IE47982B1 - Non-iridescent glass structures and processes for their production - Google Patents

Description

This invention relates to glass structures bearing a thin, functional, inorganic coating (e.g. a coating of tin oxide forming means to promote reflectivity of infra-red light) which structures have improved appearance ab a consequence of reduced iridescence historically associated with said thin coatings, and methods for achieving the aforesaid structures.

Glass and other transparent materials cdn be coated with transparent semiconductor films such as tin oxide, indium oxide or cadmium stannate, in order to reflect infra-red radiation. Such materials are useful in providing windows with enhanced insulating value (lower heat transport) in ovens, architectural windows, etc. Coatings of these same materials also conduct electricity, and are employed as resistance heaters to heat windows in vehicles in order to remove fog or ice.

One objectionable feature of these coated windows is that they show interference colors (iridescence) in reflected light, and, to a lesser extent, in transmitted light. This iridescence has been a serious barrier to widespread use of these coated windows (see, for example, American Institute of Physics Conference Proceeding No 25, New York, 1975, Page 288.) 47983 In some circumstances, i.e. when the glass is quite dark in tone (say, having a light transmittance of less than about 25%) this iridescence is muted and can be tolerated. However, in most architectural wall and window applications, the iridescent effect normally associated with coatings of less than about 0.75 microns is aesthetically unacceptable to many people (See, for example, U.S. Patent 3,710,074 to Stewart). Little or no success has been achieved in substantially reducing or eliminating the objectionable and apparent iridescence in clear, bluegreen and lightly tinted glasses.

Iridescent colors are quite a general phenomenon in transparent films in the thickness range of about 0.1 to 1 micron, especially at thicknesses below about 0.85 microns. Unfortunately, it is precisely this range of thickness which is of practical importance in most commercial applications. Semiconductor coatings thinner than about 0.1 micron do not show interference colors, but such thin coatings have a markedly inferior reflectance of infra-red light, and a markedly reduced capacity to conduct electricity.

Coatings thicker than about 1 micron also do not show visible iridescence, in daylight illumination, but such thick coatings are much more expensive to make, since larger amounts of coatings materials are required, and the time necessary to deposit the coating is correspondingly longer. Furthermore, films thicker than 1 micron have a tendency to show haze, which arises from light scattering from surface irregularities, which are larger on such a film. Also, such films show a greater tendency to crack, under thermal stress, because of differential thermal expansion. 9 8.2 As a result of these technical and economic constraints, almost all present commercial production of such coated glass articles comprise films in the thickness range of about 0.1 to 0.3 microns, which display pronounced iridescent colors. Almost no architectural use of this coated glass is made at present, despite the fact that it would be cost-effective in conserving energy to do so. For example, heat loss by infra-red radiation through the glass areas of a heated building can approximate about one-half of the heat loss through uncodted windows. The presence of iridescent colors on these coated glass products is a major reason for the failure to employ these coatings.

It is one object of the present invention to provide means to reduce substantially the visible iridescence from semiconducting thin film coatings on glass, while maintaining their desirable properties of visible transparency, infra-red reflectivity, and electrical conductivity.

Accordingly from a first aspect the present invention consists in a structure comprising a transparent glass sheet, a first inorganic coating of an infra-red reflective material which is a transparent semiconductor and which is of such a thickness as to exhibit iridescent colours in daylight illumination, and a second coating interposed between said glass sheet and said first coatinq and forming means to substantially diminish iridescent colours of said first coating by providing at least two interfaces which together with the mass of said second coating reflect and refract light to lessen iridescent reflection from said first coating.

From a second aspect the invention consists in a process for treating a transparent glass sheet comprising 2o forming on said sheet an intermediate or second coating of a metal oxide, a metal nitride or mixtures thereof, forming a primary or first coating of an infra-red reflecting semiconductor material which is of such a thickness as to exhibit iridescence in daylight, the combination of such coatings forming at least two interfaces which with the mass of said second coating reflect and refract light in such a manner as to lessen iridescent reflection from said first coating. ό It is believed desirable, because of the subjective nature of color perception, to provide a discussion of the methods and assumptions which have been used to evaluate the inventions disclosed herein. It should be realized that the application of much of the theory discussed below is retrospective in nature because the information necessarily is being provided in hindsight, i.e. by one having a knowledge of the,invention disclosed herein.

In order to make a suitable quantitative evaluation of various possible constructions which suppress iridescent colors, the intensities of such colors were calculated using optical data and color perception data. In this discussion, film layers are assumed to be planar, with uniform thickness and uniform refractive index within each layer. The refractive index changes are taken to be abrupt at the planar interfaces between adjacent film layers. Real refractive indices are used, corresponding to negligible absorption losses within the layers. The reflection coefficients are evaluated for normally incident plane waves of unpolarized light.

Using the above assumptions, the amplitudes for reflection and transmission from each interface are calculated from Fresnel's formulae. Then these amplitudes are summed, taking into account the phase differences produced by propagation through the relevant layers. These results have been found to be equivalent to the Airy formulae (see, for example, Optics of Thin Films, by F. Knittl, Wiley and Sons, New York, 1976) for multiple reflection and interference in thin films, when those formulae applied to the same cases I considered.

The calculated intensity of reflected light has been observed to vary with wavelength, and,thus is enhanced in certain colors more than in others. To calculate the reflected color seen by an observer, it is desirable first to specify the spectral distribution of the incident light. For this purpose, one may use the International Commission orf Illumination Standard Illuminant C, which approximates normal daylight illumination.

