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WO2016171627A1 - Revêtement sensiblement transparent - Google Patents

Revêtement sensiblement transparent Download PDF

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Publication number
WO2016171627A1
WO2016171627A1 PCT/SG2016/050192 SG2016050192W WO2016171627A1 WO 2016171627 A1 WO2016171627 A1 WO 2016171627A1 SG 2016050192 W SG2016050192 W SG 2016050192W WO 2016171627 A1 WO2016171627 A1 WO 2016171627A1
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WIPO (PCT)
Prior art keywords
nitride
oxide
coating
substrate
region
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PCT/SG2016/050192
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English (en)
Inventor
Tian Poh KHOO
Li Kang Cheah
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Wangi Industrial Co (private) Ltd
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Wangi Industrial Co (private) Ltd
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Publication of WO2016171627A1 publication Critical patent/WO2016171627A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/027—Graded interfaces
    • 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
    • C23C14/0605—Carbon
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/91—Coatings containing at least one layer having a composition gradient through its thickness

Definitions

  • the present invention generally relates to a substantially transparent coating for coating a substantially transparent substrate and a method for making the same.
  • the disclosed substantially transparent coating may be a high wear resistance coating on glass which has good transmission and hardness .
  • Transparent substrates like glass are extensively used due to their optical transparency.
  • glass products include eyeglass and sunglass lenses, architectural glass, analytical instrument windows, automotive windshields and laser bar code scanners.
  • abrasions occur easily as glass is not a particularly hard material.
  • glass is chemically reactive with alkalis and strong acids like hydrofluoric acid, thereby limiting its applications.
  • diamond-like carbon coatings in hydrogenated and non-hydrogenated forms have been developed.
  • the term “DLC” is commonly used to designate the hydrogenated form of diamond-like carbon (a- C:H), while the term “ta-C” (tetrahedral amorphous carbon) refers to diamond-like carbon with high diamond content.
  • Diamond-like carbon contain significant fractions of sp 3 type carbon bonds, giving them attractive physical and mechanical properties that are, to a certain extent, similar to diamond, which is well known for being the hardest natural material.
  • Coatings made of a-C:H usually contain sp 3 fractions smaller than 50%, while tetrahedral amorphous carbon (ta-C) coatings contain 85% or more Bp 3 bonds.
  • DLC has been extensively studied since the 1970s, and the growth mechanisms, material properties and usage in industrial applications are well known. Among the many desirable properties of DLC, its low coefficient of friction, high wear resistance, hardness and chemical inertness make it particularly attractive for industrial applications. On the other hand, ta-C is at a much younger stage of development and a deep understanding of its properties and practical applications have yet to be developed. Thus, there is a need to make use of ta-C as a coating so that its properties and practical applications can be investigated.
  • diamond-like carbon will impart improved abrasion resistance and other attractive physical and mechanical properties to the substrate only if the adherence of the coating to the substrate is good.
  • a common approach to coating a substrate is to apply the coating directly on the clean surface of. the substrate.
  • this approach often results in a coating which displays poor adhesion, and consequently poor abrasion resistance.
  • significant compressive stress greatly affects the ability of the coating to remain adherent to the substrate.
  • the bonding of the Si0 2 in glass to the carbon atoms in the DLC coating may be inhibited due to the presence of alkali oxides.
  • a substantially transparent coating for coating a substantially transparent substrate, the substantially transparent coating comprising a stress reducing layer intermediate to the substrate and a carbon layer, the carbon layer being comprised of tetrahedral carbon atoms that are substantially free of hydrogen atoms.
  • the carbon layer which comprises tetrahedral carbon atoms that are substantially free of hydrogen atoms may impart the hardness, wear and/or scratch resistance properties to the substantially transparent substrate, particularly in glass.
  • the stress reducing layer comprises a first region that is adjacent to the transparent substrate and a second region between the first region and the carbon layer, wherein the stress reduces between the first region and second region.
  • This may lead to a coating with reduced stress and high hardness. It has been found that this arrangement allows for the deposition of a thicker coating, where the thickness as compared to a coating without a layered structure may be adjusted accordingly.
  • a method of forming a substantially transparent coating for coating a substantially transparent substrate comprising the step of depositing a carbon layer on a substrate having a stress reducing layer therein, wherein the carbon layer comprises tetrahedral carbon atoms that are substantially free of hydrogen atoms .
