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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 of 3
`
`Fig. |
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`US 2001/0041252 Al
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`LEEOPSDESot
`
`DANNANANAAAAN
`ELLELELET LOWE
`
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`COATING
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`SUBSTRATE
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`GLASS
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`Ex. 1034, Page 2
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`Ex. 1034, Page 2
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`

`

`EE
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`—4—Transb*
`—a—Transa*
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`< 2D2 £Gc ©
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`Sample
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`UOISSIWISUBL] %
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`Ex. 1034, Page 3
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`US 2001/0041252 Al
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`Patent Application Publication Nov. 15,2001 Sheet 2 of 3
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`
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`senjea ,q ‘,e
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`Ex. 1034, Page 3
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`

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`Patent Application Publication Nov. 15,2001 Sheet 3 of 3
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`
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`US 2001/0041252 Al
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`
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`“Nis AeOls
`
`|
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`—Al2p
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`@Si2p
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`600
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`Depth(Avs.Si02)
`
`Fig.3 &
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`CS
`Cl
`Tt
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`CS
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`oS
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`TT
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`Co
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`co
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`CS
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`co
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`S
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`ey
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`o
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`% SILUO}e
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`Ex. 1034, Page 4
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`Ex. 1034, Page 4
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`

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`US 2001/0041252 Al
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`Nov. 15, 2001
`
`
`
`BRIEF DESCRIPTION OF THE
`
`
`
`ACCOMPANYING DRAWINGS
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`
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`
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`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, U.S. 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 SUMMARYOF THE
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`INVENTION
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`[0003] Low-E coatings for glass are well known. In this
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`regard, commonly owned U.S. 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 layerof a transparentdielectric material (e.g., TiO,, Bi,O3,
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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, Si,N,, nickel
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`(Ni), nichrome (Ni:Cr), 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—thatis, 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 U.S. 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
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`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
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`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
`Thickness
`Thickness
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`between the layer of dielectric material and the layer of
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`Layer Constituent
`Preferred (A)
`Range (A)
`nitrided nichrome.
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`(u)
`about 125
`about 100-200
`transparentdielectric
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`[0006] These and other aspects and advantages will
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`(a)_silicon nitride (Si,N,) about 25-200 about 125
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`(b)—nitrided nichrome (NiCrN) about 2-40 about 10
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`become more apparentafter careful consideration is given to
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`(c)_silver (Ag)* about 100-200=about 145
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`the following detailed description of the preferred exem-
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`plary embodimentsthereof.
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`[0007] Reference will hereinafter be made to the accom-
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`panying drawings, wherein like reference numerals through-
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`out the various FIGURESdenote 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 glassarticle of
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`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 SiAlO,N
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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 ofitself, 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
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`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
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`will be formed of one of the soda-lime-silica types of glass
`well knownto 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 U'S. Pat.
`
`
`
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`
`
`
`No. 5,344,718 (the entire content of which is incorporated
`
`
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`
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`expressly herein by reference). One particularly preferred
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`sputter-coating system is commercially available from
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`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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`Ex. 1034, Page 5
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`Ex. 1034, Page 5
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`

`

`
`US 2001/0041252 Al
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`Nov. 15, 2001
`
`
`
`-continued
`
`
`
`Layer Constituent
`
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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 gradientlayer is in part
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`Thickness
`Thickness
`responsible for improved mechanical durability in sputter
`Preferred (A)
`Range (A)
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`coated glass products which are subsequently heat treated.
`(d)
`about 20
`about 2-40
` nitrided nichrome (NiCrN)
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`[0020] The oxygen gradient that may be present in the
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`(e)_silicon nitride (Si,N,) about 350-600 about 480
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`coatings of the present invention is most typically embodied
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`+Silver is sputter-coated onto the glass substrate surface in a nitrogen-con-
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`in a decrease in the oxygen concentration, expressed in
`taining atmosphere.
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`atomic percent(at. %), which is present in the layer per unit
`depth of the layer, expressed in Angstroms (A), of about 0.6
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`at. %/A orless. Oxygen gradients of between about 0.1 to
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`about 0.6 at. %/A are thus embodied in 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 0.25at.
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`%/A is 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 A in the
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`coating, to a relatively constant value of about 5 at. % at a
`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/orvariationsin 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
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`achieved by careful consideration of the following non-
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`limiting Examples.
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`[0014] The undercoat layer (u) in FIG. 1 is selected soit
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`has an indexofrefraction 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) includesat least one transparent dielec-
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`tric selected from TiO,, BiO;, PbO and mixtures thereof.
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`TiO,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.c., 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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`-3.0)
`-4.0 (preferably about
`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) andsilver targets to
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`form the nitrided nichromeandsilverlayers, respectively, in
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`an amount between about 5% to about 25%. A ratio 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
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`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
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`about 30% N,, about 10% O, and about 60% Ar
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`[0018] According to the present
`invention,
`the rate at
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`which oxygen gasis 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 meantthat 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 ofthe 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
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`oxygen concentrations that are both linear and non-linearat
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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 gasat the leading section of
`
`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 (e) as identified generally in FIG. 1 was applied
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`onto a float glass substrate using a multi-chambersputter-
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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-MAGcathodes (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 zoneis run identically - DC Reactive sputtering
`
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`Pressure = 3.5 mTorr
`
`
`Gas Ratio (60% O2/40% Ar)
`
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`Total gas flow = 1850 (sccm)
`
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`Power - ~80 kW pertarget
`
`
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`SixNy - 3 Dual C-MAGcathodes (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 (30% N2, 70% Ar)
`
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`Total gas flow = 1425 sccm
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`Power - ~5 kW pertarget
`
`
`NiCrN - 1 Planar cathode (80% Ni/20% Cr)
`
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`DC Sputtered
`
`
`Pressure = 2.5 mTorr
`
`
`Gas Ratio (85% Ar, 15% No)
`
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`Total gas flow = 1125 sccm
`
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`Power - ~4.0 kW pertarget (Range 3 to 5 kW)
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`Ex. 1034, Page 6
`
`Ex. 1034, Page 6
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`

