Detailed description of the invention

This patent or application documents include the attached drawing that at least one is drawn with colour.This patent or special with color drawings Benefit applies for that disclosed copy will be provided after requesting and paying required cost by Patent Office.

Fig. 1 is the cross-sectional view of the coating product of exemplary implementation scheme according to the present invention.

Fig. 2 is the cross-sectional view of the coating product of another exemplary embodiment according to the present invention.

Fig. 3 is the cross-sectional view of the coating product of another exemplary embodiment according to the present invention.

Fig. 4 is the relational graph of percentage (%) and wavelength (nm), and which depict in coating state (AC) and rear HT (HT) state two It include high refractive index TiO under kind state₂Transmissivity (T) %, glass side reflectance rate (G) % and the film lateral reflection rate of the lamination stack of layer (F) relationship of % and wavelength (nm).

Fig. 5 is the coating system for showing embodiment 1 and comparative example 1 (CE1) according to a preferred embodiment of the invention The chart of the optical/thermal data of product.

Fig. 6 be show preferred embodiment according to the present invention embodiment 2 and embodiment 3 coating product optics/ The chart of dsc data.

Fig. 7 is the relational graph of percentage (%) and wavelength (nm), and which depict embodiments 2 in coating state (AC) and rear HT (HT) including transmissivity (T) %, glass side reflectance rate (G) % of high refractive index HfSiAlN layers of lamination stack under state two states With the relationship of film lateral reflection rate (F) % and wavelength (nm).

Fig. 8 is the relational graph of percentage (%) and wavelength (nm), and which depict embodiments 3 in coating state (AC) and rear HT (HT) including transmissivity (T) %, glass side reflectance rate (G) % of high refractive index HfSiAlN layers of lamination stack under state two states With the relationship of film lateral reflection rate (F) % and wavelength (nm).

Fig. 9 be show preferred embodiment according to the present invention embodiment 4 and embodiment 5 coating product optics/ The chart of dsc data.

Figure 10 is the relational graph of percentage (%) and wavelength (nm), which depict embodiment 4 coat state (AC) and after It include transmissivity (T) %, the glass side reflectance rate of high refractive index HfSiAlN layers of lamination stack under HT (HT) state two states (G) relationship of % and film lateral reflection rate (F) % and wavelength (nm).

Figure 11 is the relational graph of percentage (%) and wavelength (nm), which depict embodiment 5 coat state (AC) and after It include transmissivity (T) %, glass side reflectance rate (G) % of high refractive index HfAlN layers of lamination stack under HT (HT) state two states With the relationship of film lateral reflection rate (F) % and wavelength (nm).

Specific embodiment

Referring now to the drawings, wherein identical drawing reference numeral indicates identical component in several views.

Coating product herein can be used for using such as monolithic window, IG window unit such as residential window, garden door, vehicle window And/or in any other suitable application including single or multiple substrates (such as substrate of glass).

Conventional high-index material (has low light absorption or without light absorption such as in visible-range TiO₂) commonly used in the low E coating in window application.However, TiO₂(such as it is related to the HT at about 650 DEG C to hold in hot drawing process Continuous 8 minutes) after it is not usually heat-staple, this is because (or crystallinity becomes membrane crystallization under rigid deposition or rear annealed strip Change), this then can cause thermal stress or crystal lattice stress on the adjacent layer during film stacks.This stress can also cause the object stacked The variation of characteristic or material property is managed, and therefore influences the reflecting layer IR based on Ag, this causes low E to stack performance deterioration.TiO₂ Layer also has low-down sputter deposition rate.

