CN106045332A - Thermochromic intelligent light control film with low phase-transition temperature and preparation method of thermochromic intelligent light control film - Google Patents

Thermochromic intelligent light control film with low phase-transition temperature and preparation method of thermochromic intelligent light control film Download PDF

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CN106045332A
CN106045332A CN201610392784.6A CN201610392784A CN106045332A CN 106045332 A CN106045332 A CN 106045332A CN 201610392784 A CN201610392784 A CN 201610392784A CN 106045332 A CN106045332 A CN 106045332A
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layer
vanadium oxide
intelligent light
film
alloy
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CN106045332B (en
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詹勇军
徐刚
肖秀娣
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
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    • 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
    • C03C17/3644—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 metal being silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C17/3435—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 at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
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    • 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
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    • C03C17/3626—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 one layer at least containing a nitride, oxynitride, boronitride or carbonitride
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    • 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
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    • 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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    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • 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
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    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/0009—Materials therefor
    • G02F1/009—Thermal properties
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    • C03C2218/00—Methods for coating glass
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    • C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering

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Abstract

The invention provides a thermochromic intelligent light control film with low phase-transition temperature and a preparation method of the thermochromic intelligent light control film. The thermochromic intelligent light control film is characterized in that a vanadium oxide layer with a phase transition property is arranged on a substrate of the light control film, and particularly, a crystallization promoting layer is compounded on at least one surface of the vanadium oxide layer; the crystallization promoting layer is made of one or more of metal nitride, alloy nitride, silicon nitride and silicon alloy nitride capable of promoting the vanadium oxide layer to form small nano-grains. According to the thermochromic intelligent light control film, doping of other phase-transition temperature reducing elements into the vanadium oxide material with the phase transition property is not needed, all that is required is to control the vanadium oxide layer with the phase transition property to be crystallized into small nano-grain sizes through material selection and setting of the film layer, and the phase-transition temperature of the film layer can be controlled in a certain range.

Description

A kind of thermocolour intelligent light modulation film of low transformation temperature and preparation method thereof
Technical field
The present invention relates to technical field of function materials, be specifically related to a kind of low transformation temperature thermocolour intelligent light modulation film and Preparation method.
Background technology
VO2As a kind of novel energy-saving material, it can occur the phase transformation of uniqueness near 68 DEG C of phase transformation temperature pointses.Work as ring When border temperature is higher than phase transition temperature, VO2In tetragonal crystalline structure, there is metal phase behaviour, it is possible to reflection infrared ray；When environment temperature When degree is less than phase transition temperature, VO2In monoclinic structure, there is quasiconductor phase behaviour, it is possible to through infrared ray.Therefore VO2Film layer Can sunlight irradiate under undergo phase transition and obtain up to no less than 20% solar energy regulation rate.Therefore since nineteen fifty-nine Morin sends out Now since its phase transition function characteristic, VO2Material is by the energy-conservation market of door and window and the extensive concern of domestic and international research institution.
Vanadium oxide thermocolour intelligent dimming glass in order to make obtains wider application in energy-saving field, in prior art, Having employing sputtering sedimentation vanadium metal film on substrate, annealing obtains the phase transition temperature with as little as 43 DEG C the most in atmosphere The method of mono-layer oxidized vanadium intelligent light modulation film, but its annealing process time is long, is unfavorable for that batch machining produces；Meanwhile, because of film Rotating fields is simple, and non-oxidizability, wearability, strange land machinability are poor, is also unfavorable for batch production.Patent documentation CN 104250068A discloses technical scheme prepared by a kind of multilayer complex films layer preparing low transformation temperature, effectively reduces thermocolour The phase transition temperature of smart membrane, improves the antioxygenic property etc. of this film layer, but, this technical scheme have employed and is first coated with doping gold Belong to film layer, anneal the most at relatively high temperatures, then on thermocolour film layer after annealing, be coated with other protection tunic layer or antireflective Film layer.Owing to the oxidizing annealing temperature of metal film is higher and annealing time is longer, coating process controls difficulty to be increased, this skill simultaneously Art scheme adds the complexity of technique, is unfavorable for that batch machining produces.Additionally, can reduce by the way of element doping Phase transition temperature, but different phase transition temperature needs the materials such as the target of offer different levels of doping, owing to element doping can cause The reduction of light thermal property, therefore element doping amount needs accurately to control.Therefore, the thin film of the actual control of which or preparation Phase transition temperature region is subject to certain restrictions.
The influence factor of phase transition temperature is more, and phase transition temperature is had substantially by the difference such as stress, composition, grain size etc. Influence.There are some researches show that the difference of vanadium oxide grain size can regulate phase transition temperature.Crystal grain is shown from variation tendency The least then phase transition temperature of size is the lowest.
Based on prior art analysis, in order to solve undoped p external elements realize phase transition temperature regulate and control by a relatively large margin problem, Intelligent light modulation film light calorifics poor performance, non-oxidizability is poor, wear no resistance, the problem of strange land processability difference, it is necessary to research and development Go out a kind of can be without being reduced the thermocolour intelligent light modulation film of low transformation temperature of the element of vanadium oxide material phase transition temperature by doping.
Summary of the invention
The present invention is to solve prior art prepare low transformation temperature thermocolour intelligent light modulation film during limitation, solve Quantitatively doping external elements target configuration, preparation technology flow process, preparation or production efficiency and lifting intelligent light modulation film light calorifics Problem in terms of performance, antioxygenic property and strange land processability, it is proposed that a kind of low transformation temperature intelligent light modulation film and Its preparation method.