  • substantially transparent means that more than 75% of the visible light which is incident to the carbon layer is allowed to pass through the coating.
  • the word “substantially” does not exclude “completely” e.g. a layer which is “substantially free” from Y may be completely free from Y. Where necessary, the word, “substantially” may be omitted from the definition of the invention.
  • the tetrahedral carbon layers are substantially free of hydrogen atoms when the amount of hydrogen is less than 10 at.%, or less than 1 at . %.
  • stress reducing layer means a layer that is composed of materials selected to reduce the stress between the substrate and the carbon layer.
  • hard or “hardness” refers to the property of high hardness in the mechanical sense with good tribological properties.
  • the coating has a hardness in the range of 10 to 40 GPa. The Vickers hardness test was used to determine the hardness of the coating.
  • atomic percent refers to the percentage of one kind of atom relative to the total number of atoms.
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
  • certain embodiments may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range.
  • Exemplary, non-limiting embodiments of a substantially transparent coating for coating a substantially transparent substrate and a method for making the same will now be disclosed.
  • the substantially transparent coating for coating a substantially transparent substrate comprises a stress reducing layer intermediate to the substrate and a carbon layer, the carbon layer being comprised of tetrahedral carbon atoms that are substantially free of hydrogen atoms.
  • the substantially transparent coating may be layered to create the desired thickness. This may lead to a coating with reduced stress and high hardness. It has been found that this arrangement may allow for the deposition of a thicker coating, where the thickness as compared to a coating without a layered structure may be adjusted accordingly.
  • the thickness of the coating may vary from angstroms to micrometers.
  • the thickness of the coating may be selected from the group consisting of about 10 nm to about 50 /xm, about 10 nm to about 40 /xm, about 10 nm to about 30 /xm, about 10 nm to about 20 /xm, about 10 nm to about 10 /xm, about 10 nm to about 5 /xm, about 50 nm to about 50 /xm, about 100 nm to about 50 /xm, about 500 nm to about 50 /xm, about 1 /xm to about 50 /xm and about 2 /xm to about 15 /xm.
  • the coating may have a hardness selected from the group consisting of about 10 GPa, about 12 GPa, about 14 GPa, about 16 GPa, about 18 GPa, about 20 GPa, about 22 GPa, about 24 GPa, about 26 GPa, about 28 GPa, about 30 GPa, about 32 GPa, about 34 GPa, about 36 GPa, about 38 GPa and about 40 GPa.
  • a stress reducing layer may be deposited intermediate to the substrate.
  • the stress reducing layer may comprise a first region that is adjacent to the transparent substrate and a second region between the first region and the carbon layer, wherein the stress reduces between the first region and second region.
  • the first region may be doped with a dopant selected from an oxide, a nitride or mixtures thereof.
  • the dopant in the first region may promote bonding and act as a buffer region that can prevent the diffusion of impurities that may be present in the .
  • the substrate layer such as alkali metal ions, fluorine and other additives, thereby reducing the stress of the coating.
  • the first region may be thinner than the second region and the choice of the oxide or the nitride may be determined by the compatibility of the oxide or nitride with the substrate.
  • the oxide may be a metal oxide or silicon oxide.
  • the metal of the metal oxide may be selected from the group consisting of titanium, tantalum, vanadium, niobium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, gold, silver, copper, zirconium, zinc, cadmium, mercury, aluminium, boron, gallium, indium, thallium, tin, lead and germanium.
  • the nitride may be a metal nitride or silicon nitride.
  • the metal of the metal nitride may be selected from the group consisting of titanium, tantalum, vanadium, niobium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, gold, silver, copper, zirconium, zinc, cadmium, mercury, aluminium, boron, gallium, indium, thallium, tin, lead and germanium.
  • the first region may be doped with a dopant selected from the group consisting of titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, vanadium oxide, vanadium nitride, niobium oxide, niobium nitride, chromium oxide, chromium nitride, molybdenum oxide, molybdenum nitride, tungsten oxide, tungsten nitride, manganese oxide, manganese nitride, technetium oxide, technetium nitride, rhenium oxide, rhenium nitride, iron oxide, iron nitride, ruthenium oxide, .
  • a dopant selected from the group consisting of titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, vanadium oxide, vanadium nitride, niobium oxide, niobium nitrid
  • the ratio of the oxide to nitride may be adjusted to reduce the residue stress of the coating.
  • the ratio may be selected from a range of 0.1 to 1.0 or 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0.
