CN116445872B - Amorphous molybdenum doped tungsten oxide electrochromic material and preparation method thereof - Google Patents
Amorphous molybdenum doped tungsten oxide electrochromic material and preparation method thereofInfo
- Publication number
- CN116445872B CN116445872B CN202310421200.3A CN202310421200A CN116445872B CN 116445872 B CN116445872 B CN 116445872B CN 202310421200 A CN202310421200 A CN 202310421200A CN 116445872 B CN116445872 B CN 116445872B
- Authority
- CN
- China
- Prior art keywords
- tungsten oxide
- doped
- electrochromic material
- amorphous molybdenum
- doped tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
-
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
-
- 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
-
- 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
- G02F1/01—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 for the control of the intensity, phase, polarisation or colour
- G02F1/15—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 for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—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 for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—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 for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1524—Transition metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Nonlinear Science (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
本发明公开了一种非晶态钼掺杂氧化钨电致变色材料及其制备方法，所述方法包括以下步骤，使磁控溅射镀膜仪预真空度达到2*10‑4Pa以下，并在氩气‑氧气混合气氛中，将非晶态钼掺杂WO3靶材在导电玻璃基底表面进行射频反应沉积溅射，得到Mo掺杂WO3薄膜，将Mo掺杂WO3薄膜进行退火处理，得到非晶态钼掺杂氧化钨电致变色材料。本发明褪色态透过率较高，着色态透过率较低，对比度可达56.6％～72.8％，可以在不同电压下实现透明与灰黑色的可逆转换，实现了氧化钨薄膜变色过程中的色度变化。可应用于电致变色智能窗、防眩目后视镜、新能源车天窗等多种场合。
The present invention discloses an amorphous molybdenum-doped tungsten oxide electrochromic material and a preparation method thereof. The method comprises the following steps: maintaining a pre-vacuum degree of a magnetron sputtering coating apparatus below 2*10 ‑4 Pa, and performing radio frequency reactive deposition sputtering of an amorphous molybdenum-doped WO 3 target on the surface of a conductive glass substrate in an argon-oxygen mixed atmosphere to obtain a Mo-doped WO 3 thin film; and annealing the Mo-doped WO 3 thin film to obtain the amorphous molybdenum-doped tungsten oxide electrochromic material. The present invention has a high transmittance in a faded state and a low transmittance in a colored state, with a contrast ratio of 56.6% to 72.8%. It can achieve reversible conversion between transparent and gray-black at different voltages, realizing chromaticity changes during the color change process of the tungsten oxide film. The material can be applied to various applications, such as electrochromic smart windows, anti-glare rearview mirrors, and sunroofs of new energy vehicles.
Description
Technical Field
The invention relates to the field of electrochromic, in particular to an amorphous molybdenum doped tungsten oxide electrochromic material and a preparation method thereof.
Background
Electrochromic refers to the change of optical properties such as transmissivity, reflectivity, absorptivity and the like of a material under the condition of external potential driving, and macroscopic appearance is changed in color, transparency and the like. Electrochromic materials typically change between a colored state and a fade state, or directly between two different colored states. Electrochromic materials require electrochromic films to be prepared on a substrate, and are largely divided into chemical and physical methods. The chemical method comprises chemical vapor deposition, hydrothermal method, spin coating, chemical solution deposition, electrodeposition, etc., and the physical method comprises sputtering, thermal evaporation, etc. Tungsten oxide is one of the first cathodic electrochromic materials studied and can be classified into crystalline tungsten oxide and amorphous tungsten oxide. The tungsten oxide electrochromic film has the advantages of wide optical modulation range in visible light and infrared wave bands, high coloring efficiency, good reversibility and the like, and compared with the organic electrochromic material, the tungsten oxide electrochromic film can keep stable and reversible color change in a plurality of circulating processes and continuously work in a severe environment.
In the process of realizing industrialization, the existing tungsten oxide electrochromic material has the characteristic of blue or deep blue in the coloring state, and the blue can cause depression in the color psychology in the actual use process, so that a certain negative emotion is generated.