For achieving the above object, the present invention adopts the following technical scheme that
The thermocolour intelligent light modulation film of a kind of low transformation temperature, is provided with the vanadium oxide layer with phase-change characteristic on substrate；Special Not: at least one surface of described vanadium oxide layer, be compounded with rush crystallizing layer；The material of described rush crystallizing layer is selected from having rush Vanadium oxide is made to be formed in the nitride of the metal nitride of the little crystal particle function of nanometer, alloy nitride, the nitride of silicon, silicon alloy One or more.
Heretofore described vanadium oxide layer can form the little crystal grain of nanometer, the little crystalline substance of so-called nanometer under the effect promoting crystallizing layer Grain refers to be induced by this rush crystallizing layer material, cause vanadium oxide layer crystallize in heating process formed little to 25nm and following Crystal grain.The technical scheme is that by arranging synergistic film layer structure, and by selecting different rush crystallizing layers Material, in conjunction with different preparation process conditions so that vanadium oxide layer forms the grain size of crystallization and can adjust within the specific limits Control, thus also realize undope reduce vanadium oxide phase transition temperature element in the case of, it is possible in a big way in regulation and control aoxidize The phase transition temperature of vanadium layers.Vanadium oxide layer in the present invention refers to comprise the oxide of a kind of vanadium with thermocolour characteristic, particularly Vanadium dioxide.Further, described vanadium oxide layer refers to the vanadium oxide composite including at least vanadium dioxide, is represented by VOx, wherein x ＜ 2；Further, it is preferable to 1.5 ＜ x ＜ 2；Or comprise a kind of peroxide crossing vanadium, be represented by VOx, its In 2 ＜ x≤2.5；Or be the oxide of the vanadium of multiple vanadium ion valence state, but the average V:O atom of the oxide formed Than the mixture with thermocolour characteristic close to 1:2.Vanadium oxide material in the present invention can be understood as the average V O formed Atomic ratio crystallization is close to the mixture of the multivalent state with thermocolour characteristic of 1:2.In the present invention, the thickness of vanadium oxide layer is 50nm～150nm.
Heretofore described vanadium oxide layer can be the smart membrane with low transformation temperature obtained through Overheating Treatment Noncrystalline precursor layer.Described vanadium oxide layer can select the vanadium oxide material layer of the element of undoped reduction phase transition temperature, After forming crystal grain, its phase transition temperature can be reduced to about 35 DEG C from the 68 of pure phase hypovanadic oxide DEG C.In order to obtain the phase of wider model The regulation space of temperature, described vanadium oxide layer is also optional is doped with the oxidation reducing himself phase transition temperature functional element Vanadium material, after forming crystal grain, its phase transition temperature can be reduced to about 10 DEG C from the 68 of pure phase hypovanadic oxide DEG C.
The thermocolour intelligent light modulation film of a kind of low transformation temperature provided by the present invention, further, is preferably additionally provided with first Dielectric layer and/or second dielectric layer.Described first medium layer is arranged between described substrate and vanadium oxide layer；Described second medium Layer is arranged on the top layer of the vanadium oxide layer opposite side relative with substrate.Described first medium layer and second dielectric layer specifically may be used The material selected respectively is TiOx, TiNx, AlOx, AlNx, SiNx, SiOx, SiNxOy, HfOx, NbOx, TaOx, ZrOx, One or more in ZrNx, ZnOx, SnOx, ZnSnOx, ZnS, ITO, ATO, AZO, FTO, IGO.Described first medium layer and The thickness of second dielectric layer is respectively 30nm～200nm.Preferably, described second dielectric layer is at least in most surface, i.e. with oxidation The opposite side that vanadium layers is relative, comprises the nitride good no less than the heat resistance of 20nm thickness, anti-wear performance or nitrogen oxidation Thing material, such as SiNx, SiNxOy, ZrNx.Preferably, the side that described first medium layer is relative with substrate, including at least many SiNx, SiNxOy, ZrNx, CrNx in 20nm thickness.Described conductive oxide ITO, ATO, AZO, FTO, IGO be have red External reflectance function, form composite bed in the most preferably being arranged at any one layer of first medium layer or second dielectric layer；Or When being provided with rush crystallizing layer between first medium layer and vanadium oxide layer, it is also possible to be preferably provided at first medium layer and promote crystallization Between Ceng；Or when being provided with rush crystallizing layer between second dielectric layer and vanadium oxide layer, it is also possible to it is preferably provided at second medium Between layer and rush crystallizing layer.Described first medium layer and second dielectric layer may select heterogeneity material, form difference respectively The composite bed of structure.If first medium layer can be the composite bed of SiNx+ITO+SiNx.It is preferably further, described oxidation The vanadium layers side relative with substrate is provided with first medium layer, and the opposite side of described vanadium oxide layer also is provided with second dielectric layer.
The thermocolour intelligent light modulation film of a kind of low transformation temperature provided by the present invention, further, is preferably additionally provided with antioxygen Change layer.Described anti oxidation layer is arranged between described first medium layer and vanadium oxide layer and/or second dielectric layer and vanadium oxide layer Between.Described anti oxidation layer and described rush crystallizing layer can be arranged on the homonymy of vanadium oxide layer and/or be separately positioned on vanadium oxide Layer both sides, and when vanadium oxide layer homonymy both be provided with rush crystallizing layer also be provided with anti oxidation layer when, the most successively with oxidation The order of vanadium layers/rush crystallizing layer/anti oxidation layer is arranged.Specifically, situation arranged below is i.e. included: (1) anti oxidation layer/rush knot Crystal layer/vanadium oxide layer；(2) anti oxidation layer/the first promotees crystallizing layer/vanadium oxide layer/the second and promotees crystallizing layer；(3) first anti oxidation layers/ First promotees crystallizing layer/vanadium oxide layer/the second promotees crystallizing layer/the second anti oxidation layer；(4) anti oxidation layer/vanadium oxide layer/rush crystallization Layer；(5) the first anti oxidation layers/vanadium oxide layer/rush crystallizing layer/the second anti oxidation layer.
