Photocatalytic window and method of making same

(54) Title: PHOTOCATALYTIC WINDOW AND METHOD FOR MANUFACTURING THE SAME (30) Unionist Priority: 27/04/2006 us 11 / 412,120 (73) Holder (s): Guardian Industries Corp.

(72) Inventor (s): Jose Nunez-Regueiro, Scott V. Thomsen, Vijayen S. Veerasamy (74) Attorney (s): Dannemann, Siemsen, Bigler & Ipanema Moreira (86) International Application: pct US2007008972 of 12/04 / 2007 (87) International Publication: wo 2007 / 127060de 08/11/2007 (57) Abstract: photocatalytic window and method for MANUFACTURING THE SAME The present invention relates to a photocatalytic coated article and a method for manufacturing it . In certain exemplary embodiments, a coated article includes an inclusive layer of nitrite and / or zirconium oxide before heat treatment (HT). The coated article is treated with heat in such a way that after heat treatment (for example, thermal quenching) a layer based on zirconium oxide is provided. A photocatalytic layer (for example, a titanium oxide) can be formed on top of the zirconium oxide based layer after heat treatment.

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Apply photocatalytic coating

TiO, crystalline (anatase)

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Dielectric film

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Glass substrate

ΡΙ0710892

Descriptive Report of the Invention Patent for PHOTOCATALYTIC WINDOW AND METHOD FOR MANUFACTURING THE SAME.

The present invention relates to a photocatalytic window having self-cleaning properties, and a method for making it.

5 BACKGROUND OF THE INVENTION

Vehicle windows (such as windshields, rear windows, sunroofs and side windows) are known in the art. For example purposes, vehicle windshields include a pair of curved glass substrates laminated together through a polymer interlayer 10 such as polyvinyl butyral (PVB). It is known that one of the two glass substrates can have a coating (such as a low E coating) on ​​it for solar control purposes such as reflecting IR and / or UV radiation, such that the interior of the vehicle can be more comfortable in certain atmospheric conditions. Conventional vehicle windshields 15 are made as follows. The first and second flat glass substrates are provided, one of which optionally has a low E coating cast in particles on it. The two glass substrates are washed and joined together (ie, stacked on top of each other), and then while they are stacked 20 are curved together with heat in the desired windscreen shape at a high temperature or temperatures (such as 8 minutes at about 600 to 625 degrees C). The two curved glass substrates are then laminated together through the inner polymer layer to form vehicle windshields.

Insulating glass (IG) windows are also known in the art. Conventional IG windows include at least one first and a second glass substrate (one of which may have a solar control coating on an internal surface of the same) that are joined to each other through at least one fence or fences or spacers . The resulting space or gap between the glass substrates may or may not be filled with gas and / or evacuated to low pressure at different events. However, many of the IG units are required to be tempered.

The thermal tempering of the glass substrates for these IG units typically requires heating the glass substrates to a temperature or at temperatures of at least about 600 degrees C, for a period of time sufficient to permit thermal tempering. Monolithic windows for architecture to be used in homes or buildings are also known in the art. Likewise, monolithic windows are almost always thermally tempered for safety purposes, this tempering involving high temperature during heat treatment.

Other types of coated articles also require heat treatment (HT) (such as quenching, heat bending and / or heat reinforcement) in certain applications. For example, and without limitation shower windows and doors, glass table tops and the like require HT on certain occasions.

Diamond-type carbon (DLC) is sometimes known 15 for its scratch-resistant properties. For example, different types of DLC are discussed in the following US Patents: 6,303,226; 6,303,225; 6,261,693; 6,338,901; 6,312,808; 6,280,834; 6,284,377; 6,335,086; 5,858,477; 5,635,245; 5,888,593; 5,135,808; 5,900,342; and 5,470,661, all of which are incorporated herein, in this patent application 20 by reference.

Sometimes it would be desirable to provide a window unit or other glass article with a protective coating including DLC ​​in order to protect it from scratches and the like. Unfortunately, DLC tends to oxidize and burn at temperatures from approximately 380 to 400 degrees C or higher, as heat treatment is typically performed in an atmosphere that includes oxygen. Thus, it will be appreciated that DLC as a protective coating cannot withstand heat treatments (HT) at the extremely high temperatures described above which are almost always required in the manufacture of vehicle windows, IG window units, table tops glass and / or the like. As a result, DLC cannot be used in isolation as a coating to be treated with heat, as it will oxidize during heat treatment and disappear substantially as a result of the same treatment (ie, it will be burned ).

Other specific types of scratch-resistant materials' 5 are also not able to withstand treatment with sufficient heat for tempering, heat reinforcement and / or curvature of an underlying glass substrate.

Consequently, those skilled in the art will note that there is a need for a method for manufacturing a scratch-resistant coated article to be used on a window or the like that may be capable of being heat treated (HT) such that after the heat treatment the coated article is resistant to scratches. There is also a need with regard to corresponding coated articles, either heat treated and heat pretreated or non-heat treated.

Photocatalytic coatings are also sometimes desirable in window applications. Photocatalytic coatings are also known as self-cleaning coatings, where the coating reacts with and breaks down organic or polluting compounds into non-harmful inorganic compounds such as CO₂ and / or H₂O.

Accordingly, in certain exemplary embodiments of this invention, it will be noted that there is a need in the art for a scratch-resistant coated article that has a combination of anti-scratch and self-cleaning properties. In 25 finished contexts of examples, it would be advantageous to provide a window that is both scratch resistant and that can work in a self-cleaning manner. In yet other exemplary embodiments, it would be desirable to provide a window that has both photocatalytic and antifungal and antibacterial functions. Although coatings here, in this patent application are almost always used in the context of windows, they can also be used in the context of glass tops for tables or other applications in certain example contexts.

BRIEF SUMMARY OF EXAMPLES OF THE INVENTION

In certain exemplary embodiments of this invention, a method is provided for manufacturing a coated article (such as a window such as for a vehicle, building, shower door, or the like) that is capable of being treated with heat in such a way that after being treated with heat (HT) the coated article is resistant to scratches to a greater degree than untreated glass. In addition, certain exemplary embodiments of this invention relate to a window that has self-cleaning properties, and a method for manufacturing them. Optionally, the window can also have anti-fungal and antibacterial properties in certain contexts.

In certain exemplary embodiments of this invention, a photocatalytic layer is provided (such as, for example, from or including TiO₂crystalline (such as the “anatase” type) on the layer including zirconium 15 in a window, glass table top and the like. These modalities may or may not be used in combination with the characteristic of antibacterial silver and antifungals discussed here, in this patent application (such as, for example, the photocatalytic layer and the layer including zirconium oxide can both be porous and can both be located on silver 20 in antibacterial and antifungal modalities). The use of the zirconium oxide layer under the photocatalytic layer significantly increases the durability of the coated article, while allowing the article to achieve a low contact angle (Θ) and self-cleaning which are both desirable in many situations.

Coated articles according to certain embodiments of this invention can be used in the context of shower doors, architectural windows, vehicle windows, IG windows, glass for photo frames, and the like. Although articles coated according to this invention are specifically adapted for use on 30 windows, this invention is not limited in that way as articles coated according to this invention can also be used for table tops or any other suitable application .

