Coated article with ir reflecting layer(s) and method for its production

0001This application relates to a coated article including at least one infrared (IR) reflecting layer of a material such as silver or the like. The provision of a layer comprising titanium oxide over the IR reflecting layer has been found to improve the quality of the IR reflecting layer thereby permitting the coated article for example to realize improved thermal properties such as one or more of emittance, U-value, and/or specific resistivity. Coated articles herein may be used in the context of insulating glass (IG) window units, or in other suitable applications such as monolithic window applications, laminated windows, and/or the like.

BACKGROUND AND SUMMARY OF EXAMPLE EMBODIMENTS OF THE INVENTION

0002Coated articles are known in the art for use in window applications such as insulating glass (IG) window units, vehicle windows, monolithic windows, and/or the like. In certain example instances, designers of coated articles often strive for a combination of high visible transmission, substantially neutral color, low emissivity (or emittance), low sheet resistance (R_s), low U-values in the context of IG window units, and/or low specific resistivity. High visible transmission and substantially neutral color may permit coated articles to be used in applications where these characteristics are desired such as in architectural or vehicle window applications, whereas low-emissivity (low-E), low sheet resistance, and low specific resistivity characteristics permit such coated articles to block significant amounts of IR radiation so as to reduce for example undesirable heating of vehicle or building interiors.

0003Consider a typical coated article with the following layer stack. This coated article is suitable for use in an IG (insulation glass) window unit. For the coated article listed below, the coating includes layers that are listed from the glass substrate outwardly. <tables id="tabl0001" num="0001"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><thead><row><entry valign="top">Layer Glass</entry><entry valign="top">Thickness (Ǻ)</entry></row></thead><tbody><row><entry>TiO_x</entry><entry>140 Ǻ</entry></row><row><entry>SnO_x</entry><entry>100 Å</entry></row><row><entry>ZnAlO_x</entry><entry>70 Ǻ</entry></row><row><entry>Ag</entry><entry>118 Ǻ</entry></row><row><entry>NiCrO_x</entry><entry>20 Ǻ</entry></row><row><entry>SnO_x</entry><entry>223 Å</entry></row><row><entry>SiN_x</entry><entry>160 Ǻ</entry></row></tbody></tgroup></table></tables>

0004The silver (Ag) layer of the above coated article has a thickness of 118 angstroms (Å) and a sheet resistance (R_s) of 4.6 ohms/square. This translates into a specific resistivity (R_s multiplied by thickness of the IR reflecting layer) for the silver IR reflecting layer of 5.43 micro-ohms.cm.

0005While the aforesaid specific resistivity (SR) of the silver IR reflecting layer is adequate in many situations, it would be desirable to improve upon the same. For example, if the specific resistivity (SR) of the silver layer could be lowered, then the coating could realize improved thermal properties (e.g., lower U-value, lower emittance, and/or the like) given an IR reflecting layer of the same thickness. Thus, a lower specific resistance of the IR reflecting layer(s) is desirable, as it permits thermal properties of the coating to be improved.

0006Document <patcit id="pcit0001" dnum="US6210784B1"><text>US 6,210,784 B1</text></patcit> relates to a transparent substrate provided with a thin-film stack including at least one metallic layer with infrared reflection properties arranged between two dielectric-based coatings, the underlying coating having a wetting layer based on zinc oxide ZnO directly in contact with the metallic layer.

0007Document <patcit id="pcit0002" dnum="US6589658B1"><text>US 6,589,658 B1</text></patcit> refers to coated articles provided with an anti-reflective (AR) layer(s) system which enables reduced reflection, increased visible transmission, and/or neutral color. The AR layer(s) system may include one or more layers. Silicon nitride layer(s) may optionally be provided below and/or over the IR reflecting layer.

0008Document <patcit id="pcit0003" dnum="WO2004026633A2"><text>WO 2004/026633 A2</text></patcit> relates to a mirror reflective element assembly for a vehicle, and to a rearview mirror reflective element assembly which provides transmission of display information or illumination or radiant energy through the reflective element of the mirror reflective element assembly, while providing sufficient reflectance of the reflective element.

0009Document <patcit id="pcit0004" dnum="US2003186064A1"><text>US 2003 186 064 A1</text></patcit> relates to a transparent laminate having low emissivity, wherein a ZnO layer is formed as a dielectric layer on an amorphous layer, a columnar crystal structure of ZnO is put into disorder and whereby not only the amorphous layer but also the dielectric layer functions as a barrier for preventing the invasion of moisture and gas from outside.

0010In view of the above, it will be appreciated that there exists a need in the art for a coated article including a coating which has good thermal properties. Certain example embodiments of this invention relate to a coated article which permits thermal properties to be improved.

0011The present invention provides a solution according to the subject-matter of independent claim 1.

