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`Samsung Electronics Co., Ltd. v. Demaray LLC
`Samsung Electronic's Exhibit 1034
`Exhibit 1034, Page 1
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`Patent Application Publication Nov. 15, 2001 Sheet 1 0f 3
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`US 2001/0041252 A1
`
`
`Fig. 1
`
`
`
`
`
`
` WMMWWM
`“““\\\\“
`
`
`g m“\\\\\\‘!
`
`
`(u) ““““““
`
` LOW-E
`
`
`GLASS
`SUBSTRATE
`
`
`
`Ex. 1034, Page 2
`
`Ex. 1034, Page 2
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`
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`Patent Application Publication Nov. 15, 2001 Sheet 2 0f 3
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`US 2001/0041252 A1
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`sanleA *q 22
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`+Transb*
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`|—.
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`—I—Transa*
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`Sample
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`c
`.9U)
`.Q
`Eu:
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`c E
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`UO!SS!U.ISUBJ_|_ %
`
`Ex. 1034, Page 3
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`Ex. 1034, Page 3
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`Patent Application Publication Nov. 15, 2001 Sheet 3 0f 3
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`US 2001/0041252 A1
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`:2.
`53
`(I)
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`'—'Cls
`
`-I-le
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`4
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`—Al2p
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`600
`
`Fig.3
`
`Depth(Kvs5:02)
`
`C
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`N
`
`'1"-
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`
`C)
`
`o
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`'l—
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`CD
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`co
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`O
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`to
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`g
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`a
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`O
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`CD
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`% 3!LU01B
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`Ex. 1034, Page 4
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`Ex. 1034, Page 4
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`US 2001/0041252 A1
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`Nov. 15, 2001
`
`
`
`BRIEF DESCRIPTION OF THE
`
`
`
`ACCOMPANYING DRAWINGS
`
`
`
`LOW-EMISSIVITY GLASS COATINGS HAVING A
`
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`
`
`LAYER OF NITRIDED NICHROME AND
`
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`METHODS OF MAKING SAME
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`CROSS-REFERENCE TO RELATED
`
`APPLICATION
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`[0001] This application is based on, and claims domestic
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`priority benefits under 35 USC §119(e) from, US. Provi-
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`sional Application No. 60/187,039 filed on Mar. 6, 2000, the
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`entire content of which is expressly incorporated hereinto by
`reference.
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`FIELD OF THE INVENTION
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`[0002] The present invention relates generally to coatings
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`for glass substrates. More specifically, the present invention
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`relates to glass substrate coatings which exhibit low emis-
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`sivity (so-called “low-E” coatings) and substantially no
`color characteristics.
`
`
`BACKGROUND AND SUMMARY OF THE
`
`
`
`INVENTION
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`[0003] Low-E coatings for glass are well known. In this
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`regard, commonly owned US. Pat. Nos. 5,344,718, 5,425,
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`861, 5,770,321, 5,800,933 (the entire content of each being
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`incorporated expressly herein by reference) disclose coat-
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`ings formed of a multiple layer coating “system”. Generally,
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`such conventional multiple layer low-E glass coatings have
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`a layer of a transparent dielectric material (e.g., TiOz, Bi203,
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`PbO or mixtures thereof) adjacent the glass substrate and a
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`sequence of multiple layers of, for example, Si3N4, nickel
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`(Ni), nichrome (NizCr), nitrided nichrome (NiCrN) and/or
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`silver (Ag). These conventional low-E coatings are, more-
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`over, heat-treatable—that is, the coating is capable of being
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`subjected to the elevated temperatures associated with con-
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`ventional tempering, bending, heat-strengthening or heat-
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`sealing processes without significantly adversely affecting
`its desirable characteristics.
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`low-E coating systems
`[0004] While the conventional
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`disclosed in the above-cited US. patents are satisfactory,
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`there exists a continual need to improve various properties
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`of low-E coating systems generally. For example, continued
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`improvements in the durability and/or color (or more accu-
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`rately, lack of color) characteristics in low-E glass coatings
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`are desired. Improvements in such characteristics are impor-
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`tant to ensure that the coatings retain their low-E property
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`for prolonged periods of time (even after being subjected to
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`potentially abrasive environment encountered during the
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`manufacturing process—e.g.,
`the washing and cutting of
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`glass articles having such low-E coatings) and have the
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`desired light transmission properties. It is toward fulfilling
`such needs that the present invention is directed.
