CN1160273C - Solar control coatings and coated articles - Google Patents

Abstract

A multi-layer coating composites on transparency or glass substrates comprise alternating layers of coatings having high and low refractive index from predominantly inorganic coatings to at least block UV light by a combination of thin film interference and absorption effects. The multilayered coated article has a substrate of clear glass, tinted glass, solar control glass, or colored glass having which is visually transparent to some degree. A first metal-containing predominantly inorganic coating layer that also has some degree of visual transparency and has a refractive index selected from the group of high and low is over the substrate. Over the first coating layer is a second metal-containing predominantly inorganic coating layer that to a degree is visually transparent and has a refractive index opposite from the refractive index of the first coating. Over the second coating layer is a third metal-containing predominantly inorganic coating layer that has a degree of visual transparency and has a refractive index in the range of that of the first coating layer. Additional coating layers can be over, under or interlayered with these first three coating layers to provide different reflective and/or absorption properties.

Description

Solar control coatings and coated workpiece

(present patent application is that the U.S. Patent application of 60/107677 by name " solar control coatings and coated workpiece " is a right of priority with the sequence number of submitting on November 9th, 1998, and this patent application is drawn at this and is reference.)

The present invention relates to be used for the solar control coatings of transparent workpiece, this coating is improved ultraviolet reflection and/or near infrared ray reflective, and/or increase the visible transmission of coated workpiece.

Transparent workpiece, for example glass, plastics and the glass plastic laminate that uses in commerce and/or dwelling construction transformation and carplane manufacturing field requires to have specific sunlight characteristic for specific area.For example in automotive industry, the planner is incorporated into the not only practical but also attractive vehicle window and the transparency of windshield glass in their design.Automobile can be handled with air-conditioning system because of be exposed to the heat that accumulates under the sunlight in passenger accommodation.Certainly, heat accumulation must be many more, and is just big more to the needs of this kind system.Minimizing has become one of focus of planner's concern by the heat of vehicle window accumulation.In addition since ultraviolet ray (" UV ") and IR sun power act on the car passenger chamber interior, so more need consideration indoor design quality meticulously.Another factor that need consider simultaneously is to meet the visible transmission requirement of government to the special transparent substance defined of windshield glass etc.Therefore, the transparent substance of lower infrared transmission rate and lower total solar energy transmission is provided, be desirable not only, and also be desirable for the color of coordinating the windshield glass transparent substance to a certain extent for reducing the heat that vehicle interior obtains.Glass with these character is not only used automobile but also all is unusual ideal to Application in Building.If this glass also with the sheet glass manufacture method compatibility that is easy to use, then be better.

For example in some automobiles are used, require the UV optical transmittance of glass transparent object be lower than 10% and total solar energy transmission (" TSET ") be lower than 50%.A kind of method that satisfies these market demands is to use the substrate of uncoated, by add titanium dioxide TiO in glass ingredient ₂, cesium dioxide CeO ₂Stop UV light.These additives generally all increase the cost of substrate.This product is feasible as green glass the time only.Organic coating can use with UV and near infrared light (" NIR ") absorbing additives, thereby is not using CeO ₂Situation under obtain the object technology requirement.Compare with the weather resistance that the glass substrate of uncoated obtains, these organic coatings lack weather resistance usually.

The purpose of this invention is to provide coated transparent substance or glass, the ultraviolet light transmission of this transparent substance or glass reduces, especially in using, some automobile is lower than 10%, its NIR is loss of transmission simultaneously, if possible, adopt those can be with the production technique of industrial-scale production sunlight feed glass transparent substance.

Laminated coating mixture on transparent substance or the glass substrate comprises the alternately coating that mainly contains inorganic coating and have high and low refractive index, can stop UV light at least by combination film interference and sorption.UV optical transmission amount is the function of the number of plies and substrate character.For example, being low to moderate trilaminar coating most UV is reduced on the sunlight feed glass.Alternative titanium dioxide and silicon dioxide layer are possible for the filtering UV-light.In the case, the thickness of titanium dioxide layer and silicon dioxide layer is respectively about 300 and 550 .

As an alternative or subplan, coated layered composite can have thickness be respectively about 1041 and the titanium dioxide layer of 1725 and silicon dioxide layer with filtering NIR.If suitably select the multiwalled bed thickness, the TSET of so coated glass can obtain reducing.For example, four layers of coating on green sunlight feed glass can have and are lower than 37% TSET, obtain to be lower than the UV target of ISO standards (" ISO ") simultaneously.This kind reduces UV and the light transmissive coating of NIR is applicable to that in theory other does not possess the substrate of good sunlight control character.And the present invention can be included in four layers of coating mixture on transparent substance or the glass substrate.Four layers of coating on the thick green sunlight feed glass of about 4.0mm, promptly titania/silica/titania/silica layer can obtain to be lower than 10% ISO UV transmissivity, keeps transmission of visible light greater than 70% simultaneously.This kind coating also can visible reflectance be reduced to about 8.0% and total solar energy transmission (" TSET ") be lower than about 45%.In addition, four layers of transparent substance of this kind can obtain to be lower than 10% ISO UV transmissivity, keep a transmission of visible light and a total solar energy transmission greater than 70% to be reduced to about 36% simultaneously.This laminated coating can also be reduced to visible reflectance less than 8%.When the four layer coating of this kind on the sunlight feed glass were used as windshield glass, can adjust the windshield glass installation angle was about 65 °.This will be reduced to about 13% to visible reflectance.

Another kind of suitable laminated coating mixture on transparent substance or glass substrate can have the coating that contains subsidiary material, and these subsidiary material are for example for mixing up the stannic oxide of fluorine or antimony.The coating that contains these materials can obtain such as electroconductibility or absorb other character of sunlight.Zhi Bei the stannic oxide that mixes up antimony can absorb green glow in a suitable manner, thus such as the Solex of PPG Industries Inc. ^Or Solargreen ^The color of the green glass transmission of glass etc. becomes grey from green.By setting deposition conditions and mix up the concrete composition of the doped tin oxide coatings of antimony, coated substrate is carried out thermal treatment such as tempering or annealing etc., might controlledly change the optical property of the doped tin oxide coatings that mixes up antimony.

By comprising subsidiary material or coating, realize the coated transparent substance or the optional auxiliary character of glass.For example, by the tapered titanium dioxide of deposit, above-mentioned laminated coating mixture on substrate can possess automatically cleaning or character easy to clean.Even the surface silica dioxide layer also can have self-cleaning character.In addition, by being the titanium dioxide or the high refractive index coating replacement transition metal oxide of all or part, can change the color of sunlight coating transmission.In above-mentioned three layers of coating mixture, four layers of coating can increase anti-reflection effect and have more outward appearance to select.And, for the color that keeps within the required range being reflected, the thickness of these laminated coatings of may command.

Fig. 1 is theoretic luminous reflectance factor and spectrum medium wavelength relation curve A and B, wherein, reflectance unit is per-cent (%), wavelength unit is nanometer (nm), light source is the white light source in the air dielectric, substrate is being transparent glass under the reference wavelength 380nm and is being 0.0 degree when detecting with standard detectors, and curve A is illustrated in specific refractory power on the transparent glass to be 2.55 coating of titanium dioxide and to be illustrated in reflectivity on the visible spectrum.Curve B is the reflectivity-wavelength relationship curve of three layers of SHLH coating on the float glass, and wherein H is titanium dioxide layer (high refractive index), and L is silicon-dioxide (low-refraction).

Fig. 2 illustrates theoretic reflectivity-wavelength relationship curve A and B, and wherein, curve A and curve B are illustrated respectively in such as SOLARGREEN ^SHLH coating heap on the green glass of glass and SHLHLL coating heap.Light source, dielectric detector and angle be identical with Fig. 1 all.

Fig. 3 illustrates theoretic reflectivity-wavelength relationship curve A and B, and wherein, the SLHL coating when curve A and curve B represent respectively that design wavelength is 330nm on transparent glass substrate piles up TiO ₂Be with or without the situation of absorption in the coating, they are at SiO ₂All do not have in the coating to absorb.Other condition is similar to Fig. 1's.

Fig. 4 illustrates respectively theoretic relation curve A and the B that piles for S3H3L3H3 coating heap and S3H3L3H3LL coating.Last coating of curve B coating heap is SiO ₂, this coating is 1/4 wavelength and be 1/8 wavelength in NIR in visible light.Except design wavelength was 350nm, other condition was similar to Fig. 1's.

Fig. 5 illustrates theoretic reflectivity-wavelength relationship curve A and B, and wherein, curve A is the S3H3L3H3 coating heap among Fig. 4, the relation curve when curve B represents that a part in three minutes of inner silica dioxide coating is mixed up the stannic oxide of fluorine and replaced.Other condition is identical with Fig. 4's.

Fig. 6 illustrates theoretic reflectivity-wavelength relationship curve A and B, and wherein, curve A is the S3H3L3H3LL coating heap among Fig. 4, the relation curve when curve B represents that a part in three minutes of inner silica dioxide coating is mixed up the stannic oxide of fluorine and replaced.Other condition is identical with Fig. 4's.