The material of described anti oxidation layer is selected from: Ti or its alloy, Al or its alloy, Ni or its alloy, Cr or its alloy, Ti Or the oxide of the oxide of the oxide of the oxide of its alloy, Al or its alloy, Ni or its alloy, Cr or its alloy, Ti Or the nitride of the nitride of the nitride of the nitride of its alloy, Al or its alloy, Ni or its alloy, Cr or its alloy, Ti Silicide, the silicide of Al, the silicide of Ni, Cr silicide in one or more.Described Ti or its alloy, Al or its Alloy, Ni or its alloy, Cr or its alloy preferably comprise the alloy material of Si element doping.Described antioxygen layer specifically may select Material include but do not limit: NiCr, NiCrOx, NiCrNx, NiCr+NiCrOx, NiCr+NiCrNx, NiCrOx+NiCrNx, NiCrOx+NiCr, NiCrNx+NiCr, NiCrNx+NiCrOx, NiSi, CrAlSi etc..Described material non-limiting NiCr base This material, in other compound present invention, the material of protection can form such structure.And light modulation film comprises more than one During the anti oxidation layer of layer, the composite material of the anti oxidation layer of diverse location and composite construction can be different.Such as wherein one layer of antioxygen Change layer is NiCrOx, and other one layer of anti oxidation layer is Ti layer.The thickness of described anti oxidation layer is 2nm～25nm, the most excellent Elect 5nm～20nm as.According to different heat treatment modes, as long as it can be avoided that vanadium oxide membrane layer in heat treatment process by oxygen The light such as changing, corresponding barrier layer can use the thinnest thickness, the visible light transmissivity of this most overall thermocolour intelligent dimming layer The lifting of thermal property.Simple and easy to control for preparation process, it is preferred to use same target prepares monolayer or two-layer compound Barrier layer.
In the present invention, the material of described rush crystallizing layer is selected from the nitride (CrNx) of chromium, the nitride (ZrNx) of zirconium, silicon Nitride (SiNx), the nitrogen oxides (SiNxOy) of silicon, silicon alloy nitride in one or more.Described can material selection For self having stronger heat resistance, particularly can bear several minutes in the environment of temperature up to 700 DEG C and not cause Promote the be full of cracks of crystallizing layer self or come off.Further, when described rush crystallizing layer and described first medium layer or second dielectric layer Or anti oxidation layer compound tense, vanadium oxide layer can be played more stable heatproof antioxidative multiple protective so that the present invention designs Film layer structure can be deposited in substrate of glass and carry out tempering heat treatment.Secondly, the material that described rush crystallizing layer selects is 700 Near DEG C temperature, the situation of heat treatment 600s time is not easy crystallization or for amorphous state, to such an extent as to vanadium oxide layer is in annealing crystallization During hardly suffer from the unmanageable problem of phase transition temperature that possible Lattice Matching causes, inhibited oxidation vanadium layers is selected simultaneously Eugenic product, promotes that the randomness in its production process crystallizes, thus reaches on purpose to reduce vanadium oxide material in vanadium oxide layer The size of crystal grain formed by material.Again, the material that described rush crystallizing layer selects has preferably stop for the diffusion of other element Effect, especially, when selecting such as NiCr material such as anti oxidation layer, Ni has stronger scattering nature, and its diffusion will result in oxidation The increase of vanadium layers phase transition temperature and the situation such as be reduced occur, and then affect the combination property of vanadium oxide layer, therefore this material One of effect can also play the effect of barrier metal Elements Diffusion.Consideration based on above-mentioned factor and film layer light calorifics The design of energy, described rush crystallizing layer further preferably has the nitride that heat resistance is good, such as SiNx, ZrNx etc., its thickness For for 3nm～70nm, further preferred thickness is 5nm～40nm, and further preferably thickness is 10nm～30nm.Work as oxygen When the both sides of change vanadium layers are equipped with rush crystallizing layer, the rush crystallizing layer of vanadium oxide layer both sides can select different composition materials respectively Material, the thickness of both also can have difference.When the wherein side of vanadium oxide layer arranges rush crystallizing layer, the most preferred described rush is tied Crystal layer is arranged on the vanadium oxide layer side toward second dielectric layer.The most preferably promote the SiNx material that crystallizing layer is monolayer Material, easily, technological process is simple for the supply of its target.
Further, the thermocolour intelligent light modulation film of a kind of low transformation temperature that the present invention provides, it is also desirable to be provided with infrared ray Reflecting layer.Described infrared-reflecting layers is arranged at least one surface of described vanadium oxide layer.Preferably, described infrared reflection The thickness of layer is 1nm～15nm.Preferably, the gold of at least one element during described infrared-reflecting layers is Pt, Au, Ag, Cu, Al Belong to the doping of at least one element in the alloy-layer of at least one element, Pt, Au, Ag, Cu, Al in layer, Pt, Au, Ag, Cu, Al Metal level or the composite bed of described layer.Described infrared-reflecting layers may also be arranged between first medium layer and second dielectric layer Optional position.If a wherein side surface of vanadium oxide layer is provided with rush crystallizing layer, then infrared-reflecting layers is preferably provided in described Promote the crystallizing layer surface toward the opposite side of described vanadium oxide layer.Further, described infrared-reflecting layers is preferably It is arranged on the vanadium oxide layer side near first medium layer, is so conducive to increasing the efficiency of annealing.