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`[0005] Broadly,
`the present
`invention is embodied in
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`low-E glass coated glass articles comprised of a glass
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`substrate and a multiple layer coating on a surface of the
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`glass substrate, wherein the coating includes a layer of a
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`transparent dielectric material adjacent the surface of the
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`glass substrate, a layer of nitrided nichrome, and a layer of
`silver which is sputter coated onto the glass substrate in a
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`nitrogen-containing atmosphere. Most preferably, the coat-
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`ing further includes a layer of silicon oxynitride interposed
`between the layer of dielectric material and the layer of
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`nitrided nichrome.
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`[0006] These and other aspects and advantages will
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`become more apparent after careful consideration is given to
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`the following detailed description of the preferred exem-
`plary embodiments thereof.
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`[0007] Reference will hereinafter be made to the accom-
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`panying drawings, wherein like reference numerals through-
`out the various FIGURES denote like structural elements,
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`and wherein;
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`[0008] FIG. 1 is a is a greatly enlarged cross-sectional
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`schematic representation of a surface-coated glass article of
`this invention which includes a glass substrate and a mul-
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`tiple layer low-E coating system coated on a surface of the
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`glass substrate;
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`[0009] FIG. 2 is a graph of % Transmission and transmit-
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`ted a*, b* Values for glass articles containing a low-E
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`coating of this invention compared against other coatings
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`not within the scope of this invention; and
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`[0010] FIG. 3 is a graph showing the concentration, in
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`atomic percent
`(at. %), of constituents of a SiAlOXNy
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`coating on a Si substrate according to Example III, Test
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`Sample 3 below versus the depth of the coating in Ang-
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`stroms (A).
`DETAILED DESCRIPTION OF THE
`
`
`INVENTION
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`[0011] Accompanying FIG. 1 depicts in a schematic fash-
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`ion one particularly preferred embodiment of the present
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`invention. In this regard, the multiple layer low-E coating of
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`the present invention will necessarily be applied onto a glass
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`substrate 10 which is, in and of itself, highly conventional.
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`Specifically, the glass substrate 10 is most preferably made
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`by a conventional float process and is thus colloquially
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`known as “float glass”. Typical thicknesses of such float
`glass may be from about 2 mm to about 6 mm, but other
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`glass thicknesses may be employed for purposes of the
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`present invention. The composition of the glass forming the
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`substrate 10 is not critical, but typically the glass substrate
`will be formed of one of the soda-lime-silica types of glass
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`well known to those in this art.
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`[0012] The process and apparatus used to form the various
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`layers comprising the low-E coating of the present invention
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`may be a conventional multi-chamber (multi-target) sputter-
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`coating system such as that disclosed generally in US. Pat.
`
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`No. 5,344,718 (the entire content of which is incorporated
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`expressly herein by reference). One particularly preferred
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`sputter-coating system is commercially available from
`Airco, Inc. As is well known,
`the glass substrate 10 is
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`advanced sequentially through the contiguous chambers or
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`zones which have respective atmospheres to form sputter-
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`coating layers of desired constituency and thickness.
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`[0013] As depicted in FIG. 1, one particularly preferred
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`low-E coating may be formed of the following layers and
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`layer thicknesses (identified sequentially from adjacent the
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`glass substrate 10 toward the outside):
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`Layer Constituent
`
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`(u)
`transparent dielectric
`
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`silicon nitride (Si3N4)
`(a)
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`nitrided nichrome (NiCrN)
`(b)
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`silver (Ag)1
`(c)
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`Thickness
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`Range (A)
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`about 100—200
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`about 25—200
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`about 2—40
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`about 100—200
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`Thickness
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`Preferred (A)
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`about 125
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`about 125
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`about 10
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`about 145
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`Ex. 1034, Page 5
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`Ex. 1034, Page 5
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`US 2001/0041252 A1
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`Nov. 15, 2001
`
`
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`Layer Constituent
`
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`-c0ntinued
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`Thicknessu
`Thickness
`
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`Preferred (A)
`Range (A)
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`about 20
`about 2—40
`nitrided nichrome (NiCrN)
`(d)
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`about 480
`about 350—600
`silicon nitride (Si3N4)
`(e)
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`1Silver is sputter-coated onto the glass substrate surface in a nitrogen-con-
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`taining atmosphere.