0012It has surprisingly been found that the provision of a layer comprising titanium oxide over an IR reflecting layer (e.g., of silver or the like) unexpectedly improves the quality of the IR reflecting layer thereby permitting the coated article to realize improved thermal properties with a given thickness of the IR reflecting layer. The titanium oxide layer is provided over the IR reflecting layer, and may be located between a first layer comprising NiCrO_x and a second layer comprising a metal oxide such as tin oxide. Even though the titanium oxide need not be directly contacting the IR reflecting layer, it still surprisingly improves the quality of the underlying IR reflecting layer thereby permitting thermal properties of the coating to be improved.

0013The provision of the titanium oxide layer over the IR reflecting layer surprisingly results in an IR reflecting layer with a lower specific resistivity (SR). The lower the SR of an IR reflecting layer, the lower the emittance of the coated article with an IR reflecting layer of a given thickness. Likewise, the lower the SR of an IR reflecting layer, the lower the U-value of an IG unit including a similar coating having an IR reflecting layer of a given thickness. Thus, lowering the SR of an IR reflecting layer permits thermal properties of a coated article to be improved given an IR reflecting layer(s) of like thickness. Alternatively, lowering the SR of an IR reflecting layer permits thermal properties of a coated article to remain substantially the same while reducing the thickness of the IR reflecting layer(s) which may be desirable for increasing visible transmission or the like in certain situations.

0014Thus, it can be seen that lowering the SR of an IR reflecting layer is advantageous. As discussed herein, it has been found that the provision of the titanium oxide layer over the IR reflecting layer surprisingly results in an IR reflecting layer with a lower SR.

0015According to the invention, the titanium oxide layer over the IR reflecting layer is oxidation graded. In certain comparative example embodiments, the titanium oxide layer may be more oxided at a location further from the IR reflecting layer than at a location closer to the IR reflecting layer. Surprisingly, this has been found to improve the adhesion of the titanium oxide layer to the underlying layer such as a layer comprising NiCrO_x or silver. In embodiments of this invention, the titanium oxide layer is more oxided at a location proximate a central portion of the layer than at respective locations closer to the upper and lower surfaces of the layer. Again, this has been found to improve the adhesion of the layer comprising titanium oxide to the layers below and above the titanium oxide.

0016In certain example embodiments of this invention, there is provided a coated article including a coating supported by a glass substrate, the coating comprising a dielectric layer; an infrared (IR) reflecting layer comprising silver located on the substrate over the dielectric layer; a layer comprising an oxide of Ni and/or Cr located over and directly contacting the IR reflecting layer comprising silver; a layer comprising titanium oxide located over and directly contacting the layer comprising the oxide of Ni and/or Cr; a layer comprising a metal oxide located over and directly contacting the layer comprising titanium oxide; and a layer comprising silicon nitride located over the layer comprising the metal oxide.

0017There is provided a coated article including a coating supported by a glass substrate, the coating comprising a layer comprising zinc oxide; an infrared (IR) reflecting layer comprising silver located on the substrate over and contacting the layer comprising zinc oxide; a layer comprising titanium oxide located over the IR reflecting layer; a layer comprising silicon nitride and/or metal oxide located over the layer comprising titanium oxide; and wherein the IR reflecting layer has a specific resistivity (SR) of no greater than 5.0 micro-ohms.cm.

0018In comparative example embodiments, there is provided a method of making a coated article, the method comprising providing a glass substrate; forming a dielectric layer on the substrate; forming an IR reflecting layer comprising silver on the substrate over at least the dielectric layer; depositing a layer comprising titanium oxide on the substrate over the IR reflecting layer in a manner so that the layer comprising titanium oxide as deposited is more oxided at a location therein further from the IR reflecting layer than at a location closer to the IR reflecting layer.

0019The method according to the present invention is defined in independent claim 4 and dependent claims 5 and 6.

BRIEF DESCRIPTION OF THE DRAWINGS

0020<ul id="ul0001" list-style="none" compact="compact"><li><figref idref="f0001">FIGURE 1</figref> is a cross sectional view of a coated article according to an example embodiment of this invention.</li><li><figref idref="f0002">FIGURE 2</figref> is a cross sectional view of part of an insulating glass (IG) window unit including the coated article of <figref idref="f0001">Fig. 1</figref> (or <figref idref="f0003">Fig. 3</figref>) according to an example embodiment of this invention.</li><li><figref idref="f0003">FIGURE 3</figref> is a cross sectional view of a coated article according to another example embodiment of this invention.</li><li><figref idref="f0004">FIGURE 4</figref> is a cross sectional view illustrating that according to this invention a layer comprising titanium oxide is deposited in an oxidation graded manner.</li></ul>

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS OF THE INVENTION

0021Referring now to the drawings in which like reference numerals indicate like parts throughout the several views.