Fig. 7 illustrates theoretic reflectivity-wavelength relationship curve A and B, and wherein, curve A is represented to pile the NIR reflectance peak that obtains from SHLH, TiO in this SHLH heap ₂The stannic oxide that mixes up fluorine for high refractive index coating is low refractive index coating.Curve B is represented to be increased to the TCO coating below the SHLH coating heap and to become SMHMH coating heap.Except design wavelength was 1000nm, other condition is identical with Fig. 1 all.

Fig. 8 illustrates theoretic reflectivity-wavelength relationship curve A and B, and the coating heap that does not have color to suppress the coating heap of layer and to have a configuration of SM/2HLH heap is compared.The former is the curve A among Fig. 7, and the latter is a curve B.Other condition is identical with Fig. 7's.

Fig. 9 illustrates theoretic reflectivity-wavelength relationship curve A and B and both is compared, curve A represents not have the coating heap of color inhibition layer, also be the curve A among Fig. 7, curve B represents to have the graded coating, and (" G ") piles SGHLH as the coating that its color suppresses layer.Other condition is identical with Fig. 7's.

Figure 10 illustrates theoretic reflectivity-wavelength relationship curve A and B and both is compared, and wherein, curve A is the curve A among Fig. 7, and curve B is represented coating heap SGLHLH.Other condition is identical with Fig. 7's.

Figure 11 illustrates theoretic reflectivity-wavelength relationship curve A and B and both is compared, and wherein, curve A is the curve A among Fig. 7, and curve B is represented coating heap SMHMHL.Other condition is identical with Fig. 7.

Figure 12 illustrates theoretic reflectivity-wavelength relationship curve A and B and both is compared, and wherein, curve A is the curve A among Fig. 7, and curve B is represented coating heap SHLMLMH.Other condition is identical with Fig. 7's.

Figure 13 illustrates theoretic reflectivity-wavelength relationship curve A and B and both is compared, and wherein, curve A is the curve A among Fig. 7, and curve B is represented coating heap SHLMH.Other condition is identical with Fig. 7's.

Figure 14 illustrates the sunlight absorption-wavelength relationship curve that mixes up the doped tin oxide coatings of antimony for several, and this figure shows that electroconductibility reduces and coating begins to absorb in a large number solar radiation along with antimony content increases.

Figure 15 illustrates theoretic transmissivity-wavelength relationship curve A and B and both is compared, and transmissivity unit is per-cent (%), and it is represented that the coating heap that curve A is represented is among Fig. 7 curve A, and curve B represents to have only the coating heap of single tin-antiomony oxide coating.Other condition is identical with Fig. 7's.

Figure 16 illustrates theoretic optical transmittance-wavelength curve A and B, and wherein, the coating heap that curve A is represented is the coating heap that curve A is represented among Fig. 7, the coating heap that curve B is represented G and mixed up the stannic oxide of antimony and mix up the stannic oxide of fluorine.Other condition is identical with Figure 15's.

Figure 17 illustrates theoretic optical transmittance-wavelength curve A and B, and wherein, curve A represents similar to curve B among Figure 16 but it mixes up the thicker coating heap of stannic oxide layer of antimony, and curve B is represented similar to curve B among Figure 16 and outside TiO is arranged ₂The coating heap of coating.Other condition is identical with Figure 15's.

Figure 18 illustrates theoretic optical transmittance-wavelength curve A and B, and wherein, coating that curve A is represented heap is the coating heap that curve A is represented among Figure 17, and curve B is represented to remove the stannic oxide that mixes up fluorine and had the graded layer, mixes up the stannic oxide and the TiO of antimony ₂Coating heap.Other condition is identical with Figure 15's.

Figure 19 illustrates theoretic optical transmittance-wavelength curve A and B, wherein, curve A is represented the single doped tin oxide coatings that mixes up antimony similar to curve B among Figure 15, on transparent glass substrate, and curve B represents that thickness is reduced to 1800 dusts and has the doped tin oxide coatings that mixes up antimony of titanium dioxide external coating (EC) to pile.It is that 1/4 glistening light of waves is learned thickness that the curve B coating piles up under the 100nm.Other condition is identical with Figure 15's.

Figure 20 illustrates theoretic optical transmittance-wavelength curve A and B, and wherein, curve A represents to be configured to five layers of coating of SHLHLH, and wherein H is TiO ₂, L is a silicon-dioxide, curve B represents to have the coating heap of identical configuration, but wherein L is the stannic oxide that mixes up fluorine.Other condition is identical with Figure 15's.

The transmission of light in transparency carrier can obtain changing by the coating inorganic coating.But the inorganic coating absorb light, and can be by the thin film physics phenomenon by reflection and absorption and filtering light.Generally speaking, film refers to that thickness is 1 micron or littler film.

Automobile and building field often require the light transmission of different levels according to light wavelength.For example, the solar radiation light of filtering simultaneously outside visible spectrum is exactly very important so that the driver can see outside the car to have higher relatively transmission of visible light in automobile.Substrate can play the effect of bandpass filter, the visible light that transmission in theory equally is all, but UV in the solar spectrum and all filterings of NTR part.Use this kind glass, it is more comfortable that the passenger can feel in vehicle, and because of using littler conditioner to make vehicle that better fuel efficiency be arranged.

Usually compromise attractive in appearance, sunlight performance and the restriction of considering glass to making.The sunlight feed glass is the glass of a part of light in a kind of reflection or absorption rather than the transmitted spectrum, for example, reflects and/or absorb a part of UV spectrum and/or infrared spectra and/or visible spectrum, reduces the transmission of spectrum specific part thus.For example, the product that is colored is the sunlight feed glass, and wherein, the total content of iron is generally in the scope of about 0.5-2wt% (weight percent) in the finished product.Usually, the 20wt% at least in the finished glass in the total content of iron is preferably 30-45wt%, comprises ferrous.Usually, in glass with iron protoxide (FeO) or ferric oxide (Fe ₂O ₃) equilibrium of the iron that exists of form has direct and substantial influence to the color and the transmission properties of glass.In addition, the sunlight feed glass comprises that those reduce direct solar heat transmissivity (DSHT) and/or reduce the glass that the ultraviolet radiation transmission rate allows required visible transmission simultaneously to a certain extent.But this kind sunlight feed glass also might be secret glazing.The sunlight feed glass can reduce the problem relevant with superheated in the fine day, allows the visible light of requirement to pass through simultaneously.In addition, these glass might be kept the setting that vehicle interior is maintained secrecy.As the glass of substrate of the present invention is to have the to a certain degree glass of transmission of visible light, and perhaps this glass has transparency to a certain degree at least so that can recognize object on the opposite side by glass.This transparency is lower than secret glazing.Consider sunlight performance and attractive in appearance, current trend three types sunlight feed glass arranged.They are the SOLARGREEN that are respectively green and blue ^Glass and SOLEXTRA ^Glass.The SOLARGREEN glass substrate is the sunlight feed glass of PPG Industries Inc., and this glass has 71% LTA, 42.9% TSET and 1.65 performance rate (performance ratio).The predominant wavelength of this kind glass substrate is 512nm, and its color is described as L in the CIELAB color system ^★=88.3, a ^★=-8.7, b ^★=3.5 and C ^★=9.4.In addition, substrate hue-angle (hue angle) is 158 °.Should be appreciated that, although the color characteristic of this substrate is " green ", from its a ^★And b ^★It is faint yellow that coordinate can find out obviously that this kind glass comprises.To the manufacturing restriction and the federal regulation of visible transmission, limited the commercialization of sunlight feed glass (TSET=50%) with other outward appearance.Generally speaking the sunlight feed glass has the total solar energy transmission that is lower than 50% (TSET＜50%).The example of this kind glass is those industrial available glass or Solargreen ^Glass and Solextra ^Glass and be the glass of describing in United States Patent (USP) 5830812,5023210,4873206, all these patents draw at this and are reference.

Solargreen ^And Solextra ^The purpose of glass is that total solar energy transmission (TSET) is minimized, and its target does not lie in specific part such as the UV light in the spectrum.Recently, Japanese car industry has begun trend and has required gloss, promptly has to be lower than 10% UV optical transmittance and to keep simultaneously and TSET size like the Solargreen glassy phase.A kind of commercial version of this kind glass is the Solarblock of PPG Industries Inc. ^Glass.Its lower UV optical transmittance is owing to add more expensive additive CeO ₂Obtain.Can obtain UV transmission target and have the possibility that increases feature according to coating of the present invention, obtain the cost advantage that can compare favourably with the substrate of uncoated simultaneously, the substrate of this uncoated does not contain CeO substantially ₂

Various film coatings with certain transparency of the present invention will reduce the UV optical transmission, can also obtain simultaneously other character such as antireflection, lower TSET and/or automatically cleaning attribute and different be reflected or by the color of transmission alternatively.Various coating integrated applications can provide several character simultaneously in a coated glassy product, this can all obtain advantage on the cost He on the performance.Membrane structure described below has by different materials, preferably be made up of one to four kind of material one to five layer.Select these materials according to different characteristics.In order to utilize the physical phenomenon of film, use material with different refractivity (RI).In addition, this material should be physically and chemically is competent, and if possible, should have other character, for example can absorb the light in the solar spectrum different piece.