Heretofore described substrate is selected from organic flexible substrate, inorganic flexible substrate, organic non-flexible substrate, inorganic non- One in flexible base board.Concrete such as flexible macromolecule film, flexible glass, flexible metal；The pottery of inflexibility, glass, metal, Polymeric substrate.It is preferably PET film, flexibility/inflexibility glass substrate material.The claims in the present invention do not limit substrate thickness and The color of himself.
The material of the related film layer in the present invention, so-called nitride, oxide or nitrogen oxides etc., the preparation of its film layer Realize corresponding metal targets, metal-oxide or metal nitride ceramic target at the gas comprising reactive sputtering gas accordingly Film forming in atmosphere environment, is obtained in that in usual sputter coating environment, it is not required that the film layer of necessary composite chemical metering ratio becomes Point.
Above-mentioned cited concrete material, film layer structure in the present invention, be not intended as accompanying claims in the present invention and protect Any restriction protected, the expression implication being only used as helping to understand in the present invention and the common material listed or version.
Present invention also offers the preparation method of the thermocolour intelligent light modulation film of a kind of low transformation temperature, comprise the following steps:
(1) offer can be used for the clean substrate of plated film；
(2) mode using sputter coating at normal temperatures has plated amorphous thermocolour intelligence successively according to the film layer structure set Can light modulation film；When wherein preparing described vanadium oxide layer, Ar:O2Flow-rate ratio is 95:5～0.5, sputtering atmosphere pressure be 0.3Pa～ 0.8Pa；
The amorphous state thermocolour intelligent light modulation film on plated film substrate that step (2) is formed be placed in base vacuum less than 10Pa, It is filled with vacuum protection gas in the environment of 20Pa～1000Pa, uses radiation fluorescent tube heating and/or the mode of PULSE HEATING, greatly Compression ring border uses tempering annealing and/or the mode of Hot-blast Heating, to the amorphous state thermocolour intelligent dimming on described plated film substrate Film carries out heating anneal；Wherein annealing temperature 400 DEG C～700 DEG C, annealing time 30s～600s.
During in this programme, so-called vacuum protection atmosphere refers to the gas being filled with it is believed that not oxydant gas with And the gas without reproducibility effect, can be filled with such as Ar, N2And mixed gas based on this.
The preparation of the vanadium oxide layer in the present invention program uses target can be doping or be the vanadium metal target of doping, vanadium oxygen Compound ceramic target.
Further, it is also possible to include step (4), the thermocolour intelligent light modulation film that substrate is glass is entered with other vitreous body Row is compound, forms interlayer, hollow, the intelligent dimming glass of interlayer hollow structure.
The intelligent light modulation film of a kind of low transformation temperature provided by the present invention, it is also possible to be prepared as being combined by said method Become interlayer, hollow, the intelligent dimming glass of interlayer hollow structure, be especially suitable for building, car and boat energy saving door and window.
The beneficial effects of the present invention is:
(1) designed and promote the selection of crystallizing layer material by film layer, make vanadium oxide layer form the little crystal grain of vanadium oxide nanometer, and Realize crystallite dimension controllable, it is achieved the purpose that the phase transition temperature of the vanadium oxide material of vanadium oxide layer reduces.
(2) by promoting the selection of crystallizing layer material, regulation and control vanadium oxide layer grain size effectively, expand the outside unit of undoped The modification scope of phase transition temperature in the case of element, is beneficial to reduce difference doping external elements target configuration.
(3) the structure design of multilayer complex films layer is obviously improved the light thermal property of thermocolour intelligent light modulation film, solves antioxygen The property changed is poor, wear no resistance, problem that strange land processability is poor.
(4) structure of composite film can carry out heat treatment of annealing in atmospheric environment, especially can realize film layer tempering, heat Curved and keep the performance of intelligent light modulation film, its result breaks through tempering heat-treatment of annealing technical bottleneck, and batch production is greatly lowered Cost.
(5) this technical scheme provides technical process simple, easy to control.
Accompanying drawing explanation
Fig. 1 is the film layer structure of the thermocolour intelligent light modulation film of embodiment 1；
Fig. 2 is the film layer structure of the thermocolour intelligent light modulation film of embodiment 2；
Fig. 3 is the film layer structure of the thermocolour intelligent light modulation film of embodiment 3；
Fig. 4 is the film layer structure of the thermocolour intelligent light modulation film of embodiment 4；
Fig. 5 is the film layer structure of the thermocolour intelligent light modulation film of embodiment 5；
Reference:
1-substrate；2-first medium layer；3-vanadium oxide layer；4-promotees crystallizing layer；5-anti oxidation layer；6-second dielectric layer；
11-substrate；21-first medium layer；31-the first anti oxidation layer；41-first promotees crystallizing layer；51-vanadium oxide layer；61- Second promotees crystallizing layer；71-the second anti oxidation layer；81-second dielectric layer；
12-substrate；22-first medium layer；32-the first anti oxidation layer；42-first promotees crystallizing layer；52-vanadium oxide layer；62- Second promotees crystallizing layer；72-the second anti oxidation layer；82-second dielectric layer；
13-substrate；23-first medium layer；33-vanadium oxide layer；43-promotees crystallizing layer；53-infrared-reflecting layers；63-antioxygen Change layer；73-second dielectric layer；
14-substrate；24-first medium layer；34-the first anti oxidation layer；44-first promotees crystallizing layer；54-vanadium oxide layer；64- Second promotees crystallizing layer；74-the second anti oxidation layer；84-second dielectric layer；
Detailed description of the invention
Embodiment 1
As it is shown in figure 1, the thermocolour intelligent light modulation film of a kind of low transformation temperature, include substrate 1, first medium layer 2, oxygen successively Change vanadium layers 3, promote crystallizing layer 4, anti oxidation layer 5 and second dielectric layer 6.Described substrate 1 is glass material, and first medium layer 2 is TiOx material, vanadium oxide layer 3 is the vanadium oxide material with phase-change characteristic, and promoting crystallizing layer 4 is SiNx material, and anti oxidation layer 5 is NiCr material, second dielectric layer 6 is SiNx material.