The spectral distribution of the reflected light is the product of the calculated reflection coefficient and the spectrum of Illuminant C. The color hue and color saturation as seen in reflection by a human observer, are then calculated from this reflected spectrum, using the uniform color scales such as those known to the art. One useful scale is that disclosed by Hunter in Food Technology, Vol. 21, pages 100-105, 1967. This scale has been used in deriving the relationship now to be disclosed.

The results of calculations, for each combination of refractive indices and thicknesses of the layers, are a pair of numbers, i.e. a and b. a represents red (if positive) or green (if negative) color hue, while b describes a yellow (if positive) or blue (if negative) hue. These color-hue results are useful in checking the calculations against the observable colors of samples including those of the invention. A single 2 2 1/2 number, c, represents the color saturation: c=(a +b ) ' . This color saturation index, c, is directly related to the ability of the eye to detect the troublesome iridescent color hues. When the saturation index is below a certain value, one is not able to see any color in the reflected light. The numerj cal value of this threshold saturation for observability depends on the particular uniform color scale used, and on the viewing conditions and level of illumination (see, for example, R. S. Hunter, The Measurement of Appearance, Wiley and Sons, New York, 1975, for a recent review of numerical color scales). 4798 In order to establish a basis for comparison of structures a first series of calculations was carried out to simulate a single semiconductor layer on glass. The refractive index of the semiconductor layer was taken at 2.0, which is a value approximating tin oxide, indium oxide, or cadmium stannate films The value 1.52 was used for the glass substrate; this is a value typical of commercial window glass. The calculated color satura tion values are plotted in Figure 1 as a function of the semiconductor film thickness. The color saturation is found to be high for reflections from films in the thickness range 0.1 to 0.5 microns. For films thicker than 0.5 microns, the color saturation decreases with increasing thickness. These results are in accord with qualitative observations of actual films.

The pronounced oscillations are due to the varying sensitivity of the eye to different spectral wavelengths. Each of the peaks corresponds to a particular color, as marked on the curve (R=red, Y=yellow, G=green, B=blue). !0 Using these results, the minimum observable value of color saturation was established by the following experiment: Tin oxide films with continuously varying thickness, up to about 1.5 microns, were deposited on glass plates, by the oxidation of tetramethyltin vapor. The thickness profile was established by a temperature variation from about 450°C’to 500°C across the glass surface. The thickness profile was then measured by observing the interference fringes under monochromatic light.

When observed under diffuse daylight, the films showed interference colors at the correct positions shown in Figure 1.

The portions of the films with thicknesses greater than 0.85 micron showed no observable interference colors in diffuse daylight. The green peak calculated to lie at a thickness of 0.88 micron could not be seen. Therefore, the threshold of observability is above 8 of these color units. Likewise, the calculated blue peak at 0.03 p could not be seen, so the threshold is above 11 color units, the calculated value for this peak. However, a faint red peak at 0.81 p could be seen under good viewing conditions, e.g. using a black velvet background and no colored objects in the field of view being reflected, so the threshold is below the 13 color units calculated for this color. I conclude from these studies that the threshold for observation of reflected color is between 11 and 13 color units on this scale, and therefore we have adopted a value of 12 units to represent the threshold for observability of reflected color under daylight viewing conditions. In other words, a color saturation of more than 12 units appears as a visibly colored iridescence, while a color saturation of less than 12 units is seen as a neutral. Colour saturation of below about 5 can be achieved by practice of the invention.

It is believed that there will be little objection to commercialization of products having color saturation values of 13 or below. However, it is much preferred that the value be 12 or below and, as will appear in more detail hereinafter, there appears to be no practical reason why the most advantageous products according to the invention, e.g. those characterized by wholly color-free surfaces, i.e. below about 8, cannot be made economically.

A value of 12 or less is indicative of ef reflection which does not distort the color of a reflected image in an observable way. This threshold value of 12 units is taken to be a quantitative standard with which one can evaluate the success or failure of various multilayer designs, in suppressing the iridescence colors.

Coatings with a thickness of 0.85 micron or greater have color saturation values less than this threshold of 12, as may be seen in Figure 1. Experiments reported in example 15 confirm that these thicker coatings do not show objectionable iridescence colors in daylight illumination. 47983 One embodiment of the invention involves using a single undercoat to avoid reflected color saturation. This requires use of a carefully selected single layer of a refractive-index (n^) which is intermediate between the refractive index of the glass (ngl or about 1.52) and the refractive index of the semiconductor (nsc or about 2.0). An intermediate refractive index which is the geometric mean η^=(ηδ(=η^^) or about 1.744, will result in the reflections from the two surfaces of the intermediate layer having the same amplitude. By choosing the thickness of the intermediate layer to be 1/4 wavelength, these two reflected waves cancel each other, and do not contribute to the iridescent colors. This cancellation is exact at only a single wavelength value, and the wavelength must be carefully selected. Therefore, an investigation was carried out to find those values which reduced the color saturation index for semiconductor films, particularly in the thickness range 0.15 to 0.4 ji, which semiconductors are of most interest for heat reflection and have been a particular problem with respect to iridescence. The optimum intermediate film thickness for an undercoat (i.e. a coat intermediate between glass and semiconductor) was found to be about 0.072 μ (72 nanometers), which corresponds to 1/4 wavelength for a (vacuum) wavelength of 500 nanometers. The color saturation remains below the threshold value of 12 units, for semiconductor films of all thicknesses, as may be seen from the curve in Figure 1. Thus, the usual strong iridescence colors from a heat-reflecting film of, say, 0.3ji thickness, can be suppressed even by this single intermediate film undercoat.