With regard to specific refractory power, general high refractive index only is higher than low-refraction, also is like this for low-refraction conversely.Preferably, high refractive index greater than 1.9 and low-refraction less than 1.6, medium refractive index is between 1.6-1.9.But the boundary of these scopes is not strict boundary, and extreme RI can stride across adjacent area to a certain extent in the bonding land.

The example that is used for the suitable material of high and low refractive index coating include but not limited to various metal oxides, nitride with and alloys and mixts.More the material of high refractive index comprises: zinc oxide (specific refractory power=1.90), titanium oxide (TiO ₂) (specific refractory power=2.3-2.7), CeO ₂(specific refractory power=1.95), weisspiessglanz (Sb ₂O ₅) (specific refractory power=1.71), SnO ₂, ITO (specific refractory power=1.95), Y ₂O ₃(specific refractory power=1.87), La ₂O ₃(specific refractory power=1.95), zirconium white (ZrO ₂) (specific refractory power=2.05), stannic oxide and Indium sesquioxide.And can use their alloys and mixts.The oxide compound that is mixed up has low-down specific refractory power because of the unbound electron in the material near infrared region.The stannic oxide that mixes up fluorine and/or indium has higher specific refractory power than the stannic oxide that mixes up antimony.The non-proprietary example that is used for the material of low refractive index coating can comprise silicon-dioxide SiO ₂(about 1.45), Al ₂O ₃(about 1.65), B ₂O ₃(about 1.60), silicon polymer, magnesium oxide and sodium aluminum fluoride.

Following preferred coatings is made up of four different coatings.The first layer can be titanium oxide or TiO ₂This material has very high specific refractory power and absorbs UV light, chemically is being inert and competent simultaneously, and this material has photocatalysis when with the anatase form deposit.Second material is silicon oxide or SiO ₂This material chemically is being an inert and competent equally, and low-down specific refractory power is arranged.

Most of structure described below can only be made by these two kinds of materials, but also can use two kinds of subsidiary material with peculiar property.First kind is the stannic oxide that mixes up fluorine.This kind material conducts electricity, and partly has high refractive index and partly has low-refraction at spectrographic NIR at spectrographic UV and visible light.This kind character allows this unique feature is incorporated in the design of various coatings.The 4th kind of material is the stannic oxide that mixes up antimony.Light in the whole solar spectrum of this kind absorbed, and the more important thing is, by changing depositing technics, realize control to the relative absorption under the different wave length.Thereby might adjust coating, make it to absorb more relatively visible light or UV light or NIR light.A very unique character of this kind material is that it has very high specific absorption to green glow.Be placed on the green glass by this is coated with, we can become smoked glass to this glass, thereby produce the high performance sunlight feed glass with achromaticity outward appearance.

Handle by the competent oxide coating of whole usefulness, these structures should be suitable for the tempering parts of automobile.

In this basic setup, can use other material, optionally can consider them.But these four kinds of materials can be used for making the various coatings that many optical properties have a great difference.The online float glass process that is well known to those skilled in the art (on-line float) glasswork by selecting deposition material, coating order and coat-thickness, can be used for making all these products.

All these underlying coating layers generally all can adopt with the windshield glass conductive coating similar methods described in the United States Patent (USP) 4610771 and apply, and this patent is drawn at this and is reference.This kind can utilize similar equipment to produce these new coatings on sunlight feed glass substrate at line method.Any in the art other method that is used for deposit any of these coating all can be used, and for example can use the radio frequency vacuum splashing and plating.Also can use other technology, (cathode) sputtering for example comes sputter by the CVD plasma body that sends from suitable siliceous precursor (siliceous precursor) or by gas phase pyrolysis under environmental stress specifically.

Follow-up chapters and sections are described the structure of concrete coating, the result and the sensitivity analysis of optical model in detail.Not excessive when more functionality is incorporated into coating, can not limited by the present invention, introduce the principle of various structures.

The UV barrier coat is the simplest solar control coatings of discussing at this paper, and its physics principle is a common for many other designs.

No matter whether substrate applies, the interaction of light and substrate all must be followed following formula:

A+R+T=100% formula 1

The per-cent of absorbed light (A) adds that the per-cent (R) of the light that is reflected is added by the per-cent of the light of transmission and must equal 100%.Reflect manyly more if light is coated, be absorbed so and/or will be few more by the light of transmission.For coated glass pieces, the effect of UV reflectance coating is the UV light that reflects as much as possible, is lower than 10% transmission target so that satisfy.Some UV light absorb coated and glass substrate, but most of transmission lost, and this is because obtain high-reflectivity by suitable selection coated material and thickness.But the layer more or less according to the UV absorbent properties needs of substrate.Specific examples below is discussed.

The maximum reflection that obtains by the single high refractive index layer of coating on substrate is to calculate easily, and the layer of this type is called 1/4 ripple layer (i.e. 1/4 wavelength layer).The thickness of 1/4 ripple layer calculates according to following formula:

H=λ/4n ₁Formula 2

Herein: h is a bed thickness; λ is the wavelength (design wavelength) when maximum reflection takes place; n ₁Be the specific refractory power of coating under design wavelength.

If the specific refractory power of one or more materials of coating is bigger or higher, this layer is represented with " H " so; Use " L " expression if specific refractory power is low; If specific refractory power falls between or for medium use " M " expression.The coating heap can easily be represented with this term abbreviation.For example, have 1/4 ripple antireflecting coating of medium-index materials in coating on glass, the half-wave (two 1/4 wavelength) of high refractive index is then arranged thereon, 1/4 ripple layer of low-index material is arranged thereon again, this can be expressed as SMHHL, and S refers to substrate herein.Should point out, each layer only to spectrum required part to have under the wavelength of maximum reflectivity be 1/4 wavelength.

Calculate the intensity of reflection with formula 3.

R=[(n ₁ ²-n ₀n _s)/(n ₀n _s+ n ₁ ²)] ²Formula 3

Herein: R is a reflectivity; n _sSpecific refractory power for substrate; n ₀Specific refractory power for incident medium; n ₁Specific refractory power for coating.Incident medium is substrate or the existing environment of other stepped construction, i.e. air.For in specific refractory power being coating of titanium dioxide on 1.51 the transparency carrier, its specific refractory power is 2.55 under 380 nanometers (nm) wavelength, and 1/4 wavelength thickness of coating of titanium dioxide is that 372 and reflectivity are 26.5%.This reflectivity only is coated surface.For the several examples in back, the absorption in the coating is left in the basket, but when comprising that it can be pointed out when absorbing.

The reflectivity of visible spectrum is represented by curve A among Fig. 1.Curve A can be found out from Fig. 1, and maximum reflectivity takes place under design wavelength 380nm, and reflectivity all reduces under all other wavelength of solar spectrum.

When normal incident, the reflectivity of substrate first surface is provided by following formula:

R=[(n ₀-n _s)/(n ₀+ n _s)] ²Formula 4

Herein: n ₀And n _sBe respectively the specific refractory power of incident medium and substrate.1/4 ripple layer is coated on the substrate, and it is n that generation has equivalent refractive index _1eCoated substrate, n _1eProvide by following formula:

n _1e=n ₁ ²/ n _sFormula 5

In the substrate specific refractory power of new equivalent refractive index substitution formula 4, calculate the new reflectivity of coated substrate then.This new formula is listed as follows:

R=[(n ₀-n _1e)/(n ₀+ n _1e)] ²Formula 6

Formula 6 is equivalent to formula 4.

For substrate be expressed as SH (LH) ^mThe equivalent refractive index of coating heap can calculate with following formula:

n _e=(n _H ²) ^M+1/ (n _L ²) ^mn _sFormula 7

Available then formula 6 and 7 calculates the reflectivity of the layer of any amount, and " m " is HL or the right quantity of LH in the coating heap herein.

In three layers of SHLH coating on float glass, H is a titanium dioxide, and L is a silicon-dioxide, and the equivalent refractive index that this coating has is:

n _e=(2.6 ²) ^M+1/ (1.452) ^m1.51=14.4, and reflectivity is:

R＝[(1-14.4)/(1+14.4)] ²＝75.6％

Reflectivity-wavelength curve for this coating is illustrated by curve B in Fig. 1.

Table 1 has been summed up respectively at transparent glass, sunlight feed glass SOLEX ^And SOLARGREEN ^On the exemplary embodiment of one, three and five layer of coating and the performance of prophetic examples are arranged.

