Method of producing coated article, involving ion beam treatment of metal oxide protective film

This application is a continuation in part (CIP) application US № 11/699080, filed January 29, 2007, and CIP applications № 11/798920, filed May 17, 2007, the entire contents of which are incorporated herein by reference.

Certain embodiments of the present invention relate to a method of manufacturing a heat-treated (Heat treated - HT) coated article to be used in relation to the doors of shower cabins, windows, table tops or any other possible applications. For example, certain embodiments of the invention relate to a method of manufacturing a coated article comprising a step of heat treating a glass substrate coated with at least one layer comprising DLC ​​(diamond-like carbon - DLC), and on top of it a protective film. In certain embodiments, the protective film may include one or two layers of (a) or oxygen impermeable barrier layer, and (b) a separation layer. In certain exemplary embodiments the protective film (e.g., composed of zinc oxide or comprising it) before the heat treatment is subjected to ion beam treatment in order to introduce therein the ions of carbon (C) in order to improve durability of the coated article to corrosion (i.e. to increase the shelf life). After and / or during heat treatment (such as quenching and the like) the protective film may be entirely or partially removed. Other embodiments of the invention relate to a coated article before the heat treatment, or a coated article after heat treatment, or methods of manufacture.

BACKGROUND

Coated articles such as transparent shower doors and windows booths pulse generators are often subjected to heat treatment such as hardening, to ensure safety and / or increase the strength. For example, a glass substrate with a coating designed for use in shower door and / or window units are often heat treated at a high temperature (e.g., at least about 580 ° C, more typically about 600-650 ° C) to quench .

Diamond-like carbon (DLC) sometimes known due to its resistance to scratching. For example, different types of DLC are described in the following U.S. Patents: 6303226; 6303225; 6261693; 6338901; 6312808; 6280834; 6284377; 6335086; 5858477; 5635245; 5888593; 5135808; 5900342 and 5470661, each of which is incorporated herein by reference.

Sometimes it is desirable that the window unit or other glass article has a protective coating comprising DLC, with a view to protect it from scratches and the like Unfortunately, DLC tends to oxidize and burn at a temperature of from about 380 to 400 ° C, since the heat treatment is generally carried out in an atmosphere containing oxygen. Consequently, it is clear that DLC as a protective outer coating can not withstand the heat treatment under the above very high temperatures which are often necessary in the manufacture of glass for automobiles, window units for the pulse generators, glass table tops, and / or the like

Hence, those skilled in the art will appreciate that a need exists for a method for producing the heat-treated product with a protective coating (one or more layers) comprising DLC. A need also exists in the corresponding coated articles, both heat treated and before the heat treatment.

In this connection, US patent application number 11/798920 (incorporated herein by reference) describes a method of making a coated article comprising a step of heat treating a glass substrate coated with at least one layer comprising diamond-like carbon (DLC), and an outer protective film of zinc oxide on top of it. In certain exemplary embodiments, the protective film may be composed of the following layers or both layers comprise: (a) an oxygen-impermeable barrier layer, or (b) a separation layer. After and / or during heat treatment (such as quenching and the like) the protective film may be entirely or partially removed.

Unfortunately, the shelf life and / or stability of the product before the heat treatment of the coated application 11/798920 limited. For example, it has been found that the protective film of zinc oxide to corrode the heat treatment (heat treatment after the protective film is often lost). Samples stored in moderately humid environment begin to fade (when viewed from the glass side) suggesting that over time moisture penetrates through the protective film based on zinc oxide and reaches the DLC. Furthermore, according to the application 11/798920 film immediately after application can not stand one hour under test, which combines high temperature and high humidity (50 ° C / 95 RH. Is.).

Consequently, it is clear that in the art there is a need to improve the shelf life and / or stability of coated articles such as a 11/798920, so that they are less likely to be dimmed to a heat treatment.

SUMMARY examples of the present invention

Certain exemplary embodiments of the present invention relate to a method of manufacturing a heat treated (HT) coated article to be used in relation to the doors of shower cabins, windows, table tops or any other possible applications. For example, certain embodiments of the invention relate to a method of manufacturing a coated article comprising a step of heat treating a glass substrate coated with at least one layer comprising diamond-like carbon (DLC), and, on top of it a protective film. In certain other exemplary embodiments, the protective film may consist of or include both of (a) or oxygen impermeable barrier layer, and (b) separation layer. In certain exemplary embodiments the protective film (e.g., composed of zinc oxide or comprising it) before the heat treatment is subjected to ion beam treatment in order to introduce therein the ions of carbon (C) in order to improve durability of the coated article to corrosion (i.e. to increase the shelf life). After and / or during heat treatment (such as quenching and the like) the protective film may be entirely or partially removed. Certain embodiments of the present invention relate to a coated article before the heat treatment, or a coated article after heat treatment, or methods of manufacture.

