WO2025199629A1 - Structure d'isolation thermique transparente - Google Patents

Structure d'isolation thermique transparente

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Publication number
WO2025199629A1
WO2025199629A1 PCT/CA2025/050414 CA2025050414W WO2025199629A1 WO 2025199629 A1 WO2025199629 A1 WO 2025199629A1 CA 2025050414 W CA2025050414 W CA 2025050414W WO 2025199629 A1 WO2025199629 A1 WO 2025199629A1
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Prior art keywords
functional layer
low
control structure
layer
sputtering
Prior art date
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Application number
PCT/CA2025/050414
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English (en)
Inventor
Nazir Pyarali Kherani
Moein Shayegannia
Navid Soheilnia
Govind Nanda
Paulo Cesar DE MOURA
Jose Nunez-Regueiro
Alexey Krasnov
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3e Nano Inc
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3e Nano Inc
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Publication date
Application filed by 3e Nano Inc filed Critical 3e Nano Inc
Publication of WO2025199629A1 publication Critical patent/WO2025199629A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3464—Sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5853—Oxidation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/281—Interference filters designed for the infrared light
    • G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection

Definitions

  • the present invention relates to low-emissivity (low-E) solar-control structures and, particularly, to low-E structures with infrared (IR) reflective silver (Ag) functional electrically conductive layers having enhanced corrosion resistance and bendability, as well as methods of fabrication of such structures thereof.
  • low-E low-emissivity
  • IR infrared
  • Ag reflective silver
  • the solar heat gain coefficient also known as the g-value or the total solar energy transmittance (TST, TSET or TTS), is the fraction of the impinging total solar radiation transmitted through the glazing (including re-radiation of the energy absorbed in the glazing).
  • TST total solar energy transmittance
  • TSET total solar energy transmittance
  • TTS total solar energy transmittance
  • Tvis visible light transmittance
  • VLT visible light transmittance
  • LSG light-to-solar heat gain
  • LESC coatings are typically deposited by magnetron sputtering and comprise at least one highly electrically conductive and optically transparent functional metal layer, such as silver, deposited in pure argon.
  • Properly deposited silver offers optimal values of index of refraction (IOR) and extinction coefficient in the visible spectral range and in the infrared.
  • IOR index of refraction
  • it is essential to deposit the Ag functional layer with a preferred ⁇ 111 > crystal orientation, achieve a smooth interface with the underlying bottom layer, and realize a well-developed crystalline silver (c-Ag) grain structure to minimize scattering of free electrons. Additional important requirements include the high purity of the sputter-deposited silver.
  • a traditional LESC sputtered stack processing comprises, starting with a transparent substrate, deposition of a barrier layer to prevent unwanted diffusion of alkaline elements; then having a so-called wetting layer disposed just below the silver functional layer to promote its proper crystalline orientation; then a so-called blocker layer deposited right above the silver to provide some protection against corrosion; and followed by a protection layer on top of the stack.
  • LESC structures are either laminated between two panes of glass, like in the case of automotive glazing, or exposed to an argon- filled interior of an insulating glass unit (IGU). In both cases, the coating is protected from the ingress of oxygen from the atmosphere.
  • the thin-film IR-reflective functional layer made from pure silver is known to be highly susceptible to corrosion, primarily caused by the electrochemical anodic reaction due to the ingress of atmospheric oxygen and moisture, as well as sulphur-inclusive species, such as hydrogen sulfide (H2S), which occurs through pinholes and other imperfections in protective sputtered layer.
  • H2S hydrogen sulfide
  • the ⁇ 111 > crystal orientation yields dense silver layers with closely packed large grains which result in a high specific conductivity of LESC functional layers, in turn enabling high IR reflectance.
  • the close-packed structure makes the Ag layer susceptible to oxygen, moisture or sulphur-induced corrosion, which starts from the grain boundaries where oxygen, moisture or sulphur, after reaching the silver layer, initiate the oxidation or reduction reactions.