[table 1]

Example	Substrate	The coating of heap substrate	Visible reflectance	Transmission of visible light	ISO UV transmissivity	Total solar energy transmission
							Exemplary embodiment A	Transparent 1	SH	28.99	69.14	43.41	69.66
Example 1	Transparent 1	SHLH	27.51	70.51	20.24	69.49
							Example 2	Transparent 1	SHLHLH	15.59	82.2	8.39	68.71
Exemplary embodiment B	Transparent 1	None	7.9	89.71	64.59	82.74
							Exemplary embodiment C	Solex glass 1	SH	28.47	62.08	20.14	45.53
Example 3	Solex glass 1	SHLH	27.11	62.94	9.03	44.86
							Example 4	Solex Glass 1	SHLHLH	15.04	73.78	3.47	44.3
Exemplary embodiment D	Solex Glass 1	None	7.37	80.5	30.73	55.32
							Exemplary embodiment E	Solargreen Glass 2	SH	28.16	56.33	12.17	35.44
Example 5	Solargreen Glass 2	SHLH	26.78	57.08	5.42	34.83
							Example 6	Solargreen Glass 2	SHLHLH	14.6	67.11	2.06	34.52
Exemplary embodiment F	Solargreen Glass 2	None	6.84	73.16	19.37	43.54

The S=substrate

H=TiO ₂, 1/4 ripple layer under 380nm

L=SiO ₂, 1/4 ripple layer under 380nm

The 1=substrate thickness is 4m

The 2=substrate thickness is 3.6m

Consider constituent element, deposit mode and the coat-thickness of coated component, with manner known in the art research silicon-dioxide and the optical constant of other material for wavelength.Reflectance curve is made of TFCalc among the figure, and TFCalc is a kind of business software that film calculates that is used for of software spectrum company.

Antireflecting UV reflection

The feature of above-mentioned simple SHLH configuration is that higher relatively visible reflectance is arranged.When this kind approach was applied to before coated its transmission of visible light near the sunlight feed glass of 65%-70% scope, high-reflectivity limited the application of this kind approach.For example ought be coated to the SOLARGREEN that is used for windshield glass ^During glass, high-reflectivity reduces to transmission of visible light and is lower than 70% restriction.

Top coating half wave layer by at the SHLH heap can alleviate this kind restriction.Half wave layer is a dead level under design wavelength, because it is the optics visible under design wavelength.Therefore, under design wavelength, substrate is piled up the identical effect with heap SHLH with the SHLHLL coating, and UV filtering performance does not change.For the situation of design wavelength in UV, the silicon-dioxide LL half-wavelength at top is 1/4 wavelength in visible spectrum.This layer just reduces layer as the reflectivity of visible spectrum.Design wavelength and/or bed thickness then can require optimization according to required UV reflectivity and visible transmission.SHLH and SHLHLL coating are as shown in Figure 2.These coatings have the design wavelength of 330nm.This design wavelength minimizes ISO UV, simultaneously for 3.6mmSolargreen ^Glass keeps transmission of visible light to be higher than 70%.Curve B represents to pile SHLHLL, and curve A is heap SHLH.

It is right to add auxiliary LH between top H layer and LL layer, so that further reduce the UV light filtering character of coating heap.This kind is at Solargreen ^The visible reflectance for various design wavelengths of heap on glass is as shown in table 2.From then on table can be found out, selects suitable design wavelength that the character of resulting coating is had obvious effects.As noted above, these prophetic examples TFCalc software development.

[table 2]

Substrate	Substrate thickness	The coating heap	Design wavelength	Visible reflectance	Transmission of visible light	ISO UV transmissivity
							Solargreen	3.6mm	SHLHLL	220nm	4.04	75.41	18.54
Solargreen	3.6mm	SHLHLL	230nm	3.79	75.58	18.35
							Solargreen	3.6mm	SHLHLL	240nm	3.86	75.5	17.95
Solargreen	3.6mm	SHLHLL	250nm	4.2	75.21	17.26
							Solargreen	3.6mm	SHLHLL	260nm	4.73	74.78	16.23
Solargreen	3.6mm	SHLHLL	270nm	5.37	74.26	14.93
							Solargreen	3.6mm	SHLHLL	280nm	6.06	73.71	13.51
Solargreen	3.6mm	SHLHLL	290nm	6.72	73.19	12.12
							Solargreen	3.6mm	SHLHLL	300nm	7.31	72.73	10.87
Solargreen	3.6mm	SHLHLL	310nm	7.82	72.33	9.81
							Solargreen	3.6mm	SHLHLL	320nm	8.26	72	8.96
Solargreen	3.6mm	SHLHLL	330nm	8.67	71.7	8.33
							Solargreen	3.6mm	SHLHLL	340nm	9.12	71.35	7.87
Solargreen	3.6mm	SHLHLL	350nm	9.71	70.88	7.58
							Solargreen	3.6mm	SHLHLL	360nm	10.55	70.21	7.43
Solargreen	3.6mm	SHLHLL	370nm	11.73	69.25	7.42
							Solargreen	3.6mm	SHLHLL	380nm	13.35	67.93	7.54
Solargreen	3.6mm	No coating		6.84	73.16	19.37

The example of back is exemplary in table 2, and other then is a predictability.

As can be seen from Figure 2, the reflectivity of two kinds of coatings keeps identical down at design wavelength (330nm), and reflectance curve all changes basically at the spectrum rest part.Because the silicon-dioxide half-wave is as antireflection (" AR ") layer, it keeps or increases visible optical transmission, makes this UV filtering coating can be applicable to more substrate thus.If the transmission of light in coated substrate increases, so adjustable integral basis plate is kept its visible transmission requirement simultaneously to absorb more solar radiation.The glass ingredient of sunlight feed glass can change, thus TSET be reduced to about 40% but evenly the visible transmission of character AR coating increase.

Above-mentioned example uses the optical constant of the coating that does not have uptake factor, proves the influence of interference coatings to the glass optical property easily.But in fact, coating absorbs a part of light, has the uptake factor of non-zero thus.Above several examples will repeat with the coating with different optical constant, with the influence of demonstration absorption to the coating transmitted spectrum.In fact, can select suitable material and project organization to satisfy the required whole attributes of coated glass best.

Fig. 3 is illustrated in TiO ₂Be with or without the transmission curve of the SLHL heap of absorption in the layer.At SiO ₂All do not have in the layer to absorb.Curve A has absorption to curve B less than absorbing.

Stop UV and NIR

Can realize by being different from above-mentioned alternate manner coated substrate increase sunlight control or reduction TSET.The TSET that this section is described the coated substrate of several reductions reduces the approach of its UV transmission simultaneously.

A.HLH

The example of front illustrates and how to add half wave layer and do not change its performance under design wavelength in the table 2.Therefore, be that each layer interpolation half wave layer of the initial SHLH heap of 350nm obtains piling S3H3L3H (HHHLLLHHH) to design wavelength.This coating serves the same role under the 350nm design wavelength, but the SHLH heap becomes near 1050nm now.Maximum reflectivity can accurately not take place under 1050nm, and this is because the specific refractory power of coating reduces under longer wavelength.Therefore peak value is shifted to shorter wavelength, promptly is positioned at the nearly IR of spectrographic (" NIR ") district.In this way, we obtain the coating that reflects now under two design wavelengths.This example uses the TiO that considers absorption ₂Do not consider the SiO that absorbs ₂, and coating is on the 4.0mm transparent glass.Its curve is seen curve A among Fig. 4.

B.HLHL/2

Reflection strength in the visible spectrum can change by 1/4 ripple in the coating visible spectrum.This layer can be 1/8 ripple in the NIR under the 1050nm and 1.5 ripples in the UV under the 350nm.Reflection strength among the NIR can consider that low visible light reflectivity and high visible light transmissivity reduce slightly because of compromise.The curve of this coating is shown in curve B among Fig. 4.Reflectivity for coating on the transparent glass drops to about 6% from about 17%.Curve B has SiO ₂Top layer and curve A does not have.

C. other character

Two embodiment of front relate to a kind of three layers of coating, the light in this coating reflection spectrum UV and the NIR zone.The front points out that intensity of reflected light is the function of the quantity of high low-refraction alternating layer.More layer means higher reflectivity.But when adding more layer along with past bireflectance coating, total thickness just has been a problem: cost increases, and need more applicator production coating in the float glass line environment.

Can increase the intensity of UV reflection, and not increase the total thickness of heap or do not sacrifice the intensity that NIR reflects.This can finish by replace in three minutes of inner silicon dioxide layer a part with the stannic oxide that mixes up fluorine.But the middle layer has become several layers combination conversely speaking.Mix up the SnO of fluorine ₂, as most of transparent conductive oxides, have unique character: promptly in UV and visible spectrum, have high refractive index and lower specific refractory power is arranged in NIR.Coating is S3HLHL3H in UV, and is SHLH in NIR.This coating is five layers of coating and be reduced to three layers of coating in NIR in UV and visible light.The reflectivity of this coating and S3H3L3H has this kind coating of 1/4 visible wavelength silicon dioxide layer and S3H3L3HLL as shown in Figure 6 as shown in Figure 5.Curve among these figure " B " is for being added with the design of the stannic oxide that mixes up fluorine, and curve " A " does not then have.

