Coated article with IR reflecting layer(s) and method of making same
09738561 · 2017-08-22
Assignee
- Centre Luxembourgeois De Recherches Pour Le Verre Et La Ceramique S.A. (C.R.V.C.) (Grand Duchy de Luxembourg, LU)
- Guardian Industries Corp. (Auburn Hills, MI)
Inventors
- Jochen Butz (Wolfen, DE)
- Uwe Kriltz (Jena, DE)
- Artur Siwek (Czestochowa, PL)
- Anton Dietrich (Fontnas, CH)
- Jens-Peter Müller (Differdange, LU)
- Jean-Marc Lemmer (Wincheringen, DE)
- Richard Blacker (Lino Lakes, MN, US)
Cpc classification
C03C17/3668
CHEMISTRY; METALLURGY
E06B3/6715
FIXED CONSTRUCTIONS
C03C17/3626
CHEMISTRY; METALLURGY
C03C17/3681
CHEMISTRY; METALLURGY
C03C17/3694
CHEMISTRY; METALLURGY
C03C17/3657
CHEMISTRY; METALLURGY
C03C17/3639
CHEMISTRY; METALLURGY
B32B37/18
PERFORMING OPERATIONS; TRANSPORTING
C03C2217/78
CHEMISTRY; METALLURGY
C03C17/3618
CHEMISTRY; METALLURGY
B32B17/06
PERFORMING OPERATIONS; TRANSPORTING
C03C17/3652
CHEMISTRY; METALLURGY
International classification
B05D5/06
PERFORMING OPERATIONS; TRANSPORTING
B32B17/06
PERFORMING OPERATIONS; TRANSPORTING
B32B37/18
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A coated article is provided with at least one infrared (IR) reflecting layer. The IR reflecting layer may be of silver or the like. In certain example embodiments, a titanium oxide layer is provided over the IR reflecting layer, and it has been found that this surprisingly results in an IR reflecting layer with a lower specific resistivity (SR) thereby permitting thermal properties of the coated article to be improved.
Claims
1. 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 over and directly contacting the IR reflecting layer comprising silver 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.
2. The method of claim 1, wherein said depositing comprises sputtering.
3. The method of claim 1, wherein said forming the IR reflecting layer comprises sputtering the IR reflecting layer.
4. The method of claim 1, further comprising depositing a layer comprising zinc oxide located between the dielectric layer and the IR reflecting layer, the layer comprising zinc oxide directly contacting the IR reflecting layer.
5. The method of claim 4, wherein the dielectric layer comprises an oxide of titanium.
6. The method of claim 4, wherein the dielectric layer comprises tin oxide.
7. The method of claim 1, wherein the IR reflecting layer comprising silver has a specific resistivity (SR) of no greater than 5.0 micro-ohms.Math.cm.
8. The method of claim 1, wherein the IR reflecting layer comprising silver has a specific resistivity (SR) of no greater than 4.8 micro-ohms.Math.cm.
9. The method of claim 1, wherein the IR reflecting layer comprising silver has a specific resistivity (SR) of no greater than 4.6 micro-ohms.Math.cm.
10. The method of claim 1, wherein the coated article has a visible transmission of at least 70%.
11. The method of claim 1, wherein the coated article has a glass side visible reflectance (R.sub.gY) of from 1-10%, measured monolithically.
12. The method of claim 1, wherein the coated article has a film side visible reflectance (R.sub.fY) of from 1-7%, measured monolithically.
13. The method of claim 1, wherein the coated article has a glass side reflective a* value from −5.0 to +4.0, and a glass side reflective b* value from −14.0 to +10.0.
14. The method of claim 1, wherein the coated article has a glass side reflective a* value from −1.5 to +3.0, and a glass side reflective b* value from −10.0 to 0.
15. The method of claim 1, further comprising depositing a layer comprising silicon nitride located over and contacting a layer comprising tin oxide, wherein said layer comprising silicon nitride is an overcoat and thus an uppermost layer of the coating.