  • the second region may be doped with a compound selected from an oxide, a nitride or mixtures thereof. Consequently, this region may help to provide a hard structural support layer and the thickness of this region may help to achieve the required degree of abrasion resistance. Similar to the first region, the second region may act as a buffer region that can prevent internal buildup of stress during the deposition process, thereby reducing the stress of the coating.
  • the oxide may be a metal oxide or silicon oxide.
  • the metal of the metal oxide may be selected from the group consisting of titanium, tantalum, vanadium, niobium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, gold, silver, copper, zirconium, zinc, cadmium, mercury, aluminium, boron, gallium, indium, thallium, tin, lead and germanium.
  • the nitride may be a metal nitride or silicon nitride.
  • the metal of the metal nitride may be selected from the group consisting of titanium, tantalum, vanadium, niobium, chromium, molybdenum, tungsten, manganese, technetium, . rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, gold, silver, copper; . zirconium, zinc, cadmium, mercury, aluminium, boron, gallium, indium, thallium, tin, lead and germanium.
  • the second region may be doped with a dopant selected from the group consisting of titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, vanadium oxide, vanadium nitride, niobium oxide, niobium nitride, chromium oxide, chromium nitride, molybdenum oxide, molybdenum nitride, tungsten oxide, tungsten nitride, manganese oxide, manganese nitride, technetium oxide, technetium nitride, rhenium oxide, rhenium nitride, iron oxide, iron nitride, ruthenium oxide, ruthenium nitride, osmium oxide, osmium nitride, cobalt oxide, cobalt nitride, rhodium oxide, rhodium' nitride, iridium oxide, irid
  • the ratio of the oxide to nitride may be adjusted to vary the stress and hardness of the second region.
  • the ratio may be selected from a range of 0.1 to 1.0 or 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0.
  • a carbon layer intermediate to the stress reducing layer may be used.
  • An organo-ceramic layer may be used.
  • the carbon layer may consist of layers with different densities and different sp 3 carbon-carbon bond percentages.
  • the ratio of sp 3 to sp 2 carbon-carbon bonds may be different in different layers of the coating.
  • Such a coating with varying compositions therein may be continuously formed by varying the energy of the ions used in the deposition process.
  • the proportion of total sp 3 carbon-carbon bonds in the carbon layer may be selected from the group consisting of at least about 45%, at least about 50%, at least about 55%, at least about 65%, at least about 70%, at least about 75%, at least about 85% and at least about 90%.
  • a greater percentage of sp 3 carbon-carbon bonds may correlate to a greater percentage of diamond-like bonding, which consequently may lead to an increase in the density of the carbon layer and its hardness strength.
  • Diamond-like bonding may give the carbon layer gross physical properties approaching those of diamond, such as high hardness, high density and chemical inertness. Due to the good adhesion of the coating to the substrate, these desirable properties may be imparted to the substrate. Consequently, the coated substrate may demonstrate high hardness, high density and chemical inertness.
  • the carbon layer may contain hydrogen.
  • the hydrogen content in the carbon layer is a primarily independent variable that can differ considerably depending on the deposition method, hydrogen source gas and the deposition parameters used, which determines the structure and properties of the carbon coating.
  • the hydrogen content critically determines the structure of the carbon coating at the atomic level and therefore, the physical properties of the coating.
  • the carbon layer may be a diamond-like carbon layer that has high diamond content. This may result in a coating that has a low friction coefficient, high hardness, high density and close to diamond structure, with the exception that the carbon layer is amorphous instead of crystalline.
  • the resultant coating may be smooth, but may sometimes have particles on the surface of the carbon layer due to the nature of the deposition process. As such, buffing may be carried out to remove the particles from the carbon layer.
  • the carbon layer is substantially free of hydrogen atoms wherein the carbon layer contains less than 10 at.% or less than 1 at.% of hydrogen atoms.
  • the hydrogen atoms present in the carbon layer may be selected from the group consisting of about 0.1 at.%, about 0.2 at.%, about 0.3 at.%, about 0.4 at . %, about 0.5 at . %, about 1 at . %, about 2 at . %, about 3 at . %, about 4 at . %, about 5 at . %, about 6 at . %, about 7 at.%, about 8 at.%, about 9 at.% and about 10 at.%. Consequently, the disclosed coating has a greater hardness than a coating made from DLC.