  • Another drawback of the dense silver functional layer is its limited bendability, which often results in cracking when the LESC stack is processed on flexible substrates or subjected to high- temperature bending.
  • a number of methods have been suggested to make the functional Ag layer more air stable by quasi-uniform distribution of corrosion-resistant elements in silver or, in other words, by alloying the silver with other metals, such as gold (Au), copper (Cu), aluminum (Al), platinum (Pt), palladium (Pd), or nickel (Ni).
  • other metals such as gold (Au), copper (Cu), aluminum (Al), platinum (Pt), palladium (Pd), or nickel (Ni).
  • Examples include the use of a 5-30 nm thick functional layer made of a corrosion resistant alloy comprising 90-70 wt.% of Ag and 10-30 wt.% of copper [https://doi.Org/10.1016/j.solmat.2022.112033]; a Ag-AI alloy with an Al concentration ranging from 0.29 to 0.77 atomic % (at.%) [US 11 ,685,688 B2]; or an alloy from the following list: Ag-Cu-AI, Ag-Cu-Ni, or Ag-Cu-Pt [CN103802379] with respective content wt.% ratios of Ag: 80-95%, Cu: 2.5-10%, Al: 2.5-10%; Ag: 85-95%, Cu: 4-10%, Ni: 1-5%; and Ag: 90-98%, Cu: 1-5%, Pt: 1-5%.
  • a corrosion resistant alloy comprising 90-70 wt.% of Ag and 10-30 wt.% of copper [https://doi.Org/10.1016/j.solmat.202
  • Alternative corrosion resistant measures include protecting a pure silver functional layer from the air side with a planar silver-inclusive alloy layer [A. Dirks, J. Van den Broek, P. Wierenga, Mechanical properties of thin alloy films: ultra-microhardness and internal stress, J. Appl. Phys. 55 (1984) 4248-4256]; [D.-Y. Song, R. Sprague, H.A. Macleod, M.R. Jacobson, Progress in the development of a durable silver-based high-reflectance coating for astronomical telescopes, Appl. Opt.
  • the present invention discloses a method for making a corrosion resistant LESC structure by adding nitrogen to argon plasma during the sputter deposition of Ag-Cu-AI functional layer or layers.
  • the role of nitrogen in this process is three-fold: i) to add some level of porosity to the silver, primarily by expanding the spacing between the closely packed ⁇ 111 >-oriented c-Ag grains via increasing the number of ⁇ 100>-oriented fine a-Ag crystallites at the grain boundaries.
  • Al bronze nitrogenated Cu-AI
  • the present invention advantageously enhances the resistance of the layer stack to oxygen-, moisture- and sulphur-induced corrosion in case of occasional microcracking or other localized damage, as well as improves its bendability.
  • the former can be explained by the fact that cracking of the functional layer, such as due to a high intrinsic compressive stress or another type of mechanical damage, almost exclusively occurs between the grain boundaries.
  • the boundaries are filled with a Cu-AI oxynitride I oxide, the pure-Ag grains are “sealed off”, and no further corrosion caused by oxidation takes place.
  • the nitrogenated functional layer or bilayer is exposed to an oxygen-containing plasma immediately after the deposition to convert the nitrogenated alloy of the protective shell to an oxynitride I oxidized alloy shell.
  • the exposure can be done in a defined oxygen plasma chamber, appropriately situated after the nitrogenated alloy sputter deposition chamber or chambers.
  • the gas chemistry of the oxygen plasma chamber can comprise pure oxygen, oxygen-argon mixtures, oxygen-nitrogen-argon mixture, or a mixture of argon with nitrous oxide.
  • other inert gases such as helium can also be used to alter plasma conditions and thus influence the desired oxidation process of the functional layer.
  • Other non-reactive or mildly-reacting gases can also be used at appropriate concentrations to achieve optimum reaction and alloy chemistry.