Methods for making such coated articles for use on windows or the like are also provided. In certain example embodiments, a layer of or including zirconium nitride and / or zirconium oxide is formed on a glass substrate. In certain example cases, the zirconium nitrite and / or oxide and zirconium layer can be added with other materials such as F. C and / or Ce. Optional fluorine (F) or carbon (C) additives, for example, have been considered to increase the visible transmission of the coated article. Although zirconium nitrite and / or zirconium oxide are formed on top of the glass substrate, there may be another layer (for example, a silver based layer) between them, so the word "about" is not limited here , in this patent application, to directly over. Optionally, an inclusive carbon layer (such as diamond-type carbon (DLC)) can be provided over the included zirconium layer. This included layer of carbon can be used for power generation during heat treatment (HT) for the transformation of at least one other layer in the coating to form a new layer or layers of HT post that were not present in the post form HT before HT (as for example, zirconium nitrite can be transformed into zirconium oxide 20 as a result of HT; and / or the zirconium based layer may have a degree of tensile strength over the same HT powder that was not present in the pre HT layer). The coated article which includes the zirconium nitrite and / or zirconium oxide layer, the silver-based layer (optional) and the included carbon layer (optional) is heat treated for thermal tempering or similar. As a result of the heat treatment, the included zirconium nitrite layer if used becomes a layer comprising zirconium oxide (this post HT HT zirconium oxide layer may or may not include nitrogen in different modalities). The post HT layer of or whether it includes zirconium oxide is scratch resistant (SR) DM of 30 finished example modalities. In certain example cases, heat treatment also causes a change in the strength of the zirconium-based layer (for example, the zirconium-based layer may have a degree of tensile strength after HT that was not present in the pre-layer HT) this resistance allowing the crystal grain boundaries or small holes to be present in the layer to allow the optional migration of silver through them over time. Following heat treatment, a photocatalytic layer (such as, or that includes TiO₂ crystalline, such as anatase type) can be formed on the glass substrate on the included zirconium oxide layer and on the optional silver-based layer. The photocatalytic layer can be formed using a colloidal solution and / or a sol / gel, with subsequent curing, in certain exemplary modalities of this invention.

In certain exemplary embodiments of this invention, a method for making a heat-treated coated article is provided, the method comprising: providing a coating supported by a glass substrate, the coating comprising a layer based on zirconium nitrite, thermally tempering the glass substrate with the layer based on zirconium nitrite on it, such that the tempering causes the zirconium nitrite-based layer becomes a layer comprising zirconium oxide (Zr_xO_y) where x / y 20 is from about 1.2 to 2.5; and following said tempera, the formation of a catalytic layer comprising anatase of TiO₂ on the glass substrate and directly contacting the layer comprising zirconium oxide (Zr_xO_y).

In other exemplary embodiments of this invention, a method for making a heat-treated coated article is provided, the method comprising: providing a coating supported by a glass substrate, the coating comprising a layer based on zirconium nitrite and / or a layer based on zirconium oxide; thermally tempering the glass substrate with the layer based on zirconium nitrite 30 and / or zirconium oxide, fold it in such a way that the tempering is then provided with a layer comprising zirconium oxide; thereafter said tempering, forming a photocatalytic layer comprising a metal oxide on the glass substrate on at least the layer comprising zirconium oxide.

In other exemplary embodiments of this invention, a coated article (such as for use in a window) is provided comprising: a glass substrate supporting at least one layer comprising zirconium oxide (Zr_xO_y) where x / y are from about

1.2 to 2.5; a photocatalytic layer on the glass substrate provided on and in direct contact with the zirconium oxide layer, in which the photocatalytic layer comprises a titanium oxide and has a refractive index (n) that is no different than about 0.1 from the refractive index of the layer comprising zirconium oxide.

In yet other exemplary embodiments of this invention, a coated article is provided which comprises: at least one layer provided on a glass substrate; a photocatalytic layer provided above the glass substrate on at least one layer, wherein the photocatalytic layer comprises each of: (a) an active metal oxide to react with and decompose at least some organic and / or pollutant compounds which may come into contact with a surface of the coated article, and (b) silver.

In certain exemplary embodiments of this invention, an included layer of antifungal and / or antibacterial silver is provided beneath one or more layers. The layer or layers on the silver are specially designed in such a way as to be porous thereby allowing silver particles to migrate or diffuse across the entire surface of the window for long periods of time. The layer or porous layers on the silver may be, or include a metal oxide in certain exemplary embodiments of this invention, such as a titanium or zirconium oxide. For example, the layer or porous layers on the silver can be designed in such a way that they have a resistance and / or a density that causes some degree of porosity in them, which allows the silver to migrate / diffuse to the surface of the window through zigzagging through the grain boundaries defined in the layer or porous layers. In other example modalities, the layer or porous layers on the silver can be designed in such a way as to have very small pinholes and / or nano-holes defined in them that allow the silver to migrate / or diffuse through the entire surface of the window over time. Alternatively, the porous layer or layers can allow silver particles to migrate to the surface over time through a combination of tiny pinholes and grain boundaries in the porous layer or layers. When the silver 10 particles reach the surface in a substantially continuous manner over time, they work to kill at least some bacteria and / or fungi that may come in contact with, or close to, silver, on the surface. from the window.

In certain exemplary embodiments, silver is protected from the environment through the porous layer (s) provided on the silver. It is observed that the silver layer can be a continuous layer of or based on silver in certain example modalities, but alternatively it can be a non-continuous layer made of a plurality of particles, or spaced silver or silver based lumps. some 20 of the others (eg colloids) in other example modalities. One or more of the porous layers on silver can be photocatalytic (self-cleaning) in certain exemplary embodiments of this invention.

In certain exemplary embodiments of this invention, a coated article is provided which includes a coating supported by a glass substrate, the coating comprising: a layer comprising silver on the glass substrate; a layer comprising zirconium oxide (Zr_xO_y) where x / y are from about 1.2 to 2.5, on the glass substrate above at least the layer comprising silver; a photocatalytic layer comprising an anatase of titanium oxide 30 on the glass substrate above at least the layer comprising silver and the layer comprising zirconium oxide. and wherein each of the layers comprising zirconium oxide and the photochalitic layer comprising the titanium oxide anatase is porous in such a way as to allow silver from the layer comprising silver to migrate and / or diffuse to the upper outer surface of the coated article over time.

In other exemplary embodiments of this invention, a coated article is provided which includes a coating supported by a glass substrate, the coating comprising: a layer comprising silver, a layer comprising zirconium oxide on the glass substrate above the layer which comprises silver; a photocatalytic layer 10 comprising at least one metal oxide on the glass substrate above at least the layer comprising silver and the layer comprising zirconium oxide; and wherein each of the layer comprising zirconium oxide and the photocatalytic layer comprising metal oxide are porous in such a way as to allow silver from the layer comprising silver to migrate and / or diffuse into the outermost upper surface of the coated article over time.

In yet other exemplary embodiments of this invention, an antibacterial window is provided that includes an antibacterial coating supported by a glass substrate, the coating comprising: a layer comprising silver; at least one layer comprising a metal oxide on the glass substrate above at least the layer comprising silver; and wherein all the layers on the glass substrate above the layer comprising the silver are porous in such a way as to allow the silver from the layer comprising the silver 25 to migrate and / or diffuse to the upper outer surface of the coated article over time, said upper outer surface of the coating also being a main window surface.