The preparation method of the thermocolour intelligent light modulation film of described low transformation temperature is as follows: use magnetron sputtering plating mode, Use TiOx (at Ar, O successively2Atmosphere under), V is (at Ar, O2Atmosphere under), Si is (at Ar, N2Atmosphere under), NiCr is (at Ar Atmosphere under), Si is (at Ar, N2Atmosphere under) as target, successively at clean glass substrate (G) upper deposition first medium layer 2, vanadium oxide layer 3, rush crystallizing layer 4, anti oxidation layer 5, second dielectric layer 6, and form the film layer with following structure: G/TiOx/ VOx/SiNx/NiCr/SiNx.Wherein, the thickness of described first medium layer 2 (TiOx) is 30nm, the thickness of vanadium oxide layer 3 (VOx) Degree is 30nm, and the thickness promoting crystallizing layer 4 (SiNx) is 10nm, and the thickness of anti oxidation layer 5 (NiCr) is 2nm, second dielectric layer 6 (SiNx) thickness is 150nm.
Wherein, preparing vanadium oxide layer 3 (VOx) when, Ar:O2Flow-rate ratio be 95:2, sputtering pressure is 0.5Pa. Diaphragm after above-mentioned plated film on a glass substrate is put in the vacuum chamber being provided with infra-red radiation fluorescent tube, treats vacuum chamber It is filled with N to 10Pa～2Pa2It is 550 DEG C to 500Pa as protective atmosphere, infra-red radiation fluorescent tube annealing heating, heating-up temperature, It is cooled to less than 100 DEG C after heating 180s, ultimately forms the thermocolour intelligent dimming glass with phase transformation regulatory function, obtained heat The phase transition temperature of color intelligent dimming glass is 45.5 DEG C.
Embodiment 2
As in figure 2 it is shown, the thermocolour intelligent light modulation film of a kind of low transformation temperature, include successively substrate 11, first medium layer 21, First anti oxidation layer 31, first promotees crystallizing layer 41, vanadium oxide layer 51, second promotees crystallizing layer the 61, second anti oxidation layer 71 and second Dielectric layer 81.Described substrate 11 is glass material, and first medium layer 21 is TiOx material, and the first anti oxidation layer 31 is NiCrOx material Material, the first rush crystallizing layer 41 is ZrNx material, and vanadium oxide layer 51 is the vanadium oxide material with phase-change characteristic, and second promotees crystallizing layer 61 is SiNx material, and the second anti oxidation layer 71 is NiCr material, and second dielectric layer 81 is SiNx material.
The preparation method of the thermocolour intelligent light modulation film of described low transformation temperature is as follows: use magnetron sputtering plating mode, Use TiOx (at Ar, O successively2Atmosphere under), NiCr is (at Ar, O2Atmosphere under), Zr is (at Ar, N2Atmosphere under), V ( Ar、O2Atmosphere under), Si is (at Ar, N2Atmosphere under), NiCr (under the atmosphere of Ar), Si be (at Ar, N2Atmosphere under) conduct Target, deposits first medium layer the 21, first anti oxidation layer 31, first successively in clean glass substrate and promotees crystallizing layer 41, oxygen Change vanadium layers 51, second and promote crystallizing layer the 61, second anti oxidation layer 71 and second dielectric layer 81, and form the film layer of following structure: G/ TiOx/NiCrOx/SiNx/VOx/SiNx/NiCr/SiNx.Wherein, the thickness of first medium layer 21 (TiOx) is 30nm, first The thickness of anti oxidation layer 31 (NiCrOx) is 25nm, and the first thickness promoting crystallizing layer 41 (ZrNx) is 20nm, vanadium oxide layer 51 (VOx) thickness is 100nm, and the second thickness promoting crystallizing layer 61 (SiNx) is 70nm, the thickness of the second anti oxidation layer 71 (NiCr) Degree is 5nm, and the thickness of second dielectric layer 81 (SiNx) is 150nm.
Wherein, preparing vanadium oxide layer 51 (VOx) when, Ar:O2Flow-rate ratio be 95:5, sputtering pressure is 0.8Pa. Diaphragm after above-mentioned plated film on a glass substrate is put in the vacuum chamber being provided with infra-red radiation fluorescent tube, treats vacuum chamber To 5Pa, it is filled with N2It is 400 DEG C to 1000Pa as protective atmosphere, infra-red radiation fluorescent tube annealing heating, heating-up temperature, heating It is cooled to less than 100 DEG C after 600s, ultimately forms the thermocolour intelligent dimming glass with phase transformation regulatory function, obtained thermocolour intelligence The phase transition temperature of energy dimming glass is 48 DEG C.
