WO2020077705A1 - 调控硬质涂层颜色的方法、硬质涂层及其制备方法 - Google Patents

调控硬质涂层颜色的方法、硬质涂层及其制备方法 Download PDF

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WO2020077705A1
WO2020077705A1 PCT/CN2018/114470 CN2018114470W WO2020077705A1 WO 2020077705 A1 WO2020077705 A1 WO 2020077705A1 CN 2018114470 W CN2018114470 W CN 2018114470W WO 2020077705 A1 WO2020077705 A1 WO 2020077705A1
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hard coating
layer
amorphous
metal oxide
color
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French (fr)
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陈娜
张盈祺
郑凯鸣
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Tsinghua University
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Tsinghua University
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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
    • C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
    • 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
    • C23C14/0021—Reactive sputtering or evaporation
    • 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
    • C23C14/08—Oxides
    • 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
    • C23C14/08—Oxides
    • C23C14/085—Oxides of iron group metals
    • 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
    • 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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron 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
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/542—Controlling the film thickness or evaporation rate

Definitions

  • the present application relates to the field of coatings, in particular to methods for regulating the color of hard coatings, hard coatings and methods for their preparation.
  • the coating is widely used in various fields, and can improve the surface quality of the base material and increase the appearance of the appearance. It has very important application prospects in industries including mobile phones, computers and other IT fields, micro-nano optoelectronic devices, automobiles, medical devices, oil and gas pipelines, power generation, oil drilling, pharmaceutical, chemical and coal industries.
  • existing coating materials are generally only capable of producing single color coatings.
  • a method for regulating the color of hard coating includes the following steps:
  • the band gap of the amorphous metal oxide layer ranges from 2eV to 5eV, and the color of the hard coating layer can change in the visible wavelength range with the thickness of the amorphous metal oxide layer;
  • the amorphous metal oxide layer with a predetermined color is obtained by controlling the thickness of the amorphous metal oxide layer.
  • the amorphous metal oxide layer has a band gap ranging from 2.2 eV to 4.5 eV.
  • the amorphous alloy layer and the amorphous metal oxide layer contain the same kind of elements other than oxygen.
  • the elements of the amorphous alloy layer include cobalt, iron, tantalum, and boron; the elements of the amorphous metal oxide layer include cobalt, iron, tantalum, boron, and oxygen.
  • the composition of the amorphous metal oxide layer is (Co, Fe, Ta, B) 1-x O x , where 0.46 ⁇ x ⁇ 1.
  • it further includes providing a substrate and an adhesive layer provided on the substrate, the amorphous alloy layer is formed on the adhesive layer, and is bonded to the substrate through the adhesive layer.
  • the bonding layer is a two-phase composite nano-amorphous mixture layer
  • the two-phase composite nano-amorphous mixture layer includes the same type of amorphous alloy as the amorphous alloy layer and the The amorphous metal oxide having the same kind of elements as the amorphous metal oxide layer.
  • the composition of the two-phase composite nano-amorphous mixture layer is (Co, Fe, Ta, B) 1-y O y , where 0.1 ⁇ y ⁇ 0.46.
  • the composition of the mixture is (Co, Fe, Ta, B) 1-y O y , where 0.2 ⁇ y ⁇ 0.4.
  • the thickness of the amorphous alloy layer is greater than 20 nm and less than 10 ⁇ m.
  • the thickness of the amorphous metal oxide changes the color of the hard coating layer in the visible light wavelength range from 50 nm to 300 nm.
  • the amorphous metal oxide layers having different thicknesses are formed in different regions of the amorphous alloy layer to obtain the hard coating layers having different colors in different regions.
  • the amorphous metal oxide layer with a continuously varying thickness is formed on the amorphous alloy layer to obtain a color hard coating with a gradual color change.
  • a color-variable hard coating a hard coating characterized by comprising an amorphous alloy layer and an amorphous metal oxide layer with a band gap ranging from 2eV to 5eV, the amorphous metal oxide layer Laminating on the amorphous alloy layer and forming the hard coating layer together with the amorphous alloy layer, the color of the hard coating layer can be adjusted by any of the above methods for adjusting the color of the hard coating layer Regulation and determination.
  • the surface roughness of the hard coating is less than 0.2 nanometers.
  • a method for preparing a variable-color hard coating includes the following steps:
  • Inert gas is introduced into the chamber to make the interior of the chamber in an inert atmosphere free of oxygen, in which the alloy target is vaporized and an amorphous alloy layer is formed on the substrate ;
  • the color of the hard coating can vary with the thickness of the amorphous metal oxide layer The change varies in the visible wavelength range.
  • the alloy target includes iron, cobalt, tantalum, and boron.
  • the composition of the alloy target is (Co, Fe) a Ta b B c , where a, b, and c are all atomic percentages, 35 ⁇ a ⁇ 80, 0 ⁇ b ⁇ 25, 15 ⁇ c ⁇ 25.
  • the partial pressure ratio of the first oxygen to the inert gas is 0.01 to 0.1.
  • the adhesive layer is formed on the substrate.
  • the adhesive layer is a two-phase composite nano-amorphous mixture layer containing an amorphous alloy and an amorphous metal oxide.
  • the method before introducing the inert gas into the chamber, the method further includes pre-evacuating the chamber so that the degree of vacuum in the chamber is lower than 10 -3 Pa.
  • the method for adjusting the color of the hard coating layer can be obtained by stacking an amorphous alloy layer and an amorphous metal oxide layer with a band gap ranging from 2eV to 5eV, and adjusting the thickness of the amorphous metal oxide layer.
  • the hard coating of color, the color change range of the hard coating is all visible light range.
  • the method for controlling the color of the hard coating is simple and easy to implement, and the color of the hard coating has a wide range of changes.
  • the color of the hard coating layer can be determined by adjusting and controlling the color of the hard coating layer.
  • a predetermined hard coating layer can be obtained by forming an amorphous alloy layer and an amorphous metal oxide layer in the band gap range, and controlling the thickness of the formed amorphous oxide layer Color, simple operation, low process cost, easy to achieve large-scale production of hard coating.