The sensitivity of this single layer, anti-iridescent under· coat to variations in refractive index and thickness was studied. Changes of -.02 in refractive index or ^10% in thickness are sufficient to raise the color saturation to observable values. Accurate control of these parameters can be achieved in known glass coating operations. For example, U.S. Patent 3,850,679 describes an apparatus capable of coating to -2% thickness uniformity.

In practice the intermediate layer shodld have a refractive index in the range of 1.7 to 1.8 and should be between 64 and 80 nanometres thick.

An effective product also can be formed using two layers of intermediate refractive indices on the glass under the semiconductor film. For semiconductor films in the thickness range of 0.1 to 0.4 ji, it was found to be possible to provide color saturation of only about one (1) unit or less! This range is very much below the threshold for observability. For example, the two intermediate refractive (n^ and n/ indices for such a construction are given by n,= (n )‘2®(n ,)'74 or about 1.63 l sc gi n2=(nsc)‘74(ngl)‘2® or about 1.86 The optimum thicknesses are about 1/4 wavelength for (vacuum) wavelength 500 nanometers or about d^=76.7 nm d2=67.2 nm The layer of lower refractive index (n^) is next to the glass, while the higher index (n2) is next to the semiconductor film.

This double undercoat design is even more tolerant of deviations of its parameters from the optimum values, than is the single undercoat design. Variations of -25% away from the optimum thickness still suppress the iridescence values below the observable limit,i.e. below a color saturation value of 10. Thus, very effective designs can be based on refractive indices in the ranges „ , ..26-.03, ,.74±.O3 Dl3(nSC> (ngl} , 74±.03,_ ,.26±.O3 ^-^sc’ (ngl’ which corresponds to a range of n^ from 1.62 to 1.65, and a range of n2 from 1.88 to 1.84. The degree of manufacturing accuracy required to maintain coating thickness to a tolerance of -25%, is readily achieved with state-of-the art procedures. Likewise, the accuracy needed for the refractive indices is entirely practicable even when mixed materials are needed to obtain the required values. 47983 Ιό It has also been discovered that a film intermediate between the glass substrate and a semiconductor layer can be built up of a graded composition, e.g. gradually changing from a silica film to a tin oxide film. Such a film is best pictured as one comprising a very large number of intermediate layers. \Ί Λ wide range of transparent materials are among those which can be selected to make products meeting the aforesaid criteria by forming anti-iridescent undercoat layer or layers. Various metal oxide;; and nitrides, and their mixtures have the correct optical properties of transparency and refractive index. Table A lists some mixtures which have the correct refractive index for a single layer coating between glass and a tin oxide or indium oxide film. The weight percents necessary are taken from measured refractive index vs. composition curves, or are jq calculated from the usual Lorentz-Lorenz law for refractive indices of mixtures (Z. Knittl, Optics of Thin Films, Wiley and Sons, New York, 1976, page 473), using measured refractive indices for the pure films. This mixing law generally gives sufficiently accurate interpolations for optical work, although the calculated refractive indices are sometimes slightly lower than the measured values. Film refractive indices also vary somewhat with deposition method and conditions employed. 7 9 8 2 A routine pre-production check can be made easily, and, it necessary, one can adjust the compositions to optimum values if such performance is really required.

Aluminum oxide films, for example, show some variability 5 in refractive index, from about 1.64 to 1.75, depending on deposition conditions. In Tables A, B and C, Al^O^-h designates the high-index (n=1.75) films, while AljO^-l designates the low index (n=1.64) films. Films of intermediate index of refraction require intermediate compositions to produce the desired refractive indices.

Tables B and C list some mixtures which have the correct refractive index (of about 1.63 and 1.86, respectively) for use in a double interlayer between glass substrate and a primary semiconductor coating. in addition to these optical properties, suitable undercoat layers are selected to be chemically durable and resistant to air, moisture, cleaning solutions, etc. Such a requirement eliminates, for most purposes, germanium dioxide films of the type which are subject to easy water hydrolysis. Films formed 20 of about half GeO2 and half SnO2 do appear to be insoluble and resistant to attack by water.