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`[0014] The undercoat layer (u) in FIG. 1 is selected so it
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`has an index of refraction at 550 nm wavelength of about 2.5
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`to about 2.6, and preferably about 2.52. Preferably,
`the
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`undercoat layer (u) includes at least one transparent dielec-
`tric selected from TiOz, BiO3, PbO and mixtures thereof.
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`TiO2 is especially preferred.
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`[0015] The low-E coated glass article embodying the
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`present invention will exhibit a relatively high light trans-
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`missivity (i.e., greater than about 72%) and will have
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`acceptable a* and b* transmission of between about —2.0 to
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`—4.0 (preferably about —3.0)
`for a* transmission, and
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`between about —0.5 to about 1.5 (preferably about 0.5) for
`b* transmission.
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`[0016] According to the present invention, nitrogen gas is
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`used in the sputtering zone to form the NiCr layer and the Ag
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`layer. Most preferably, the gas will be a mixture of nitrogen
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`and argon, wherein less than about 25% of the gas is
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`nitrogen and greater than about 75% of the gas is argon.
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`Most preferably, nitrogen is present in the sputter zones
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`using nichrome (i.e., 80% Ni/20% Cr) and silver targets to
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`form the nitrided nichrome and silver layers, respectively, in
`an amount between about 5% to about 25%. Aratio of argon
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`to nitrogen of 85:15 is especially preferred in each such
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`sputtering zone.
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`[0017] Advantageously, oxygen is employed in the sput-
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`tering zone during the formation of layer (a) so as to form
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`a silicon oxynitride. Most preferably, the silicon oxynitride
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`layer (a) is sputter-coated in a gaseous atmosphere com-
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`prised of nitrogen, oxygen and argon, wherein at
`least
`between about 5% to about 50%, most preferably about
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`10%, of the gas is oxygen. A particularly preferred atmo-
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`sphere for sputter-coating the silicon oxynitride layer (a) is
`about 30% N2, about 10% O2 and about 60% Ar
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`[0018] According to the present
`invention,
`the rate at
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`which oxygen gas is incorporated into a silicon nitride layer
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`(a) during formation can be varied so as to obtain a silicon
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`oxynitride layer having an oxygen gradient. By the term
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`“oxygen gradient” is meant that the concentration of oxygen
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`(atomic percent (at. %)) decreases from one location in a
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`silicon oxynitride layer to another location at a different
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`depth in that same layer. If present, the oxygen gradient is
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`most preferably such that the greater amount of oxygen
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`concentration is nearer the bottom of the layer (i.e., towards
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`the glass substrate) with the lesser amount of oxygen con-
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`centration being nearer the top of the layer (i.e., away from
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`the glass substrate). In terms of the decrease in oxygen
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`concentration, the oxygen gradient layer may throughout the
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`layer depth be substantially linear or non-linear. Alterna-
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`tively (or additionally), the layer may include decreasing
`oxygen concentrations that are both linear and non-linear at
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`selected regions thereof throughout the layer depth.
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`[0019] The oxygen gradient layer may be obtained by
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`introducing a portion of oxygen gas at the leading section of
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`the coater zone where the deposition of silicon nitride
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`occurs. While not wishing to be bound by any particular
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`theory, it is believed that the oxygen gradient layer is in part
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`responsible for improved mechanical durability in sputter
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`coated glass products which are subsequently heat treated.
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`[0020] The oxygen gradient that may be present in the
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`coatings of the present invention is most typically embodied
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`in a decrease in the oxygen concentration, expressed in
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`atomic percent (at. %), which15 present in the layer per unit
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`depth of the layer, expressed1n Angstroms (A), of about 0.6
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`at. %/A or less. Oxygen gradients of between about 0.1 to
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`about 0.6 at. %/A are thus embodied1n the present inven-
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`tion. According to some especially preferred embodiments,
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`an oxygen gradient of between about 0.15 to about 0.25 at.