Embodiment 3
As it is shown on figure 3, the thermocolour intelligent light modulation film of a kind of low transformation temperature, include successively substrate 12, first medium layer 22, First anti oxidation layer 32, first promotees crystallizing layer 42, vanadium oxide layer 52, second promotees crystallizing layer the 62, second anti oxidation layer 72 and second Dielectric layer 82.Described substrate 12 is glass material, and first medium layer 21 is SiNx material, and the first anti oxidation layer 31 is NiCrOx material Material, the first rush crystallizing layer 42 is SiNx material, and vanadium oxide layer 51 is the vanadium oxide material with phase-change characteristic, and second promotees crystallizing layer 61 is SiNx material, and the second anti oxidation layer 71 is NiCrOx-NiCr composite bed, and second dielectric layer 81 is ITO-SiNx composite bed.
The preparation method of the thermocolour intelligent light modulation film of described low transformation temperature is as follows: use magnetron sputtering plating mode, Use Si (at Ar, N successively2Atmosphere under), NiCr is (at Ar, O2Atmosphere under), Si is (at Ar, N2Atmosphere under), V2O3( Ar、O2Atmosphere under, the atomic ratio of V:O is about 2:3), Si is (at Ar, N2Atmosphere under), NiCr is (at Ar, O2Atmosphere under), NiCr (under the atmosphere of Ar), ITO are (at Ar, O2Atmosphere under), Si is (at Ar, N2Atmosphere under) as target, at clean glass It is sequentially depositing first medium layer the 22, first anti oxidation layer 32, first on glass substrate and promotees crystallizing layer 42, vanadium oxide layer the 52, second rush Crystallizing layer the 62, second anti oxidation layer 72 and second dielectric layer 82, and form the film layer with following structure: G/SiNx/NiCrOx/ SiNx/VOx/SiNx/NiCrOx/NiCr/ITO/SiNx.Wherein, the thickness of first medium layer 22 (SiNx) is 50nm, and first resists The thickness of oxide layer 32 (NiCrOx) is 15nm, and the first thickness promoting crystallizing layer 42 (SiNx) is 20nm, vanadium oxide layer 52 (VOx) Thickness be 150nm, second promote crystallizing layer 62 (SiNx) thickness be 20nm, the gross thickness of the second anti oxidation layer 72 is 10nm (wherein NiCrOx be 5nm, NiCr are 5nm), the gross thickness of second dielectric layer 82 is that (wherein ITO is that 50nm, SiNx are to 200nm 150nm)。
Wherein, preparing vanadium oxide layer 52 when, it is to use V2O3Ceramic target, Ar:O2Flow-rate ratio be 95:1, spatter Injection pressure is 0.3Pa.Diaphragm after above-mentioned plated film on a glass substrate is put in the vacuum chamber being provided with infra-red radiation fluorescent tube, This vacuum chamber base vacuum is less than 1Pa, is filled with N2Atmosphere is to 20Pa, and ambient temperature is 700 DEG C, is cooled to 100 DEG C after heating 30s Hereinafter, the thermocolour intelligent dimming glass with phase transformation regulatory function, the phase transformation of obtained thermocolour intelligent dimming glass are ultimately formed Temperature is 29.5 DEG C.
Embodiment 4
As shown in Figure 4, the thermocolour intelligent light modulation film of a kind of low transformation temperature, include successively substrate 13, first medium layer 23, Vanadium oxide layer 33, rush crystallizing layer 43, infrared-reflecting layers 53, anti oxidation layer 63 and second dielectric layer 73.Described substrate 13 is glass Glass material, first medium layer 23 is SiNx material, and vanadium oxide layer 33 is the vanadium oxide material with phase-change characteristic, promotees crystallizing layer 43 For SiNx material, infrared-reflecting layers 53 is Ag material, and anti oxidation layer 63 is Ti material, and second dielectric layer 73 is SiNx material.
The preparation method of the thermocolour intelligent light modulation film of described low transformation temperature is as follows: use magnetron sputtering plating mode, Use SiAl (at Ar, N successively2Atmosphere under), V is (at Ar, O2Atmosphere under), SiAl is (at Ar, N2Atmosphere under), Ag is (at Ar Atmosphere under), Ti (under the atmosphere of Ar), SiAl are (at Ar, N2Atmosphere under) as target, successively in clean glass substrate Upper deposition first medium layer 23, vanadium oxide layer 33, rush crystallizing layer 43, infrared-reflecting layers 53, anti oxidation layer 63 and second medium Layer 73, and form the film layer with following structure: G/SiNx/VOx/SiNx/Ag/Ti/SiNx.Wherein, first medium layer 23 (SiNx) thickness is 80nm, and the thickness of vanadium oxide layer 33 (VOx) is 100nm, and the thickness promoting crystallizing layer 43 (SiNx) is 20nm, The thickness of infrared-reflecting layers 53 (Ag) is 15nm, and the thickness of anti oxidation layer 63 (Ti) is 5nm, second dielectric layer 73 (SiNx) Thickness is 100nm.
Wherein, preparing vanadium oxide layer 53 when, Ar:O2Flow-rate ratio be 95:3.2, sputtering pressure is 0.4Pa.Will Diaphragm after above-mentioned plated film on a glass substrate is put in the vacuum chamber being provided with infra-red radiation fluorescent tube, treats that vacuum chamber is extremely 10-2After Pa magnitude, it is filled with N2Annealing to 300Pa as protective atmosphere, infra-red radiation fluorescent tube, heating-up temperature is 500 DEG C, heating It is cooled to less than 100 DEG C after 400s, ultimately forms the thermocolour intelligent dimming glass with phase transformation regulatory function, obtained thermocolour intelligence The phase transition temperature of energy dimming glass is 46 DEG C.