Disclosure of Invention
The invention aims to provide an amorphous molybdenum doped tungsten oxide electrochromic material and a preparation method thereof, which realize the transition of the coloring state of amorphous tungsten oxide from dark blue to gray black in a PC/LiClO 4 solution under the doping effect of molybdenum element by using a Physical Vapor Deposition (PVD) method of magnetron sputtering, and are suitable for various occasions such as electrochromic intelligent windows, anti-glare rearview mirrors, new energy vehicle skylights and the like.
In one aspect of the invention, the invention provides a method for preparing a molybdenum doped tungsten oxide electrochromic material. According to an embodiment of the invention, the method comprises the steps of:
And (3) enabling the pre-vacuum degree of a magnetron sputtering coating instrument to be below 2 x 10 -4 Pa, carrying out radio frequency reaction deposition sputtering on the surface of the conductive glass substrate by using an amorphous molybdenum-doped WO 3 target material in an argon-oxygen mixed atmosphere to obtain a Mo-doped WO 3 film, and carrying out annealing treatment on the Mo-doped WO 3 film to obtain the amorphous molybdenum-doped tungsten oxide electrochromic material.
In addition, the preparation method of the amorphous molybdenum doped tungsten oxide electrochromic material according to the embodiment of the invention can also have the following additional technical characteristics:
In some embodiments of the present invention, the conductive glass substrate is sequentially ultrasonically cleaned in acetone, absolute ethyl alcohol, and deionized water for 10-20 minutes before magnetron sputtering, and is dried, and the conductive glass substrate is ITO conductive glass or FTO conductive glass.
In some embodiments of the present invention, the Mo doping amount of the amorphous molybdenum doped WO 3 target is 1wt% to 10wt%.
In some embodiments of the invention, the volume fraction of oxygen in the radio frequency reactive deposition sputtering is 5% -30%, the sputtering power is 50% -100W, the sputtering air pressure is 0.8-3.0 Pa, the sputtering time is 100-150 min, the working distance is 5-10 cm, and the temperature of the conductive glass substrate is 20-110 ℃.
In some embodiments of the present invention, the oxygen volume fraction in the mixed atmosphere varies from 5% -20% with sputtering time in a uniform gradient per 1% with time.
In some embodiments of the present invention, the annealing temperature of the annealing treatment is 300 to 400 ℃ and the annealing time is 0.5 to 2 hours.
In some embodiments of the invention, the thickness of the amorphous molybdenum doped tungsten oxide electrochromic material is 300-350nm, the film is compact and uniform, and the sputtering morphology is in the shape of columnar grains.
In another aspect of the invention, the invention provides an amorphous molybdenum doped tungsten oxide electrochromic material prepared by the preparation method of the amorphous molybdenum doped tungsten oxide electrochromic material.
In addition, the amorphous molybdenum doped tungsten oxide electrochromic material according to the above embodiment of the present invention may further have the following additional technical features:
In some embodiments of the present invention, the amorphous molybdenum doped tungsten oxide electrochromic material is initially colorless and transparent, and achieves a color transition in the colored state of gray black and the faded state of colorless and transparent in a lithium ion liquid electrolyte (e.g., PC/LiClO 4 solution).
In another aspect of the invention, an electrochromic device is provided that includes a base layer, a conductive layer, and an electrochromic material layer. According to an embodiment of the present invention, the electrochromic material layer is the amorphous molybdenum doped tungsten oxide electrochromic material.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention utilizes the magnetron sputtering method to reduce the randomness brought by wet chemistry in the experimental process, adopts the method of doping Mo into the WO 3 target material, reduces the cost on equipment and the target material by using single-target sputtering instead of double-target sputtering, and obtains the amorphous tungsten oxide with more uniform components by reactive sputtering of the doped target.