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`%/A15 obtained
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`[0021] As one specific example, a plot of atomic percent
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`vs. depth was generated for Test Sample 3 of Example III
`
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`below and is presented as accompanying FIG. 3. As shown
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`therein, the oxygen concentration decreases from between
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`about 35 to about 40 at. % at a depth of about 375 A1n the
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`coating, to a relatively constant value of about 5 at. % at a
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`layer depth of about 200 A.
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`[0022] Those skilled in this art will recognize that a wide
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`variety of oxygen gradient layers may be produced depend-
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`ing on the particular process techniques employed. For
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`example, variations in the line speed of the glass substrate
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`through the sputter coater and/0r variations in the quantity of
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`oxygen introduced at the leading edge of the coater zone
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`may be employed so as to produce a silicon oxynitride layer
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`having the desired oxygen gradient.
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`[0023] A greater understanding of this invention will be
`achieved by careful consideration of the following non-
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`limiting Examples.
`
`EXAMPLES
`
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`[0024] Example I
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`[0025] A low emissivity coating comprised of layers (u)
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`through (6) as identified generally in FIG. 1 was applied
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`onto a float glass substrate using a multi-chamber sputter-
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`coater (Airco, Inc.) at a line speed of 175 in/min under the
`
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`following conditions:
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`Layer (u):
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`Layer (a):
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`Layer (b):
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`TiO2 - 6 Dual C-MAG cathodes (12 Ti metal targets)
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`Three cathodes are in the first coat zone (CZ1) and three
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`are in the second Coat Zone (CZ2).
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`Each coat zone is run identically - DC Reactive sputtering
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`Pressure = 3.5 mTorr
`
`
`Gas Ratio (60% 02/40% Ar)
`
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`Total gas flow = 1850 (sccm)
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`Power - ~80 kW per target
`
`
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`SixNy - 3 Dual C-MAG cathodes (6 Plasma Sprayed Si/Al
`
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`targets ~8% Al)
`
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`Bi-Polar Pulsed DC power
`
`
`
`Pressure = 2.5 mTorr
`
`
`Gas Ratio (30% N2, 70% Ar)
`
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`Total gas flow = 1425 sccm
`
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`Power - ~5 kW per target
`
`
`NiCrN - 1 Planar cathode (80% Ni/20% Cr)
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`DC Sputtered
`
`
`Pressure = 2.5 mTorr
`
`
`Gas Ratio (85% Ar, 15% N2)
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`Total gas flow = 1125 sccm
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`Power - ~4.0 kW per target (Range 3 to 5 kW)
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`Ex. 1034, Page 6
`
`Ex. 1034, Page 6
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`
`US 2001/0041252 A1
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`Nov. 15, 2001
`
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`Layer (c):
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`Layer (d)
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`Layer (e):
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`-continued
`
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`
`Ag - 1 Planar Cathode (100% Silver)
`
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`DC Sputtered
`
`
`Pressure = 2.5 mTorr
`
`
`Gas Ratio (85% Ar, 15% N2)
`
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`Total gas flow = 1125 sccm
`
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`Power - ~7.75 kW per target (Range 5 to 9 kW,
`
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`
`Rs = 3 to 10 Ohm per square)
`
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`
`
`NiCrN - 1 Planar cathode (80% Ni/20% Cr)
`
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`DC Sputtered
`
`
`Pressure = 2.5 mTorr
`
`
`Gas Ratio (85% Ar, 15% N2)
`
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`Total gas flow = 1125 sccm
`
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`Power - ~4.0 kW per target (Range 3 to 5 kW)
`
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`
`SixNy - 3 Dual C-MAG cathodes (6 Plasma Sprayed Si/Al
`
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`targets ~8% Al)
`
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`Bi—Polar Pulsed DC power
`
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`
`Pressure = 2.5 mTorr
`
`
`Gas Ratio (60% N2, 40% Ar)
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`Total gas flow = 2050 sccm
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`Power - ~28 kW per target
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`[0026] Example II
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`[0027] Example I was repeated except that layer (a) was
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`sputter-coated using the following conditions to form a
`
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`silicon oxynitride:
`
`Layer (a):
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`SiOxNy - 3 Dual C-MAG cathodes (6 Plasma Sprayed
`
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`Si/Al targets ~8% Al)
`
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`Bi—Polar Pulsed DC power
`
`
`
`Pressure = 2.5 mTorr
`
`
`Gas Ratio (30% N2, 10% O2, 60% Ar)
`
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`Total gas flow = 1425 sccm
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`Power - ~7 kW per target
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`[0028] Example III
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`[0029] Test Samples obtained from Example I (identified
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`as Sample Nos. 4 and 5) and Example II (identified as
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`Sample Nos. 6 and 7) were tested for light transmissivity and
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`transmitted a*, b* Values. In comparison, Test Sample Nos.