First medium layer described in the present embodiment 23 also can be considered rush crystallizing layer, and selected materials also has rush crystallization.
Embodiment 5
As it is shown in figure 5, the thermocolour intelligent light modulation film of a kind of low transformation temperature, include successively substrate 14, first medium layer 24, First anti oxidation layer 34, first promotees crystallizing layer 44, vanadium oxide layer 54, second promotees crystallizing layer the 64, second anti oxidation layer 74 and second Dielectric layer 84.Described substrate 14 is glass material, and first medium layer 24 is SiNx material, and the first anti oxidation layer 34 is NiCr material Material, the first rush crystallizing layer 44 is SiNx material, and vanadium oxide layer 54 is the vanadium oxide material with phase-change characteristic, and second promotees crystallizing layer 64 is SiNx material, and the second anti oxidation layer 74 is NiCr material, and second dielectric layer 84 is SiNx material.
The preparation method of the thermocolour intelligent light modulation film of described low transformation temperature is as follows: use magnetron sputtering plating mode, Use SiAl (at Ar, N successively2Atmosphere under), NiCr (under the atmosphere of Ar), Si are (at Ar, N2Atmosphere under), V is (at Ar, O2 Atmosphere under), Si is (at Ar, N2Atmosphere under), NiCr (under the atmosphere of Ar), Si be (at Ar, N2Atmosphere under) as target, In clean glass substrate, deposit first medium layer the 24, first anti oxidation layer 34, first successively promote crystallizing layer 44, vanadium oxide layer 54, second promotees crystallizing layer the 64, second anti oxidation layer 74 and second dielectric layer 84, and forms the film layer with following structure: G/ SiNx/NiCr/SiNx/VOx/SiNx/NiCr/SiNx.Wherein the thickness of first medium layer 24 (SiNx) is 50nm, the first antioxygen The thickness changing layer 34 (NiCr) is 8nm, and the first thickness promoting crystallizing layer 44 (SiNx) is 20nm, the thickness of vanadium oxide layer 54 (VOx) Degree for 100nm, the second thickness promoting crystallizing layer 64 (SiNx) be 20nm, the thickness of the second anti oxidation layer 74 (NiCr) is 10nm, The thickness of second dielectric layer 84 (SiNx) is 50nm.
Wherein, preparing vanadium oxide layer 54 when, Ar:O2Flow-rate ratio be 95:2.0, sputtering pressure is 0.5Pa.Will Diaphragm after above-mentioned plated film on a glass substrate puts into annealing furnace tempering, tempering temperature 685 DEG C, whole heat treatment time 6min, The final phase transition temperature obtaining thermocolour intelligent dimming glass is 56 DEG C.
Embodiment 6
For the present embodiment is compared to embodiment 5, difference is, preparing vanadium oxide layer when, V target adulterates Molar concentration is the W of 1.5%, and the final phase transition temperature obtaining thermocolour intelligent dimming glass is 19 DEG C.
Embodiment 7
For the present embodiment is compared to embodiment 5, difference is, on the basis of the film layer structure of embodiment 5, The outer surface of second medium layer with the addition of the 3rd anti oxidation layer (NiCr material) and the 3rd dielectric layer (SiNx material) the most successively, is formed There is the film layer of following structure: G/SiNx (thickness is 50nm)/NiCr (thickness is 8nm)/SiNx (thickness is 20nm)/VOx (thick Degree is 100nm) (thickness is /SiNx (thickness is 20nm)/NiCr (thickness is 10nm)/SiNx (thickness is 50nm)/NiCr 10nm)/SiNx (thickness is 50nm).Next to that, the method for the thermocolour intelligent light modulation film that the present embodiment prepares low transformation temperature is, Mode initially with magnetron sputtering is sequentially depositing above-mentioned film layer, then by after plated film on a glass substrate on the right substrate of glass Diaphragm be placed in atmospheric environment, be preheated to 400 DEG C through infra-red radiation fluorescent tube, then through flash lamp heat treated, finally obtain Intelligent dimming Phase transition temperature is 51 DEG C.
Embodiment 8
For the present embodiment is compared to embodiment 5, difference is, substrate is PET film, and uses LASER HEATING Film layer is annealed by mode, and the final intelligent dimming Phase transition temperature that obtains is 48.5 DEG C.
Embodiment 9
The film layer structure of the intelligent light modulation film in the present embodiment be G/ZrNx (thickness is 60nm)/VOx (thickness is 80nm)/ ZrNx (thickness is 80nm), wherein ZrNx is as promoting crystallizing layer.Wherein when preparing VOx layer, use metal V target, at Ar:O2 Flow-rate ratio is preparation under conditions of 95:3.5, and the film layer of preparation, after background vacuum is extracted into less than 10Pa, is filled with Ar extremely 50Pa as ambiance, uses infra-red radiation fluorescent tube heating anneal, annealing temperature 550 DEG C, heat time heating time 150s；Final acquisition The phase transition temperature of intelligent light modulation film be 39 DEG C.
Embodiment 10
For embodiment 9, difference is, the film layer structure of the intelligent light modulation film of the present embodiment is G/SiOx (thickness is (thickness is 50nm)/ZrNx (thickness is 25nm)/VOx (thickness is 90nm)/ZrNx (thickness is 25nm)/TiOx 70nm), the phase transition temperature of the intelligent light modulation film finally preparing gained is 43 DEG C.