16. The method of claim 1, wherein the coating includes only one IR reflecting layer comprising silver.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
(5)
DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS OF THE INVENTION
(6) Referring now to the drawings in which like reference numerals indicate like parts throughout the several views.
(7) Coated 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.
(8) In certain example embodiments of this invention, it has surprisingly been found that the provision of a layer consisting essentially of or comprising titanium oxide (e.g., TiO.sub.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 realized 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.
(9) In certain example embodiments, the titanium oxide layer may be 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. In certain example embodiments of this invention, 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.
(10) In certain example embodiments of this invention, the 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.Math.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).
(11)
(12) In monolithic instances, the coated article includes only one substrate such as glass substrate 1 (see
(13) In 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/(m.sup.2K), more preferably no greater than 1.20 W/(m.sup.2K), even more preferably no greater than 1.15 W/(m.sup.2K), and most preferably no greater than 1.10 W/(m.sup.2K). U-value is measured in accordance with EN 673, the disclosure of which is hereby incorporated herein by reference.
(14) The 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.sub.x, where x is from 1.5 to 2.5, most preferably about 2.0. The titanium oxide may be deposited via splittering 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.
(15) Dielectric 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).
(16) Lower contact layer 7 in certain embodiments 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 ZnAl.sub.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.
(17) Infrared (IR) reflecting layer 9 is preferably substantially or entirely metallic and/or conductive, and may comprise or consist essentially of silver (Ag), gold, or any other suitable, ER reflecting material. 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.
(18) In 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 ER 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.sub.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 U.S. Provisional Patent Application 60/619,687, the disclosure of which is hereby incorporated herein by reference.
(19) The 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.sub.x), or other suitable material(s). The use of, for example, NiCrO.sub.x in this layer allows durability to be improved. The NiCrO.sub.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.sub.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 U.S. Pat. No. 6,576,349, the disclosure of which is hereby incorporated herein by reference. 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.
(20) Titanium oxide layer 12 is provided on and over the IR reflecting layer 9, and directly on and contacting the contact layer 11 in the
(21) Dielectric 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).
(22) Dielectric layer 15, which may be an overcoat in certain example instances, may be of or include silicon nitride (e.g., Si.sub.3N.sub.4) or any other suitable material in certain example embodiments of this invention such as silicon oxynitride. 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.
(23) Other 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
(24) While 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
(25) TABLE-US-00002 TABLE 1 (Example Materials/Thicknesses; FIG. 1 Embodiment) Preferred Range More Preferred Example Layer ({acute over (Å)}) ({acute over (Å)}) (Å) TiO.sub.x (layer 3) 30-400 {acute over (Å)} 80-250 {acute over (Å)} 180 Å SnO.sub.2 (layer 5) 10-300 {acute over (Å)} 10-100 {acute over (Å)} 20 Å ZnAlO.sub.x (layer 7) 10-300 {acute over (Å)} 60-120 {acute over (Å)} 50 Å Ag (layer 9) 50-250 {acute over (Å)} 80-150 {acute over (Å)} 130 Å NiCrO.sub.x (layer 11) 10-80 {acute over (Å)} 20-70 {acute over (Å)} 30 Å TiO.sub.x (layer 12) 10-300 {acute over (Å)} 20-100 {acute over (Å)} 40 Å SnO.sub.2 (layer 13) 40-400 {acute over (Å)} 100-200 {acute over (Å)} 160 Å Si.sub.3N.sub.4 (layer 15) 50-750 {acute over (Å)} 150-350 {acute over (Å)} 210 Å
(26) In 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.
(27) TABLE-US-00003 TABLE 2 Low-E/Solar Characteristics (Monolithic; no HT) Characteristic General More Preferred Most Preferred R.sub.s (ohms/sq.): <=6.0 <=4.5 <=3.5 Ag SR (microohms.cm): <=5.0 <=4.8 <=4.6 E.sub.n: <=0.10 <=0.06 <=0.040 T.sub.vis (%): >=70 >=80 >=85
(28) It 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.Math.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.
