CN106045332B - A kind of thermocolour intelligent light modulation film of low transformation temperature and preparation method thereof - Google Patents

A kind of thermocolour intelligent light modulation film of low transformation temperature and preparation method thereof Download PDF

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CN106045332B
CN106045332B CN201610392784.6A CN201610392784A CN106045332B CN 106045332 B CN106045332 B CN 106045332B CN 201610392784 A CN201610392784 A CN 201610392784A CN 106045332 B CN106045332 B CN 106045332B
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layer
vanadium oxide
alloy
film
light modulation
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CN106045332A (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
    • 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
    • C03C17/3644—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
    • C—CHEMISTRY; METALLURGY
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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
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—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
    • 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
    • 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
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    • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C03C17/3626—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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    • C03C17/3602—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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    • 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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    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
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    • 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
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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
    • C23C14/0641—Nitrides
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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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    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • 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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    • B32—LAYERED PRODUCTS
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    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
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    • 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

The present invention provides thermocolour intelligent light modulation films of a kind of low transformation temperature and preparation method thereof.The thermocolour intelligent light modulation film is equipped with the vanadium oxide layer with phase-change characteristic on substrate；Particularly, at least one surface recombination of the vanadium oxide layer has rush crystallizing layer；The material for promoting crystallizing layer is selected from one of nitride with the metal nitride for promoting the vanadium oxide layer to form nanometer little crystal grain function, alloy nitride, the nitride of silicon, silicon alloy or a variety of.Thermocolour intelligent light modulation film provided by the invention is not necessarily to reduce the element of phase transition temperature by adulterating other in the vanadium oxide material with phase-change characteristic, it need to only be select and set by the material of film layer, the size that there is the vanadium oxide material layer of phase-change characteristic to form nanometer little crystal grain is controlled, the phase transition temperature of 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, and in particular to a kind of thermocolour intelligent light modulation film of low transformation temperature and its Preparation method.
Background technique
VO2As a kind of novel energy-saving material, unique phase transformation can occurs in it near 68 DEG C of phase transformation temperature points.Work as ring When border temperature is higher than phase transition temperature, VO2In tetragonal crystalline structure, there is metal phase behaviour, infrared ray can be reflected；When environment temperature When degree is lower than phase transition temperature, VO2In monoclinic structure, there is semiconductor phase behaviour, infrared ray can be penetrated.Therefore VO2Film layer Up to no less than 20% solar energy regulation rate can be undergone phase transition and obtained under sunlight irradiation.Therefore since nineteen fifty-nine Morin is sent out Now since its phase transition function characteristic, VO2Material is by door and window energy conservation market and the extensive concern of domestic and international research institution.
In order to which the vanadium oxide thermocolour intelligent dimming glass made obtains widely application in energy-saving field, in the prior art, Have using sputtering sedimentation vanadium metal film on substrate, then annealing is obtained with the phase transition temperature down to 43 DEG C in air The method of mono-layer oxidized vanadium intelligent light modulation film, but its annealing process time is long, is unfavorable for batch machining production；Meanwhile because of film Layer structure is simple, and inoxidizability, wearability, strange land machinability are poor, are also unfavorable for producing in batches.Patent document CN 104250068A discloses a kind of technical solution of MULTILAYER COMPOSITE film layer preparation for preparing low transformation temperature, effectively reduces thermocolour The phase transition temperature of smart membrane improves the antioxygenic property etc. of the film layer, however, the technical solution, which uses, is first coated with doping gold Belong to film layer, then anneal at relatively high temperatures, then is coated with other protective layer film layers or antireflective in thermocolour film layer after annealing Film layer.Since the oxidizing annealing temperature of metal film is higher and annealing time is longer, coating process controls difficulty and increases, while the skill Art scheme increases the complexity of technique, is unfavorable for batch machining production.In addition, can be reduced by way of element doping Phase transition temperature, but different phase transition temperatures need to provide the materials such as the target of different levels of doping, since element doping will lead to The reduction of light thermal property, therefore element doping amount needs accurate control.Therefore, the film of the practical control or preparation of which Phase transition temperature region is subject to certain restrictions.
The influence factor of phase transition temperature is more, such as the difference of stress, ingredient, grain size has obviously phase transition temperature Influence.Some researches show that the differences of vanadium oxide grain size can adjust phase transition temperature.Show crystal grain from variation tendency The smaller then phase transition temperature of size is lower.
It is analyzed based on the prior art, in order to solve the problems, such as to regulate and control by a relatively large margin undoped with external elements realization phase transition temperature, Intelligent light modulation film light thermal property is poor, inoxidizability is poor, wears no resistance, the problem of strange land processability difference, it is necessary to research and develop A kind of thermocolour intelligent light modulation film of the low transformation temperature for the element that can be not necessarily to reduce vanadium oxide material phase transition temperature by doping out.
