, and silver alloy is covered in the inboard in the outside at least of sealing.Cr thickness preferably is adjusted, and the transmissivity of only passing the back plate that makes ITO add the Cr layer is 50%.In at least one embodiment, second surface preferably comprises the HWITO layer.The reflectivity and the transmissivity of element are shown with line 4901a and 4901b in Figure 49 a～49d respectively.The Cr layer can be adjusted (thickening or attenuation) to adjust the final transmissivity of half-transmitting and half-reflecting element.Along with Cr layer thickening, transmissivity will descend.And when the Cr attenuation, transmissivity will increase.The advantage of the increase of Cr layer is that for the normal vacuum sputtering deposition process fluctuation in the substrate I TO layer, lamination is relative colour stable.The physical thickness of chromium layer is preferably approximately

More preferably Most preferably be

The model reflectivity is about 57% under about 550nm, and transmissivity is about 21.4%.

Example 2b

Coated with beyond only measuring chromium/ruthenium combination stack that back during plate (, in adding mirror element before) obtains 50% transmissivity except having, example 2b and example 2a are similar.The stability of improvement is provided in the curing that is added on epoxy sealing of Ru.Ru and chromium thickness ratio can be adjusted, and, there are some design tolerances (design latitude).The adding of chromium mainly is the adhesiveness that will improve Ru and ITO.Ru preferential and Ag or Ag alloy bond.As long as keep suitable material and physical property, can between Cr and Ru layer, place other (one or more) metal so.In Figure 49 c, with

line

4901c and 4902c reflectivity and transmission characteristics are shown respectively.

Example 2c

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

Example 3a

In the present example, the 3rd surface applied of EC element is had an appointment T _iO ₂, be approximately afterwards ITO, be approximately afterwards

Silver, be approximately at last

Izo-Tco.

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

Example 3b

Covered and do not cover on the zone deposit the 3rd surface whole basically except the viewing area and comprise the lamination of Cr/Ru, the configuration of example 3b and example 3a 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 that the general metal that uses can extend to the edge of glass basically to provide bridge joint in relevant electrically contacting between folder and the silver alloy in opaque layer.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 applied of EC element is had an appointment

ITO, be approximately afterwards

Silicon, be approximately at last

Ru or Rh.

All each layers all can be applied to the edge of glass basically.Scheme as an alternative, glass can sheet form processed and be cut into the single-piece that is used for adding mirror element subsequently.Ru or Rh layer can be by a kind of replacements in the metal or alloy of several high reflection.In at least one embodiment, the second surface preferred coated has HWITO.This example is illustrated in the advantage that increases transmissivity under the different wavelength.The layer that substrate I TO layer can be had different thickness replaces.In certain embodiments, preferred ITO is the odd-multiple of 1/4 wavelength.In these cases, reflectivity will increase a little by ITO.Along with the ITO thickening, how many this effects is eliminated.The benefit of thicker ITO generally is lower surface resistance, and this causes the time of element deepening faster.The model reflectivity is about 57% under about 550nm, and transmissivity is about 11.4%.Respectively in modeled reflectivity and transmissivity shown in Figure 51 a and the 51b.The reflectivity and the transmissivity of measurement are shown with line 5101c, 5102c respectively in Figure 51 c.

Example 5

ITO, be approximately afterwards

Chromium, be approximately afterwards

Ru, can randomly apply and have an appointment at last

Rh.

All each layers all can be applied to the edge of glass basically, and perhaps, the form that glass can sheet is processed and be cut into the single-piece that is used for adding mirror element subsequently.The Ru layer can perhaps, can be added the interpolation layer such as rhodium by a kind of replacement in the metal or alloy of several high reflection.Metal level is adjustable to obtain higher or lower reflectance/transmittance balance.In at least one embodiment, the second surface preferred coated has the HWITO layer.The benefit of thicker ITO is lower surface resistance, and this causes the time of element deepening faster.Thicker ITO can increase by the 3rd surperficial lamination roughness, and this can cause lower reflectivity.When respectively model transmissivity and the reflectivity of Figure 52 a and 52b when comparing, being observed this effect with the transmissivity and the reflectivity (being respectively line 5201c1, the 5201c2 of Figure 52 c) that obtain from experiment.The model reflectivity is about 57% under about 550nm, and transmissivity is about 7.4%.

Example 6a the 3rd lip-deep opacifier layer

In the present example, the opacifier layer is added in the 3rd surface coating lamination.To make an appointment with

Chromium, be approximately then

Basic unit's lamination of ITO be deposited on the glass substrate, wherein, perhaps in the deposition process of basic unit's lamination, the viewing area is covered, perhaps, subsequently in the viewing area with basic unit's lamination laser deletion.Subsequently, apply approximately

ITO layer peace treaty

Silver alloy Ag-X layer (wherein, X represents to be used for the option of the alloy of Ag).This method is opaque basically in viewing area, and is half-transmitting and half-reflecting in the viewing area.

