CA1278771C - Solar reflector with transparent base and transparent films of metal oxide or nitride and metal - Google Patents

Solar reflector with transparent base and transparent films of metal oxide or nitride and metal

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Publication number
CA1278771C
CA1278771C CA 495592 CA495592A CA1278771C CA 1278771 C CA1278771 C CA 1278771C CA 495592 CA495592 CA 495592 CA 495592 A CA495592 A CA 495592A CA 1278771 C CA1278771 C CA 1278771C
Authority
CA
Grant status
Grant
Patent type
Prior art keywords
film
metal
stainless steel
transparent
article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA 495592
Other languages
French (fr)
Inventor
Russell C. Criss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Inc
Original Assignee
PPG Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3607Coatings of the type glass/inorganic compound/metal
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3613Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3626Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3642Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing a metal layer
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3652Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366Low-emissivity or solar control coatings
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3681Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0015Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • C23C14/085Oxides of iron group metals
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • C23C14/087Oxides of copper or solid solutions thereof
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/18Metallic material, boron or silicon on other inorganic substrates
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24HEATING; RANGES; VENTILATING
    • F24SSOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S50/00Arrangements for controlling solar heat collectors
    • F24S50/80Arrangements for controlling solar heat collectors for controlling collection or absorption of solar radiation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00Integration of renewable energy sources in buildings
    • Y02B10/20Solar thermal
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/40Solar thermal energy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12576Boride, carbide or nitride component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611Oxide-containing component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12493Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611Oxide-containing component
    • Y10T428/12618Plural oxides
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31507Of polycarbonate

Abstract

ABSTRACT OF THE DISCLOSURE
A transparent article, particularly an architectural glass product, for reflecting solar energy comprising a transparent metal compound film which is an oxide or nitride and which exhibits color by absorption and interference effects on a transparent substrate and a highly reflective metal film on the metal oxide or nitride film. A method of making the products in which both the compound film and the metal film are deposited by sputtering is also described.

Description

~'~7~

ARCHITECTURAL COATING WITH INTERFERENCE COLORS

Background of the Invention The present invention relates generally to the art of transparent coatings and more particularly to multiple layer colored tran&parent coatings, especially for use on architectural glass products.
Architectural glass products with metallic and/or metal oxide films are growing in importance as energy demands for heatlng and cooling become increasingly expensive. Coated glass architectural products generally fall into two categories, solar energy control and high transmittance, low emissivity coated products, Solar energy control glass products nre generally glass substrAtes, often tinted, coated with a low visible transmittance colored film which reduce3 solar energy transmittance through the windows into the building interior, thereby reducing alr condltioning costs. These products are mo~t effective ln warnl climate~ nnd nre most often seen in commercinl construction. In nrea~ where heutlng costs are of greater concern, and particularly in residential construction, high transmittance, low emissivity coatings are desirable in order to allow high transmlttance of visible light into the interior while reflecting infrared radiation to retain heat inside the building. High transmittance, low emissivity coatings are typically multiple layer films whereln an infrared reflecting metal such as silver, gold or copper is sandwiched between anti-reflective metal oxide layers such as bismuth, indium and/or tin oxides. Solar energy control films, on the other hand, are typically single layer films of one or more of the metals or oxides of metals such as cobalt, iron, chromium, nickel, copper, etc.

- 1 - ~.

~2'~'8~

Wet chemical methods for producing metallic films for solar energy control are well known from U.S. Patents 3,846,152; 4,091,172;
3,723,158 and 3,457,138. Pyrolytic methods for producing metal oxide films for solar energy control are well known from U.S. Patents 3,660,061; 3,658,568; 3,97~,272 and 4,100,330.
Sputtcring technologles for producing high tran6mittance, low em1ssivity multiple layer coatlngs are dl6closed in U.S. Pstents 4,462,884, and 4,508,~89. Sputter~ng techniques for produc1n8 aolar control f~1ms aro disclosed in U.s. Pstents 4,512,863 and 4,594,137.