`

`
`US 2001/0041252 Al
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`Nov. 15, 2001
`
`
`
`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
`
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`Gas Ratio (85% Ar, 15% N,)
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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 persquare)
`
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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% N>)
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`Total gas flow = 1125 sccm
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`Power - ~4.0 kW pertarget (Range 3 to 5 kW)
`
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`
`SixNy - 3 Dual C-MAGcathodes (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
`
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`Gas Ratio (60% N2, 40% Ar)
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`Total gas flow = 2050 sccm
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`Power - ~28 kW pertarget
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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-MAGcathodes (6 Plasma Sprayed
`
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`Si/Al targets ~8% Al)
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`Bi-Polar Pulsed DC power
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`
`
`Pressure = 2.5 mTorr
`
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`Gas Ratio (30% N2, 10% 02, 60% Ar)
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`Total gas flow = 1425 sccm
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`Power - ~7 kW pertarget
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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 TiO, 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.c., greater than about 72%) with
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`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 lesscritical.
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`Thus, it was noted that when the transmission is high, the
`“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.
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`Whatis claimedis:
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`
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`1. A surface-coated glass article comprised of a glass
`
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`
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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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`
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`sputter-coated onto the glass substrate in a nitrogen-contain-
`
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`ing atmosphere.
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`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 betweensaid 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.
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`4. The surface-coated glass article of claim 3, wherein
`
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`
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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
`
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`from one location in the layer to another location at a
`
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`
`
`different depth in the layer.
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`5. The surface-coated glass article of claim 4, wherein
`
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`
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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.
`
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`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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`
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`tration which is greater at a location nearer to the glass
`substrate.
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`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 TiO,, BiO,, 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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`
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`wardly, a second layer of nitrided nichrome, and an outer
`
`
`layer of Si,N,.
`
`
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`
`
`9. The surface-coated glass article as in claim 1, wherein
`
`
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`
`
`
`
`the coating further includes a layer of Si,N, interposed
`
`
`
`
`
`
`
`between said dielectric material and said layer of nichrome.
`
`
`
`
`
`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,
`
`
`
`
`from the surface outwardly:
`
`
`
`
`
`(1) a layer of transparent dielectric material;
`
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`
`
`(2) an innerlayer of Si,N,or a layer of silicon oxynitride;
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`(3) a first layer of nitrided nichrome;
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`(4) a layer ofsilver 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 Si,N,.
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`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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`
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`consisting of TiO,, BiO,, 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%.
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`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.
`
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`
`
`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
`
`Ex. 1034, Page 7
`
`

`

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`US 2001/0041252 Al
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`
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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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`
`
`15. A method of making a surface-coated glass article
`
`
`
`
`comprising sputter-coating on a surface of a glass substrate
`
`
`
`
`
`
`a multiple layer coating comprised ofa layer of a transparent
`
`
`
`
`
`
`dielectric material adjacent the surface of the glass substrate,
`
`
`
`
`
`
`
`
`and respective layers of nichrome and silver which are
`
`
`
`
`
`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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`
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`nichromeandsilver 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
`amountless 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.
`
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`
`
`20. The method of claim 15, wherein said layer of silicon
`
`
`
`
`oxynitride is formed by sputter-coating in a gaseous atmo-
`
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`
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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 oxygenis present in
`
`
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`
`the atmosphere in an amountof about 10%.
`
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`
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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
`
`
`60% argon.
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`
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`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.
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`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
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`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.
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`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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