  • Example 1A is an XRD spectrum of the hard-coated amorphous alloy layer obtained in Example 1 of the present application;
  • Example 1B is an XRD spectrum of the hard-coated amorphous metal oxide obtained in Example 1 of the present application;
  • FIG. 1C is an XRD spectrum of the adhesive layer of the hard coating obtained in Example 1 of the present application.
  • Example 2 is a photograph of a hard coating obtained in Example 1 of this application;
  • Example 3 is a photograph of a hard coating obtained in Example 2 of this application.
  • Example 4 is a photograph of a hard coating obtained in Example 3 of this application.
  • Example 5 is a photograph of a hard coating obtained in Example 4 of this application.
  • Example 6 is a reflection spectrum diagram of the hard coating layer obtained in Example 3 of the present application in different color regions.
  • the embodiments of the present application provide a method for regulating the color of a hard coating, including the following steps:
  • the band gap of the amorphous metal oxide layer ranges from 2eV to 5eV, and the color of the hard coating layer can change in the visible wavelength range with the thickness of the amorphous metal oxide layer;
  • the amorphous metal oxide layer with a predetermined color is obtained by controlling the thickness of the amorphous metal oxide layer.
  • the method for adjusting the color of the hard coating layer can be obtained by stacking an amorphous alloy layer and an amorphous metal oxide layer with a band gap ranging from 2eV to 5eV, and adjusting the thickness of the amorphous metal oxide layer.
  • the hard coating of color, the color change range of the hard coating is all visible light range. The operation process is simple and easy to implement, and the color of the hard coating has a wide range of changes.
  • the method for adjusting the color of the hard coating layer may be to form amorphous metal oxides with different thicknesses on different regions of the amorphous alloy layer on the same substrate, or to form different thicknesses on different substrates ( A certain thickness) of amorphous metal oxide. That is, the method may be used to form a hard coating of multiple colors or a single color. For example, an amorphous metal oxide layer with a continuously varying thickness can be formed on the amorphous alloy layer to obtain a hard coating with a gradation of color; for another example, it can be on two different amorphous alloy layers, or the amorphous alloy layer In different areas, two hard coatings with a certain thickness but different thicknesses are formed to obtain hard coatings with different colors.
  • the amorphous alloy layer is a light reflection layer, and the material of the amorphous alloy layer is not limited, and it can have a high light reflectance.
  • the material of the amorphous alloy layer may include at least one of metals such as iron, cobalt, tantalum, platinum, gold, silver, or copper and / or boron.
  • the amorphous alloy layer includes iron, cobalt, tantalum and boron.
  • the thickness of the amorphous alloy layer can ensure that the amorphous alloy layer has a high reflectance. When the thickness is too low, it will have a certain transparency to light, so preferably, the amorphous alloy layer The thickness is greater than 20nm. At this thickness, the amorphous alloy layer has high hardness and high wear resistance.
  • the thickness of the amorphous alloy layer can also be adjusted to the micron level according to the actual needs of actual products, so that the amorphous alloy layer has better hardness and wear resistance, preferably, the thickness of the amorphous alloy layer Less than 10 ⁇ m.
  • the band gap of the amorphous metal oxide layer preferably ranges from 2.2 eV to 4.5 eV.
  • the metal element contained in the amorphous metal oxide layer is the same as the metal element contained in the amorphous alloy layer (the metal elements mentioned herein include metalloid elements and metalloid elements).
  • the amorphous alloy layer and the amorphous metal oxide layer can be obtained from the same target material, omitting the step of replacing the target material, and improving the color-variable hard material The production efficiency of the coating, and avoids the possibility of polluting the surface of the amorphous alloy layer and affecting the quality of the overall hard coating during the replacement of the target material, and improves the quality of the hard coating.
  • the thickness of the amorphous metal oxide changes the color of the hard coating layer in the visible light wavelength range from 50 nm to 300 nm. Within this range, the color of the hard coating can be changed in the entire visible range. And the change of its color can be continuously adjusted according to the change of thickness.
  • the amorphous alloy layer may include cobalt, iron, tantalum, and boron; the elements of the amorphous metal oxide layer include cobalt, iron, tantalum, boron, and oxygen.
  • the variable color hard coating composed of an amorphous alloy layer and an amorphous metal oxide layer composed of these elements in addition to having good color adjustability, also has excellent high hardness, high wear resistance and high corrosion resistance .
  • the surface of the hard coating layer can reach an atomic level of smoothness, and the roughness of the surface of the hard coating layer can be less than 0.2 nm.
  • it further includes providing a substrate and an adhesive layer provided on the substrate, the amorphous alloy layer is formed on the adhesive layer, and is bonded to the substrate through the adhesive layer.
  • the material of the bonding layer is not limited, and it is sufficient for the amorphous alloy layer to form a good bond with the substrate.
  • the bonding layer is a two-phase composite nano-amorphous mixture layer
  • the two-phase composite nano-amorphous mixture layer includes an amorphous alloy with the same kind of elements as the amorphous alloy layer and the amorphous metal Nanometer two-phase composite material of amorphous metal oxide with the same kind of oxide layer elements.
  • the composition of the bonding layer may be that the composition of the mixture layer is (Co, Fe, Ta, B) 1-y O y , where 0.1 ⁇ y ⁇ 0.46, in this case, the bonding The layer is a two-phase composite nano-amorphous mixture layer.
  • the two-phase composite nano-amorphous mixture layer includes two phases of an amorphous alloy and an amorphous metal oxide, which improves the adhesion between the substrate and the amorphous alloy layer.
  • the amorphous alloy layer, the amorphous metal oxide layer, and the adhesive layer can be obtained from the same target material, omitting the step of replacing the target material, and improving the color variability
  • the production efficiency of the hard coating and avoids the possibility of polluting the surface of the bonding layer and the surface of the amorphous alloy layer during the replacement of the target material, affecting the overall quality of the hard coating, and improving the quality of the hard coating .
  • the composition of the mixture is (Co, Fe, Ta, B) 1-y O y , where 0.2 ⁇ y ⁇ 0.4.
  • the thickness of the bonding layer is not limited in this application, and can be adjusted according to the actual needs of the product, so as to achieve a good bond between the substrate and the amorphous alloy layer.