In certain embodiments, the present invention provides a method of manufacturing a heat treated coated article, the method comprising: providing a glass substrate; formation on this glass substrate, at least one layer comprising diamond-like carbon (DLC); forming on the glass substrate over at least one layer comprising DLC, the protective film comprising zinc oxide; ion beam treatment of the protective film comprising zinc oxide with at least carbon ions; heat treating the glass substrate with the layer comprising DLC, and a protective film on top of it so that during the heat treating the protective film prevents significant burning layer comprising DLC, wherein the heat treating comprises heating the glass substrate to a temperature sufficient for tempering, heat strengthening and / or thermal bending; impact on the protective film separating liquid and removing at least a portion of the protective film during and / or after heat treatment.

In other exemplary embodiments of the present invention, a method of manufacturing a heat treated coated article, the method comprising: providing a glass substrate; formation on this glass substrate, at least one layer comprising carbon; forming on the glass substrate over at least one layer of a carbonaceous protective film comprising at least one metal oxide; ion beam treatment of the protective film, at least carbon ions; heat treating the glass substrate with the layer comprising carbon and the protective film on top of it so that during the heat treating the protective film prevents significant burning layer comprising carbon, wherein the heat treating comprises heating the glass substrate to a temperature sufficient for tempering, heat strengthening and / or thermal bending.

In other exemplary embodiments, the invention provides a coated article comprising: a glass substrate; a layer comprising diamond-like carbon (DLC), on the glass substrate; a protective film comprising zinc oxide on the glass substrate over at least one layer comprising DLC; layer (or portion of a layer) containing oxycarbide zinc and located in the surface portion of the protective film comprising zinc oxide, so that the protective film comprising zinc oxide, characterized by changing, continuously or stepwise, the carbon content so that the farthest from the glass substrate side protective film contains more carbon than in the proximal part of the glass-based protective film.

In other exemplary embodiments of the present invention, a method of manufacturing a heat treated coated article, the method comprising: providing a glass substrate; formation on this glass substrate, at least one layer comprising diamond-like carbon (DLC); forming on the glass substrate over at least one layer comprising DLC, the protective film comprising zinc oxide, wherein said protective film comprising zinc oxide is formed using at least one sputtering target comprising zinc that sprayed into the atmosphere, at least carbon gas; heat treating the glass substrate with the layer comprising DLC, and a protective film on top of it, so that during the heat treating the protective film prevents significant burning layer comprising DLC, and heat treating comprises heating the glass substrate to a temperature sufficient for tempering, heat strengthening and / or thermal deformations ; impact on the protective film separating liquid and removing at least part of the protective film during and / or after heat treatment. In this embodiment, it is possible that ion beam treatment may not be required.

BRIEF DESCRIPTION OF DRAWINGS

1 is a schematic cross-sectional view of a coated article, before and after heat treatment in accordance with an exemplary embodiment of the present invention.

2 is a schematic cross-sectional view of a coated article, before and after heat treatment in accordance with another exemplary embodiment of the present invention.

Figure 3 is a schematic cross-sectional view of a coated article, before and after heat treatment in accordance with another exemplary embodiment of the present invention.

4 is a cross-sectional diagram showing the method of manufacturing a coated article in accordance with one exemplary embodiment of the present invention.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Consider in more detail the accompanying drawings, in which like numerals on different types indicate similar parts.

Certain exemplary embodiments of the present invention relate to methods of making a coated article which can be used in the heat treatment (HT), wherein the coated article includes a coating (one or more layers) comprising diamond-like carbon (DLC). In certain instances, the HT may involve heating the supporting glass substrate with the DLC to a temperature of 550 to 800 ° C, more preferably from 580 to 800 ° C (which is much higher than the temperature burnout DLC). In particular, certain exemplary embodiments of the present invention relate to a method allowing DLC ​​to withstand such HT without significant burnup during it. In certain embodiments, the temporary protective film (for example, consisting of or comprising one (or more) layer comprising zinc oxide and the like) is formed on the glass substrate over the DLC so as to reduce the likelihood of burnout DLC during HT. In certain embodiments, a protective film (for example, composed of zinc oxide or comprising it and the like) is subjected to ion-beam treatment, to introduce into it carbon ions (C). It has surprisingly been found that this introduction of carbon in the protective film improves the durability of the coated article to corrosion (i.e., prolongs the shelf life) prior to heat treatment. After and / or during heat treatment (such as quenching and the like) the protective film may be entirely or partially removed. Thus, the majority (if not all) DLC remains on the glass substrate and does not burn during HT. In various embodiments, the temporary protective film (which may comprise one or more layer) after HT may be removed or not.

In certain exemplary embodiments, the temporary protective film may be formed from or include both of (a) or oxygen impermeable barrier layer, and (b) separation layer. An example of the advantages of using different layers of differing - oxygen-impermeable layer and a separating layer - 17 in the film is that each layer (17a and 17b) can be optimally selected in accordance with her function. Consequently, it is possible to improve the time characteristics of the film 17 and, if necessary, to make it thinner. Ion-beam treatment of the protective film may cause the formation of a thin layer 17c composed of zinc or oxycarbide it contains, at least in the surface region of the film 17. In certain exemplary embodiments, after having HT DLC layer provides protection from abrasion and corrosion, and adhesion of minerals in hard water (e.g., easy to clean when used in hard water). In alternative exemplary embodiments, the protective film 17 (e.g., consisting of or containing zinc oxide, which may or may not include dopants Al, etc.) can be a single layer which may or may not have a gradient of oxidation.

1 is a schematic cross-sectional view of a coated article, before and after heat treatment in accordance with an exemplary embodiment of the present invention. Typically, the coated article on the left of Figure 1 takes place at the manufacturing stage before the heat treatment (HT), but also, in certain cases, it may exist after HT. The coated article shown in Figure 1 includes glass substrate 1, a layer 11 comprising DLC, and a temporary protective film 17 which may consist of one or more layers. In certain exemplary embodiments, the temporary protective film 17 includes first and second layers 17a and 17b, which can be formed by the same or different materials, and a layer or layer portion 17c containing zinc oxycarbide resulting from the ion beam treatment. Glass substrate 1 is typically composed of calcium-sodium silicate glass or includes, though in certain cases may be used other types of glass.

In certain exemplary embodiments comprising DLC ​​layer 11 may have a thickness of from about 5 to 1,000 angstroms (Å), more preferably 10-300 Å, most preferably from 20 to 65 Å, possibly about 25-50 Å, for example, a thickness of about 30 Angstroms. In certain exemplary embodiments comprising DLC ​​layer 11 may have an average hardness of at least about 10 GPa, more preferably at least about 20 GPa, most preferably from about 20 to 90 GPa. With such hardness layer (s) 11 resistant to scratching, certain solvents, and / or the like In certain exemplary embodiments, layer 11 may be formed of or include a special type of DLC, known as a substantially tetrahedral amorphous carbon (t-aC), and in some embodiments, may be hydrogenated (t-aC: H). In certain embodiments, where the hydrogenated DLC, t-aC type or any other suitable type of DLC may include from 1 to 30% hydrogen, more preferably 5-20% H, more preferably 10-20% H. This t-aC type DLC has more sp3 carbon-carbon (C-C) bonds than sp2 carbon-carbon (C-C).

In certain exemplary embodiments, at least about 30% or 50% of carbon-carbon-containing DLC ​​layer 11 may be sp3 carbon-carbon (C-C), more preferably at least about 60% of the linkages carbon-carbon bonds in the layer 11 may be sp3 carbon-carbon (C-C), most preferably at least about 70% of carbon-carbon bonds in the layer 11 may be sp3 carbon-carbon (C-C). In certain exemplary embodiments, the DLC may have an average density of at least about 2.4 g / cm3, more preferably at least about 2.7 g / cm3. Examples of linear ion sources which may be used for the deposition of DLC layer 11 comprising a substrate 1 include any of those described in US Patents number 6,261,693, 6,002,208, 6,335,086 or 6,303,225 (each of which is incorporated herein by reference). When using an ion source for the deposition of layer (s) 11 in that the source for the purpose of emission of the ion beam on the substrate 1 for forming layer (s) 11 may be used by the source hydrocarbon gas (s) (e.g., C2H2), HMDSO, or any other suitable gas . It is noted that the hardness and / or density of layer (s) 11 can be adjusted by varying the ion energy deposition apparatus.

Due comprising DLC ​​layer 11 becomes coated article more resistant to scratching than the product without the layer 11. It is noted that in certain embodiments of the present invention based on the glass simultaneously with the layer 11 may or may not be present additional layer (s) under the layer 11 between the 1 and the foundation layer 11, in accordance with certain embodiments of the present invention. Thus, the phrase "based on" as used herein is not limited to the meaning of "in direct contact with the substrate," as the other layer (s) may be located therebetween.

For example, and without limitation, layer 11 consisting of DLC or containing it may be any one containing DLC ​​layers according to U.S. Patent number 6,592,993; 6592992; 6531182; 6461731; 6447891; 6303226; 6303225; 6261693; 6338901; 6312808; 6280834; 6284377; 6335086; 5858477; 5635245; 5888593; 5135808; 5900342 and 5470661 (each of which is incorporated herein by reference), or alternatively may be any other suitable type of DLC containing layer. Containing DLC ​​layer 11 may be hydrophobic (high contact angle), hydrophilic (low contact angle), or neither, in various other embodiments. DLC layer 11 may comprise about 5-30% Si, more preferably about 5-25% Si, possibly about 10-20% Si or containing Si in certain embodiments of the present invention. In some cases, the DLC may also be provided by the presence of hydrogen.

Temporary protective film 17 is provided to protect the DLC layer 11 during HT. If film 17 were not, DLC layer 11 during HT subjected to substantial oxidation and burned off, thus leaving the final product vulnerable to scratching. However, the presence of a temporary protective film 17 prevents access of oxygen or the amount of oxygen reaching the DLC layer 11 during HT from the surrounding atmosphere, thereby preventing oxidation of the material DLC during HT. As a result, after HT DLC layer 11 remains on the glass substrate 1 and provides resistance to scratching and / or the like In certain embodiments, the protective film 17 includes both an oxygen-impermeable barrier or layer 17a and a separation layer 17b.

Surprisingly it has been found that the use zinc and / or zinc oxide in a temporary protective film 17 is particularly beneficial in terms of reducing and / or preventing oxygen diffusion to the DLC during HT. As shown in Figure 1 an exemplary embodiment of the present invention includes a first temporary film containing zinc layer 17a and second layer 17b containing zinc. The first zinc-containing layer 17a in various embodiments of the present invention may be metallic, substantially metallic dostehiometricheskim or zinc oxide, while the second zinc-containing layer 17b in certain embodiments of the present invention may consist of or comprise zinc oxide it. In certain embodiments, layer 17a is more metallic than layer 17b. In other words, layer 17b contains more oxygen than layer 17a. Thus, layer 17 may function as the separation layer, whereas the layer 17b can function as impermeable or oxygen barrier layer, along with zinc oxycarbide containing layer 17c. "Impermeable" Oxygen or "barrier" layer means that the layer prevents significant penetration of oxygen to the DLC during HT.

In certain exemplary embodiments of the present invention, the layer 17a may be formed ZnOy or contain it, and the layer 17b may be formed or include ZnOx, where x> y (that is, layer 17b contains more oxygen than layer 17a). Moreover, in certain exemplary embodiments, y is from about 0 to 0.9, more preferably from about 0.1 to 0.9, more preferably from about 0.1 to 0.8, maybe from about 0 1 to 0.7. Thus, in certain exemplary embodiments, x is greater than y and ranges from about 0.3 to 1.0, more preferably from about 0.3 to 0.99, even more preferably from about 0.5 to 0.95 may from about 0.6 to 0.90. Thus, it should be understood that in certain special cases, both layers 17a and 17b may be composed of zinc oxide or contain it, and both layers 17a and 17b may have dostehiometrichesky composition.

It was discovered, the use containing zinc oxide layer 17a that is more metallic than containing zinc oxide layer 17b (in which is formed 17c) allows surprisingly more effectively and easily remove the protective film 17 during and / or after heat treatment ( HT). In other words, layer 17a is a separating layer. Various compositions containing zinc oxide layers 17a and 17b are used to create in the layers 17a and 17b of different voltages, wherein the voltage is adjusted so as to allow for easier removal of the film 17 during and / or after HT. In particular, a metal layer 17a on the basis of zinc oxide can be regarded as a spacer layer for the unimpeded removal of the film 17 with DLC or warp during and / or after HT due to the reduced or zero content therein oxygen, whereas the less metallic (more oxidized ) layer 17b on the basis of zinc oxide can be considered as impermeable or oxygen barrier layer that reduces or prevents burning and / or oxidation of the DLC during HT. Zinc oxide as a material for the film 17 is advantageous because it is easily removed (e.g., using water and / or vinegar) during and / or after HT without using toxic materials.

As indicated above, one or both layers 17a and 17b, when they consist of zinc and / or zinc oxide, or contain them may be dostehiometrichesky composition. This is advantageous in terms of absorption of oxygen during HT. If the zinc oxide of the entire film 17 is too oxidized (i.e., to stoichiometric) prior to HT, then oxygen can diffuse through the zinc oxide. However, due dostehiometricheskomu composition of these layers 17a and / or 17b zinc contained therein during HT absorb oxygen, however, at least layer 17a (and possibly layer 17b) does not burn during HT. It is noted that the upper layer is based on zinc oxide 17b and / or zinc oxycarbide (or zinc aluminum oxycarbide) 17c during HT may burn (fully or partially) or not fade in various exemplary embodiments of the present invention. It is noted that another example advantage of using dostehiometricheskogo zinc oxide (compared to a completely stoichiometric zinc oxide) is that it can quickly be precipitated (such as by spraying, and the like). One or both layers 17a, 17b may be deposited by spraying in the form dostehiometricheskoy any suitable manner, for example by changing the flow rate of the oxygen gas chamber (s) for spraying. For example, but without limitation, the layer 17a can be deposited by sputtering using 10 ml / kW (regarding content of oxygen gas), whereas layer 17b may be deposited by sputtering using 12 ml / kW (with the rest of the gas is Ar and etc.) in some instances.