  • the density of the carbon layer may be selected from the group consisting of 3.0 g/cm 3 , 3.1 g/cm 3 , 3.2 g/cm 3 , 3.3 g/cm 3 , 3.4 g/cm 3 , 3.5 g/cm 3 and 3.6 g/cm 3 .
  • the coating may have a coefficient of friction selected from the group consisting of less than about 0.17, less than about 0.15, less than about 0.13 and less than about 0.11.
  • the coating may have an optical transmission selected from the group consisting of about 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93% and 94%.
  • the method of forming a substantially transparent coating for coating a substantially transparent substrate comprising a step of depositing a carbon layer on a substrate having a stress reducing layer therein, wherein the carbon layer comprises tetrahedral carbon atoms that are substantially free of hydrogen atoms.
  • the first region may be doped with a dopant selected from an oxide, a nitride or mixtures thereof.
  • the dopant in the first region may promote bonding and act as a buffer region that can prevent the diffusion of impurities that may be present in the substrate layer such as alkali metal ions, fluorine and other additives, thereby reducing the stress of the coating.
  • the first region may be thinner than the second region and the choice of the oxide or the nitride may be determined by the compatibility of the oxide or nitride with the substrate.
  • the oxide may be a metal oxide or silicon oxide.
  • the metal of the metal oxide may be selected from the group consisting of titanium, tantalum, vanadium, niobium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, gold, silver, copper, zirconium, zinc, cadmium, mercury, aluminium, boron, gallium, indium, thallium, tin, lead and germanium.
  • the nitride may be a metal nitride or silicon nitride.
  • the metal of the metal nitride may be selected from the group consisting of titanium, tantalum, vanadium, niobium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, gold, silver, copper, zirconium, zinc, cadmium, mercury, aluminium, boron, gallium, indium, thallium, tin, lead and germanium.
  • the first region may be doped with a dopant selected from the group consisting of titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, vanadium oxide, vanadium nitride, niobium oxide, niobium nitride, chromium oxide, chromium nitride, molybdenum oxide, molybdenum nitride, tungsten oxide, tungsten nitride, manganese oxide, manganese nitride, technetium oxide, technetium nitride, rhenium oxide, rhenium nitride, iron oxide, iron nitride, ruthenium oxide, ruthenium nitride, osmium oxide, osmium nitride, cobalt oxide, cobalt nitride, rhodium oxide, rhodium nitride, iridium oxide, iridium
  • the ratio of the oxide to nitride may be adjusted to reduce the residue stress of the coating.
  • the ratio may be selected from a range of 0.1 to 1.0 or 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0.
  • the second region may be doped with a compound selected from an oxide, a nitride or mixtures thereof. Consequently, this region may help to provide a hard structural support layer and the thickness of this region may help to achieve the required degree of abrasion resistance. Similar to the first region, the second region may act as a buffer region that can prevent the diffusion of impurities that may be present in the substrate layer such as alkali metal ions, fluorine and other additives, thereby reducing the stress of the coating.
  • the oxide may be a metal oxide or silicon oxide.
  • the metal of the metal oxide may be selected from the group consisting of titanium, tantalum, vanadium, niobium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, gold, silver, copper, zirconium, zinc, cadmium, mercury, aluminium, boron, gallium, indium, thallium, tin, lead and germanium.
  • the nitride may be a metal nitride or silicon nitride.
  • the metal of the metal nitride may be selected from the group consisting of titanium, tantalum, vanadium, niobium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, gold, silver, copper, zirconium, zinc, cadmium, mercury, aluminium, boron, gallium, indium, thallium, tin, lead and germanium.
  • the second region may be doped with a dopant selected from the group consisting of titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, vanadium oxide, vanadium nitride, niobium oxide, niobium nitride, chromium oxide, chromium nitride, molybdenum oxide, molybdenum nitride, tungsten oxide, tungsten nitride, manganese oxide, manganese nitride, technetium oxide, technetium nitride, rhenium oxide, rhenium nitride, iron oxide, iron nitride, ruthenium oxide, ruthenium nitride, osmium oxide, osmium nitride, cobalt oxide, cobalt nitride, rhodium oxide, rhodium nitride, iridium oxide, iridium
  • the ratio of the oxide to nitride may be adjusted to vary the stress and hardness of the second region.
  • the ratio may be selected from a range of 0.1 to 1.0 or 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0.
