CN117551970A - VO (Voice over Internet protocol) 2 /W-VO 2 /VO 2 Composite film and preparation method and application thereof - Google Patents
VO (Voice over Internet protocol) 2 /W-VO 2 /VO 2 Composite film and preparation method and application thereof Download PDFInfo
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- CN117551970A CN117551970A CN202311525280.3A CN202311525280A CN117551970A CN 117551970 A CN117551970 A CN 117551970A CN 202311525280 A CN202311525280 A CN 202311525280A CN 117551970 A CN117551970 A CN 117551970A
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010408 film Substances 0.000 claims abstract description 172
- 230000008021 deposition Effects 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 16
- 239000010409 thin film Substances 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims description 46
- 238000000137 annealing Methods 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910000756 V alloy Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000013077 target material Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 4
- 239000012855 volatile organic compound Substances 0.000 description 44
- 230000007704 transition Effects 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 241000272186 Falco columbarius Species 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
- E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
-
- 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
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
- C03C17/09—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the vapour phase
-
- 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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
- C22C27/025—Alloys based on vanadium, niobium, or tantalum alloys based on vanadium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
Abstract
The invention provides a VO 2 /W‑VO 2 /VO 2 A composite film, a preparation method and application thereof belong to the technical field of thermochromic films. The composite film provided by the invention comprises a first heatElectrochromic functional film layer VO 2 Layer, second thermochromic functional thin film layer W-VO 2 Layer, third thermochromic functional thin film layer VO 2 A layer; the first thermochromic functional film layer is formed on the transparent glass substrate through deposition, the second thermochromic functional film layer is formed on the first thermochromic functional film layer through deposition, and the third thermochromic functional film layer is formed on the second thermochromic functional film layer through deposition; the W-VO 2 W in the layer is VO 2 The doping amount in (2 at.%). VO provided by the invention 2 /W‑VO 2 /VO 2 The three-layer composite structure realizes VO 2 Base thermochromic film T lum 、ΔT sol 、T c The three aspects are comprehensively improved, and the preparation process is simple.
Description
Technical Field
The invention relates to the technical field of thermochromic films, in particular to a VO (volatile organic compound) 2 /W-VO 2 /VO 2 Composite film and its preparation method and application.
Background
Energy conservation and emission reduction are an important problem facing the world. The energy consumption of the building occupies a large proportion in the field of energy consumption, and is up to one third of the whole energy demand, the window is used as a heat exchange channel between the building and the outside, the energy loss of the window accounts for about 50% of the total energy consumption of the building, and therefore the intelligent window with the function of dynamically adjusting the solar radiation is considered as one of key technologies for reducing the energy consumption of the building. Vanadium dioxide (VO) 2 ) As a thermochromic material, a material having a specific molecular structure at a phase transition temperature (T c A reversible metal-insulator transition (MIT) occurs at 68 c, exhibiting high transmission to high blocking of the near infrared band (780-2650 nm) of sunlight, while the visible band (380-780 nm) remains substantially unchanged. VO doped with tungsten element 2 (W-VO 2 ) Is to reduce T c Is reported to be 1at.% W per addition 6+ Can make VO 2 The phase transition temperature of (C) is reduced by 20-28 ℃, but at the same time, the visible light transmittance (T) lum ) And solar energy regulating efficiency (delta T) sol ) Is degraded. Due to doped W 6+ Replace VO 2 Middle V 4+ Is to promote VO 2 Transition from monoclinic phase to tetragonal rutile phase while causing lattice distortion, thereby resulting in VO 2 The crystallization quality is reduced, which is unfavorable for obtaining high thermochromic propertyCan be used. W-VO 2 T of film lum And DeltaT sol Closely related to the crystallization quality, the glass substrate and the W-VO are usually adopted 2 The buffer layer is inserted between the films or is adopted to be connected with W-VO 2 Single crystal substrates with the same crystal structure can improve