Note that in certain exemplary embodiments of the present invention, one or more of the containing zinc oxide layers 17a, 17b and 17c may include dopants of other materials such as Al, N, Zr, Ni, Fe, Cr, Ti, Mg mixtures thereof and etc.

In certain exemplary embodiments, the spacer layer 17a (eg, composed of zinc oxide or zinc dostehiometricheskogo composition) may be deposited (e.g. by sputtering) so that its thickness is approximately 50-20000 Å, more preferably about 50-3000 Å , still more preferably about 100-1000 Å, for example, a thickness of about 100-300 Å. In certain embodiments of the present invention containing zinc oxide layer 17b may be deposited (e.g. by sputtering) so that its thickness is approximately 200-10000 Å, more preferably about 500-5000 Å, more preferably about 1000-3000 Å, for example, thickness of about 2000 Å. In certain embodiments of the present invention contains the zinc oxycarbide or zinc aluminum oxycarbide layer or layer portion 17c may have a thickness of at least about 50 Å in certain exemplary embodiments (e.g., 50-500 Å), more preferably at least about 100 Å (for example, 100-500 Å), 150 Å (e.g., 150-400 Å) or 200 Å (e.g., 200-400 Å). More metallic layer 17a may be thicker than less metallic layer 17b (17b in this regard include 17c) in certain exemplary embodiments of the present invention; in some instances up to HT layer 17a may be at least twice as thick as layer 17b. Preferably, the total thickness of the temporary film 17 in certain exemplary embodiments, is less than about 10000 Å, more preferably less than about 3000 Å, most preferably less than about 1000 Å.

2 illustrates another exemplary embodiment of the present invention. The embodiment shown in Figure 2 is similar to that described above with reference to Figure 1 except that in the embodiment shown in Figure 2, between the glass substrate 1 and the layer comprising DLC ​​11 provides a barrier layer 6. The barrier layer 6 in certain exemplary embodiments of the present invention may be a dielectric. Optional barrier layer 6 is for preventing or reducing the migration of oxygen and / or sodium (Na) glass 1 to the DLC 11 during HT. In this sense, such an optional barrier layer 6 may improve the overall optical properties of the coated article following HT. Barrier layer 6 may consist of or include silicon oxide, silicon nitride, silicon oxynitride and / or the like, although it is also possible to use other materials with barrier properties. Barrier layer (s) 6 is formed on the glass substrate 1 by spraying or by other suitable method. The thickness of the barrier layer 6, in certain exemplary embodiments may be from about 10 to 1000 Å, more preferably from 50 to 500 Å, most preferably from 50 to 200 Å. It is noted that, if needed, in other exemplary embodiments of the present invention, such as any of the embodiments shown in Figures 4-7, a barrier layer (s) 6 may also be provided between the DLC 11 and the glass substrate 1.

Figure 3 illustrates another exemplary embodiment of the present invention. The embodiment shown in Figure 3, similar to the embodiment shown in Figure 1 (or the same embodiment, illustrated in Figure 2, if a barrier layer 6, which may also occur in the embodiment shown in Figure 3) for except that instead of two separate layers 17a and 17b the protective film 17 is formed with one layer having an oxidation gradient (continuous or stepwise) in thickness. In the embodiment shown in Figure 3, film 17 is such that this film 17 includes more oxygen in the layer farthest from the DLC 11 portion than in another part of this film, which lies closer to the DLC layer 11. Note that the film 17 in the embodiments of the invention, the illustrated Figures 1-2 may also be viewed as having a gradient oxidation film 17 as a whole in a more oxidized layer 17b that lies further from the DLC layer 11 than in layer 17a lying closer to the DLC layer 11. However, in embodiment shown in Figure 3, in certain cases it is also possible that the entire or substantially the entire film 17 has a continuous or substantially continuous gradient of oxidation.

In each of the embodiments of the invention, the illustrated figures 1-3, the protective film 17 (e.g., consisting of zinc oxide, or containing it) may be subjected to ion beam treatment in order to introduce, at least, carbon (C) film 17, at least in its surface portion. Surprisingly it has been found that this introduction of carbon in the protective film improves the durability of the coated article to corrosion (i.e., to increase the shelf-life) prior to heat treatment. Ion-beam treatment may be performed using one (or more) ion source 18. The source (s) 18 such ions during ion beam treatment may be used in a gas such as acetylene (C2H2), carbon dioxide, etc., to produce carbon ions flow toward and into film 17. In certain exemplary embodiments, the carbon may be implanted to a depth of at least about 50 Å from the surface of the film 17, more preferably at least about 100 Å, 150 Å or 200 Å from the surface of film 17. The ion beam treatment causes formation at least some zinc oxycarbide at least at a surface portion of the film 17. For example, in certain exemplary embodiments of the invention comprising zinc oxycarbide layer 17c may have a thickness of at least about 50 Å, more preferably at least about 100 Å, 150 Å or 200 Å. Because zinc oxycarbide has strong adhesion and is relatively insoluble, the film 17 becomes more resistant to corrosion and more resistant to wear, thereby increasing its shelf life prior to HT. It was found that the samples subjected to treatment with carbon dioxide, have extended shelf life compared with samples deposited using only oxygen.

In various embodiments, the ion beam treatment of film 17 may be carried out: (a) after deposition of film 17 sputter and / or (b) during the sputtering deposition of the film 17. The first case can be regarded as a surface hardening, while the second may be considered in certain instances, as deposition with ion bombardment (ion beam assisted deposition - IBAD). Ion-beam treatment is performed simultaneously IBAD type spray, so that the ion beam is used to process the film 17 during its sputtering deposition.

An example of ion beam treatment, relating to the type of ion beam treatment (a) surface strengthening film 17 can be described as follows. A film 17 (including one or both layers 17a, 17b) (e.g., ZnOx) is deposited on the glass substrate 1 by spraying. In various embodiments, the sprayed zinc oxide film 17 may or may not contain dopants of other elements (e.g., Al). After spraying comprising ZnOx film 17 on the substrate 1 over the DLC 11, the coated article is moved relative to the at least one ion source 18 so as to be in a position suitable for spraying. At least one carbon-containing gas (e.g., hydrocarbon gas such as C2H2, etc.) is used or supplied through the source (s) 18 ions, so that the source () creates a beam of ions comprising at least carbon ions (C) directed at the film 17 of ZnOx. Ions in the ion beam C possess sufficient energy for introduction into comprising ZnOx film 17, as shown in Figures 1-3. It is noted that, in various embodiments, the ion beam from source 18 may be focused, diffused, or collimated.

The introduction of ions / atoms in the resultant sputtering comprising ZnOx film 17 is formed by a layer comprising zinc oxycarbide 17c, at least near the surface of said film, as shown in Figures 1-3. Through the introduction of ions / atoms in film 17, the corrosion resistance of the resulting film 17 is significantly higher than that of the film 17 before the introduction of ions / atoms C.

In certain instances, the introduction into comprising ZnOx film 17 carbon ions have sufficient energy to cause ejection of oxygen (O) from molecular ZnOx so that it becomes possible to form a substantially continuous layer or of the layer containing oxycarbide zinc 17c on the surface of the previously obtained spray layer as shown in Figures 1-3. In certain exemplary embodiments, the zinc oxycarbide layer 17c may be represented, at least in part, by the formula ZnOxCy, where x / y is from 0.5 to 1.5.

Source (s) 18 of the ions to be high-to in the created them beam carbon ions have an energy sufficient to: (a) the introduction of the resulting coated containing ZnOx film 17, (b) push oxygen molecules ZnOx, (c) implementation (and ) and (b) in an amount sufficient to form a substantially continuous layer of zinc oxycarbide 17c. To obtain sufficient in this regard to energy in accordance with certain exemplary embodiments of the present invention, the source (source) 18 ions using voltage anode-cathode, at least about 800, more preferably at least about 1500, more preferably at least about 2000 V and even more preferably at least about 2,500 V. In certain cases, it may be used in the source voltage of at least about 3500 V. The above "stress" (or accelerating voltage) relating to a voltage which is used in the source (s) 18 of the ions to cause ion implantation / atoms in film 17, is a voltage between the anode and cathode of the ion source. As is well known in the art, "the ion energy" associated with this "stress" anode-cathode, but differs from it. For example, molecules of acetylene (C2H2), the energy of the ionized molecule fragment of one half (1/2) of the accelerating voltage. Thus, when a voltage of 2000 V energy ionized molecule fragment is equal to 2000/2 = 1 000 V. Furthermore, in the case of C ions formed from acetylene (C2H2) used as a source gas in the ion source, in a fragment of the molecule has two atoms carbon. Thus, when the starting gas for producing a beam of ions for use acetylene (C2H2), the energy of one carbon atom will be half the energy of the ionized molecule fragment. In other words and for example only, in the case where ions are formed using C2H2 as the source gas in the ion source, the voltage in the ion source (i.e., at least about 800, 1500, 2000 and / or 2500 B, as explained above) corresponds to the energy of the ions of at least about 200 eV per ion, more preferably at least about 375 eV per ion C, more preferably at least about 500 eV per ion C and even more preferably at least about 625 eV per C ion If used with low energy ions (or low voltage in the ion source), it can not lead to the introduction of C ions and / or the formation of a continuous layer comprising titanium oxycarbide.