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

Example 6b

Example 6b and example 6a are similar.In the present example, the 3rd surface initially applies in addition in the viewing area and has an appointment

Chromium, be approximately then ITO, be approximately then

TiO ₂, be approximately at last

Basic unit's lamination of chromium.Basically whole the 3rd surface applies subsequently has an appointment

T _iO ₂, be approximately then ITO, be approximately at last

Silver-colored billon.The model reflectivity is about 54% under about 550nm, and transmissivity is about 41%.

For the electrochromism mirror, if wish high transmittance (T) level, can have limited reflectivity (R) so, perhaps, higher if desired reflectivity can have limited transmissivity so.Suppose that absorption (A) keeps constant, so can be with concerning R+T+A=1 explanation this point.In some demonstrations or optical sensor, mirror were used, the transmitted light (or brightness) that may wish to have higher level was to observe relevant demonstration satisfactorily or to see through enough light by mirror element.This usually causes mirror to have reflectivity less than the reflectivity of hope.

In other example here the scheme of tackling described restriction has been discussed, wherein, metal layer thickness for reflectivity is enough, and only is thin on the viewing area in viewing area.Other example uses the layer or the coating lamination of different metal on the viewing area, to attempt the color and/or the reflectivity of coupling zones of different.Invariably, the sudden change of reflectivity or color are that observer institute is unsatisfied.With reference to Figure 55 and Figure 56 a, for example, the border (C) between two zones suddenlys change.Zone (A) has than zone (B) high transmissivity.Two zones of drawing, border (C).In Figure 63, the border the during beginning of the transition between the high low reflectivity regions also suddenlys change.When transition between the zone, the slope approach infinity of the reflectance varies of per unit distance.

In at least one embodiment, the transition of metal layer thickness is the mode with gradually.For human eye, it is more difficult that the detection that gradually changes of reflectivity in the transitional region and/or transmissivity is got up.Two zones still have visibly different reflectivity and transmittance values, and still, the border between two zones is by mildization (grade).The gentle slope has been eliminated unexpected uncontinuity and has been used transition gradually to replace it.When the interface was changed gently, human eye was attracted by it no longer like that.The gentle slope can be linear, curve or Figure 56 b～56d shown in the transition of other form.The distance that the gentle slope occurs can change.In at least one embodiment, this distance becomes with the reflection differences between two zones.When the reflection differences between two zones was relatively low, the distance on gentle slope can be shorter relatively.When reflection differences is big, can wish bigger gentle slope so that the observability of transition minimizes.In at least one embodiment, the length on gentle slope becomes with the purposes of using and expect, observer, illumination etc.

In at least one embodiment shown in Figure 56 e, transmissivity can be reduced in one or more part near zero.Here under Shuo Ming other situation, reflectivity can be identical or different.Can use " secret " embodiment of other places explanation here, be constant relatively to keep reflectivity, allows simultaneously to adjust transmissivity as desired in the various piece of mirror element.

The invention is not restricted to have two or more zones of constant transmissivity or reflectivity.At embodiment shown in Figure 56 f.Area B has can be zero relatively low transmissivity.If one of design object is to make area B stop light from the object of the coated substrates back that is positioned at half-transmitting and half-reflecting, this can be desirable so.The coating lamination can have gradually transition from area B by slope C.Zone A can have another gradient in self.There is the possible benefit that is discussed later in this point.

In some applications, may not obtain enough length to obtain two platform situations.In these cases, to use continuous gentle slope be favourable in striding across like that shown in Figure 57 a zone of wishing the half-transmitting and half-reflecting performance.The variation of reflectivity is gradually, and obtains the benefit of high transmittance; The interface that between the zone, does not have sudden change.

Various forms can be taked in gentle slope between two zones.On the most wide in range meaning, element can comprise the zone of obvious difference and uniform transmissivity and reflectivity.In the example shown in Figure 57 a～57c, there are not the constant reflectivity and the zone of transmissivity.These situations have on optical property gradually and continuous variation.The advantage of this method shown in Figure 58.