  • An embodiment of the present application further provides a hard coating, including an amorphous alloy layer and an amorphous metal oxide layer with a band gap ranging from 2eV to 5eV, the amorphous metal oxide layer is stacked on the amorphous alloy Layer together with the amorphous alloy layer to form the hard coating, the color of the hard coating is prepared by the above method for adjusting the color of the hard coating and adjusted to obtain a predetermined color.
  • the hard coating layer can be obtained by stacking an amorphous alloy layer and an amorphous metal oxide layer with a band gap ranging from 2eV to 5eV, and adjusting the thickness of the amorphous metal oxide layer to obtain hard metals of different colors
  • the color change range of the hard coating is the entire visible light range. The operation process is simple and easy to implement, and the color of the hard coating has a wide range of changes.
  • the color of the hard coating under different viewing angles also shows a certain difference, becoming a variable color hard coating with excellent visual appearance.
  • the embodiments of the present application also provide a method for preparing a hard coating
  • Inert gas is introduced into the chamber to make the interior of the chamber in an inert atmosphere free of oxygen, in which the alloy target is vaporized and an amorphous alloy layer is formed on the substrate ;
  • the color of the hard coating can vary with the thickness of the amorphous metal oxide layer The change varies in the visible wavelength range.
  • the color of the hard coating can be changed by controlling the thickness of the amorphous oxide layer formed, and the same alloy target is used in the preparation process, avoiding the step of replacing the target , Improve the production efficiency, and avoid the possibility of polluting the surface of the bonding layer and the surface of the amorphous alloy layer during the replacement of the target material and affecting the quality of the overall hard coating, improving the quality of the hard coating, operation It is simple and convenient for mass production of hard coatings.
  • this method can complete the preparation of hard coatings of multiple colors only through the same process equipment and the same alloy target material as raw materials, which is economical and practical, and greatly reduces production costs.
  • the alloy target includes iron, cobalt, tantalum, and boron.
  • the variable color hard coating prepared by the alloy target has the advantages of high hardness, high wear resistance and good corrosion resistance, and the energy band gap of the prepared amorphous metal oxide layer is 2eV Between 5eV, the color of the hard coating is adjustable.
  • the component of the alloy target may be the component of the alloy target (Co, Fe) a Ta b B c , where a, b and c are all atomic percentages, 35 ⁇ a ⁇ 80, 0 ⁇ b ⁇ 25, 15 ⁇ c ⁇ 25.
  • the ratio between the elements in the obtained amorphous metal oxide layer can be adjusted.
  • the partial pressure ratio of the first oxygen to the inert gas is 0.04 to 0.1, and more preferably, 0.05 to 0.08.
  • the partial pressure of the first oxygen the oxidation of the amorphous metal can be adjusted The composition of the material layer.
  • the method for preparing the color-variable hard coating layer further includes passing a second oxygen gas into the chamber before forming the amorphous alloy layer, the second oxygen gas and the alloy target After the gasification of the target material atoms react and form a bonding layer on the substrate, the bonding layer is a two-phase composite nano-amorphous mixture layer containing an amorphous alloy and an amorphous metal oxide.
  • the second oxygen gas may be simultaneously introduced with the inert gas, or both may be separately introduced into the chamber.
  • the atmosphere in the chamber is Mixing of inert gas and oxygen.
  • the partial pressure ratio of the second oxygen to the inert gas is less than or equal to 0.04.
  • the composition of the amorphous metal oxide in the bonding layer can be adjusted.
  • the second oxygen and the first oxygen come from the same oxygen source, the only difference is that the partial pressure formed in the chamber is different.
  • the oxygen supply after the formation of the adhesive layer, the oxygen supply must be suspended, and the inert gas should be continuously evacuated or evacuated for a period of time to completely exhaust the oxygen in the chamber, so that the target material can be
  • the amorphous alloy layer is formed in an inert atmosphere containing oxygen.
  • the thickness of each layer in the hard coating layer, especially the thickness of the amorphous metal oxide layer can be controlled by changing the deposition time of the vaporized target on the substrate or changing the angle of the substrate .
  • the position of the substrate can be moved so that the deposition time of the target component on each area of the substrate is different to obtain layers with different thicknesses; for example, the angle of the substrate can be rotated during the deposition of the target to make the target
  • the uniformity of the thickness of the components formed on the various regions on the substrate is not uniform, thereby obtaining layers with different thicknesses.
  • the substrate may be fixed, a hard coating layer of amorphous metal oxide having a first thickness is formed in the first region of the substrate, and an amorphous metal oxide having a second thickness is formed in the second region of the substrate Hard coating with different color areas; similarly, a hard coating with multiple color areas can also be prepared.
  • a hard coating with multiple color areas can also be prepared.
  • the inert gas may continuously pass into the chamber during the formation of the bonding layer, amorphous alloy layer, and amorphous metal oxide layer.
  • the color-variable hard coating Before the method of preparing the inert gas is initially introduced into the chamber, the method may further include pre-evacuating the chamber.
  • the degree of vacuum in the chamber is lower than 10 -3 Pa; more preferably, lower than 10 -4 Pa.
  • the substrate is preferably a metal, polymer, glass, ceramic, or other material.
  • the inert gas is argon, and more preferably, the purity of the argon is 99.999 wt%.
  • the method for preparing the variable color hard coating may be physical vapor deposition, such as magnetron sputtering, evaporation, pulsed laser deposition, molecular beam epitaxy, etc .; chemical vapor deposition, such as laser enhanced chemical vapor deposition, Plasma enhanced chemical vapor deposition, metal organic chemical vapor deposition, etc .; or thermal spraying, etc.
  • physical vapor deposition such as magnetron sputtering, evaporation, pulsed laser deposition, molecular beam epitaxy, etc .
  • chemical vapor deposition such as laser enhanced chemical vapor deposition, Plasma enhanced chemical vapor deposition, metal organic chemical vapor deposition, etc .
  • thermal spraying etc.
  • composition and other characteristics of the color-variable hard coating obtained by the above-mentioned method for preparing the color-variable hard coating and the corresponding technical effects There are records in the layers, so I won't repeat them one by one here.