Embodiment 11
The present embodiment is thermocolour intelligent light modulation film embodiment 6 obtained, by PVB and another glass substrate bonding system Become the thermocolour intelligent dimming glass of sandwich format, the most also the thermocolour intelligent dimming glass after annealing (is contained by metal framework Adhesive glue) it is compounded to form hollow form intelligent dimming glass with another glass substrate, the heat of the sandwich format being again here formed as Color intelligent dimming glass is compounded to form interlayer hollow structure form by metal framework (containing adhesive glue) and another glass substrate Thermocolour intelligent dimming glass.
Embodiment 12
Compared to embodiment 1, the difference of the present embodiment is, prepares the oxide pottery for vanadium that vanadium oxide layer uses Porcelain target, wherein the atomic ratio of V:O is about 1:2 it can be understood as VO2Or V2O4Ceramic target, its sputter procedure Ar:O2Stream Amount ratio is 95:0.5sccm.The phase transition temperature of final the obtained intelligent light modulation film of the present embodiment is 49 DEG C.
In above-described embodiment, so-called SiAl target essence is so-called for Si, be intended merely to the electric conductivity increasing Si with And heat conductivility, therefore a small amount of Al that adulterates in Si, SiAl target can be expressed as.

Claims (10)

1. a thermocolour intelligent light modulation film for low transformation temperature, is provided with the vanadium oxide layer with phase-change characteristic on substrate；It is special Levy and be: at least one surface of described vanadium oxide layer, be compounded with rush crystallizing layer；The material of described rush crystallizing layer is selected from having Vanadium oxide is promoted to form the metal nitride of the little crystal particle function of nanometer, alloy nitride, the nitride of silicon, the nitride of silicon alloy In one or more.
The thermocolour intelligent light modulation film of a kind of low transformation temperature the most as claimed in claim 1, it is characterised in that: it is additionally provided with first Jie Matter layer and/or second dielectric layer；Described first medium layer is arranged between described substrate and vanadium oxide layer；Described second dielectric layer It is arranged on the top layer of the vanadium oxide layer opposite side relative with substrate.
The thermocolour intelligent light modulation film of a kind of low transformation temperature the most as claimed in claim 2, it is characterised in that: described first medium Layer and the material of second dielectric layer be respectively TiOx, TiNx, AlOx, AlNx, SiNx, SiOx, SiNxOy, HfOx, NbOx, One or more in TaOx, ZrOx, ZrNx, ZnOx, SnOx, ZnSnOx, ZnS, ITO, ATO, AZO, FTO, IGO.
The thermocolour intelligent light modulation film of a kind of low transformation temperature the most as claimed in claim 2, it is characterised in that: it is additionally provided with antioxidation Layer；Described anti oxidation layer be arranged between described first medium layer and vanadium oxide layer and/or second dielectric layer and vanadium oxide layer it Between.
The thermocolour intelligent light modulation film of a kind of low transformation temperature the most as claimed in claim 4, it is characterised in that: described anti oxidation layer Material selected from Ti or its alloy, Al or its alloy, Ni or its alloy, Cr or the oxide of its alloy, Ti or its alloy, Al or The nitride of the oxide of the oxide of the oxide of its alloy, Ni or its alloy, Cr or its alloy, Ti or its alloy, Al or One or more in the nitride of the nitride of the nitride of its alloy, Ni or its alloy, Cr or its alloy.
The thermocolour intelligent light modulation film of a kind of low transformation temperature the most as claimed in claim 1, it is characterised in that: described rush crystallizing layer Material selected from the nitride of chromium, the nitride of zirconium, the nitride of silicon, the nitrogen oxides (SiNxOy) of silicon, the nitridation of silicon alloy One or more in thing.
The thermocolour intelligent light modulation film of a kind of low transformation temperature the most as claimed in claim 1, it is characterised in that: described rush crystallizing layer The granularity of the little crystal grain of nanometer promoting described vanadium oxide layer to be formed is for less than 25nm.
The thermocolour intelligent light modulation film of a kind of low transformation temperature the most as claimed in claim 1, it is characterised in that: described vanadium oxide Layer is for be doped with the element reducing himself phase transition temperature function.
The thermocolour intelligent light modulation film of a kind of low transformation temperature the most as claimed in claim 1, it is characterised in that: it is additionally provided with infrared ray Reflecting layer；Described infrared-reflecting layers is arranged at least one surface of described vanadium oxide layer.
The preparation method of the thermocolour intelligent light modulation film of a kind of low transformation temperature the most as claimed in claim 1, it is characterised in that Comprise the following steps:
(1) offer can be used for the clean substrate of plated film；
(2) mode using sputter coating at normal temperatures has been plated amorphous thermocolour intelligence successively according to the film layer structure set and has been adjusted Light film；When wherein preparing described vanadium oxide layer, Ar:O2Flow-rate ratio is 95:5～0.5, sputtering atmosphere pressure be 0.3Pa～ 0.8Pa；
(3) the amorphous state thermocolour intelligent light modulation film on the plated film substrate that step (2) is formed be placed in base vacuum less than 10Pa, fill Enter vacuum protection gas in the environment of 20Pa～1000Pa, use radiation fluorescent tube heating and/or the mode of PULSE HEATING, at air Environment uses tempering annealing and/or the mode of Hot-blast Heating, to the amorphous state thermocolour intelligent light modulation film on described plated film substrate Carry out heating anneal；Wherein annealing temperature 400 DEG C～700 DEG C, annealing time 30s～600s.
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