When the observer watches when showing by the glass substrate of mirror element or coating, exist about the nearer part that shows with respect to show than the path of distal part and the continuity of angle.The orientation that shows according to mirror element, size of component, to observer's distance etc., effective relative angle of incident will change.This causes having on the various piece of viewing area different transmission amounts to pass glass.Different transmission amounts causes the variation of the brightness that shows again.When hope during from the constant output of the light of the All Ranges that shows, the half-transmitting and half-reflecting coating can be changed to consider the loss by the transmission that is derived from viewing angle and path difference of glass.If effectively viewing angle becomes 60 degree from about 45 degree, the transmissivity of passing glass so will change about 6%.Therefore, how many half-transmitting and half-reflecting coatings that has mildization in the zone that shows can compensate this effect, and therefore can cause the light intensity that perceives along the more impartial quilt that shows.

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

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; Moving or velocity variations on substrate or the paint-on source; Changes of magnetic field in the magnetron or such as layer thinning technique or other the suitable means of the ion beam milling of explanation here.

Figure 59 illustrates an example of electrochromism mirror structure, and this electrochromism mirror structure has: the back plate 5914 of glass; Comprise approximately

The layering peace treaty of titania

ITO layering the layer 5972; The layer 5978 of 6Au94Ag, wherein, a zone has approximately

Thickness, another zone has approximately

Thickness, the 3rd zone between these two zones, wherein, the transition gradually of thickness between; Electrochromism fluid/gel 5925 with about 140 microns thickness; Approximately

Layer 5928 and the glass plate 5912 of 2.1mm of ITO.The variation range of the reflectivity of the element that obtains for from the major part of mirror about 63% to showing about 44% in the region in front.

Structure and the above-mentioned similar electrochromic device of electrochromic device, wherein, by the combination that the magnetic that uses concealing technique and deposit source is handled, the thickness of layer 5978 is to change with the similar mode of mode that illustrates in Figure 57 c and illustrate.The method of selecting will depend on the definite feature and what disposal route that need in final element be available.Figure 60 and Figure 61 illustrate the corresponding reflectivity data that becomes with the position on the mirror.In this case, show the regional back that is positioned at antiradar reflectivity, high-transmission rate.

The Another Application of the transition of mildization is the electric driven color-changing part with second surface reverberator of hiding epoxy sealing; Can realize " ring " and reflectivity and color-match between the 3rd or the 4th lip-deep reverberator.Best coupling is when the reflection strength of ring and reverberator reflection strength coupling.In at least one embodiment, the reflectivity of reverberator further increases when not changing ring.Because therefore permanance, manufacturing or other consideration this situation can occur.When the reflectivity that makes reverberator like that as discussed above is changed gently, can obtain to be used to keep the means of the coupling between reverberator and the ring.When gradually the variation of reflectivity occurring, the reflectivity of reverberator can be adjusted near the reflectivity of coupling ring ring and then along with the increase gradually away from ring.Like this, shown in Figure 62, in the heart reflectivity is higher relatively in the viewing area.

Similarly, ITO can be from encircling center that the zone tapers to viewing area to keep the required thickness range of acceptable color, and allowing simultaneously has higher relatively reflectivity at the center of element.Like this, compare along the relative thin situation of element with the ITO coating, mirror is with deepening relatively promptly.

Identical design can be extended to the solid metal reflector electrode.In this case, can use mildization, make the surface resistance of coating gradually change with the position.This method cooperates various bus configuration and causes faster and more uniform deepening.The embodiment of the mirror element of the state of the prior art before Figure 63 illustrates according to the present invention.

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

Claims

1. a rearview mirror assemblies comprises the electrochromism EC element with half-transmitting and half-reflecting zone and zone of opacity, and this EC element comprises:

The substrate of substantial transparent;

With the following reflection horizon that support base is adjacent to be provided with, this time reflection horizon covers the half-transmitting and half-reflecting zone;

Be arranged on outside the half-transmitting and half-reflecting zone and with the adjacent opaque layer in following reflection horizon; And

Reflection horizon on extending on the half-transmitting and half-reflecting of EC element zone and the opaque layer, reflection horizon has common surface with following reflection horizon on this at least a portion in half-transmitting and half-reflecting zone.

2. according to the rearview mirror assemblies of claim 1, wherein, has uneven thickness at least one in half-transmitting and half-reflecting zone and zone of opacity of following reflection horizon.

3. according to the rearview mirror assemblies of claim 1, wherein, zone of opacity is no more than 10% to the reflectivity of surround lighting and half-transmitting and half-reflecting zone to the difference of the reflectivity of surround lighting.

4. according to the rearview mirror assemblies of claim 1, wherein, zone of opacity is no more than 5% to the reflectivity of surround lighting and half-transmitting and half-reflecting zone to the difference of the reflectivity of surround lighting.

5. according to the rearview mirror assemblies of claim 1, wherein, by the zone of opacity reflected ambient and by the colour-difference between the light of half-transmitting and half-reflecting regional reflex less than 10C ^*Unit.