In still other exemplary embodiments of this invention, a method for making an antibacterial coated article is provided, the method comprising providing a glass substrate; forming a layer comprising silver on the glass substrate, forming a porous layer comprising metal oxide on the glass substrate above at least the layer comprising silver, such that the porous layer comprising silver oxide metal is sufficiently porous in such a way as to cause the layer comprising the silver to migrate and / or diffuse outwardly towards the surface of the coated article 5 over time.

In yet other exemplary embodiments of this invention, a method for making a coated article is provided, the method comprising: providing a glass substrate; depositing in liquid form on the glass substrate a colloidal dispersion that includes each of 10 metal oxide colloids and silver colloids, and curing the colloidal dispersion in such a way as to form an antibacterial and / or antifungal layer that comprises each of metal oxide and silver as an outermost layer of a coating on the glass substrate.

In certain exemplary embodiments of this invention, silver can be replaced or supplemented with copper (Cu).

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a schematic diagram illustrating a method for making an antibacterial and / or antifungal coated article according to an example embodiment of this invention, before and after the optional heat treatment.

Figure 2 is a schematic diagram illustrating a method for making a photocatalytic coated article according to another embodiment of this invention, before and after heat treatment.

Figure 3 is a cross-sectional view of a coated article made according to the embodiment of Figure 1, the view showing schematically how the silver particles migrate or diffuse to the surface of the article over time for an effect antibacterial or antifungal.

Figure 4 is a cross-sectional view of a coated article according to an example of this invention, illustrating the silver ions stored between the zirconia layers.

Figure 5 is a top view illustrating how the resistance is involved in relation to the article of Figure 4 after heat treatment, to provide microchannels perpendicular to the plane of the film.

DETAILED DESCRIPTION OF EXAMPLE MODALITIES OF THIS INVENTION '5 Referring more specifically to the accompanying drawings in which equal reference numerals indicate equal parts or layers during all of the different views.

In certain exemplary embodiments of this invention, a method is provided for manufacturing a coated article (such as for example, window such as for vehicle, building, shower box door or the like) that is capable of being treated with heat from such that after being treated with heat (HT) the coated article is resistant to scratches to a greater degree than uncoated glass. In addition, certain exemplary embodiments of this invention relate to a window that has antibacterial and antifungal properties and / or self-cleaning properties. Coated articles according to certain exemplary embodiments of this invention can be used in the context of shower door glass, architectural windows, vehicle windows, IG windows, picture frame glass or the like. Although articles coated according to this invention are specifically adapted for use in windows, this invention is not limited in that way, as articles coated according to this invention can also be used for table tops or any other applications appropriate.

Figure 1 is a schematic diagram illustrating a method 25 for the manufacture of an antibacterial and antifungal coated article for use in a window or the like according to an example embodiment of this invention, before and after the optional heat treatment; and Fig. 3 is a cross-sectional view of a coated article made according to the embodiment of figure 1. The embodiment of figures 1 and 3 may or may not include the photocatalytic top layer in alternatives other than this invention. However, the modality of figure 2 does not have a silver based layer and instead is a schematic diagram that illustrates a method for the manufacture of a photocatalytic coated article according to another modality of this invention, before and after heat treatment. . Before going into much detail, a general description of the different modalities will be made in relation to figures 1 and 3.

Germs have become a growing concern across the world, especially in view of the large amount of international travel that takes place in today's society. Diseases such as “bird flu” Severe Acute Respiratory Syndrome (SARS) and other types of flu have emerged around the world in recent years and have resulted in many deaths. There is a need in the art with regard to elements such as windows that are capable of killing germs and / or bacteria, thereby reducing the likelihood of people becoming ill from influenza, SARS, bird flu, and the like. It would be highly advantageous if these characteristics of a window could be combined with characteristics of scratch resistance. Thus, in certain exemplary embodiments of this invention, optimum silver in the form of layer 6 and / or in the photocatalytic layer is provided for antibacterial purposes.

In certain exemplary embodiments of this invention, with reference to figures 1 and 3, an included layer of anti-fungal silver and anti-fungus 6 is provided on a glass substrate 1 under one or more layers (for example, one or more layers 7, 9 11 and / or 12). In the final product, layers 11 and 12 (or only layer 11 if layer 12 is not used) on the silver layer 6 are specially designed in such a way as to be porous and thereby allow the silver particles to originate from the silver-based layer 6 migrate or diffuse across the entire surface 15 of the window over long periods of time. The porous layers (11, 12 on silver 6 can be of or include a metal oxide in certain exemplary embodiments of this invention, such as a titanium or zirconium oxide.

For example, the layer or porous layers 11, 12 on the silver 6 can be designed in such a way as to have a resistance and / or a density that causes some degree of porosity within them which allows the silver based particles of the silver layer 6 migrate or diffuse to the window surface 15 by means of zigzag through the grain boundaries defined in the layer or porous layers 11, 12 (see, for example, Fig. 3). In certain embodiments of e'5 example, the layer or porous layers 11 and / or 12 on the silver 6 can be designed in such a way as to have tiny pinholes and / or nano-holes defined within them that allow the silver particles that originate from layer 6 migrate / diffuse across the entire surface 15 of the window over time, (see, for example, figure 10 3). Alternatively, the layer or porous layers 11 and / or 12 may allow the silver particles from the silver-based layer 6 to migrate to surface 15 over time through a combination of tiny pinholes and through the grain boundaries in the layer or porous layers (see, for example, figure 3). When the silver particles from the silver layer 6 reach the surface 15 in a substantially continuous manner over time, they work to kill at least some bacteria and / or fungi that may come in contact with or near the silver silver, on the window surface 15.

It is observed that the amount or degree of migration / diffusion of silver can be controlled through environmental factors such as humidity and / or temperature. For example, little or no migration can occur at very low temperatures and / or in low humidity conditions. However, increased silver migration / diffusion to the surface 25 15 can occur when the window is exposed to high humidity and / or high temperature conditions. Thus, it will be observed that the migration / diffusion of silver does not have to be constant as far as the degree of existence is concerned.

In certain example embodiments, the silver-based layer 30 where the silver-based particles originate is protected from the environment by the porous layer or layers 1 and / or 12 provided on the silver-based layer 6.

It is noted that the silver layer 6 may be a continuous or silver-based layer in certain exemplary embodiments, but alternatively it may be a non-continuous layer made of a plurality of particles or lumps (e.g., colloids) of silver or with 5 silver bases spaced from each other DM other example modalities.

Referring to Figures 1 and 3, one or more porous layers on silver 6 can be photocatalytic (self-cleaning) in certain exemplary embodiments of this invention. In certain exemplary embodiments of this invention, a photocatalytic layer 32 (as per, for example, de, or including TiO₂ crystalline like anatase type) is provided on a layer that includes titanium oxide 11 in a window unit. These modalities may or may not be used in combination with the inclusive silver layer 6 with the antibacterial 15 and antifungal characteristics discussed here, in this patent application (such as, for example, the photocatalytic layer 12 and the inclusive titanium oxide layer 11 may both are porous and can both be located on silver 6 in antibacterial and antifungal modalities, however, they do not need to be porous in modalities in which silver 6 is not used as in the modality20 of figure 2). The use of the zirconium oxide layer 11 under the photocatalytic layer 12 significantly increases the durability of the coated article, while at the same time allowing the article to form a low contact angle θ and self-cleaning which are both desired in many situations.