  • the argon-to-nitrogen flow ratio in the sputtering chamber ranges between 100:1 to 70:30, with a preferred range between 96:4 to 90:10.
  • the oxidation is achieved during post-deposition high- temperature processing steps on a completed LESC structure.
  • the functional layer is capped by an AIN layer.
  • the resultant unique silver functional layer comprising encapsulated silver grains can be integrated within a range of dielectric layers to create appropriate layer stacks and thus achieve spectrally selective coatings with desired properties.
  • Potential dielectric layers include other nitrides (for example, silicon nitride), oxynitrides (for example, aluminum oxynitride, silicon oxynitride), and oxides.
  • the method also assists with an improved bendability of the LESC structure as well as its survivability against corrosion in case of local cracking or other mechanical damage.
  • Fig. 1 schematically demonstrates a PRIOR ART LESC coating.
  • Fig. 2B is a schematic cross-sectional representation of the silver grain of Fig. 2A with depiction of Ag atoms.
  • Fig. 3B is a schematic cross-sectional representation of the silver grain of Fig. 3A after nitrogen in Cu-AI-N is replaced with the arriving oxygen.
  • Fig. 3C is a schematic cross-sectional representation of the silver grain of Fig. 3B depicting the formation of oxidized aluminum bronze corrosion protective layer around the silver grain.
  • Fig. 4 schematically demonstrates a LESC coating comprising a bilayer functional layer.
  • the terms, “comprises” and “comprising” are to be construed as being inclusive and open ended, and not exclusive. Specifically, when used in the specification and claims, the terms, “comprises” and “comprising” and variations thereof mean the specified features, steps or components are included. These terms are not to be interpreted to exclude the presence of other features, steps or components.
  • exemplary means “serving as an example, instance, or illustration,” and should not be construed as preferred or advantageous over other configurations disclosed herein.
  • the terms “about” and “approximately”, when used in conjunction with ranges of dimensions of particles, compositions of mixtures or other physical properties or characteristics, are meant to cover slight variations that may exist in the upper and lower limits of the ranges of dimensions so as to not exclude embodiments where on average most of the dimensions are satisfied but where statistically dimensions may exist outside this region. It is not the intention to exclude embodiments such as these from the present disclosure. Unless otherwise specified, the terms “about” and “approximately” mean plus or minus 25 percent or less.
  • any specified range or group is as a shorthand way of referring to each and every member of a range or group individually, as well as each and every possible sub-range or sub-group encompassed therein and similarly with respect to any sub-ranges or sub-groups therein.
  • the present disclosure relates to and explicitly incorporates each and every specific member and combination of sub-ranges or sub-groups.
  • the term "on the order of”, when used in conjunction with a quantity or parameter refers to a range spanning approximately one tenth to ten times the stated quantity or parameter.
  • the present invention discloses methods of making a corrosion resistant LESC structure by adding nitrogen to argon plasma during the sputter deposition of at least one Ag-Cu-AI functional layer.
  • nitrogen adds some level of porosity to the silver functional layer, primarily by increasing the spacing between the closely packed ⁇ 111 >-oriented c-Ag grains via the introduction of ⁇ 100>-oriented fine a-Ag crystallites at the grain boundaries.
  • nitrogen binds the Cu and Al atoms and forces them to segregate outside the crystalline Ag grain and to the porous grain periphery due to the fulfilment of thermodynamic considerations and the system’s minimum energy requirements.
  • the nitrogenated aluminum bronze layer therefore, serves as a temporary sacrificial layer which converts into a permanent oxidized protective layer.
  • the thickness of the oxidized aluminum bronze layer depends on the concentration of the alloying elements as well as the concentration of nitrogen in the mixture of argon and nitrogen. It may range between 0.1 and 3 nm with a preferred range of 0.3 - 2 nm. It is noteworthy that the thickness of the oxidized aluminum bronze layer is determined by the thickness of the nitrogenated sacrificial layer and will not significantly change after the process of oxidation. All of the above-mentioned considerations also apply to the Cu-Ni or Al-Ni.
