CN110128027B - Multi-stage gradual-change type spontaneous temperature-adjusting composite coating and preparation method thereof - Google Patents
Multi-stage gradual-change type spontaneous temperature-adjusting composite coating and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 230000002269 spontaneous effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000004544 sputter deposition Methods 0.000 claims abstract description 46
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 29
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- 238000000034 method Methods 0.000 claims abstract description 26
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- 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
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
-
- 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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- 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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3615—Coatings of the type glass/metal/other inorganic layers, at least one layer being non-metallic
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- 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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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- 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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
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- 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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3681—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
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- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
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- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
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Abstract
MultistageThe gradual-change type spontaneous temperature-regulating composite coating and the preparation method thereof are characterized by sequentially comprising a substrate layer, a diffusion barrier layer, a main light-regulating layer and a antireflection layer; wherein the diffusion barrier layer is a metal Ta film, and the main dimming layer is three VOs with W content in gradient distribution2A W sublayer, with an anti-reflection layer of anatase TiO2(ii) a The thicknesses of the diffusion barrier layer, the main dimming layer and the antireflection layer are respectively 1.5-2.5 nm, 60-150 nm and 30-60 nm. Depositing a metal Ta layer on a substrate by adopting a direct current sputtering method; then depositing the first VO by adopting a double-target co-sputtering method2A W sublayer, a second VO2the-W sublayer and the third VO2-a W sublayer; then depositing anatase phase TiO on the third sublayer by adopting a radio frequency sputtering method2(ii) a Finally, annealing treatment is carried out to prepare the multi-stage gradual-change type spontaneous temperature-regulating composite coating. The method has the advantages of simple operation, good repeatability, cleanness without pollution and good realization effect. The method can be widely applied to the field of intelligent window green buildings.
Description
Technical Field
The invention relates to a multi-stage gradual self-temperature-adjusting composite coating and a preparation method thereof, in particular to a near-mid infrared adjustable high-efficiency energy-saving composite coating and a preparation method thereof, which can be widely applied to green building doors, windows and curtain wall glass.
Technical Field
The high-efficiency energy-saving building glass is required to reduce the outward energy consumption of a building and utilize clean solar energy to the maximum extent, so that the coated glass is required to have the capability of independently regulating and controlling sunlight and infrared rays along with the change of the environmental temperature. The wavelength range of solar radiation is about 0.25-3 μm, wherein the light waves carrying heat energy are mainly near-mid infrared light above 0.7 μm, and the wavelength of heat radiation of indoor and outdoor objects is above 3 μm. In view of lighting, the higher the transmittance of the glazing in the visible region, the better, while the requirements for transmission and reflection of infrared light are different in cold and hot seasons. In cold seasons, in order to transmit solar radiation as much as possible and reflect indoor heat radiation, glass is required to have a light transmittance of 1 in the range of 0.4 to 3 μm and a reflectance of 1 for infrared light of 3 μm or more. In hot summer, the requirement on the glass is that the light transmittance is 1 in the interval of 0.4-0.7 μm and the reflectivity is 1 for infrared light with the wavelength of more than 0.7 μm, which is the working principle of an ideal intelligent window.
Since the first observation that vanadium oxides have thermotropic phase transition propertiesThere are 8 kinds of vanadium oxide having a property of transition from a high-temperature metal phase to a low-temperature semiconductor phase due to vanadium dioxide (VO)2) The phase transition temperature is close to normal temperature and is concerned by researchers in various countries. VO (vacuum vapor volume)2The phase transition temperature is 68 ℃, and is closest to the room temperature, and the unique property makes the material the best choice for coating materials of intelligent windows. VO at ambient temperature below the phase transition temperature2The film has the characteristics of a semiconductor, the electrical property is high resistivity, and the optical property is high transmission of near infrared wave bands; VO when the ambient temperature is higher than the phase transition temperature2The material is converted into a metal state, and the material electrically shows good conductivity and optically becomes infrared barrier property. VO (vacuum vapor volume)2Compared with a chemical vapor deposition method and a liquid phase method, the high vacuum magnetron sputtering method has the characteristics of no pollution, low cost, convenience for large-scale industrial production and the like, is simple in operation process, high in film deposition rate, good in repeatability, capable of realizing layered preparation of a multilayer structure, capable of accurately regulating and controlling components and easy to realize large-area deposition of uniform nano-structure coatings.