Methods for making these coated articles for use in windows or the like are also provided. In certain example embodiments, a layer 7 of or that includes zirconium nitrite and / or zirconium oxide is formed on a glass substrate 1. In certain example embodiments, layer 7 of zirconium nitrite and / or zirconium oxide can be added with other materials such as F, C and CE. The additional 30 fluorine additives (FL and carbon (C), for example, were found to increase the visible transmission of the coated article after HT. Although layer 7 of zirconium nitrite and / or zirconium oxide is formed on the glass substrate, there may be other or other layers (such as a layer based on silver 6 and / or a dielectric film 3) between the same; therefore, the word "about" is not limited directly above, here, in this patent application. Optionally3, '5 an inclusive layer of carbon (for example, diamond-type carbon (DCL) 9 can be provided over the inclusive zirconium layer 7. This inclusive layer of carbon 9 can be used for power generation during heat treatment (HT) for the transformation of at least one other layer (eg 7) in the coating to form new or 10 ninth post HT layers ( for example, 11), which was not or were present in post HT form before HT (such as, zirconium nitrite can be transformed into zirconium oxide as a result of HT and / or the zirconium based layer may have a degree of tensile strength in the same HT post that was not present in the pre HT layer). The coated article15 including layer 7 of zirconium nitrite and / or zirconium oxide, layer 6 with a silver base (optional), and the inclusive layer 9 (optional) is heat treated for thermal tempering or the like. As a result of heat treatment, the inclusive layer 7 of zirconium nitrite if used turns into a layer comprising zirconium oxide 11. Es20 s layer 11 of zirconium oxide after HT treatment may or may not include nitrogen in different modalities of this invention. The HT post layer, or that includes zirconium oxide 11, is scratch resistant (SR) in certain example embodiments.

In certain cases, heat treatment (HT) may involve heating the glass support substrate, with the layers on it, for temperatures from 550 to 800 degrees C, more preferably from 580 to 800 degrees C (which is well above the combustion temperature of the DCL). Certain exemplary embodiments of this invention relate to a technique for allowing the coated HT 30 post article to be more resistant to scratches than uncoated glass.

In certain example cases, the zirconium-based layer 7 can be formed initially in a way that causes heat treatment to cause a change in the strength of the zirconium-based layer from layer 7 pre HT to the layer 11 post

HT. For example, the zirconium nitrite-based layer 7 before HT may have compressive strength, or substantially no resistance, and following HT treatment the inclusive zirconium 11 post HT layer may have, as a result of HT a degree of tensile strength that allows or causes the crystal boundaries of the grain or nano-orifices to be present in layer 11 to allow silver to migrate through all of them over time. Following heat treatment, optionally, a photocatalytic layer (for example, of or containing TiO₂Crystalline I, such as the anatase type) can be formed on the glass substrate 1 above the inclusive layer of zirconium oxide 11 and above the optional layer based on silver 6. The photocatalytic layer 12 can be formed with the use of a colloidal solution, and / or a sol-gel, 15 with subsequent curing, in certain exemplary embodiments of this invention.

Figure 4 is a cross-sectional view of a coated article according to an example of this invention, illustrating the silver ions of layer 6 stored between layers 3 and 11 of zirconia (20 zirconium oxide). Meanwhile, Fig. 5 is a top view that illustrates how the resistance engages with respect to the item in Figure 4 after heat treatment, to provide microchannels or nano-holes perpendicular to the plane of the film. As explained above, these microchannels or nano-orifices in at least layer 11 allow silver to migrate through them over time towards the top surface of the coated article.

In the following, a more detailed discussion will be made regarding certain exemplary modalities of this invention and how these modalities can be manufactured.

Returning first to the modality of figures 1 and 3 of this invention, a description of the example of how this modality can be done in certain cases of examples is provided.

Figure 1 is a schematic diagram illustrating how a coated article can be made according to an example embodiment of this invention. Initially, a coated article is formed using a glass substrate 1 as a support. The coated article includes, supported by the glass substrate 1, at least one dielectric barrier film 3, a layer of or including silver (provided for antifungal or antibacterial purposes, a layer of or including zirconium nitrite 7 ( for example, ZrN, or any other suitable stoichiometry), and an optional top layer of 9, or that includes carbon such as DCL. Glass substrate 1 is typically made of or includes soda lime feldspar glass, although other types of glass may be used in certain cases.

The film 3 of the dielectric barrier includes one or more layers and is provided for the purpose of preventing the diffusion of sodium from the glass substrate 15 into the silver 6 during and / or after HT (for example, a barrier for diffusion). The dielectric barrier film 3 comprises a layer or layers of or including zirconium oxide, zirconium nitrite, zirconium nitrite oxide, zinc oxide, silica nitrite, silica nitrite oxide, silica oxide, or the like. The barrier film 3 can have resistance to compression both before and after HT in certain exemplary embodiments of this invention, since the resistance to compression helps the film to block the migration of sodium from the glass substrate. The barrier layer or layers 3 is formed on the substrate 1 by crackling or by another suitable technique. The dielectric barrier film 3 is from about 50 to 1,000 Å in thickness, more preferably from about 80 to 500 Å in thickness, in certain exemplary embodiments of this invention.

The silver based layer 6 is provided on the glass substrate 1 above at least the optional barrier film 3 in certain example embodiments. However, it is possible that the silver-based layer 6 is formed directly on the glass substrate 1 when the dielectric barrier film 3 is not used. The silver layer can be from about 20 to 400 Ã… thick, more preferably from about 20 to 200 Ã… thick, even more preferably from about 20 to 100 Ã… thick, in certain exemplary embodiments of this invention. Because the coated article is used in applications of windows or the like, the silver layer 6 is thin enough to be substantially transparent in certain example embodiments, yet thick enough to provide enough with respect to anti-bacterial and anti-fungal purposes. In addition, the silver-based layer 6 can also function as a blocking layer 10 of infrared (IR) radiation in certain exemplary embodiments of this invention, thereby allowing the window to block additional IR radiation from entering a building or similar. The silver layer 6 can be continuous or discontinuous in different embodiments of this invention

Still with reference to the product of Figure 1 before Fo HT, the dielectric layer 7 inclusive of zirconium nitrite or zirconium oxide, can be provided on the glass substrate 1 between the silver based layer 6 and the inclusive layer of carbon 9 in certain exemplary embodiments of this invention, as shown in Fig. 1. In certain example embodiments, the inclusive zirconium nitrite layer 7 may be located directly between layers 6 and 9; however in other example embodiments another layer or layers (not shown) may be provided between the inclusive zirconium nitrite layer 7 and one or both layers 6 and 9. The inclusive zirconium nitrite layer 7 may consist essentially of (a) zirconium and nitrite; (b) zirconium and oxygen, or 25 (c) zirconium, oxygen and nitrogen in different example modalities.

However, the inclusive dielectric layer of zirconium nitrite 7 may also include other materials which include, but are not limited to additives such as Al, F, CE, C or the like, in certain embodiments of this invention. The zirconium nitrite 7 inclusive dielectric layer can be formed by crackling or the like in certain exemplary embodiments of this invention.