  • the main phenomenon behind the disclosed method is selective reaction of nitrogen with copper and aluminum of the sputtered Ag-Cu-AI alloy, but not with silver.
  • This can be understood by considering the standard enthalpy of formation, which represents enthalpy changes (measure of the energy released or consumed) resulting from the formation of one mole of a substance from its constituent elements in their standard states.
  • the standard enthalpies of formation of CusN, AIN, and AgsN are respectively -88, -318, and + 199 kJ/mol, indicating that energetically it is far more favorable for the system to form copper and aluminum nitrides but not silver nitride.
  • the released small amount of nitrogen uniformly and harmlessly occupies available spaces along the porous amorphous silver grain boundaries or diffuses outside the crystal lattice.
  • the formation of said oxidized bronze protective layer has the benefit of added flexibility to the otherwise rigid closely packed silver layer - typically having a high intrinsic compressive stress owing to metal-to- metal grain bonding - due to the introduction of oxides between/at the grain boundaries.
  • the fine-grained oxide covering in this case plays the role of a soft glue between the silver grains due to the large electronegativity of oxygen.
  • the enhanced flexibility of Ag functional layers can be beneficial during the deposition process and fabrication of window inserts on flexible substrates as well as in LESC structures disposed on glass and later subjected to postdeposition high-temperature processing, such as thermal bending.
  • nitrogen tuning gas is added to the argon working gas during sputter deposition of the Ag-Cu-AI functional layer. There are no other Ag-inclusive layers in direct contact with the nitrogenated Ag-Cu-AI functional layer.
  • composition of the alloy of the functional layer sputter deposited in the atmosphere comprising nitrogen is limited to Ag-AI.
  • composition of the alloy of the functional layer sputter deposited in the atmosphere comprising nitrogen is limited to Ag-Ni.
  • the nitrogenated alloyed Ag-Cu-AI layer is deposited as a corrosion-protection layer on top of a pure silver functional layer, thus forming a functional bilayer.
  • the nitrogenated alloyed Ag-Cu-AI layer is deposited as a protective layer on top of another nitrogenated Ag-Cu-AI functional layer having a different composition than the first nitrogenated alloyed layer.
  • the oxidation is achieved inline or offline during a postdeposition treatment of the completed LESC structure, hence the oxidation is facilitated due to the ingress of the environmental oxygen.
  • a source of convectional or radiative heat energy radiofrequency, intense light, or another source of radiation, or a combination thereof.
  • Such treatment methods are appropriate for coated glass but are also amenable where polymeric substrates are used; that is, where the thermal effects are appropriately controlled in relation to the transition temperature of the polymeric material.
  • the LESC structure comprises more than one alloyed functional layer, separated from one another by a dielectric or a dielectric stack.
  • At least one functional layer or bilayer is in direct contact with at least one aluminum nitride (AIN) layer.
  • AIN aluminum nitride
  • At least one functional layer is separated by a layer from at least one aluminum nitride (AIN) layer.
  • AIN aluminum nitride
  • the percentage of nitrogen in argon atmosphere during the deposition ranges between 0.01 and 50%, with a preferred range of 0.5 to 20%.
  • the atomic percentage of nitrogen in the alloyed functional layer ranges between 0.01 and 7%, with a preferred range of 0.5 to 4%.
  • the architecture of the structure is monolithic, i.e., the LESC layer stack is deposited on a substrate and is exposed to atmosphere, such as to the air in case of window inserts or to argon in case of encapsulated integrated-glass units.
  • atmosphere such as to the air in case of window inserts or to argon in case of encapsulated integrated-glass units.
  • the use of a plastic substate is advantageous in lowering the total weight of the combined glazing while improving heat insulation.
  • the use of a glass substrate, such as that made of soda-lime glass, may be preferred if, for instance, a tempered-glass structure is required for safety reasons.