Summary of the invention
The present invention solves to solve the limitation during prior art preparation low transformation temperature thermocolour intelligent light modulation film It quantitatively adulterates the configuration of external elements target, preparation process flow, preparation or production efficiency and promotes intelligent light modulation film photo-thermal The problem of in terms of performance, antioxygenic property and strange land processability, propose a kind of low transformation temperature intelligent light modulation film and Preparation method.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of thermocolour intelligent light modulation film of low transformation temperature is equipped with the vanadium oxide layer with phase-change characteristic on substrate；It is special Not: being compounded with rush crystallizing layer at least one surface of the vanadium oxide layer；The material for promoting crystallizing layer, which is selected to have, to be promoted Form vanadium oxide in the nitride of the metal nitride of nanometer little crystal grain function, alloy nitride, the nitride of silicon, silicon alloy It is one or more.
Heretofore described vanadium oxide layer will form a nanometer little crystal grain, so-called nanometer small crystalline substance under the action of promoting crystallizing layer Grain, which refers to, crystallizes layer material induction by the rush, and vanadium oxide layer is caused crystallize formation as low as 25nm and its following during heating Crystal grain.The technical scheme is that the film layer structure to be interacted by setting, and by selecting different rush crystallizing layers Material, in conjunction with different preparation process conditions, so that the grain size that vanadium oxide layer forms crystallization can be adjusted in a certain range Control, so that oxidation can be regulated and controled in a big way in the case where also realizing the element for reducing vanadium oxide phase transition temperature that undopes The phase transition temperature of vanadium layers.Vanadium oxide layer in the present invention refers to the oxide comprising a kind of vanadium with thermocolour characteristic, especially Vanadium dioxide.Further, the vanadium oxide layer refers to the vanadium oxide composite material including at least vanadium dioxide, is represented by VOx, wherein x < 2；Further, it is preferable to 1.5 < x < 2；Or comprising a kind of peroxide for crossing vanadium, it is represented by VOx, In 2 x≤2.5 <；It is either the oxide of the vanadium of a variety of vanadium ion valence states, but is formed by the average V:O atom of oxide 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 to be formed Atomic ratio crystallizes the mixture close to the multivalent state with thermocolour characteristic of 1:2.In the present invention vanadium oxide layer with a thickness of 50nm~150nm.
Heretofore described vanadium oxide layer can be the smart membrane with low transformation temperature obtained through Overheating Treatment Noncrystalline precursor layer.The vanadium oxide layer can choose the vanadium oxide material layer of the undoped element for reducing phase transition temperature, Its phase transition temperature can be reduced to 35 DEG C or so from 68 DEG C of pure phase vanadium dioxide after forming crystal grain.In order to obtain the phase of wider model The adjusting space of temperature, the vanadium oxide layer also may be selected to be doped with the oxidation for reducing its own phase transition temperature functional element Vanadium material, its phase transition temperature can be reduced to 10 DEG C or so from 68 DEG C of pure phase vanadium dioxide after forming crystal grain.
A kind of thermocolour intelligent light modulation film of low transformation temperature provided by the present invention is further preferably additionally provided with first Dielectric layer and/or second dielectric layer.The first medium layer is arranged between the substrate and vanadium oxide layer；The second medium The most surface layer of the vanadium oxide layer opposite side opposite with substrate is arranged in layer.The 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 of ZrNx, ZnOx, SnOx, ZnSnOx, ZnS, ITO, ATO, AZO, FTO, IGO or a variety of.The first medium layer and The thickness of second dielectric layer is respectively 30nm~200nm.Preferably, the second dielectric layer is at least in most surface, i.e., with oxidation The opposite opposite side of vanadium layers, heat resistance, the good nitride of wear-resisting property or nitrogen oxidation comprising being no less than 20nm thickness Object material, such as SiNx, SiNxOy, ZrNx.Preferably, the first medium layer side opposite with substrate includes at least many In SiNx, SiNxOy, ZrNx, CrNx of 20nm thickness.Described conductive oxide ITO, ATO, AZO, FTO, the IGO be have it is red External reflectance function, then it is preferably set in first medium layer or any one layer of second dielectric layer and forms composite layer；Or When being equipped with rush crystallizing layer between first medium layer and vanadium oxide layer, first medium layer can also be preferably provided at and promote to crystallize Between layer；Or when being equipped with rush crystallizing layer between second dielectric layer and vanadium oxide layer, second medium can also be preferably provided at Between layer and rush crystallizing layer.The first medium layer and second dielectric layer may be selected heterogeneity material, be respectively formed difference The composite layer of structure.As first medium layer can be the composite layer of SiNx+ITO+SiNx.It is further preferably the oxidation The vanadium layers side opposite with substrate is equipped with first medium layer, and the other side of the vanadium oxide layer also is provided with second dielectric layer.
A kind of thermocolour intelligent light modulation film of low transformation temperature provided by the present invention is further preferably additionally provided with antioxygen Change layer.The anti oxidation layer is arranged between the first medium layer and vanadium oxide layer and/or second dielectric layer and vanadium oxide layer Between.The anti oxidation layer and the rush crystallizing layer can be set in the ipsilateral of vanadium oxide layer and/or be separately positioned on vanadium oxide Layer two sides, and when vanadium oxide layer it is ipsilateral both be equipped with promote crystallizing layer also be provided with anti oxidation layer when, preferably successively with oxidation Vanadium layers/rush crystallizing layer/anti oxidation layer sequence setting.Specifically, including situation arranged below: (1) anti oxidation layer/rush knot Crystal layer/vanadium oxide layer；(2) anti oxidation layer/first promotees crystallizing layer/vanadium oxide layer/second and promotees crystallizing layer；(3) first anti oxidation layers/ First, which promotees crystallizing layer/vanadium oxide layer/second, promotees crystallizing layer/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 the 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 its alloy, the oxide of Al or its alloy, Ni or the oxide of its alloy, the oxide of Cr or its alloy, Ti Or the nitride of its alloy, the nitride of Al or its alloy, Ni or the nitride of its alloy, the nitride of Cr or its alloy, Ti Silicide, the silicide of Al, the silicide of Ni, Cr one of silicide or a variety of.The Ti or its alloy, Al or its Alloy, Ni or its alloy, Cr or its alloy preferably include the alloy material of Si element doping.The antioxygen layer specifically may be selected Material include but do not limit: NiCr, NiCrOx, NiCrNx, NiCr+NiCrOx, NiCr+NiCrNx, NiCrOx+NiCrNx, NiCrOx+NiCr, NiCrNx+NiCr, NiCrNx+NiCrOx, NiSi, CrAlSi etc..The material and non-limiting NiCr base This material, the material protected can form such structure in other compound present invention.It and include more than one in light modulation film When the anti oxidation layer of layer, the composite material and composite construction of the anti oxidation layer of different location can be different.Such as wherein one layer of antioxygen Change layer is NiCrOx, and in addition one layer of anti oxidation layer is Ti layers.The anti oxidation layer with a thickness of 2nm~25nm, it is further excellent It is selected as 5nm~20nm.According to different heat treatment modes, as long as can be avoided vanadium oxide film layer during heat treatment by oxygen Change, corresponding barrier layer can use thickness thin as far as possible, this is conducive to the light such as the visible light transmittance of whole thermocolour intelligent dimming layer The promotion of thermal property.It is simple and easy to control for preparation process, it is preferred to use same target preparation single or double layer is compound Barrier layer.
In the present invention, the material for promoting 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 one of nitride or a variety of.The optional material It is that itself has stronger heat resistance, is especially able to bear in the environment that temperature is up to 700 DEG C several minutes without causing Promote the cracking of crystallizing layer itself or falls off.Further, when the rush crystallizing layer and the first medium layer or second dielectric layer Or anti oxidation layer compound tense, the oxidation resistant multiple protective of more stable heatproof can be played to vanadium oxide layer, so that the present invention designs Film layer structure can be deposited in substrate of glass progress tempering heat treatment.Secondly, the material for promoting crystallizing layer selection is 700 DEG C temperature is nearby heat-treated the case where 600s time and is not easy to crystallize or for amorphous state, so that vanadium oxide layer is in annealing crystallization The problem being hardly difficult to control in the process by phase transition temperature caused by possible Lattice Matching, while vanadium oxide layer being inhibited to select Aristogenesis produces, and promotes the randomness in its production process to crystallize, so that reaching purposefully reduces vanadium oxide material in vanadium oxide layer Material forms the size of crystal grain.Again, the material for promoting crystallizing layer selection has preferable stop for the diffusion of other elements Effect, particularly, when such as anti oxidation layer selection such as NiCr material, Ni has stronger scattering nature, and diffusion will cause to aoxidize The increase of vanadium layers phase transition temperature and situations such as be reduced, and then the comprehensive performance of vanadium oxide layer is influenced, therefore the material One of effect can also play the role of barrier metal elements diffusion.Based on the considerations of above-mentioned factor and film layer photo-thermal The design of energy, the rush crystallizing layer further preferably have the good nitride of heat resistance, such as SiNx, ZrNx, thickness It is further preferred with a thickness of 5nm~40nm for for 3nm~70nm, still more preferably with a thickness of 10nm~30nm.Work as oxygen When the two sides of change vanadium layers are equipped with rush crystallizing layer, the rush crystallizing layer of vanadium oxide layer two sides can select different ingredient materials respectively Material, the thickness of both can also have difference.When the wherein side of vanadium oxide layer, setting promotees crystallizing layer, then the preferably described rush is tied Vanadium oxide layer is arranged in toward the side of second dielectric layer in crystal layer.It is further preferred to promote the SiNx material that crystallizing layer is single layer Material, target supply are easy, and process flow is simple.
Further, the thermocolour intelligent light modulation film of a kind of low transformation temperature provided by the invention, it is also desirable to be equipped with infrared ray Reflecting layer.At least one surface of the vanadium oxide layer is arranged in the infrared-reflecting layers.Preferably, the infrared reflection Layer with a thickness of 1nm~15nm.Preferably, the infrared-reflecting layers are the gold of at least one of Pt, Au, Ag, Cu, Al element Belong to the doping of at least one of alloy-layer, Pt, Au, Ag, Cu, Al of at least one of layer, Pt, Au, Ag, Cu, Al element element The composite layer of metal layer or the layer.The infrared-reflecting layers may also be arranged between first medium layer and second dielectric layer Any position.If a wherein side surface for vanadium oxide layer, which is equipped with, promotees crystallizing layer, infrared-reflecting layers are preferably provided in described Promote crystallizing layer toward the vanadium oxide layer opposite side surface.Further, the infrared-reflecting layers are preferably Vanadium oxide layer is set close to the side of first medium layer, is conducive to the efficiency for increasing annealing in this way.
Heretofore described substrate is selected from organic flexible substrate, inorganic flexible substrate, organic non-flexible substrate, inorganic non- One of flexible base board.Specific such as flexible macromolecule film, flexible glass, flexible metal；Inflexible ceramics, glass, metal, Polymeric substrate.Preferably PET film, flexibility/non-flexible glass substrate material.The claims in the present invention do not limit substrate thickness and The color of its own.
The material of related film layer in the present invention, so-called nitride, oxide or nitrogen oxides etc., the preparation of film layer Realize that corresponding metal targets, metal oxide or metal nitride ceramic target are including the gas of reactive sputtering gas accordingly Form a film in atmosphere environment, can be obtained in usual sputter coating environment, do not require must composite chemical metering ratio film layer at Point.
Above-mentioned cited specific material, film layer structure in the present invention are not intended as accompanying claims in the present invention and protect Any restrictions of shield, only as helping to understand the expression meaning in the present invention and the common material or structure type listed.
The present invention also provides a kind of preparation methods of the thermocolour intelligent light modulation film of low transformation temperature, comprising the following steps:
(1) the clean substrate that can be used for plated film is provided；
(2) amorphous thermocolour intelligence has successively been plated according to the film layer structure of setting by the way of sputter coating at normal temperature It can light modulation film；When wherein preparing the vanadium oxide layer, Ar:O2Flow-rate ratio be 95:5~0.5, sputtering atmosphere pressure be 0.3Pa~ 0.8Pa；
By step (2) formed plated film substrate on amorphous state thermocolour intelligent light modulation film be placed in base vacuum lower than 10Pa, It is filled in the environment of vacuum protection gas to 20Pa~1000Pa, by the way of the heating of radiation fluorescent tube and/or PULSE HEATING, big In compression ring border by the way of tempering annealing and/or Hot-blast Heating, to the amorphous state thermocolour intelligent dimming on the plated film substrate Film carries out heating anneal；Wherein 400 DEG C~700 DEG C of annealing temperature, annealing time 30s~600s.
In this programme so-called vacuum protection atmosphere refer in the gas being filled with it is considered that not the gas of oxydant with And the gas without reproducibility effect, it can be filled with such as Ar, N2And its mixed gas based on this.
The preparation of vanadium oxide layer in the present invention program use target can for adulterate or be doping vanadium metal target, vanadium oxygen Compound ceramic target.
Further, can also include step (4), by substrate be glass thermocolour intelligent light modulation film and other vitreums into Row is compound, forms interlayer, hollow, interlayer hollow structure intelligent dimming glass.
A kind of intelligent light modulation film of low transformation temperature provided by the present invention can also be prepared into compound by the above method At interlayer, hollow, interlayer hollow structure intelligent dimming glass, it is especially suitable for building, car and boat energy saving door and window.
The beneficial effects of the present invention are:
(1) selection that crystallization layer material is designed and promoted by film layer makes vanadium oxide layer form vanadium oxide nanometer little crystal grain, and It realizes that crystallite dimension is controllable, realizes the purpose that the phase transition temperature of the vanadium oxide material of vanadium oxide layer reduces.
(2) by promoting the selection of crystallization layer material, effectively regulate and control vanadium oxide layer grain size, expand undoped external member The modification scope of phase transition temperature in plain situation is conducive to reduce different doping external elements target configurations.
(3) the structure design of MULTILAYER COMPOSITE film layer is obviously improved the light thermal property of thermocolour intelligent light modulation film, solves antioxygen The property changed is poor, wears no resistance, the problem of strange land processability difference.
(4) structure of composite film can carry out annealing heat-treatment in atmospheric environment, can especially realize film layer tempering, heat Performance that is curved and keeping intelligent light modulation film, result break through tempering heat-treatment of annealing technical bottleneck, batch production are greatly lowered Cost.
(5) technical solution offer technical process is simple, easy to control.
Detailed description of the invention
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；
Appended drawing 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；The first anti oxidation layer of 31-；41- first promotees crystallizing layer；51- vanadium oxide layer；61- Second promotees crystallizing layer；The second anti oxidation layer of 71-；81- second dielectric layer；
12- substrate；22- first medium layer；The first anti oxidation layer of 32-；42- first promotees crystallizing layer；52- vanadium oxide layer；62- Second promotees crystallizing layer；The second anti oxidation layer of 72-；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；The first anti oxidation layer of 34-；44- first promotees crystallizing layer；54- vanadium oxide layer；64- Second promotees crystallizing layer；The second anti oxidation layer of 74-；84- second dielectric layer；
Specific embodiment
Embodiment 1
As shown in Figure 1, a kind of thermocolour intelligent light modulation film of low transformation temperature, successively includes substrate 1, first medium layer 2, oxygen Change vanadium layers 3, promote crystallizing layer 4, anti oxidation layer 5 and second dielectric layer 6.The substrate 1 is glass material, and first medium layer 2 is TiOx material, vanadium oxide layer 3 are the vanadium oxide material with phase-change characteristic, and rush crystallizing layer 4 is SiNx material, and anti oxidation layer 5 is NiCr material, second dielectric layer 6 are SiNx material.
The thermocolour intelligent light modulation film of the low transformation temperature the preparation method is as follows: using magnetron sputtering plating mode, Successively using TiOx (in Ar, O2Atmosphere under), V is (in Ar, O2Atmosphere under), Si is (in Ar, N2Atmosphere under), NiCr is (in Ar Atmosphere under), Si is (in Ar, N2Atmosphere under) be used as target, successively in clean glass substrate (G) deposit 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 having the following structure: G/TiOx/ VOx/SiNx/NiCr/SiNx.Wherein, the first medium layer 2 (TiOx) with a thickness of 30nm, the thickness of vanadium oxide layer 3 (VOx) Degree is 30nm, promote crystallizing layer 4 (SiNx) with a thickness of 10nm, anti oxidation layer 5 (NiCr) with a thickness of 2nm, second dielectric layer 6 (SiNx) with a thickness of 150nm.
Wherein, when preparing vanadium oxide layer 3 (VOx), Ar:O2Flow-rate ratio be 95:2, sputtering pressure 0.5Pa. Diaphragm after above-mentioned plated film on a glass substrate is put into the vacuum chamber for being provided with infra-red radiation fluorescent tube, to vacuum chamber N is filled with after to 10Pa~2Pa2To 500Pa as protective atmosphere, infra-red radiation fluorescent tube annealing heating, heating temperature is 550 DEG C, 100 DEG C are cooled to hereinafter, ultimately form the thermocolour intelligent dimming glass with phase transformation regulatory function after heating 180s, obtain heat The phase transition temperature of color intelligent dimming glass is 45.5 DEG C.
Embodiment 2
As shown in Fig. 2, a kind of thermocolour intelligent light modulation film of low transformation temperature, successively include substrate 11, first medium layer 21, First anti oxidation layer 31, first promotees crystallizing layer 41, vanadium oxide layer 51, second promotees crystallizing layer 61, the second anti oxidation layer 71 and second Dielectric layer 81.The substrate 11 is glass material, and first medium layer 21 is TiOx material, and the first anti oxidation layer 31 is NiCrOx material Material, first promotees crystallizing layer 41 as ZrNx material, and vanadium oxide layer 51 is the vanadium oxide material with phase-change characteristic, and second promotees crystallizing layer 61 be SiNx material, and the second anti oxidation layer 71 is NiCr material, and second dielectric layer 81 is SiNx material.
The thermocolour intelligent light modulation film of the low transformation temperature the preparation method is as follows: using magnetron sputtering plating mode, Successively using TiOx (in Ar, O2Atmosphere under), NiCr is (in Ar, O2Atmosphere under), Zr is (in Ar, N2Atmosphere under), V ( Ar、O2Atmosphere under), Si is (in Ar, N2Atmosphere under), NiCr (under the atmosphere of Ar), Si is (in Ar, N2Atmosphere under) conduct Target successively deposits first medium layer 21 in clean glass substrate, the first anti oxidation layer 31, first promotees crystallizing layer 41, oxygen Change vanadium layers 51, second and promote crystallizing layer 61, the second anti oxidation layer 71 and second dielectric layer 81, and forms the film layer such as flowering structure: G/ TiOx/NiCrOx/SiNx/VOx/SiNx/NiCr/SiNx.Wherein, first medium layer 21 (TiOx) with a thickness of 30nm, first Anti oxidation layer 31 (NiCrOx) with a thickness of 25nm, first promote crystallizing layer 41 (ZrNx) with a thickness of 20nm, vanadium oxide layer 51 (VOx) with a thickness of 100nm, second promote crystallizing layer 61 (SiNx) with a thickness of 70nm, the thickness of the second anti oxidation layer 71 (NiCr) Degree be 5nm, second dielectric layer 81 (SiNx) with a thickness of 150nm.
Wherein, when preparing vanadium oxide layer 51 (VOx), Ar:O2Flow-rate ratio be 95:5, sputtering pressure 0.8Pa. Diaphragm after above-mentioned plated film on a glass substrate is put into the vacuum chamber for being provided with infra-red radiation fluorescent tube, to vacuum chamber To 5Pa, it is filled with N2To 1000Pa as protective atmosphere, infra-red radiation fluorescent tube annealing heating, heating temperature is 400 DEG C, heating 100 DEG C are cooled to after 600s hereinafter, ultimately form 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 shown in figure 3, a kind of thermocolour intelligent light modulation film of low transformation temperature, successively include substrate 12, first medium layer 22, First anti oxidation layer 32, first promotees crystallizing layer 42, vanadium oxide layer 52, second promotees crystallizing layer 62, the second anti oxidation layer 72 and second Dielectric layer 82.The substrate 12 is glass material, and first medium layer 22 is SiNx material, and the first anti oxidation layer 32 is NiCrOx material Material, first promotees crystallizing layer 42 as SiNx material, and vanadium oxide layer 52 is the vanadium oxide material with phase-change characteristic, and second promotees crystallizing layer 62 be SiNx material, and the second anti oxidation layer 72 is NiCrOx-NiCr composite layer, and second dielectric layer 82 is ITO-SiNx composite layer.
The thermocolour intelligent light modulation film of the low transformation temperature the preparation method is as follows: using magnetron sputtering plating mode, Successively using Si (in Ar, N2Atmosphere under), NiCr is (in Ar, O2Atmosphere under), Si is (in Ar, N2Atmosphere under), V2O3( Ar、O2Atmosphere under, the atomic ratio of V:O is about 2:3), Si is (in Ar, N2Atmosphere under), NiCr is (in Ar, O2Atmosphere under), NiCr (under the atmosphere of Ar), ITO are (in Ar, O2Atmosphere under), Si is (in Ar, N2Atmosphere under) be used as target, in clean glass First medium layer 22 is sequentially depositing on glass substrate, the first anti oxidation layer 32, first promotees crystallizing layer 42, vanadium oxide layer 52, second promotees Crystallizing layer 62, the second anti oxidation layer 72 and second dielectric layer 82, and form the film layer having the following structure: G/SiNx/NiCrOx/ SiNx/VOx/SiNx/NiCrOx/NiCr/ITO/SiNx.Wherein, first medium layer 22 (SiNx) is anti-with a thickness of 50nm, first Oxide layer 32 (NiCrOx) with a thickness of 15nm, first promote crystallizing layer 42 (SiNx) with a thickness of 20nm, vanadium oxide layer 52 (VOx) With a thickness of 150nm, second promote crystallizing layer 62 (SiNx) with a thickness of 20nm, the overall thickness of the second anti oxidation layer 72 is 10nm (wherein NiCrOx is 5nm, NiCr 5nm), the overall thickness of second dielectric layer 82 is that (wherein ITO is 50nm to 200nm, and SiNx is 150nm)。
It wherein, is using V when preparing vanadium oxide layer 522O3Ceramic target, Ar:O2Flow-rate ratio be 95:1, splash Injection pressure is 0.3Pa.Diaphragm after above-mentioned plated film on a glass substrate is put into the vacuum chamber for being provided with infra-red radiation fluorescent tube, The vacuum chamber base vacuum is less than 1Pa, is filled with N2For atmosphere to 20Pa, environment 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 is ultimately formed, the phase transformation of obtained thermocolour intelligent dimming glass Temperature is 29.5 DEG C.
Embodiment 4
As shown in figure 4, a kind of thermocolour intelligent light modulation film of low transformation temperature, successively include substrate 13, first medium layer 23, Vanadium oxide layer 33 promotees crystallizing layer 43, infrared-reflecting layers 53, anti oxidation layer 63 and second dielectric layer 73.The substrate 13 is glass Glass material, first medium layer 23 are SiNx material, and vanadium oxide layer 33 is the vanadium oxide material with phase-change characteristic, promote crystallizing layer 43 For SiNx material, infrared-reflecting layers 53 are Ag material, and anti oxidation layer 63 is Ti material, and second dielectric layer 73 is SiNx material.
The thermocolour intelligent light modulation film of the low transformation temperature the preparation method is as follows: using magnetron sputtering plating mode, Successively using SiAl (in Ar, N2Atmosphere under), V is (in Ar, O2Atmosphere under), SiAl is (in Ar, N2Atmosphere under), Ag is (in Ar Atmosphere under), Ti (under the atmosphere of Ar), SiAl are (in Ar, N2Atmosphere under) be used as target, successively in clean glass substrate Upper deposition first medium layer 23, promotees crystallizing layer 43, infrared-reflecting layers 53, anti oxidation layer 63 and second medium at vanadium oxide layer 33 Layer 73, and form the film layer having the following structure: G/SiNx/VOx/SiNx/Ag/Ti/SiNx.Wherein, first medium layer 23 (SiNx) with a thickness of 80nm, vanadium oxide layer 33 (VOx) with a thickness of 100nm, promote crystallizing layer 43 (SiNx) with a thickness of 20nm, Infrared-reflecting layers 53 (Ag) with a thickness of 15nm, anti oxidation layer 63 (Ti) with a thickness of 5nm, second dielectric layer 73 (SiNx) With a thickness of 100nm.
Wherein, when preparing vanadium oxide layer 33, Ar:O2Flow-rate ratio be 95:3.2, sputtering pressure 0.4Pa.It will Diaphragm after above-mentioned plated film on a glass substrate is put into the vacuum chamber for being provided with infra-red radiation fluorescent tube, extremely to vacuum chamber 10-2After Pa magnitude, it is filled with N2To 300Pa as protective atmosphere, the annealing of infra-red radiation fluorescent tube, heating temperature is 500 DEG C, heating 100 DEG C are cooled to after 400s hereinafter, ultimately form 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 that rush crystallizing layer, selected materials also have rush crystallization.
Embodiment 5
As shown in figure 5, a kind of thermocolour intelligent light modulation film of low transformation temperature, successively include substrate 14, first medium layer 24, First anti oxidation layer 34, first promotees crystallizing layer 44, vanadium oxide layer 54, second promotees crystallizing layer 64, the second anti oxidation layer 74 and second Dielectric layer 84.The substrate 14 is glass material, and first medium layer 24 is SiNx material, and the first anti oxidation layer 34 is NiCr material Material, first promotees crystallizing layer 44 as SiNx material, and vanadium oxide layer 54 is the vanadium oxide material with phase-change characteristic, and second promotees crystallizing layer 64 be SiNx material, and the second anti oxidation layer 74 is NiCr material, and second dielectric layer 84 is SiNx material.
The thermocolour intelligent light modulation film of the low transformation temperature the preparation method is as follows: using magnetron sputtering plating mode, Successively using SiAl (in Ar, N2Atmosphere under), NiCr (under the atmosphere of Ar), Si are (in Ar, N2Atmosphere under), V is (in Ar, O2 Atmosphere under), Si is (in Ar, N2Atmosphere under), NiCr (under the atmosphere of Ar), Si is (in Ar, N2Atmosphere under) be used as target, First medium layer 24 is successively deposited in clean glass substrate, the first anti oxidation layer 34, first promotees crystallizing layer 44, vanadium oxide layer 54, second promotees crystallizing layer 64, the second anti oxidation layer 74 and second dielectric layer 84, and forms the film layer having the following structure: G/ SiNx/NiCr/SiNx/VOx/SiNx/NiCr/SiNx.Wherein first medium layer 24 (SiNx) with a thickness of 50nm, the first antioxygen Change layer 34 (NiCr) with a thickness of 8nm, first promote crystallizing layer 44 (SiNx) with a thickness of 20nm, the thickness of vanadium oxide layer 54 (VOx) Degree is 100nm, second promote crystallizing layer 64 (SiNx) with a thickness of 20nm, the second anti oxidation layer 74 (NiCr) with a thickness of 10nm, Second dielectric layer 84 (SiNx) with a thickness of 50nm.
Wherein, when preparing vanadium oxide layer 54, Ar:O2Flow-rate ratio be 95:2.0, sputtering pressure 0.5Pa.It will Diaphragm after above-mentioned plated film on a glass substrate is put into annealing furnace tempering, and 685 DEG C of tempering temperature, entire heat treatment time 6min, The final phase transition temperature for obtaining thermocolour intelligent dimming glass is 56 DEG C.
Embodiment 6
The present embodiment for embodiment 5, the difference is that, when preparing vanadium oxide layer, V target doping The W that molar concentration is 1.5%, the final phase transition temperature for obtaining thermocolour intelligent dimming glass are 19 DEG C.
Embodiment 7
The present embodiment for embodiment 5, the difference is that, on the basis of the film layer structure of embodiment 5, The outer surface of second medium layer is also successively added to third anti oxidation layer (NiCr material) and third dielectric layer (SiNx material), is formed The film layer having the following structure: G/SiNx (with a thickness of 50nm)/NiCr (with a thickness of 8nm)/SiNx (with a thickness of 20nm)/VOx is (thick Degree is 100nm)/SiNx (with a thickness of 20nm)/NiCr (with a thickness of 10nm)/SiNx (with a thickness of 50nm)/NiCr (with a thickness of 10nm)/SiNx (with a thickness of 50nm).Followed by, the method that the present embodiment prepares the thermocolour intelligent light modulation film of low transformation temperature is, It is sequentially depositing above-mentioned film layer on the right substrate of glass first by the way of magnetron sputtering, it then will be on a glass substrate after plated film Diaphragm be placed in atmospheric environment, be preheated to 400 DEG C through infra-red radiation fluorescent tube, heat using flash lamp, it is final to obtain Intelligent dimming Phase transition temperature is 51 DEG C.
Embodiment 8
The present embodiment for embodiment 5, the difference is that, substrate be PET film, and using laser heat Mode anneals to film layer, and the final intelligent dimming Phase transition temperature that obtains is 48.5 DEG C.
Embodiment 9
The film layer structure of intelligent light modulation film in the present embodiment be G/ZrNx (with a thickness of 60nm)/VOx (with a thickness of 80nm)/ ZrNx (with a thickness of 80nm), wherein ZrNx is as rush crystallizing layer.Wherein when preparing VOx layers, using metal V target, in Ar:O2 Flow-rate ratio is prepared under conditions of being 95:3.5, and the film layer of preparation is filled with Ar extremely after background vacuum is extracted into less than 10Pa 50Pa is as ambiance, using infra-red radiation fluorescent tube heating anneal, 550 DEG C of annealing temperature, and heating time 150s；It is final to obtain Intelligent light modulation film phase transition temperature be 39 DEG C.
Embodiment 10
For embodiment 9, the difference is that, the film layer structure of the intelligent light modulation film of the present embodiment is G/SiOx (with a thickness of 50nm)/ZrNx (with a thickness of 25nm)/VOx (with a thickness of 90nm)/ZrNx (with a thickness of 25nm)/TiOx (with a thickness of 70nm), the phase transition temperature for finally preparing resulting intelligent light modulation film is 43 DEG C.
Embodiment 11
The present embodiment is to make the thermocolour intelligent light modulation film obtained of embodiment 6 by PVB and another glass substrate bonding At the thermocolour intelligent dimming glass of sandwich format, secondly also the thermocolour intelligent dimming glass after annealing (is contained by metal framework Adhesive glue) with another glass substrate be compounded to form hollow form intelligent dimming glass, the heat for the sandwich format being here formed as again Color intelligent dimming glass is compounded to form interlayer hollow structure form with another glass substrate by metal framework (containing adhesive glue) Thermocolour intelligent dimming glass.
Embodiment 12
Compared to embodiment 1, the present embodiment the difference is that, prepare vanadium oxide layer and use be vanadium oxide pottery Porcelain target, wherein the atomic ratio of V:O is about 1:2, it can be understood as VO2Or V2O4Ceramic target, sputtering process Ar:O2Stream Amount is than being 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 be substantially commonly referred to as be intended merely to for Si increase the electric conductivity of Si with And heating conduction, therefore a small amount of Al is adulterated in Si, SiAl target can be expressed as.

Claims (7)

1. a kind of thermocolour intelligent light modulation film of low transformation temperature, it is characterised in that: be at least sequentially depositing first Jie on substrate Matter layer, promotees crystallizing layer, anti oxidation layer and second dielectric layer at the vanadium oxide layer with phase-change characteristic；The material for promoting crystallizing layer Selected from metal nitride, alloy nitride, the nitride of silicon, silicon alloy for promoting vanadium oxide to form nanometer little crystal grain function One of nitride or a variety of；The first medium layer and the material of second dielectric layer be respectively TiOx, TiNx, AlOx, AlNx、SiNx、SiOx、SiNxOy、HfOx、NbOx、TaOx、ZrOx、ZrNx、ZnOx、SnOx、ZnSnOx、ZnS、ITO、ATO、 One of AZO, FTO, IGO or a variety of；The surface of opposite side of the rush crystallizing layer toward the vanadium oxide layer is also set There are infrared-reflecting layers；The infrared-reflecting layers be at least one of Pt, Au, Ag, Cu, Al element metal layer or Pt, The doping metals layer of at least one of the alloy-layer or Pt, Au, Ag, Cu, Al of at least one of Au, Ag, Cu, Al element element, Or the composite layer of the layer；The granularity for promoting the nanometer little crystal grain that crystallizing layer promotes the vanadium oxide layer to be formed be no more than 25nm。
2. a kind of thermocolour intelligent light modulation film of low transformation temperature as described in claim 1, it is characterised in that: from first medium layer To being also disposed with rush crystallizing layer between vanadium oxide film layer, or it is successively arranged anti oxidation layer and promotees crystallizing layer.
3. a kind of thermocolour intelligent light modulation film of low transformation temperature as described in claim 1, it is characterised in that: the anti oxidation layer Material be selected from Ti or its alloy, Al or its alloy, Ni or its alloy, Cr or its alloy, the oxide of Ti or its alloy, Al or The oxide of its alloy, the oxide of Ni or its alloy, Cr or the oxide of its alloy, the nitride of Ti or its alloy, Al or The nitride of its alloy, the nitride of Ni or its alloy, Cr or its alloy one of nitride or a variety of.
4. a kind of thermocolour intelligent light modulation film of low transformation temperature as described in claim 1, it is characterised in that: the rush crystallizing layer Material be selected from the nitride of chromium, the nitride of zirconium, the nitride of silicon, silicon nitrogen oxides (SiNxOy), silicon alloy nitridation One of object is a variety of.
5. a kind of thermocolour intelligent light modulation film of low transformation temperature as described in claim 1, it is characterised in that: the vanadium oxide Layer reduces the element of its own phase transition temperature function to be doped with.
6. a kind of thermocolour intelligent light modulation film of low transformation temperature as described in claim 1, it is characterised in that: be additionally provided with infrared ray Reflecting layer；At least one surface of the vanadium oxide layer is arranged in the infrared-reflecting layers.
7. a kind of preparation method of the thermocolour intelligent light modulation film of low transformation temperature as described in claim 1, which is characterized in that packet Include following steps:
(1) the clean substrate that can be used for plated film is provided；
(2) amorphous thermocolour has successively been plated according to the film layer structure of setting by the way of sputter coating at normal temperature intelligently to adjust Light film；When wherein preparing the vanadium oxide layer, Ar:O2Flow-rate ratio be 95:5~0.5, sputtering atmosphere pressure be 0.3Pa~ 0.8Pa；
(3) by step (2) formed plated film substrate on amorphous state thermocolour intelligent light modulation film be placed in base vacuum lower than 10Pa, fill In the environment of entering vacuum protection gas to 20Pa~1000Pa, by the way of the heating of radiation fluorescent tube and/or PULSE HEATING, in atmosphere In environment by the way of tempering annealing and/or Hot-blast Heating, to the amorphous state thermocolour intelligent light modulation film on the plated film substrate Carry out heating anneal；Wherein 400 DEG C~700 DEG C of annealing temperature, annealing time 30s~600s.
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