Coated article having low-e coating with ion beam treated ir reflecting layer and corresponding method

Description

EP 1786739 B1

[0001] The present invention relates to a coated article comprising a coating that controls the transmission of solar radiation, such as a low-E (low-E) coating. The low-E coating comprises an ion beam treated (IR) reflecting (reflecting) infrared (IR) layer (s) of material such as silver (Ag) or the like. In certain example embodiments, the ion beam treatment is performed such that a compressive stress (as opposed to normal tensile stress) is obtained in the infrared reflecting layer and / or the resistance (sheet resistance, R_sand / or volumetric resistance) of the coated article. Coated articles, in accordance with certain example embodiments of this invention, may be used in the context of vehicle windshields, insulating glass units, other types of glazing, or any other suitable application.

STATE OF THE ART

Coated articles are known in the art for glazing applications such as insulating glazing units, automotive glazing, etc. Exemplary non-limiting low-E (low-E) coatings are illustrated and / or set forth in US Pat. US US 6723211, US 6576349, US 6447891, US 6461731, US 3682528, US 5514476, US 5425861 and US Patent Application No. US Of America No. US 2003/015071.

[0003] In some situations, designers of coated articles with low-E coatings often seek to combine a high visible transmission rate, substantially neutral color, low emission factor (or emittance), low surface resistance (R_s) and good durability. For example, a high visible radiation transmission coefficient may make coated products more likely to be used in applications such as vehicle windshields etc., where low-E (low-E) and low surface resistance (R_s) will enable such coated articles to block significant amounts of infrared (IR) radiation so as to limit e.g. undesirable heating of a vehicle or building interiors. It is often difficult to obtain a high visible radiation transmission coefficient and adequate solar control properties, such as good infrared radiation blocking, in combination with good durability (chemical and / or mechanical) as the materials used to improve the durability often lead to an undesirable decrease in visible transmission coefficient and / or undesirable discoloration of the product after heat treatment.

[0004] Low-E coatings typically include one or more infrared reflecting layers. The infrared reflecting layer is typically metallic or largely metallic, and is often made of a material such as silver (Ag), gold (Au), etc. In some instances, silver or gold may be enriched with other materials. The purpose of the infrared reflecting (reflecting) layer (s) is to block significant amounts of infrared radiation, thereby preventing undesirable heating of the vehicle and / or the interior of the buildings that the coated article protects.

Generally speaking, the lower the resistance (sheet resistance R_s and / or the volumetric resistance) of the infrared radiation reflecting layer, the better its infrared reflecting properties. Until now, however, it has been difficult to reduce the resistive properties (and thus improve the IR reflecting properties) of the IR reflecting layer without adversely affecting the optical properties of the coated article (e.g. visible transmission coefficient, color etc.) and / or durability of the coated article. For example, significant changes in the thickness of the IR reflecting layer alone can affect the strength but at the same time have a detrimental effect on the durability and / or the optical properties of the coating.

[0006] US Patent No. US No. 6,077,621 relates to a two-beam process supplying an ion-conducting membrane with a metal or metal oxide thin film.

[0007] US Patent No. US US 5,080,455 similarly relates to a method for treating a substrate using the ion beam sputtering method. Said document describes methods and an apparatus for treating a material by ion bombardment over material deposited by sputtering with an ion beam.

[0008] European Patent No. EP 0 010 971 describes vacuum deposition methods suitable for coating plastic substrates with transition metals such as chromium. In the methods described in said document, the materials are first deposited onto the substrate by vapor deposition, and then the deposited material is bombarded with high-energy particles to reduce tension and / or to compress the deposited material to obtain a better finish.

[0009] In view of the foregoing, it will be apparent to those skilled in the art that there is a need in the art for a technique to reduce the resistive properties of the infrared reflecting (reflecting) layer (s) thereby improving its infrared reflecting properties and thus radiation transmission controlling properties. the solar coated article without significantly adversely affecting the durability and / or the optical properties of the coated article. There is also a need in the art for a method of making such a coated article.

SUMMARY OF THE SUMMARY OF EXAMPLE SOLUTIONS OF THE INVENTION

[0010] In certain example embodiments of this invention, the infrared (IR) reflecting layer (s) is (are) treated with an ion beam using at least ions of an inert gas such as argon. It has surprisingly been found that, when the ion treatment is properly carried out, it will (a) reduce the resistance of the IR reflecting layer compared to when such ion beam treatment has not been performed, thereby improving its IR reflecting properties, and / or ( b) increasing the durability of the coated article.

[0011] In certain example embodiments of this invention, it has been surprisingly found that ion beam treatment of an infrared reflecting layer of a material such as Ag, Au, and the like changes the stress of the layer from tensile to compressive stress. In this regard, it has been found that the stress compressive properties of the infrared reflecting (reflecting) layer (s) can increase the durability (chemical and / or mechanical) of the coated article.

[0012] Accordingly, it has been found that in certain example embodiments of this invention, appropriate ion beam treatment of the infrared (reflecting) reflecting layer (s) results in a combination of: (i) improved resistance of the infrared reflecting layer, (ii) improved solar control properties of the coated article such as blocking infrared radiation, and (iii) increased durability of the coated article.

[0013] In certain example embodiments of this invention, the infrared reflecting layer may be formed as follows. First, a seed layer (e.g. Ag etc.) is formed by sputtering. Then, after sputtering the seed layer, ion beam assisted deposition (IBAD) is used to form an additional or a remainder of the infrared reflecting layer. The ion beam ion beam treatment method (IBAD) uses both the ion beam source (s) and the sputtering target (s). Ion beam from an ion beam source (e.g., containing Ar ions⁺) intersects with the material sputtered from the sputtering target (s) near the surface on which an additional or the remainder of the infrared reflecting layer is grown, such that an additional or the remainder of the infrared reflecting layer grows / forms by combining both the beam ion and sputtering.

[0014] In other example embodiments of this invention, the infrared reflecting layer may be entirely formed by IBAD. At the beginning of the formation of the IR reflecting layer using IBAD, the voltage applied to the ion source is low or zero, so that the ion beam is not generated or has little power (i.e., a low eV per ion). Then, during the formation of the infrared reflecting layer, after a certain portion of the layer has been deposited, the voltage applied to the ion source is increased so as to increase the eV per ion in the ion beam. In other words, the ionic energy is progressively or gradually increased during the formation of the infrared reflecting layer. This prevents or reduces damage to the underside of the layer and / or the layer beneath it.

[0015] In certain example embodiments of this invention, there is provided a method of making a coated article, the method comprising: providing a glass substrate; forming at least one dielectric layer on the substrate; forming a silver-containing infrared (IR) reflecting layer on the substrate over at least the first dielectric layer, said forming the infrared reflecting layer comprises (a) sputtering the first silver-containing layer portion or seed layer; and (b) applying the simultaneous combination of the ion beam and material moving towards the substrate from the sputtering target to form a second layer portion immediately above and in contact with the first layer portion; and forming at least one additional dielectric layer on the substrate over at least the infrared reflecting layer.

In other example embodiments of this invention, there is provided a method of making a coated article comprising forming an infrared (IR) reflecting layer on a glass substrate, said forming an infrared reflecting layer comprises: sputtering a first layer portion, or a seed layer, ; an infrared reflecting layer and using the simultaneous combination of the ion beam and material moving towards the substrate from the sputtering target to form a second layer portion immediately above and in contact with the first layer portion; and forming at least one additional layer on the substrate over at least the infrared reflecting layer.