W-VO 2 The crystallinity of the film is improved to a certain extent 2 Thermochromic properties of the film. This is because the lattice structure of the buffer layer is matched to the film, which can provide a better template effect for the film. However, general buffer layer preparation conditions and W-VO 2 The film has differences (such as temperature, oxygen pressure, oxygen flow, laser frequency and the like), and the preparation cost and the process complexity of the composite film are increased to a certain extent. Such as: using SnO 2 、HfO 2 And ZrO(s) 2 The buffer layer may be diffused by Sn, hf and Zr elements to W-VO 2 The thermochromic properties of the film have an adverse effect that is difficult to predict. In general, VO is higher than the transformation temperature 2 And W-VO 2 Are all tetragonal rutile structures, and VO 2 Film and W-VO 2 The preparation conditions of the film are basically consistent, and the W-VO can be improved while other nonfunctional layers are not introduced 2 Crystallization properties of the film. In recent years, although VO can be realized by a composite structure, doping and the like 2 Effective regulation and control of surface morphology and thermochromic performance, and can maintain T of the film lum And DeltaT sol At a higher level but in a very small number of cases a low T is considered c Cannot obtain a high T at the same time lum 、ΔT sol And low T c VO of (2) 2 Film is unfavorable for VO 2 Thin film smart windows are moving towards practical commercial applications.
Disclosure of Invention
In view of the above, the present invention aims to provide a VO 2 /W-VO 2 /VO 2 The composite film structure provided by the invention can effectively regulate and control the surface morphology of the film, and improves the thermochromic performance while reducing the phase transition temperature.
In order to achieve the above object, the present invention provides the following technical solutions: VO (Voice over Internet protocol) 2 /W-VO 2 /VO 2 The composite film comprises a first thermochromic functional film layer 3, a second thermochromic functional film layer 2 and a third thermochromic functional film layer 1; the first thermochromic functional film layer 3 is formed on the transparent glass substrate 4 through deposition, the second thermochromic functional film layer 2 is formed on the first thermochromic functional film layer 3 through deposition, and the third thermochromic functional film layer 1 is formed on the second thermochromic functional film layer 2 through deposition;
the thermochromic functional film layer 1 and the thermochromic functional film layer 3 are VO 2 A film; the second thermochromic functional film layer 2 is W-VO 2 A layer; the W-VO 2 W in the layer is VO 2 The doping amount in (2 at.%).
In the invention, the first thermochromic functional film layer 3 is used as a template layer and mainly provides a template effect for the growth of the second thermochromic functional film layer 2, so that the crystallization quality of the second thermochromic functional film layer 2 is improved, the thermochromic performance is improved, and the third thermochromic functional film layer 1 further optimizes the thermochromic performance of the whole composite film. In the present invention, VO 2 And W-VO 2 The film is in a polycrystalline state, and the obtained three-layer functional film has no obvious boundary and is a composite structure film.
In general, W-VO is to be improved 2 Either using a single crystal substrate or between a glass substrate and W-VO 2 An additional buffer layer is interposed between the films, but this results in an increase in raw material cost and a cumbersome preparation process. The invention uses VO without introducing extra buffer layer and expensive single crystal substrate 2 As buffer layer and thermochromic performance enhancement layer of composite structure, realizes intermediate layer W-VO 2 And regulating and controlling the surface morphology, thermochromic performance and phase transition temperature of the film.
Preferably, the thicknesses of the first thermochromic functional film layer 3, the second thermochromic functional film layer 2 and the third thermochromic functional film layer 1 are all 10-20 nm.
Preferably, the invention also comprises the VO 2 /W-VO 2 /VO 2 Other film layers are introduced above or below the composite film structure to enable the composite film to obtain better performance or function.
The invention also provides the VO according to the technical scheme 2 /W-VO 2 /VO 2 The preparation method of the composite film adopts a pulse laser deposition method to respectively grow a first thermochromic functional film layer 3, a second thermochromic functional film layer 2 and a third thermochromic functional film layer 1, wherein the temperature of a chamber is 400-550 ℃ during growth, and the back vacuum is 3 multiplied by 10 -4 ～2×10 -3 Pa, the growth rate of the thermochromic functional film is 0.5-2 nm/min.