It is understood that when the source 18 as the source gas is a hydrocarbon gas such as C2H2, and the resulting beam contains ions, and ions of N. Thus, in certain embodiments of the present invention, the layer or layer portion 17c may have zinc oxycarbide dopant N (in addition to Al and the like). In certain exemplary embodiments, the layer 17c may include from 0 to 20% H, more preferably from 1 to 18% H, more preferably from 5% to 15 N.

In certain embodiments, the ions are introduced deeply enough into the floor teachings sputtering comprising ZnOx film 17, however, the formation of a substantially continuous layer comprising zinc oxycarbide 17c, at least near its top. In certain exemplary embodiments, at least some of the ions (and / or C atoms) are introduced into the resulting plated film 17 to a depth «d», at least 25 Å from the upper surface of the resulting plated film 17 (more preferably at least 50 Å, more preferably at least 100 Å). If implantation occurs insufficiently, it may not affect the wear resistance, etc. or the film will wear quickly.

In certain exemplary embodiments, the source (s) 18 can operate ions in such a mode that only radiate in the direction of the film 17 enough C ions in order to cause the introduction of ions / atoms in film 17, as shown in Figure 1 3, but does not cause the formation of a layer of amorphous DLC (e.g., ta-C or ta-C: H) over the zinc oxycarbide layer 17c. Alternatively, in other embodiments, the source (s) 18 ions operates in this mode to over the layer 17c oxycarbide zinc formed a thin layer (not shown) comprising amorphous DLC (e.g., ta-C or ta-C: H ). Exemplary parameters such DLC layers are described in US patent number 6261693, which is incorporated herein by reference. This thin DLC layer (not shown) in certain exemplary embodiments of the present invention may have a thickness of 1-30 Å, more preferably about 1-20 Å. It is noted that in some cases over oxycarbide also can be provided to other layers. Moreover, this very thin layer comprising DLC ​​in certain embodiments may be temporary in the sense that it provides the possibility of wear (i.e., disappearances) over time, especially during HT. For example, such a thin layer comprising DLC ​​may be used to protect the coated article from scratching, etc. during transportation, handling, etc. and then, after some time, it may wear out (or burn during HT). If desired, in certain cases, this overlying layer comprising DLC ​​(not shown) may be even thicker than 30 Å. Such overlying containing DLC ​​layer (s) may include a large number of sp3 carbon-carbon bonds (e.g., at least 40% of C-C bonds in the layer may be such bonds, more preferably at least 50%) can or may not be hydrogenated (e.g., about 1-25% H, more preferably about 3-18% H) or include other dopants in different embodiments of the present invention and / or, in certain cases, may have a density of at least 2 4 g / cm3.

Examples of the ion sources 18 that may be used for ion beam treatment of film 17 are disclosed in U.S. Patent number 6,002,208, 7,052,585 and 2005/0258029, each of which is incorporated herein by reference.