TABLE A Dielectric Films with Refractive Indices of Approximately 1.73 - Mixtures Componen 5 1Si3N4 2A12°3 •h 3 ZnO 4A12°3 -1 5 MgO 10 6 SnO2 7 SnO2 8 MgO 9In2°3 10In2°3 15 11 MgO 12 GeO2 13 GeO2 14 GeO2 15Ga2°3 20 16Ga2°3 17 MgO 18Ga2°3 Weight % Component Β Weight 1 67-4 Si°2 33 ί 4 100 — 78 ί 3Si02 22-3 55 ± 8 ZnO 45-8 76 ± 11 ZnO 24 i 11 81-3 si°2 19 ± 3 50 ί 7A12°3_1 50-7 73 ± 11 Sn°2 27 ί 11 81 ί 3 sio2 19-3 50-7 ai2o3-i 50 ί 7 73 - 12In2°3 27 ί 12 55-7 ZnO 45-7 52 ± 7 Sn°2 48-7 51 ί 7In2°3 49-7 91 ί 3 sio2 9^3 71 10 29 ί 10 53 ί 20Ga2°3 47 - 20 70 Τ 10 GeO2 30 - 10 47983 TABLE Β Dielectric Films with Reflective Indices of Approxiamtely 1.62 - 1.65 Mixture Component A Weight % Component B (balance) 1 SiO2 53 ί 4Si3N4 2A12°3-1 100 — 3A12°3-1 97-3 sio2 4 Al203-h 74 ί 5 Si02 5 zno 59 ± 4 SiO2 10 6 MgO 79 ί 5 SiO2 7Sn02 62 ± 3 SiO2 8 In203 63-3 SiO2 9 Ge°2 100 — 10Ga2°3 71 ί 3 SiO2 47883 TABLE C Dielectric Films which have Refractive + indices of Approximately 1.86 - .02 Mixture Component A Weights Component B (balance) 1 Si3N4 84 + 3 SiO2 2 ZnO 91 + 2 sio2 3 ZnO 76 + 5 ai203-i 4 ZnO 59 + 9 Al203-h · 5 ZnO 68 ± 7 MgO 6 SnO2 91 + 2 sio2 7 SnO2 78 + 5 Αΐ2θ3-1 8 SnO2 60 + 8 Al203-h 9 SnO2 70 + 6 MgO 10In2°3 91 + 2 SiO2 11In2°3 78 + 5Α12Ο3-1 12In2°3 61 + 8Al203“h 13 ln2°3 71 + 6 MgO 14 ZnO 75 + 7 Ge°2 15 SnO2 76 + 7 Ge°2 16 3 76 4 GeO2 17Ga2°3 80 + 14 ZnO 18Ga2°3 79 + 14 Sn°2 19Ga2°3 78 + 15In2°3 Note: AljOg-h = high density aluminum oxide film n of about 1.75 Al2°3-1 = low densit7 aluminum oxide film n of about 1.64 479 8 2 All of these films can be formed by simultaneous vacuum evaporation of the appropriate materials of an appropriate mixture. For coating of large areas, such as window glass, chemical vapor deposition (CVD) at normal atmospheric pressure is more convenient and less expensive. However, the CVD method requires suitable volatile compounds for forming each material. The most convenient sources for CVD are gases at room temperature. Silicon and germanium can be deposited by CVD from gases such as silane, SiHj, dimethylsilane (CHgJjSiHj, and germane (GeHj). Liquids which are sufficiently volatile at room temperature are almost as convenient as gases; tetramethyltin is such a source for CVD of tin compounds, while (CjHgJjSiHj and SiClj are volatile liquid sources for silicon. Similarly, trimethyl aluminum and dimethyl zinc, and their higher alkyl homologs, furnish volatile sources for these metals. Less convenient, but still useful, sources for CVD are solids or liquids which are volatile at some temperature above room temperature but still below the temperature at which they react to deposit films. Examples of this latter category are the acetylacetonates of aluminum, gallium, indium and zinc (also called 2, 4 pentanedionates), aluminum alkoxides such as aluminum isopropoxide and aluminum ethylate, and zinc propionate. For magnesium, no convenient compounds are known which are volatile below deposition temperature, so CVD processes are not believed to be applicable to the preparation of magnesium oxide films.

Typical conditions under which metal oxide films have been successfully formed by chemical vapor deposition are summarized in Table D. Typically, the organometallic vapor is present in about one percent (by volume) in air. The films thus formed show good adhesion to both the glass substrate, and to subsequently deposited layers of tin oxide or indium oxide. Mixed oxide layers have been formed between all these pairs of metals, using CVD techniques (except for magnesium, for which a conveniently volatile compound was not available). The refractive indices of the mixed films are measured conveniently by taking the visible reflection spectra as a function of wavelength. The positions and heights of the maxima and minima in the reflected intensity can then be related to the refractive index of the deposited film. The concentrations of the reagent species are then adjusted to form the desired refractive index.

Using these methods, a number of samples have been made on borosilicate glass (Pyrex,, using (SiO2 - Si^N^), (SiO2 - SnO2), (GeO2 - SnO2), (Al203 - SnC>2), (Al203 - Ga203), or (AljOj - ZnO) mixed layers under a 0.3 ji thick Sno2 semiconductor layer. When the refractive index and thickness are correctly adjusted, the reflected daylight is neutral and colorless to the eye. The coatings are clear and transparent, and free of visible haze (scattered light). 479 8 2 TABLE D Some Volatile Oxidizable Organometallic Compounds Suitable for Depositing Metal Oxide Layers, and Mixed Metal Oxide Layers with Oxidizing Gases Such as O2 or N20 Compound Volatization Temperature (°C) Deposition Temperature (°C) 1 SiH4 gas at 20 300-500 2 (CH3)2SiH2 gas at 20 400-600 10 3 (C2H5’2SiH2 20 400-600 4 GeH4 gas at 20 300-450 5 (CH3) 3A1 20 400-650 6A1<°W3 200-300 400-650 7 A1(OC3H?)3 200-220 400-600 15 8A1^C5H7°2)3 200-220 500-650 9 Ga(C5H702)3 200-220 350-650 10 In(C5H702)3 200-220 300-600 11 (CH3)2Zn 20 100-600 12 Zn(C3H502)2 200-250 450-650 20 13 (CH3)4Sn 20 450-650 14 Ta(OC4Hg)5 150-250 400-600 15 Ti(OC3H7)4 100-150 400-600 16 Zr(OC4Hg)4 200-250 400-600 17 Hf(OC4Hg)4 200-250 400-600 7983 When these same depositions were tried on ordinary window glass (soda-line or soft glass) many of the resulting coatings showed considerable haze or scattered light. When the layer first deposited on soft glass is amorphous and consists of Si02, S‘*'3N4 or GeOj or mixtures thereof, the coating is free of haze, no matter what the subsequent layers are. Al20g a3-so gives clear coatings, provided it is deposited in the amorphous form, advantageously below a temperature of about 550°C. If the initial layer contains large proportions of Ga20g, ZnO, ln20g, or SnO2, then haze formation is likely.

The first anti-iridescence layer to be deposited on a window glass surface is advantageously amorphous , rather than crystalline, in structure so as to avoid haze-formation cn application of subsequent layers. Silicon oxy-nitride is preferred. Subsequently deposited layers can thus be of a polycrystalline form.