0022Coated articles herein may be used in applications such as monolithic windows, IG window units, vehicle windows, and/or any other suitable application that includes single or multiple substrates such as glass substrates.

0023It has surprisingly been found that the provision of a layer consisting essentially of or comprising titanium oxide (e.g., TiO_x, where x may be from about 1.5 to 2.5, more preferably from about 1.65 to 2, even more preferably from about 1.75 to 2, or any other suitable value) over an IR reflecting layer unexpectedly improves the quality of the IR reflecting layer thereby permitting the coated article to realize improved thermal properties with a given thickness of the IR reflecting layer. Another example advantage of the provision of the titanium oxide layer over the IR reflecting layer is that it permits antireflection characteristics of the coated article to be improved, which results in a higher visible transmission through the coating. Thus, the titanium oxide layer also permits visible transmission to be increased in certain example embodiments, and/or permits a thicker silver-based IR reflecting layer to be used without sacrificing visible transmission, in certain example embodiments of this invention.

0024The titanium oxide layer is provided over the IR reflecting layer, and may be located between (a) a first layer comprising an oxide of Ni and/or Cr, and (b) a second layer comprising a metal oxide such as tin oxide or alternatively a layer comprising silicon oxynitride and/or silicon nitride. The provision of the titanium oxide layer over the IR reflecting layer surprisingly results in an IR reflecting layer with a lower specific resistivity (SR). The lower the SR of an IR reflecting layer, the lower the emittance of the coated article with an IR reflecting layer of a given thickness. Likewise, the lower the SR of an IR reflecting layer, the lower the U-value of an IG unit including a similar coating having an IR reflecting layer of a given thickness. Thus, lowering the SR of an IR reflecting layer permits thermal properties of a coated article to be improved given an IR reflecting layer(s) of like thickness. Alternatively, lowering the SR of an IR reflecting layer permits thermal properties of a coated article to remain substantially the same while reducing the thickness of the IR reflecting layer(s) which may be desirable for increasing visible transmission or the like in certain situations.

0025The coating is designed in a manner so that the IR reflecting layer 9 (e.g., silver layer) has a specific resistivity (SR) of no greater than 5.0, more preferably no greater than 4.8, and even more preferably no greater than 4.6 micro-ohms.cm. Such low SR values permit U-values and emittance of the coating to be lowered given a particular thickness for the IR reflecting layer(s).

0026<figref idref="f0001">Fig. 1</figref> is a cross sectional view of a coated article according to an example embodiment of this invention. The coated article includes glass substrate 1 (e.g., clear, green, bronze, or blue-green glass substrate from about 1.0 to 10.0 mm thick, more preferably from about 1.0 mm to 6.0 mm thick), and a multi-layer coating (or layer system) provided on the substrate either directly or indirectly. As shown in <figref idref="f0001">Fig. 1</figref>, the coating 25 comprises dielectric layer 3, dielectric layer 5, zinc oxide inclusive layer 7, IR reflecting layer 9 of or including silver, upper contact layer 11 of or including an oxide of nickel chrome (e.g., NiCrO_x), a layer 12 consisting of or comprising titanium oxide (TiO_x), a metal oxide inclusive layer 13, and dielectric layer 15 of or including a material such as silicon nitride and/or silicon oxynitride which may in certain example instances be a protective overcoat. Other layers and/or materials may also be provided in certain example embodiments of this invention, and it is also possible that certain layers may be removed or split in certain example instances.

0027In monolithic instances, the coated article includes only one substrate such as glass substrate 1 (see <figref idref="f0001">Fig. 1</figref>). However, monolithic coated articles herein may be used in devices such as IG window units for example. Typically, as shown in <figref idref="f0002">Fig. 2</figref>, an IG window unit may include two spaced apart substrates 1 and 2, with a gap 4 defined therebetween. Example IG window units are illustrated and described, for example, in <patcit id="pcit0005" dnum="US5770321A"><text>U.S. Patent Nos. 5,770,321</text></patcit>, <patcit id="pcit0006" dnum="US5800933A"><text>5,800,933</text></patcit>, <patcit id="pcit0007" dnum="US6524714B"><text>6,524,714</text></patcit>, <patcit id="pcit0008" dnum="US6541084B"><text>6,541,084</text></patcit> and <patcit id="pcit0009" dnum="US20030150711A"><text>US 2003/0150711</text></patcit>. An example IG window unit as shown in <figref idref="f0002">Fig. 2</figref> may include, for example, the coated glass substrate 1 shown in <figref idref="f0001">Fig. 1</figref> coupled to another glass substrate 2 via spacer(s), sealant(s) or the like with a gap 4 being defined therebetween. This gap 4 between the substrates in IG unit embodiments may in certain instances be filled with a gas such as argon (Ar). An example IG unit may comprise a pair of spaced apart substantially clear glass substrates each about 4 mm thick one of which is coated with a coating 25 herein in certain example instances, where the gap 4 between the substrates may be from about 5 to 30 mm, more preferably from about 10 to 20 mm, and most preferably about 16 mm. In certain example instances, the coating 25 may be provided on the side of the inner glass substrate 1 facing the gap (although the coating may be on the other substrate in certain alternative embodiments).