  • a white Al 2 O 3 ceramic substrate was placed in the chamber of the magnetron sputtering equipment; pre-evacuated to below 10 -4 Pa, and Argon and oxygen, adjust the partial pressure ratio of oxygen and argon to 0.03, and get a bonding layer by sputtering, whose composition is Co 25.2 Fe 8.3 Ta 6.4 B 19.5 O 40.6 , and its structure includes amorphous alloy and amorphous Phase metal oxide two-phase nanocomposite structure. Close the oxygen inlet valve and sputter under argon atmosphere to obtain a single-phase CoFeTaB amorphous alloy layer with a thickness greater than 20 nanometers.
  • composition is Co 55 Fe 24.5 Ta 0.1 B 20.4 ;
  • a single-phase amorphous metal oxide layer with a thickness of 120 nanometers was obtained by sputtering in a mixed atmosphere with a partial pressure ratio of gas and oxygen of 0.06, and its composition was Co 19.1 Fe 7.8 Ta 7.6 B 18.6 O 46.9 .
  • each layer in the hard coating layer obtained in this embodiment is amorphous. It can be seen from FIG. 2 that the hard coating is local gold.
  • Example 2 The preparation method of Example 2 is substantially the same as that of Example 1, except that the substrate is a black ceramic substrate and the amorphous metal oxide layer is 180 nm.
  • Example 2 The XRD and atomic force microscope results of the sample prepared in Example 2 are similar to the sample obtained in Example 1, and therefore will not be repeated.
  • FIG. 3A when the sample is viewed from the front, the hard coating is blue, and in conjunction with FIG. 3B, it can be seen that when the sample is viewed from the side, the hard coating is purple. Therefore, the hard coating obtained in this example has different colors when viewed from different angles.
  • Example 3 The preparation method of Example 3 is substantially the same as that of Example 1, except that the substrate is quartz glass, and the thickness of each region on the substrate varies continuously from 50 nm to 300 nm.
  • Example 3 provides a method for preparing a color hard coating, which makes the thickness of the amorphous metal oxide on the amorphous alloy layer continuously change, so that the hard coating exhibits different colors, and the hard coating
  • the color of the layer is a color gradient (as shown in Figure 4).
  • the XRD and atomic force microscope results of the sample prepared in Example 3 are similar to the sample obtained in Example 1, and therefore will not be repeated. It can be seen from FIG. 6 that different regions of the sample reflect light waves of different wavelengths, that is, the reflectivity of light of different colors is different.