Transparent conductive oxide (" TCO ")

Transparent conductive oxide (" TCO ") can be used for having in the HLH heap of above-mentioned high-index material, to be increased in the reflection of light among the nearly IR, this is to cause it to have low-refraction in the NIR zone because of the unbound electron of this oxide compound and the flowability in lattice thereof.Thereby except being used for above-mentioned example, TCO also can be used for comprehensively stopping the design of UV/NIR.Curve A illustrates the reflectance peak that obtains from the SHLH heap among Fig. 7, TiO in the SHLH heap ₂The stannic oxide that mixes up fluorine for high refractive index layer is low-index layer.

Curve A can be found out from Fig. 7, and it is about 58% that coating piles up 1 micron following reflectivity of design wavelength.Specific refractory power in the visible region also is different, and this color that produces interference peak and be reflected.This characteristic is considered to unfavorable, keeps reflectance peak and make the mode of reflection minimized can pass through two kinds of methods simultaneously, promptly on pile or below a kind of acquisition the in the coating.Key is to increase the layer that changes the visible light reflectivity properties and significantly do not reduce the NIR peak value.A kind of method of accomplishing this point is to be increased in the visible region optically-active and optically inactive coating in the NIR zone.Transparent conductive oxide (" TCO ") is applicable to this purpose.As mentioned above, with TiO ₂Compare, the specific refractory power of TCO is lower and be medium in visible spectrum in NIR.When coating below SHLH heap, we can obtain the heap of following configuration: substrate, be respectively the layer and the SL/3HLH in NIR spectrum of medium refractive index, high refractive index, medium refractive index and high refractive index in visible light.This coating is not used code name SMHMH, because these layers are not the optical thicknesses of 1/4 wavelength in the visible region.Shown in curve B among Fig. 7, the L/3 layer is optically inactive, at this, the curve and the curve A of this heap is compared.Curve A is a normal line, and is thick line corresponding to the curve B of the heap that contains L/3.Can find out that the NIR peak value is geostationary, the visible light peak value is by big lossy simultaneously.The TSET of this heap is about 57%, and transmission of visible light is about 76%.Because long wavelength's light is reflected by transparent conductive oxide, this heap also has lower radiation.As previously mentioned, along with the LH that increases coating is right, reflectance peak can obtain increasing.

It is that to be increased in visible light and the NIR spectrum all be the coating of medium refractive index that another kind makes the mode of the color relax that is reflected.Can reckon with that the medium refractive index layer between the substrate and first high refractive index layer can weaken the NIR reflection, strengthen the required normal HLH order of reflection because this can upset.Surprisingly, the peak value of reflection strength is not lowered, but this peak value only in wavelength direction slight skew takes place.By adjusting other layer in the heap, this peak value can be retracted original position.The color that this result allows to pile obtains adjusting, and does not sacrifice the NIR reflecting properties simultaneously.The color that relatively do not have Fig. 8 suppresses the coating heap of layer and has the coating heap of SM/2HLH heap configuration, and the former is represented by curve A, that is the curve A among Fig. 7.Can find out that the visible reflectance peak value is lowered, a little a bit skew of NIR peak value simultaneously.

Also has a kind of mode of color relax that makes for below the coating heap, increasing the refractive index gradient change layer.This layer generally has the specific refractory power of increase (or minimizing) along with the thickness increase of rete.The color that the color of this type suppresses for the single coating of inhibition is well-known (see United States Patent (USP) 5356718,5599387, drawing at this is reference).Can the color of this type suppress also not obtain check for being applied to the color that suppresses the coating heap, and more importantly be that it does not also obtain check to the influence of the NIR reflection of this heap.Refractive index gradient changes coating both can have been suppressed color and also can improve performance in the HLH heap in some cases.The graded layer that uses in these examples is made into ten layers of coating representing with G, and wherein every layer is that 10nm is thick, and its specific refractory power changes to 2.0 of graded layer top from 1.55 of glass interface.Its reflectance curve is shown in Figure 9, and once more with Fig. 7 in the SHLH heap shown in the curve A compare.Our heap is SGHLH now.For the curve B of expression graded layer, peak reflectivity only descends slightly, and is offset in wavelength direction, and visible reflectance then significantly reduces.

Because the graded layer produces the interface higher than glass interface, can further increase reflectance peak now, and, another stannic oxide layer that mixes up fluorine that in the middle of refractive index gradient change layer and first high refractive index layer, increases can be now optically-active and can cause reflectance peak to increase.This heap is SGLHLH.Its color still can decay but performance can improve.This heap is very suitable when the lower radiation of needs.Reflectance spectrum shown in Figure 10, and with Fig. 7 in curve A compare.

Therefore the doped tin oxide coatings that mixes up fluorine also absorbs a part of NIR light, is unusual ideal for the application of sunlight control.They help to reduce its transmission in reflection and absorption of N IR light time.

And be to learn the color of high/low folding rate layer to can be used for decaying and being reflected of thickness much smaller than 1/4 glistening light of waves unexpectedly.They also can obviously not influence the NIR reflection.

As previously mentioned, increase layer and can cause reflection to reduce on heap, this method also is suitable at this.By on coating heap and below increase layer, can influence the color that is reflected and make the intensity reduction.This heap has medium refractive index, height, medium, height is low-refraction (MHMHL) then.The heap of resulting coating shown in Figure 11, and compare with curve A among Fig. 7.Visual intensity is weakened greatly and color is achromatic.The intensity of reflectance peak has some skews, but this can correct by the thickness of adjusting the HLH layer.

As mentioned above, for two NIR/UV filtering coatings, SiO ₂Can one be used from low-index layer with the TCO combination.Have substrate, TiO shown in Figure 12 ₂, SiO ₂, mix up stannic oxide, the SiO of fluorine ₂, mix up the stannic oxide of fluorine and contain SiO ₂TiO with the stannic oxide that mixes up fluorine ₂Heap (SHLMLMH), this comprehensive optical thickness that piles up among the NIR is 1/4 wavelength, and compares with curve A among Fig. 7.Can see from Figure 12, reflectance peak is enhanced by this multilayer low-refraction 1/4 ripple approach.Be also pointed out that the visible reflectance peak value is lowered a little.

The new function of utilizing this multilayer low-index layer approach and visible reflectance spectrum being decayed can be used for relevant visible reflectance spectrum, the color that is reflected is weakened keep the NIR reflectance peak simultaneously.For example, as shown in figure 13, have substrate, TiO ₂, SiO ₂, SnO2:F and TiO ₂Heap (SHLMH) do not have the color that is reflected and its reflection peak strengthens.Comprise the reflectivity curve A among Fig. 7 among Figure 13, and as a comparison.In visible light be optically-active and in NIR spectrum the layer combination for low-refraction can be used for obtaining the required any visible light optical effect of planner, rather than only be used for color simply and suppress.

In stannic oxide, can obtain electroconductibility to mix up level adding antimony.Along with antimony content increases, electroconductibility reduces and coating begins significantly to absorb solar radiation.Figure 14 illustrates several sunlights that mix up the doped tin oxide coatings of antimony and absorbs.List the parameter of chemical vapour deposition (" the CVD ") technology of producing these coatings in the table 3.Certainly also can adopt other known depositing technics, as the pyrolysis coating technology with resemble the dash coat technology of MSVD magnetron sputtering vacuum deposition etc.Spraying coating is made into the mixture of 5wt%.

[table 3] (SLM is a standard liters per minute)

Test piece number (Test pc No.)	The Fahrenheit temperature of glass (F)	MBTC concentration (mol%)	Water concentration (mol%)	Air-flow SLM	The delivery ratio of gas (%)	Thickness of glass (MM)	Linear velocity (inch per minute clock)
								1	1000	0.5	0.5	55	115	4	50
2	1200	0.5	0.5	55	115	4	50
								4	1200	0.5	0.0	55	115	4	50
6	1200	0.1	0.5	55	115	4	50
								8	1200	0.1	0.0	55	115	4	50
9	1000	0.5	1.0	55	115	4	50
								10	1000	1.0	0.5	55	115	4	50
11	1000	1.0	1.0	55	115	4	50

This mixture is for there to be butter of antimony in monobutyl-tin-trichloride (MBTC), and this mixture hand spray is to the transparent glass substrate that is heated to about 1150 Fahrenheit temperature.Antimony adds with the amount of the 20wt% constant with respect to MBTC, carries out CVD test 1-11.Applicator is provided with central authorities' inlet in the upstream, be provided with outlet in the downstream.The width of the area of application is 4 inches, and the wire length between the outlet is 5 inches.Air is as vector gas.

In table 3, coating 4 and the 8 NIR light ratio visible lights that absorb are more, make that these coatings can be applicable to sunlight control well when the needs high visible light transmissivity.Coating 2 and 6 has the peak absorption rate under about 550nm.These coatings are very suitable for weakening Solex ^Glass and Solargreen ^The green of glass.The visible light that coating 10 absorbs is more than NIR light, and the light in the solar spectrum that coating 1 absorbs is constant substantially, and coating 9 and 11 absorbs a large amount of UV light.