0028In certain example IG unit embodiments of this invention, the coating 25 is designed such that the resulting IG unit (e.g., with, for reference purposes, a pair of 4 mm clear glass substrates spaced apart by 16 mm with Ar gas in the gap) has a U-value of no greater than 1.25 W/(m²K), more preferably no greater than 1.20 W/(m²K), even more preferably no greater than 1.15 W/(m²K), and most preferably no greater than 1.10 W/(m²K). The U-value is measured in accordance with EN 673.

0029The bottom dielectric layer 3 may be of or include titanium oxide in certain example embodiments of this invention. The titanium oxide of layer 3 may in certain example instances be represented by TiO_x, where x is from 1.5 to 2.5, most preferably about 2.0. The titanium oxide may be deposited via sputtering or the like in different embodiments. In certain example instances, dielectric layer 3 may have an index of refraction (n), at 550 nm, of at least 2.0, more preferably of at least 2.1, and possibly from about 2.3 to 2.6 when the layer is of or includes titanium oxide. In certain embodiments of this invention, the thickness of titanium oxide inclusive layer 3 is controlled so as to allow a* and/or b* color values (e.g., transmissive, film side reflective, and/or glass side reflective) to be fairly neutral (i.e., close to zero) and/or desirable. Other materials may be used in addition to or instead of titanium oxide in certain example instances. In certain alternative embodiments, the Ti in oxide layer 3 may be replaced with another metal.

0030Dielectric layer 5 is optional, and may be of or include a metal oxide such as tin oxide in certain example embodiments of this invention. Metal oxide inclusive layer 5 may be provided in order to improve adhesion between titanium oxide layer 3 and zinc oxide layer 7 in certain example embodiments. The tin oxide layer 5 may be doped with other materials such as nitrogen in certain example embodiments of this invention. In certain instances, tin oxide inclusive layer 5 may be advantageous in that it may increase the throughput of the coater producing the coating or save costs, compared to if this portion of the coating was of titanium oxide or silicon nitride which are slower to sputter and/or more expensive (although these materials are also possible).

0031Lower contact layer 7 of this invention is of or includes zinc oxide (e.g., ZnO). The zinc oxide of layer(s) 7 may contain other materials as well such as Al (e.g., to form ZnAlO_x) in certain example embodiments. For example, in certain example embodiments of this invention, zinc oxide layer 7 may be doped with from about 1 to 10% Al (or B), more preferably from about 1 to 5% Al (or B), and most preferably about 2 to 4% Al (or B). The use of zinc oxide 7 under the silver in layer 9 allows for an excellent quality of silver to be achieved.

0032Infrared (IR) reflecting layer 9 is preferably substantially or entirely metallic. Further, the infrared (IR) reflecting layer 9 comprises or consists essentially of silver (Ag). IR reflecting layer 9 helps allow the coating to have low-E and/or good solar control characteristics such as low emittance, low sheet resistance, and so forth. The IR reflecting layer may, however, be slightly oxidized in certain embodiments of this invention.

0033In certain example embodiments of this invention, the target-to-substrate distance of the silver target (e.g., silver planar target) used in sputtering IR reflecting layer 9 is reduced compared to conventional practice. Surprisingly and unexpectedly, it has been found that properties of the IR reflecting layer 9 can be improved by reducing the distance between the substrate 1 and the sputtering target(s) used in forming the IR reflecting layer(s) 9. For example, it has been found that a reduction in the target-substrate distance for a target(s) used in sputtering an IR reflecting layer(s) 9 results in an IR reflecting layer 9 having one or more of: (a) reduced sheet resistance (R_s), (b) reduced emittance or emissivity, (c) improved crystallinity, and/or (d) a higher and thus improved extinction coefficient (k). Accordingly, in certain example embodiments of this invention, IR reflecting layer(s) 9 are formed by sputtering a target which is located closer to the substrate 1 than conventionally. In certain example embodiments of this invention, IR reflecting layer(s) 9 is/are formed by sputtering where the Ag target being sputtering is located in accordance with a target-substrate distance of less than or equal to about 110 mm, more preferably less than or equal to about 100 mm, more preferably less than or equal to about 95 mm, still more preferably less than or equal to about 90 mm, even more preferably less than or equal to about 80 mm. Further details of the target-to-substrate distance for the silver target used in forming IR reflecting layer 9 are discussed in <patcit id="pcit0010" dnum="US2006099428A"><text>US 2006/099428</text></patcit> (based on <patcit id="pcit0011" dnum="US619687P" dnum-type="L"><text>U.S. Provisional Patent Application 60/619,687</text></patcit>).