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`1-2 and 8-9 having non-nitrided NiCr and Ag layers (all
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`other layers in the stack being substantially the same as
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`Sample Nos. 4-7) were also tested for light transmissivity
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`and a*, b* Values. Comparative Test Sample No. 3 was
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`identical to Test Sample Nos. 1-2, except that a layer of
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`silicon oxynitride was interposed between the TiO2 and NiCr
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`layers. The data appear in accompanying FIG. 2.
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`[0030] As will be observed, the transmissivity of Samples
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`4-7 was acceptably high (i.e., greater than about 72%) with
`low a* transmission Values. In this regard, it was noted that,
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`even though the b* Value of Sample Nos. 4-7 increased as
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`compared to Test Sample Nos. 1-3 and 8-9,
`the greater
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`transmissivity of the former made the b* Value less critical.
`Thus, it was noted that when the transmission is high, the
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`“blue” color hue is less sensitive.
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`[0031] While the invention has been described in connec-
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`tion with what
`is presently considered to be the most
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`practical and preferred embodiment, it is to be understood
`the invention is not
`to be limited to the disclosed
`that
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`embodiment, but on the contrary,
`is intended to cover
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`various modifications and equivalent arrangements included
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`within the spirit and scope of the appended claims.
`
`What is claimed is:
`
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`1. A surface-coated glass article comprised of a glass
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`substrate and a multiple layer coating on a surface of the
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`glass substrate, wherein said coating includes a layer of a
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`transparent dielectric material adjacent the surface of the
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`glass substrate, respective layers nichrome and silver each
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`sputter-coated onto the glass substrate in a nitrogen-contain-
`
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`ing atmosphere.
`2. The surface-coated glass article of claim 1, wherein the
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`coating further includes a layer of silicon oxynitride inter-
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`posed between said layer of dielectric material and said layer
`of nichrome.
`
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`3. The surface-coated glass article of claim 2, wherein
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`said silicon oxynitride layer includes an oxygen gradient
`
`layer.
`4. The surface-coated glass article of claim 3, wherein
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`said oxygen gradient layer has an oxygen concentration
`
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`which decreases between about 0.1 to about 0.6 at. %/A
`from one location in the layer to another location at a
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`different depth in the layer.
`5. The surface-coated glass article of claim 4, wherein
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`said oxygen gradient layer has an oxygen concentration
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`which decreases between about 0.15 to about 0.25 at. %/A.
`6. The surface-coated glass article of claim 3, 4 or 5,
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`wherein said oxygen gradient layer has an oxygen concen-
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`tration which is greater at a location nearer to the glass
`substrate.
`
`7. The surface-coated glass article of claim 1, wherein the
`
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`dielectric material is at least one selected from the group
`
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`consisting of TiOz, BiO3, PbO and mixtures thereof.
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`8. The surface-coated glass article as in claim 1, wherein
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`the coating further includes, from the layer of silver out-
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`wardly, a second layer of nitrided nichrome, and an outer
`
`
`layer of Si3N4.
`9. The surface-coated glass article as in claim 1, wherein
`
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`the coating further includes a layer of Si3N4 interposed
`between said dielectric material and said layer of nichrome.