The metal W is for lowering VO2The phase transition temperature of the most effective doping element can be reduced by 20 ℃ for every 1 at% W of doping, and the phase transition temperature can be reduced to room temperature or below by W doping. However, there are several major problems, first, that of conventional W-doped VO2Only one phase transition temperature is needed, and the gradual change regulation and control of the room temperature cannot be realized; secondly, the whole VO has only one phase transition temperature2The phase change of the coating causes large change of the volume, and the service life of the coating is reduced due to the repeated volume expansion and contraction; finally, W-doped VO2The visible light transmittance and the infrared adjustment rate of (2) need to be further improved.
Disclosure of Invention
The invention aims to develop a multi-stage gradual-change type spontaneous temperature-adjusting composite coating, and the invention also aims to provide a preparation method of the multi-stage gradual-change type spontaneous temperature-adjusting composite coating, which has the advantages of gradually adjusting the indoor temperature at different temperatures, avoiding the great change of the indoor temperature, improving the indoor human body comfort level, not only efficiently saving energy, but also effectively utilizing solar energy, having high working reliability, and being widely applied to green building doors and windows, exterior wall glass, automobile window glass and the like.
The technical scheme of the invention is as follows: a multi-stage gradual-change type spontaneous temperature-regulating composite coating is characterized by sequentially comprising a substrate layer, a diffusion barrier layer, a main light-regulating layer and an antireflection layer; wherein the diffusion barrier layer is a metal Ta film, and the main dimming layer is three VOs with W content in gradient distribution2A W sublayer, with an anti-reflection layer of anatase TiO2(ii) a The thicknesses of the diffusion barrier layer, the main dimming layer and the antireflection layer are respectively 1.5-2.5 nm, 60-150 nm and 30-60 nm.
Preferably, the substrate layer is quartz glass; three sub-layers VO in the main light modulation layer2The molar contents of W in W are respectively 1.9-2.1%, 2.4-2.6% and 2.9-3.1%; VO adjacent to diffusion barrier layer2The molar content of W in the W sublayer is highest; each sublayer having a thickness of 20-50 nm.
We firstly design three-layer main dimming sublayer VO with gradient W content2W, the contents of W in the three sub-layers are different, namely the three sub-layers have different phase change temperatures, phase change is carried out layer by layer at different temperatures, the indoor temperature is adjusted in a gradual change mode, great change of the indoor temperature is avoided, the indoor human body comfort level is improved, energy is saved, the efficiency is higher, meanwhile, large-size change caused by phase change is also avoided, and the working reliability is better. The anti-reflection layer is anatase phase TiO2The coating improves the visible light transmittance, promotes the sunlight regulation rate, and can also play a role in protecting the coating and self-cleaning.
The invention also provides a method for preparing the multistage gradual change type spontaneous temperature adjustment composite coating, which comprises the following specific steps:
A. depositing a metal Ta layer on the substrate by a direct-current sputtering method;
B. depositing the first VO by adopting a double-target co-sputtering method2-a W sublayer;
C. depositing a second VO by double-target co-sputtering2-a W sublayer;
D. depositing a third VO by adopting a double-target co-sputtering method2-a W sublayer;
E. depositing anatase phase TiO on the third sublayer by radio frequency sputtering2；
F. Finally, annealing treatment is carried out to prepare the multi-stage gradual-change type spontaneous temperature-regulating composite coating.
Preferably, the thickness of the metal Ta layer in the step A is 1.5-2.5 nm; the sputtering power is 150-250W.
Preferably the first VO in step B2The thickness of the-W sub-layer is 20-50nm, and the W content is 2.9-3.1%.
Preferably the second VO in step C2The thickness of the-W sub-layer is 20-50nm, and the W content is 2.4-2.6%.
Preferably, third VO in step D2The thickness of the-W sub-layer is 20-50nm, and the W content is 1.9-2.1%.