  • the deposition of the stress reducing layer further comprises the step of depositing a second region on the carbon layer followed by the step of depositing a first region on the second region. This may advantageously reduce the stress of the coating, thereby increasing the abrasion resistance, wear resistance and hardness.
  • the coating may be deposited using physical vapor deposition (PVD) .
  • the carbon layer may be deposited using a filtered cathodic arc process. Pure carbon plasma may be used to give rise to a carbon layer having high diamond content and low hydrogen content as only residue gas is present.
  • the resultant coating may have a low friction coefficient, high hardness, high density and close to diamond structure, with the exception that the carbon layer is amorphous instead of crystalline.
  • the resultant coating may be smooth, but may sometimes have particles on the surface of the carbon- layer due to the nature of the deposition process. For instance, when a filtered cathodic arc process is used, arcing creates a lot of particles . As such, filtering is required to remove the particles. However, in some instances, filtering is not sufficient to remove the particles, which may consequently end up on the surface of the carbon layer. As such, buffing may be carried out to remove the particles from the carbon layer.
  • the deposition method may be selected from the group consisting of cathodic arc vapor (plasma or arc ion plating) deposition, magnetron sputtering (or sputter ion plating) , and combined magnetron and arc processes.
  • the deposition method is cathodic arc vapor deposition
  • the deposition method may be selected from the group consisting of filtered cathodic arc deposition or unfiltered cathodic arc deposition.
  • the preferred method for depositing the carbon layer is filtered arc deposition process .
  • the magnetron sputtering may be selected from the group consisting of meta stable magnetron sputtering, direct current (DC) magnetron sputtering, radiofrequency (RF) magnetron sputtering, pulsed DC magnetron sputtering, mid frequency (MF) alternative current (AC) magnetron sputtering and High Power Impulse Magnetron Sputtering (HIPIMS)
  • the preferred methods for depositing the stress reducing layer are meta stable magnetron sputtering, RF magnetron sputtering, DC magnetron sputtering and DC pulsed magnetron sputtering.
  • the carbon layer may be deposited using a highly activated pure carbon plasma.
  • a highly activated pure carbon plasma may be produced by pulse laser deposition (PLD) or pulsed arc discharge evaporation of pure graphite under vacuum conditions.
  • the film deposition is mainly dominated by highly energetic carbon ions, which are able to penetrate into the surface of the material to be coated. There they form local sp 3 bonds, which are stabilized at a low temperature (below 100 °C) .
  • the temperature of the substrate may be less than about 200 °C, most preferably from about 60 °C to about 80 °C during deposition of the coating. This is to minimize graphitization during the deposition process. Consequently, there is no need for elevated temperatures and substrates which are sensitive to chemical or physical alteration or decomposition by exposure to elevated temperatures, such as polymer, materials, may be suitable for such processes.
  • the hardness of the carbon layer may be achieved by the high energies of the impinging particles that form the films.
  • the required high energies of the depositing species may be achieved by different variations of vacuum or cathodic arc discharges such as filtered arc, pulsed arc, laser controlled arc, pulsed laser depositions, or mass selected beams.
  • the energy of the carbon ion generated by the source may be tuned to control the properties of the carbon layer.
  • the arc source may be tuned by adjusting the biasing in the chamber. This may be achieved by connecting the negative electrical field to the substrate holder. More advantageously, the adhesion and film properties of the resultant carbon layer may be tuned as desired.
  • the resultant carbon layer may be free from hydrogen due to the fact that the carbon plasma is generated by a pure graphite solid in high vacuum environment. This is unlike other deposition methods, such as chemical vapor deposition (CVD) processes, where hydrogen is usually required. As such, the resultant Carbon layer may have extremely low hydrogen content and structure similar to diamond in amorphous form.
  • CVD chemical vapor deposition
  • Such a coating with varying compositions therein may be continuously formed by varying the energy of the ions used in the deposition process .
  • the energy of the ions used in the deposition process may be selected from the range consisting of about 1 eV to about 2000 eV, about 1 eV to about 1000 eV, about 1 eV to about 500 eV, about 10 eV to about 2000 eV, about 10 eV to about 1000 eV, about 10 eV to about 500 eV, about 50 eV to about 2000 eV, about 50 eV to about 1000 eV, about 100 eV to about 2000 eV, about 100 eV to about 1000 eV, and about 100 eV to about 500 eV.