Pre HT layer 7 can include from about 10 to 70% of

Zr, more preferably from about 30 to 65% Zr, even more preferably from about 40 to 60% Zr, 3e most preferably from about 45 to 55% Zr in terms % atomic, and from about 20 to 60% N, more preferably from about 30 to 50% N in terms of atomic% in certain exemplary embodiments of this invention. In certain exemplary embodiments of this invention, the inclusive zirconium nitrite layer 7 can have a density of at least 6 g / cm³, more preferably at least 7 g / cm³. In addition, in certain example embodiments, the inclusive zir10 nitrate layer 7 can have an average hardness of at least 650 kgf / mm, more preferably at least 700 kgf / mm, and / or can have a population of superimposed connection of at least 0.25 (more preferably at least about 0.30), for strength purposes. In certain example cases, many of the Zr-N bonds in layer 7 may be of the covalent type, which are stronger than the ionic bonds, with respect to resistance purposes. It is also noted that in certain exemplary embodiments of this invention, layer 7 ZrN can have a melting point of at least 2,500 degrees C, and it can be about 2980 degrees C in certain example cases. In certain example embodiments 20 of this invention, layer 7 zirconium nitrite can be represented by

Zr_xN_y, in which the x / y ratio is from 0.8 to 12, and is preferably about 1: 0 in certain example embodiments. The inclusive zirconium layer 7 may have a compressive strength as originally formed on the glass substrate prior to HT. These same 25 characteristics of zirconium nitrite that are explained above with respect to layer 7 also apply to layer 3 when layer 3 is formed of nitrite and / or zirconium oxide.

The optional layer 9 comprising the DLC can be of any suitable type of DLC, including, but not limited to, any of the 30 types of DLC described in any of US Patent Nos.²⁵ 6.592.993;

6.592.992; 6.531.182; 6.461.731; 6.447.891; 6.303.226; 6.303.225; 6.261.693;

6.338.901; 6.312.808; 6.280.834; 6.284.377; 6.335.086; 5.858.477; 5.635.245;

5,888,593; 5,135,808; 5,900,342; and / or 5,470,661, all of which are incorporated herein, in this patent application, by reference. For example purposes only, the inclusive layer of DLC 9 may be from about 5 to 1,000 angstroms (Â) thick in certain exemplary embodiments of this invention, more preferably from 10 to 300 Á thick, and most preferably from 45 to 65 Â in thick. In certain exemplary embodiments of this invention, the DLC layer 9 may have an average hardness of at least about 10 GPs, more preferably at least about 20 GPs, and most preferably from 10 at least 20 to 90 GPs. This hardness makes layer 9 resistant to scratches, certain solvents and / or the like. Layer 9, in certain example embodiments, may be of, or include a special type of DLC known as highly tetrahedral amorphous carbon (t-aC) and may be hydrogenated (t-aC: H) in certain embodiments. In certain 15 hydrogenated modalities, the t-aC: H type of the layer 9 DLC can include from 4 to 39% hydrogen, more preferably from 5 to 30% H, and most preferably from 10 to 20% H. This type of DLC for layer 9 t-BC or t-BC: H may include more sp³ carbon-carbon (C - - C) bonds than sp² carbon-carbon (C - - C). In certain 20 example embodiments, at least about 50% of the carbon-carbon bonds in the DLC layer 9 can be of the sp type³ carbon-carbon (C - - C), more preferably at least about 60% of the carbon-carbon bonds in layer 9 can be sp bonds³ carbon-carbon) (C - - C), and more preferably at least 70% of the carbon25 carbon bonds in layer 9 can be sp bonds³ carbon-carbon (C - - C).

In certain exemplary embodiments of this invention, the DLC in layer 9 can have an average density of at least about 2.4 g / cm³, more preferably at least about 2.7 g / cm³.

The DLC-based layer 9 can be formed in any suitable manner, such as by using ion beams from at least one ion source. Examples of linear ion beam sources that can be used to deposit the Inclusive layer of DLC 9 on substrate 1 includes any of those in any of US Patent Nos. 6,261,693, 6,002,208 or 6,303,225 (all incorporated herein, in this patent application by reference). When an ion beam source is used to deposit layer 9, gas or gases from hydrocarbon feed material '5 (for example, (C₂H₂), HMDSO, or any other suitable gas at the source or ion sources for the purpose of causing the source to emit an ion beam towards the substrate 1 for the formation of layer 9. It is observed that the hardness and / or the The density of layer 9 can be adjusted by varying the ion energy of the deposition apparatus. In certain example modalities, at least about 2,000 V (volts from anode to cathode), such as about 3,000 V, can be used in the ion source to deposit layer 9. It is observed that the phrase “about substrate ”in the form used here, this patent application is not limited to being in direct contact with the substrate insofar as another layer or layers may still be provided between them.

For the purpose of example only, certain sample thicknesses with respect to the pre HT layers shown at the top of figure 1 are shown below, with the layers being related in order from the glass substrate in the outward direction.

Example Coating (top of figure) - Layer thicknesses (Pre HT)

General Layer

Dielectric (film 3) 50-1,000A

Silver (layer 6) 20-400Â

ZrN (layer 7) 40-500Â

DLC (layer 9) 5-1,000Â

More preference

80-500 Á

20-200 Á

50-400 Â

10-300 Á

Highest Preference

120-250 Á

20-100 Â

90-220 Â

40-65 Á

Once the pre HT coated article shown at the top of figure 1 is formed, it can be subjected to sufficient heat treatment for at least one heat bend, thermal temper and / or heat cement. With reference to Fig. 1, when subjected to HT (for example, in an oven using temperatures from 550 to 800 degrees C), more preferably from 580 to 800 degrees C) the inclusive layer of upper or outer DLC if provided , burns due to combustion caused by the high temperatures used during HT. Specifically, at least layer 9 of DLC (which can be hydrogenated) can act as a fuel that when combustion with oxygen from the atmosphere during HT produces carbon dioxide and water. This exothermic reaction, caused by the combustion of hydrogenated carbon from at least layer 9 of DLC, can cause the spontaneous propagation of a combustion wave through the initial reagents. The high temperature developed during this combustion heats the layer 10 7, which comprises zirconium nitrite and / or zirconium oxide for a

I temperature or temperatures well above the temperature of the heat treatment used by the oven. For example, combustion of DLC 9 and / or from HT can heat part or all of layer 7 comprising nitrite and / or zirconium oxide to a temperature of at least about 1200 ° C, more preferably at least about 1500 degrees C, and most preferably at least about 2,000 degrees C. The new layer 11 HT post comprising zirconium oxide, shown in the middle or bottom parts of figure 1 can also include nitrogen (and / or other additives) in certain exemplary embodiments of this invention (such as, for example, ZrO: N; ZrO₂: N; or any other suitable stoichiometry). The new 11 post HT layer comprising zirconium oxide (optionally with nitrogen) is surprisingly resistant to scratches, thereby providing a coated article treated with heat resistant to scratches. It is noted that the phrase “zirconium oxide” in the form used here, in this patent application includes ZrO₂ and / or any other stoichiometry to which Zr is at least partially oxidized.