  • Example 4 The preparation method of Example 4 is substantially the same as that of Example 3, except that the shape of the hard coating is the shape of the second school gate of Tsinghua University.
  • Example 4 The XRD, reflection spectrum and atomic force microscope results of the sample prepared in Example 4 are similar to the sample obtained in Example 3, so they are not repeated. It can be seen from FIG. 5 that the hard coating is an opaque hard coating, which can cover the text on the paper sample under the glass substrate.

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Abstract

调控硬质涂层颜色的方法，包括以下步骤：提供非晶合金层；在非晶合金层表面形成非晶金属氧化物层，使非晶金属氧化物层层叠设置于非晶合金层并与非晶合金层共同形成硬质涂层，非晶金属氧化物层的带隙范围为2eV至5eV，硬质涂层的颜色能够随非晶金属氧化物层的厚度的变化在可见光波长范围内变化；以及在形成非晶金属氧化物层的过程中通过控制非晶金属氧化物层的厚度得到预定颜色的非晶金属氧化物层。还公开了硬质涂层及其制备方法。

Description

调控硬质涂层颜色的方法、硬质涂层及其制备方法
相关申请
本申请要求2018年10月19日申请的，申请号为201811222261.2，名称为“调控硬质涂层颜色的方法、硬质涂层及其制备方法”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本申请涉及涂层领域，特别是调控硬质涂层颜色的方法、硬质涂层及其制备方法。
背景技术
涂层广泛地应用在各个领域，可以改善基体材料的表面质量、增加外观的美观度等。在包括手机、电脑等IT领域、微纳光电器件、汽车、医疗器械、油气管道、发电、石油钻探、医药化工及煤炭等行业具有非常重要的应用前景。然而，现有的涂层材料通常仅能制备单一颜色的涂层。
发明内容
基于此，有必要提供一种调控硬质涂层颜色的方法、硬质涂层及其制备方法。
一种调控硬质涂层颜色的方法，包括以下步骤：
提供非晶合金层；
在所述非晶合金层表面形成非晶金属氧化物层，使所述非晶金属氧化物层层叠设置于所述非晶合金层并与所述非晶合金层共同形成所述硬质涂层，所述非晶金属氧化物层的带隙范围为2eV至5eV，所述硬质涂层的颜色能够随所述非晶金属氧化物层的厚度的变化在可见光波长范围内变化；
在形成所述非晶金属氧化物层的过程中通过控制所述非晶金属氧化物层的厚度得到预定颜色的所述非晶金属氧化物层。
在其中一个实施例中，所述非晶金属氧化物层的带隙范围为2.2eV至4.5eV。
在其中一个实施例中，所述非晶合金层与所述非晶金属氧化物层中包含的除氧以外的元素的种类相同。
在其中一个实施例中，所述非晶合金层的元素包括钴、铁、钽和硼；所述非晶金属氧 化物层的元素包括钴、铁、钽、硼和氧。
在其中一个实施例中，所述非晶金属氧化物层的组成为(Co,Fe,Ta,B) 1-xO x，其中0.46＜x＜1。
在其中一个实施例中，还包括提供基底及设置在所述基底上的粘结层，所述非晶合金层形成在所述粘结层上，通过所述粘结层与所述基底结合。
在其中一个实施例中，所述粘结层为双相复合纳米非晶混合物层，所述双相复合纳米非晶混合物层包括与所述非晶合金层元素种类相同的非晶合金和与所述非晶金属氧化物层元素种类相同的非晶金属氧化物。
在其中一个实施例中，所述双相复合纳米非晶混合物层的组成为(Co,Fe,Ta,B) 1-yO y，其中0.1＜y＜0.46。
在其中一个实施例中，所述混合物的组成为(Co,Fe,Ta,B) 1-yO y，其中0.2＜y＜0.4。
在其中一个实施例中，所述非晶合金层的厚度大于20nm且小于10μm。
在其中一个实施例中，所述非晶金属氧化物使所述硬质涂层的颜色在可见光波长范围内变化的厚度范围为50纳米至300纳米。
在其中一个实施例中，在所述非晶合金层的不同区域形成具有不同厚度的所述非晶金属氧化物层得到不同区域具有不同颜色的所述硬质涂层。
在其中一个实施例中，在所述非晶合金层上形成厚度连续变化的所述非晶金属氧化物层得到颜色渐变的彩色硬质涂层。
一种颜色可变硬质涂层，一种硬质涂层，其特征在于，包括非晶合金层和带隙范围为2eV至5eV的非晶金属氧化物层，所述非晶金属氧化物层层叠设置于所述非晶合金层并与所述非晶合金层共同形成所述硬质涂层，所述硬质涂层的颜色通过上述任一所述的调控硬质涂层颜色的方法的调控而确定。
在其中一个实施例中，所述硬质涂层的表面粗糙度小于0.2纳米。
一种颜色可变硬质涂层的制备方法，包括以下步骤：
将合金靶材和基底置于密闭的腔室；
向腔室内通入惰性气体使所述腔室内部为不含氧的惰性气氛，在所述不含氧的惰性气氛中使所述合金靶材气化并在所述基底上形成非晶合金层；
向所述腔室内通入第一氧气，使所述第一氧气与所述合金靶材气化后的靶材原子反应，在所述非晶合金层上形成带隙范围为2eV至5eV非晶金属氧化物层，所述非晶金属氧化物层与所述非晶合金层共同形成所述硬质涂层，所述硬质涂层的颜色能够随所述非晶金属氧化物层的厚度的变化在可见光波长范围内变化。
在其中一个实施例中，所述合金靶材包括铁、钴、钽及硼。
在其中一个实施例中，所述合金靶材的组分为(Co,Fe) aTa bB c，其中a、b和c均为原子百分数，35≤a≤80，0＜b≤25，15≤c≤25。
在其中一个实施例中，所述第一氧气与所述惰性气体的分压比为0.01至0.1。
在其中一个实施例中，还包括，在形成所述非晶合金层之前，向所述腔室内通入第二氧气，所述第二氧气与所述合金靶材气化后的靶材原子反应并在所述基底上形成粘结层，所述粘结层为含有非晶合金与非晶金属氧化物的双相复合纳米非晶混合物层。
在其中一个实施例中，在向所述腔室内通入惰性气体之前，还包括对所述腔室预抽真空，使所述腔室内的真空度低于10 -3Pa。
所述调控硬质涂层颜色的方法通过叠置非晶合金层与带隙范围为2eV至5eV的非晶金属氧化物层，并调控所述非晶金属氧化物层的厚度，即可得到不同颜色的硬质涂层，所述硬质涂层的颜色变化范围为全部可见光范围。所述调控硬质涂层颜色的方法简单，易于实现，且硬质涂层的颜色的变化范围广。所述硬质涂层的颜色可以通过前述调控硬质涂层颜色的方法调控而确定。所述硬质涂层的制备方法，通过形成非晶合金层和所述带隙范围的非晶金属氧化物层，并控制形成的非晶氧化物层的厚度即可得到预定的硬质涂层颜色，操作简便，工艺成本低，便于实现硬质涂层的大规模生产。
附图说明
图1A为本申请实施例1得到的硬质涂层的非晶合金层的XRD谱图；
图1B为本申请实施例1得到的硬质涂层的非晶金属氧化物的XRD谱图；
图1C为本申请实施例1得到的硬质涂层的粘结层的XRD谱图；
图2为本申请实施例1得到硬质涂层的照片；
图3为本申请实施例2得到硬质涂层的照片；
图4为本申请实施例3得到硬质涂层的照片；
图5为本申请实施例4得到硬质涂层的照片；
图6为本申请实施例3得到的硬质涂层在不同颜色区域的反射光谱图。
具体实施方式
为了使本申请的目的、技术方案及优点更加清楚明白，以下通过实施例，并结合附图，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。
本申请实施例提供调控硬质涂层颜色的方法，包括以下步骤：
提供非晶合金层；
在所述非晶合金层表面形成非晶金属氧化物层，使所述非晶金属氧化物层层叠设置于所述非晶合金层并与所述非晶合金层共同形成所述硬质涂层，所述非晶金属氧化物层的带隙范围为2eV至5eV，所述硬质涂层的颜色能够随所述非晶金属氧化物层的厚度的变化在可见光波长范围内变化；
在形成所述非晶金属氧化物层的过程中通过控制所述非晶金属氧化物层的厚度得到预定颜色的所述非晶金属氧化物层。
所述调控硬质涂层颜色的方法通过叠置非晶合金层与带隙范围为2eV至5eV的非晶金属氧化物层，并调控所述非晶金属氧化物层的厚度，即可得到不同颜色的硬质涂层，所述硬质涂层的颜色变化范围为全部可见光范围。操作过程简单，易于实现，且硬质涂层的颜色的变化范围广。
所述调节硬质涂层颜色的方法，可以是在同一基底上的非晶合金层的不同区域上形成不同厚度的非晶金属氧化物，也可以是在不同的基底上，形成具有不同厚度(厚度一定)的非晶金属氧化物。即所述方法可以是用于形成多种颜色的硬质涂层，也可以是用于形成单一颜色的硬质涂层。例如，可以在非晶合金层上形成厚度连续变化的非晶金属氧化物层得到颜色渐变的硬质涂层；又例如，可以在两个不同的非晶合金层上，或非晶合金层的不同区域内，形成厚度一定，但是厚度不同的两个硬质涂层，得到颜色不同的硬质涂层。
在上述调控硬质涂层颜色的方法中，所述非晶合金层为光反射层，所述非晶合金层的材料不做限制，能具有高的反光率即可。例如，可以包括铁、钴、钽、铂、金、银或铜等金属中的至少一种和/或硼元素。优选地，所述非晶合金层包括铁、钴、钽和硼。
所述非晶合金层的厚度能保证所述非晶合金层具有高反射率即可，当厚度过低时，会对光产生一定的透过性，所以优选地，所述非晶合金层的厚度大于20nm。在此厚度下，所述非晶合金层具有高硬度、高耐磨性。也可以根据实际产品的实际需要，调节所述非晶合金层的厚度到微米级别，使所述非晶合金层具备更优的硬度和耐磨性，优选地，所述非晶合金层的厚度小于10μm。
所述非晶金属氧化物层的带隙范围优选地为2.2eV至4.5eV。
优选地，所述非晶金属氧化物层中包含的金属元素与所述非晶合金层中包含的金属元素的种类相同(本文中提到的金属元素包括准金属元素及类金属元素)。以这样方式，在制备颜色可变硬质涂层的过程中，可以通过同一靶材得到非晶合金层和非晶金属氧化物层，省略了更换靶材的步骤，提高了颜色可变硬质涂层的生产效率，并且避免了更换靶材 的过程中，对非晶合金层表面产生污染影响整体硬质涂层质量的可能性，提高了硬质涂层的品质。
所述非晶金属氧化物使所述硬质涂层的颜色在可见光波长范围内变化的厚度范围为50纳米至300纳米。在这一范围内，硬质涂层的颜色可以在全部可见光范围内改变。且其颜色的变化可以根据厚度的变化连续可调。
具体地，所述非晶合金层可以包括钴、铁、钽和硼；所述非晶金属氧化物层的元素包括钴、铁、钽、硼和氧。由这些元素构成的非晶合金层和非晶金属氧化物层构成的颜色可变硬质涂层，除了具备良好的颜色可调性，还具备优异高硬度、高耐磨性和高耐腐蚀性。且所述硬质涂层的表面可以达到原子级别的光滑度，硬质涂层表面的粗糙度可低于0.2纳米。
在一些实施例中，还包括提供基底及设置在所述基底上的粘结层，所述非晶合金层形成在所述粘结层上，通过所述粘结层与所述基底结合。所述粘结层的材料不做限定，能使所述非晶合金层与基底形成良好的粘结即可。
优选地，所述粘结层为双相复合纳米非晶混合物层，所述双相复合纳米非晶混合物层包括与所述非晶合金层元素种类相同的非晶合金和与所述非晶金属氧化物层元素种类相同的非晶金属氧化物的纳米双相复合材料。例如，所述粘结层的组成可以为所述混合物层的组成成分为(Co,Fe,Ta,B) 1-yO y，其中0.1＜y＜0.46，这种情况下，所述粘结层为双相复合纳米非晶混合物层，所述双相复合纳米非晶混合物层包括非晶合金和非晶金属氧化物两相，提高了基底与非晶合金层的粘结性。并且，在制备颜色可变硬质涂层的过程中，可以通过同一靶材得到非晶合金层和非晶金属氧化物层及粘结层，省略了更换靶材的步骤，提高了颜色可变硬质涂层的生产效率，并且避免了更换靶材的过程中，对粘结层表面及非晶合金层表面产生污染影响整体硬质涂层质量的可能性，提高了硬质涂层的品质。更优选地，所述混合物的组成成分为(Co,Fe,Ta,B) 1-yO y，其中0.2＜y＜0.4。所述粘结层的厚度在本申请中不做限定，可根据产品的实际需要进行调节，能实现基底及非晶合金层形成良好的粘结即可。
本申请实施例还提供一种硬质涂层，包括非晶合金层和带隙范围为2eV至5eV的非晶金属氧化物层，所述非晶金属氧化物层层叠设置于所述非晶合金层并与所述非晶合金层共同形成所述硬质涂层，所述硬质涂层的颜色通过上述调控硬质涂层颜色的方法制备并调控得到预定颜色。
所述硬质涂层通过叠置非晶合金层与带隙范围为2eV至5eV的非晶金属氧化物层，并调控所述非晶金属氧化物层的厚度，即可得到不同颜色的硬质涂层，所述硬质涂层的颜色 变化范围为全部可见光范围。操作过程简单，易于实现，且硬质涂层的颜色的变化范围广。
由于非晶合金层的高反光率，当光线射入所述硬质涂层，并经过光路返回在观察者眼睛时，由于非晶合金层的反射光与非晶金属氧化物层的反射光的干涉作用，所述硬质涂层在不同的观察视角下呈现的颜色也呈现一定差别，成为一种颜色可变硬质涂层，具有优异的外观视觉效果。
本申请实施例还提供一种硬质涂层的制备方法，
包括以下步骤：
将合金靶材和基底置于密闭的腔室；
向腔室内通入惰性气体使所述腔室内部为不含氧的惰性气氛，在所述不含氧的惰性气氛中使所述合金靶材气化并在所述基底上形成非晶合金层；
向所述腔室内通入第一氧气，使所述第一氧气与所述合金靶材气化后的靶材原子反应，在所述非晶合金层上形成带隙范围为2eV至5eV非晶金属氧化物层，所述非晶金属氧化物层与所述非晶合金层共同形成所述硬质涂层，所述硬质涂层的颜色能够随所述非晶金属氧化物层的厚度的变化在可见光波长范围内变化。
所述硬质涂层的制备方法，通过控制形成的非晶氧化物层的厚度即可改变硬质涂层的颜色，并且在制备过程中使用相同的合金靶材，避免了更换靶材的步骤，提高了生产效率，并且避免了更换靶材的过程中，对粘结层表面及非晶合金层表面产生污染影响整体硬质涂层质量的可能性，提高了硬质涂层的品质，操作简便，便于实现硬质涂层的大规模生产。另外，该方法仅通过同一工艺设备和同一作为原料的合金靶材即可完成多种颜色的硬质涂层的制备，经济实用，大大降低生产成本。
在其中一个实施例中，所述合金靶材包括铁、钴、钽及硼。通过所述合金靶材制备出的颜色可变硬质涂层具有硬度高、耐磨性高、抗腐蚀性好等优点，且制备出的所述非晶金属氧化物层的能带间隙在2eV至5eV之间，硬质涂层的颜色可调性好。优选地，所述合金靶材的组分可以为所述合金靶材的组分为(Co,Fe) aTa bB c，其中a、b和c均为原子百分数，35≤a≤80，0＜b≤25，15≤c≤25。
进一步的，通过调节腔室内惰性气体与氧气的分压比，可调节得到的非晶金属氧化物层中元素之间的比例。优选地，所述第一氧气与所述惰性气体的分压比为0.04至0.1，更优选地，为0.05至0.08，通过调节所述第一氧气的分压，可以调节所述非晶金属氧化物层的组分。
在另外一个实施例中，所述颜色可变硬质涂层的制备方法还包括在形成非晶合金层之前，向所述腔室内通入第二氧气，所述第二氧气与所述合金靶材气化后的靶材原子反应并 在所述基底上形成粘结层，所述粘结层为含有非晶合金与非晶金属氧化物的双相复合纳米非晶混合物层。所述第二氧气可以与所述惰性气体同时通入，或者这两者可以单独地被通入到所述腔室内，在形成所述粘结层的过程中，所述腔室中的气氛为惰性气体与氧气的混合。优选地，所述第二氧气与所述惰性气体的分压比小于或等于0.04，通过调节第二氧气的分压力，可以调节粘结层中非晶金属氧化物的组分。优选地，所述第二氧气与所述第一氧气来自同一个氧气源，区别仅在于，在腔室内的形成的分压不同。
在这个实施例中，形成粘结层之后，需暂停通入氧气，通过抽真空或者持续通入一段时间的惰性气体，使腔室内的氧气完全排出，使所述靶材气化后能在不含氧的惰性气氛中形成非晶合金层。在一些实施例中，可以通过改变气化后的靶材在基底上的沉积时间或者改变基底的角度等方式，从而控制硬质涂层中各个层的厚度，尤其是非晶金属氧化物层的厚度。例如，可以通过移动基底的位置，使得靶材成分在基底上各个区域上沉积时间不同从而得到厚度不同的各个层；又例如，可以在靶材沉积的过程中，转动基底的角度，使得靶材成分在基底上各个区域的上形成的厚度的均匀性不一致，从而得到厚度不同的各个层。这些方法尤其适用于改变非晶金属氧化物层的厚度，从而可以得到彩色渐变硬质涂层。再例如，也可以将基底固定，在基底的第一区域在形成具有第一厚度的非晶金属氧化物的硬质涂层，并在基底的第二区域形成具有第二厚度的非晶金属氧化物的硬质涂层，从而得到具有两个不同颜色区域的硬质涂层；同理，也可以制备出具有多种颜色区域的硬质涂层。当在同一基底上的非晶合金层上的不同区域形成具有不同厚度的非晶金属氧化物的硬质涂层时，可以得到彩色的硬质涂层，使硬质涂层具有更好的视觉效果。
所述惰性气体可以在形成所述粘结层、非晶合金层和非晶金属氧化物层的过程中持续通入所述腔室，在一实施例中，所述颜色可变硬质涂层的制备方法，在最初向所述腔室内通入惰性气体之前，还可包括对所述腔室预抽真空。优选地，所述腔室内的真空度低于10 -3Pa；更优选地，低于10 -4Pa。
所述基底优选为金属、高分子、玻璃、陶瓷等材料。
优选地，所述惰性气体为氩气，更优选地，所述氩气的纯度为99.999wt％。
用于制备所述颜色可变硬质涂层的方法可以为物理气相沉积，例如磁控溅射、蒸镀、脉冲激光沉积、分子束外延生长等；化学气相沉积，例如激光增强化学气相沉积、等离子体增强化学气相沉积、金属有机化学气相沉积等；或热喷涂等。
通过上述制备颜色可变硬质涂层的方法得到的颜色可变硬质涂层的组成成分及其他特征以及相应的技术效果在前面的调控硬质涂层颜色的方法及颜色可变硬质涂层中均有记载，在此不再一一赘述。
实施例1——制备土豪金色硬质涂层
以组分为Co 45Fe 21Ta 10B 24合金靶材为原料，在磁控溅射设备的腔室中置入白色Al 2O 3陶瓷基底；预抽真空至10 -4Pa以下，通入氩气和氧气，调节氧气和氩气分压比例在0.03，溅射得到一层粘结层，其组成为Co 25.2Fe 8.3Ta 6.4B 19.5O 40.6，其结构为包括非晶态合金和非晶态金属氧化物的双相纳米复合结构。关闭氧气进气阀门，在氩气氛围下溅射得到厚度大于20纳米的单相CoFeTaB非晶合金层，其组成为Co 55Fe 24.5Ta 0.1B 20.4；随后再重新打开氧气进气阀门，在氩气和氧气分压比为0.06的混合气氛下溅射得到120纳米厚的单相非晶态金属氧化物层，其成分组成为Co 19.1Fe 7.8Ta 7.6B 18.6O 46.9。
通过图1A、图1B及图1C可以看出，本实施例得到的硬质涂层中的各个层均为非晶态。通过图2可以看出，所述硬质涂层为土豪金色。
实施例2——制备蓝色硬质涂层
实施例2的制备方法与实施例1大体相同，其区别仅在于，基底为黑色陶瓷基底，所述非晶金属氧化物层为180纳米。