Preferably, in the step B, C, D, the sputtering power is 250-350W, and the substrate temperature is 300-500 ℃.
Preference is given to anatase phase TiO in step E2The thickness of (A) is 30-60 nm; introducing a reaction gas O2Gas, O2The partial pressure is 0.01-0.30Pa, the sputtering power is 150-250W, and the substrate temperature is 250-350 ℃.
Preferably, the annealing temperature in the step f is 200-400 ℃, and the annealing time is 1-2 h. Reducing internal stress, improving interface binding force and obtaining the multi-stage gradual-change type spontaneous temperature-regulating composite coating.
The invention adopts a multi-target radio frequency reaction magnetron sputtering method, and the sputtering target materials are respectively VO with the purity of 99.9 wt%299.9 wt% of TiO2And 99.9 wt% metallic Ta, the substrate preferably being quartz glass. Preferably, before coating, the substrate is cleaned by ultrasonic wave, and after the target material and the substrate are loaded, the substrate is vacuumized to 1.0 x 10-5Pa, introducing high-purity Ar gas with the flow of about 20sccm, adjusting the vacuum degree of the vacuum chamber to 5.0Pa through a gate valve, and then starting airglow; in order to remove the stains on the surface of the target material and ensure the purity of the thin film, pre-sputtering is carried out for about 20min to perform the treatment on VO2，TiO2And the W target was subjected to pre-sputtering for about 20min to remove oil stains, impurities and the like on the surface, and after the pre-sputtering, the degree of vacuum was adjusted to a working pressure of 1.0 Pa.
Firstly, the film plating is carried out under the ultrahigh vacuum degree, the influence of impurities and the like on the components and the structure of the composite coating can be avoided, the regulation and control of the components and the phase are realized, the comprehensive optical characteristic of the composite coating is improved, meanwhile, the adhesion force of the deposited coating and the substrate is strong, and the large-area controllable preparation can be carried out.
Secondly, selecting metal W as VO2The doping metal of (1 at%) can reduce the phase transition temperature by 20 ℃ to make the phase transition temperature close to room temperature. Three VOs2The content of W in the W sub-layer is distributed in a gradient mode and is respectively 1.9-2.1%, 2.4-2.6% and 2.9-3.1%, the phase change temperatures of the three sub-layers from top to bottom are respectively about 28 ℃, 18 ℃ and 8 ℃, and when the temperature is lower than 28 ℃, the indoor temperature of the first layer is adjusted; the first and second layers simultaneously regulate the room temperature as the temperature continues to drop to 18 ℃; when the temperature is reduced to below 8 ℃, the three layers simultaneously regulate the indoor temperature. Thereby the effect of multistage gradual change thermoregulation has been realized, very big promotion energy-conserving efficiency by a wide margin, has also improved the comfort level that the body was felt, and successive layer phase transition has reduced the volume change in the phase transition process, has reduced the internal stress change, has improved coating working life.
Thirdly, the anti-reflection layer is anatase phase TiO2The coating has high refractive index, can effectively improve the visible light transmittance of the composite coating, improves the solar energy regulation rate, and has photocatalysis characteristic to achieve defogging and self-cleaning effects.
In addition, the diffusion barrier layer Ta has high thermal stability, effectively prevents the mutual diffusion of the coating and the deposition, improves the interface bonding force of the coating and the deposition, and improves the thermal stability and the working reliability of the composite coating.
Has the advantages that:
the invention provides a composite coating capable of carrying out multistage gradual change type spontaneous indoor temperature regulation and a preparation method thereof. The Ta with high thermal stability is used as a diffusion barrier layer and still has the effect after heat preservation for 1h at 450 DEG CThe coating has good blocking effect, and the heat stability of the coating is improved; selecting W as a doped metal light modulation layer VO2The content of W is distributed in a gradient way and is respectively 1.9-2.1%, 2.4-2.6% and 2.9-3.1%, the phase transition temperatures of three sublayers from top to bottom are respectively 28 ℃, 18 ℃ and about 8 ℃, and anatase phase TiO is utilized2As the anti-reflection layer, the visible light transmittance and the sunlight regulation rate of the coating are improved, and the coating has a photocatalytic property and has defogging and self-cleaning effects. The method also has better repeatability and controllability. The nano-structure composite coating has high visible light transmittance and high-efficiency sunlight regulation rate which are respectively up to 60 percent and 13 percent, has the interface binding force up to 1.3GPa, and has excellent comprehensive performance.