These coatings can be by glazing in annealing and Annealed Strip, and its tangible result is that fastness or color can not change when coated glass heats.The outward appearance of coating is identical before and after thermal treatment preferably with performance.Whether the doped tin oxide coatings that mixes up antimony that is used for the research of this project can change when heating, depends on its deposition parameters.The character of various samples and some character because of how thermal treatment changes are all listed in table 4.The sample that one H is arranged after the numbering is the sample after the thermal treatment.

[table 4] (A part)

Average film		The mobile MMR H-50 of Hall (cm 2/Vs)	Hall carrier concn MMRH-50 ( *E20 live/cm 3) 1	Hall surface resistivity MMRH-50 (ohm/sq.)	Unweighted specific absorption
												UV-visible light 300-700nm	UV-visible light 300-2500nm
Sample	Thickness	Mean value	Mean value	Mean value
							1 2 4 8 10 11 1H 2H 4H 8H 10H 11H	665 795 310 153 675 879	7.52 0.72 0.54 0.54 6.70 4.90 1.02 0.47 0.42 0.35 0.04 8.35	2.35 1.49 4.57 4.95 6.03 9.48 1.07 2.23 4.89 4.84 3.41 1.92	3.E+05 7.E+03 9.E+03 2.E+04 2.E+06 6.E+05 3.E+05 8.E+03 1.E+04 2.E+04 2.E+05 2.E+05	0.159 0.307 0.173 0.142 0.203 0.254	0.191 0.298 0.256 0.211 0.214 0.224

¹=power (E) * 10 ²⁰Live/cm ³

[table 4] (B part)

Sample	T	Tx	Ty	R1Y	R1x	R1y	R2Y	R2x	R2y
											1	67.7	0.312	0.312	21.0	0.299	0.307	17.6	0.294	0.303
2	50.2	0.295	0.298	21.8	0.333	0.337	16.3	0.324	0.327
										4	76.5	0.306	0.316	12.2	0.294	0.297	09.2	0.280	0.284
8	85.0	0.307	0.317	09.2	0.301	0.308	08.0	0.295	0.302
										10	76.0	0.313	0.321	16.0	0.294	0.302	13.4	0.295	0.305
11	67.9	0.309	0.316	21.3	0.318	0.330	17.6	0.318	0.333
										1H	70.1	0.312	0.320	19.2	0.298	0.306	16.6	0.293	0.303
2H	52.5	0.296	0.301	21.5	0.326	0.330	16.0	0.315	0.318
										4H	76.7	0.306	0.316	12.2	0.294	0.297	09.2	0.280	0.284
8H	85.1	0.307	0.317	09.2	0.301	0.308	08.0	0.295	0.302
										10H	72.1	0.312	0.320	18.3	0.295	0.304	16.1	0.291	0.302
11H	69.3	0.309	0.317	20.5	0.313	0.325	16.1	0.309	0.326

[table 4] (C part)

Sample	ΔT	ΔR1	ΔR2	Macadam T	Macadam R1	Macadam R2
								1	2.38	-1.78	-0.96	3.21	4.98	3.32
2	2.25	-0.32	-0.30	3.79	5.16	6.56
							4	0.14	-0.02	0.01	0.26	0.10	0.19
8	0.12	-0.07	-0.02	0.18	0.31	0.15
							10	-3.9	2.32	2.68	4.74	7.38	9.96
11	1.34	-0.81	0.49	1.90	4.48	6.94

R1 is the reflectivity on the coated side of glass, and R2 is the reflectivity on the not coated side of glass, and T is an optical transmission.

H sample in the table 4 is exposed to reaches about 4 minutes under 1200 Fahrenheit temperature, then cool to room temperature.The optical constant of sample 8 before thermal treatment is shown in the following table 5.These optical constants are used in following other example.

[table 5]

Wavelength	Specific refractory power	Virtual specific refractory power
			350.0 360.0 370.0 380.0 390.0 400.0 410.0 420.0 430.0 440.0 450.0 460.0 470.0 480.0 490.0 500.0 510.0 520.0 530.0 540.0 550.0 560.0 570.0 580.0 590.0 600.0 610.0 620.0 630.0 640.0 650.0 660.0 670.0 680.0 690.0 700.0 710.0 720.0 730.0 740.0 750.0 760.0 770.0 780.0 790.0 800.0	1.89450 1.88140 1.86920 1.85800 1.84750 1.83770 1.82850 1.81990 1.81180 1.80420 1.79700 1.79020 1.78370 1.77760 1.77170 1.76610 1.76070 1.75550 1.75060 1.74580 1.74120 1.73670 1.73240 1.72820 1.72420 1.72020 1.71630 1.71250 1.70880 1.70520 1.70160 1.69810 1.69470 1.69120 1.68790 1.68460 1.68130 1.67800 1.67480 1.67150 1.66830 1.66520 1.66200 1.65880 1.65570 1.65260	0.09050 0.07227 0.05884 0.04934 0.04301 0.03929 0.03770 0.03783 0.03938 0.04209 0.04573 0.05013 0.05514 0.06065 0.06655 0.07276 0.07922 0.08586 0.09265 0.09954 0.10650 0.11351 0.12054 0.12759 0.13463 0.14165 0.14865 0.15563 0.16256 0.16947 0.17633 0.18315 0.18993 0.19667 0.20337 0.21003 0.21665 0.22323 0.22979 0.23631 0.24280 0.24926 0.25570 0.26212 0.26852 0.27491

(continuing)

Wavelength	Specific refractory power	Virtual specific refractory power
			810.0 820.0 830.0 840.0 850.0 860.0 870.0 880.0 890.0 900.0 910.0 920.0 930.0 940.0 950.0 960.0 970.0 980.0 990.0 1000.0 1010.0 1020.0 1030.0 1040.0 1050.0 1060.0 1070.0 1080.0 1090.0 1100.0 1110.0 1120.0 1130.0 1140.0 1150.0 1160.0 1170.0 1180.0 1190.0 1200.0 1210.0 1220.0 1230.0 1240.0 1250.0 1260.0 1270.0 1280.0 1290.0 1300.0 1310.0 1320.0 1330.0 1340.0 1350.0 1360.0 1370.0 1380.0 1390.0	1.64940 1.64630 1.64310 1.64000 1.63680 1.63370 1.63050 1.62730 1.62410 1.62090 1.61770 1.61450 1.61120 1.60790 1.60460 1.60130 1.59800 1.59460 1.59120 1.58780 1.58440 1.58090 1.57740 1.57390 1.57040 1.56680 1.56320 1.55950 1.55580 1.55210 1.54840 1.54460 1.54080 1.53700 1.53310 1.52920 1.52520 1.52120 1.51720 1.51310 1.50900 1.50480 1.50070 1.49640 1.49220 1.48790 1.48350 1.47910 1.47470 1.47020 1.46570 1.46110 1.45650 1.45180 1.44710 1.44240 1.43760 1.43280 1.42790	0.28128 0.28764 0.29399 0.30033 0.30668 0.31302 0.31936 0.32571 0.33206 0.33842 0.34480 0.35118 0.35759 0.36401 0.37045 0.37691 0.38339 0.38990 0.39644 0.40301 0.40961 0.41624 0.42290 0.42960 0.43634 0.44311 0.44993 0.45679 0.46369 0.47064 0.47763 0.48467 0.49175 0.49889 0.50608 0.51332 0.52061 0.52796 0.53536 0.54282 0.55033 0.55791 0.56554 0.57324 0.58099 0.58881 0.59669 0.60463 0.61264 0.62072 0.62886 0.63707 0.64534 0.65369 0.66210 0.67058 0.67914 0.68777 0.69647

(continuing)

Wavelength	Specific refractory power	Virtual specific refractory power
			1400.0 1410.0 1420.0 1430.0 1440.0 1450.0 1460.0 1470.0 1480.0 1490.0 1500.0 1510.0 1520.0 1530.0 1540.0 1550.0 1560.0 1570.0 1580.0 1590.0 1600.0 1610.0 1620.0 1630.0 1640.0 1650.0 1660.0 1670.0 1680.0 1690.0 1700.0 1710.0 1720.0 1730.0 1740.0 1750.0 1760.0 1770.0 1780.0 1790.0 1800.0 1810.0 1820.0 1830.0 1840.0 1850.0 1860.0 1870.0 1880.0 1890.0	1.42300 1.41800 1.41300 1.40790 1.40280 1.39760 1.39240 1.38720 1.38190 1.37650 1.37110 1.36560 1.36010 1.35460 1.34900 1.34330 1.33760 1.33190 1.32610 1.32020 1.31430 1.30830 1.30230 1.29630 1.29020 1.28400 1.27780 1.27150 1.26520 1.25880 1.25230 1.24580 1.23930 1.23270 1.22600 1.21930 1.21260 1.20580 1.19890 1.19190 1.18500 1.17790 1.17080 1.16370 1.15650 1.14920 1.14190 1.13450 1.12700 1.11950	0.70524 0.71408 0.72300 0.73200 0.74107 0.75022 0.75944 0.76874 0.77812 0.78758 0.79712 0.80674 0.81643 0.82621 0.83607 0.84601 0.85604 0.86614 0.87633 0.88661 0.89697 0.90741 0.91794 0.92855 0.93926 0.95004 0.96092 0.97188 0.98293 0.99407 1.00530 1.01660 1.02800 1.03950 1.05110 1.06280 1.07460 1.08640 1.09840 1.11040 1.12260 1.13480 1.14720 1.15960 1.17210 1.18470 1.19740 1.21020 1.22310 1.23610