Sodium and other alkali ions exert a deleterious effect on the infra-red reflectivity and electrical conductivity of tin oxide and indium oxide films.

The aforesaid amuiphons films ami especially silicon oxynitride film:; .ne good barriers to Llie diffusion of sodium ions from Llie glass into the semiconductor layer. By changing the oxygen/nitrogen ratio in the films, the entire range of refractive index from that of glass with a refractive index of about 1.5 to that of tin oxide or indium oxide with refractive indices of » about 2, can be covered. Thus with the same basic reagents, anti-iridescence structures with any number of refractive index steps can be fabricated. Indeed, even filmstwith continually changing proportion of reactants can be prepared. Only abundant and inexpensive materials are needed to form silicon oxynitride.

Numerous volatile reagents are available to form silicon oxynitride films. Table E lists some of the more convenient volatile materials for chemical vapor deposition of silicon oxynitride. The reaction Sillj + N 0 + NjHj is preferred, because it appears to give higher deposition rates in the temperature range of interest for window glass, i.e. 500°C to 60 0°C. However, numerous other combinations of reagents can also give successful silicon oxynitride films.

TABLE Ε Source Materials for Chemical Vapor Deposition of Silicon Oxynitride Films Sources of silicon: SiH4 (CH3)2 SiH2 (c2h5)2 sih2 (ch3,4 si SiCl4 SiBr4 Sources of oxygen: °2 h2° n2o Sources of nitrogen: n2h4 ch3nhnh2 NH3 (CH3)2NNH2 HN3 Sources of both oxygen and nitrogen: NO nh2oh n2h4h2o Interference colors, i.e. the iridescence, may be reduced by use of reflections from two thin coatings of a functional inorganic coating on separate, but parallel, glass surfaces.

When coating thicknesses, e.g. thicknesses of tin oxide coatings, are selected to differ by about 1/4 of a wavelength (about .07 micron for k= 0.50 pm and n = 2.0), the interference coloration practically disappears. Certainly it is reduced to the point where it ceases to become an aesthetic problem for supplier and customer. The additive- coloration of, say, a red reflection in one coating and a green reflection of an adjacent interference order in a second coating, combine to produce a practically white (neutral) reflection. Similarly, the transmission of light through such a combination of complementary coatings is also neutral in color.

This color compensation is used in double glazing to reduce the strength of the interference colors from the heat-reflecting semiconductor coatings. For example, if coatings of SnO2 are used on the two inner surfaces of a double glazed window, they can be chosen to differ in thickness by .07ji. For extended light sources, the reflection colors are well cancelled if the glass surfaces are reasonably parallel. For small light sources, or ones with sharp boundaries, the compensation in reflection will not be complete unless the coating surfaces are highly parallel. For observations in transmission, the requirements for parallel surfaces are not nearly as severe. 47983 It should also be noted that films in which the interference colors have been reduced in intensity by an undercoat of intermediate or graded refractive index, can also be combined in pairs to produce still further color compensation.

In order that the present invention may be more readily understood, reference will now be made to the accompanying drawings, in which:Figure 1 is a graph illustrating the variation of calculated color intensity of various colors with semiconductor film thickness.

Figure 2 illustrates, schematically and in section, a non-iridescent coated glass constructed according to the invention, with a single anti-iridescent interlayer.

Figure 3 illustrates, schematically, and in section, a non-iridescent coated glass, constructed according to the invention, with plural anti-iridescent interlayers.

Referring to Figure 2, it is seen that transparent sheet 20 comprises a glass substrate 22, carrying an intermediate film 24 of 0.072 microns of Si3N4/Si02 (or of any of the other materials in Table A) having an index of refraction of 1.744. Over film 24 is a coating 26 of 0.4 microns of an infra-red reflecting semiconductor, tin oxide.

Figure 3 illustrates a window 36 constructed of the same semi-conductor film 26 and the same glass 22 and two intermediate coatings as follows: Coating 30 which is 0.077 microns thick and has a refractive index of about 1.63. Coating 32 is about 0.067 microns and has a refractive index of about 1.86. Coating 30 is formed by any of the materials disclosed in Table B. Coating 32 is formed of any of the materials disclosed in Table C. . 47982 3ϋ Example 1 A glass with a single anti-iridescent undercoat layer, was produced hy heating a clear window glass disc, 15.24 cm (6 inches) diameter, to about 580°C. A gas mixture containing about 0.4% silane (SiH4), 0.1% nitric oxide (N 0), 2% hydrazine (N2H4), and balance nitrogen (N2) was passed over the glass surface for about one minute, at a rate of 1 liter/minute. This coated the glass surface with a uniform, transparent,film of silicon oxynitride. The surface was then further coated with a fluorine-doped tin oxide layer, by flowing a gas mixture of 1% tetramethyltin (CH3)4Sn, 3% bromotrifluoromethane CP3Br, % oxygen O2, balance nitrogen N2, past the silicon oxynitride surface at 560°C for about one minute. Then the coated glass was allowed to cool slowly in air to room temperature, over a period of about one hour.

The glass coated by this procedure did not show visible interference colors in reflected or transmitted daylight.

The surface reflected about 90% of infrared radiation at a 10 micron wavelength, and transmitted about 90% of visible light.

The electrical sheet resistance was measured to be about 3 ohms/ square.