[0017] In yet another example embodiment of the present invention, there is provided a coated article comprising glass substrates supporting a coating, the coating comprising: at least one dielectric layer; an infrared reflecting layer applied to the substrate over at least the dielectric layer; another dielectric layer applied to the substrate over at least an infrared reflecting layer and at least one dielectric layer; and wherein the infrared reflecting layer comprises silver and exhibits a compressive stress.

[0018] In other example embodiments of this invention, there is provided a coated article comprising glass substrates supporting the coating, the coating comprising: at least one dielectric layer; an infrared reflecting layer applied to the substrate over at least the dielectric layer; another dielectric layer applied to the substrate over at least an infrared reflecting layer and at least one dielectric layer; and wherein the infrared reflecting layer has different portions which differ in the content of the neutral element such that the upper portion of the infrared reflecting layer contains more neutral element than the lower portion of the infrared reflecting layer.

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Fig. 1 is a flowchart illustrating certain steps involved in producing a coated article according to an example embodiment of this invention.

[0020] Figs. 2 (a) to 2 (c) are cross views illustrating various stages of a process for making a coated article according to an example embodiment of this invention.

[0021] Fig. 3 is a side view of a coated article according to an example embodiment of this invention.

[0022] Fig. 4 is a side view of an exemplary ion source that may be used for ion beam treatment of layers in accordance with example embodiments of this invention.

[0023] Fig. 5 is a perspective view of the ion source shown in Fig. 4. [0024] Fig. 6 is a diagram illustrating ion beam assisted deposition (IBAD) of a layer, according to an example embodiment of the invention; this method can be used for ion beam treatment of any of the layers listed herein that may be treated with an ion beam.

[0025] Fig. 7 is a flowchart illustrating certain steps involved in making a coated article according to another example embodiment of this invention.

DETAILED DESCRIPTION OF EXAMPLES OF THE INVENTION

[0026] Throughout this part, specific reference to the accompanying drawing will be used, the same reference numerals indicating corresponding parts in all views.

Coated articles of the invention may be used in applications such as, e.g., vehicle windshields, monolithic glazing, insulating glass units, and / or any other suitable application involving one or more substrates such as glass substrates with at least one control coating applied. penetration of solar radiation. In applications as a vehicle windshield, e.g. a pair of glass substrates can be laminated together using a polymer-based layer of a material such as PVB, and a solar control coating (e.g. a low-emissivity coating or a low-E coating) is applied to the inner surface of one of the glass substrates adjacent to the polymer-based layer. ). In certain example embodiments of this invention, a solar control coating (e.g. low-E coating) comprises a plurality of two-layer silver layers, although the invention is not so limited in all cases (e.g., one silver layer series and a layer series containing other layers may also be used in some embodiments of the invention).

In certain example embodiments of this invention, the infrared (IR) reflecting layer (s) (e.g., see Ag-inclusive layer 9 and / or 19 discussed below) is ion beam treated using at least an inert gas ion such as like argon. It has surprisingly been found that, when the ion treatment is properly performed, it will (a) reduce the resistance of the IR reflecting (reflecting) layer (s) compared to when such an ion beam treatment has not been performed, thereby improving its radiation reflecting properties. infrared, and / or (b) increasing the durability of the coated article.

[0029] Moreover, in certain example embodiments of this invention, it has surprisingly been found that ion beam treatment of an IR reflecting layer (e.g., 9 and / or 19) of a material such as Ag, Au, and the like changes the stress of the layer from tensile to compressive stress. A tensile stress is typically present in infrared reflecting layers deposited solely by sputtering. However, it has surprisingly been found that applying ion beam treatment in an appropriate manner causes the stress of the infrared reflecting layer (s) to be compressive. In this regard, it has been found that the stress compressive properties of the infrared reflecting (reflecting) layer (s) can increase the durability (chemical and / or mechanical) of the coated article. Furthermore, it has also been found that such ion beam treatment also reduces the resistance of the coated article (i.e., the infrared reflecting (reflecting) layer (s) in particular) thereby improving its solar control properties.

[0030] Accordingly, it has been found that in certain example embodiments of this invention, appropriate ion beam treatment of the infrared reflecting (reflecting) layer (s) results in an excellent combination of: (i) improved resistance of the infrared reflecting layer, (ii) improved solar control properties of the coated article such as blocking infrared radiation, and (iii) increased durability of the coated article. Regarding durability, for example, the coating is less likely to corrode quickly when exposed to environmental conditions such as high temperatures, high humidity, etc.

Referring to Figs. 1-3, in certain example embodiments of this invention, an infrared reflecting layer (9 and / or 19) may be formed as follows. At least one sub-layer is formed on the glass substrate 1 by sputtering or the like, as shown in Fig. 2 (a), (see step S1 in Fig. 1). In Figure 3, the underlining layers would be layers 3 and 7. Thereafter, a seed layer (e.g., Ag etc.) is formed on the substrate over the underlying layer (s) by sputtering at least one target Ag etc. as shown in Fig. 2 (b) (see

S2 in Fig. 1). The seed layer is typically metallic or largely metallic and consists of a material such as Ag, Au etc. In some embodiments, however, the seed layer may consist essentially of Ag and / or Au, and be enriched with small amounts of other materials such as oxygen or metal (metals). Preferably, the seed layer is essentially of the same material (e.g. Ag) as the last infrared reflecting layer (9 and / or 19) to be formed. As the seed layer will be formed by sputtering, the seed layer will typically be formed to obtain a tensile stress. In certain example embodiments of this invention, an Ag seed layer is sputtered onto the substrate to a thickness from about 10 to 100 Å, more preferably from about 30 to 80 Å, even more preferably from about 40 to 70 Å, with an exemplary thickness of about 60 Å. .

[0032] Then, after the seed layer has been sputtered onto the substrate as shown in Fig. 2 (b), Ion Beam Assisted Deposition (1BAD) is applied to form an additional or a remainder of the IR reflecting layer (9 and / or 19). as shown in Fig. 2 (c) (see S3 in Fig. 1). Figures 2 (c) and 6 illustrate that in ion beam treatment / forming IBAD, both the ion beam source (a) 26 and the sputtering machine containing the sputtering target (s) 50 are used. The ion beam B from the ion beam source 26 intersects with the material M sputtered from the sputtering target (s) 50 near the surface on which an additional or remainder of the IR reflecting layer is grown, such that an additional or a remainder grows / forms IR reflecting layer by combining both the ion beam and the sputtering. In certain example embodiments of this invention, a first Ag sputtering target is used to sputter the seed layer and a second Ag sputtering target remote from the first target is used to deposit / form additional or a remainder of the IBAD infrared reflecting layer.

[0033] The use of a seed layer followed by the subsequent formation of an additional or the remaining part of the infrared reflecting layer (9 and / or 19) with the use of IBAD as shown in Figs. 1-2 and 6 leads to a gradually changing infrared reflecting layer. argon content. In particular, the top of the infrared reflecting layer contains more Ar than the bottom of the infrared reflecting layer. This is because the Ar ions will not hit the layer as it is being formed until a seed layer is formed. Accordingly, the upper part of the resulting infrared reflecting layer has a higher Ar content than the lower part of the layer. This gradual change in content would apply to a different element (e.g., Kr and / or Xe) if, in alternative embodiments of the invention, other element (s) were used in the ion beam instead or in place of Ar. In certain example embodiments, the argon (or other neutral element) content in the top of the infrared reflecting layer (9 and / or 19) is at least 10% greater than that of the bottom of the infrared reflecting layer, more preferably at least 20% greater. and most preferably at least 30% greater. The term "bottom portion" is merely an arbitrarily selected portion of the ply located at least partially below the center of the ply, wherein an "top portion" of the ply is any arbitrarily selected portion of the ply located at least partially above the center of the ply. In certain example instances, the top portion may be the top 20 A of the IR reflecting layer, and the bottom portion may be the bottom 60 A (or 20 A) of the layer.