  • the substantially optically transparent substrate may be a glass window.
  • polycarbonate 1.0 to 13.0 mm and preferably 1.5 -6.0 mm thick
  • the PC may be primed with an appropriate hard coating, such as siloxane disposed, e.g., by a gravitational flow or “doctor blade” process.
  • the substrate is made of glass, such as soda-lime, borosilicate, alumino-silicate, or any other type of glass with a thickness between 0.5 to 16.0 mm and preferably between 1 .5 and 5.0 mm.
  • the ratio of the ⁇ 111 > to ⁇ 100 crystal orientation peaks of the functional layer, as measured by X-ray diffraction is at least 50:1 , preferably between 20:1 and 10:1.
  • a wetting layer 140 Directly above the AR layer 130 is a wetting layer 140, about 5-30 nm thick, which serves to improve the crystal orientation, smoothness, and chemical adhesion of functional layer 150.
  • Functional layer 150 is cladded with a blocker layer 160, about 0.5-5 nm thick, the main role of which is to provide an additional level of protection for the silver layer from corrosion, as well as to minimize the damage from energetic sputtering species during the deposition of the layer above the functional layer, such as optional color-control layer 170 made of ZnSnOx, TiOx, NbOx, ZrOx, or TiZrOx. Its thickness ranges between 10 and 80 nm, preferably between 30 and 70 nm.
  • All layers of a LESC thin-film stack can be preferentially deposited using metal or ceramic sputtering targets.
  • the targets can be planar, rotatable, or any combination thereof.
  • Other apparatus and additions to the plasma process such as collimators, electron-confining magnets, or high-power impulse magnetron sputtering, can also be used.
  • the process of using sputtering to produce the low- emissivity solar-control structure comprises producing at least one functional layer on substantially optically transparent substrate, by a process of sputtering Ag along with at least one alloying agent being any one of Cu, Al, and Ni, in the presence of Ar and N, and once sputtering is complete, exposing the as sputtered functional layer is exposed to oxygen.
  • the at least one sputtered functional layer characterized in that the functional layer comprises a plurality of Ag grains with preferentially ⁇ 111 > crystal orientation with the Ag grains enveloped in a peripheral protective bronze layer around each said grain having preferentially a ⁇ 100 crystal orientation, wherein the detectable nitrogen content in the at least one functional layer ranges between 0.01 and 7%, and wherein a ratio of the ⁇ 111 > to ⁇ 100> crystal orientation peaks of the functional layer, as measured by X-ray diffraction, is at least 50:1.
  • the low-emissivity solar-control structure is characterized by an integrated visible light transmittance of at least 25 %, as defined by IS09050 and has a sheet resistance of no greater than 9 Q/sq.
  • the sputtered produced functional layer is characterized in that the detectable nitrogen content in the at least one functional layer ranges between about 0.5 and about 4 at.%.
  • the process of sputtering may be performed in which the at least one alloying agent being concurrently sputtered is any combination of Cu, Al, and Ni such that the protective bronze layer is comprised of any combination of Cu, Al, and Ni bound with oxygen.
  • the functional layer may have a thickness in a range from about 5 to about 30 nm.
  • the sputtering is performed with the substantially optically transparent substrate not being intentionally heated.
  • the combined atomic percentage range of the elements in the targets is as follows. Ag: 90-99%; Cu: 0-10%; Al: 0-5%; Ni: 0-2%. It should be appreciated, however, that the concentration range of the elements in the sputtering target or targets may not directly represent the concentration range of the elements in the deposited film.
  • FIG. 2A Depicted in Fig. 2A is a schematic cross-sectional representation of a sputtered silver grain deposited on a wetting layer 240 and consisting of a c-Ag core 215 surrounded by grain boundaries 225, separated from the core by an ultrathin a-Ag layer 235, naturally formed along the boundaries.
  • Fig. 2B further explains the crystalline silver grain 215 as comprising Ag atoms 245.
  • Ag atoms 245 as well as atoms of other elements depicted in subsequent figures of the present invention are only a stylistic representation of the respective elements and are used for illustrative purpose only and without any other limitations to demonstrate the migration and segregation of those elements. It is also noteworthy that in reality and, as mentioned earlier in the Detailed Description, the Ag atoms are organized in the grain as a close-packed crystal lattice structure surrounded by a less dense amorphous Ag shell.
  • Fig. 2C depicts a cross-section of a silver grain alloyed with atoms of aluminum 255 and copper 265. As shown in the figure, without any additional measures taken, the grain comprises a quasi-uniformly distributed network of Ag, Cu, and Al. Although having improved corrosion resistant properties, such a uniformly alloyed functional layer has a significant drawback of compromised LSG due to inferior optical performance of Cu and Al compared to that of Ag in the visible and IR spectral regions.
  • the nitrogenated Al bronze segregated at the grain boundaries undergoes an oxidation reaction, during which nitrogen atoms 375 are permanently replaced with oxygen atoms 385, as depicted in a cross-sectional view of Fig. 3B.
  • Fig. 3C is a schematic cross-sectional representation of the core silver grain 345 with an oxidized Al bronze layer or sheath 395 formed around the silver grains 345.
  • the oxidation takes place during the exposure of the Ag functional layer comprising nitrogenated Al bronze to an oxygen-containing plasma immediately after its deposition.
  • the grain therefore, becomes a core-shell like structure in which a preferentially highly crystalline pure-Ag core is surrounded by a preferentially porous layer filled with a protective oxidized Cu-AI alloy, so no further corrosion of the alloy or the grain that it protects can take place.
  • Fig. 4 is a schematic representation of a solar-control stack comprising an alloyed functional bilayer comprising silver-based sublayers 450 and 451.
  • the present invention discloses a LESC structure with a coating 110 comprising at least one functional layer 150 with improved corrosion resistance and having a visible light transmittance measured at 8 degrees greater than 70%.
  • Example 1 is a LESC structure comprising a 1.5 mm thick PMMA substrate primed with a siloxane hard coating and a sputtered coating having one functional layer comprising silver, copper, aluminum, oxygen, and nitrogen in the following proportions: 95 at.% Ag; 3 at.% Cu; 0.5 at.% Al; 1 at.% O; 0.5 at.% N.
  • the thickness of the functional layer is 12 nm.
  • the ratio of the ⁇ 111 > to ⁇ 100> crystal orientation peaks of the functional layer, as measured by X-ray diffraction, is 10:1.
  • the coating also comprises an AIN layer, 35 nm thick, on each side of the functional layer.
  • Example 2 similar to Example 1 but the substrate is a 3.0 mm thick PMMA, and the LESC sputtered coating comprises additional 7 nm thick ZnAIOx wetting layer just below the functional layer.
  • the functional layer comprises silver, copper, aluminum, oxygen, and nitrogen in the following proportions: 92 at.% Ag; 4 at.% Cu; 1.5 at.% Al; 1.5 at.% O; 1 at.% N.
  • the coating additionally comprises an AR layer, 22 nm thick, made of NbOx.
  • a NiCrOx blocker layer is disposed above the Ag functional layer for ever more enhanced corrosion protection.
  • Example 3 is similar to Example 2 but the substrate is a 3.2 mm thick soda-lime glass, and the functional layer is a bilayer comprising two alloyed sublayers.
  • the first sublayer (starting from the substrate side) of the bilayer functional layer comprises silver, copper, aluminum, oxygen, and nitrogen in the following proportions: 95 at.% Ag; 3 at.% Cu; 0.5 at.% Al; 1 at.% O; 0.5 at.% N.
  • the second sublayer of the functional bilayer comprises silver, copper, aluminum, oxygen, and nitrogen in the following proportions: 90 at.% Ag; 5 at.% Cu; 0.5 at.% Al; 4 at.% O; 0.5 at.% N.
  • the structure is post-deposition heat treated at 630 C for 10 minutes.
  • Example 4 is similar to Example 3 but the glass substrate is 2.1 mm thick Clear soda-lime glass.
  • the first sublayer (starting from the substrate side) of the functional bilayer comprises pure silver.
  • the second sublayer of the functional bilayer comprises silver, copper, aluminum, oxygen, and nitrogen in the following proportions: 91 at.% Ag; 4 at.% Cu; 2 at.% Al; 2 at.% O; 1 at.% N.
  • the coated LESC structure is subjected to post-deposition high-temperature gravitational bending at 630 C, followed by its lamination to a second protecting glass pane, 2.1 mm thick and bent to the same shape, with the help of a 0.76 mm thick polyvinyl butyral thermoplastic bonding layer.

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  • Physical Vapour Deposition (AREA)

Abstract

Selon la présente invention, le dépôt d'une couche fonctionnelle comprenant de l'argent et un ou plusieurs agents d'alliage de cuivre, d'aluminium et de nickel en présence d'azote peut améliorer considérablement la résistance à la corrosion et l'aptitude au pliage de structures de commande solaire à faible émissivité. Les améliorations sont obtenues par un processus en deux étapes. Dans la première étape, une couche de cristallites de type noyau-enveloppe est formée pendant le dépôt, chaque grain d'argent cristallin étant entouré par une enveloppe ultramince de bronze d'aluminium azoté séparé le long des limites de grain. Essentiellement aucun nitrure d'argent n'est formé à cette étape en raison de son enthalpie de formation exceptionnellement élevée. Dans une seconde étape, l'enveloppe de bronze azoté réagit avec l'oxygène environnemental arrivant ou l'oxygène volontairement introduit immédiatement après la formation de la couche fonctionnelle. Ceci conduit à la formation d'un bronze d'aluminium oxydé à protection permanente qui encapsule les grains d'argent cristallins et arrête toute oxydation ou attaque supplémentaire par d'autres espèces corrosives, telles que des agents incluant du soufre. Le procédé est également avantageux pour une flexibilité améliorée de structures de commande solaire à faible émissivité déposées sur des substrats pliables ou soumises à un processus de pliage à haute température. Ce dépôt par pulvérisation à teneur en azote du paradigme à enveloppe de bronze à noyau d'argent peut être conçu pour rendre un collecteur de variations de forme de taille de grain, structurales, de composition pour obtenir des couches fonctionnelles d'argent qui présentent des améliorations souhaitées dans des propriétés électriques, optiques-photoniques-plasmoniques, de résistance à la corrosion et thermomécaniques, en particulier dans le cadre d'empilements diélectrique-métal-diélectrique multicouches disposés sur une variété de matériaux de substrat de forme rigide et flexible.
PCT/CA2025/050414 2024-03-28 2025-03-25 Structure d'isolation thermique transparente Pending WO2025199629A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140347722A1 (en) * 2011-11-29 2014-11-27 Agc Glass Europe Solar-control glazing unit
WO2017040563A1 (fr) * 2015-09-01 2017-03-09 Ppg Industries Ohio, Inc. Revêtement de contrôle solaire à performances améliorées de contrôle solaire
CA3061105A1 (fr) * 2017-04-17 2018-10-25 Nazir Pyarali Kherani Revetements de regulation d'energie, structures, dispositifs, et procedes de fabrication associes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140347722A1 (en) * 2011-11-29 2014-11-27 Agc Glass Europe Solar-control glazing unit
WO2017040563A1 (fr) * 2015-09-01 2017-03-09 Ppg Industries Ohio, Inc. Revêtement de contrôle solaire à performances améliorées de contrôle solaire
CA3061105A1 (fr) * 2017-04-17 2018-10-25 Nazir Pyarali Kherani Revetements de regulation d'energie, structures, dispositifs, et procedes de fabrication associes

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