In order to measure the properties of the silicon oxynitride layer, the tin oxide film was removed from an area of the coated surface by rubbing with a mixture of zinc dust and diluted hydrochloric acid. This etchant does not affect the silicon oxynitride undercoat. The refractive index of the silicon oxynitride film was measured to be 1.74 by the CH2l2 liquid test described below. The visible reflectivity of the silicon o oxynitride film was measured, finding a maximum at 5000A and a thickness of 0.072 micron, corresponding to the desired 1/4 o wavelength thickness for 5000A light. 47883 3; The refractive indices of these silicon oxynitride films depend on the nitrogen to oxygen ratio in the films. This composition is easily adjusted by varying the N2H4/NO ratio in the gas. Increasing the N/O ratio increases the refractive index. The exact refractive index also depends on the purity of the starting materials, and particularly On the amount of water present as an impurity in the hydrazine. Commercial hydrazine always contains at least a few percent water. By drying the hydrazine through distillation from a drying agent, such as sodium hydroxide, potassium hydroxide, or barium oxide, one can increase the refractive index of the film. Conversely, one can decrease the refractive index by adding water to the hydrazine. The film refractive index also depends on the exact conditions of film growth, including deposition temperature, gas flow rate, etc. Therefore the conditions disclosed above cannot be expected to give a film of precisely n=1.74, when other reagents or deposition conditions are used. However, small adjustments of the composition should be sufficient to produce films of the desired refractive index values.

The semiconductor films may also have refractive indices different from the value 2.0 observed for the tin oxide films described herein. The corresponding optimum value(s) for a single (or double) undercoat layer (s.) may then be adjusted, by the relationships given above. The corresponding gas-phase compositions which produce the desired refractive index films for anti-iridescent undercoat(s) may then be found by routine experimentation, to fit the precise conditions of any manufacturer or investigator having ordinary skill in the CVD art.

The thickness of a film of measured refractive index is easily determined by measuring its reflection spectrum in visible and infra-red light. This spectrum is readily calculated, as a function of film thickness, using the standard optical formulas of Fresnel and Airy. In most of the practical designs disclosed above, one desires to form a film of 1/4 wavelength , thickness, for a wavelength (in air) of about 5000A. In this case the reflection spectrum of a single such film on glass, o shows a broad maximum centered at a wavelength of 5000A. 47983 Example 2 Aluminum 2,4 pentanedionate, Al (CgHyOzJ-j, (also known as aluminum acetylacetonate) is a white solid which melts at 189°C to a clear liquid, which boils at 315°C. This material was placed in a bubbler heated to about 250°C, through which nitrogen carrier gas was passed. When this gas mixture was mixed with dry oxygen at 250°C, no reaction was noted. However, when moisture was added to the oxygen, intense white fumes formed in the gas mixture. Such fumes are indicative of hydrolysis.

Xn order to prevent this premature hydrolysis reaction, the gas streams must be kept as dry as possible.

The mixture of aluminum 2,4 pentanedionate vapor, nitrogen carrier gas and 20% oxygen was passed over heated glass surfaces. At 500°C, a faint deposit was formed, less than 0.1 μ thick, which was evident only by its increased reflectivity. At 525°C a film 0.3 ji thick was grown in about 3 minutes. This film showed faint interference colors under white light, and distinct interference bands under monochromatic illumination.

At 550°C the aluminum oxide films grew even faster, and a small amount of powder formed by homogeneous nucleation, and deposited on the apparatus surface.

Next, fluorine-doped tin oxide films were grown on top of the aluminum oxide films at temperatures in the range of 500°C to 540°C. Thickness in the range of 0.3 to 0.5 μ were examined carefully, for these thicknesses show the strongest interference colors. The intensity of the colors were substantially reduced, when compared to tin oxide films of the same thickness, without the aluminum oxide undercoat. l''ilms in which Lhe aluminum oxide film has 1/4 wavelength thickness (500 nm wavelength, which is near the peak of the spectral sensitivity of the eye for daylight illumination) exhibit the greatest suppression of iridescent color. For this thickness (approximately .072 v for 1/4 wavelength), the reflections from the glassAl203 and A^O-j-SnOj interfaces cancel each other most effectively. However, there is also some substantial reduction in color intensity, even when the thickness of the Al203 is not optimum.

As glass substrates, both Pyrex borosilicate glass, and soda lime (window) glass were used. Good results were obtained on both substrates.

The aluminum oxide layer also was effective in preventing surface devitrification of the soda lime glass surface when tin oxide was deposited at 500°C to 540°C. Thus, the aluminum oxide is believed to act in protecting the soda lime glass surface from crystallizing around the nuclei provided by the tin oxide crystals and, consequently, serving to avoid any hazing of the glass during the coating process. 4-79 8 2 Example 3 Experiments were carried out to prepare graded refractive index layers between glass (n of about 1.5) and tin oxide (n of about 2.0) coatings. A graded layer of SixSn^_x 02 was utilized with x gradually decreasing from 1 to zero as the layer was built upon the glass surface. The SnO2 layer was of about 0.3 microns thick; the underlying, graded area was about 0.3 microns thick. The resulting structures exhibit markedly reduced interference coloration, compared to layers of SnO2 of the same thickness but without the graded interlayer region between glass and the SnO2· The volatile sources of silicon are, in one instance, Sin^ {from a 1% mixture in N2 carrier gas) and, in another instance, (CII3)2siH2 (from a cylinder of the pure gas).

Deposition was carried out at a surface temperature of 480°C.