U.S, Patent ~lo. 4,022,947 to Grubb et al discloses a transparent panol capable of transmitting a deslred portion of visible radiatlon whila rcflecting 8 large portion of incident solar radiation, and a method of prapari~g samo, by ~puttering an iron, nickel and chromium alloy to obtain a transparent metal film, and reactively 6puttering th~ samQ or a similar alloy in the presence of oxygen to form an oxide film. In one preferrcd embodiment, the metal film lies between the substratQ and the metal oxide fllm. In another preferred embodiment, the metal oxide film lies b¢tween the substrate and the metal film.

Here disclosed is a solar energy control f ilm deposited on a substrate such as glass by cathode sputtering, preferably ~agnetron sputtering. The film comprises a layer of a reflective metal and a layer of 8 colorcd metal compound, prcferably a metal oxide. The metallic layer provides brightness and reflectivity ~hile the metal oxide layer can be varied in relative thicknes6 to provide a variety of D~

1'2~7~

reflected colors by interference effects. In addition, because the metal oxide exhibits significant absorption at ~ particular wavelength, a desired color can be produced with a relatively thin film compared with ~etal oxides which exhibit interference effects but no significant absorption.
~iore particularly in accordance with one aspect of the invention there is provided, ~n article of manufacture for the reflectance of solar energy compri~ing:
a. a transparent substrate;
b. a transparent metal compound film selected from metal oxides and metal nitrides ~hich exhibits color by absorption and interference effects deposited on a surface of said substrate; and c. a highly infrared reflective transparent metallic fllm deposited on said metal co~pound film.
In accordance with a second aspect of the invention there i~
provided, a method of making a solar energy reflecting coated article comprising the steps of:
a. sputtering onto a ~urfacs of a transparent substrate a first transparent coating of a m~tal oxid~ which ~xhibits color by absorption and interference effects; and b. sputtering over said metal oxide film a highly reflective transparsnt met~llic film.
~sscription of the ~referred Embodiments A transparent ~ubstrate, preferably gla88, is coated by cathode sputtering, preferably magnetron sputtering, to provlds a solar energy control product. The coating comprises at least one layer of a reflective metal, such as gold, copper, aluminum and preferably s$1ver, snd at least one layer of a metal compound whlch can provide color by both absorption and lnterference effects at various relative thicknesse~, such as the oxides ant/or nitrides of metals such as iron alloysi nickel alloys, copper, iron and cobalt. A preferred metal compound is oxidised stainless steel (herein also "stainless steel oxide").
In a preferred embodiment of the present invention, a gla8s surface is first coated with a layer of stainless steel oxide by ~2~L

~puttering a stalnless steel cathote tar8et Ip an oxidlzlng reactlve atmosphere. The stainless steel oxlde coated surfac~ ls then further coated wlth a layer of sllver by sputterlng a silv¢r cathode targ~t ln a nonreactlve atmosphere such as argon. Preferably, a protectlve coatlng 18 deposlted over the sllver. In a most preferred embodlment of the present lnventlon, the protec~lve coating ls stalnle~s steel deposlted by ~putterlng a stainless stcel cathode target ln a nonresctive atmosphere such a~ argon. The relative thlcknesses of the coatlng layers csn be varled to yleld a varlety of reflected colors. Whlle lnterference colors . .
, ~, . ,, ,.,,.~ .