[0034] Thus, the obtained infrared reflecting layer (9 and / or 19) shown in Figs. 2 (c) and 3 is obtained by combining an Ag-inclusive seed layer and an Ag-inclusive layer formed directly thereon using IB AD. Note that the seed layer will be modified by the IBAD process - Ar ions will be injected into it and / or its tension will be changed from tensile to compressive. As explained above, it has surprisingly been found that: (a) forming the Ag-containing portion of the germ layer in an appropriate manner by IBAD changes the stress of the germ layer from tensile to compressive stress in the last infrared reflecting layer 9 and / or 19; and (b) forming by IBAD the additional Ag-containing layer portion directly above and in contact with the seed layer results in an infrared reflecting layer with improved resistance properties and thus improved solar control function.

[0035] Further, after the infrared reflecting layer 9 and / or 19 has been formed, an additional layer (s) is deposited on the substrate 1 over at least the infrared reflecting layer (see step S4 in Fig. 1). These additional layers in the embodiment shown in Fig. 3 may be layers 11 and / or 21-25.

[0036] In certain example embodiments, the resulting IR reflecting layer 9 and / or 19 is from about 60 to 200 Å thick, more preferably from about 80 to 170 Å thick, even more preferably from about 100 to 140 Å, such as about 120 Å thick. , in certain example embodiments of this invention, the infrared reflecting (reflecting) layer (s) 9 and / or 19 is substantially oxygen free (free). For example, the infrared reflecting (reflecting) layer (s) 9 and / or 19 includes (are) from about 0 to 10% oxygen, more preferably from about 0 to 5% oxygen, even more preferably from about 0 to 2% oxygen, and most preferably 0 to 1% oxygen. This property (substantial lack of oxygen) can be achieved throughout the thickness of the layer, or alternatively in at least the middle portion of the layer not immediately adjacent to the layers it is in contact with.

[0037] In certain example embodiments of this invention, the ion beam comprises at least ions of the inert gas used in ion source 26. For example, ion beam B may be composed of or include Ar + ions as long as Ar + gas is used in ion source 26. In certain example embodiments of this invention, the ion beam is substantially free of oxygen and the gas used in ion source 26 is substantially free of oxygen. Thus, ion beam B and the gas introduced into the ion source 26 contain 0 to 10% oxygen, more preferably 0 to 5% oxygen, even more preferably 0 to 2% oxygen, and most preferably 0 to 1% oxygen (in many cases 0% oxygen may be preferable). In certain example embodiments of this invention, the ion beam is also substantially free of nitrogen ions.

[0038] Further, in certain example embodiments of this invention, an ionic energy of from about 150 to 700 eV per Ar ion is used to form the additional or the remainder of the IR reflecting (reflecting) layer (s) 9 and / or 19 by IBAD.⁺, more preferably from about 200 to 600 eV per Ar ion⁺and most preferably about 500 eV per Ar ion⁺. For example, when only Ar gas is used in ion source 26, then a voltage of about 300 to 1400 V, more preferably about 400 to 1200 V, and most preferably about 1000 V may be applied to the anode / cathode source 26.

[0039] Fig. 3 is a side view of a coated article according to an exemplary non-limiting embodiment of this invention. Coated article comprises substrate 1 (e.g., a colorless, green, brown, or cyan glass substrate from about 1.0 to 10.0 mm thick, more preferably from about 1.0 mm to 3.5 mm thick), and directly or indirectly 1 low-emission coat (or layer system) on the substrate 2.

Coating (or layer system) 2 includes, in this example embodiment: silicon nitride dielectric layer 3 (which may be ion beam treated), S13N4 stoichiometry or other embodiments of the invention with any other suitable stoichiometry, first lower contact layer 7 (which contacts IR reflecting layer 9), first conductive and preferably a metallic or largely metallic infrared (IR) reflecting layer 9, first upper contact layer 11 (which contacts layer 9), dielectric layer 13 (which, in various embodiments of the present invention may be deposited in one or more steps), another silicon nitride layer 14, second lower contact layer 17 (which contacts IR reflecting layer 19), a second conductive and preferably metallic IR reflecting layer 19, a second upper contact layer 21 (which is in contact with layer 19), a dielectric layer 23 and finally a protective silicon nitride dielectric layer 25 (which may be ion beam treated). Each "contact" layer 7, 11, 17 and 21 contacts at least one infrared reflecting layer. The aforementioned layers 3-25 build a low-E (i.e., low-emission) coating 2 which is disposed on a glass or plastic substrate 1. The silicon nitride layer 25 is the outermost layer of the coating 2.

In the embodiments set forth herein, where ion beam treatment of an infrared reflecting layer is discussed, the ion beam treatment / forming may be applied to the Ag, 9, and / or 19 layers.

[0041] In the case of monolithic articles, the coated article comprises only one glass substrate 1 as illustrated in Fig. 3. The monolithic coated articles of the present invention can, however, be used in devices such as laminated vehicle windshields, insulating glass units, etc. such as a windshield, includes first and second glass substrates laminated together using a polymer-based interlayer (e.g., see US Patent No. No. 6,686,050, the disclosure of which is hereby incorporated by reference). In certain example embodiments, a coating 2 may bear upon the inside of one of these laminate substrates. In an insulating IG unit, the insulating glass unit may include two separate substrates 1. An exemplary insulating IG unit is illustrated and illustrated, e.g. in U.S. Patent No. US No. US 6632491. An exemplary insulating glazing unit may include, for example, a coated glass substrate 1 shown in Fig. 3 bonded to another glass substrate via a spacer (s), sealant (s), etc. while maintaining a gap. This gap between the substrates in insulating glazing solutions may be filled with a gas such as argon (Ar) in some cases. An exemplary IG unit may include a pair of discrete colorless glass substrates, each about 4 mm thick, one of which is coated in certain example instances with a coating, wherein the gap between the substrates can be from about 5 to 30 mm, more preferably from about about 4 mm. 10 to 20 mm and most preferably about 16 mm. In certain example instances, coating 2 may be disposed on the inner slit-facing surface of each substrate.

[0042] Exemplary details of layers 3, 7, 9, 11, 13, 14, 17, 19, 21, 23 and 25 of the coating of Fig. 3 are discussed in US patent application no. US No. 10/800012, the disclosure of which is hereby incorporated by reference. For example, in certain embodiments of this invention, dielectric layers 3 and 14 may be composed of or include silicon nitride. Silicon nitride layers 3 and 14 can, inter alia, improve the heat treatability of coated articles, e.g. such as thermal tempering and the like. In various embodiments of the invention, the silicon nitride of layers 3 and / or 14 may be of the stoichiometric type (S13N4), of the ion beam enriched type as discussed herein, or alternatively of the high Si type. In certain example embodiments of this invention, any and / or all of the silicon nitride layers discussed herein may be enriched with other materials, such as stainless steel or aluminum. For example, in certain example embodiments of this invention, any and / or all of the silicon nitride layers discussed herein may optionally include from about 0 to 15% aluminum, more preferably from about 1 to 10% aluminum, most preferably from 1 to 4% aluminum. In certain embodiments of the present invention, silicon nitride may be deposited through a Si or SiAl sputter target. In addition, the silicon nitride layer 3 may be ion beam treated in any manner discussed herein (e.g. by IB AD using at least nitrogen ions) to limit sodium migration from the glass substrate towards the infrared reflecting (reflecting) layer (s) during the heat treatment.