Compared with the existing preparation method, the invention has the following characteristics:
(1) VO main light modulation layer2W is divided into three sublayers, wherein the content of W is distributed in a gradient manner, so that the W has three phase change temperature points, the effect of multi-stage gradual temperature adjustment is realized, the energy-saving efficiency is greatly improved, the body feeling comfort level is also improved, the volume change in the phase change process is reduced through layer-by-layer phase change, the internal stress change is reduced, and the service life of the coating is prolonged.
(2) Using anatase phase TiO2As the anti-reflection layer, the visible light transmittance and the sunlight regulation rate of the coating are improved, and the coating has a photocatalytic property and has defogging and self-cleaning effects.
(3) The high-melting-point metal Ta is introduced into the composite coating to serve as a diffusion barrier layer, so that the heat stability and the interface bonding force of the coating are improved.
(4) The method is simple and convenient to operate, good in controllability, clean and pollution-free, and suitable for large-scale industrialization.
Drawings
FIG. 1 is a schematic diagram of a multi-step gradual self-temperature-regulating composite coating.
Detailed Description
The schematic diagram of the multi-stage gradual-change type spontaneous temperature-adjusting composite coating in the following embodiment is shown in fig. 1, and the multi-stage gradual-change type spontaneous temperature-adjusting composite coating comprises a substrate, a diffusion barrier layer, a main light-adjusting layer and an antireflection layer.
Example 1
Background vacuum of 1.0X 10-5Pa, working pressure of 1.0Pa, high-purity Ar gas as an ion source, and flow rate of 20 sccm.
Firstly, a metal Ta film with the thickness of 2nm is deposited on a quartz glass substrate, the sputtering power is 200W, the metal Ta film is used as a diffusion barrier layer, and the substrate temperature is room temperature.
VO of main light modulation layer2-W, deposition of VO by radio frequency co-sputtering2Layer of-W, VO2And W double-target co-sputtering, wherein the sputtering power is 300W, the substrate temperature is 300 ℃, and the thicknesses of the three sub-layers are 20 nm. The W content was 2 at%, 2.5 at% and 3 at%, respectively.
Anatase phase TiO of anti-reflection layer2Radio frequency reactive sputtering method, O2The partial pressure is 0.01Pa, the substrate temperature is 300 ℃, the power is 200W, and the thickness is 30 nm.
Finally, annealing treatment is carried out for 1.5 hours at 300 ℃ to prepare the multi-stage gradual-change type spontaneous temperature-regulating composite coating.
The visible light transmittance and the solar light regulation rate of the composite coating respectively reach 50 percent and 8 percent, and the interface bonding force is 1.3 GPa.
Example 2
Background vacuum of 1.0X 10-5Pa, working pressure of 1.0Pa, high-purity Ar gas as an ion source, and flow rate of 20 sccm.
Firstly, a metal Ta film with the thickness of 1.6nm is deposited on a quartz glass substrate, the sputtering power is 150W, the metal Ta film is used as a diffusion barrier layer, and the temperature of the substrate is room temperature.
VO of main light modulation layer2-W, deposition of VO by radio frequency co-sputtering2Layer of-W, VO2And W double-target co-sputtering, wherein the sputtering power is 250W, the substrate temperature is 400 ℃, and the thicknesses of the three sub-layers are all 30 nm. The W content was 1.9 at%, 2.4 at% and 2.9 at%, respectively.
Anatase phase TiO of anti-reflection layer2Radio frequency reactive sputtering method, O2The partial pressure was 0.08Pa, the substrate temperature was 300 deg.C, the power was 150W, and the thickness was 30 nm.
Finally, annealing treatment is carried out for 1.5 hours at 300 ℃ to prepare the multi-stage gradual-change type spontaneous temperature-regulating composite coating.
The visible light transmittance and the solar light regulation rate of the composite coating respectively reach 55 percent and 9 percent, and the interface bonding force is 1.3 GPa.
Example 3
Background vacuum of 1.0X 10-5Pa, working pressure of 1.0Pa, high-purity Ar gas as an ion source, and flow rate of 20 sccm.
Firstly, a metal Ta film with the thickness of 2.5nm is deposited on a quartz glass substrate, the sputtering power is 250W, the metal Ta film is used as a diffusion barrier layer, and the temperature of the substrate is room temperature.
VO of main light modulation layer2-W, deposition of VO by radio frequency co-sputtering2Layer of-W, VO2And W double-target co-sputtering, wherein the sputtering power is 350W, the substrate temperature is 500 ℃, and the thicknesses of the three sub-layers are 45 nm. The W content was 2.1 at%, 2.6 at% and 3.1 at%, respectively.
Anatase phase TiO of anti-reflection layer2Radio frequency reactive sputtering method, O2The partial pressure was 0.08Pa, the substrate temperature was 350 deg.C, the power was 250W, and the thickness was 30 nm.
Finally, annealing treatment is carried out for 1.2 hours at 350 ℃ to prepare the multi-stage gradual-change type spontaneous temperature-regulating composite coating.
The visible light transmittance and the solar light regulation rate of the composite coating respectively reach 57 percent and 10 percent, and the interface bonding force is 1.3 GPa.
Example 4
Background vacuum of 1.0X 10-5Pa, working pressure of 1.0Pa, high-purity Ar gas as an ion source, and flow rate of 20 sccm.
Firstly, a metal Ta film with the thickness of 2nm is deposited on a quartz glass substrate, the sputtering power is 200W, the metal Ta film is used as a diffusion barrier layer, and the substrate temperature is room temperature.
VO of main light modulation layer2-W, deposition of VO by radio frequency co-sputtering2Layer of-W, VO2And W double-target co-sputtering, wherein the sputtering power is 300W, the substrate temperature is 400 ℃, and the thicknesses of the three sub-layers are 25 nm. The W content was 2 at%, 2.5 at% and 3 at%, respectively.
Anatase phase TiO of anti-reflection layer2Radio frequency reactive sputtering method, O2The partial pressure was 0.10Pa, the substrate temperature was 300 deg.C, the power was 200W, and the thickness was 50 nm.
Finally, annealing treatment is carried out for 1.5 hours at 300 ℃ to prepare the multi-stage gradual-change type spontaneous temperature-regulating composite coating.
The visible light transmittance and the solar light regulation rate of the composite coating respectively reach 58 percent and 12 percent, and the interface bonding force is 1.3 GPa.
Example 5
Background vacuum of 1.0X 10-5Pa, working pressure of 1.0Pa, high-purity Ar gas as an ion source, and flow rate of 20 sccm.
Firstly, a metal Ta film with the thickness of 2nm is deposited on a quartz glass substrate, the sputtering power is 200W, the metal Ta film is used as a diffusion barrier layer, and the substrate temperature is room temperature.
VO of main light modulation layer2-W, deposition of VO by radio frequency co-sputtering2Layer of-W, VO2And W double-target co-sputtering, wherein the sputtering power is 300W, the substrate temperature is 400 ℃, and the thicknesses of the three sub-layers are all 30 nm. The W content was 2 at%, 2.5 at% and 3 at%, respectively.
Anatase phase TiO of anti-reflection layer2Radio frequency reactive sputtering method, O2The partial pressure was 0.012Pa, the substrate temperature 300 deg.C, the power 200W, and the thickness 40 nm.
Finally, annealing treatment is carried out for 2 hours at 200 ℃ to prepare the multi-stage gradual-change type spontaneous temperature-regulating composite coating.
The visible light transmittance and the solar light regulation rate of the composite coating respectively reach 60 percent and 13 percent, and the interface bonding force is 1.3 GPa.
Example 6
Background vacuum of 1.0X 10-5Pa, working pressure of 1.0Pa, high-purity Ar gas as an ion source, and flow rate of 20 sccm.
Firstly, a metal Ta film with the thickness of 2nm is deposited on a quartz glass substrate, the sputtering power is 200W, the metal Ta film is used as a diffusion barrier layer, and the substrate temperature is room temperature.