2. The invention adjusts the stoichiometric ratio of tungsten oxide by introducing argon-oxygen mixed gas to participate in reactive sputtering, takes argon as protective atmosphere to ionize under the action of a magnetron sputtering electric field to form plasma (argon ions), bombards a target under the action of a magnetic field to enable atoms on the surface of the target to be bombarded by the argon ions to be sputtered, and deposits the target on a substrate to form a film. Oxygen reacts the target atoms therein to form oxides or to regulate oxygen defects. The sputtering yield, that is, the ratio of the sputtering speed to the molybdenum element can be adjusted by adjusting the ratio of the argon to the oxygen. The doping content of the molybdenum element is regulated and controlled by regulating the proportion of argon and oxygen, so that the sputtering yield and the doping content are changed, gradient distribution of the doping content of the molybdenum element in the tungsten oxide electrochromic material from inside to outside is formed from small to large, the inner layer keeps the binding force of the substrate while the enrichment of the molybdenum element is prevented, and the effect of chromaticity conversion is realized on the surface layer. The stability of the amorphous tungsten oxide film structure and the improvement of electrochromic performance are realized on the whole.
3. The coloring state of the tungsten oxide electrochromic material without doping molybdenum is blue or dark blue, molybdenum element is introduced by doping means, an impurity energy level is added into the wide-band semiconductor tungsten oxide, so that light absorption is changed, the absorption of amorphous tungsten oxide is improved, the coloring state color of the tungsten oxide electrochromic film is changed to be more neutral gray black on a macroscopic scale, the color of the fading state color is changed to be more transparent, the color change is less involved in the coloring-fading change process, the concentrated reflection is realized as gray black to colorless transparent reversible conversion, and the color change of the tungsten oxide film is realized.
4. The invention has higher transmittance in the fading state (which can reach 79.0% -85.1%), lower transmittance in the coloring state (which can reach 9.1% -26.4%), and 56.6% -72.8% contrast, can realize reversible conversion between transparency and gray black under different voltages, and realizes chromaticity change (absolute value of a * and b * coordinates is smaller than 0.5) in the color change process of the tungsten oxide film. Can be applied to various occasions such as electrochromic intelligent windows, anti-dazzle rearview mirrors, new energy vehicle skylights and the like.
5. The preparation method is a magnetron sputtering method, has simple and stable preparation process, and controllable size and thickness of the sample, and is beneficial to large-scale industrial production.
Drawings
FIG. 1 is an X-ray diffraction pattern of an amorphous undoped tungsten oxide electrochromic film prepared in accordance with a comparative example of the present invention;
FIG. 2 is an X-ray diffraction pattern of a molybdenum-doped tungsten oxide electrochromic film prepared in example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern of a molybdenum doped tungsten oxide electrochromic film prepared in example 2 of the present invention;
FIG. 4 is an X-ray diffraction pattern of a molybdenum-doped tungsten oxide electrochromic film prepared in example 3 of the present invention;
FIG. 5 is a Raman spectrum of the molybdenum doped tungsten oxide electrochromic film prepared in example 2 of the present invention;
FIG. 6 is a Raman spectrum of a molybdenum doped tungsten oxide electrochromic film prepared in example 3 of the present invention;
FIG. 7 is a scanning electron microscope image of a molybdenum doped tungsten oxide electrochromic film prepared in example 2 of the present invention;
FIG. 8 is a graph showing the transmission spectrum of a molybdenum doped tungsten oxide electrochromic film prepared in example 1 of the present invention;
FIG. 9 is a graph showing the transmission spectrum of a molybdenum doped tungsten oxide electrochromic film prepared in example 2 of the present invention;
FIG. 10 is a graph showing the transmission spectrum of a molybdenum doped tungsten oxide electrochromic film prepared in example 3 of the present invention;