6. according to the rearview mirror assemblies of claim 1, wherein, by the zone of opacity reflected ambient and by the colour-difference between the light of half-transmitting and half-reflecting regional reflex less than 5C ^*Unit.

7. according to the rearview mirror assemblies of claim 1, wherein, opaque layer comprises the material that is selected from the group that is made of chromium, stainless steel, silicon, titanium, nickel, molybdenum, inconel, indium, palladium, osmium, tungsten, rhenium, iridium, rhodium, ruthenium, tantalum, copper, gold, platinum and alloy thereof.

8. according to the rearview mirror assemblies of claim 1, also comprise:

Be sandwiched in the material flash layer at the zone of opacity place between reflection horizon and the opaque layer, this flash layer covers opaque layer in essence fully.

9. rearview mirror assemblies according to Claim 8, wherein, flash layer comprises at least a in conductive oxide, platinum group metal or its alloy, nickel or its alloy and molybdenum or its alloy.

10. according to the rearview mirror assemblies of claim 1, also comprise being arranged on down under the reflection horizon and the basalis on the substrate of substantial transparent.

11. according to the rearview mirror assemblies of claim 10, basalis comprises the coating that is selected from by in nonmetal bilayer with quarter-wave optical thickness and the group that metal level constitutes.

12. according to the rearview mirror assemblies of claim 1, wherein, opaque layer will descend the part in reflection horizon and the part in last reflection horizon to carry out isolation.

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

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

15. according to the rearview mirror assemblies of claim 1, wherein, the transmissivity of zone of opacity is no more than 0.5%, the transmissivity in half-transmitting and half-reflecting zone is no more than 25%.

16. according to the rearview mirror assemblies of claim 1, wherein, following reflection horizon and last reflection horizon comprise silver or silver alloy.

17., also comprise being selected from by the interior lighting assembly according to any one rearview mirror assemblies in the claim 1 to 8, the digital speech processing system, power supply, GPS, the exterior light controller, wetness sensor, information display, optical sensor, the blind spot indicator, direction signal indicator, near warning horn, operator interface, compass, temperature indicator (TI), the voice-activated device, microphone, light adjusting circuit, the GPS device, telecommunication system, the navigation assistor, the deviation warning system, the adaptive cruise controller, at least a device in the group that vision system and tunnel detection system constitute.

18. according to the rearview mirror assemblies of claim 1, wherein, the EC element has the uniform basically reflectivity above at least 50% on the entire emission device.

19. a rearview mirror assemblies comprises the electrochromism EC element with half-transmitting and half-reflecting zone and zone of opacity and the transitional region between these two zones, this EC element comprises:

The substrate of substantial transparent;

Reflection horizon on extending on the half-transmitting and half-reflecting of EC element zone and the opaque layer,

Wherein, the thickness of at least one in opaque layer and the last reflection horizon is little by little changing corresponding to first one-tenth-value thickness 1/10 of zone of opacity with between corresponding to second one-tenth-value thickness 1/10 in half-transmitting and half-reflecting zone in transitional region, thereby makes the little by little variation between zone of opacity and half-transmitting and half-reflecting zone by the reflectivity of the surround lighting of EC element reflects and color.

20. according to the rearview mirror assemblies of claim 19, wherein, the transmissivity of EC element is close to zero in zone of opacity.

21. the rearview mirror assemblies according to claim 19 also comprises:

Following reflection horizon, this time reflection horizon covers the half-transmitting and half-reflecting zone, and is adjacent to be provided with support base below opaque layer, makes that going up the reflection horizon has common surface with following reflection horizon at least a portion in half-transmitting and half-reflecting zone.

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

23. according to the rearview mirror assemblies of claim 21, wherein, following reflection horizon and last reflection horizon comprise silver.

24. according to the rearview mirror assemblies of claim 21, wherein, the thickness of at least one in following reflection horizon and the last reflection horizon has gradient in the half-transmitting and half-reflecting zone.

25. according to any one rearview mirror assemblies in the claim 19 to 21, wherein, by the zone of opacity reflected ambient and by the colour-difference between the light of half-transmitting and half-reflecting regional reflex less than 5C ^*Unit.

26., also comprise being selected from by the interior lighting assembly according to any one rearview mirror assemblies in the claim 19 to 21, the digital speech processing system, power supply, GPS, the exterior light controller, wetness sensor, information display, optical sensor, the blind spot indicator, direction signal indicator, near warning horn, operator interface, compass, temperature indicator (TI), the voice-activated device, microphone, light adjusting circuit, the GPS device, telecommunication system, the navigation assistor, the deviation warning system, the adaptive cruise controller, at least a device in the group that vision system and tunnel detection system constitute.