The NIR reverberator that more than illustrates helps to control the transmission of sunlight from window.Sunlight is the multiwalled function perhaps that has than large population's thickness by the amount of filtering.Need many layers further to reduce the transmission that light passes glass.Be coated with optionally or absorption of N IR sunlight and the coating of non-visible light helps to make good sunlight control heap preferentially.The stannic oxide that individual layer with above-mentioned optical property mixes up antimony has about 69% transmission of visible light and 58% TSET when thickness is 800 dusts.Figure 15 illustrates transmission curve, and with Fig. 7 in curve A compare.This coating does not have so high transmissivity in the visible region but its TSET is similar.When not needing the ratio of higher visible light-TSET, or the transmission of passing window when light needs when low, and when for example needing to weaken high light, it is reasonable increasing the antimony layer so in heap.The stannic oxide layer that mixes up antimony can use with the stannic oxide that mixes up fluorine or other TCO, to obtain low-E and to reduce transmission.Figure 16 illustrates the graded layer and mixes up the stannic oxide of antimony and mix up the theoretic light transmission of the doped tin oxide coatings of fluorine.TSET drops to 51%, and visible transmission is about 69%.For this design, can by change mix up antimony stannic oxide layer thickness or change the concentration of antimony in the coating, change TSET and visible transmission.

Statutory regulation is just promoting the raising of window performance.In U.S. south, be to have about 0.45 concealment coefficient for the new capability target of window.This available TSET of about 37% realizes.Mix up the thickness of the stannic oxide layer of antimony by increase, can change the described coating of Figure 16 to reach this target.The transmission curve of this coating is shown in curve A among Figure 17.

This coating has about 52% transmission of visible light and about 37% TSET.The doped tin oxide coatings that mixes up fluorine as top layer can make the radiant ratio of this coating be lower than 0.35.The thickness of graded layer is 800 dusts, and the thickness that mixes up the stannic oxide of antimony is 1800 dusts, and the thickness that mixes up the doped tin oxide coatings of fluorine is 1800 dusts.

Based on the above discussion, by at stannic oxide graded, that mix up antimony and mix up on the top of stannic oxide of fluorine coating such as TiO ₂1/4 wavelength and high refractive index layer, can further reduce the TSET of this coating.TSET drops to 32.5% but visible transmission only drops to 51%.These have or do not have TiO ₂The transmission curve of the heap of layer is illustrated by curve B and A respectively in Figure 17.

If do not require low-E for coating, the stannic oxide or other the suitable transparent conductive oxide that mix up fluorine so can be cancelled only remaining graded layer, the stannic oxide that mixes up antimony and TiO ₂The transmission curve of this coating is shown in Figure 18, and compares with the coating with the stannic oxide that mixes up fluorine.

The doped tin oxide coatings that mixes up antimony that 2100 dusts on the transparent glass are thick has 49% transmission of visible light and about 37% TSET.Be increased under the 1000nm is the TiO of 1/4 wavelength optical thickness ₂Layer can be reduced to 1800 dusts to the thickness of the stannic oxide that mixes up antimony.TSET remains unchanged, but transmission of visible light is increased to 54%.Article two, curve is all shown in Figure 19.Thick line is for having TiO ₂The stannic oxide that mixes up antimony of layer.

To TiO ₂Or high refractive index layer suppresses layer with respect to the color of graded and the position of mixing up the stannic oxide of antimony and mixing up the stannic oxide layer of fluorine is studied.In all cases, the refractive index gradient change layer on glass all be the first layer.Heap configuration abbreviation is as follows: the S-substrate; The color that the refractive index gradient that the G-800 dust is thick changes suppresses layer; The stannic oxide that mixes up fluorine that the Sn-1600 dust is thick; The TiO that the Ti-1100 dust is thick ₂Layer; And the thick stannic oxide that mixes up antimony of Sb-1800 dust.Its result lists in table 6.Increase TiO ₂Or high refractive index layer can improve TSET in all cases.

[table 6]

Example #	Heap	Transmission of visible light	TSET
					1	SGSbSnTi	50.6	32.4
2	SGSbTiSn	50.9	35.9
				3	SGTiSbSn	52.2	35.1
4	SGTiSnSb	51.8	35.3
				5	SGSnTiSb	51.5	36.0
6	SGSnSbTi	50.3	32.4
				7	SGSnSb	51.4	36.8
8	SGSbSn	51.8	36.9

Make two five layers of different coatings, with expression to hour obtain the demand of the absorption layer of low TSET at coat-thickness.Curve A is five layers of coating with SHLHLH configuration, wherein, and TiO ₂As high refractive index layer, silicon-dioxide is as low-index layer.Curve B has identical configuration, but uses F:SnO ₂As low-index layer.Comprise SiO ₂The total thickness of design be about 6747 and be preferably 6747 dusts that it has the TSET that is about and is preferably 60% and has the transmission of visible light that is about and is preferably 85%.Total thickness with design of the stannic oxide that mixes up fluorine is about and is preferably 6461 dusts, and it has the TSET that is about and is preferably 50% and has the visible transmission that is about and is preferably 71.1%.Obviously, increase supplementary layer and can reduce the NIR transmission, but this approach is owing to there are many thick-layers, cost is too high and can't produce.Even increase auxiliary stannic oxide and the TiO that mixes up fluorine ₂Layer is right, and coat-thickness increases by 2700 dusts, only can make TSET reduce 5% and be cost to lose 3.5% transmission of visible light.Clearly, the novel stannic oxide that mixes up antimony described herein is preferred for reach required TSET with minimum cover thickness.

A. pigment

Below at length check two specific exampless.First kind of situation is for sheltering Solex ^Glass or Solargreen ^Glass green and be glass transition gray coating.At this, the thin layer that comprises the stannic oxide that mixes up antimony is coated to glass or coated on glass.Thickness increase along with coating can be moved on to grey from green by the color of transmission, if coating increases abundantly, can be moved on to scarlet by the color of transmission.For through heat treated coating, can be offset to a certain extent by transmission and color that be reflected.

The sunlight control and the antireflection of windshield glass

Along with the installation angle increase of windshield glass, reflectivity increases.For Solargreen ^Glass, when installation angle was about 65 °, the reflectivity of antireflection (AR) coating can be reduced to about 12-13% from 18%.These traditional AR coatings can not get any other sunlight control character, but the visible transmission increase that causes because of AR character can be used for making the substrate deepening and TSET is reduced.The alternative route of AR can be used for further reducing TSET, has similar AR performance for traditional design simultaneously.This alternative route need not change the substrate composition can obtain lower TSET.The above-mentioned UV/NIR coating that has the silicon-dioxide of 1/4 wavelength at the top is used as the basis (being adjusted into SHLHL/2 for NIR) of this application.Along with installation angle increases, the optical thickness of coating reduces.The physical thickness that can increase layer is to compensate this influence.Reflectivity is reduced to 13%, and TSET is calculated as about 37%.

The application of these solar control coatings provides the unique chance TSET with further reduction windshield glass.If the AR coating is optional, the sunlight reflection can be set in the windshield glass interlayer.Can imagine that two coatings all have one and be adjusted to the different wavelength of reflection at each interlayer, all can be reduced to TSET and be lower than 37%, keep the target visible transmission simultaneously.Also can be described in United States Patent (USP), the AR coating is coated to Sungate ^In the intraformational bed of windshield glass.The NIR reverberator character of this coating further improves the performance of this product, has antireflective property simultaneously.

Automatically cleaning character

When titanium dioxide with the anatase form deposit and when being exposed in the UV light it to become be self-cleaning.Titanium dioxide can be used as high refractive index layer in these designs.This can make this design obtain automatically cleaning character, strengthens sunlight control character simultaneously.These automatic cleaning coatings can apply according to the PCT application WO98/41480 that published on September 24th, 1998, and this application is drawn at this and is reference.

NIR with coloured coating

Use for automobile, transition metal oxide can be used for changing that glass is reflected and by the color of transmission.These coatings can provide the color gamut of broad, but the TSET of coated glass can improve.This can be by obtaining the color gamut of sunlight control and broad in conjunction with transition metal oxide in above-mentioned design.

Transition metal oxide with high refractive index can be used as high refractive index layer in these designs.If color is too strong when only using transition metal oxide, transition metal oxide can be only as a high refractive index layer so, or even as the part of high refractive index layer.Scheme as an alternative, the colour transition metal oxide can together use with the achromaticity oxide compound, and the color of coating is weakened.Use in these technology any, not only can obtain sunlight control but also the color gamut of broad is arranged.For different high refractive index layers even different color materials can be arranged, make the planner more selection can be arranged to control the color of coated glass.