FIG. 11 is a graph showing the transmission spectrum of a molybdenum doped tungsten oxide electrochromic film prepared in example 4 of the present invention;
FIG. 12 is a graph showing electrochromic kinetics of a molybdenum-doped tungsten oxide film prepared in example 2 of the present invention (633 nm, -1 v);
FIG. 13 is a graph showing electrochromic kinetics of a molybdenum-doped tungsten oxide film prepared in example 3 of the present invention (633 nm, -1 v);
FIG. 14 is a graph (-1 v) of the electrochromic dynamic CA cycle current density of the molybdenum-doped tungsten oxide film prepared in example 3;
FIG. 15 is a graph (-1 v) of the electrochromic dynamic CA cycle current density of the molybdenum doped tungsten oxide film prepared in example 4.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation process of amorphous molybdenum doped electrochromic tungsten oxide material includes the following steps:
(1) Respectively ultrasonically cleaning an ITO glass substrate in acetone, absolute ethyl alcohol and deionized water for 15 minutes, and drying;
(2) Mounting a Mo-doped WO 3 target and a dried ITO glass substrate in a magnetron sputtering coating instrument, and vacuumizing;
(3) Performing radio frequency reactive deposition sputtering at a substrate temperature of 110 ℃ in an argon-oxygen mixed atmosphere with a mass fraction of molybdenum doped WO 3 with a purity of 99.99% and a mass fraction of 5% as a target material under the condition that the pre-vacuum degree is below 2 x 10 -4 Pa, wherein the oxygen volume fraction in the mixed atmosphere is 15%, the sputtering power is 100W, the sputtering air pressure is 2Pa, the sputtering time is 150 minutes, and the working distance is 10cm, so as to obtain a Mo doped WO 3 film;
(4) And (3) placing the Mo-doped WO 3 film obtained in the step (3) in a tube furnace for annealing treatment, wherein the annealing temperature is 300 ℃ and the annealing time is 0.5 hour, so as to obtain the amorphous molybdenum-doped tungsten oxide electrochromic film.
Example 2
The preparation process of amorphous molybdenum doped electrochromic tungsten oxide material includes the following steps:
(1) Ultrasonically cleaning an ITO glass substrate in acetone, absolute ethyl alcohol and deionized water for 15 minutes, and drying;
(2) Mounting a Mo-doped WO 3 target and a dried ITO glass substrate in a magnetron sputtering coating instrument, and vacuumizing;
(3) Performing radio frequency reactive deposition sputtering at a substrate temperature of 25 ℃ in an argon-oxygen mixed atmosphere with an oxygen volume fraction of 5% and a sputtering power of 50W, a sputtering air pressure of 1Pa, a sputtering time of 120 minutes and a working distance of 5cm by taking molybdenum doped WO 3 with a purity of 99.99% and a mass of 8% as a target material under the condition that the pre-vacuum degree is below 2 x 10 -4 Pa, so as to obtain a Mo doped WO 3 film;
(4) And (3) placing the Mo-doped WO 3 film obtained in the step (3) in a tube furnace for annealing treatment, wherein the annealing temperature is 350 ℃ and the annealing time is 1.5 hours, so as to obtain the amorphous molybdenum-doped tungsten oxide electrochromic film.
Example 3
The preparation process of amorphous molybdenum doped electrochromic tungsten oxide material includes the following steps:
(1) Respectively ultrasonically cleaning an ITO glass substrate in acetone, absolute ethyl alcohol and deionized water for 15 minutes, and drying;
(2) Mounting a Mo-doped WO 3 target and a dried ITO glass substrate in a magnetron sputtering coating instrument, and vacuumizing;
(3) Performing radio frequency reactive deposition sputtering at a substrate temperature of 25 ℃ by taking molybdenum doped WO 3 with the mass percentage of 2% and the purity of 99.99% as a target material under the condition that the pre-vacuum degree is below 2 x 10 -4 Pa, and performing the sputtering in an argon-oxygen mixed atmosphere, wherein the oxygen volume fraction in the mixed atmosphere uniformly changes in a gradient manner along with the time from 5% -20% at a rate of 1% changing every 8 minutes along with the sputtering time, the sputtering power is 50W, the sputtering air pressure is 1Pa, the sputtering time is 120 minutes, and the working distance is 5cm, so as to obtain the Mo doped WO 3 film;
(4) And (3) placing the Mo-doped WO 3 film obtained in the step (3) in a tube furnace for annealing treatment, wherein the annealing temperature is 350 ℃ and the annealing time is 1.5 hours, so as to obtain the amorphous molybdenum-doped tungsten oxide electrochromic film.