The method specifically comprises the following steps:
step 1: placing glass substrate into the chamber, and vacuum-pumping the chamber to 3×10 -4 ～2×10 -3 Pa；
Step 2: depositing a first thermochromic functional film layer 3 on a glass substrate, wherein the target for deposition is a V target, the oxygen pressure is 1-10 Pa, the oxygen flow rate is 30-120 sccm, the temperature of a chamber is 400-550 ℃, the laser frequency is 2-12 Hz, and the growth rate of the first thermochromic functional film layer 3 is 0.5-2 nm/min; after the deposition is finished, carrying out annealing treatment for 5-45min on the first thermochromic functional film layer 3, wherein the annealing temperature is 400-550 ℃;
step 3: depositing a second thermochromic functional film layer 2 on the first thermochromic functional film layer 3, wherein a target material for deposition is a W-V alloy target, the oxygen pressure is 1-10 Pa, the oxygen flow rate is 30-120 sccm, the temperature of a chamber is 400-550 ℃, the laser frequency is 2-12 Hz, and the growth rate of the second thermochromic functional film layer 2 is 0.5-2 nm/min; after the deposition is finished, carrying out annealing treatment for 5-45min on the second thermochromic functional film layer 2, wherein the annealing temperature is 400-550 ℃;
step 4: depositing a third thermochromic functional film layer 1 on the second thermochromic functional film layer 2 again, wherein the target for deposition is a metal V target, the oxygen pressure is 1-10 Pa, the oxygen flow rate is 30-120 sccm, the temperature of the chamber is 400-550 ℃, the laser frequency is 2-12 Hz, and the growth rate of the third thermochromic functional film layer 1 is 0.5-2 nm/min; and after the deposition is finished, carrying out annealing treatment for 5-45min on the third thermochromic functional film layer 1, wherein the annealing temperature is 400-550 ℃.
Preferably, the atomic percentages of W and V in the W-V alloy target of step 3 are W: v=2at%: 98at.%.
The invention also provides the VO according to the technical scheme 2 /W-VO 2 /VO 2 Application of the composite film in thermochromic intelligent windows.
The beneficial technical effects are as follows:
1. VO prepared by the invention 2 (hereinafter abbreviated as V)/W-VO 2 (hereinafter abbreviated as WV)/V three-layer film structure by forming a film on W-VO 2 VO is introduced into thermochromic functional film system 2 Buffer layer and pair W-VO 2 Annealing treatment is carried out to form transparent functional films with different surface morphologies, and the traditional VO is changed on the premise of ensuring the photoelectric performance of the films 2 The dilemma of the film visible light transmittance and the solar energy adjusting efficiency, the inconvenience and the high cost of adopting the template or micro-nano processing technology, and the higher environmental application temperature as the intelligent window material can prepare the VO with high performance by using the lower cost and the simple technology 2 Thermochromic functional films.
2. The invention adopts V metal and WV alloy as raw materials, does not introduce an extra buffering anti-reflection layer structure, and has simple preparation process and low preparation cost.
3. The invention adopts a V/WV/V composite film structure, which is beneficial to further introducing other functional films.
4. The invention adopts the pulse laser deposition system to prepare the V/WV/V composite film structure, reduces the energy consumption in the preparation process, and does not depend on high-cost and high-precision process conditions and equipment such as templates, photoetching and the like.
Drawings
FIG. 1 is a schematic view showing the structure of a V/WV/V composite film according to the present invention, wherein 1-VO 2 Thermochromic functional film layer, 2-W-VO 2 Thermochromic functional film layer, 3-VO 2 A thermochromic functional thin film layer, a 4-glass substrate;
FIG. 2 is an X-ray diffraction pattern of the V/WV/V composite film of example 2;
FIG. 3 is a W-VO in the middle of the V/WV/V composite film in example 2 2 A surface topography of the layer;
FIG. 4 is a summary bar graph of data for visible light transmittance, solar energy conditioning efficiency, and phase transition temperature for the V/WV/V composite film of example 2.