The post HT layer 11 comprising zirconium oxide may include from 0 to 30% nitrogen in certain exemplary embodiments of this invention, more preferably from 0 to 20% nitrogen 30, even more preferably from from 0 to 19% nitrogen, and more preferably from about 1 to 5% nitrogen in certain exemplary embodiments of this invention. The HT post layer 11 comprising zirconium oxide may include from about 10 to 70% Zr, more preferably from about 20 to 60% Zr, even more preferably from about 30 to 55% Zr, and most preferably from about 30 to 45% Zr in terms of atomic percentage. In addition, 'HT 11 layers comprising zirconium oxide in certain exemplary embodiments of this invention may include from about 10 to 85% oxygen, more preferably from about 30 to 80% oxygen , even more preferably from about 40 to 70% oxygen, and most preferably from about 50 to 70% oxygen.

In certain exemplary embodiments of this invention, the 11 post HT layer comprising zirconium oxide includes a nanocrystalline cubic lattice structure (although the pre HT layer comprising zirconium nitrite does not have it in certain cases). As explained above, zirconium nitrite typically does not grow in a cubic phase unless at a temperature of at least 2,000 degrees C. It has been surprisingly discovered that the combustion generated during HT of layer 7 containing pre HT zirconium nitrite, can cause at least part of layer 7 containing pre HT zirconium nitrite, sufficiently heated to cause it to grow in the cubic phase and become a layer 11 post HT that comprises a cubic nanocrystalline lattice structure including zirconium oxide (with or without nitrogen) that is very resistant to scratches in certain example embodiments of this invention. It has been surprisingly discovered that the use of zirconium nitrite (such as ZrN) in layer 7 pre HT is especially advantageous 25 in terms of allowing layer 11 post HT with phase transformation including Zr to be formed, which is very resistant to scratches.

Following heat treatment the silver layer 6 is still present as shown in the middle and bottom parts of Figure 1. However, HT can cause the silver in layer 6 to migrate or 30 to diffuse from the direction outwardly from the glass substrate towards the surface 15 of the coated article (for example from layers 11 and 12). Prior to heat treatment, the Ί-inclusive layer with zirconium may have a compressive strength and / or substantially no strength. However, layer 7 can be designed in such a way as to produce tensile strength after HT. In certain exemplary embodiments of this invention, layer 7 inclusive with zirconium nitrite and / or zirconium oxide 5 can be transformed through the HT process into a layer 11 of or including zirconium oxide which has a degree of strength . the traction within it that was not present in the pre HT layer. The tensile strength in layer 11 is advantageous in that it allows layer 11 to be porous, thereby allowing silver particles 10 from silver layer 6 to diffuse and / or migrate outwardly in the direction

I of the surface 15 over time. In certain cases, the tensile strength allows or causes crystal grain boundaries and / or tiny pinholes or nano-holes to be present in layer 11 to allow silver to migrate through the entire surface towards the article 15 15 coated over time. Note that when photocatalytic sidewalk 12 is not used, surface 15 of the coated article is the top of layer 11 with a zirconium base (ie the final product can be as shown in the middle of figure 1 in certain cases). An example of how to make layer 11 comprising 20 zirconium oxide post HT have enough tensile strength to allow migration / diffusion of silver is to add layer 7 of zirconium nitrite and / or zirconium oxide formed originally with CE or similar. As explained above, silver reaching the surface 15 of the coated article is advantageous in that it assists in killing bacteria and / or germs on the surface of the coated article, 25 functioning for this reason as an antibacterial and antifungal agent.

In the embodiment of figures 1 and 3, the photocatalytic layer 12 can be provided on the glass substrate 1 above the inclusive layer 11 of zirconium oxide. When HT is used (thermal tempering), the application of the photocatalytic layer 12 is typically performed after the HT as shown in Fig. 1. The photocatalytic layer 12 can be of any suitable photocatalytic material in different modalities of this invention, however the titanium oxide (such as TiO₂) is preferably in certain cases. Layer 12 is of, or includes an active photocatalytic composition containing an active photocatalytic oxide of a transition metal (MO) or (MO₂) such as the TiO catalyst₂ for the production of a substantially transparent self-cleaning coating. Layer 12 will then react with and decompose organic compounds or pollutants deposited on it from the environment, under the effects of exposure to sunlight such as UV radiation. Organic pollutants are broken down into simple organic compounds such as CO₂ and / or H₂O and / or several mineral acids, which can re-enter the atmosphere and / or be washed 10 due to rain, wind or similar, such that the coated article is self-cleaning with an efficiency that is dependent on the degree of photocatalytic activity in the catalyst, which can be proportional to the total surface area of ​​the particles of the photocatalytic material to which the pollutant is exposed. For example and without limitation, when the TiO anatase₂ is illuminated by ultraviolet (UV) radiation with a wavelength below about 390 nm, the electrons in the valence range are excited to the conduction range leaving behind positively charged holes that are reactive with the hydroxide ions of the vapor of water absorbed, 0 which results in the formation of positively charged hydroxyl radicals (OH)⁺. Hydroxyl radicals in the photocatalytic layer 12 are strong oxidizing radicals that can react with and extract pollutants to produce simpler, non-offensive products such as 0 CO₂ and / or H₂O, or HCI that are halogen pollutants is involved. It is noted that the photocatalytic layer 12 may include other or other materials such as an acrylic urethane polymer that can be used 25 to increase liquid-forming properties and / or to reduce any potential yellow color formation due to layer 12.

It is noted that many layers of titanium oxide are not photocatalytic. Thus, simply providing a layer of titanium oxide as the outermost coating of a coated article does not mean that the layer is photocatalytic. However, the anatase form of titanium oxide is photocatalytic and is used in certain exemplary embodiments of this invention.

The photocatalytic layer 12 can be formed on the glass substrate in any suitable manner. For example, the photocatalytic layer 12 can be deposited on the glass substrate 1 over layers 3, 6 and 11 using a spraying technique, a rotation coating technique 5, a flow coating technique, or similar. The photocatalytic layer 12 can be initially deposited in a wet form including colloids (such as titania colloids) in solution. For example and without limitation, the photocatalytic layer 12 can be initially deposited as the application of a colloidal form of anatase 10 (for example, from 0.1 to 2%, more preferably from 0.2 to

I 1.2% TiO anatase₂ in solution such as with water or similar). The colloidal anatase material can be added with Zn cations or similar in certain example cases. Anatase is a special crystalline form of titanium oxide that is photocatalytic. That colloidal material can be deposited after application of an underlying initiator layer in certain exemplary embodiments of this invention, and can be deposited in any suitable manner which includes but is not limited to spraying, meniscus flow, or flame combustion. . In certain exemplary embodiments, a catalyzed acid silica can be provided in the dispersion together with the titania colloids, or in an initiator, in order to produce a good humidification capacity. An example of catalyzed acid silica is glycidoxypropyl trimethoxysilane. For example, and without limitation, the photocatalytic layer 12 can be formed in any way described in, and can be of any material described in any of the 25 US Patent Documents Nos. 6,884,752. 2005/0234178. 6,107,241.

and / or 6,939,611. 6,235,401, the description of which are all incorporated here, in this patent application by reference.

Then the heat can be used to cure the colloid layer, with heat either generated from a heat treatment oven 30, radiant heaters or from a heat treatment carried out just before the colloidal dispersion is applied. . The examples of heat treatment for curing the photocatalytic layer in order to perform the removal of the solution from it, leaving titania for the formation of the photocatalytic layer 12, can be from about 200 to

600 degrees C. most preferably from about 400 to 550 degrees C, with an example being for about 3 minutes at about 500 degrees C.