Example 4
The preparation process of amorphous molybdenum doped electrochromic tungsten oxide material includes the following steps:
(1) Ultrasonically cleaning an ITO glass substrate in acetone, absolute ethyl alcohol and deionized water for 15 minutes, and drying;
(2) Mounting a Mo-doped WO 3 target and a dried ITO glass substrate in a magnetron sputtering coating instrument, and vacuumizing;
(3) Performing radio frequency reactive deposition sputtering at a substrate temperature of 25 ℃ in an argon-oxygen mixed atmosphere with the oxygen volume fraction fixed to 15%, wherein the sputtering power is 50W, the sputtering air pressure is 1Pa, the sputtering time is 120 minutes, and the working distance is 5cm, so as to obtain a Mo-doped WO 3 film, wherein the pre-vacuum degree is less than 2 x 10 -4 Pa, and the molybdenum-doped WO 3 with the purity of 99.99% and the mass percentage is 2% as a target material;
(4) And (3) placing the Mo-doped WO 3 film obtained in the step (3) in a tube furnace for annealing treatment, wherein the annealing temperature is 350 ℃ and the annealing time is 1.5 hours, so as to obtain the amorphous molybdenum-doped tungsten oxide electrochromic film.
Comparative example
The preparation process of amorphous non-doped electrochromic tungsten oxide material includes the following steps:
(1) Ultrasonically cleaning an ITO glass substrate in acetone, absolute ethyl alcohol and deionized water for 15 minutes, and drying;
(2) Mounting a WO 3 target material and a dried ITO glass substrate in a magnetron sputtering coating instrument, and vacuumizing;
(3) Carrying out radio frequency reactive deposition sputtering at a substrate temperature of 110 ℃ by taking WO 3 with purity of 99.99% as a target material under the condition that the pre-vacuum degree is below 2 x 10 -4 Pa, and carrying out the sputtering in an argon-oxygen mixed atmosphere, wherein the oxygen volume fraction in the mixed atmosphere is 15%, the sputtering power is 100W, the sputtering air pressure is 2Pa, the sputtering time is 150 minutes, and the working distance is 10cm;
(4) And (3) placing the amorphous undoped tungsten oxide film obtained in the step (3) into a tube furnace for annealing treatment, wherein the annealing temperature is 300 ℃ and the annealing time is 0.5 hour, and obtaining the amorphous undoped tungsten oxide electrochromic film.
As can be seen from the X-ray diffraction patterns of FIGS. 1-4, the diffraction peak of the tungsten oxide electrochromic material prepared by using the comparative example as a control group is consistent with that of the ITO substrate, and no new phase diffraction peak exists, so that the tungsten oxide electrochromic material can be inferred to be amorphous. The molybdenum-doped tungsten oxide electrochromic materials prepared in example 1, example 2 and example 3 also agree with diffraction peaks of the ITO substrate, and it can be confirmed that the prepared electrochromic films are all amorphous.
The broad peak at about 650-850 cm -1 in the raman spectra of fig. 5-6, attributable to W 6+ -O, was found to indicate the amorphous nature of examples 2 and 3 and was consistent with the results obtained from XRD testing, and the peak at about 950cm -1 in the spectra was attributable to water molecule induced end-stretching of W + =o.
Fig. 7 shows that the amorphous molybdenum doped tungsten oxide electrochromic material prepared in example 2 has a compact and flat surface and a thickness of about 300-350 nm.