Gas concentrations were initially about 0.4% silane (or alkylsubstituted silane), 10% oxygen, balance nitrogen. Then tetramethyltin (CH3)4Sn was gradually introduced up to a concentration of 1% over a period of about 3 minutes, while the silane concentration was gradually decreased to zero over the same period. Then the carrier gas for the tetramethyltin was cut off and the apparatus purged for about 5 minutes with air to remove the last traces of the silane. Then a gas flow of 1% (CH3)4Sn, 3% CF3Br, 20% 02, balance nitrogen, was passed under the surface for three minutes to deposit a layer of fluorine-doped tin oxide about 0.4 p thick.

The interference colors were considerably less vivid on these coatings with a graded refractive index undercoat.

/ Example 4 Λ similar process is carried out using GeH^ in place of Sillij- The graded layer is formed of θβχδη·^_χ02 with x gradually decreasing from one to zero as the layer is built up on the glass. Since the refractive’ index of pure GeOj is about 1.65, the graded layer still has a refractive index discontinuity from that of glass (about 1.5). However, the uniformity of the deposition was somewhat'better than that obtained with the SiH^. Reductions in visibility of iridescence were noted similar to those noted with respect to Example 3. 47983 3/ Examples 5-8 Example 1 is repeated utilizing, as the intermediate layer between glass and tin oxide, the following materials selected from Table A: Example 5: 82% XnyOg/iei Si02 Example 6 : 58% GeC>2/42% ZnO Example 7 : 70% 68303/30% A^O-j-l Example 8; 60% Αΐ2θ3~1/4Ο% ZnO Low iridescence is realized in each of these cases. ^-79 8 2 The ful lowing materials, .iLJ. selected from Table B and C, are used as the two intermediate layers replacing the single intermediate layers of Example 1 and 5-8.

Hof about 1.63 > N of about 1.86 Example 9: 97¾ Al203-l/3% SiO2 84% Si3N,j/16% SiO2 Example 10: 60¾ ZnO/40% SiO2 90% ZnO/10% SiO2 Example 11: 63¾ In203/37% SiO2 60% Sn02/40% AljO^-h Example 12; 70¾ Ga203/29% Si02 7.6% SnO /24% Ge02 Example 13: 62% Sn02/38% Si02 61% Xn203/39% Al203-h 3? Example 14 A tin oxide coating is placed on a glass substrate at different thicknesses. (The glass substrate is first coated with an ultra-thin film of silicon oxynitride to provide an amorphous, haze-inhibiting surface.) Thickness of Tin Oxide Iridescence Visibility 0.3 0.6 0.9 1.3 strong * distinct, but weaker barely detectable except in fluorescent light weak, even in fluorescent light The latter two materials are not aesthetically objectionable for architectural use. 4ϋ A simple method for quickly checking the refractive index of thin films was developed, in order to be able to find deposition conditions for films of the desired refractive index. Suppose, for example, a film with refractive index n=1.74 is desired for an undercoat layer. A liquid with this refractive index is selected. For this example, diiodomethane, n=1.74, is used. A film whose thickness is about 0.2 to 2 microns, is deposited on a glass surface. The coated glass is observed by reflected light from a monochromatic light source, such as a , o filtered mercury lamp atA=5461A. The coated glass shows an interference pattern of dark and bright bands, if the thickness of the film varies over the glass surface. A drop of the liquid with known refractive index is placed on the film. If the refrac tive index of the film exactly matches that of the liquid, then the interference pattern disappears under the drop.

If the refractive indices of film and drop do not match exactly, then the interference pattern is still visible under the drop, but is weaker in intensity there. If this weak interference pattern under the drop is a direct continuation of the band pattern on the rest of the film, then the refractive index of the film is larger than that of the reference liquid.

If, on the other hand, the band pattern under the drop is reversed (light and dark areas reversed) from what is present without the liquid drop, then the refractive index of the film is smaller than that of the reference liquid. 4; By using this simple, but accurate, measurement of film refractive index, the conditions for forming a film can be adjusted easily in a series of test runs, to match the desired value. By choosing other reference liquids, one can adjust films to various other values. n=1.63, used in a two-layer undercoat, can be set using 1,1,2,2 tetrabrbmoethane as a reference liquid. n=1.86,for the other layer in a two layer undercoat design, can be adjusted to a solution of sulfur and phosphorous in diiodomethane, described by W4st in American Mineral, Vol. 21, pg. 245 (1936). From the above it will also be apparent to those skilled in the art that the general procedure can be used as a quality control tool in manufacture. Liquids of known refractive index are also furnished by Cargille Laboratories, New Jersey.

It is to be realized the advantageous processes of the invention include the conservation of heat in buildings with substantial areas of glass and also include the electrical heating of windows, as in automobiles and airplanes, using the resistive features of the coatings of the invention. In general, these coatings are ohmic, usually semiconductive.

Claims (36)

1. CLAIMS:1. A structure comprising a transparent glass sheet, a first Inorganic coating of an infra-red reflective material which is a transparent semiconductor and which 5 is of such a thickness as to exhibit iridescent colours in daylight illumination, and a second coating interposed between said glass sheet and said first coating and forming means to substantially diminish iridescent colours of said first coating by oroviding at least two interfaces which 10 together with the mass of said second coating reflect and refract light to lessen iridescent reflection from said first coating.

2. A structure according to claim 1, wherein said second coating has a refractive index which is substantially 15 the square root of the multiple of the refractive indices of the glass of said glass sheet and said first coating.

3. A structure according to claim 1 or 2, wherein said second coating is an amorphous material and forms means to avoid haze-formation on said glass sheet 20 during application of said first coating.

4. A structure according to Claim 1, 2 or 3, wherein said second coating has a thickness of about 1/4 wavelength of light having a vacuum wavelength of about 500 nanometers.