'5 Curing time and temperature, as well as the original particle size in the colloidal material determines the scratch resistance of layer 12. When the heat used in curing causes the solution and / or solvent to evaporate or burn thereby leaving metal oxide (for example, TiO₂) by making layer 12 photocatalytic, the resulting photocatalytic layer 12 is porous in nature. This is because the metal oxide molecules (for example, TiO₂) that make the photocatalytic layer 12 not closely joined (the layer is not specifically dense) due to the previous presence of the solution or solvent that has taken up the space between the metal oxide molecules (for example, TiO₂). The amount of nano-porosity 15 in layer 12 can be used to (a) substantially match the refractive index (n) of photocatalytic layer 12 to that of inclusive zirconium layer 11, (b) increase the photocatalytic behavior of layer 12, and / or (c) create nano pores, pin holes and / or crystal grain boundaries that can be used as the diffusion and / or migration paths of the silver particles from the silver layer 6 to migrate towards the surface of the coated article for antifungal and antibacterial purposes .

When TiO₂ it is formed through crackle deposition, it is typically very dense (it is not porous), it is not anatase and it has a refractive index (n) of at least 1.4. This would not be desirable due to the fact that this layer of TiO₂ deposited through crackling would not be photocatalytic, could not substantially match the refractive index of the underlying layer based on zirconium oxide 11, and would not be porous to allow silver migration or diffusion to surface 15 over time. However, when TiO₂ is formed using a colloidal dispersion or a sol including titania, and is then heat treated to remove the liquid, the resulting layer 12 based on TiO₂ it is highly desirable in that (a) it comprises the TiO anatase₂ such that it is photocatalytic, (b) it is not very dense (due to the area previously occupied by the liquid) such that the retraction index is much less, and (c) due to its not very dense nature , it is porous and includes the migration and diffusion paths for silver to make its way 5 to the surface 15 of the coated article over time to cause the antibacterial and antifungal effects. Thus, in effect, silver from the silver layer can be substantially continuously pumped onto the surface of the coated article over time so that silver can be provided on the surface of the coated article for long periods of time. time (for example, months or even years in determining typical environmental conditions).

Typical T1O2 layers deposited by crackling have a refractive index (n) of at least about 2.4 or 2.45. However, an advantage of certain exemplary embodiments of this invention is that it provides an inclusive layer of titanium oxide that has a much lower refractive index (n) such that it can substantially and optically match the layer based in titanium oxide under it, thereby providing a coated article with a better appearance. In certain exemplary embodiments of this invention, the photocatalytic 12 bed20 based on the titanium oxide anatase (eg T1O2) has a refractive index (n) from about 1.75 to 2.15, more preferably from about 1.865 to 2.15, and most preferably from about 1.9 to 2.1, in order to substantially match the refractive index of the inclusive titanium oxide layer 11 below the same. In some finished example modalities of this invention, the inclusive layer of titanium oxide 11 has a refractive index (n) from about 1.95 to 2.15, more preferably from about 2.0 to 2.1, with an example being around 2.05. In certain example embodiments, the refractive index of layer 12 is no different from that of layer 11 by more than 30 than 0.1, more preferably by no more than about 0.05. Thus, it will be appreciated that the refractive indices (n) of layers 11 and 12 can be surprisingly matched in the final product in certain exemplary embodiments of this invention, even though they are of different materials that typically have very different refractive indices. This equality of refractive indices in layers 11 and 12 is advantageous in that it allows a more desirable color to be achieved in the final product, and a lower reflectance is achieved.

Another advantage of a TiO catalytic layer 12₂ formed in the manner described above is that it can be made to have a very low contact angle and is therefore hydrophilic. In certain exemplary embodiments of this invention, the article coated with such a layer 12 may have a contact angle Θ of not more than about 12 degrees, more preferably not more than about 10 degrees, and possibly not more than about 7 or 5 degrees. This is an advantage in that it allows fog or water to be removed more easily from the window in certain embodiments of this invention.

In certain window or table top embodiments of this invention, the coated article shown in figures 1 and 3 has a visible transmission of at least about 50%, more preferably at least about 60%, and possibly at least about 70%. These high visible transmissions are desired for window applications.

For example purposes only, certain sample thicknesses for the HT post coated article shown at the bottom of figure 1 are shown below, with the layers being listed in order from the glass substrate upwards.

Example Coating (Fig.1) - Layer thickness (Post HT)

Layer

Dielectric (film 3) Silver (layer 6) ZrN: O (layer 11) TiO₂ (layer 12)

General

50-1,000 Á

20-400 Á

50-80 Á

100-900 Á

More preference

80-500 Â

20-200 Â

70-600 Â

300-600 Â

Highest Preference 120-250 Â

20-100 Â

100-350 Â

350-450 Â

It can be seen from the above that the inclusive layer 11 HT post is typically thicker than the inclusive layer of Zr pre HT. In other words, the thickness of the inclusive Zr layer can increase during HT. In certain exemplary embodiments of this invention, the thickness of the inclusive Zr layer (for example, from layer 7 to layer 11) may increase by at least about 5% during or due to HT, more preferably at least about 10%, and most preferably about at least 40%. This increase in thickness is caused by the transformation of layer 7 into layer 11, in which oxygen migrates into layer 11 post HT (that is, more oxygen migrates into layer 11 post HT than nitrogen leaves in terms of atomic percentage and / or size in certain cases).

In certain exemplary embodiments of this invention, the heat treated layer 11 comprising zirconium oxide includes Zr_xO_y where x / y is from about 1.2 to 2.5, more preferably from about 1.4 to 2.1. In addition, it is possible that the residual carbon remains in layer 11 of zirconium oxide after HT due to the presence of layer DJC 9 pre HT. In certain exemplary embodiments of this invention in which DLC 9 was present before HT, zirconium oxide layer 11 includes from 0.25 to 20% C, more preferably from 0.25 to 10% of C, and more preferably from 0.25 to 5% of C.

It has been found that adding zirconium nitrite and / or zirconium oxide 7 with F and / or C before heat treatment tends to increase the visible transmission of the heat treated coated article. Additivating with F and C, results in a film with a lower absorption when compared to non-additive films. Furthermore, it has been found that the addition of F and / or C to these layers does not significantly change the optical properties of the coated article, or the biaxial strength of the film prior to

HT. Furthermore, when F and / or C are provided in layer 7, both the scratch resistance and environmental stability (for example, measured by salt spray test) of the product with HT are not substantially affected by the presence of F and / or C. Certainly, after heat treatment the layers 11 comprising zirconium oxide can also be added with F and / or C in a corresponding way, since they were present before HT. This additive of zirconium nitrite (and / or zirconium oxide) with F and / or C can be used in conjunction with any of the modalities discussed here, in this patent application. In certain exemplary embodiments of this invention, one or more of layers 7 and 11 can be added with from about 0.01 to 10.0% F, more preferably from 0.1 to 8, 0% F, even more preferably from about 0.3 to 5% F, even more preferably from about 0.4 to 2% F, and most preferably from about 0.5 to 1.0% F (in terms of atomic percentage). Furthermore, in certain exemplary embodiments of this invention, one or 10 more of layers 7 and 11 can be added with from about 0.01 to

10% C, more preferably from about 0.1 to 8.0% C, even more preferably from about 0.3 to 5% C, even more preferably from about from 0.4 to 2% C, and more preferably from about 0.5 to 1.9% C (in terms of atomic percentage). The additive 15 with F and C can be used together in such a way that one or more of the layers or 11 are additive with both the F and the C in those quantities. Alternatively, only one of the additives F and C can be used for one layer. Thus, in these alternative modalities, one or more of the layers 7, 11 can be added with F in the amount or quantities mentioned above, but not added with C As yet another alternative, one or more of layers 7, 11 can be added with C in the amount or quantities mentioned above, but not added with F.