The transmission light spectrum performance graphs and electrochromic dynamic performance graphs of figures 8-13 show that in a three-electrode system, a platinum wire is used as a counter electrode, ag/AgCl is used as a reference electrode, the prepared amorphous molybdenum doped tungsten oxide electrochromic material is used as a working electrode, a voltage of-1V is applied to perform performance test, the color fading state transmittance of the molybdenum doped tungsten oxide electrochromic film sample of example 1 at 633nm is 79.0% at most, the color coloring state transmittance is 26.4% at least, and the electrochromic contrast is 52.6%. The electrochromic film prepared in example 2 had a maximum transmittance of 84.0% at 633nm, a minimum transmittance of 13.9%, an electrochromic contrast of 70.1%, a coloring time of 48.6 seconds, and a fading time of 63.0 seconds. The electrochromic film prepared in example 3 has a highest transmittance of 85.1% at 633nm, a lowest transmittance of 12.3%, and an electrochromic contrast of 72.8%, and the response time for coloring and fading is greatly improved compared with that of example 2. The electrochromic film prepared in example 4 has a highest transmittance of 81.2% at 633nm, a lowest transmittance of 9.1% and an electrochromic contrast of 72.1%.
The electrochromic kinetics CA circulating current density diagrams in fig. 14-15 show that after 400 cycles, compared with the electrochromic film prepared in example 3, the peak current is very stable, which shows that the electrochromic film prepared in example 3 realizes the change of doping content by dynamically adjusting the proportion of argon and oxygen under the condition of reducing doping amount, the gradient distribution of molybdenum element in the tungsten oxide electrochromic material from inside to outside with the doping content from less to more is formed, the substrate binding force is reserved in the inner layer while the enrichment of molybdenum element is prevented, and the effect of chromaticity conversion is realized in the surface layer. The stability of the amorphous tungsten oxide film structure and the improvement of the electrochromic performance are realized on the whole, and the stability of the amorphous tungsten oxide film structure and the improvement of the electrochromic performance are realized on the whole.
Table 1 shows CIE L *a*b* chromaticity coordinate comparison lists of chromaticity of the molybdenum doped tungsten oxide electrochromic film control groups prepared in examples 1, 2 and 3, wherein L * represents brightness degree, a * represents red-green tendency degree, and b * represents yellow-blue tendency degree. Comparing the amorphous molybdenum doped tungsten oxide electrochromic materials prepared in examples 1-3 with the comparative examples, we found that examples 2 and 3 increased the b * value and the absolute value was more nearly 0 in the bleached state, indicating that the film color was lighter from blue in the change in the bleached state, i.e., the bleached state would be more nearly colorless and transparent. At the same time, b * of the colored state of example 1 and example 2 was also raised relative to the undoped comparative example, and the absolute value was closer to 0, indicating that in the change of colored state, the film color changed from dark blue to gray black. As can be seen from the chromaticity coordinates of example 2, this example involves less color change during the coloring-fading change, and more of the change in the film L *, i.e., the change in the degree of darkness, i.e., the reversible transition of the film from gray-black to colorless-transparent, is realized as a change in the color of the tungsten oxide film.
TABLE 1
Example 5
An electrochromic device comprises a basal layer, a conductive layer and an electrochromic material layer. The electrochromic material layer is the amorphous molybdenum doped tungsten oxide electrochromic material prepared in the embodiments 1-4.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention, as it is intended to provide those skilled in the art with various modifications, additions and substitutions to the specific embodiments disclosed and those skilled in the art without departing from the scope of the invention as disclosed in the accompanying claims.
Claims (8)
1. The preparation method of the amorphous molybdenum doped tungsten oxide electrochromic material is characterized by comprising the following steps of:
Enabling the pre-vacuum degree of a magnetron sputtering coating instrument to be below 2 x 10 -4 Pa, carrying out radio frequency reaction deposition sputtering on an amorphous molybdenum-doped WO 3 target material on the surface of a conductive glass substrate in an argon-oxygen mixed atmosphere to obtain a Mo-doped WO 3 film, and carrying out annealing treatment on the Mo-doped WO 3 film to obtain the amorphous molybdenum-doped tungsten oxide electrochromic material;
the oxygen volume fraction in the mixed atmosphere is uniformly and gradient changed along with the sputtering time from 5% -20% along with the time of each 1%, the annealing temperature of the annealing treatment is 300-400 ℃, and the annealing time is 0.5-2 h.