[0043] The infrared (IR) reflecting layers 9 and 19 are preferably substantially or entirely metallic and / or conductive, and may include or consist essentially of silver (Ag), gold, or any other suitable IR reflecting material. One or both of the infrared reflecting layers 9 and / or 19 may be formed by techniques involving the use of an ion beam, as discussed herein with reference to Figs. 1-2. The infrared reflecting layers 9 and 19 contribute to the coating having a low emissivity and / or good solar control properties. In certain embodiments of the invention, however, the infrared reflecting layers may be slightly oxidized.

[0044] Dielectric layer 13 may be constructed of or include tin oxide in certain example embodiments of this invention. However, as with the other layers described herein, different materials may be used in various instances. In certain embodiments of the invention, lower contact layers 7 and / or 17 are zinc oxide (e.g., ZnO) or contain zinc oxide. The zinc oxide of layer (s) 7, 17 may also contain other materials such as Al (e.g. to form ZnAlO_x). For example, in certain example embodiments of this invention, one or more of the zinc oxide layers 7, 17 may be enriched with from about 1 to 10% Al, more preferably from about 1 to 5% Al, and most preferably from about 2 to 4% Al. The use of zinc oxide 7, 17 under silver 9, 19 makes it possible to obtain excellent quality silver. In various example embodiments of this invention, upper contact layers 11 and / or 21 may be constructed of or including NiCr, NiCrO_x and / etc.

[0045] Dielectric layer 23 may be constructed of or include tin oxide in certain example embodiments of this invention. However, layer 23 is an optional layer and need not be present in certain example embodiments of this invention. The protective silicon nitride layer 25 may be initially deposited by sputtering or IB AD and may be ion beam treated in any manner discussed herein.

[0046] Other layer (s) may also be present below or above the illustrated coating. Thus, although the layer system or coating is "on" or "abutting" the substrate 1 (directly or indirectly), other layer (s) may be included therebetween. And so, for example, the coating shown in Fig. 3 can be considered as being "on" and "resting" on the substrate 1 even if other layer (s) have been (have) been introduced between layer 3 and substrate 1. Further, in certain embodiments, some layers of the illustrated coating may be removed, while in other embodiments of the invention others may be added between different layers, or different layers may be separated with different (other) layer (s) added (s) between separated parts, without departing from general thought. of certain embodiments of the invention.

[0047] Fig. 7 is a flowchart illustrating how an infrared reflecting layer 9 and / or 19 may be formed according to another exemplary embodiment of the present invention. In the embodiment shown in Fig. 7, the infrared reflecting layer can be completely formed using the 1BAD method. At the beginning of the formation of the IR reflecting layer using IBAD, the voltage applied to the ion source is low or zero, so that the ion beam is not generated or has little energy (i.e., a low eV per ion). Then, in forming the infrared reflecting layer after depositing at least some of the layer, the voltage applied to the ion source is increased so as to increase the eV per ion in the ion beam. In other words, the ionic energy is progressively or gradually increased during the formation of the infrared reflecting layer. This prevents or reduces damage to the underside of the layer and / or the underlying layer as a low energy ion beam is used to form the initial portion of the infrared reflecting layer, and provides the advantages discussed herein with respect to the last infrared reflecting layer because the greater energy is used to form at least the upper portion of the infrared reflecting layer.

[0048] Referring in detail to Fig. 7, one or more backing layers are deposited on the substrate 1 (ST1). This step is similar to the step S1 of the embodiment shown in Figure 1. Then, when depositing the first IR reflecting layer portion (9 and / or 19), IBAD is used, but the ion beam is relatively low energy (ST2). For example, in ST2, an ionic energy of about 0 to 200 eV per Ar ion is used when forming the initial portion of the IR reflecting layer.⁴, more preferably from about 1 to 150 eV, more preferably from about 5 to 100 eV per Ar A ion Again, other inert gas (s) may be used in place of or in addition to argon. The ionic energy is then increased after the part of the infrared reflecting layer (s) is formed, to form additional or the remainder of the infrared reflecting (reflecting) layer (s) 9 and / or 19 by IBAD (ST3). In certain example embodiments, in ST3, the ionic energy is increased to an ionic energy of from about 150 to 700 eV per Ar ion.⁺, more preferably from about 200 to 600 eV per ion

Ar⁺and most preferably about 500 eV per Ar ion⁺. In certain example embodiments of this invention, the ionic energy in step ST3 is increased by at least about 10%, more preferably at least about 25%, even more preferably at least about 50%, sometimes at least about 100%. After the additional and / or the remainder of the infrared reflecting layer 5 has been formed with more ionic energy, additional layer (s) (ST4) is deposited / formed on the substrate 1 over at least the infrared reflecting layer.

[0049] While different thicknesses and materials may be used for the layers in different embodiments of the invention, examples of thicknesses and materials for the respective layers 10 on the glass substrate 1 according to the embodiment shown in Fig. 3 are (from the glass substrate 1 outwardly). One or both of the infrared reflecting layers 9 and / or 19 is formed / deposited using at least an IBAD in accordance with any of the embodiments discussed herein.

<td> 15</td><td colspan="4">Sample materials / thicknesses; the solution shown in Fig. 3</td>

<td></td><td>Layer Glass (1-10mm thickness)</td><td colspan="2">Preferred range More preferred (A) (AND)</td><td>Example (A)</td>

<td></td><td>S13N4 (layer 3)</td><td>40-450 A.</td><td>70-250 A.</td><td> 100</td>

<td></td><td>ZnO_x (layer 7)</td><td>10-300 A.</td><td>40-150 A.</td><td> 100</td>

<td></td><td>Ag (layer 9) (IBAD)</td><td>50-250 A.</td><td>80-120 A.</td><td> 98</td>

<td></td><td>NiCrO_x (layer 11)</td><td>10-100 A.</td><td>30-45 A.</td><td> 35</td>

<td></td><td>SnO2 (layer 13)</td><td>0-1000 A.</td><td>350-630 A.</td><td> 570</td>

<td></td><td>Si_xN_y (layer 14)</td><td>50-450 A.</td><td>90-150 A.</td><td> 120</td>

<td></td><td>ZnO_x (layer 17)</td><td>10-300 A.</td><td>40-150 A.</td><td> 95</td>

<td></td><td>Ag (layer 19) (IBAD)</td><td>50-250 A.</td><td>80-220 A.</td><td> 96</td>

<td></td><td>NiCrO_x (layer 21)</td><td>10-100 A.</td><td>30-45 A.</td><td> 35</td>

<td></td><td>SnO2 (layer 23)</td><td>0-750 A.</td><td>150-300 A.</td><td> 200</td>

<td></td><td>S13N4 (layer 25)</td><td>10-750 A.</td><td>100-320 A.</td><td> 180</td>

[0050] Optionally, one or both of the layers including silicon nitride 3 and / or 25 may be treated with the ion beam in certain example embodiments of this invention. It has been surprisingly found that the ion beam treatment of the layer comprising silicon nitride 3 reduces sodium migration during the optional heat treatment, thereby improving the properties of the coating, while in the case of ion beam treatment of the silicon nitride protective layer 25, it has been found to increase the durability of the resultant coated article. Ion beam treatment of layer (s) 3 and / or 25 can be carried out by IBAD using nitrogen ions from at least nitrogen gas in the ion source, and / or by so-called peeling, where the ion source directs the ion source onto the layer after it has been sputtered at least nitrogen ions.

[0051] In various embodiments of the invention, the ion beam treatment of the silicon nitride containing layer 3 and / or 25 may be performed: (a) during sputtering the layer and / or (b) after sputtering the layer. In certain example instances, the second case (b) may be referred to as peeling, while the preceding case (a) may be referred to as ion beam assisted deposition (IBAD). IBAD solutions (e.g. see fig. 8) are particularly useful because they surprisingly cause the deposited layer to exhibit anti-migration properties with respect to sodium migration relative to layer 3. However, any of the ion beam treatment disclosed herein may also employ ion beam treatment (or sputtering) after sputtering. In certain example embodiments of this invention, the ion beam treatment is performed such as to cause some or all of the silicon nitride-containing layer 3 and / or 25 to acquire a high nitrogen content. In such embodiments, hanging Si bonds are reduced or eliminated and excess nitrogen is introduced into the layer (e.g. see layer 3 and / or 25). This, in some cases, may be referred to as high N silicon nitride solid solution. Thus, in certain example instances, layer (s) 3 and / or 25 may (may) include S13N4 which is further enriched with additional nitrogen. In certain example embodiments, S13N4 may be enriched with at least 0.1% (atomic%) nitrogen, more preferably from about 0.5 to 20% nitrogen, even more preferably from about 1 to 10% nitrogen, and most preferably from about 2 to 10% nitrogen. % nitrogen (or excess nitrogen). In certain example instances, enrichment with nitrogen can mean enrichment with nitrogen of at least about 2%. Unlike nitrogen in the S13N4 layer, excess nitrogen (or the enriching nitrogen mentioned above) is not bound to Si (but may or may not be bound to other (other) element (s)). This nitrogen enrichment of S13N4 may take place in the entire layer containing silicon nitride, or alternatively only in the part of the layer containing silicon nitride (e.g. closest to its top surface in solutions with peening). It has surprisingly been found that this excess nitrogen in the layer (i.e., due to the enrichment of S13N4 with N) is advantageous in that it leads to fewer structural defects, reduced sodium migration during possible heat treatment when used in the layer in under the layer (s) reflecting (reflecting) infrared radiation and makes the layer react less with oxygen, thus improving its durability. In certain example embodiments of this invention, at least nitrogen (N) ions are used in ion treating the layer (s) comprising silicon nitride. In certain example embodiments, using ion beam treatment after sputtering (i.e., peeling), such ion beam treatment may involve using an energy of at least about 550 eV per N2 ion.⁺, more preferably from about 550 to 1200 eV per N2 ion⁺, even more preferably from about 600 to 1100 eV per N2 ion⁺and most preferably from about 650 to 900 eV per N2 ion⁺ (e.g. 750 eV per N2 ion⁺). It has been surprisingly found that such ionic energies will allow excellent properties in the form of a gradual change in nitrogen content in a typically sputtered layer of appropriate thickness, significantly reducing the number of hanging Si bonds, at least closest to the surface of the layer containing silicon nitride, giving the coating / layer improved stress properties, imparting excellent enrichment properties, limiting the possibility of sodium migration, and / or leading to an increase in nitrogen content in some or all of the layer, which is favorable with respect to durability. It is possible that in certain example instances such ion beam treatment after sputtering may even change the stress of the layer from tensile to compressive stress. In IB AD embodiments where ion beam treatment is performed concurrently with the sputtering of layer 3 and / or 25, it has surprisingly been found that lower ionic energy at a treated surface area of ​​at least about 100 eV per N2 ion⁺, more preferably from about 200 to 1000 eV per N2 ion⁺, more preferably from about 200 to 600 eV per N2 ion⁺, even more preferably from about 300 to 500 eV per N2 ion⁺ (e.g. 400 eV per N2 ion⁺) is the most appropriate. It has been surprisingly found that such ionic energies in IBAD solutions significantly reduce the number of hanging Si bonds, giving the coating / layer improved stress properties, imparting excellent beneficiation properties, limiting sodium migration during heat treatment, leading to an increase in nitrogen content in part or all of the layer, which is favorable with regard to durability. It has surprisingly been found that this range of ionic energy is particularly advantageous in order to create a compressive stress in the silicon nitride layer 3 and / or and / or to avoid or limit sodium migration during possible heat treatment. If the ionic energy is too low, the layer will not thicken sufficiently. On the other hand, if the ionic energy is too high, it may damage the layer and / or cause the stress of the treated layer to become tensile. Thus, this range of ionic energy produces unexpected and favorable results. In certain example instances, it has surprisingly been found that ion treating layer 3 and / or 25 can improve durability, heat treatability, and / or color of a coated article by at least one of the following mechanisms: (i) forming S13N4 with increased nitrogen content by at least portions of the layer, thereby reducing the number of hanging Si bonds and the susceptibility to sodium migration after heat treatment; (ii) creating a layer with a gradually varying nitrogen content in which the nitrogen content is greater in the portion of the outer layer proximate the outer surface of the layer than in the portion of the layer further away from the outer surface of the layer; (iii) increasing the density of the ion beam treated layer, (iv) applying ionic energy suitable to cause an improvement in the stress properties of the layer; (v) improving the control of the stoichiometry of the layer, (vi) reducing the chemical reactivity of the layer after ionic treatment, (vii) making the layer less susceptible to significant oxidation after ion treatment, and / or (viii) reducing the amount and / or size of voids in ion treated layer. In certain example embodiments of this invention, ion treatment is ion beam treatment from at least one ion source, with Ar, or Ar and N being preferred.

[0052] In certain embodiments of IB AD, if adequate ionic energy is used for a given material, then the compressive stress of the IB AD deposited layer 3, 9, 19, and / or 25 may be from about 50 MPa to 2 GPa, more preferably from about 50 MPa to 1 GPa, and most preferably from about 100 MPa to 800 MPa. Such IBAD techniques may be used in conjunction with infrared reflecting (reflecting) layer (s), base (s) layer (s), protective (protective) layer (s), or any other layer described herein that may be treated with an ion beam.

[0053] In the various embodiments discussed herein, in various embodiments of the invention, the ion beam may be a focused ion beam, a collimated ion beam, or a scattered ion beam.

[0054] In various instances, coated articles according to various embodiments of the invention may or may not be heat treated (HT). The terms "heat treated" and "heat treated" as used herein mean heating the article to a temperature 'sufficient to effect heat toughening, hot bending and / or heat strengthening of the glass-containing article. This definition includes e.g. heating the coated article in an oven at a temperature of at least about 580 degrees Celsius, more preferably at least about 600 degrees Celsius, for a period of time sufficient to permit tempering, bending, and / or heat strengthening. In some cases, the heat treatment may be for at least about 4 or 5 minutes. In certain example embodiments of this invention, ion beam treated silicon nitride backing and / or protective layers are advantageous in that they vary less with color and / or permeation during optional heat treatment; this can improve the adhesion of the interlayer and therefore the durability of the final product; and the ion beam treated silicon nitride treatment of the lower layer helps to limit sodium migration during heat treatment.

It should be noted that each of the silicon nitride layers 3 and / or 25 to be ion beam treated herein may be initially sputtered in any suitable stoichiometric form including, inter alia, S13N4 or a type of high Si content silicon nitride. An example of high Si content types of silicon nitride is discussed in US Patent No. US No. 2002/0064662, and any high Si layer discussed herein may be initially sputtered here for each suitable silicon nitride layer. Moreover, in certain example embodiments of this invention, the silicon nitride layers discussed herein may of course be enriched with aluminum (e.g., 1-10%) and the like. It has also been found in certain example embodiments of this invention that ion beam treatment (e.g. by IB AD or peening) a layer containing silicon nitride (3 and / or 25) increases the hardness of such layer. The silicon nitride containing layer typically sputtered has a hardness of 10 to 14GPa. In certain example embodiments of this invention, however, the ion beam treated silicon nitride layer (3 and / or 25) has a hardness of at least 20 GPa, more preferably at least 22 GPa, and most preferably at least 24 GPa.

[0056] In certain example embodiments of this invention, one or both of the NiCr or NiCrO layers_x 11 and / or 21 can be ion beam treated using at least oxygen ions to obtain a gradual alternation of oxidation as set forth in US Pat. US No. 10/847672, filed May 18, 2004.

Figs. 4-5 illustrate, for example, a linear or direct ion beam source 26 that may be used to form an additional or a remainder of the IR reflecting layer (9 and / or 19) as discussed above in connection with Figs. 1-3. , or to ion beam treatment of layer (s) 3 and / or at least with nitrogen ions in certain example embodiments of this invention (by peening or IB AD). Ion beam source (or ion source) 26 includes gas inlet / power supply 31, racetrack-shaped anode 27, magnet portion being grounded cathode 28, magnet poles, and insulators 30. An electrical gap is established between anode 27 and cathode 29. In some embodiments, 3 kV or any other suitable DC power source may be used at source 26. The gas (s) discussed (discussed) herein for use in the ion source during ion beam treatment may be introduced into the source through the gas inlet 31, or through any other suitable location. Ion beam source 26 is based on a known gridless ion source design. The linear source may include a linear sheath (which is the cathode and is grounded) within which lies an anode concentrically (which is positive potential). This cathode and anode geometry and the magnetic field 33 can result in drift-like conditions. Feed gases (e.g., nitrogen, argon, nitrogen-argon mixture, etc.) may be introduced through cavity 41 between anode 27 and cathode 29. The electrical energy between the anode and cathode breaks down the gas, creating plasma in the source. 34 ions (e.g. nitrogen ions) are ejected (e.g. by nitrogen gas in the source) and directed as an ion beam towards the layer to be ion beam treated / formed. The ion beam can be diffused, collimated, or focused. Exemplary ions 34 in bundle (B) are shown in Fig. 4.

[0058] In certain example instances, a line source of 0.5 to 4 meters in length may be made and used, although sources of different lengths are contemplated in other embodiments of the invention. The electron layer 35 shown in FIG. 4 completes the circuit, thereby allowing the ion beam source to function properly. Exemplary but non-limiting ion beam sources that can be used are disclosed in US Pat. US North America U.S. Patent No. 6,303,226, 6,359,388 and / or U.S. Patent Application No. US No. US 2004/0067363.

[0059] In certain example embodiments of this invention, coated articles described herein comprising two IR reflecting layers 9, 19 may have the following optical and solame properties measured for monolithic articles (prior to any optional heat treatment). In determining surface resistances (R._s) all layers reflecting infrared radiation (e.g. silver layers 9, 19) are considered here.

Optical properties / solame (monolithic product, two layers of Ag; before heat treatment)

<td>Property</td><td>Generally</td><td>More advantageously</td><td>Most preferably</td>

<td>R_s (ohms / square):</td><td> &lt;=5,0</td><td> &lt;=3,5</td><td> &lt;= 2,5</td>

<td>E._n^:</td><td> &lt;= 0,08</td><td> &lt;= 0,03</td><td> &lt;= 0,025</td>

<td>T._vis (III. C 2 °):</td><td> &gt;= 70%</td><td> &gt;= 75%</td><td> &gt;=75,5%</td>

[0060] In certain example embodiments, coated articles described herein may have the following properties, as measured for monolithic articles, e.g., after heat treatment (HT):

Optical properties / solame (monolithic product, two layers of Ag; after treatment

<td>thermal)</td><td></td><td></td><td></td>

<td>Property</td><td>Generally</td><td>More advantageously</td><td>The most advantageous</td>

<td>R_s (ohms / square):</td><td> &lt;= 5,0</td><td> &lt;=3,0</td><td> &lt;= 2,0</td>

<td>E._n:</td><td> &lt;= 0,07</td><td> &lt;= 0,03</td><td> &lt;= 0,0025</td>

<td>Tyis (^ - C 2 °):</td><td> &gt;= 70%</td><td> &gt;= 75%</td><td> &gt;= 80%</td>

<td>Haze:</td><td> &lt;= 0,40</td><td> &lt;= 0,35</td><td> &lt;= 0,30</td>

[0061] It should however be noted that for coatings having only one IR reflecting layer, the surface resistance and the emission factor values ​​will of course be higher.

In addition, in certain example laminate embodiments of this invention, coated articles described herein that have been heat treated to an extent sufficient for quenching and / or hot bending and that have been grained with another glass substrate may have the following optical / solame properties. :

Optical properties / solame (laminated product, two Ag layers; after heat treatment)

<td>Property</td><td>Generally</td><td>More advantageously</td><td>Most preferably</td>

<td>R_s (ohms / square):</td><td> &lt;= 5,0</td><td> &lt;=3,0</td><td> &lt;=2,0</td>

<td>E._n:</td><td> &lt;= 0,07</td><td> &lt;= 0,03</td><td> &lt;= 0,025</td>

<td>T._vis (UL D65 10 °):</td><td> &gt;= 70%</td><td> &gt;= 75%</td><td> &gt;= 77%</td>

<td>Haze:</td><td> &lt;= 0,45</td><td> &lt;= 0,40</td><td> &lt;= 0,36</td>

In addition, coated articles comprising coatings according to certain example embodiments of this invention have the following optical properties (e.g., when the coating (s) is applied to a 1 to 10 mm thick clear soda-lime glass substrate; In certain example non-limiting instances, 2.1 mm (laminated) may be used as the reference thickness of the glass substrate.

Examples of optical properties (laminated product, two layers of Ag; after heat treatment)

<td>Property</td><td>Generally</td><td>More advantageously</td>

<td>T._vis (or TY) (III. D65 10 °):</td><td> &gt;=75%</td><td> &gt;= 77%</td>

<td>and*_vol(IIL D65 10 °):</td><td>-6 to + 1.0</td><td>-4 to 0.0</td>

<td>b *_vol (III. D65 10 °):</td><td>-2.0 to +8.0</td><td>0.0 to 4.0</td>

<td>L * (III. D65 10 °):</td><td> 88-95</td><td> 90-95</td>

<td>RfY (III. C 2 °):</td><td>1 to 12%</td><td>1 to 10%</td>

<td>a * f (IU.C2 °):</td><td>-5.0 to +2.0</td><td>-3.5 to +0.5</td>

<td>b * f (III. C 2 °):</td><td>-14.0 to + 10.0</td><td>-10.0 toO</td>

<td>L * (III. C 2 °):</td><td> 30-40</td><td> 33-38</td>

<td>R_gY (III. C 2 °):</td><td>1 to 12%</td><td>1 to 10%</td>

<td>and*_g (III. C 2 °):</td><td>-5.0 to +2.0</td><td>-2 to +2.0</td>

<td>b *_g (ΙΠ. C 2 °):</td><td>-14.0 to + 10.0</td><td>-11.0 toO</td>

<td>L * (III. C 2 °):</td><td> 30-40</td><td> 33-38</td>

[0064] The following examples are offered for illustrative purposes only and are not intended to be limiting.