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`10. A surface-coated glass article comprised of a glass
`
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`substrate and a multiple layer coating comprising the fol-
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`
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`lowing layers formed on a surface of the glass substrate,
`
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`
`
`from the surface outwardly:
`
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`
`
`(1) a layer of transparent dielectric material;
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`(2) an inner layer of Si3N4 or a layer of silicon oxynitride;
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`(3) a first layer of nitrided nichrome;
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`(4) a layer of silver which is sputter-coated onto the glass
`
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`substrate in a nitrogen-containing atmosphere;
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`
`(5) a second layer of nitrided nichrome; and
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`
`(6) an outer layer of Si3N4.
`11. The surface-coated glass article of claim 10, wherein
`
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`the dielectric material is at least one selected from the group
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`consisting of TiOz, BiO3, PbO and mixtures thereof.
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`12. The surface-coated glass article of claim 1 or 10,
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`having a light transmission of at least about 72%.
`13. The surface-coated glass article of claim 12, having
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`transmitted a*, b* Values of between about —2.0 to —4.0, and
`
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`between about —0.5 to about 1.5, respectively.
`14. The surface-coated glass article of claim 1 or 10,
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`wherein the layers have the following thicknesses in Ang-
`stroms:
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`
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`(1) between about 100-200;
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`(2) between about 25-200;
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`Ex. 1034, Page 7
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`Ex. 1034, Page 7
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`US 2001/0041252 A1
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`Nov. 15, 2001
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`(3) between about 2-40;
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`(4) between about 100-200;
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`(5) between about 2-40; and
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`(6) between about 350-600.
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`
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`15. A method of making a surface-coated glass article
`
`
`
`
`comprising sputter-coating on a surface of a glass substrate
`
`
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`
`
`a multiple layer coating comprised of a layer of a transparent
`
`
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`
`
`dielectric material adjacent the surface of the glass substrate,
`
`
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`
`
`and respective layers of nichrome and silver which are
`
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`
`
`
`sputter-coated onto the glass substrate in a nitrogen-contain-
`
`
`ing atmosphere.
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`
`
`16. The method of claim 15, wherein said layers of
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`nichrome and silver are each formed by sputter-coating in a
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`gaseous atmosphere comprised of nitrogen and argon,
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`wherein the nitrogen is present in the atmosphere in an
`amount less than about 25%.
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`17. The method of claim 16, wherein nitrogen is present
`in an amount between about 15% to about 25%.
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`18. The method of claim 16, wherein the ratio of argon to
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`nitrogen is about 85:15.
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`19. The method of claim 16, which further comprises
`
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`
`
`
`forming a silicon oxynitride layer between said layer of
`
`
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`
`
`dielectric material and said layer of nichrome.
`20. The method of claim 15, wherein said layer of silicon
`
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`
`
`oxynitride is formed by sputter-coating in a gaseous atmo-
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`sphere comprised of nitrogen, oxygen and argon, wherein
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`in the atmosphere in an amount
`the oxygen is present
`between about 5 to about 50%.
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`21. The method of claim 20, wherein oxygen is present in
`
`
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`the atmosphere in an amount of about 10%.
`
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`
`
`22. The method of claim 21, wherein the atmosphere
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`comprises about 30% nitrogen, about 10% oxygen and about
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`60% argon.
`23. The method of any one of claims 15-22, wherein the
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`sputter-coating of the silicon oxynitride layer includes using
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`an aluminum-containing silicon target.
`24. The method of claim 23, wherein the target includes
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`about 8% by weight aluminum.
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`25. The method of claim 19 or 20, comprising forming the
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`silicon oxynitride layer so as to include an oxygen gradient
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`layer therein.
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`26. The method of claim 25, wherein said oxygen gradient
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`layer is formed so as to exhibit an oxygen concentration
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`which decreases between about 0.1 to about 0.6 at. %/A
`from one location in the layer to another location at a
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`different depth in the layer.
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`27. The method of claim 26, wherein said oxygen gradient
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`layer has an oxygen concentration which decreases between
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`about 0.15 to about 0.25 at. %/A.
`28. The surface-coated glass article of claim 25, wherein
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`said oxygen gradient layer has an oxygen concentration
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`which is greater at a location nearer to the glass substrate.
`*
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`*
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`Ex. 1034, Page 8
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`Ex. 1034, Page 8
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