Detailed Description
The structure schematic diagram of the V/WV/V composite film is shown in fig. 1, the V/WV/V composite film comprises a thermochromic functional film layer 1, a thermochromic functional film layer 2 and a thermochromic functional film layer 3, wherein the thermochromic functional film layer 3 is formed on a glass substrate 4 through deposition, the thermochromic functional film layer 2 is formed on the thermochromic functional film layer 3 through deposition, and the thermochromic functional film layer 1 is formed on the thermochromic functional film layer 2 through deposition; the thermochromic functional film layer 1 and the thermochromic functional film layer 3 are VO 2 A film; the thermochromic functional film layer 2 is W-VO 2 A film. The VO is 2 And W-VO 2 The thin film is polycrystalline and has a high dielectric constant. The thickness of each layer of film is 10-20 nm.
The preparation method specifically comprises the following steps:
step 1: placing glass substrate into the chamber, and vacuum-pumping the chamber to 3×10 -4 ～2×10 -3 Pa；
Step 2: depositing a first thermochromic functional film layer 3 on a glass substrate, wherein the target for deposition is a V target, the oxygen pressure is 1-10 Pa, the oxygen flow rate is 30-120 sccm, the temperature of a chamber is 400-550 ℃, the laser frequency is 2-12 Hz, and the growth rate of the first thermochromic functional film layer 3 is 0.5-2 nm/min; after the deposition, the first thermochromic functional thin film layer 3 is preferably subjected to annealing treatment for 5-45min, the annealing temperature is 400-550 ℃, and more preferably the first thermochromic functional thin film layer 3 is subjected to annealing treatment for 15-45min, and the annealing temperature is 450-500 ℃;
step 3: depositing a second thermochromic functional film layer 2 on the first thermochromic functional film layer 3, wherein a target material for deposition is a W-V alloy target, the oxygen pressure is 1-10 Pa, the oxygen flow rate is 30-120 sccm, the temperature of a chamber is 400-550 ℃, the laser frequency is 2-12 Hz, and the growth rate of the second thermochromic functional film layer 2 is 0.5-2 nm/min; the atomic percentages of W and V in the W-V alloy target are W: v=2at%: 98at.%; after the deposition, the second thermochromic functional thin film layer 2 is preferably subjected to annealing treatment for 5-45min, the annealing temperature is 400-550 ℃, and more preferably the second thermochromic functional thin film layer 2 is subjected to annealing treatment for 15-45min, and the annealing temperature is 450-500 ℃;
step 4: depositing a third thermochromic functional film layer 1 on the second thermochromic functional film layer 2 again, wherein the target for deposition is a metal V target, the oxygen pressure is 1-10 Pa, the oxygen flow rate is 30-120 sccm, the temperature of the chamber is 400-550 ℃, the laser frequency is 2-12 Hz, and the growth rate of the third thermochromic functional film layer 1 is 0.5-2 nm/min; after the deposition, the third thermochromic functional thin film layer 1 is preferably annealed at 400 to 550 ℃ for 5 to 45 minutes, more preferably 15 to 45 minutes, and 450 to 500 ℃.
The invention prepares the V/WV/V three-layer film structure with different surface morphology and excellent photoelectric property, and realizes VO through the V/WV/V three-layer composite structure 2 Base thermochromic film T lum 、ΔT sol The comprehensive improvement of the Tc and the Tc is realized, the preparation process is simple without the help of micro-nano processing technologies such as templates, photoetching and the like, and the obtained composite film has high visible light transmittance and strong solar energy regulating capability. Meanwhile, the V/WV/V three-layer film structure can further regulate and control the microscopic surface morphology of the middle WV layer by adjusting the thickness and the annealing time of the WV layer under the condition of ensuring higher transparency.