2. The method for preparing the amorphous molybdenum-doped tungsten oxide electrochromic material according to claim 1, wherein the conductive glass substrate is ITO conductive glass or FTO conductive glass, and is prepared by sequentially ultrasonic cleaning in acetone, absolute ethyl alcohol and deionized water for 10-20 minutes and drying before magnetron sputtering.
3. The method for preparing the amorphous molybdenum-doped tungsten oxide electrochromic material according to claim 1, wherein the Mo doping amount of the amorphous molybdenum-doped WO 3 target is 1-10 wt%.
4. The method for preparing the amorphous molybdenum-doped tungsten oxide electrochromic material according to claim 1, wherein the volume fraction of oxygen sputtered by radio frequency reactive deposition is 5% -30%, the sputtering power is 50% -100W, the sputtering air pressure is 0.8-3.0 Pa, the sputtering time is 100-150 min, the working distance is 5-10 cm, and the temperature of the conductive glass substrate is 20-110 ℃.
5. The method for preparing the amorphous molybdenum-doped tungsten oxide electrochromic material according to claim 1, wherein the thickness of the amorphous molybdenum-doped tungsten oxide electrochromic material is 300-350nm, the film is compact and uniform, and the sputtering morphology is in the shape of columnar grains.
6. An amorphous molybdenum-doped tungsten oxide electrochromic material prepared by the method of preparing an amorphous molybdenum-doped tungsten oxide electrochromic material according to any one of claims 1-5.
7. The method of claim 6, wherein the amorphous molybdenum doped tungsten oxide electrochromic material is transparent in an initial state and achieves a gray black in a colored state and a transparent color transition in a faded state in a lithium ion liquid electrolyte.
8. An electrochromic device comprises a substrate layer, a conductive layer and an electrochromic material layer, and is characterized in that the electrochromic material layer is an amorphous molybdenum doped tungsten oxide electrochromic material according to claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310421200.3A CN116445872B (en) | 2023-04-19 | 2023-04-19 | Amorphous molybdenum doped tungsten oxide electrochromic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310421200.3A CN116445872B (en) | 2023-04-19 | 2023-04-19 | Amorphous molybdenum doped tungsten oxide electrochromic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116445872A CN116445872A (en) | 2023-07-18 |
| CN116445872B true CN116445872B (en) | 2025-09-19 |
Family
ID=87126981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310421200.3A Active CN116445872B (en) | 2023-04-19 | 2023-04-19 | Amorphous molybdenum doped tungsten oxide electrochromic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116445872B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119562756B (en) * | 2024-12-02 | 2026-02-24 | 华东师范大学 | Memristors Based on Molybdenum-Doped Vanadium Dioxide Phase Change Thin Films and Their Preparation Methods |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112558369A (en) * | 2020-12-30 | 2021-03-26 | 浙江上方电子装备有限公司 | All-solid-state electrochromic device and preparation method thereof |
| CN112626459A (en) * | 2020-12-14 | 2021-04-09 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of tungsten oxide layer in electrochromic composite film system |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534611A (en) * | 2010-12-27 | 2012-07-04 | 鸿富锦精密工业（深圳）有限公司 | Shell and manufacturing method for shell |
| CN102636931A (en) * | 2011-02-15 | 2012-08-15 | 鸿富锦精密工业（深圳）有限公司 | Electro-chromic layer, coated element and preparation method of coated element |
| CN104423114B (en) * | 2013-09-05 | 2018-03-06 | 华为技术有限公司 | A kind of full-solid electrochromic multiple device and preparation method thereof |
| CN104004990B (en) * | 2014-06-03 | 2016-08-24 | 上海理工大学 | The method of preparation amorphous state transparent zinc oxide thin film |
| CN107574415B (en) * | 2017-08-16 | 2020-01-14 | 电子科技大学 | Gradual transition layer for metal-based thin film sensor and preparation method |