0034The upper contact layer 11 may be of or include an oxide of Ni and/or Cr. In certain example embodiments, upper contact layer 11 may be of or include nickel (Ni) oxide, chromium/chrome (Cr) oxide, or a nickel alloy oxide such as nickel chrome oxide (NiCrO_x), or other suitable material(s). The use of, for example, NiCrO_x in this layer allows durability to be improved. The NiCrO_x layer 11 may be fully oxidized in certain embodiments of this invention (i.e., fully stoichiometric), or alternatively may only be partially oxidized. In certain instances, the NiCrO_x layer 11 may be at least about 50% oxidized. Contact layer 11 (e.g., of or including an oxide of Ni and/or Cr) may or may not be oxidation graded in different embodiments of this invention. Oxidation grading means that the degree of oxidation in the layer changes throughout the thickness of the layer so that for example a contact layer may be graded so as to be less oxidized at the contact interface with the immediately adjacent IR reflecting layer than at a portion of the contact layer(s) further or more/most distant from the immediately adjacent IR reflecting layer. Descriptions of various types of oxidation graded contact layers are set forth in <patcit id="pcit0012" dnum="US6576349B"><text>U.S. Patent No. 6,576,349</text></patcit>. Contact layer 11 (e.g., of or including an oxide of Ni and/or Cr) may or may not be continuous in different embodiments of this invention across the entire IR reflecting layer.

0035Titanium oxide layer 12 is provided on and over the IR reflecting layer 9, and directly on and contacting the contact layer 11 in the <figref idref="f0001">Fig. 1</figref> embodiment. As explained herein, it has unexpectedly been found that the provision of a layer 12 consisting essentially of or comprising titanium oxide over IR reflecting layer 9 unexpectedly improves the quality of the IR reflecting layer thereby permitting the coated article to realize improved thermal and/or optical properties. The titanium oxide layer 12 may be stoichiometric (TiO₂), according to a comparative example embodiment, or non-stoichiometric according to this invention.

0036Dielectric layer 13 may be of or include a metal oxide such as tin oxide in certain example embodiments of this invention. Metal oxide inclusive layer 13 is provided for antireflection purposes, and also improves the emissivity of the coated article and the stability and efficiency of the manufacturing process. Moreover, tin oxide in layer 13 provides good adhesion to the titanium oxide in layer 12, and provides for good durability in this respect. The tin oxide layer 13 may be doped with other materials such as nitrogen in certain example embodiments of this invention. In certain instances, tin oxide inclusive layer 5 may be advantageous in that it may increase the throughput of the coater producing the coating or save costs, compared to if this portion of the coating was of titanium oxide or silicon nitride which are slower to sputter and/or more expensive (although these materials are also possible to replace the layer 13).

0037Dielectric layer 15, which may be an overcoat in certain example instances, is of or includes silicon nitride (e.g., Si₃N₄). Optionally, other layers may be provided above layer 15. Layer 15 is provided for durability purposes, and to protect the underlying layers. In certain example embodiments, layer 15 may have an index of refraction (n) of from about 1.9 to 2.2, more preferably from about 1.95 to 2.05.

0038Other layer(s) below or above the illustrated coating 25 may also be provided. Thus, while the layer system or coating is "on" or "supported by" substrate 1 (directly or indirectly), other layer(s) may be provided therebetween. Thus, for example, the coating of <figref idref="f0001">Fig. 1</figref> may be considered "on" and "supported by" the substrate 1 even if other layer(s) are provided between layer 3 and substrate 1. Moreover, certain layers of the illustrated coating may be removed in certain embodiments, while others may be added between the various layers or the various layer(s) may be split with other layer(s) added between the split sections in other embodiments of this invention. For example and without limitation, layer 5 and/or layer 13 may be removed in certain example situations.