VO proposed by the invention 2 /W-VO 2 /VO 2 The composite film adopts V metal and WV alloy as raw materials to prepare the transparent functional film with the composite structure, can reduce the preparation difficulty of the transparent functional film, improve the process compatibility and is based on VO 2 The commercial application of the energy-saving intelligent window of the thermochromic film has important practical value.
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1
The preparation method of the V/WV/V composite film comprises the following steps:
step 1: placing glass substrate into the chamber, and vacuum-pumping the chamber to 5×10 -4 Pa；
Step 2: depositing a first thermochromic functional film layer 3 on a glass substrate, wherein the target for deposition is a V target, the oxygen pressure is 1.8Pa, the oxygen flow rate is 50sccm, the temperature of a chamber is 450 ℃, the laser frequency is 5Hz, and the growth rate of the first thermochromic functional film layer 3 is 1nm/min; after the deposition, the first thermochromic thin film layer was annealed for 10min at 500 ℃.
Step 3: depositing a second thermochromic functional film layer 2 on the first thermochromic functional film layer 3, wherein a target material for deposition is a W-V alloy target, the oxygen pressure is 1.8Pa, the oxygen flow rate is 50sccm, the temperature of a chamber is 450 ℃, the laser frequency is 5Hz, and the growth rate of the second thermochromic functional film layer 2 is 1nm/min; and after the deposition is finished, carrying out annealing treatment on the second thermochromic functional film layer for 45min, wherein the annealing temperature is 500 ℃.
Step 4: and depositing a third thermochromic functional film layer 1 on the second thermochromic functional film layer 2 again, wherein the target for deposition is a metal V target, the oxygen pressure is 1.8Pa, the oxygen flow rate is 50sccm, the temperature of the chamber is 450 ℃, the laser frequency is 5Hz, and the growth rate of the third thermochromic functional film layer 1 is 1nm/min. And after the deposition is finished, carrying out annealing treatment on the third thermochromic functional film layer for 10min, wherein the annealing temperature is 500 ℃.
Example 2
The difference is that in the step (3), W-VO is reacted with 2 The annealing time of the layer was 30min.
Example 3
In the same manner as in example 1,the difference is that in the step (3), W-VO is treated 2 The annealing time of the layer was 15min.
Example 4
The present invention uses this example as a control, and the preparation method is the same as that of example 1, except that there is no W-VO 2 The layers are annealed.
The phases of the V/WV/V composite films obtained in examples 1-4 were characterized by a trans-target X-ray diffractometer (SmartLab), the surface morphology by FESEM (Zeiss Merlin Compact), and the transmittance spectra were measured by an ultraviolet-visible-infrared spectrophotometer (UV-3600, shimazu), all under atmospheric conditions.
As can be seen from the X-ray diffraction pattern of FIG. 2, VO 2 Is the (011) plane.
As can be seen from the surface topography of FIG. 3, VO compared with the control group 2 The morphology is changed to different degrees, and the VO is densely arranged 2 The nanoparticles become more dispersed spherical VO 2 And (3) nanoparticles.
As can be seen from the data summarizing bar chart of visible light transmittance, solar energy adjustment efficiency and phase transition temperature of FIG. 4, the V/WV/V composite films of examples 1-3 can achieve higher T lum 、ΔT sol And low T c The composite film has the best thermochromic property when the annealing time is 30min.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. VO (Voice over Internet protocol) 2 /W-VO 2 /VO 2 The composite film is characterized by comprising a first thermochromic functional film layer (3), a second thermochromic functional film layer (2) and a third thermochromic functional film layer (1); the first thermochromic functional film layer (3) is formed on the transparent glass substrate (4) through deposition, and the second thermochromic functional film layer is formed on the transparent glass substrate2) The third thermochromic functional film layer (1) is formed on the second thermochromic functional film layer (2) through deposition;
the thermochromic functional film layer (1) and the thermochromic functional film layer (3) are VO 2 A film; the second thermochromic thin film layer (2) is W-VO 2 A layer; the W-VO 2 W in the layer is VO 2 The doping amount in (2 at.%).