Claims (37)

1. multilayer coated workpiece, comprising:

A) transparency carrier of from the group that comprises transparent glass, stained glass, sunlight feed glass and stained glass, selecting;

B) comprise first inorganic coating of metal, this coating has visual clarity and have the specific refractory power of selecting from the group that comprises high and low-refraction;

C) comprise second inorganic coating of metal, this coating has visual clarity and has and the opposite specific refractory power of the first coating specific refractory power;

D) comprise the 3rd inorganic coating of metal, this coating has visual clarity and has specific refractory power in the ranges of indices of refraction of first coating.

2. workpiece as claimed in claim 1 wherein, has the low-refraction height of another coating of refractive index ratio of the coating of high refractive index; And the high refractive index of refractive index ratio high refractive index coating of coating with low-refraction is low.

3. workpiece as claimed in claim 1, wherein, the specific refractory power of coating with high refractive index is greater than about 1.75; And the specific refractory power of coating with low-refraction is less than about 1.75.

4. workpiece as claimed in claim 1, wherein, the specific refractory power of coating with high refractive index is greater than 1.9; And the specific refractory power of coating with low-refraction is less than 1.6.

5. workpiece as claimed in claim 1, wherein, first coating is selected from titanium dioxide and silicon-dioxide; Second coating is a silicon-dioxide when first coating is titanium dioxide, and second coating is a titanium dioxide when first coating is silicon-dioxide; The 3rd coating is identical with first coating.

6. workpiece as claimed in claim 5, wherein, this workpiece has the transparent conductive oxide as the middle(-)third part of inner silica dioxide coating, thereby has the middle layer that comprises that several coatings are combined, therefore, transparent conductive oxide provides high refractive index but low-refraction is provided in NIR in UV and visible light, obtain to pile five layers of coatings heap that are configured to S3HLHL3H and pile three layers of coatings heap that are configured to SHLH in UV in NIR; This coating becomes five layers of coating heap effectively in UV and visible light, but is reduced to three layers of coating in NIR, thereby causes the reflection strength of UV to increase but do not increase the total thickness of coating heap, and the reflection strength of not sacrificing NIR.

7. coated multilayer workpiece as claimed in claim 1, wherein, the NIR that coating absorbs is more than visible light.

8. coated multilayer workpiece as claimed in claim 1, wherein, NIR part and visible light in the spectrum that coating absorbs partly equate.

9. coated multilayer workpiece as claimed in claim 1, wherein, the visible light that coating absorbs is more than NIR.

10. coated multilayer workpiece as claimed in claim 1, wherein, at least one coating has the stannic oxide that mixes up antimony, and the concentration of antimony is doping concentration, and light absorbing coat-thickness is about 500 nanometers, changes the color of green substrate transmission thus.

11. workpiece as claimed in claim 1, wherein, the material of coating with high refractive index UV and visible region in spectrum have high refractive index, and the NIR zone has low-refraction in spectrum.

12. workpiece as claimed in claim 1, wherein, specific refractory power is from the stannic oxide that mixes up fluorine.

13. workpiece as claimed in claim 1, wherein, this workpiece has the 4th coating that absorbs all light in the whole solar spectrum, adjust this coating is relatively more selected its absorption from the group that comprises visible light, UV light and NIR light light, the relative absorption of control different wave length by changing depositing technics.

14. workpiece as claimed in claim 13, wherein, the 4th coating is to mix up the stannic oxide of antimony.

15. workpiece as claimed in claim 1, wherein, this workpiece has sightless at least one half-wave coating on the optics on the top of SHLH heap, makes that heap SHLHLL plays the effect identical with piling SHLH and UV filtering performance does not change.

16. workpiece as claimed in claim 15, wherein, for the design wavelength among the UV, the silicon-dioxide LL of the half-wavelength at top is 1/4 wavelength in visible spectrum, and this 1/4 wavelength layer is used to stop that by possessing the bed thickness of UV and visible light transmissive is used as visible spectrum reflectivity reduction layer.

17. workpiece as claimed in claim 1, wherein, design wavelength is 330nm, and this makes ISO UV minimize simultaneously to keep transmission of visible light greater than 70% for the thick green glass of 3.6mm.

18. workpiece as claimed in claim 1, wherein, this workpiece is inserted in every layer of initial SHLH heap that all is designed to 350nm half-wave coating and obtains S3H3L3H, thereby this coating is piled up under the 350nm design wavelength to be served the same role, but this coating is the SHLH heap when piling up near 1050nm, this moment, reflectivity was about maximum, thereby make the specific refractory power of this coating littler under longer wavelength, its peak value moves to the more short wavelength who is positioned at spectrum NIR zone, thereby this coating piles up reflection under two design wavelengths.

19. workpiece as claimed in claim 1, wherein, this workpiece has a kind of coating to change the reflection strength of visible spectrum, and this coating is 1/4 wavelength in visible spectrum; It in NIR 1/8 wavelength; In UV 1.5 wavelength.

20. workpiece as claimed in claim 1, wherein, this workpiece has the transparent conductive oxide coating at least one side of HLH coating heap.

21. workpiece as claimed in claim 20, wherein, transparent conductive oxide is the stannic oxide that mixes up fluorine, and high refractive index coating is a titanium dioxide.

22. workpiece as claimed in claim 20, wherein, this workpiece comprises that at least one LH refractive index coating is right, to increase reflectance peak.

23. workpiece as claimed in claim 1, wherein, this workpiece comprises the medium refractive index coating between the substrate and first high refractive index coating, thereby makes the color relax that is reflected.

24. workpiece as claimed in claim 1, wherein, this workpiece is included in the medium refractive index coating on last high refractive index coating, thereby makes the color relax that is reflected.

25. workpiece as claimed in claim 1, wherein, this workpiece comprises graded coating and at least one the HLH coating heap that its specific refractory power changes along coat-thickness.

26. workpiece as claimed in claim 1, wherein, this workpiece is by temper.

27. workpiece as claimed in claim 1, wherein, this workpiece has two NIR/UV filtering coating heaps, and the silicon-dioxide and the transparent conductive oxide coating that are used as low-index layer.

28. workpiece as claimed in claim 27, wherein, the coating that coating on glass substrate heap has titanium oxide, at least one pair of silicon-dioxide and a transparent conductive oxide to and titanium dioxide, wherein the coating of silicon-dioxide and transparent conductive oxide is to having the comprehensive optical thickness of 1/4 ripple in NIR.

29. workpiece as claimed in claim 27, wherein, transparent conductive oxide is the stannic oxide that mixes up fluorine.

30. workpiece as claimed in claim 27, wherein, coating heap has layer that specific refractory power changes in gradient, mix up the stannic oxide of antimony and mix up the stannic oxide of fluorine.

31. workpiece as claimed in claim 1, wherein, this workpiece has five layers of coating heap selecting from following group, and this group comprises: be configured to the coating heap of SHLHLH, wherein TiO ₂For high refractive index layer, silicon-dioxide are low-index layer, total thickness is that about 6747 dusts, TSET are about 60%, transmission of visible light is about 85%; With the identical heap of last coating heap configuration, but F:SnO ₂Be low-index layer, and total thickness is that about 6461 dusts, TSET are about 50%, transmission of visible light is about 71.1%.

32. workpiece as claimed in claim 1, wherein, glass substrate is for green and have the stannic oxide shallow layer that mixes up antimony, the thickness of coating to make by the color of transmission to become scarlet from green.

33. workpiece as claimed in claim 1, wherein, high refractive index coating comprises the transition metal oxide with high refractive index as high refractive index layer, at this, transition metal oxide is with the whole high refractive index layer in the making coatings heap or as the part of high refractive index layer, colour intensity is weakened, and the colour transition metal oxide can use and make coating color decay with the achromaticity oxide compound, thereby not only obtain sunlight control but also have multiple color.

34. a multilayer coated windshield glass, wherein this windshield glass has ultraviolet light transmission, the total solar energy transmission less than 50% less than 10%, and has the transmission of visible light greater than 70% simultaneously, and this windshield glass comprises:

A) transparency carrier of from the group that comprises stained glass, sunlight feed glass and stained glass, selecting;

B) comprise first coating of metal, this coating has the specific refractory power of selecting from the group that comprises high and low-refraction;

C) comprise second coating of metal, this coating has the specific refractory power opposite with first specific refractory power;

D) comprise the 3rd inorganic coating of metal, this coating has the specific refractory power in the ranges of indices of refraction of first coating.

35. workpiece as claimed in claim 34, wherein, the UV/NIR coating that comprises the silicon-dioxide of top 1/4 wavelength has the SHLHL/2 configuration of adjusting for NIR, windshield glass installation angle increase along with automotive window, the optical thickness of coating reduces and the physical thickness of coating increases compensating, thereby further reduces the TSET of windshield glass.

36. workpiece as claimed in claim 34 wherein, is used for being coated with of sunlight reflection and is placed on different substrate surfaces, thereby place between the substrate as the interlayer that does not have the windshield glass of antireflecting coating.

37. workpiece as claimed in claim 1, wherein, substrate is substantially free of CeO ₂

Images