5. A structure according to any one of the preceding 25 claims, wherein said second coating has a refractive index of from 1.7 to 1.8 and is from 64 to 80 nanometers thick, and wherein said first coating has a refractive index of substantially 2, and the glass of said transparent glass sheet has a refractive index of substantially 1.5.

6. A structure according to claim 5, in which said second coating is formed from metal oxide, metal nitride, or a mixture thereof.

7. A structure according to claim 6, wherein the second coating is silicon oxynitride.

8. A structure according to claim 6, in which the metal oxide and/or nitride compositions are selected from those disclosed in Table A of the specification.

9. A structure according to claim 6, wherein said second coating is principally formed of aluminium oxide.

10. A structure according to any one of the preceding claims wherein the refractive index of said second coating changes between said glass sheet and said first coating.

11. A structure according to claim 10, wherein said change is stepwise, with the second coating being formed as a plurality of coating increments each of a different refractive index.

12. A structure according to claim 10, wherein said gradient is continuous with a gradually changing refractive index between said glass sheet and said first coating.

13. A structure according to claim 12, wherein said second coating comprises the silicon oxynitride mixture XSiO 2 (1-X)Si^N^ where X changes from near unity at the surface of said glass sheet to near zero at the boundary of said second coating with said first coating.

14. A structure according to claim 12, wherein said second coating comprises mixtures of δ1 χ 5η^- χ 0 2 or Ge x Sn 1 _ x O 2 , where X ranges from near unity at the surface of the glass sheet, to zero at the boundary of said second 5 coating with said first coating.

15. A structure according to claim 11, wherein said second coating comprises two layers including: a) one film closer to said glass sheet and having a refractive index approximately given by the 10 formula 0.26 0.74 n a = n sc · n gl and b) a second having a refractive film closer to said first coating and index approximately given by the formula 0.74 sc .1 I gi 0.26 wherein n gc is the refractive index of said first coating and n is the refractive index of the glass.

16. A structure according to claim 11, wherein said second coating comprises two layers including 20 a) one film, closer to said glass sheet and having a refractive index in a range of 1.6 to 1.7; b) a second film closer to said first coating and having a refractive index in a range of 1.8 to 1.9, said first coating having a refractive index of substantially 2, and the glass of said glass sheet having a refractive index of substantially 1.5.

17. A structure according to either of claims 15 or 16, wherein the film closer to said glass sheet has a composition disclosed in Table B; and the second film has a composition disclosed in Table C of the specification.

18. A structure according to any one of the preceding claims and exhibiting a colour saturation value as hereinbefore defined which is below 13.

19. A structure according to any one of claims 1 to 17, and exhibiting a colour saturation value as hereinbefore defined which is below 8.

20. A structure according to any one of claims 1 to 17, exhibiting a colour saturation value as hereinbefore defined which is below 5.

21. A structure according to any one of the preceding claims wherein the combined width of said first and second coatings is from .1 to 1 micron.

22. A structure according to any one of the preceding claims wherein said semiconductor layer is less than 0.4 microns in thickness.

23. A structure according to any one of the preceding claims wherein said transparent glass sheet is clear glass or glass of light tint. 479 82

24. . A structure according to claim 23, vfcerein the glass of said glass sheet is free from metallic, grey or bronze and other dark-toned tones capable of suppressing the visibility of iridescence and reducing the transmittance of the structure 5 to less than approximately 25%.

25. A structure as claimed in any one of the preceding claims wherein the first coating is stannic oxide.

26. A process for treating a transparent glass sheet comprising forming on said sheet an intermediate or second 10 coating of a metal oxide, a metal nitride or mixtures thereof, forming a primary or first coating of an infra-red reflecting semiconductor material which is of such a thickness as to exhibit iridescence in daylight, the combination of such coatings forming at least two interfaces which with 15 the mass of said second coating reflect and refract light in such a manner as to lessen iridescent reflection from said first coating.

27. A process according to claim 26, wherein said second coating is of an amorphous material at least at its inter20 face with said glass sheet so as to avoid haze-formation on said glass sheet.

28. A process according to claim 26 or 27, wherein said second coating is formed as a graduated composition containing silica in which the silica content decreases 25 from its interface with the glass sheet to an interface with said first coating. 4/

29. A process according to any one of claims 26 to 28, wherein said second coating has a refractive index defined as substantially the square root of the multiple of the refractive indices of the glass of said glass sheet and said first coating.

30. A process according to any one of claims 26 to 29, wherein said second coating has a thickness of substantially 1/4 wavelength of light having a vacuum wavelength of about 500 nanometers.

31. A process according to claim 29, wherein the second coating has a refractive index of about 1.7 to 1.8 and is about 64 to 80 nanometers in thickness.

32. A process according to any one of claims 26 to 31, wherein said second coating comprises silicon oxynitride.

33. A process according to any one of claims 26 to 32, wherein said second coating is deposited in two layers as follows: namely as one film which is closer to the glass sheet and has a refractive index in a range of substantially 1.6 to 1.7; and as a second film closer to said first coating and having a refractive index in a range of substantially 1.8 to 1.9; and wherein the glass of said transparent glass sheet has a refractive index of substantially 1.5 and said primary coating has a refractive index of 2.0.

34. A process according to any one of claims 26 to 33, wherein said first coating has a thickness of less than 0.4 microns. 4-7982

35. A process for coating transparent glass with a primary thin transparent coating of infra-red reflecting semiconductor, substantially as hereinbefore described.

36. A structure formed of at least one transparent 5 glass sheet of the type comprising a first inorganic coating of an infra-red reflective material and of the type that is a transparent semiconductor and exhibits iridescent colours in daylight illumination, substantially as hereinbefore described with reference to the accompanying drawings.