0039While various thicknesses may be used in different embodiments of this invention, example thicknesses and materials for the respective layers on the glass substrate 1 in the <figref idref="f0001">Fig. 1</figref> embodiment are as follows, from the glass substrate outwardly (e.g., the Al content in the zinc oxide layer 7 may be from about 1-10%, more preferably from about 1-3% in certain example instances): <tables id="tabl0002" num="0002"><table frame="none"><title>Table 1 (Example Materials/Thicknesses; Fig. 1 Embodiment)</title><tgroup cols="4" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="30mm" /><colspec colnum="2" colname="col2" colwidth="33mm" /><colspec colnum="3" colname="col3" colwidth="31mm" /><colspec colnum="4" colname="col4" colwidth="23mm" /><thead><row><entry valign="top">Layer</entry><entry valign="top">Preferred Range (Ǻ)</entry><entry valign="top">More Preferred (Ǻ)</entry><entry valign="top">Example (Å)</entry></row></thead><tbody><row><entry>TiO_x (layer 3)</entry><entry>30-400 Ǻ</entry><entry>80-250 Ǻ</entry><entry>180 Å</entry></row><row><entry>SnO₂ (layer 5)</entry><entry>10-300 Å</entry><entry>10-100 Å</entry><entry>20 Å</entry></row><row><entry>ZnAlO_x (layer 7)</entry><entry>10-300 Ǻ</entry><entry>60-120 Ǻ</entry><entry>50 Å</entry></row><row><entry>Ag (layer 9)</entry><entry>50-250 Ǻ</entry><entry>80-150 Ǻ</entry><entry>130 Å</entry></row><row><entry>NiCrO_x (layer 11)</entry><entry>10-80 Ǻ</entry><entry>20-70 Ǻ</entry><entry>30 Å</entry></row><row><entry>TiO_x (layer 12)</entry><entry>10-300 Ǻ</entry><entry>20-100 Ǻ</entry><entry>40 Å</entry></row><row><entry>SnO₂ (layer 13)</entry><entry>40-400 Å</entry><entry>100-200 Å</entry><entry>160 Å</entry></row><row><entry>Si₃N₄ (layer 15)</entry><entry>50-750 Ǻ</entry><entry>150-350 Ǻ</entry><entry>210 Å</entry></row></tbody></tgroup></table></tables>

0040In certain example embodiments of this invention, coated articles herein may have the following low-E (low emissivity), solar and/or optical characteristics set forth in Table 2 when measured monolithically. The specific resistivity (SR) is of the silver IR reflecting layer 9. <tables id="tabl0003" num="0003"><table frame="none"><title>Table 2: Low-E/Solar Characteristics (Monolithic; no HT)</title><tgroup cols="4" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="38mm" /><colspec colnum="2" colname="col2" colwidth="17mm" /><colspec colnum="3" colname="col3" colwidth="26mm" /><colspec colnum="4" colname="col4" colwidth="26mm" /><thead><row><entry valign="top">Characteristic</entry><entry valign="top">General</entry><entry valign="top">More Preferred</entry><entry valign="top">Most Preferred</entry></row></thead><tbody><row><entry>R_s (ohms/sq.):</entry><entry><= 6.0</entry><entry><= 4.5</entry><entry><= 3.5</entry></row><row><entry>Ag SR (microohms.cm):</entry><entry><= 5.0</entry><entry><= 4.8</entry><entry><= 4.6</entry></row><row><entry>E_n:</entry><entry><= 0.10</entry><entry><= 0.06</entry><entry><= 0.040</entry></row><row><entry>T_vis (%):</entry><entry>>= 70</entry><entry>>= 80</entry><entry>>= 85</entry></row></tbody></tgroup></table></tables>

0041It can be seen that the coated article has a reduced (i.e., better) SR for the silver IR reflecting layer 9 compared to the 5.43 micro-ohms.cm value mentioned above when the titanium oxide layer 12 is not present. Thus, it can be seen that the presence of the titanium oxide layer 12 surprisingly results in improved specific resistivity of the IR reflecting layer, and thus improved thermal properties.

0042Moreover, coated articles including coatings according to certain example embodiments of this invention have the following optical characteristics (e.g., when the coating(s) is provided on a clear soda lime silica glass substrate 1 from 1 to 10 mm thick, preferably about 4 mm thick). In Table 3, all parameters are measured monolithically. <tables id="tabl0004" num="0004"><table frame="none"><title>Table 3: Example Optical Characteristics (Monolithic)</title><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="40mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><colspec colnum="3" colname="col3" colwidth="32mm" /><thead><row><entry valign="top">Characteristic</entry><entry valign="top">General</entry><entry valign="top">More Preferred</entry></row></thead><tbody><row><entry>T_vis (or TY)(Ill. C, 2 deg.):</entry><entry>>= 70%</entry><entry>>= 80% (or >= 85%)</entry></row><row><entry> a*_t (Ill. C, 2°):</entry><entry>-2.5 to +1.0</entry><entry>-2.0 to 0.0</entry></row><row><entry> b*_t (Ill. C, 2°):</entry><entry>-1.0 to +4.0</entry><entry>0.0 to 2.5</entry></row><row><entry> L*_t:</entry><entry>>=90</entry><entry>>=93</entry></row><row><entry>RfY (Ill. C, 2 deg.):</entry><entry>1 to 7%</entry><entry>1 to 6%</entry></row><row><entry> a*_f (Ill. C, 2°):</entry><entry>-5.0 to +4.0</entry><entry>-1.5 to +3.0</entry></row><row><entry> b*_f (Ill. C, 2°):</entry><entry>-14.0 to +10.0</entry><entry>-10.0 to 0</entry></row><row><entry> L*_f:</entry><entry>22-30</entry><entry>24-27</entry></row><row><entry>R_gY (Ill. C, 2 deg.):</entry><entry>1 to 10%</entry><entry>1 to 9%</entry></row><row><entry> a*_g (Ill. C, 2°):</entry><entry>-5.0 to +4.0</entry><entry>-1.5 to +3.0</entry></row><row><entry> b*_g (Ill. C, 2°):</entry><entry>-14.0 to +10.0</entry><entry>-10.0 to 0</entry></row><row><entry> L*_g:</entry><entry>27-36</entry><entry>30-35</entry></row></tbody></tgroup></table></tables>