~,Y2~Ji8~, can be obtained with relatively nonabsorbing materials such as lndium oxide or tin oxide, much thicker films are required to produce colors equivalent to those of thinner films of absorbing compounds such as stainless steel oxide. For example, an indium oxide film about 1375 Angstroms thick is required to produce a gold color compared to about 300 to 600 Angstroms for stainless steel oxide. Moreover, the gold reflectance of the stainless steel oxide is more intensely colored due to the absorptance of the stainless steel oxide in the blue wavelength range of the spectrum.
In a most prèferred embodiment, Ytainless steel oxide, silver and stainless steel layers are combined to produce a rich gold colored coating. The present invention will be further understood from the descriptions of specific examples which follow.
~XAI~L~ I
A multiple layer coating of stainless steel oxide and silver witl1 a stainless steel protective coattng is deposited on a glass substrate under the following conditions, in one pass under multiple cathodes in sequence. A clean glass substrate is maintained in a vacuum chamber in an atmosphere of 50 percent oxygen and 50 percent argon at a pressure of 4 ~icrons. I~ith two stainless steel cathodes powered at 43 kilowatts each and a line speed of 100 inches (2.54 meters) per minute, a stainless steel oxide coating is deposited at a thickness of 300 to 600 Angstroms, decreasing the luminous transmittance of the glass from about 90 percent to about 75 percent. Next, a silver cathode is sput~ered in an inert argon atmosphere. ~ith the s&me line speed and a power of 6 kilowatts, a silver coating about 200 to 250 Angstroms thick is deposited over the stainless steel oxide coating, further reducing the luminous ~;~7~

t~ansmittance to about 14 percent. Finally, since an exposed silver film is particularly vulnerable, a very thin protective film is deposited over ~he silver by sputtering a stainless steel cathode in an inert argon atmosphere. With the same line speed and minimal power of about 1 kilowatt, the stainless steel pro~ective coating is deposited to a thickness of about 10 to 50 Angstroms, resulting in a final luminous transmittance of about 12 percent. The thickness of the protective layer is minimized ln order to minimize the decrease in transmittance as well as to minimlæe any decrea~e in the reflectivity of the silver layer. The coated article has a bright gold appearance from the glass side resulting from both interference effects and absorption properties of the stainless steel oxide, which absorbs nearly 30 percent at a wavelength of 4000 Angstroms but only about 5 percent at wavelengths of 5500 Angstroms and higher. The stain]ess steel composition used in this ~xample is the 316 alloy, which comprises about 6~ percent iron, 17 percent chromium, 12 percent nickel and 2.25 percent molybdentlm. The luminous reflectance of the coated article is 67,7 ~ercent from the coated surace and 52.9 percent from the glas~ slde. The reflected color has dominant wavelengths of 579 and 576 and excitation puritie~ of 15.2 and 42.4 from the coated and glass sides respectlvely. In a double glazed unit, the coated article provides a shading coefficient of 0.17 and summer and wlnter U-values of 0.30.
EXA~LES II-X
Coated articles reflecting various colors ranging from greenish yellow through yellow, yellowish orange, orange, reddish orange and red to purple are prepared by depositing stainless steel oxide, silver and stainless steel as in Example I to various relative thicknesses. Uhile ~æ~

the thicknesses are not measured directly, the transmlttances after each sputtering step are indicative of the individual layer thicknesses. The varying thicknesses are obtained by varying the power to the cathode and/or the number of passes under a cathode. In the following table, the transmittances are shown after the deposition of the first layer of stainless steel oxide (SS oxide), after the layer of silver, and after the protective layer of stainless steel (SS). The table also includes the luminous reflectance from the coated side, P~1, and the glass slde, R2.

Table Example % Transmittance % Reflectance Color SS Oxide Silver SS R1 R2 R2 II 62.1 45.0 29.4 37.4 9.5 Orange III 55.3 40.4 28,7 40.5 6.1 Red IV 51.8 37.3 26.8 43.3 5.8 Purple V 58.2 16,1 11,4 62.927.6 Yellowlsh Orange VI 62.9 17.7 13.0 62.334.2 Yellow VII 70.0 17.6 13.3 63.645.9 Yellow VIII 77.8 21.3 12.4 78.962.8 Greenlsh Yellow IX 77.9 25.8 14.9 53.647.2 Greenlsh Yellow X 78.3 16.2 14.6 51.546.3 Gold The thlDner silver films of Examples II to IV produce high reflectance from the coated side, but thicker silver films of Examples V
to IX are preferred to provide high reflectance from the glass side as well.
The above examples are offered only to illustrate the present invention. Various other absorbing metal oxides and nitrides whi ch 12~87~L

produce interference colors, such as o~ides or nitrides of nickel alloys, copper, iron and cobalt may be used, along with other higllly reflective metals such as gold, copper or aluminum. Any suitable transparent protective layer may be employed, The scope of the present invention is defined by the following claims.

Claims (20)

1. An article of manufacture for the reflectance of solar energy comprising:
a. a transparent substrate;
b. a transparent metal compound film selected from metal oxides and metal nitrides which exhibits color by absorption and inter-ference effects deposited on a surface of said substrate; and c. a highly infrared reflective transparent metallic film deposited on said metal compound film.
2. An article of manufacture according to claim l, wherein the substrate is glass.
3. An article of manufacture according to claim 2, wherein the reflective metallic film comprises a metal selected from the group consisting of silver, gold, copper, aluminum and mixtures thereof.
4. An article of manufacture according to claim 3, wherein the metal is silver and which further comprises a transparent protective film deposited over the silver film.
5. An article according to claim 4, wherein the metal compound is selected from the group consisting of the oxides and nitrides of stainless steel, nickel alloys, copper, iron, cobalt and mixtures thereof.
6. An article according to claim 5, wherein the metal compound film comprises stainless steel oxide.
7. An article according to claim 6, wherein the transparent protective layer comprises stainless steel.
8. An article according to claim 7, wherein the stainless steel comprises about 68 percent iron, 17 percent chromium, 12 percent nickel and 2.25 percent molybdenum.
9. An article according to claim 7, wherein said article exhibits a gold color in reflectance from the glass surface.
10. An article according to claim 1, wherein said transparent metal compound and reflective metal films are sputtered films.
11. A method of making a solar energy reflecting coated article comprising the steps of:
a. sputtering onto a surface of a transparent substrate a first transparent coating of a metal oxide which exhibits color by absorption and interference effects; and b. sputtering over said metal oxide film a highly reflective transparent metallic film.
12. A method according to claim 11, wherein said substrate is glass and said sputtering is magnetically enhanced.
13. A method according to claim 12, wherein said metal oxide film is deposited by sputtering a metal selected from the group consisting of stainless steel, nickel alloys, copper, iron, cobalt and mixtures thereof in an oxidizing atmosphere.
14. A method according to claim 13, wherein stainless steel is sputtered.
15. A method according to claim 14, wherein said metallic film is deposited by sputtering over the oxide film a metal selected from the group consisting of silver, gold, copper, aluminum and mixtures thereof in an inert atmosphere.
16, A method according to claim 15, wherein silver is sputtered in an atmosphere comprising argon.
17, A method according to claim 16, wherein a transparent protective film is deposited over said silver film,
18, A method according to claim 17, wherein a transparent protective film comprising stainless steel is deposited over said silver film.
19. A method according to claim 18, wherein the protective film is deposited by sputtering stainless steel in an inert atmosphere.
20, A method according to claim 19, wherein the stainless steel oxide film and the stainless steel protective film are both deposited by sputtering of stainless steel comprising about 68 percent iron, 17 percent chromium, 12 percent nickel and 2.25 percent molybdenum.
CA 495592 1984-12-17 1985-11-18 Solar reflector with transparent base and transparent films of metal oxide or nitride and metal Expired - Fee Related CA1278771C (en)

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US06682136 US4902581A (en) 1984-12-17 1984-12-17 Architectural coating with interference colors
US682,136 1984-12-17

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FI854891A (en) 1986-06-18 application
KR930001970B1 (en) 1993-03-20 grant
JPH0660037B2 (en) 1994-08-10 grant
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DE3570644D1 (en) 1989-07-06 grant
JP1946861C (en) grant
US4902581A (en) 1990-02-20 grant
FI854891D0 (en) grant
CN1016605B (en) 1992-05-13 application
EP0185314B1 (en) 1989-05-31 grant
DK582685A (en) 1986-06-18 application
ES550001A0 (en) 1986-10-16 application
ES8700642A1 (en) 1986-10-16 application
EP0185314A1 (en) 1986-06-25 application
DK582685D0 (en) 1985-12-16 grant
CN85108851A (en) 1986-08-20 application
FI854891A0 (en) 1985-12-11 application
JPS61151045A (en) 1986-07-09 application

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