EXAMPLES

[0065] In example 1, an infrared reflecting Ag layer on a ZnO layer with a thickness of 100 A was formed. In forming the infrared reflecting layer, an Ag seed layer with a thickness of about 60 A was first sputtered and then the rest of the infrared reflecting layer was formed using IBAD. In IBAD, at room temperature, a silver sputtering target and an argon ion beam were used, with the average ionic energy ranging from about 200 to 250 eV per Ar ion.⁺.

[0066] Comparative Example 1 was the same as Example 1 above except that the entire IR reflecting Ag layer was formed using sputtering only (no IBAD was used). The results of the comparison of Example 1 and Comparative Example are shown below.

<td></td><td>Example 1</td><td>Comparative example 1</td>

<td>Ag thickness (total):</td><td>120 A.</td><td>120 A.</td>

<td>Surface resistance</td><td>(R_s,3,0</td><td> 3,8</td>

<td>ohms / square):</td><td></td><td></td>

<td>IBAD:</td><td>Yes</td><td>no</td>

<td>Ion energy to Ar ion⁺:</td><td>200-250 eV</td><td> 0</td>

<td>Tension Type:</td><td>compressive</td><td>stretching</td>

[0067] It can be seen from the above that the use of an IBAD (see example 1) in facilitating the formation of the infrared reflecting layer resulted in a much improved (i.e., lower) surface resistance of the infrared reflecting layer. Indeed, the surface resistance (R._s) was about 21% lower in Example 1 using IBAD than Comparative Example 1 where only sputtering was used to form the IR reflecting layer (3.8 - 3.0 = 0.8; and 0.8 / 3.8 = 21%). In certain example embodiments of this invention, the use of IBAD results in a sheet resistance (R._s) is at least about 5% less than when no ion beam treatment such as IBAD is applied , more preferably at least about 10% less, sometimes at least 15% less, and even in some cases at least 20% less. Moreover, the compressive stress of the infrared reflecting layer in Example 1 resulted in a significantly increased durability compared to Comparative Example 1 because Comparative Example 1 is characterized by the tensile stress caused by the deposition of the layer using only sputtering.

[0068] In example 2, an infrared reflecting Ag layer about 139 A was formed on a ZnO layer 600 A thick. In forming the infrared reflecting layer, a part of an Ag seed layer about 60 A was deposited by sputtering first, and then using IBAD , the remainder of the infrared reflecting layer was formed. In IBAD, at room temperature, a silver sputtering target and an argon ion beam were used, with an average ionic energy of about 250 eV per Ar ion.⁺.

[0069] Comparative Example 2 was the same as Example 2 except that the entire IR-reflecting Ag layer was formed using sputtering without IB AD.

[0070] Comparative example 3 did not contain a seed layer and IBAD of the same ion energy was used interchangeably to deposit all the reflecting infrared radiation.

<td>Ag layers.</td><td>Example 2</td><td>Comparative example 2</td><td>Comparative example 3</td>

<td>Ag thickness (total):</td><td>139 A.</td><td>153 A.</td><td>144 A.</td>

<td>Volume resistance [μΩ cm]:</td><td> 4,6</td><td> 4,8</td><td> 4,9</td>

<td>The germ layer</td><td>Yes</td><td>no</td><td>no</td>

<td>IBAD:</td><td>Yes</td><td>no</td><td>Yes</td>

<td>Ion energy to Ar ion⁺:</td><td>250 eV</td><td> 0</td><td>250 eV</td>

<td>Tension Type:</td><td>compressive</td><td>stretching</td><td>compressive</td>

It can be seen from the above that the use of an IBAD (see example 2) in facilitating the formation of the IR reflecting layer resulted in improved (i.e., lower) IR reflecting layer resistance compared to the sputtering layer of Comparative Example 2 only. that the volume resistance (BR) from the table above can be converted to sheet resistance as follows: R._s = BR / d, where "d" is the thickness of the infrared reflecting layer. Moreover, the compressive stress of the infrared reflecting layer of Example 2 led to a significantly improved durability compared to Comparative Example 2 because Comparative Example 2 had tensile stress due to the deposition of the layer using only sputtering.

[0072] The comparison between example 2 and comparative example 3 illustrates the advantage of the Ag seed layer. In particular, when the seed layer was absent and the same, rather high ionic energy was used to deposit the entire infrared reflecting Ag layer by IBAD, then the resistivity was actually worse (greater) than using only sputtering (compare Comparative Example 3 with Comparative Example 2 ). It is assumed that this is due to the high ionic energy used at the beginning of the formation of the IR reflecting layer due to substantial mixing of ions with the underlying ZnO layer and thus damage to the structure of the resulting IR reflecting layer. This illustrates the advantage of the solution shown in Fig. The method of claim 7, wherein IBAD may be used to form the entire infrared reflecting layer, except that the ionic energy is increased during deposition of the layer such that the bottom of the layer is not damaged or less damaged.

[0073] The following examples relate to ion beam treatment (IBAD or pelletizing) of a silicon nitride layer (e.g., layers 3 and / or 25 and without limitation).

[0074] Examples 3-5 illustrate exemplary techniques for forming layers 3 and / or 25, or any other suitable layer in accordance with example embodiments of this invention. IBAD-type ion beam treatment was used in Examples 3-5 and was performed and tested as follows. The layer of silicon nitride was deposited on a quartz plate (used for ease of stress testing) using IBAD (e.g. see Fig. 6) in the deposition chamber under the following conditions: pressure of 2.3 milli liters; anode and cathode voltage of the ion beam source of about 800 V; Ar gas flow in an ion source of 15 sccm (standard cubic centimeters); N2 gas flow in ion source 26 15 sccm; Si sputtering target enriched with about 1% boron; a voltage of 460 V was applied to the sputter cathode; 5.4 A was used for sputtering; a flow of 60 sccm Ar and 40 sccm gas N2 was used for sputtering; 50 inch / minute line speed; wherein the quartz wafer substrate is circular and has a thickness of from about 0.1 to 0.15 mm. The ion beam treatment time for a given surface was approximately 3 seconds.

[0075] Example 4 was the same as Example 3 except that the anode and cathode voltage of the ion source was increased to 1500 V.

[0076] Example 5 was the same as example 3 except that the anode and cathode voltage in the ion source was increased to 3000 V.

[0077] The stress results for Examples 3-5 were as follows, and all achieved compressive stress:

Example Compressive Stress Anode and cathode voltage of an ion source

750 800 V MPa

1.9 GPa 1500V

1 GPa 3000 V

[0078] It can be seen from Examples 3-5 that the compressive stress of the silicon nitride layers obtained by IBAD deposition is a function of the ionic energy (i.e., a function of the voltage applied to the anode and cathode of ion source 26). In particular, the voltage of 1500 V applied to the anode and cathode resulted in the highest compressive stress, while the application of too much voltage caused a tendency again towards tensile stress.

EXAMPLE 6

[0079] Example 6, after sputtering, was ion beam bead treatment, and was performed and tested as follows. A silicon nitride layer approximately 425 Å thick was deposited onto the substrate by a conventional sputtering method using an Al-enriched Si target. After starting the sputtering, the silicon nitride layer had a tensile stress of 400 MPa as tested on a quartz plate. After sputtering and stress testing, the silicon nitride layer was ion beam treated using an ion source 26 as shown in Figures 4-5 under the following conditions: Ion energy 750 eV per N ion; treatment time of about 18 seconds (3 passages of 6 seconds per passage); and N2 gas was used in the ion source. After ion beam treatment, the silicon nitride layer was re-tested for stress and had a tensile stress of only 50 MPa. Thus, after sputtering, the ion beam treatment reduced the tensile stress of the silicon nitride layer from 400 MPa to 50 MPa (a decrease of 87.5%).

EXAMPLE 7

[0080] The following hypothetical Example 7 is provided for illustrative purposes only, and is not intended to use colorless glass substrates with a thickness of 2.1 mm to give approximately the array of layers shown below and in Figure 3. Layer thicknesses are approximate and are given. them in angstroms (A).

A series of layers according to example 7

<td>Layer</td><td>Thickness (A)</td>

<td>Glass substrate</td><td></td>

<td>S13N4 enriched with 0N</td><td> 100</td>

<td>FoundAlO_x</td><td> 109</td>

<td>Ag</td><td> 96</td>

<td>NiCrO_x</td><td> 25</td>

<td>SnO2</td><td> 535</td>

<td>Si_xN_y</td><td> 126</td>

<td>ZnA10_x</td><td> 115</td>

<td>Ag</td><td> 95</td>

<td>NiCrO_x</td><td> 25</td>

<td>SnO2</td><td> 127</td>

S13N4 enriched with N

237

[0081] The processes used to form a coated article according to Example 7 are set out below. The flow of the sputtering gases (argon (Ar), oxygen (O) and nitrogen (N)) is given in sccm in the table below (here, for argon gas flow a gas correction factor of about 5 1.39 may be appropriate) and includes both the tuning gas and the gas introduced through the main pipe.

The line speed was approximately 5 m / minute. The pressures are given in units of mbar χ 1θΆ Silicon (Si) targets, and thus the silicon nitride layers, were enriched with aluminum (Al). Zn targets were similarly enriched with about 2% Al. The IBAD method was used to form each of the Ag infrared reflecting layers, as well as the upper and lower silicon nitride layers.

Sputtering process used in example 7

<td>Cathode</td><td>Target</td><td>Power (kW)</td><td>Ar</td><td>ABOUT</td><td>N</td><td>Voltage (V)</td><td>Pressure</td>

<td>IBAD</td><td colspan="2">Enriched with nitrogen</td><td>layer</td><td>S13N4</td><td colspan="3">3, formed according to any one of</td>

<td></td><td colspan="2">examples 3-6</td><td></td><td></td><td></td><td></td><td></td>

<td>C14</td><td>Zn</td><td> 19,5</td><td> 250</td><td> 350</td><td> 0</td><td> 276</td><td> 2,24</td>

<td>C15</td><td>Zn</td><td> 27,8</td><td> 250</td><td> 350</td><td> 0</td><td> 220</td><td> 1,88</td>

<td>C24</td><td colspan="5">The process according to any of the examples 1-2</td><td></td><td></td>

<td>C25</td><td>NiCr</td><td> 16,5</td><td> 350</td><td> 0</td><td> 0</td><td> 510</td><td> 2,33</td>

<td>C28</td><td>Sn</td><td> 27,3</td><td> 250</td><td> 454</td><td> 350</td><td> 258</td><td> 2,30</td>

<td>C29</td><td>Sn</td><td> 27,3</td><td> 250</td><td> 504</td><td> 350</td><td> 246</td><td> 1,97</td>

<td>C39</td><td>Sn</td><td> 30</td><td> 250</td><td> 548</td><td> 350</td><td> 257</td><td> 2,29</td>

<td>C40</td><td>Sn</td><td> 28,5</td><td> 250</td><td> 458</td><td> 350</td><td> 245</td><td> 2,20</td>

<td>C41</td><td>Sn</td><td> 30,8</td><td> 250</td><td> 518</td><td> 350</td><td> 267</td><td> 2,45</td>

<td>C43</td><td>Si</td><td> 59,7</td><td> 350</td><td> 0</td><td> 376</td><td> 285</td><td> 2,47</td>

<td>C45</td><td>Zn</td><td> 26,9</td><td> 250</td><td> 345</td><td> 0</td><td> 209</td><td> 3,78</td>

<td>C46</td><td>Zn</td><td> 26,8</td><td> 250</td><td> 345</td><td> 0</td><td> 206</td><td> 1,81</td>

<td>C49</td><td colspan="3">The process according to any of the</td><td colspan="2">examples 1-2</td><td></td><td></td>

<td>C50</td><td>NiCr</td><td> 16,6</td><td> 250</td><td> 75</td><td> 0</td><td> 575</td><td> 1,81</td>

<td>C54</td><td>Sn</td><td> 47,3</td><td> 250</td><td> 673</td><td> 350</td><td> 314</td><td> 1,92</td>

<td>IBAD</td><td colspan="2">Enriched with nitrogen</td><td>layer</td><td>S13N4</td><td colspan="3">25, formed according to any one of</td>

examples 3-6

[0082] It can be seen that in the previously mentioned example 7, both silicon nitride layers 3 and 25 were ion beam treated such that each nitrogen enriched S13N4 layer was enriched with nitrogen, and both IR reflecting layers were formed at least partially using the IB method. AD.

[0083] After spraying onto glass substrates, the hypothetical coated article of Example 7 was heat treated sufficiently for quenching and hot bending, and after this heat treatment, it had the following properties when measured for the monolithic article.

Properties of Example 7 (monolithic product; after heat treatment) Property Example 7

Visible radiation transmission coefficient (T_vj_s or 80.0%

TY) (IIL C 2 °): a * -4.8 b * 10.7

Glass side reflectance (RY) (III C 2 °): 8.3% a * -3.5 b * 7.8

Film side reflectance (FY) (III. C 2 °): 7.5% a * -5.8 b * 14.2

R_s (ohms / square) (before heat treatment): 2.74

R_s (ohms / square) (after heat treatment): 2.07

Haze: 0.28

[0084] The coated article of Example 7 was then laminated to another suitably heat treated and folded glass substrate to provide a laminated vehicle windshield product. After lamination, the obtained coated article - laminate (or windshield) had the following properties. Property Example 7 (Laminated Product; Heat Treated) Property Example 7

Visible radiation transmission coefficient (T_vj_s or 77.8% TY) ​​(III. D65 10 °): a * -3.1 b * 3.5

Glass side reflectance (RY) (III C 2 °): 9.0% a * 1.5 b * -9.1

Film side reflectance (FY) (IIL C 2 °): 8.9% a * -1.1 b * -7.8

R_s (ohms / square): see above

Haze: 0.32

[0085] Although the aforementioned examples of the ion beam treated layers included silicon nitride and / or silver, the invention is not so limited. Other layers can be treated in a similar manner with the ion beam.

[0086] In certain other embodiments of the invention, any of the aforementioned embodiments may be applied to different coatings. By way of example and without limitation, any of the aforementioned embodiments may also be applied to coated articles, and thus solar control coatings, of one of the many US patent applications and patents. US North America No. US 2003/0150711, US 2003/0194570, US 6723211, US 6576349, US 5514476, US 5425861.

[0087] While many of the embodiments set forth above are used in the context of coated articles with solar control coatings, the invention is not so limited. For example, ion beam treatment of layers as discussed herein may also be used in the context of other types of product and associated coatings.

[0088] While the invention has been described in conjunction with what is presently believed to be the most practical and advantageous embodiment, it should be understood that the invention is not intended to be limited to the disclosed solution but, on the contrary, is intended to cover various modifications and equivalent arrangements within the scope of the appended claims. patent.