| CN108914183A (en) * | 2018-07-09 | 2018-11-30 | 中国科学院上海硅酸盐研究所 | Molybdenum doping amorphous Tungsten Trioxide Electrochromic Films and its electrochemical deposition method and application |
| US11866647B2 (en) * | 2018-07-18 | 2024-01-09 | Comberry, Llc | Electrochromic material and method of manufacturing thereof |
| CN109021962B (en) * | 2018-08-30 | 2021-05-07 | 合肥工业大学 | Crystalline tungsten trioxide/titanium doped amorphous tungsten oxide nanowire array and preparation method thereof |
| CN110357626B (en) * | 2019-07-26 | 2022-02-18 | 中国建筑材料科学研究总院有限公司 | Doped tungsten oxide target material and preparation method thereof |
-
2023
- 2023-04-19 CN CN202310421200.3A patent/CN116445872B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112626459A (en) * | 2020-12-14 | 2021-04-09 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of tungsten oxide layer in electrochromic composite film system |
| CN112558369A (en) * | 2020-12-30 | 2021-03-26 | 浙江上方电子装备有限公司 | All-solid-state electrochromic device and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 大面积电致变色玻璃的制备与研究;张元宁;《中国优秀硕士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》;20190115;第B015-607页 * |
| 张元宁.大面积电致变色玻璃的制备与研究.《中国优秀硕士学位论文全文数据库（电子期刊）工程科技Ⅰ辑》.2019,第B015-607页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116445872A (en) | 2023-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5848887B2 (en) | Method for manufacturing an oxide film | |
| Sivakumar et al. | Preparation and characterization of electron beam evaporated WO3 thin films | |
| CN109021962B (en) | Crystalline tungsten trioxide/titanium doped amorphous tungsten oxide nanowire array and preparation method thereof | |
| Liu et al. | Preparation of Nb-doped TiO2 films by sol-gel method and their dual-band electrochromic properties | |
| CN104178731B (en) | A kind of electrochromism WO3The controllable method for preparing of film | |
| CN110040976B (en) | Tungsten oxide electrochromic film material and preparation method thereof | |
| Lu et al. | A complementary electrochromic device based on W 18 O 49 nanowire arrays and Prussian blue thin films | |
| CN114940897B (en) | A niobium-doped ultra-thin TiO2 nanosheet electrochromic material and its preparation method and application | |
| CN116445872B (en) | Amorphous molybdenum doped tungsten oxide electrochromic material and preparation method thereof | |
| Malik et al. | Surface modification of sputter deposited γ-WO3 thin film for scaled electrochromic behaviour | |
| Thongpan et al. | Electrochromic properties of tungsten oxide films prepared by sparking method using external electric field | |
| CN106746724A (en) | A kind of molybdenum oxide electrochromism nano thin-film and preparation method thereof | |
| CN109881198B (en) | Preparation method of multi-color electrochromic film with tin dioxide/vanadium pentoxide core-shell structure | |
| CN108227332B (en) | An electrochromic device based on organic-inorganic composite materials | |
| CN109872835A (en) | A kind of infrared transparent conductive film, and its preparation method and application | |
| CN113433751A (en) | Multicolor electrochromic device and preparation method thereof | |
| CN110331367B (en) | Preparation method of stannous tungstate film | |
| CN113652753A (en) | Vanadium-doped single-crystal tungsten oxide electrochromism and energy storage material and preparation method thereof | |
| CN113130136A (en) | Nano silver wire MXENE composite transparent conductive film, preparation method and application | |
| CN110981217A (en) | A kind of preparation method of electrochromic film with fast response and high cycle stability | |
| CN114751655B (en) | Indium sulfide-based heterostructure thin film electrode and preparation method thereof | |
| CN116722076A (en) | Ce-doped ZnO nano-pillar array and preparation method thereof | |
| Kumar et al. | Tailoring WO3 Thin Films for Smart Windows: Role of Ar/O2 Ratio in Reactive Sputtering on Film Quality and Electrochromism | |
| Zhao et al. | Facile solution-grown Mo-doped vanadium dioxide thermochromic films with decreased phase transition temperature and narrowed hysteresis loop width | |
| TWI405826B (en) | Tungsten oxide film and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |