NZ505140A - A near infrared (NIR) wavelength film containing a tin oxide with a NIR dopant - Google Patents

Abstract

The specification describes a NIR film comprising tin oxide containing a NIR dopant selected from antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt and nickel and containing a fluorine dopant at an atomic concentration less than the concentration of the NIR dopant.

Description

PATENTS FORM 5 PATENTS ACT 1953 COMPLETE SPECIFICATION Number Dated Divided out of application no. 337160 filed 9 August 1999 SOLAR CONTROL COATED GLASS We, ELF ATOCHEM NORTH AMERICA, INC., a corporation organised under the laws of the State of Pennsylvania, United States of America of 2000 Market Street, Philadelphia, PA 19103-3222, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement. (followed by la) 182466 vl WGN* intellectual property office of n.z. 1 3 JUN 2000 REC »w rr r o - iq- Solar Control Coated Glass Background of Invention This specification is a divisional specification of NZ patent specification 337160.

This invention relates to coated glass used in residential, architectural and vehicle windows and miscellaneous applications where both solar control and low emissivity properties are desired. The coatings for solar control and low emissivity contain tin oxide having various dopants. The invention avoids the need for an anti-5 iridescence underlayer. The glass articles may be of any shape but are typically flat or curved. The glass composition can very widely but is typically soda lime glass produced by the float process. It may be annealed, heat strengthened or tempered.

Description of Prior Art Solar-control is a term describing the property of regulating the amount of solar 10 heat energy which is allowed to pass through a glass article into an enclosed space such as a building or an automobile interior. Low emissivity is a term describing the property of an article's surface wherein the absorption and emission of mid-range infrared radiation is suppressed, making the surface a mid-range infrared reflector and thereby reducing heat flux through the article by attenuating the radiative component of heat transfer to and from the low emissivity surface (sometimes referred to as Low E). By suppressing solar heat gain, building and automobile interiors are kept cooler; allowing a reduction in air conditioning requirements and costs. Efficient low emissivity coatings improve comfort during both summer and winter by increasing the thermal insulating performance of a window.

Important to commercially acceptable coated glass articles which possess both solar-control and low emissivity properties are, of course, economic processes for producing the articles and durability and maintenance of associated properties such as light transmission, visibility, color, clarity and reflection.

As explained below, various technologies have been employed to meet the requirement for solar-control and low emissivity glass, however, no one system has successfully met all of the performance requirements in an economic manner.

Many coatings and coating systems cause iridescent colors to develop in the coated article. This may be caused by the chemical composition of the coating , the thickness of an individual layer or layers, or an interaction of the substrate and coatings to incident light. Such iridescence can, in some cases, be minimized or eliminated by placing an anti-iridescence layer between the glass substrate and the first coating. The use of an interference layer between the glass and a subsequent functional layer or layers to suppress iridescence or color reflection was first demonstrated by Roy G. Gordon, and was the subject of U. S. Patent 4,187,336, issued Feb 5, 1980. The Gordon technology has been the state of the art for coated solar control glass as evidenced by recently issued U.S. Patent 5,780,149 (McCurdy el al, July 14, 1998) which applied two layers to obtain solar control on top of a Gordon type interference layer. The interference layer frequently contains silicon dioxide. Surprisingly, the present invention represents a dramatic breakthrough and eliminates the need for a Gordon type underlayer to control reflected color.

US Patent 3.149.989 discloses compositions of coatings useful in producing radiation reflecting (solar-control) glass. At least two coatings are used with the first coating, adhered to the glass substrate, being comprised of tin oxide doped with a relatively high level of antimony. The second coating is also comprised of tin oxide and is doped with a relatively low level of antimony. The two films may be superimposed, one on another, or may be applied to opposite sides of the glass substrate. In either case, these solar-control coatings do not contribute significant low emissivity properties to the glass article.

US Patent 4.601.917 teaches liquid coating compositions for producing high-quality, high-performance, fluorine-doped tin oxide coatings by chemical vapor deposition. One of the uses of such coatings is in the production of energy-efficient windows, also known in the trade as low-E or low-E windows. Methods of producing the coated glass are also described. This patent does not teach how to produce coated glass articles which possess both solar-control and low emissivity properties.

US Patent 4.504.109. assigned to Kabushiki Kaisha Toyota Chou, describes glass coated with infrared shielding multilayers comprising a visible light transparent substrate and an overlying component lamination consisting of "at least one infrared shield layer and at least one interferential reflection layer alternatively lying on each other...." Indium oxide doped with Sn is used in the examples as the infrared shield layer and Ti02 was used as the interferential shield layer. In order to reduce iridescence the infrared shield layer and the interferential reflection layer thickness must have a value of one quarter lambda (lambda/4) with a permissible deviation of from 75% to 130% of lambda/4. Although other formulations are disclosed for the infrared shield layer and the interferential reflection layer such as Sn02 with or without dopants, (see column 6 lines 12 to 27), however, the specific combination of doped Sn02 layers of the present invention that accomplishes solar control, low emissivity and anti-iridescence without requiring a lambda/4 thickness limitation is neither disclosed nor exemplified to suppress iridescence or color reflection.

US Patent 4.583.815. also assigned to Kabushiki Kaisha Toyota Chou describes a heat wave shield laminate consisting of two indium tin oxide overlayers containing different amounts of tin. Antireflection layers, above or below the indium tin oxide layers are also described. Other formulations are disclosed for the infrared shield layer and the interferential reflection layer such as Sn02 with a dopant that becomes a positive ion with a valence of +5 such as Sb, P, As, Nb, Ta, W, or Mo or an element such as F which readily becomes a negative ion with a valence of -1, (see column 22 lines 17 to 23). However, the specific combination of doped Sn02 layers of the present invention that accomplishes solar shielding, low emissivity and anti-iridescence is neither disclosed nor exemplified. There is no claim to tin oxide layers nor any teaching in the specification to describe the composition of such layers, e.g. the ratio of dopant to tin oxide. It should also be noted that the teaching leads to the use of the same dopant in both layers (indium tin oxide) whereas in the instant patent application, one layer must contain a different dopant than the other layer.

US Patent 4.828,880. assigned to Pilkington PLC, describes barrier layers which act to inhibit migration of alkali metal ions from a glass surface and/or act as color suppressing underlayers for overlying infrared reflecting or electrically conducting layers. Some of these color suppressing layers are used in solar-control or low emissivity glass construction.

US Patent 5.168.003. assigned to Ford Motor Company, describes a glazing article bearing a substantially transparent coating comprising an optically functional layer (which may be low emissivity or solar control) and a thinner anti-iridescence layer which is a multiple gradient step zone layer. Antimony doped tin oxide is mentioned as a possible alternative or optional component of the exemplified low emissivity layer.

US Patent 5.780.149, assigned to Libbey-0wens-Ford describes solar control coated glass wherein at least three coating layers are present, first and second transparent coatings and an iridescence suppressing layer lying between the glass substrate and the transparent upper layers. The invention relies upon the transparent layers having a difference in refractive indices in the near infrared region greater than the difference of indices in the visible region. This difference causes solar heat to be reflected in the near IR region as opposed to being absorbed. Doped metal oxides which have low emissivity properties, such as fluorine doped tin oxide, are used as the first transparent layer. Metal oxides such as undoped tin oxide are used as the second layer. No NIR absorbing combinations are described.

EP 0-546-302-B1 issued July 16,1997 and is assigned to Asahi Glass Co. This patent describes coating systems for solar-control, heat treated (tempered or bent) glass comprising a protection layer based on a metal nitride. The protection layer or layers are used to overcoat the solar-control layer (to prevent it from oxidizing during thermal treatment). As a solar control layer, many examples are provided including tin oxide doped with antimony or fluorine. However, the specific combination of doped Sn02 layers of the present invention that accomplishes solar control, low emissivity and anti-iridescence without following Gordon's teachings is neither disclosed nor exemplified.

EP 0-735-009-A1 is a patent application that was published in February 1996 and is assigned to Central Glass Co. This patent application describes a heat-reflecting glass pane having a multilayer coating comprising a glass plate and two layers. The first layer is a high refractive index metal oxide based on Cr, Mn, Fe, Co, Ni or Cu, the second layer is a lower refractive index film based on a metal oxide such as tin oxide. Doped layers and low emissivity or NIR absorbing combinations are not disclosed.

WO 98/11031 This patent application was published in March 1998 and assigned to Pilkington PLC. It describes a high performance solar-control glass comprising a glass substrate with coatings comprising a heat-absorbing layer and a low emissivity layer of a metal oxide. The heat-absorbing layer may be a metal oxide layer. This layer may be doped tungsten, cobalt, chromium, iron molybdenum, niobium or vanadium oxide or mixtures thereof. The low emissivity layer may be doped tin oxide. In a preferred aspect of the invention, an iridescence-suppressing layer or layers is incorporated under the coating comprising a heat-absorbing layer and a low emissivity layer. This application does not disclose or suggest the specific combination of doped Sn02 layers of the present invention that accomplishes solar control, low emissivity and anti-iridescence without requiring a "Gordon" type underlayer to suppress iridescence or color reflection.

Canadian Patent 2,193.158 discloses an antimony doped tin oxide layer on glass with a tin to antimony molar ratio o 1:0.2 to 1:0.5 that reduces the light transmission of the glass.

Dopant Effects in Sprayed Tin Oxide Films, by E. Shanthi, A. Banerjee and K.L. Chopra, Thin Solid Films, Vol 88,1981 pages 93 to 100 discusses the effects of antimony, fluorine, and antimony-fluorine dopants on the electrical properties of tin oxide films. The article does not disclose any optical properties of the antimony-fluorine films nor the effect on transmitted or reflected color.

UK Patent Application GB 2.302.101 A assigned to Glaverbel describes a glass article coated with an antimony/tin oxide film of at least 400 nm containing an Sb/Sn molar ratio from 0.05 to 0.5, with a visible transmittance of less than 35%. The films are applied by aqueous spray CVD and are intended for privacy glass applications. Haze reducing undercoats are taught as well as thick layers with low Sb/Sn ratios 5 which have low emissivity properties as well as high solar absorbency. It also teaches that it is possible to provide one or more additional coating layers to achieve certain desirable optical properties. None of these properties other than haze are mentioned. The application teaches nothing about thinner layers, the use of more than one dopant, or the control of film color.

UK Patent Application GB 2.302.102 A also assigned to Glaverbel describes a glass substrate coated with a Sn/Sb oxide layer containing tin and antimony in a molar ratio of from 0.01 to 0.5, said layer having been deposited by CVD , whereby the coated substrate has a solar factor(solar heat gain coefficient) of less than 0.7. The coatings are intended for window applications and have luminous transmittances 15 between 40 and 65% and thicknesses ranging from 100 to 500 nm. Haze reducing undercoats are claimed and low emissivity can be imparted to the coatings by a judicious choice of the Sb/Sn ratio. Like the previous application, the teaching of providing one or more additional coating layers to achieve certain desirable optical properties is mentioned. Also low emissivity layers of fluorine doped tin oxide can be 2 0 _ deposited over the Sb/Sn layers or fluorine components can be addedjo the Sb/Sn reactants to give low emissivity films which contain F, Sb and Sn. The last two methods were not favored because of the added time and cost of adding a third layer and the fact that the emissivity of the Sb/F films was raised and not lowered. No mention of color control or color neutrality is found. 2 5 GB 2.200139. assigned to Glaverbel teaches a method of depositing a coating by the spray application of solutions containing tin precursors, fluorine containing compounds and at least one other dopant selected from the group antimony, arsenic, vanadium, cobalt, zinc, cadmium, tungsten, tellurium or manganese.

Previously, glass manufacturers have managed heat transport through windows by the use of absorbing and/or reflecting coatings, glass tints, and post-applied films.

Most of these coatings and films are designed to control only one portion of the solar heat spectrum, either the NIR, i.e. near infra red component of the electromagnetic spectrum having a wavelength in the range of 750 - 2500 nm or the mid IR component of the electromagnetic spectrum having a wavelength on the range of 2.5 - 25 microns.

A product has been designed to control the entire heat spectrum, however Sputtered metal/dielectric film stacks while effective, have limited durability and must be protected and sealed within the center section of a multipane insulated glass unit (IGU). What is needed is a total solar control film or combination of films that can be easily applied by pyrolytic deposition during the glass making operation which yields 10 an article which has an acceptable visible transmission, reflects or absorbs the NIR, reflects the mid-IR, and is neutral or close to neutral in color.

The above references either alone or in combination do not teach or suggest the specific combination of doped Sn02 layers of the present invention that accomplishes solar control, low emissivity and anti-iridescence without requiring a "Gordon" type 15 underlayer.

Summary of the Invention In one aspect, the present invention provides a NIR film comprising tin oxide containing a NIR dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel 2Q and containing a fluorine dopant at an atomic concentration less than the concentration of the NIR dopant.

In another aspect, the present invention provides a NIR film comprising tin oxide containing a NIR dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel and containing a color modifying dopant present in a quantity sufficient to modify 2 5 the transmitted color of light through the film and selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and fluorine, provided that the selection of color modifying dopant is different than the selection of NIR dopant and when fluorine is the selected dopant its atomic concentration is less than the concentration of the NIR dopant. -7a- The present invention as described herein and/or in NZ" patent specification 337160 provide an improved solar-control glass that has acceptable visible light transmission, absorbs near infrared wavelength light (NIR) and reflects midrange infrared light (low emissivity or Low E) along with a preselected color within the visible spectrum for reflected light that can be controlled_to a specific color or be made essentially colorless ("neutral" as defined hereinafter). Also provided is a method of producing the improved, coated, solar-control glass. The improved glass has a solar energy (NIR) absorbing layer comprising tin oxide having a dopant such as antimony and a low emissivity control layer capable of reflecting midrange infrared light and comprising tin oxide having fluorine and/or phosphorus dopant. A separate iridescence color suppressing layer as described in the prior art is generally not needed to achieve a neutral (colorless) appearance for light reflected off the coated glass, however an iridescence suppressing layer or other layers may be combined with the two layer assemblage provided by the present invention. If desired, multiple solar control and/or multiple low emissivity layers can be utilized. The NIR layer and the low emissivity layer can be separate portions of a single tin oxide film since both layers vl WGN * are composed of doped tin oxide. A method of producing the coated solar control glass is also provided. In addition, the present invention controls or changes the color of transmitted light through the addition of color additives to the NIR layer. Surprisingly the dopant fluorine that produces a noncolored tin oxide film functions as 5 a color additive when added as an additional dopant to the NIR layer and modifies the color of transmitted light through the NIR film.

Brief Description of the Drawings Figures 1 through 4 and 8 through 13 depict a cross-section of coated glass having different numbers of layers or films in different stacking sequences for the layers 10 on glass substrates. Figures 5 and 6 graphically depict the solar control achieved with antimony doped films at various concentrations of dopant and various film thicknesses on window panes, i.e. a single pane of glass, or on insulated glass units (IGU) which are a composite of at least two glass panes. Figure 7 depicts the color spectrum in terms of Commission Internationale de L'Exclairage (C.I.E.) x and y coordinates and 15 the specific color achievable with various film thickness and dopant concentrations. The English translation for C.I.E. is International Commission on Illumination Objects of The Invention An object of the invention is: (a) to prepare a transparent article with controlled reflected color (even 2 0 neutral color as defined herein,) that will absorb solar near infrared (NIR) wavelength radiation and reflect mid-range infrared heat (low emissivity) comprising two thin film layers containing doped SnC>2; and/or (b) the application of the layers by atmospheric pressure chemical vapor deposition (CVD) techniques, or by the processes such as solution spray or vaporized/sublimed liquids/solids can be utilized. The preferred method of application for this invention is atmospheric pressure CVD using vaporized liquid precursors; and/ or (c) to provide multiple solar control and/or low emissivity layers along with other layers in combination with the solar control or low emissivity layer; and/or (d) to provide a solar control film or combination of films that can be easily applied by pyrolytic deposition during the glass making operation which yields an article which has an acceptable visible trEinsmission, reflects or absorbs the NIR, reflects the mid-IR (low-E), and is neutral or close to neutral in color; and/or (e) to control the color of transmitted light independently from the color of reflected light by the addition of color additives in the NIR layer; or at least to provide the public with a useful choice.

Detailed Description of Invention and Preferred Embodiments Solar control and low emissivity coated glass is produced by depositing on a heated transparent substrate at least two layers, a low emissivity layer comprising a Sn02 film containing fluorine and/or phosphorus dopant and a NIR absorbing layer comprising a Sn02 film containing as a dopant antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel or mixtures thereof. This combination has been found to effectively control the solar and radiative heat portions of the electromagnetic spectrum such that a window coated with these films will have greatly enhanced properties.

Solar control properties are typically expressed in terms of solar heat gain coefficient (SHGC) and U-value. SHGC is a measure of the total solar heat gain through a window system relative to the incident solar radiation, while the U-value (U) is the total heat transfer coefficient for the window. The SHGC of the coated glass is primarily dependent on the thickness and the antimony content of the NIR absorbing 2 0 film (see Figures 5 and 6) while the U-value depends primarily on the film's emissivity and the window construction. SHGC measured at center of glass can range from about 0.40 to 0.80 while U values measured at center of glass can vary from about 0.7-1.2 for a single pane coated with the preferred embodiment films. In an insulated glass unit (IGU) the SHGC's decrease to -0.30 with U-values as low as ~0.28. 2 5 Both the reflected and transmitted color of the coated glass of the present invention can be controlled. In addition the amount of visible light transmitted through the coated glass can be controlled between about 25-80% by controlling the thickness of the NIR and low emmisivity films and the concentration of dopant in the NIR film. Transmitted color, i.e. the color of light transmitted through the coated glass can be 3 0 controlled separately from the reflected color by the addition of a color-effective quantity of a color additive to the NIR layer of the coating. The reflected color can vary from almost neutral to red, yellow, blue or green and can be controlled by varying the film thickness and dopant content of the layers. Surprisingly, near color neutrality as defined herein can be achieved for reflected color without the need of an anti-iridescent layer. Although the refractive indices of the NIR and low emmisivity films are different, the reflected color does not depend on classical interference phenomena originally discovered by Gordon (U.S. Patent 4,1887,336). Observed reflected color is unexpectedly controlled by the combination of absorption and reflection achieved by the NIR layer (absorption) and the reflection achieved by the low-emmisivity layer or layers. The absorption of the NIR layer can be controlled by varying the thickness of its Sn02 layer and the concentration of the dopant in the NIR layer, usually antimony. The reflectance of the low emissivity layer can be controlled by varying the thickness of its Sn02 layer and the concentration of the dopant in the low emmisivity layer, usually fluorine. The low emissivity layer composed of Sn02 containing a fluorine or phosphorous dopant is sometimes abbreviated herein as TOF or TOP while the NIR layer of Sn02 when it contains an antimony dopant is sometimes abbreviated herein as TOSb.

The preferred embodiment of this invention utilizes a combination of a fluorine doped tin oxide (TOF) film as the low emmisivity layer with an antimony doped tin oxide (TOSb) film as the NIR layer. TOF films and their deposition processes onto glass are known in the art and referred to as low emissivity films. The NIR absorbing film is also a Sn02 film but contains a different dopant than the low emissivity layer. The dopant in the NIR layer is preferably antimony although the dopant can be an element selected from the group consisting of antimony, tungsten vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel, and mixtures thereof. A mixture of one or more dopants can be used in the NIR layer, however the low emissivity layer must contain a low emissivity dopant that imparts significant conductivity to the layer such as fluorine or phosphorous, although other dopants may be used in combination with the low emissivity dopant. Since the low emissivity and the NIR layers of the present invention both utilize Sn02 as the metal oxide matrix containing a dopant, the NIR and the low emissivity layers can be part of a single film having a dopant gradient.

A single film utilizing a dopant gradient is depicted in Figure 3 as film 16. In film 16 there is a dopant gradient with the NIR dopant having a higher concentration than the other dopant(s) at one surface of the film, either surface 18 or 22, and the low emissivity dopant having a higher concentration than the other dopants at the other 5 surface of the film. This results in a change or gradient in the concentrations of the NIR and low emissivity dopants between surface 18 and surface 22. At some intermediate point 20 between surface 18 and surface 22 the concentration of the NIR dopant changes from being the highest concentration dopant on one side of point 22 to no longer being the highest concentration dopant on the other side of point 22.

Figure 8 shows the low e film, 10, above the NIR film 12, The NIR film 12 in Figure 8 has a concentration gradient for the NIR dopant in the tin oxide film with a lower concentration of the dopant closer to the low e film 10. The coated glass of Figure 9 is similar to the structure shown in figure 8 with the exception that the concentration gradient of the NIR dopant, usually antimony, is higher near the low e film 10 and lower nearer the substrate. Film 12 is different then film 16 shown in Figure 3 in that film 12 is a NIR film while film 16 has both NIR and low e properties and contains both a low e dopant and a NIR dopant with a concentration gradient for the low e dopant and a concentration gradient for the NIR dopant. Figures 10,11,12 and 13 show the NIR layer as two distinct films,28 and 30,. Film 28 is shown as being thicker than film 2 0 _ 30 and the total thickness of the NIR layer is the sum of the thicknesses of films 28 and 30 and should be within the range of thicknesses stated above for the NIR layer and preferably from 80 to 300nm. In Figures 10 and 11, films 28 and 30 are adjacent each other, while in Figures 12 and 13, films 28and 30 are on opposite sides of low e film 10. The concentration of dopant in film 28 is preferably different than the 2 5 concentration of dopant in film 30.

The preferred embodiment of this invention uses an antimony doped film as the NIR film. Such a film can be deposited by a number of techniques including spray pyrolysis, PVD and CVD methods. Spray pyrolysis is known and disclosed in patents such as Canadian patent 2,193,158. CVD methods for depositing Sn02 films with or 3 0 without dopants and the chemical precursors for forming Sn02 films containing dopants are well known and disclosed in U.S. Patents 4,601,917, and 4,285,974. Preferred is CVD deposition of the Sn02 layers containing dopants according to known methods directly on a float glass manufacturing line outside of or within the float glass chamber utilizing conventional on-line deposition techniques and chemical precursors as taught by U.S. Patent 4,853,257 (Henery). However the Sn02 films containing dopants can be applied as layers on glass utilizing other processes such as solution spray or vaporized/sublimed liquids/solids at atmospheric pressure. The preferred method of application for this invention is atmospheric pressure CVD using vaporized liquid precursors. The process is very amenable to existing commercial on-line deposition systems. The precursors of the preferred embodiments are economical to apply, will enable long coating times, will reduce the frequency of system clean-out, and should be able to be used with little or no modification to existing glass float line coating equipment, The coatings function by a combination of reflection and absorption. The low emissivity film reflects mid-IR heat in the 2.5-25 micron region of the spectrum while the NIR absorbing film absorbs heat primarily in the 750- 2500 nm region. While not to be bound thereby, the theory upon which we account for this effect is that in the NIR region, the plasma wavelength (PL - the wavelength where the low emissivity film changes from a transmitter to a reflector of light energy) for the low emissivity film falls in the NIR region. In the area around the PL, the NIR absorption is the highest for the low emissivity film and when combined with a NIR absorbing film, increased absorbency takes place. The NIR absorbing films of our preferred embodiments are also doped semi-conductors and hence have reflective properties in the mid IR. This reflection coupled with the low emissivity film reflection gives an overall higher heat reflectance in the mid IR.

Preferably the Sn02 is pyrolyticly deposited on the glass using a tin precursor, especially an organotin precursor compound such as monobutyltin trichloride (MBTC), dimethyltin dichloride, dibutyltin diacetate, methyl tin trichloride or any of the known precursors for CVD deposition of Sn02 such as those disclosed in US 4,601,917 incorporated herein by reference. Often such organotin compounds used as precursors for pyrolytic deposition of Sn02 contain stabilizers such as ethanol. Preferably the concentration of stabilizers is less than 1 % in order to reduce fire risks when contacting hot glass with such chemicals in the presence of oxygen. Precursors for the dopant in the NIR layer (antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt and nickel) are preferably halides such as antimony trichloride, however alkoxides, esters, acetylacetonates and carbonyls can be used as well. Other suitable precursors for the dopant and Sn02 are well known to those skilled in the art. Suitable precursors and quantities for the fluorine dopant in the low emissivity Sn02 layer are disclosed in U.S. Patent 4,601,917 and include trifluoroacetic acid, ethyltrifluoroacetate, ammonium fluoride, and hydrofluoric acid. Concentration of low emissivity dopant is usually less then 30% with preferred concentrations of low emissivity dopant from 1% to 15% by weight of dopant precursor based upon the combined weight of dopant precursor and tin precursor. This generally correlates to a dopant concentration in the low e film of from 1% to 5% percent based upon the weight of tin oxide in the low e film.

In our preferred embodiments, the properties depend on the thickness of the low emissivity and absorbing layers as well as the antimony content of the absorbing (NIR) film. The low emissivity film thickness can range from 200-450 nm with 280 to 320nm being most preferred. The preferred NIR absorbing films can be deposited in a similar fashion as the low emissivity films using such methods as disclosed in U.S. Patent 4,601,917. The organotin precursors for the Sn02 can be vaporized in air or other suitable carrier gases containing a source of 02 and in precursor concentrations from 0.25 - 4.0 mol% (0.5 - 3.0 mol% more preferred). Sn02 precursor concentrations are expressed herein as a percentage based upon the moles of precursor and the moles of carrier gas. Preferred concentrations of NIR dopant precursor are from about 1% to about 20% (2.5% to 7.5% more preferred and 3.0% to 6.0% most preferred) and are calculated using the weight of dopant precursor and the weight of Sn02 precursor. Particularly preferred is an antimony dopant using antimony trichloride as the precursor at about 2% to about 8% by weight with about 4.0% by weight particularly preferred. This correlates to a similar antimony mass percent in the tin oxide NIR film.

The coated glass of the present invention is depicted in the figures. Figure 1 shows the films in cross section. The film thicknesses can range from 200 to 450 nm for the low emissivity film (item 10) and for the NIR film (item 12) from 80 to 300 nm.

The preferred thickness is 250 to 350 nm for the low emmisivity film and 200 to 280 nm for the NIR film. Most preferred is 280 to 320nm for the low e film and 220-260 nm for NIR film. Using films of the preferred embodiments, solar control coated glass can be produced with a Neutral-blue Color which is defined herein as coated glass having reflected light predominately within C.I.E. chromaticity coordinates values of x between 0.285 and 0.310 and y between 0.295 and 0.325. The definition of Neutral-blue is shown in Figure 7 by the area within the box labeled Neutral-blue Color. As shown in Figure 7 the data for examples 15, 20 and 22, controlled or preselected reflected color close to neutral color but slightly to the red shade from neutral can be produced (x values of up to 0.325 and y values of up to 0.33), but such essentially neutral to slightly red shades of reflected color are not appealing to consumers. Figure 2 shows the two films or layers in the opposite sequence than that shown in Figure 1. In Figure 2, the low emissivity film is closer to the glass 14 than the NIR film 12. Figure 3 shows the NIR and the low emissivity layers integrated into a single Sn02 film 16 having a dopant gradient within filml6.Filml6 has a preponderance of one dopant (e.g. the low emissivity dopant, fluorine) at the upper surface, 18, away from the glass 14 and a preponderance of the other dopant (e.g. the NIR dopant such as antimony) at the film surface 22 nearer the glass. The concentration of dopant changes from surface 18 to surface 22, so that one dopant changes from greater than 50% of the dopants at surface 18 to approximately 0% at surface 22. At an intermediate point 20, below upper surface 18, the predominant dopant at that point in the film changes from the predominant dopant at surface 18 to the predominant dopant at surface 22. Either the NIR dopant or the low emissivity dopant (fluorine) can be the predominant dopant at surface 18 with the other dopant the predominant dopant at surface 22. Figure 4 depicts a coated glass having additional layers 24 and 26 in addition to a low emissivity layer 10 and NIR layer 12. The additional layers 24 and 26 can be additional low emissivity and/or NIR layers or other conventional layers used to coat glass such as a tinting layer. For example 12 can be a NIR layer (e.g .antimony doped tin), 10 a low emissivity layer (fluorine doped tin) and 24 another NIR layer. 26 can be another low emissivity layer or some other conventional layer. The concentration of dopant when more than one low emissivity layer is utilized may be the same or different and the thickness of each low emmisivity layers may also be the same or different. Likewise, when more than one NIR layer is utilized, the concentration of dopant and the selection of dopant (antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt and nickel) can be the same or different and the thickness of each NIR layer can be the same or different. Generally the dopant for the NIR layer has been discussed herein mostly in terms of antimony, it must be understood that the dopant in the NIR layer can be selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof. Likewise, in the gradient layer embodiment of the invention as depicted in Figure 3, the predominant dopant at the NIR surface either surface 18 or 22 can be selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof, it only being essential that the low e dopant, e.g. fluorine, be the predominant dopant at the opposite surface. Combined with a gradient layer can be one or more NIR or low emissivity layers such as layers 10 and 12 in figures 1 to 3 and/or other conventional layers.

Water is preferably used to accelerate the deposition of Sn02 film onto glass as taught by U.S. Patent 4,590,096 (Lindner) and used in concentrations from -0.75 to 12.0 mol% H20 based upon the gas composition. The preferred embodiments of our invention will be exemplified by the following examples. One skilled in the art will realize that minor variations outside the embodiments stated herein do not depart from the spirit and scope of this invention.

The most preferred embodiment at this time to obtain a coated glass with low e and NIR properties with neutral reflected color with only two films on glass is about a 3 000A thick TO:F film (fluorine doped tin oxide) in combination with about a 2400A TO:Sb (antimony doped tin oxide) film on glass. The film thickness for the TO:F layer can range from -2800-3200A and still achieve the surprising result of a neutral reflected color. The fluorine concentration can range from ~ 1-5 atomic%. TheTO:Sb film thickness can range from -2200-2600A with an antimony concentration from ~3-8% and still achieve the surprising result of a neutral reflected color for the coated glass. Within the preferred thickness and dopant concentration ranges of the present invention, a solar control coated glass can be produced having a NIR layer and a low e layer and having a Neutral-blue Color for reflected light, i.e. coated glass having reflected light predominately within C.I.E. chromaticity coordinates values of x between 0.285 and 0.310 and y between 0.295 and 0.325 as shown in Figure 7 by a box labeled Neutral-blue Color or close to the Neutral-blue Color with x values as high as about 0.32 as shown by Examples 15,20 and 22.

Examples 1 to 30 A 2.2 mm thick glass substrate (soda lime silica), two inches square, was heated on a hot block to 605 to 625°C. The substrate was positioned 25 mm under the center section of a vertical concentric tube coating nozzle. A carrier gas of dry air flowing at a rate of 15 liters per minute (1 /min) was heated to 160°C and passed through a hot wall vertical vaporizer. A liquid coating solution containing ~95 wt% monobutyltin trichloride and -5 wt% antimony trichloride was fed to the vaporizer via a syringe pump at a volume flow designed to give a 0.5 mol% organotin concentration in the gas composition. A quantity of water was also fed into the vaporizer at a flow designed to give a 1.5 mol% water vapor in the gas mixture. The gas mixture was allowed to impinge on the glass substrate at a face velocity of 0.9 m/sec for -6.1 seconds resulting in the deposition of a film of antimony doped tin oxide ~240 nm thick. Immediately following, a second gas mixture was used consisting of a precursor composition of 95 wt% monobutyltin trichloride and 5 wt% trifluoroacetic acid, along with water in the same concentrations and carrier gas as used before to deposit the antimony doped SnO, layer. This second gas mixture was allowed to impinge on the coated substrate for -6.7 seconds. A film of ~280nm of fluorine doped tin oxide was deposited. The bilayer film was very light blue in transmission and reflection. The optical properties were measured on a UV/VIS/NIR spectrophotometer and the sheet resistance was measured on a standard four point probe. The solar heat gain coefficient, U value and visible transmission for the center of the glass were calculated using the Window 4.1 program developed by Lawrence Berkeley National Laboratory, Windows and Daylight Group, Building Technologies Program, Energy and Environmental Division. The C.I.E. chromaticity x and y color coordinates were calculated using ASTM E308-96 from the visible reflectance data between 380-770 nm and the tristimulus values for Illuminant C. The analysis results for this film appears in Table 1, number 19. The procedure of this example was repeated 29 additional times with concentrations of chemical precursors and deposition times varied in order to produce coated glass samples having different thicknesses for the NIR and low emissivity layers and 5 different dopant concentrations. The results are presented in Table 1.

Example 31 to 38 The procedure of Example 1 was repeated, except that the vapor feed order was reversed. The fluorine doped tin oxide film was deposited first for ~8 seconds followed by the antimony doped tin oxide film for -6 seconds. The resulting film was -540 nm 10 thick and composed of a low emissivity layer (TOF) of about 300 nm and a NIR layer (TOSb) of about 240 nm and had a similar appearance and reflected light color (Neutral-blue Color) as the film in example 19. The analysis results appear in Table 2, number 31. The procedure of this example was repeated 7 additional times with concentrations of chemical precursors and deposition times varied in order to produce 15 coated glass samples having different thicknesses for the NIR and low emissivity layers and different dopant concentrations. The results are presented in Table 2 Example 39 The procedure of Example 1 was repeated but utilizing three precursor feed mixtures. The composition of the third mixture was 90 wt% monobutyltin trichloride, 5 wt% 2 0 trifluoroacetic acid, and 5 wt% antimony trichloride. A gradient film was deposited by first depositing only the antimony doped tin oxide precursor of Example 1 for 70% of the time needed to deposit 240 nm. Then the mixed antimony/fluorine doped precursor was started. Both precursor mixtures would continue for 20 % of the total deposition time at which point the antimony precursor mixture was turned off. The 2 5 antimony/fluorine mixed precursor was continued for the remaining 10% of the total deposition time for the 240 nm antimony film. At this point, the fluorine doped tin oxide film precursor feed was turned on. Both feeds were continued for 20% of the total time needed to deposit 300 nm of fluorine doped tin oxide. The mixed antimony/fluorine precursor feed was turned off and the fluorine doped tin precursor was continued for the remaining deposition time for the fluorine doped film. - The resultant gradient coating layer is light blue in transmitted and reflected color (x-0.292, y=0.316) a SHGC = 0.50, a U value = 0.6, and a visible transmission about 45%. As shown in Figure 3, surface 22 of gradient film 16 would have essentially 100% antimony dopant while surface 18 would have essentially 100% fluorine dopant with a gradient in dopant concentration between surfaces 18 and 22 and all within a film matrix of Sn02.

Examples 40 to 43 The procedure of Example 1 was used in Examples 40 to 43. The coating composition for the NIR layer in Examples 41 and 43 was composed of a fluorine, antimony, and tin precursor made by adding SbC13 and TFA to MBTC. This precursor contained 0-5% by weight TFA, 5.2-5.5% by weight SbC13, and the remainder MBTC, and was co-fed with water into the second vaporizer. The carrier gas used for the second vaporizer was dry air at a rate of 15 1/min. The fluorine/antimony/tin precursor was added at a rate of 0.5 mole percent of total carrier gas flow, the water was added at a rate of 1.5 mole percent total carrier gas flow, and the vaporizer temperature was maintained at 160C. A soda-lime-silica glass substrate two inches square and 2.2 mm thick was preheated on a heater block to 605 to 625C. The heater block and substrate were then moved to a position directly beneath the vertical coater nozzle, with the substrate being 25mm beneath the coater nozzle. F/Sb/Sn/H20 vapors from the second vaporizer were then directed onto the glass substrate, depositing an antimony and fluorine doped tin oxide undercoat layer in examples 41 and 43. The velocity of the carrier gas was 0.9 m/s and the thickness of the fluorine and antimony doped tin oxide film was ~240 nm. Reaction byproducts and unreacted precursor vapors were exhausted from the substrate at a rate of 18 1/min. After the antimony and fluorine doped tin oxide undercoat was deposited, the coater nozzle valve was switched from the second vaporizer feed to the first vaporizer feed. MBTC/TFA/H20 vapors from the first vaporizer feed were then directed onto the substrate, depositing a layer of fluorine doped tin oxide directly on top of the antimony/fluorine doped tin oxide undercoat. The velocity of the carrier gas was 0.9 m/s and the thickness of the fluorine doped tin oxide film was-300 nm. The bilayer films in examples 41 and 43 (containing both F and Sb in the NIR undercoat) were light grey in transmitted color and neutral in reflected color. Examples 40 and 42 essentially reproduce examples 40 and 43 respectively but without fluorine dopant in the NIR undercoat layer. The properties were measured and the results appear in Table 3. The results show how fluorine, as an additional dopant in the NIR layer, acts as a color modifier for both reflected and transmitted color. The transmitted colors, Tvis, x and y, of the films made with the TFA and Sb dopants in the NIR layer, Examples 41 and 43, are more neutral in reflected color and greyer in transmitted color then those which only contained Sb as a dopant in the antimony doped tin oxide NIR layer in examples 40 and 42. Furthermore, the antimony doped NIR layer with a color effecting quantity of fluorine dopant has greater transmission of visible light (increase in Tvis from 54.5 to 58.5 in example 41 versus example 42 with the some level of antimony dopant).

Examples 44 through 47 demonstrate the deposition of films with the following composition: TOF/TOSb (low Sb conc.)/TOSb (high Sb conc.)/Glass, TOF/TOSb (high Sb conc.)/TOSb (low Sb conc.)/Glass, TOSb (low Sb)/TOF/TOSb (high Sb conc.)/Glass, and TOSb (high Sb)/TOF/TOSb (low Sb conc.)/Glass Examples 44 The procedure of Example 1 was repeated except that the glass temperature was about 610°C and the concentration of reagents was about 0.63 mol% in air flowing at a rate of 20 liters per minute. About 400A of antimony doped tin oxide was deposited first from a liquid coating solution composed of about 10 wt% antimony trichloride and -90% monobutyltin trichloride. Immediately following, a second layer of about 2000 A of antimony doped tin oxide from a liquid coating solution composed of 3.25% antimony trichloride and 96.75% monobutlytin trichloride was deposited. A third layer composed of about 3000 A of fluorine doped tin oxide was deposited from a solution containing 5 wt% trifluoroacetic acid and 95 wt% monobutyltin trichloride. The resulting film appeared to have a light green-blue color for reflected light and light blue color for transmitted light. The film properties were measured as described in Example 1. The visible light transmission was 64% and the SHGC was calculated to be 0.5,6. The x and y coordinates for the color of reflected light were 0.304 and 0.299, respectively, putting the film in the neutral-blue color quadrant of C.I.E. color space as defined earlier.

Example 45 The procedure of Example 44 was repeated, but this time the TOSb layers were deposited in reverse order. The resulting film was blue-red in reflected color with color coordinates of (x) 0.330 and (y) 0.293, respectively. A visible transmission of 59% and a SHGC of 0.54 were obtained. One skilled in the art will realize that the TOSb 10 layers can be of different thicknesses and concentrations than described herein and still be within the scope of this invention.

Example 46 The procedure of Example 44 was repeated, but in this example the deposition sequence of the fluorine doped tin oxide layer and the 3.25% antimony trichloride 15 solution layer were reversed. The resulting film had a visible transmission of about 62%, a SHGC of 0.55, and a neutral blue-red reflected color characterized by color coordinates (x) 0.311 and (y) 0.311.

Example 47 The procedure of Example 45 was repeated, but in this example the deposition 2 0 sequence of the fluorine doped tin oxide layer and the 10.0% antimony trichloride solution layer were reversed. The resulting film had a visible transmission of about 57%, a SHGC of 0.53, and a light green reflected color characterized by color coordinates (x) 0.308 and (y) 0.341. One skilled in the art will realize that the TOSb layers can be of different thicknesses and concentrations than described herein and still 25 be within the scope of this invention.

All SHGC and U values in the tables have been determined using the single band approach of the NFRC Window 4.1 program. Use of the more accurate multiband approach (spectral data file required) will improve the SHGC's by approximately 14%. The C.I.E. tristimulus values for the reflected and transmitted colors of the coated articles can be calculated according to ASTM Standard E 308, with Illuminant C used as the standard illuminant. From this ASTM Standard E 308, the color of an object can be specified with one of several different scales. The scale used for the coated articles in this invention is the C.I.E. 1931 chromaticity coordinates x and y. One can easily translate to the C.I.E. 1976 L*, a*, b* opponent-color scale by using the following equations: x = X/(X+Y+Z) y = Y/(X+Y+Z) L* = 116(Y/Yn)l/3-16 a* = 500[(X/Xn),/3- (Y/Yn),/3] b* = 200[(Y/Yn)l/3- (Z/Zn),/3] where X, Y, and Z are the C.I.E. tristimulus values of the coated article, and Xn, Yn, and Zn, are 98.074, 100.000, and 118.232, respectively, for Standard Illuminant C. from the L*, a*, b* values, the color saturation index, c*, can be calculated by the equation c*=[(a*)2 + (b*)2 ]1/2. A color saturation index of 12 or less is considered neutral.

The definition of Neutral-blue Color for reflected light, i.e. coated glass having reflected light predominately within C.I.E. chromaticity coordinates^values of x between 0.285 and 0.310 and y between 0.295 and 0.325 as shown in Figure 7 by a box labeled Neutral-blue Color correlates with C.I.E. 1976 L*, a*, b* of 37.85, -1.25, -5.9 and 39.62, -2.25, 1.5.

A sample conversion follows: Example 40 (Table 3) .5 % SbCl3 300/240 (F/Sb/Glass) X = 9.797 Y = 9.404 Z= 12.438 x = 0.310 -22- y = 0.297 L* = 36.751 a* = 4.624 b* = -3.466 c* = 5.778 Solar control properties of glass windows has been evaluated and rated by the United States of America, Environmental Protection Agency using an Energy Star rating system. An Energy Star rating for the Central Region of the United States requires a U-factor rating of 0.40 or lower and a SHGC rating of 0.55 or below. An Energy Star rating for the Southern Region of the United States requires a U-factor rating of 0.75 or lower and a SHGC rating of 0.40 or below. Coated glass having the NIR and Low e coatings of the present invention and when incorporated into windows of conventional design achieve the Energy Star ratings for the Central and/or Southern Region. For example a Vertical slider design window 3 feet wide by 4 feet high and having a frame absorption value of 0.5 as rated by the National Fenestration Rating Council (NFRC) and assembled with coated solar control glass of the present invention having a NIR film and a low e film within the preferred ranges for aNeutral-Blue Color achieves a SHGC of less than 0.40 and a U value of less than 0.64 for a monolith glass construction with a frame U-value of 0.7 or less and achieves a SHGC of less than 0.38 and a U value of less than 0.48 for an Insulated Glass Unit (IGU) construction made up with 2.5 mm clear lite, 0.5 inch air gap and NIR and Low e coatings on the #2 surface of the outer lite and a frame U-value of 1.0 or less.

The examples substantiate that with a minimum of two doped Sn02 layers, an excellent solar control coated glass can be produced having a preselected reflected color. Tables 1,2 and 3 present the data while Figures 5 and 6 show graphically how the solar properties of the coated glass vary with dopant concentrations and film thickness primarily of the NIR film. Figure 7 plots the x and y C.I.E. chromaticity coordinates of a representative selection of coated glass of examples 1 to 39. As seen in Figure 7, specific combinations of film thicknesses for both the NIR and low emissivity films and specific dopant(s) concentrations can be utilized to produce a coated, solar control glass with any desired color for light reflected off the coated surface of the glass, such as red, green, yellow, blue and shades thereof or Neutral-blue Color. It is particularly surprising that a Neutral-blue Color can be achieved with a NIR and a low emissivity layers but without an anti-iridescence layer such as taught by Gordon.

While the inventive features of the present invention can be achieved with only two layers, a NIR layer and a low emissivity layer, multilayer embodiments are within the scope and content of the invention. The multilayers can be additional NIR and/or low emissivity layers or other functional or decorative layers. Multilayer embodiments include TOSb/TOF/TOSb/Glass, or TO/TOF/TOSb/Glass, or TO/TOSb/TOF/Glass with TO being just a tin oxide film. When multiple NIR or low emissivity layers are used, the dopant concentrations or dopant selection in each NIR or low emissivity film need not be the same. For example when two NIR layers are used in combination with at least one low emissivity layer, one NIR layer can have a low level of antimony dopant (e.g. 2.5%) to give some reflectance in the mid IR range and one layer can have a higher level (> 5%) to give NIR absorbency. The terms layer and film are generally used herein interchangeably except in the discussion of gradient film depicted in Figure 3 in which a portion of the film is referred to as a layer having a dopant concentration different than the dopant concentration in another layer of the film. In the method of making the coated glass of the present invention as demonstrated in the examples, the glass is contacted sequentially with carrier gas containing precursors. Accordingly, the glass may have a coating on it when it is contacted a second time with a carrier gas containing precursors. Therefore, the term "contacting glass" refers to either direct contact or contact with one or more coatings previously deposited on the glass.

Another embodiment of the invention provides the ability to change the transmitted color of the coated glass. Transmitted color refers to the color perceived by a viewer on the opposite side of the coated glass then the source of light being viewed while reflected color is the color perceived by a viewer on the same side as the source of light being viewed. Transmitted light can be effected by adding additional dopants to the NIR film. As previously explained, the NIR layer contains a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt and nickel. The color of transmitted light through the NIR layer can be changed by adding an additional dopant different then the first dopant in the NIR layer and selected from the group consisting of tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel, and fluorine or a combination of more then one additional dopant to the NIR layer. As shown in examples 40-43, the 5 addition of a fluorine precursor, such as trifluoroacetic acid (TFA) to a NIR precursor solution such as SbCl3/MBTC, produces a film containing fluorine as an additional dopant in the NIR layer of antimony doped tin oxide. When fluorine is present as an additional dopant in an antimony doped tin oxide layer, the transmitted color is gray versus a blue transmitted color for an antimony doped tin oxide layer without fluorine 10 dopant. The additional dopant has little or no effect on reflected light and accordingly, a coated glass can be produced having a reflected light that is different then its transmitted light.

Dopants in the NIR layer such as vanadium , nickel, chromium and non-traditional color additives such as trifluoroacetic acid (TFA) and HCl can be added to 15 the TO: Sb precursors in 1-5 wt% (based on the total wt of precursor and additive) to effect transmitted color changes in the final film construction while not significantly affecting overall reflected color neutrality.

# I # 1 2 3 4 Composit.

F/Sb/G F/Sb/G F/Sb/G F/Sb/G F/Sb/G %Sb 2.5 2.5 2.5 2.5 2.5 Thick, nm 300/240 300/160 300/80 400/240 400/80 %Asol 16.1 12.7 9.7 17.0 11.0 %Tsol 72.0 74.6 76.4 72.0 76.9 %Rsol,1 11.8 12.7 13.9 11.0 12.1 %Rsol,2 .9 11.7 12.8 .3 11.5 %Tvis 78.0 80.5 80.0 77.7 82.0 %Rvis,1 12.0 12.1 14.6 11.2 11.9 %Rvis,2 .9 11.3 13.4 .5 11.6 %Tuv 52.3 52.9 55.2 51.1 53.6 S. R, 12.4 13.2 16.0 .4 13.3 Emis-cal 0.12 0.13 0.15 0.10 0.13 SHGCc " IG 0.74 0.67 0.77 0.70 0.78 0.71 0.75 0.67 0.79 0.71 Uc " IG 0.72 0.27 0.72 0.28 0.74 0.28 0.71 0.27 0.73 0.28 Tvis-c " IG 0.78 0.71 0.81 0.73 0.80 0.73 0.78 0.71 I 0.82 0.74 X y %Rvis 0.291 0.336 . 12.0 0.329 0.289 12.1 0.295 0.377 14.7 0.326 0.317 11.2 0.323 0.282 11.9 R Colors Blue-Gr Neutral Green Green-BI Neutral Table 1 Summary of Properties of Bilayer Films TOF/TOSb 6 7 8 9 10 11 12 13 14 15 F/Sb/G F/Sb/G F/Sb/G F/Sb/G F/Sb/G F/Sb/G F/Sb/G F/Sb/G F/Sb/G F/Sb/G .6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 300/240 300/240 300/160 300/80 300/240 300/252 300/232 300/225 300/240 400/240 40.8 39.2 31.1 20.7 39.2 41.5 39.0 37.1 40.1 40.3 50.0 51.1 58.2 67.5 51.6 49.2 52.2 53.9 51.0 50.6 9.2 9.6 10.7 11.8 9.2 9.3 8.9 9.1 8.9 9.1 8.2 9.2 9.4 10.8 " 8.5 8.5 8.4 8.6 8.4 8.2 57.4 58.5 65.5 72.7 57.6 54.8 58.0 59.8 56.8 56.5 9.2 9.8 10.1 14.0 8.9 9.0 8.4 8.4 8.6 8.6 8.3 9.3 8.6 11.3 8.6 8.5 8.3 8.2 8.2 8.3 41.2 41.5 45.3 50.6 43.1 42.6 44.3 44.9 42.4 42.1 11.2 11.8 13.3 15.6 12.2 12.5 13.4 13.8 13.1 9.7 0.11 0.11 0.13 0.15 0.12 0.12 0.13 0.13 0.13 0.10 0.57 0.58 0.63 0.71 0.58 0.56 0.59 0.6 0.58 0.57 0.49 0.5 0.56 0.63 0.51 0.48 0.51 0.52 0.5 0.49 0.71 0.72 0.72 0.74 0.72 0.72 0.73 0.73 0.73 0.71 0.27 0.27 0.28 0.28 0.27 0.27 0.28 0.28 0.28 0.27 0.57 0.58 0.66 0.73 0.58 0.55 0.58 0.6 0.57 0.56 0.52 0.53 0.59 0.66 0.52 0.5 0.53 0.54 0.52 0.51 0.293 0.292 0.331 0.318 0.288 0.291 0.294 0.302 0.294 ' 0.322 0.303 0.309 0.280 0.364 0.300 0.300 0.309 0.315 0.306 0.318 9.2 9.8 10.1 13.9 9.0 9.0 8.4 8.4 8.6 8.6 Blue Blue Neutral Green-YI Blue Blue Blue Blue Blue Red Table Summary of Properties of Bilayer Films TOF/TOSb i # Composit.

%Sb Thick, nm %Asol %Tsol %Rsol,1 %Rsol,2 %Tvis %Rvis,1 %Rvis,2 %Tuv S. R, Emis-cal SHGCc " IG Uc " IG Tvis-c "IG x y %Rvis 16 F/Sb/G .6 370/240 45.0 45.4 9.6 8.0 51.0 8.8 8.3 39.8 11.5 0.11 0.53 0.45 0.72 0.27 0.51 0.46 0.306 0.320 9.0 17 F/Sb/G .6 338/240 40.2 50.7 9.1 8.4 56.5 8.8 8.7 43.0 11.3 0.11 0.57 0.49 0.71 0.27 0.56 0.51 0.296 0.308 8.8 18 F/Sb/G 5.6 300/240 40.3 50.6 9.1 8.5 56.5 8.9 8.3 42.8 13.6 0.13 0.57 0.49 0.73 0.28 0.56 0.51 0.298 0.312 8.9 19 21 22 23 24 F/Sb/G F/Sb/G F/Sb/G F/Sb/G F/Sb/G F/Sb/G .6 .6 6.5 .0 .0 43.2 46.6 .2 8.4 51.6 .0 7.9 41.6 13.7 0.13 0.54 0.46 0.73 0.28 0.52 0.47 0.303 0.321 10.0 39.4 51.2 9.4 8.5 57.0 9.0 8.0 44.8 0.14 0.58 0.5 0.73 0.28 I 0.57 0.52 0.318 0.324 9.0 29.6 46.4 9.9 8.4 51.2 9.9 8.5 40.7 12.9 0.12 0.54 0.46 0.72 0.28 0.51 0.46 0.297 0.305 9.9 54.5 37.0 8.5 7.8 36.4 8.5 7.2 .1 .4 0.15 0.47 0.38 0.74 0.29 0.36 0.33 0.320 0.327 8.5 41.8 47.8 10.4 9.1 48.6 10.0 7.8 41.0 17.7 0.16 0.55 0.47 0.74 0.29 0.49 0.44 0.353 0.294 9.9 .0 280/240 262/240 300/24 300/240 300/160 300/80 .9 62.4 11.7 11.2 64.0 13.3 9.6 48.8 18.8 0.17 0.67 0.59 0.75 0.29 0.64 0.58 0.324 0.378 13.2 » F/Sb/G 10.0 300/300 62.5 29.7 7.8 7.5 28.5 7.7 6.9 30.4 0.14 0.41 0.32 0.73 0.28 0.28 0.26 0.343 0.306 7.7 26 F/Sb/G 10.0 400/240 55.4 35.9 8.7 7.5 34.8 7.6 7.6 33.2 12.8 0.12 0.45 0.39 0.72 0.27 0.35 0.32 0.299 0.322 7.6 27 F/Sb/G .0 400/80 24.8 63.6 11.6 .7 68.3 .1 .0 48.9 .4 0.14 0.68 0.60 0.73 0.28 0.68 0.62 0.299 0.312 .1 28 F/Sb/G 14.6 300/240 59.9 31.9 8.2 7.7 28.3 8.9 7.1 27.5 .1 0.14 0.42 0.34 0.73 0.28 0.28 0.26 0.331 0.329 8.8 29 F/Sb/G 14.6 300/160 47.8 42.9 9.3 8.6 41.3 7.8 7.2 34.9 .7 0.15 0.51 0.43 0.74 0.28 0.41 0.37 0.344 0.305 ' 7.8 F/Sb/G 14.6 300/80 29.9 57.5 12.6 11.2 58.1 14.7 9.9 44.4 18.6 0.17 0.63 0.55 0.75 0.29 0.58 0.53 ' 0.335 0.393 14.6 R Colors Blue-Gr Blue Blue Blue-Gr Yl-Green Blue Yl-Neu Red Yl-Green Neutral Blue-Gr Blue Yl-Green Neutral Yl-Green Table 2 Summary of Properties of Bilayer Films TOSb/TOF # 31 Composit. Sb/F/G %Sb 5.6 Thick, nm 240/300 %Asol %Tsol %Rsol,1 %Rsol,2 %Tvis %Rvis,1 %Rvis,2 %Tuv S. R, Emis-cal SHGCc " IG Uc ~ IG Tvis-c " IG x y %Rvis 47.9 45.9 6.1 8.2 53.2 6.1 7.6 38.5 14.7 0.14 0.54 0.45 0.73 0.28 0.53 0.48 0.289 0.300 6.2 32 Sb/F/G .6 160/300 36.1 55.5 8.3 9.3 63.2 7.6 8.9 43.4 .9 0.15 0.61 0.53 0.74 0.28 0.63 0.57 0.309 0.283 7.7 33 Sb/F/G .6 138/300 29.2 61.1 9.7 .1 67.2 9.3 .7 47.0 16.5 0.15 0.66 0.58 0.74 0.29 0.67 0.61 0.310 0.274 9.3 34 Sb/F/G 5.6 120/300 27.2 63.3 9.6 9.5 69.0 9.1 .4 48.7 17.4 0.16 0.68 0.6 0.74 0.29 0.69 0.63 0.311 0.275 9.1 Sb/F/G 5.6 110/300 25.6 64.3 10.2 9.2 69.5 .1 10.5 49.2 18.8 0.17 0.69 0.61 0.75 0.29 0.69 0.63 0.313 0.306 10.1 36 Sb/F/G .6 80/300 23.5 65.8 .7 9.2 71.8 .9 .9 49.1 17.3 0.16 0.7 0.62 0.74 0.29 0.72 0.65 0.302 0.364 10.9 37 Sb/F/G 5.6 120/332 28.5 62.5 9.0 9.2 69.0 7.8 8.9 47.7 0.14 0.67 0.59 0.73 0.28 — 0.69 0.63 0.306 0.281 7.8 38 Sb/F/G 5.6 120/262 26.8 63.4 9.8 9.6 68.1 9.9 11.6 49.6 21.1 0.19 0.68 0.6 0.76 0.3 0.68 0.62 0.292 0.349 9.9 R Colors Blue Blue-Neu Blue-Gr Blue-Gr Neutral Greeen Blue-Neu Green Explanation key for Tables I and 2: # « Composit. %Sb Thick, nm %Asol %Tsol %Rsol,l %Rsol, 2 %Tvis S.R.

Emis. Cal SHGCc "IG Uc "IG Tvis-c "IG y %Rvis F/Sb/G=Fluorine doped tin oxide/Antimony doped tin oxide/Glass Sb/F/G=An(imony doped (in oxide/Fluorine doped tin oxide/Glass % SbClj (antimony trichloride) by weight in MBTC (monobutyltin trichloride) Profilometer measurement of individual TO:F (fluorine doped tin oxide) and TO:Sb (antimony doped tin oxide) films % solar absorbance1 from film side of glass (= 100-(%Tsol+%RsoI, 1)) - 300-2500 nm % solar transmission1 from the film side of glass - 300-2500 nm % solar reflection1 from Film side of glass - 300-2500 nm % solar reflection' from back side of glass - 300-2500 nm % transmission1 in the visible region of spectrum from film side of glass - 380-780 nm Sheet resistance as measured on a Alessi 4-point probe Emissivity calculated from measured sheet resistance (= 1-(1+0.0053*S.R.)2) Solar heat gain coefficient2 for center of glass/single pane Solar heat gain coefficient2 for center of glass in an IGU3 Total heat transfer coefficient2 for center of glass/single pane Total heat transfer coefficient2 for center of glass in an IGU3 transmission' in the visible region of spectrum center of glass/single pane - 380-780 nm transmission1 in the visible region of spectrum center of glass in an IGU3 - 380-780 nm color coordinates calculated from %Rvis according to ASTM E308-96, Illuminant C, 1931 Observer, 10 nm interval (Table 5.5) - 380-770 nm % reflection1 in the visible region of the spectrum from film side of glass - 380-770 nm to 00 I (1) Weighted with a solar spectral irradiance function (ASTM E891-87) using spectral data obtained on a P-E Lambda 9 spectrophotometer with 150 mm integrating sphere (2) Calculated using Windows and Daylighting Group, Lawrence Berkeley National Laboratory Window 4.1 program (3) IGU = insulated glass unit using a 2.2 mm coated glass lite (on ft2 surface) and a 2.5 mm clear lite with a 1/2" argon gas space Table 3 Summary of Properties of Bilayer Films TOSb/TOF 40 41 42 43 Composit.

F/Sb/G F/Sb-F/G F/Sb/G F/Sb-F/G %SbCI3 .5 .2 .2 .36 %TFA(under) 0 0 2.5 Thick, nm 300/240 300/240 300/240 300/240 %Asol 45.5 .7 41.8 39.1 %Tsol 45.0 54.2 48.2 50.6 %Rsol,1 9.5 .1 .0 .3 %Rsol,2 8.0 8.9 8.4 8.7 %Tvis 50.9 58.5 54.5 55.6 %Rvis,1 9.4 .1 .4 .3 %Rvis,2 8.0 9.0 8.5 9.0 %Tuv 40.1 41.1 41.6 39.8 S. R, 11.9 13.7 11.8 12.5 Emis-cal 0.12 0.13 0.11 0.12 SHGCc 0.53 0.60 0.55 0.57 " IG 0.45 0.52 0.47 0.49 Uc 0.72 0.73 0.72 0.72 " IG 0.27 0.28 0.27 0.27 Tvis-c 0.51 0.59 0.55 0.56 " IG . 0.46 0.53 0.50 0.51 R1 x 0.310 0.297 0.302 0.303 R1 y 0.297 0.313 0.299 0.307 %Rvis 9.4 .1 .4 .3 Tvis x 0.295 0.308 0.297 0.304 Tvis y 0.308 0.315 0.310 0.314

Claims (5)

WHAT WE CLAIM IS:

1. A NIR film comprising tin oxide containing a NIR dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel and containing a fluorine dopant at an atomic concentration less than the concentration of the NIR dopant.

2. The film of claim 1 wherein the fluorine dopant is present in a quantity sufficient to modify the transmitted color of light through the film.

3. A NIR film comprising tin oxide containing a NIR dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, and nickel and containing a color modifying dopant present in a quantity sufficient to modify the transmitted color of light through the film and selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and fluorine, provided that the selection of color modifying dopant is different than the selection of NIR dopant and when fluorine is the selected dopant its atomic concentration is less than the concentration of the NIR dopant.

4. A NIR film as defined in claim 1 substantially as herein described with reference to any example thereof and with or without reference to the accompanying drawings.

5. A coated, solar control glass having preselected reflected color and having a NIR solar absorbing layer and a low emissivity layer, comprising glass having a coating containing at least two layers with one layer being a solar absorbing layer comprising SnC>2 containing a dopant selected from the group consisting of antimony, tungsten, vanadium, iron, chromium, molybdenum, niobium, cobalt, nickel and mixtures thereof and another layer being a low emissivity layer comprising SnC>2 containing a dopant selected from the group fluorine or phosphorus, wherein the coated glass is produced by a method comprising sequentially treating glass at a glass temperature above 400°C. with: vl WGN *