2. The VO of claim 1 2 /W-VO 2 /VO 2 The composite film is characterized in that the thicknesses of the first thermochromic functional film layer (3), the second thermochromic functional film layer (2) and the third thermochromic functional film layer (1) are 10-20 nm.
3. The VO of claim 1 2 /W-VO 2 /VO 2 The composite film is characterized by further comprising the VO 2 /W-VO 2 /VO 2 Other film layers may be introduced above or below the composite film structure.
4. The VO of claim 1 2 /W-VO 2 /VO 2 The preparation method of the composite film is characterized in that a pulse laser deposition method is adopted to respectively grow a first thermochromic functional film layer (3), a second thermochromic functional film layer (2) and a third thermochromic functional film layer (1), the temperature of a chamber is 400-550 ℃ during growth, and the back vacuum is 3 multiplied by 10 -4 ～2×10 -3 Pa, the growth rate of the thermochromic functional film is 0.5-2 nm/min.
5. The preparation method according to claim 4, comprising the following steps:
step 1: placing glass substrate into the chamber, and vacuum-pumping the chamber to 3×10 -4 ～2×10 -3 Pa；
Step 2: depositing a first thermochromic functional film layer (3) on a glass substrate, wherein the target for deposition is a V target, the oxygen pressure is 1-10 Pa, the oxygen flow rate is 30-120 sccm, the temperature of a chamber is 400-550 ℃, the laser frequency is 2-12 Hz, and the growth rate of the first thermochromic functional film layer (3) is 0.5-2 nm/min; after the deposition is finished, carrying out annealing treatment for 5-45min on the first thermochromic functional film layer (3), wherein the annealing temperature is 400-550 ℃;
step 3: depositing a second thermochromic functional film layer (2) on the first thermochromic functional film layer (3), wherein a target material for deposition is a W-V alloy target, the oxygen pressure is 1-10 Pa, the oxygen flow rate is 30-120 sccm, the temperature of a chamber is 400-550 ℃, the laser frequency is 2-12 Hz, and the growth rate of the second thermochromic functional film layer (2) is 0.5-2 nm/min; after the deposition is finished, carrying out annealing treatment for 5-45min on the second thermochromic functional film layer (2), wherein the annealing temperature is 400-550 ℃;
step 4: a third thermochromic functional film layer (1) is deposited on the second thermochromic functional film layer (2), the target material for deposition is a metal V target, the oxygen pressure is 1-10 Pa, the oxygen flow rate is 30-120 sccm, the temperature of the chamber is 400-550 ℃, the laser frequency is 2-12 Hz, and the growth rate of the third thermochromic functional film layer (1) is 0.5-2 nm/min; and after the deposition is finished, carrying out annealing treatment for 5-45min on the third thermochromic functional film layer (1), wherein the annealing temperature is 400-550 ℃.
6. The method of claim 5, wherein the W-V alloy target in step 3 has W: v=2at%: 98at.%.
7. The VO of any one of claims 1 to 3 2 /W-VO 2 /VO 2 Application of the composite film in thermochromic intelligent windows.
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| CN202311525280.3A CN117551970A (en) | 2023-11-16 | 2023-11-16 | VO (Voice over Internet protocol) 2 /W-VO 2 /VO 2 Composite film and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311525280.3A CN117551970A (en) | 2023-11-16 | 2023-11-16 | VO (Voice over Internet protocol) 2 /W-VO 2 /VO 2 Composite film and preparation method and application thereof |
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| CN202311525280.3A Pending CN117551970A (en) | 2023-11-16 | 2023-11-16 | VO (Voice over Internet protocol) 2 /W-VO 2 /VO 2 Composite film and preparation method and application thereof |
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