VO of main light modulation layer2-W, deposition of VO by radio frequency co-sputtering2Layer of-W, VO2And W double-target co-sputtering, wherein the sputtering power is 300W, the substrate temperature is 500 ℃, and the thicknesses of the three sub-layers are 50 nm. The W content was 2 at%, 2.5 at% and 3 at%, respectively.
Anatase phase TiO of anti-reflection layer2Radio frequency reactive sputtering method, O2The partial pressure is 0.30Pa, the substrate temperature is 300 ℃, the power is 200W, and the thickness is 60 nm.
Finally, annealing treatment is carried out for 1 hour at 400 ℃, and the multi-stage gradual-change type spontaneous temperature-regulating composite coating is prepared.
The visible light transmittance and the solar light regulation rate of the composite coating respectively reach 59 percent and 11 percent, and the interface bonding force is 1.3 GPa.
Claims (10)
1. A multi-stage gradual-change type spontaneous temperature-regulating composite coating is characterized by sequentially comprising a substrate layer, a diffusion barrier layer, a main light-regulating layer and an antireflection layer; wherein the diffusion barrier layer is a metal Ta film, and the main dimming layer is three VOs with W content in gradient distribution2A W sublayer, with an anti-reflection layer of anatase TiO2(ii) a The thicknesses of the diffusion barrier layer, the main dimming layer and the antireflection layer are respectively 1.5-2.5 nm, 60-150 nm and 30-60 nm; wherein three sub-layers VO in the main light modulation layer2The molar content of W in W is respectively 1.9-2.1%, 2.4-2.6% and 2.9-3.1%, and the thickness of each sublayer is 20-50 nm.
2. The multi-stage graded self-temperature-regulating composite coating according to claim 1, wherein the substrate layer is quartz glass.
3. The method for preparing the multistage gradual change type spontaneous temperature adjustment composite coating of claim 1 comprises the following specific steps:
A. depositing a metal Ta layer on the substrate by a direct-current sputtering method;
B. depositing the first VO by adopting a double-target co-sputtering method2-a W sublayer;
C. depositing a second VO by double-target co-sputtering2-a W sublayer;
D. depositing a third VO by adopting a double-target co-sputtering method2-a W sublayer;
E. depositing anatase phase TiO on the third sublayer by radio frequency sputtering2；
F. Finally, annealing treatment is carried out to prepare the multi-stage gradual-change type spontaneous temperature-regulating composite coating.
4. The method according to claim 3, wherein the thickness of the metallic Ta layer in step A is 1.5 to 2.5 nm; the sputtering power is 150-250W.
5. The method of claim 3, wherein the first VO in step B2The thickness of the-W sub-layer is 20-50nm, and the W content is 2.9-3.1%.
6. The method of claim 3, wherein the second VO is obtained in step C2The thickness of the-W sub-layer is 20-50nm, and the W content is 2.4-2.6%.
7. The method according to claim 3, wherein the third VO in step D2The thickness of the-W sub-layer is 20-50nm, and the W content is 1.9-2.1%.
8. The method of claim 3, wherein the sputtering power of step B, C, D is 250-350W, and the substrate temperature is 300-500 ℃.
9. A process according to claim 3, characterized in that in step E anatase phase TiO is used2The thickness of (A) is 30-60 nm; introducing a reaction gas O2Gas, O2The partial pressure is 0.01-0.30Pa, the sputtering power is 150-250W, and the substrate temperature is 250-350 ℃.
10. The method according to claim 3, wherein the annealing temperature in step F is 200-400 ℃ and the annealing time is 1-2 h.
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| US20030054177A1 (en) * | 2001-09-20 | 2003-03-20 | National Inst. Of Advanced Ind. Science And Tech. | Multifunctional energy efficient window coating |
| WO2010001669A1 (en) * | 2008-06-30 | 2010-01-07 | 独立行政法人産業技術総合研究所 | Thermochromic microparticles, dispersions thereof, and manufacturing method thereof, as well as light-modulating coatings, light-modulating films and light-modulating inks |
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