Referring to Figures 1-3, an example method of manufacturing a coated article. First glass substrate 1 provided on the surface of which optionally can be applied by spraying, at least one barrier layer 6 (e.g., silicon oxide, silicon nitride, silicon oxynitride, etc.). If necessary, the surface of the glass substrate 1 opposite the barrier layer 6 may be applied (e.g. by spraying) multilayer solar control coating (not shown). At least one layer 11 consisting of DLC or containing precipitated (e.g., via ion beam deposition) on the glass substrate 1 over at least the optional barrier layer 6 if present. Then, glass substrate 1 over the DLC layer 11 containing protective film 17 is deposited, for example, comprising one or more layers (e.g., composed of zinc oxide or contains). The protective film 17 may be deposited by sputtering, CVD (chemical vapor deposition), ion beam deposition or any other suitable method. Then, the protective film 17 was subjected to ion beam treatment of at least C ions as described above. If necessary, in some cases, before HT over the film 17 may be covered with a thin protective layer comprising DLC, silicon nitride, aluminum nitride or silicon nitride, and aluminum (not shown), and designed to provide abrasion resistance and / or protection from oxygen. As shown in Figures 1-3, then the glass substrate 1 with films 6 (optional), 11 and 17 thereon is heat treated (HT) to quench the thermal deformations, thermal bonding, etc. At least partially, the HT may be for example in an atmosphere containing oxygen, as known in the art, at temperatures from 550 to 800 ° C, more preferably from 580 to 800 ° C (i.e., temperatures above burnout DLC). HT may last for at least one minute, more preferably 1-10 minutes, in accordance with some exemplary nonlimiting embodiments of the present invention. During HT having a protective film 17 protects DLC layer containing from 11 HT and prevents significant oxidation and / or burning due to significant oxidation during the HT. Although in some cases, part of the layer 11 during HT may burn, most, if not all of the layer comprising DLC ​​11 remains based on 1 even after the HT due to the presence of protective film 17. However, the film 17 may be removed during and / or after HT . A significant advantage associated with using zinc and / or zinc oxide in film 17, is the ease of removal after HT. It was found that when the film 17 is composed of zinc and / or zinc oxide, soluble in vinegar and / or water (in some preferred embodiments may use only water with no vinegar), application of vinegar and / or water allows easily without the use of toxic chemicals remove the remaining portion of the film after HT 17. Similarly, in certain exemplary embodiments, in certain cases it is possible to remove the zinc oxide with only water (no vinegar), which is advantageous in terms of cost and simplicity of process. In certain instances, rubbing with such liquids may be especially successful in removing film 17 after HT when the coated article is still warm after it (for example, when the temperature of the film 17 is about 80-200 ° C, more preferably 100-180 ° C , although in certain exemplary embodiments, removal of the film 17 may also take place at room temperature). Remaining after removal of the film 17 coated article shown on the right of Figures 1-3, it has an outer layer comprising scratch resistant DLC. An advantage of the method described above is that it allows the heat treatment the coated article comprising a protective layer comprising DLC ​​11, without burning containing DLC ​​layer 11 during such HT. In other words, it becomes possible to provide a protective layer comprising DLC ​​to 11 heat treated (e.g., tempering), the product commercially acceptable manner.

4 is a cross-sectional diagram showing the method of manufacturing a coated article according to another exemplary embodiment of the present invention. In this embodiment requires no ion beam treatment of a layer or film 17, although ion beam treatment may be used for treatment of the film 17 after deposition in accordance with shown in Figure 4 embodiment. As shown in Figure 4 embodiment, one (or more) sputtering target T (e.g., magnetron rotating target) consisting of a Zn or ZnOx or containing them, use sputter deposition film 17 on the substrate 1 at least in the direction of motion bases D, possibly over DLC 11. Film 17 can comprise zinc oxide or contain it, as in any of those described above with reference to Figures 1-3 embodiments. As shown in Figure 4 embodiment, the carbon-containing gas (for example, one or more of: carbon dioxide, acetylene and the like) is fed into the chamber (s) for spraying so that the target (s) T is sprayed in the atmosphere, containing a carbonaceous gas and possibly other gas such as oxygen gas and / or argon gas in order to sputter deposition comprising zinc oxide film 17. Due to the presence of carbon-containing gas in the sputtering chamber comprising zinc oxide film 17 is deposited so that involves carbon. In this embodiment, in certain cases, the carbon may be dispersed throughout the thickness of the film 17 (or layers) are substantially continuous.

It is also possible to deposit the layer 17a using one (or more) sputtering target T (e.g., magnetron rotating target) consisting of a Zn or ZnOx or maintain them in an atmosphere of oxygen and / or argon (no carbon or with a small amount thereof) and then to deposit the layer 17b, using one (or more) sputtering target T (e.g., magnetron rotating target) consisting of a Zn or ZnOx or maintain them in an atmosphere in which, in addition to oxygen and / or argon, there is a carbon containing gas as described above. In this case, the film 17 will have a gradient or stepwise continuous, the content of carbon in its thickness.

Presented in Figure 4 embodiment is similar to the embodiments shown in Figures 1-3 that due to the presence of carbon in the film 17 in the film 17 is formed of zinc oxycarbide (in the entire film or only part thereof, including its upper surface) . The presence of zinc oxycarbide in film 17, film 17 imparts a finite resistance to corrosion that is significantly higher than that of the zinc oxide film containing no oxycarbide. After forming the film 17 in the embodiment shown in Figure 4, the coated article may be subjected to heat treatment (HT), and the film 17 can be removed as described above for the embodiment described with reference to fig.1- 3.

In accordance with certain exemplary embodiments of the present invention, the coated article resulting HT loses no more than about 15% of the ability to pass visible light, more preferably not more than about 10%. Moreover, monolithic coated articles after HT thus have a light transmission in the visible range, at least about 50%, more preferably at least about 60 or 75%.

In certain exemplary embodiments of the present invention, Mg may replace or supplement the Zn in the protective film 17.

Although the invention has been described with respect to what is presently considered to be the most practical and preferred embodiments, it should be understood that the described embodiments of the present invention is not limited to the contrary, it is intended to cover various modifications and equivalent structures within the spirit and scope the appended claims.