Fig. 4 shows TiO₂It is not heat-staple, therefore can not be heat-treated from the viewpoint of reality.Fig. 4 is percentage The relational graph of (%) and wavelength (nm), which depict include that high refractive index aoxidizes under coating state (AC) and rear HT state two states The relationship of transmissivity (T) % of the lamination stack of titanium layer, glass side reflectance rate (G) % and film lateral reflection rate (F) % and wavelength (nm). Lamination stack is glass/TiO₂(27nm)/ZnO(4nm)/Ag(11nm)/NiTiNbO_x(2.4nm)/ZnSnO(10nm)/ZnO (4nm)/SiN (10nm), wherein ZnO layer is in the comparative example 2 (CE2) stacks doped with Al.Therefore, AC curve is before HT, And HT curve is heat-treated after about eight minutes at about 650 DEG C.In Fig. 4, right side in place of listing curve, upper three are Coat state (AC), this refers to before HT, and lower three after the heat treatment, and be therefore marked as " HT ".Fig. 4 is shown With crystallization TiO₂Lamination stack be not heat-staple, therefore can not actually be heat-treated.Specifically, the comparative example 2 of Fig. 4 (CE2) the significant offset of the IR range of transmissivity and reflectance spectrum is shown, and also found the increase of emissivity and mist degree.Scheming In 4, in the wavelength region of about 1500nm to 2400nm, exist as caused by HT from " AC T " (transmissivity, HT coating before State) curve to " HT T " (transmissivity, HT after) curve about 6% offset；In the presence of as caused by HT from " AC G " (glass side Reflectivity coats state before HT) curve to " HT G " (glass side reflectance rate, HT after) curve about 12%-14% offset； And exist as caused by HT from " AC F " (film lateral reflection rate, HT coat state before) curve to " HT F " (film lateral reflection rate, HT The offset of the about 12%-13% of curve later).Generally speaking, it is combined together, in HT, there are transmissivity and reflectance spectrums Significant offset, this shows to lack thermal stability.

Exemplary implementation scheme of the invention is used for the high refractive index (height measured at 550 nm of low E coating by providing The nitridation dielectric layer 2 containing hafnium (Hf) of refractive index value n) and low absorption (low k-value measured at 400nm) is (and possible 6) layer solves these problems.With TiO₂Dielectric layer is different, it has been found that the high refractive index dielectric layer containing hafnium 2 of this paper (and Possible layer 6) be it is heat treatable, so as to the substantially thermostabilization at heat treatment (HT), be amorphous or substantially without fixed Shape, and TiO can be compared₂Much higher sputter deposition rate sputtering sedimentation.In certain exemplary implementation schemes, containing hafnium High refractive index nitrogenizes dielectric layer 2 (and possible layer 6) And/or one or more of HfAlZrN (in terms of various stoichiometries).Wherein any of Hf, Zr and/or N herein The chemical expression for being included is to provide for purpose that is simple and understanding, and be not necessarily stoichiometry.For example, HfSiAlN is not meant to provide Hf, Si, Al and N of equivalent.On the contrary, such as, but not limited to, HfSiAlN layers may include comparing Hf More Si, the Si etc. more than Al.For another example, SiN can be any suitable stoichiometry, and one of example is Si₃N₄。

It has been found that Hf, which is for example added to SiAlN, SiN and ZrSiAlN, allows the broadening of its band gap, to significantly reduce Optical absorption (k), while there is high refractive index (n).It has also been found that these materials are heat-staple (for example, since HT is such as about Heat tempering at 650 DEG C, the variation of refractive index n can be low).In certain exemplary implementation schemes, low E coating can be used for answering With in monolithic or insulating glass (IG) window unit, vehicle window etc..Although the high refractive index discussed in this article containing Hf nitrogenizes electricity Dielectric layer is preferred in low E coating, but the present invention is not limited, and these layers can be used in other film coatings, all Such as the high refractive index layer in antireflection (AR) coating.

ZrSiAlN shows absorption coefficient k that may be excessive for certain optical coatings are applied.In certain of the invention In a little embodiments, it has been found that adding a certain amount of Hf to SiAlN, SiN and ZrSiAlN allows the broadening of its band gap, thus aobvious Writing reduces optical absorption, while providing high refractive index.Extinction coefficient k of these nitride under about 400nm (3.1eV) wavelength with Their band gap is related.The photon of wavelength with about 400nm cannot reasonably absorb in material of the band gap higher than 3.1eV, Lead to low absorption or does not absorb.On the other hand, about 3.1eV or lower band gap lead to significant optical absorption.The width of band gap Electronegativity difference between metallic element and nitrogen is related.Hf shows high electronegativity difference, is worth for 1.16 (N=3.04), this permits Perhaps Hf increases the band gap of SiAlN, SiN and ZrSiAlN when adding into SiAlN, SiN and ZrSiAlN and therefore reduces and inhales It receives, to increase transmissivity.We have found that Hf, which is added in these nitride, causes heat-staple high refractive index to nitrogenize Object, with lower optical absorption and therefore transmissivity with higher can be through heat-treated (HT), such as hot time Fire.