Another notable aspect of certain exemplary embodiments of this invention is the extreme increase in visible transmission caused by heat treatment. In certain example embodiments, visible transmission increases by at least 20% of visible transmission due to HT, more preferably at least 30%, and most preferably at least 40%. For example, in certain exemplary embodiments of this invention that were made, the visible pre-HT transmission was about 36 to 30 37%. Following heat treatment for about 400 seconds at about 640 degrees C, the visible transmission after HT was about 77 to 81%. In each case, visible transmission increased by about 40 to 45% due to HT. For purposes of example and understanding, if a pre HT coated article had a visible transmission of 36% and then to HT the post HT coated article had a visible transmission of 80%, then the visible transmission increased by 44% (ie 80% - 36% = m44%) due to

HT. The apparent reason for this significant increase in visible transmission due to HT is the disappearance of at least some DLC due to HT due to the aforementioned combustion. The DLC blocks the visible transmission to some degree and its combustion and the disappearance of dL'-^r£ o. HT allows the visible transmission of the coated article resulting from the HT to increase significantly as shown above. Of this

In this way, the combustion of the DLC acts as a fuel that allows the transformation of the inclusive Zr layer, but it also allows the visible transmission to increase significantly.

An alternative embodiment of this invention, with respect to figures 1 and 3, is to deposit the silver (Ag) simultaneously with the TiO₂. In other words, the photocatalytic layer 12 could include both TiO₂ and silver in these modalities. Such a modality may or may not be used in combination with the forecast of the silver layer 6. In other words, the silver layer 6 can be eliminated if this approach is taken in 20 certain cases, or it does not need to be eliminated if this approach is taken. For example, a simultaneous application (together with TiO₂) of a colloidal silver can be performed in such a way that the photocatalytic layer 12 could also have an antibacterial and antifungal property as deposited, without the need for migration or diffusion of the square although this may still be possible. The silver particles deposited together with layer 12 can be chosen in such a way as to have a size that allows them to fit between the TiO particles₂ in the photocatalytic layer 12 in such a way as to also mechanically reinforce the coating within a ceramic and metal composite. In certain exemplary embodiments of this invention, layer 12 may include from about 50 to 90% TiO₂ (or some other photocatalytic material or other suitable metal oxide) and from about 1 to 30% Ag. In certain of these modalities, layer 12 can include from about 1 to 20% silver, from more preferably from about 1 to 10% silver.

Figure 2 is a schematic diagram illustrating a method for making a photocatalytic coated article according to another embodiment of this invention, before and after heat treatment. Specifically, the embodiment of figure 2 illustrates that the silver layer 6 and / or the dielectric film 3 can be eliminated from the embodiment of figure 1. The mode of figure 2 is the same as the mode of figure 1 described above, except that the dielectric film 3 and / or the silver layer 6 10 are eliminated in the mode of figure 2. It is observed that the options and characteristics mentioned (such as, using a combination of silver and titanium oxide, thickness of the layer, how the layers are deposited and formed, characteristics of the layers, etc.) described in relation to the modality of the figure 1 as elements 1,7, 9 11 and 12 are also applicable to the modality of figure 2 because these layers are also present in the modality of figure 2.

With respect to any modality here, in this patent application, it is noted that silver can be replaced with copper (Cu). For example, copper can be used in place of silver for anti-bacterial and anti-fungal effects. In yet another exemplary embodiment of this invention, a mixture or combination of silver and copper can be used in place of silver alone.

Any suitable type of glass substrate 1 can be used in different embodiments of this invention. For example, several types of soda lime feldspar glass, or boron silicate glass can be used for substrate 1. However, in certain exemplary embodiments of this invention, the coating of any of the aforementioned embodiments can be supported by a special type of glass substrate that has a very high visible transmission and a very transparent color. Specifically, in such certain exemplary embodiments of this invention, the glass substrate 1 may be of any of the glass commonly described in common patent application 34 with serial number 10 / 667,975, the description of which is incorporated herein, in this patent application by reference. In certain preferred embodiments, the resulting glass has a visible transmission of at least 85%, more preferably at least 88%, and most preferably at least 90% (for example, at a reference thickness of about 0.219 inch or 5.56 mm). The advantage of using this glass substrate 1 is that the resulting HT product is made to have a similar appearance to that of uncoated clear glass - even though the coating has been provided on it. In addition to the glass base 10, examples of glass and / or final glass batches are shown below (in terms of weight percent of the total glass composition, unless otherwise noted, is in ppm).

Example of Cerium Dyes and Oxidizers on Glass Substrate

<td colspan="2">Ingredient</td><td>General</td><td>preference</td><td>more preference</td><td>best</td>

<td> 15</td><td>Total iron (Fe₂O₃):</td><td> 0,01 -0,20%</td><td> 0,01 -0,15%</td><td> 0,02-0,12%</td><td> 0,03-0,10%</td>

<td></td><td>cobalt oxide:</td><td>0 to 15 ppm</td><td>0.1 to 10ppm</td><td>0.5 to 5 ppm</td><td>0.5 to 3 ppm</td>

<td></td><td>cerium oxide:</td><td> 0-1,0%</td><td> 0,01 -1,0%</td><td> 0,01 - 0,5%</td><td> 0,05 - 0,2%</td>

<td></td><td>erbium oxide:</td><td>0 to 1.0%</td><td> 0,01 - 0,3%</td><td> 0,02 - 0,20%</td><td>0.02 to 0.15%</td>

<td></td><td>titanium oxide:</td><td>0 to 0.5%</td><td>0 to 0.2%</td><td>0.01 to 0.05%</td><td>0.01 to 0.02%</td>

<td> 20</td><td>chromium oxide:</td><td>0 to 10 ppm</td><td>0 to 8 ppm</td><td>0 to 5 ppm</td><td>1 to 5 ppm</td>

<td></td><td>redox glass:</td><td> &lt;= 0,20</td><td> &lt;= 0,12</td><td> &lt;= 0,10</td><td> &lt;= 0,08</td>

<td></td><td colspan="2">% FeO: 0.0001-0.005%</td><td> 0,0001-0,1%</td><td> 0,001-0,008%</td><td> 0,001-0,003%</td>

It is noted that in other embodiments of this invention, additional layers (not shown) can be added to the coated article discussed above, and / or a certain layer or layers can be canceled.

Although the invention has been described in connection with what is presently considered to be the most practical and preferred modalities, it is to be understood that the invention is not to be limited to the described modalities, but on the contrary, it is intended to cover several modi30 equivalent specifications and arrangements included within the spirit and scope of the appended claims.