  • the deposition rates may be in the range from about 0.1 A/s to about 15 A/s, about 0.1 A/s to about 10 A/s, about 0.5 A/s to about 15 A/s, about 0.5 A/s to about 10 A/s, about 1 A/s to about 15 A/s, about 1 A/s to about 10 A/s, about 2 A/s to about 15 A/s, about 2 A/s to about 10 A/s and about 5 A/s to about 15 A/s.
  • the deposition rate is preferably about 0.1 A/s to about 10 A/s.
  • the substrate may include virtually any non-volatile solid substrate and may be selected from the group consisting of glass substrate, plastic substrate, tile substrate, pure metal substrate, metal alloy substrate, ceramics, polymers, or mixtures or combinations of these.
  • Ex-situ substrate cleaning may be selected from the group consisting of ultrasonic cleaning, various heating cycles and even laser cleaning of the surface.
  • In-situ substrate cleaning may be performed in connection with the application of the ta-C layer or when the stress reducing layer is incorporated.
  • Suitable techniques utilized for in-situ cleaning may be selected from the group consisting of reactive plasma etching, inert plasma sputter cleaning, radiant heating, metal ion plasma cleaning and carbon ion plasma cleaning.
  • Fig. 1 is a cross-sectional view of the coated substrate product 10 formed in accordance with the present invention.
  • Fig. 2 is a graph showing the results of the Vickers hardness test used to determine the hardness of Sample A and raw glass for comparison purposes.
  • Fig. 3 is a graph showing the relationship between optical transmission as a function of wavelength, as illustrated by Samples B to F made in accordance with the present invention.
  • Fig. 4 is a schematic diagram of magnetron sputtering 20, which is used to deposit the stress reducing layer.
  • Fig. 5 is a schematic diagram of the filtered cathodic arc deposition process 30, which is used to deposit the carbon layer .
  • Fig. 1 is a cross-sectional view of the coated substrate product in accordance with the present invention.
  • the substantially transparent coating 10 comprises of a stress reducing layer (4, 6), the stress reducing layer comprising a first region 4 that is adjacent to the transparent substrate 2 and a second region 6 between the first region 4 and the carbon layer 8, wherein the stress reduces between the first region 4 and second region 6 intermediate to the substrate 2 and a carbon layer 8, the carbon layer 8 being comprised of tetrahedral carbon atoms .
  • Fig. 4 is a schematic diagram of magnetron sputtering 20, which is used to coat the glass substrate 2' , with the stress reducing layer (4, 6) .
  • the substrate is first placed on an electrical conductive plate 11, which is connected to a negatively bias and rotatable substrate holder 12.
  • the target (or cathode) plate 20 is bombarded by energetic ions generated in a glow discharge plasma, situated in front of the target plate 20.
  • Plasma is generated when an inert gas such as argon, which enters via the gas inlet 16 and leaves via the gas outlet 18, becomes ionized by an electric field. This occurs when an electron accelerates towards the anode 14 and Ionizes the Ar atoms upon collision.
  • the bombardment process causes the removal, i.e., sputtering, of target atoms, which then condense on the glass substrate 2' as the stress reducing layer (4, 6).
  • the target is pure silicon.
  • Plasma is generated when oxygen or nitrogen enters via the gas inlet 16. Silicon is deposited layer by layer on one side of the chamber due to rotation of the glass substrate 2' on the rotatable substrate holder 12. The gas is then injected in with the heater (14) at the other side of the chamber, and oxidation occurs continuously to convert the silicon to silicon dioxide layer by layer in the chamber.
  • Fig. 5 is a schematic diagram of the filtered cathodic arc deposition process 30, which is used to coat the glass substrate 2'' with the carbon layer 8''.
  • the electrical conductive backing plate 11 is connected to a negatively bias and rotatable substrate holder 12. The electrical conductive backing plate 11 is used to generate a biased substrate.
  • a pulsed or continuous high current-density, low voltage electric current is passed between two separate electrodes (cathode and anode) under low pressure vacuum of 5 x 10 "6 torr, vaporizing the cathode material while simultaneously ionizing the vapor, forming a plasma.
  • a vacuum arc 22 is used to generate carbon plasma from the graphite target and the plasma generated travels in the direction indicated by arrow 24 and a magnetic torus 26 is used to steer the carbon plasma into the chamber and filter the carbon particle.
  • a pulsed bias can be added during the deposition of the carbon layer 8'' to enhance the adhesion by implantation to the subsurface of the second region 6''.
  • the high current density (usually 104-106 A/cm 2 ) causes arc erosion by vaporization and melting while ejecting molten solid particles from the cathode surface, with a high percentage of the vaporized species being ionized with elevated energy (50-150 eV) and some multiply charged.
  • Magnetron sputtering was used to coat the substrate with the stress reducing layer, as illustrated by Fig. 4.
  • An ion beam was used to produce Ar ions that were subsequently bombarded on the surface of the transparent substrate 2 ' prior to coating.
  • a vacuum environment of up to 5 x 10 "6 torr was then created.
  • a target ⁇ or cathode) plate 20 was bombarded by energetic ions generated in a glow discharge plasma, situated in front of the target plate 20.
  • Magnetrons make use of the fact that a magnetic field configured parallel to the target surface can constrain second electron motion to the vicinity of the target.
  • the magnets are configured in such a way that one pole is positioned at the central axis of the target and the second pole is formed by a ring of magnets around the outer edge of the target. Trapping the electrons in this way substantially increases the probability of an ionizing electron-atom collision occurring.
  • the increased ionization efficiency of a magnetron results in a dense plasma in the target region. This in turn leads to increased ion bombardment of the target, giving higher sputtering rates and therefore, higher deposition rates at the substrate .
  • the carbon layer was deposited using the filtered arc deposition process, as illustrated by Fig. 5.
  • a good adhesion was achieved as a result of the intermixed reaction zone, low-processing temperatures were allowed for the coating of heat-sensitive substrates/components, and multilayered coatings and functionally graded ⁇ compositions could be easily produced.
  • Sample A made from the process described in Example 1 was investigated in this example using the Vickers hardness test.
  • Sample A is of size 100mm x 100 mm x 5 mm.
  • the substrate material is chemically strengthened low iron float glass.
  • the Vickers tests were performed as per ASTM-E- 384 whereby a Vicker diamond pyramid indenter of 136° was used. The duration of dwell was controlled at 15 sec without any lubrication. All the tests were conducted at ambient temperature.
  • the hardness of raw (uncoated) glass was also determined for comparison purposes .
  • Fig 2. and Table 1 below show the hardness of Sample A and raw glass for the various loads that were used.
  • the coated glass demonstrated greater hardness than raw glass using loads of 50 gf, 100 gf, 200 gf, 300 gf and 500 gf. It is particularly noteworthy that a superior hardness over raw glass was observed at 50 gf .
  • Table 1 Hardness of Sample A versus Uncoated glass
  • Pin on disc was used to determine the friction of coefficient in this example.
  • An inclined plane and a 1 lb weight slider were used. The test was done on 3 areas with 2 runs each, and the average reading was taken.
  • the friction of coefficient of Sample A was compared with the friction of coefficient of uncoated (raw) glass and conventional anti- reflection (AR) coating, as shown in Table 2 below.
  • AR anti- reflection
  • Sample A' which has the same composition as Sample A, was used to determine the scratch resistance of a coated substrate made from the claimed method.
  • the scratch resistance of Sample A' was tested against that of raw glass and conventional AR coating, as shown in Table 3 below. The test was carried out using a load of 0.5kgf at 1 stroke/second (to and fro), with a travelling distance of 70 mm, using a Stainless Steel Stylus with a 3mm diameter rounded tip. It was observed that Sample A' was able to withstand more than 1000 strokes, thereby demonstrating superior scratch resistance. Table 3. Testing of Scratch resistance
  • Samples A to E were of the same composition but produced over 4 coating batches.
  • the optical transmission of Samples A to E was tested using unpolarized light having a wavelength of 600 nm to 800 nm, as illustrated in Fig. 3. It is particularly noteworthy that all the samples demonstrated a high transmission of more than 84.5%.
  • Example 6 Wear Resistance of ⁇ Coated Substrate
  • the wear resistance of the coated substrate was tested under a variety of conditions, as presented in Table 4.
  • the coated glass demonstrated resistance to a variety of chemicals including acids and bases, for prolonged periods of time.
  • no staining, no delamination or any sign of corrosion was observed.
  • the coating demonstrated good adhesion to the substrate, high hardness and good wear resistance.
  • the coated glass exhibited excellent tolerance to changes in temperatures and could perform successfully in atmospheres of 50-95% relative humidity. Comparative Example 1
  • the properties of the coating made using PVD was compared with a DLC coating made using CVD, as illustrated in Table 5 below.
  • the term “ , DLC” or “a-C:H” refers to the hydrogenated form of carbon which contains more than 20 at.% hydrogen and has a sp 3 fraction smaller than 50%. It is particularly noteworthy that the claimed coating exhibited a higher transmission, greater hardness and lower wearing rate.
  • Table 5 Comparison of a coating made using PVD versus CVD
  • the disclosed coating may be used for medical implants, surgical instruments and tools for production of pharmaceutical products .
  • the coating can be advantageously applied to many industries.
  • glass products include eyeglass and sunglass lenses, architectural glass, analytical instrument windows, automotive windshields and laser bar code scanner, which are used in supermarkets and departmental stores.
  • the coating can be applied to the electronics industry and employed in radios, televisions, computers, laptops, notepads and the like.

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Abstract

La présente invention concerne un revêtement sensiblement transparent destiné à revêtir un substrat sensiblement transparent. Le revêtement sensiblement transparent comprend une couche de réduction de contrainte, intermédiaire entre le substrat et une couche de carbone, la couche de carbone étant constituée d'atomes de carbone tétraédriques qui sont sensiblement exempts d'atomes d'hydrogène. La présente invention concerne en outre un procédé de formation d'un revêtement sensiblement transparent destiné à revêtir un substrat sensiblement transparent. Le procédé comprend l'étape de dépôt d'une couche de carbone sur un substrat ayant une couche de réduction de contrainte en son sein, la couche de carbone comprenant des atomes de carbone tétraédriques qui sont sensiblement exempts d'atomes d'hydrogène.
PCT/SG2016/050192 2015-04-24 2016-04-25 Revêtement sensiblement transparent Ceased WO2016171627A1 (fr)

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US20210063609A1 (en) * 2017-08-31 2021-03-04 Corning Incorporated Hybrid gradient-interference hardcoatings
CN112992425A (zh) * 2021-02-24 2021-06-18 烟台万隆真空冶金股份有限公司 一种梯度结构铜基复合电接触材料的制备方法
CN115231832A (zh) * 2022-07-18 2022-10-25 河南镀邦光电股份有限公司 超薄、高透类金刚石涂层及其镀制方法
US11520082B2 (en) 2017-08-31 2022-12-06 Corning Incorporated Hybrid gradient-interference hardcoatings
WO2023275493A1 (fr) 2021-06-30 2023-01-05 Saint-Gobain Glass France Substrat revêtu d'au moins une couche de carbone de type diamant protégée par une couche temporaire à base de germanium ou à base d'oxyde de germanium
DE202023103844U1 (de) 2023-07-11 2023-08-01 Saint-Gobain Glass France Beheizbare Verbundscheibe
WO2023161080A1 (fr) 2022-02-23 2023-08-31 Saint-Gobain Glass France Procédé pour la production d'un substrat traité thermiquement pourvu d'un revêtement de type diamant
WO2023198554A1 (fr) 2022-04-11 2023-10-19 Saint-Gobain Glass France Vitrage ayant une fenêtre de communication pour capteurs et systèmes de caméra
WO2024008565A1 (fr) 2022-07-04 2024-01-11 Saint-Gobain Glass France Vitre feuilletée pour système de projection

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CN112992425B (zh) * 2021-02-24 2022-08-30 烟台万隆真空冶金股份有限公司 一种梯度结构铜基复合电接触材料的制备方法
WO2023275493A1 (fr) 2021-06-30 2023-01-05 Saint-Gobain Glass France Substrat revêtu d'au moins une couche de carbone de type diamant protégée par une couche temporaire à base de germanium ou à base d'oxyde de germanium
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WO2023161080A1 (fr) 2022-02-23 2023-08-31 Saint-Gobain Glass France Procédé pour la production d'un substrat traité thermiquement pourvu d'un revêtement de type diamant
WO2023198554A1 (fr) 2022-04-11 2023-10-19 Saint-Gobain Glass France Vitrage ayant une fenêtre de communication pour capteurs et systèmes de caméra
WO2024008565A1 (fr) 2022-07-04 2024-01-11 Saint-Gobain Glass France Vitre feuilletée pour système de projection
CN115231832A (zh) * 2022-07-18 2022-10-25 河南镀邦光电股份有限公司 超薄、高透类金刚石涂层及其镀制方法
DE202023103844U1 (de) 2023-07-11 2023-08-01 Saint-Gobain Glass France Beheizbare Verbundscheibe

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