In certain exemplary implementation schemes of the invention, it is or comprising HfSiAlN, HfZrSiAlN, HfSiN, HfAlN And/or high refractive index nitridation dielectric layer 2 (and possible layer 6) containing hafnium of HfAlZrN can have at least 2.21, more preferably The high refractive index (n) (at 550 nm) on ground at least 2.25, even more preferably at least 2.30, and it is not more than 0.02, more preferably Ground is not more than 0.015, even more preferably not more than 0.010 low absorption coefficient (k) (at 400nm).In addition, according to this hair The coating product of bright exemplary implementation scheme is heat-staple, and realizes and do not surpass after 650 DEG C of heat treatments continue 8 minutes 0.10, no more than 0.04 is crossed, and most preferably the refractive index (n) no more than 0.01 changes.Show in of the invention In example property embodiment, it can be used and be or comprising the such of HfSiAlN, HfZrSiAlN, HfSiN, HfAlN and/or HfAlZrN High refractive index containing hafnium nitrogenizes dielectric layer to substitute the high refractive index TiO in any low E or AR coating stack₂Or niobium oxide (for example, Nb₂O₅) layer, to realize advantage described herein.

HfZrSiAlN layers of an example metals content is as follows relative to atom ratio: Hf: Zr: Si: Al → 31.3: 31.3:6.7:30.7.In other words, 31.3%, the Zr that the tenor of nitration case is accounted for according to atom %, Hf accounts for the gold of nitration case Belong to the 3L3% of content, Si accounts for the 6.7% of the tenor of nitration case, and Al accounts for the 30.7% of the tenor of nitration case.Cause This, which has the Hf and Zr of equivalent, and the Al between each in low 6.7Si content and Hf and Zr content Amount.In certain exemplary implementation schemes, when comprising both Hf and Zr, the tenor of combined Hf and Zr are up to layer The about 45%-75% of tenor, the more preferably 50%-70% of the tenor of layer.In another exemplary embodiment party In case, the tenor of HfSiAlN layer 2 and/or 6 is made of 62.6%Hf, 6.7%Si and 30.7%Al (atom %).At this In certain exemplary implementation schemes of invention, it is or comprising HfSiAlN, HfZrSiAlN, HfSiN, HfAlN and/or HfAlZrN One or more of containing hafnium high refractive index nitridation dielectric layer 2 and/or 6 tenor may include one of following It is or a variety of: (i) 10%-75%Hf, more preferably 20%-70%Hf, even more preferably 20%-50%Hf, possibly 25%- 40%Hf (atom %)；(ii) 0%-50%Zr, more preferably 1%-40%Zr, even more preferably 10%-40%Zr, and Most preferably 20%-40%Zr (atom %)；

(iii) 2%-50%Si, more preferably 3%-20%Si, even more preferably 4%-15%Si (atom %)；With/ Or (iv) 0%-60%Al, more preferably 1%-45%Al, even more preferably 10%-40%Al, and most preferably 20%- 40%Al (atom %).It may be noted that Si is identified herein as metal.In certain exemplary implementation schemes, the layer comprising Hf Comprising the Hf more than Si, such as Si up to fewer by 10% than Hf, the more preferably Hf up to fewer by 25% than Si, and most preferably compare Si Up to lack 35% Hf (in terms of atom %).In certain exemplary implementation schemes, when layer include Hf nitride such as When HfSiAlN, HfZrSiAlN, HfSiN, HfAlN and/or HfAlZrN, Hf has the most plateau of any metal in layer 2 and/or 6 Sub- % tenor.

Contain hafnium for or comprising one or more of HfSiAlN, HfZrSiAlN, HfSiN, HfAlN and/or HfAlZrN High refractive index nitridation dielectric layer 2 and/or 6 tenor preferably free or substantially free of Ti and/or Nb.Include Hf Nitride layer 2 and/or 6 may include 0%-10% Ti, the more preferably Ti of 0%-5%, and most preferably 0%-2% Ti (atom %).The layer 2 and/or 6 of nitride comprising Hf may include the Nb of 0%-10%, more preferably the Nb of 0%-5%, And the most preferably Nb of 0%-2%.

Although being or containing comprising HfSiAlN, HfZrSiAlN, HfSiN, HfAlN and/or HfAlZrN as described herein Not preferred oxygen in high refractive index nitridation dielectric layer 2 (and possible layer 6) of hafnium, but these layers may include a small amount of oxygen.Example Such as, it is or the high refractive index nitridation electricity containing hafnium comprising HfSiAlN, HfZrSiAlN, HfSiN, HfAlN and/or HfAlZrN is situated between Matter layer 2 (and possible layer 6) may include the oxygen of 0%-10%, the more preferably oxygen of 0%-5%, and most preferably 0%- 2% oxygen (atom %).

In certain exemplary implementation schemes of the invention, it is or the high refractive index containing hafnium comprising HfAlZrN nitrogenizes electricity The tenor of dielectric layer 2 and/or 6 may include the Al more than Hf.Such as it has been found that it is or the layer comprising HfAlZrN can be real Existing significantly higher refractive index, ideal low k-value, and the heat treatment capacity for a small amount of Hf.For example, in certain exemplary realities It applies in scheme, HfAlZrN or HfAlN layers may include the Al of preferably at least twice Hf, at least be three times in the Al of Hf sometimes.Amorphous spy Property heat-staple material is provided.Even if the material still keeps amorphous under the rear heat treatment of 650C.In certain exemplary implementations In scheme, there is the Al more than each of Hf and Zr, the Al of each of for example, at least twice Hf and Zr, and should Layer may include Hf more than Zr, such as at least twice or be three times in the Hf (atomic percent) of Zr.Illustrative layers can have following Material ratios: Al: Hf: Zr: Si → 1: 0.3: 0.06: 0.2 (atom ratio), wherein Si is optional.In addition, Al: Hf: Zr: N Material has the sputter deposition rate more much higher than titanium oxide, this is advantageous as discussed herein.In short, layer 2 and/or 6 HfAlZrN have excellent characteristic, such as high refractive index, low absorption and thermal stability, wherein aluminium be can for other metals member 3 times or more of dominant element of cellulose content.

Fig. 1 is the sectional view of coating product in accordance with an exemplary embodiment of the invention.Coating product includes glass base Bottom 1 is (for example, that about 1.0mm to 10.0mm is thick, more preferably about 1.0mm to 6.0mm is thick is transparent, green, bronze or bluish-green Color substrate of glass), and laminated coating (or layer system) on the base 1 is either directly or indirectly set.According to Fig. 1 embodiment party The exemplary low E coating of case can include: be or comprising HfSiAlN, HfZrSiAlN, HfSiN, HfAlN as discussed herein And/or the high refractive index containing hafnium of HfAlZrN nitrogenizes dielectric layer 2；Containing zinc oxide and/or the contact layer of zinc stannate 3 (for example, ZnO_x, wherein " x " can be about 1；Or ZnAlO_x)；Include or for silver, gold etc. IR (infrared) reflecting layer 4；For or comprising Ni and/ Or the oxide of Cr is (for example, NiCrO_x) or other suitable materials upper contact layer 5；And be or comprising dielectric layer electricity be situated between Matter finishing coat 6 can be middle index layer such as zinc oxide and/or zinc stannate, or can be high refractive index layer such as titanium oxide (for example, TiO₂), zirconium doping titanium oxide, or be or comprising HfSiAlN, HfZrSiAlN discussed in this article, HfSiN, The high refractive index containing hafnium of HfAlN and/or HfAlZrN nitrogenizes dielectric layer；Optional middle index layer 7 is or comprising oxygen Change zinc, tin oxide, silicon nitride and/or zinc stannate or other suitable materials；And dielectric layer 8, the dielectric layer are or wrap Silicon nitride comprising and/or silicon oxynitride or other suitable materials.Silicon nitride layer (for example, layer 8) also may include Al, oxygen etc., and Layer based on zinc oxide also may include tin and/or aluminium.In certain exemplary implementation schemes of the invention, it can also mention in the coating For other layers and/or material, and it also can remove or separate certain layers in certain sample instances.For example, finishing coat may include Zirconium oxide layer or AlSiBO_xLayer (not shown) can be set up directly on 8 top of silicon nitride layer and contact silicon nitride layer 8.For another example, Another medium refractive index layer such as silicon nitride can be set between substrate of glass 1 and high refractive index layer 2.For another example, it is possible to provide two It is a based on silver the reflecting layer IR, stacked by the dielectric layer including, for example, tin oxide it is spaced apart, and the finishing coat of Fig. 1 and/ Or inner coating can be used for wherein.In addition, in certain exemplary implementation schemes of the invention, one or more layer discussed above It can be doped with other materials.The present invention is not limited to lamination stacks shown in Fig. 1, because of the purpose of Fig. 1 stacked merely for citing And provide, to show the exemplary position of the high refractive index layer 2 (and possible layer 6) discussed in this article comprising Hf.

In monolithic, coating product only includes a substrate such as substrate of glass 1 (referring to Fig. 1).However, for example originally The monolithic coating product of text can be used in such as device of IG window unit.In general, IG window unit may include two or more The substrate separated, defines air gap therebetween.Exemplary IG window unit for example U.S. Patent number 5,770,321,5,800,933, It shows and describes in 6,524,714,6,541,084 and US2003/0150711, this is incorporated herein by reference in the disclosure of which Text.For example, the substrate of glass of coating shown in Fig. 1 can be connected in another substrate of glass via spacer, sealant etc., Gap is limited between them in IG window unit.In certain illustrative examples, coating may be provided at substrate of glass 1 towards In an example in gap, that is, surface #2 or surface #3.In other example embodiments, IG window unit may include other glass Piece (for example, IG unit may include three sheet glass spaced apart rather than two).

Transparent dielectric lower contacts layer 3 can be or may include zinc oxide (such as ZnO), zinc stannate or other suitable materials Material.In certain exemplary implementation schemes, zinc oxide film 3 also may include other materials such as Al (for example, to form ZnAlO_x) Or Sn.For example, in certain exemplary implementation schemes of the invention, zinc oxide film 3 can doped with about 1% to 10% Al (or B), more preferably about 1% to 5% Al (or B), and most preferably about 2% to 4% Al (or B).Under silver in layer 4 Side allows to obtain excellent silver amount using zinc oxide 3.Zinc oxide film 3 is usually deposited with crystalline state.In certain exemplary implementations In scheme (for example, be discussed below), can include to be formed by sputtering ceramics ZnO or metal portable magnetron sputtering target The layer 3 of zinc oxide.

The infrared reflecting layer (IR) 4 preferably substantially or be entirely metal and/or conduction, and may include silver-colored (Ag), Gold or any other suitable IR reflecting material or consisting essentially of.In certain exemplary implementation schemes, the reflecting layer IR 4 Silver can be doped with other materials, such as doped with Pd, Zn or Cu.The reflecting layer IR 4 help allowed coating have low E and/or Good solar control characteristic, low-launch-rate, low sheet resistance etc..However, in certain embodiments of the invention, The reflecting layer IR can slightly aoxidize.It can include high refraction discussed in this article in certain exemplary implementation schemes of the invention During double or three silver medals of rate layer stack, multiple reflecting layer IR 4 based on silver are provided, by least one dielectric in low E coating Interlayer separates.

Upper contact layer 5 is located at 4 top of the reflecting layer IR and directly contacts the reflecting layer IR, and in certain exemplary implementations Can be in scheme or the oxide comprising Ni and/or Cr.In certain exemplary implementation schemes, upper contact layer 5 can be or wrap Nickel chromium triangle (NiCrO is such as aoxidized containing nickel oxide (Ni), chromium oxide (chromium/chrome, Cr) or oxidation nickel alloy_x) or its He is suitable material such as NiCrMoO_x、NiCrMo、Ti、NiTiNbO_x、TiO_x, metallicity NiCr etc..In difference of the invention In embodiment, contact layer 5 can be or can not be oxidation gradual change.Oxidation gradual change refers to the degree of oxidation in layer along layer Thickness change, so that for example contact layer can be gradual change, so as to further or farther/farthest apart with the adjacent reflecting layer IR 4 The contact layer of distance a part place oxidation degree compare, with the contact interface in the adjacent reflecting layer IR at oxidation degree It is lower.In different embodiments of the invention, on the entire reflecting layer IR 4, contact layer 5 be can be continuously, can also not It is continuous.

Other layers of shown Fig. 1 coating below or above can also be provided.Therefore, when layer system or coating " on the base 1 " Or when " being supported by substrate 1 " (direct or indirect), other layers be may be provided at therebetween.Thus, for example, the coating of Fig. 1 can be considered It is " on the base 1 " or " being supported by substrate 1 ", even if other layers are arranged between layer 2 and substrate 1.In addition, in certain implementations Certain layers of coating shown in can be removed in scheme, and in other embodiments of the present invention, it can be added between each layer Other layers or each layer can be separated with other layers added between segregation section without departing from certain embodiments of the invention Whole spirit.

Although various thickness can be used in different embodiments of the invention, the glass base in Fig. 1 embodiment The example thickness of equivalent layer on bottom 1 and material from substrate of glass outward can for it is following (for example, under certain exemplary cases, Al content in zinc oxide film and silicon nitride layer can be about 1% to 10%, more preferably about 1% to 5%).Thickness with angstrom For unit.

(the examples material/thickness of table 1；Fig. 1 embodiment)

In certain exemplary implementation schemes of the invention, coating product (for example, with reference to Fig. 1) herein is monolithically Can have following low E (low-launch-rate), solar property and/or the optical characteristics listed in table 2 when measurement.

Table 2: low E/ solar property (monolithic)

Although in conjunction with figure 1 above low E coating have shown and described containing Hf high refractive index transparent dielectric layer 2 (and Possible layer 6), but the present invention is not limited.It is as described herein to be or comprising HfSiAlN, HfZrSiAlN, HfSiN, HfAlN And/or high refractive index nitridation dielectric layer 2 (and possible layer 6) containing hafnium of HfAlZrN can be used as above the reflecting layer IR or High refractive index layer in any suitable low E coating of lower section.Can be provided as in any suitable low E coating or comprising The such high refractive index containing hafnium of the one or more of HfSiAlN, HfZrSiAlN, HfSiN, HfAlN and/or HfAlZrN nitrogenizes electricity Dielectric layer.Such as and it is without being limited thereto, it is discussed in this article be or comprising HfSiAlN, HfZrSiAlN, HfSiN, HfAlN and/ Or the high refractive index nitridation dielectric layer containing hafnium of HfAlZrN can be used for substituting U.S. Patent number 9,212,417,9,297,197, 7,390,572, any high folding in any low E coating in 7,153,579,9,365,450 and 9,403,345 in any one Rate is penetrated (for example, TiO_xOr TiO₂) layer, all these patents are herein incorporated by reference.

Fig. 2 is the sectional view of the coating product of another exemplary embodiment according to the present invention.Fig. 2 and as discussed above Fig. 1 is similar, unlike in Fig. 2 embodiment, be provided as or wrap between substrate of glass 1 and high refractive index layer 2 containing Hf Medium refractive index (n) layer 23 and substrate of glass 1 containing material such as silicon nitride or zinc oxide and the high refractive index layer 2 containing Hf with It is directly contacted, and provides material such as SiO₂Low-index layer 21 replace layer 8.

Fig. 3 is the sectional view of the coating product of another exemplary embodiment according to the present invention.Fig. 3 is similar to and begs for above Fig. 1 of opinion, the difference is that providing two high refractive index layers 2 and 6 in finishing coat, and the layer 7 of Fig. 1 is in Fig. 3 embodiment In be omitted.In finishing coat in Fig. 3, layer 2 is the high refractive index layer containing Hf, is or comprising as discussed in this article HfSiAlN, HfZrSiAlN, HfSiN, HfAlN and/or HfAlZrN, and layer 6 is or comprising titanium oxide (for example, TiO₂), Can be or can not be doping.

The embodiment of certain exemplary implementation schemes according to the present invention and two comparative examples (CE) discussed below.