0043Moreover, coated articles including coatings according to certain example embodiments of this invention have the following optical characteristics when the coated article is an IG unit in certain example embodiments (e.g., for purposes of reference, when the coating is provided on a clear soda lime silica glass substrate 1 from 1 to 10 mm thick, preferably about 4 mm thick) on surface #3 of an IG window unit. It is noted that U-value is measured in accordance with EN 673. <tables id="tabl0005" num="0005"><table frame="none"><title>Table 4: Example Optical Characteristics (IG Unit)</title><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="38mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><colspec colnum="3" colname="col3" colwidth="32mm" /><thead><row><entry valign="top">Characteristic</entry><entry valign="top">General</entry><entry valign="top">More Preferred</entry></row></thead><tbody><row><entry>T_vis (or TY)(Ill. C, 2 deg.)</entry><entry>>= 70%</entry><entry>>= 78%</entry></row><row><entry> a*_t (Ill. C, 2°):</entry><entry>-4.0 to +1.0</entry><entry>-3.0 to 0.0</entry></row><row><entry> b*_t (Ill. C, 2°):</entry><entry>-1.0 to +4.0</entry><entry>0.0 to 3.0</entry></row><row><entry>R_outsideY (Ill. C, 2 deg.):</entry><entry><=14%</entry><entry><=12%</entry></row><row><entry> a*_out (Ill. C, 2°):</entry><entry>-3.0 to +3.0</entry><entry>-2 to +2.0</entry></row><row><entry> b*_out (Ill. C, 2°):</entry><entry>-10.0 to +10.0</entry><entry>-6.0 to 0</entry></row><row><entry>R_insideY (Ill. C, 2 deg.):</entry><entry><=14%</entry><entry><=12%</entry></row><row><entry> a*_inside (Ill. C, 2°):</entry><entry>-5.0 to +4.0</entry><entry>-1.5 to +3.0</entry></row><row><entry> b*_inside (Ill. C, 2°):</entry><entry>-14.0 to +10.0</entry><entry>-10.0 to 0</entry></row><row><entry>U-value (IG)(W/(m²K)):</entry><entry><= 1.25</entry><entry><= 1.15 (or <= 1.10)</entry></row></tbody></tgroup></table></tables>

0044<figref idref="f0003">Fig. 3</figref> is a cross sectional view of another example embodiment of this invention. In the <figref idref="f0003">Fig. 3</figref> embodiment, the titanium oxide layer 12 is provided over and in contact with the IR reflecting layer 9 (i.e., contact layer 11 from the <figref idref="f0001">Fig. 1</figref> embodiment has been removed). The characteristics set forth above in Tables 1-4 may apply to the <figref idref="f0003">Fig. 3</figref> embodiment also (in addition to the <figref idref="f0001">Fig. 1</figref> embodiment, and other embodiments of this invention).

0045According to the invention, the titanium oxide layer over the IR reflecting layer is oxidation graded (see graded titanium oxide layer 12' in <figref idref="f0004">Fig. 4). Fig. 4</figref> illustrates an example oxidation graded titanium oxide layer 12' which may be used as layer 12 in any of the <figref idref="f0001 f0002 f0003">Fig. 1-3</figref> embodiments of this invention. As shown in <figref idref="f0004">Fig. 4</figref> for example, the titanium oxide layer 12' may be more oxided at a location further from the IR reflecting layer 9 than at a location closer to the IR reflecting layer 9. Surprisingly, this has been found to improve the adhesion of the titanium oxide layer 12' to the underlying layer such as a layer comprising NiCrO_x 11 or silver 9. In particular, the titanium oxide 12' layer is more oxided at a location proximate a central portion of the layer than at respective locations closer to the upper and lower surfaces of the layer 12'. Again, this has been found to improve the adhesion of the layer 12' comprising titanium oxide to the layers below (9 or 11) and above (13) the titanium oxide layer 12'.