实施例2制备的样品的XRD及原子力显微镜结果与实施例1得到的样品相近，因此不再重复示出。从图3A可以知道，当从正面观测样品时，硬质涂层呈蓝色，结合图3B可以看到，当从侧面观察样品时，硬质涂层呈紫色。所以本实施例得到的硬质涂层从不同的角度观察时看到的颜色不同。
实施例3——制备彩虹色硬质涂层
实施例3的制备方法与实施例1大体相同，其区别仅在于，基底为石英玻璃，且所述基底上各个区域的厚度为在50纳米至300纳米连续变化。
实施例3给出了一种制备彩色硬质涂层的方法，使得非晶金属氧化物在非晶合金层上的厚度连续变化，从而使硬质涂层呈现出不同的颜色，且硬质涂层的颜色为彩色渐变色(如图4所示)。实施例3制备的样品的XRD及原子力显微镜结果与实施例1得到的样品相近，因此不再重复示出。通过图6可以看出，样品的不同区域反射不同波长的光波，即对不同颜色的光的反射率不同。
实施例4——制备彩虹色硬质涂层
实施例4的制备方法与实施例3大体相同，其区别仅在于，硬质涂层的形状为清华的二校门的形状。
实施例4制备的样品的XRD、反射光谱及原子力显微镜结果与实施例3得到的样品相近，因此不再重复示出。且通过图5可以看出，硬质涂层为不透明硬质涂层，能对玻璃基底下的纸张样张上的文字进行覆盖。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。

Claims (21)

  1. 一种调控硬质涂层颜色的方法，其特征在于，包括以下步骤：
    提供非晶合金层；
    在所述非晶合金层表面形成非晶金属氧化物层，使所述非晶金属氧化物层层叠设置于所述非晶合金层并与所述非晶合金层共同形成所述硬质涂层，所述非晶金属氧化物层的带隙范围为2eV至5eV，所述硬质涂层的颜色能够随所述非晶金属氧化物层的厚度的变化在可见光波长范围内变化；
    在形成所述非晶金属氧化物层的过程中通过控制所述非晶金属氧化物层的厚度得到预定颜色的所述非晶金属氧化物层。
  2. 根据权利要求1所述的调控硬质涂层颜色的方法，其特征在于，所述非晶金属氧化物层的带隙范围为2.2eV至4.5eV。
  3. 根据权利要求1所述的调控硬质涂层颜色的方法，其特征在于，所述非晶合金层与所述非晶金属氧化物层中包含的除氧以外的元素的种类相同。
  4. 根据权利要求3所述的调控硬质涂层颜色的方法，其特征在于，所述非晶合金层的元素包括钴、铁、钽和硼；所述非晶金属氧化物层的元素包括钴、铁、钽、硼和氧。
  5. 根据权利要求1所述的调控硬质涂层颜色的方法，其特征在于，所述非晶金属氧化物层的组成为(Co,Fe,Ta,B) 1-xO x，其中0.46＜x＜1。
  6. 根据权利要求1所述的调控硬质涂层颜色的方法，其特征在于，还包括提供基底及设置在所述基底上的粘结层，所述非晶合金层形成在所述粘结层上，通过所述粘结层与所述基底结合。
  7. 根据权利要求6所述的调控硬质涂层颜色的方法，其特征在于，所述粘结层为双相复合纳米非晶混合物层，所述双相复合纳米非晶混合物层包括与所述非晶合金层元素种类相同的非晶合金和与所述非晶金属氧化物层元素种类相同的非晶金属氧化物。
  8. 根据权利要求7所述的调控硬质涂层颜色的方法，其特征在于，所述双相复合纳米非晶混合物层的组成为(Co,Fe,Ta,B) 1-yO y，其中0.1＜y＜0.46。
  9. 根据权利要求8所述的调控硬质涂层颜色的方法，其特征在于，所述混合物的组成为(Co,Fe,Ta,B) 1-yO y，其中0.2＜y＜0.4。
  10. 根据权利要求1所述的调控硬质涂层颜色的方法，其特征在于，所述非晶合金层的厚度大于20nm且小于10μm。
  11. 根据权利要求1所述的调控硬质涂层颜色的方法，其特征在于，所述非晶金属氧化物使所述硬质涂层的颜色在可见光波长范围内变化的厚度范围为50纳米至300纳米。
  12. 根据权利要求1所述的调控硬质涂层颜色的方法，其特征在于，在所述非晶合金层的不同区域形成具有不同厚度的所述非晶金属氧化物层得到不同区域具有不同颜色的所述硬质涂层。
  13. 根据权利要求12所述的调控硬质涂层颜色的方法，其特征在于，在所述非晶合金层上形成厚度连续变化的所述非晶金属氧化物层得到颜色渐变的彩色硬质涂层。
  14. 一种硬质涂层，其特征在于，包括非晶合金层和带隙范围为2eV至5eV的非晶金属氧化物层，所述非晶金属氧化物层层叠设置于所述非晶合金层并与所述非晶合金层共同形成所述硬质涂层，所述硬质涂层的颜色通过根据权利要求1-13中任一项所述的调控硬质涂层颜色的方法的调控而确定。
  15. 根据权利要求14所述的硬质涂层，其特征在于，所述硬质涂层的表面粗糙度小于0.2纳米。
  16. 一种硬质涂层的制备方法，其特征在于，包括以下步骤：
    将合金靶材和基底置于密闭的腔室；
    向腔室内通入惰性气体使所述腔室内部为不含氧的惰性气氛，在所述不含氧的惰性气氛中使所述合金靶材气化并在所述基底上形成非晶合金层；
    向所述腔室内通入第一氧气，使所述第一氧气与所述合金靶材气化后的靶材原子反应在所述非晶合金层上形成带隙范围为2eV至5eV非晶金属氧化物层，所述非晶金属氧化物层与所述非晶合金层共同形成所述硬质涂层，所述硬质涂层的颜色能够随所述非晶金属氧化物层的厚度的变化在可见光波长范围内变化。
  17. 根据权利要求16所述的硬质涂层的制备方法，其特征在于，所述合金靶材包括铁、钴、钽及硼。
  18. 根据权利要求16所述的硬质涂层的制备方法，其特征在于，所述合金靶材的组分为(Co,Fe) aTa bB c，其中a、b和c均为原子百分数，35≤a≤80，0＜b≤25，15≤c≤25。
  19. 根据权利要求16所述的硬质涂层的制备方法，其特征在于，所述第一氧气与所述惰性气体的分压比为0.04至0.1。
  20. 根据权利要求16所述的硬质涂层的制备方法，其特征在于，还包括，在形成所述非晶合金层之前，向所述腔室内通入第二氧气，所述第二氧气与从所述合金靶材气化后的靶材原子反应并在所述基底上形成粘结层，所述粘结层为含有非晶合金与非晶金属氧化物的双相复合纳米非晶混合物层。
  21. 根据权利要求16所述的硬质涂层的制备方法，其特征在于，在向所述腔室内通入所述惰性气体之前，还包括对所述腔室预抽真空，使所述腔室内的真空度低于10 -3Pa。
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