(29) Moreover, 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.
(30) TABLE-US-00004 TABLE 3 Example Optical Characteristics (Monolithic) Characteristic General More Preferred T.sub.vis (or TY)(Ill. C, 2 deg.): >=70% >=80% (or >=85%) a*.sub.t (Ill. C, 2°): −2.5 to +1.0 −2.0 to 0.0 b*.sub.t (Ill. C, 2°): −1.0 to +4.0 0.0 to 2.5 L*.sub.t: >=90 >=93 R.sub.fY (Ill. C, 2 deg.): 1 to 7% 1 to 6% a*.sub.f (Ill. C, 2°): −5.0 to +4.0 −1.5 to +3.0 b*.sub.f (Ill. C, 2°): −14.0 to +10.0 10.0 to 0 L*.sub.f: 22-30 24-27 R.sub.gY (Ill. C, 2 deg.): 1 to 10% 1 to 9% a*.sub.g (Ill. C, 2°): −5.0 to +4.0 −1.5 to +3.0 b*.sub.g (Ill. C, 2°): −14.0 to +10.0 −10.0 to 0 L*.sub.g: 27-36 30-35
(31) Moreover, 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.
(32) TABLE-US-00005 TABLE 4 Example Optical Characteristics (IG Unit) Characteristic General More Preferred T.sub.vis (or TY)(Ill. C, 2 deg.): >=70% >=78% a*.sub.t (Ill. C, 2°): −4.0 to +1.0 −3.0 to 0.0 b*.sub.t (Ill. C, 2°): −1.0 to +4.0 0.0 to 3.0 R.sub.outsideY (Ill. C, 2 deg.): <=14% <=12% a*.sub.out (Ill. C, 2°): −3.0 to +3.0 −2 to +2.0 b*.sub.out (Ill. C, 2°): −10.0 to +10.0 −6.0 to 0 R.sub.insideY (Ill. C, 2 deg.): <=14% <=12% a*.sub.inside (Ill. C, 2°): −5.0 to +4.0 −1.5 to +3.0 b*.sub.inside (Ill. C, 2°): −14.0 to +10.0 −10.0 to 0 U-value (IG)(W/(m.sup.2K)): <=1.25 <=1.15 (or <=1.10)
(33)
(34) In certain example embodiments of this invention, the titanium oxide layer over the IR reflecting layer may be oxidation graded (see graded titanium oxide layer 12′ in
(35) In 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.sub.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
(36) The 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:
(37) TABLE-US-00006 TABLE 5 Layer Stack for Example Layer Thickness Glass Substrate 4 mm TiO.sub.x 180 {acute over (Å)} SnO.sub.2 20 {acute over (Å)} ZnAlO.sub.x 50 {acute over (Å)} Ag 135 {acute over (Å)} NiCrO.sub.x 30 {acute over (Å)} TiO.sub.x 40 {acute over (Å)} SnO.sub.2 160 Å Si.sub.3N.sub.4 210 {acute over (Å)}
(38) The 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.
(39) TABLE-US-00007 TABLE 6 Characteristics of Example (Monolithic) Characteristic Example Visible Trans. 86.53% (T.sub.vis or TY)(Ill. C 2 deg.): a* −1.84 b* 2.15 L* 94.54 Glass Side Reflectance 6.67% (RY)(Ill C, 2 deg.): a* 1.05 b* −8.03 L* 31.05 Film Side Reflective 4.96 (FY)(Ill. C, 2 deg.): a* 2.11 b* −8.01 L* 26.61 R.sub.g (ohms/square): 3.4 E.sub.n: 0.034 Ag SR (micro-ohms .Math. cm): 4.56
(40) Compared 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.Math.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.
(41) Moreover, 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.
(42) When the aforesaid monolithic Example was used in an IG window unit, the IG window unit had a U-value of about 1.1 W/(m.sup.2K).
(43) While 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 spirit and scope of the appended claims.