0046In one example embodiment of this invention, this oxidation grading of titanium oxide layer 12' as deposited may be carried out by sputtering layer 12 onto the substrate using 3 CMAG Ti (or TiO_x) targets, or any other suitable number of Ti inclusive target(s). The second and third targets may have oxygen introduced into their respective sputtering atmospheres. However, no oxygen is intentionally introduced into the atmosphere of the first Ti inclusive target, or alternatively it is only intentionally introduced into the downstream side of the first Ti inclusive target but not the upstream side. This causes the first portion of the titanium oxide layer 12' that is deposited to be more metallic than later portions of the titanium oxide layer 12' that are sputtered to make up the overall layer 12'. The characteristics set forth above in Tables 1-4 may apply to oxidation graded embodiments.

EXAMPLE

0047The following example is provided for purposes of example only, and is not intended to be limiting. The following Example was made via sputtering so as to have approximately the layer stack set forth below, from the clear glass substrate outwardly. The listed thicknesses are approximations: <tables id="tabl0006" num="0006"><table frame="none"><title>Table 5: Layer Stack for Example</title><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="28mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><thead><row><entry valign="top">Layer</entry><entry valign="top">Thickness</entry></row></thead><tbody><row><entry>Glass Substrate</entry><entry>4 mm</entry></row><row><entry>TiO_x</entry><entry>180 Ǻ</entry></row><row><entry>SnO₂</entry><entry>20 Ǻ</entry></row><row><entry>ZnAlO_x</entry><entry>50 Ǻ</entry></row><row><entry>Ag</entry><entry>135 Ǻ</entry></row><row><entry>NiCrO_x</entry><entry>30 Ǻ</entry></row><row><entry>TiO_x</entry><entry>40 Ǻ</entry></row><row><entry>SnO₂</entry><entry>160 Å</entry></row><row><entry>Si₃N₄</entry><entry>210 Ǻ</entry></row></tbody></tgroup></table></tables>

0048The silver layer was sputtered using two silver planar targets, and using gas flows including Ar and Kr, where much more Ar than Kr was used. After being sputter deposited onto the glass substrate, the coated article of the Example had the following characteristics, measured monolithically <tables id="tabl0007" num="0007"><table frame="none"><title>Table 6: Characteristics of Example (Monolithic)</title><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="63mm" /><colspec colnum="2" colname="col2" colwidth="30mm" /><thead><row><entry valign="top"> Characteristic</entry><entry valign="top">Example</entry></row></thead><tbody><row><entry>Visible Trans. (T_vis or TY)(Ill. C 2 deg.):</entry><entry>86.53%</entry></row><row><entry> a*</entry><entry>-1.84</entry></row><row><entry> b*</entry><entry>2.15</entry></row><row><entry> L*</entry><entry>94.54</entry></row><row><entry>Glass Side Reflectance (RY)(Ill C, 2 deg.):</entry><entry>6.67%</entry></row><row><entry> a*</entry><entry>1.05</entry></row><row><entry> b*</entry><entry>-8.03</entry></row><row><entry> L*</entry><entry>31.05</entry></row><row><entry>Film Side Reflective (FY)(Ill. C, 2 deg.):</entry><entry>4.96</entry></row><row><entry> a*</entry><entry>2.11</entry></row><row><entry> b*</entry><entry>-8.01</entry></row><row><entry> L*</entry><entry>26.61</entry></row><row><entry>R_s (ohms/square):</entry><entry>3.4</entry></row><row><entry>E_n:</entry><entry>0.034</entry></row><row><entry>Ag SR (micro-ohms.cm):</entry><entry>4.56</entry></row></tbody></tgroup></table></tables>

0049Compared to the coated article discussed above in the background section, it can be seen that the addition of the titanium oxide layer 12 over the silver IR reflecting layer 9 surprisingly caused the specific resistivity (SR) of the IR reflecting layer 9 to drop, thereby permitting thermal properties of the coating to improve (compare the SR for the IR reflecting layer 9 of 4.56 micro-ohms.cm in the aforesaid Example, versus the higher value of 5.43 for the coating without titanium oxide layer 12 discussed in the background section). This evidences unexpected results.

0050Moreover, with respect to the IR reflecting layer 9 having been sputter-deposited using a mixture of Ar and Kr gases, it has surprisingly been found that the use of Kr gas during the vacuum sputtering process for the IR reflecting layer of or including Ag results in improved k values for an IR reflecting layer comprising Ag, and thus improved resistance and/or emittance properties.

0051When the aforesaid monolithic Example was used in an IG window unit, the IG window unit had a U-value of about 1.1 W/(m²K).

0052While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.