CN113867064A - Nickel oxide electrochromic composite film and preparation method and application thereof - Google Patents
Nickel oxide electrochromic composite film and preparation method and application thereof Download PDFInfo
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 193
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000004544 sputter deposition Methods 0.000 claims description 91
- 239000000758 substrate Substances 0.000 claims description 48
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 43
- 238000000151 deposition Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 25
- 239000013077 target material Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 9
- 229910001887 tin oxide Inorganic materials 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- KBEVZHAXWGOKCP-UHFFFAOYSA-N zinc oxygen(2-) tin(4+) Chemical compound [O--].[O--].[O--].[Zn++].[Sn+4] KBEVZHAXWGOKCP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 16
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 160
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 21
- 230000008569 process Effects 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- 230000008021 deposition Effects 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 238000005562 fading Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910005855 NiOx Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical group O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004984 smart glass Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000004151 rapid thermal annealing Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
- C23C14/085—Oxides of iron group metals
-
- 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
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- 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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
Abstract
The invention discloses a nickel oxide electrochromic composite film and a preparation method and application thereof. The nickel oxide electrochromic composite film comprises a nickel oxide layer and an amorphous zinc tin oxide buffer layer which are arranged in a laminated manner; wherein the nickel oxide layer has a crystallized nano-columnar structure, and the diameter of the crystallized nano-columnar structure is 10-100 nm; the charge capacity of the nickel oxide electrochromic composite film is 6.0-12.0 mC-cm‑2. The nickel oxide electrochromic composite film prepared by the invention has good optical modulation amplitude, circulation stability and charge capacity, and has good application prospect in a flexible electrochromic device with low-temperature film coating.
Description
Technical Field
The invention belongs to the technical field of electrochromic devices and application, and particularly relates to a nickel oxide electrochromic composite film and a preparation method and application thereof.
Background
In recent years, there has been an increasing emphasis on flexible electronic devices, i.e., electronic devices that can operate in the presence of a range of deformations (bending, folding, twisting, compression or stretching). Among them, flexible electrochromic devices using polyethylene terephthalate (PET) as a substrate have been gradually applied to the fields of building smart windows, automobile rearview mirrors, multifunctional display screens, smart glasses, and the like. This application has very high requirements on electrochromic devices: good cycle stability, large optical modulation amplitude, good color neutrality, good mechanical property, fast response speed, large-area production and the like.
A conventional flexible electrochromic device consists of five layers, namely a bottom transparent conductive layer, an ion storage layer (or anode electrochromic layer), an ion electrochromic layer, a cathode electrochromic layer and a top transparent conductive layer. Wherein a typical material of the cathode electrochromic layer is tungsten oxide, and a typical material of the ion storage layer is nickel oxide. The nickel oxide is an anode color-changing material, under the action of an external electric field, lithium ions and electrons are injected simultaneously, the mutual transformation of a coloring state and a fading state (formula 1) is realized, a complementary relation is formed between the coloring state and the fading state of the tungsten oxide, and the optical modulation amplitude of the electrochromic device is further improved while the lithium ions are stored.
NiOx(colored state) + yLi++ye-＜＝＞LiyNiOx(faded state) (1)
There are many factors that affect the better application of nickel oxide thin films, where optical modulation amplitude and long-term cycling stability are two key factors that limit the commercialization of electrochromic devices. During a long-term electrochromic cycle process, lithium ions are repeatedly inserted into and extracted from the reaction channel, and phenomena such as trapping of partial lithium ions, blocking of ion transmission channels, structural collapse and the like can occur, so that the cycle stability performance of the film is reduced. Therefore, an effective procedure must be adoptedThe method is used for improving the long-term circulation stability of the nickel oxide film, wherein the post high-temperature treatment process of the film which is just deposited is a common means. For example, Tuba
A method for carrying out heat treatment on a nickel oxide film by using high temperature is disclosed in (Vacuum, 2019, 167: 189-194), and researches show that the high-temperature heat treatment increases the grain size, effectively improves the crystal structure of the film and increases the stability of the film. Gamze Atak, et al (Solid State Ionics, 2017, 305: 43-51) disclose that the nickel oxide film prepared by magnetron sputtering is treated by using a high-temperature heat treatment process, and the high-temperature treatment can improve the crystallinity and the transmittance of a fading State of the film, but the modulation amplitude of the film is reduced to some extent along with the increase of the temperature, and the modulation amplitude of the whole device is only 35%; wu et al (Journal of Alloys and Compounds 2021, 862: 158665, patent CN202011462486.2) disclose a method for treating a Li-Si co-doped nickel oxide thin film on a glass substrate by rapid thermal annealing at 400 ℃ to produce a thin film having excellent stability, a modulation width of 37%, and a charge capacity of 14.8mC cm-2And the film has good fading state and neutral color.
Although the high-temperature post-treatment process is helpful for improving the performance of the nickel oxide film on the rigid substrate such as glass and the like, the high-temperature post-treatment process is not suitable for devices on a high-molecular flexible substrate such as PET and the like, because the temperature resistance of the PET material is not high and is difficult to exceed 150 ℃. Therefore, a flexible nickel oxide electrochromic film and a flexible nickel oxide electrochromic structure which are prepared at a lower temperature and have stable performance are urgently needed to be found.
Disclosure of Invention
The invention mainly aims to provide a nickel oxide electrochromic composite film and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a nickel oxide electrochromic composite film, which comprises a nickel oxide layer and an amorphous zinc tin oxide buffer layer which are arranged in a laminated manner; whereinThe nickel oxide layer has a crystallized nano columnar structure, and the diameter of the crystallized nano columnar structure is 10-100 nm; the charge capacity of the nickel oxide electrochromic composite film is 6.0-12.0 mC-cm-2。
The embodiment of the invention also provides a preparation method of the nickel oxide electrochromic composite film, which comprises the following steps:
providing a substrate provided with a transparent conductive layer;
depositing a nickel oxide layer on the surface of the transparent conductive layer by adopting a magnetron sputtering technology and taking a nickel oxide target as a target material;
and depositing an amorphous zinc tin oxide buffer layer on the surface of the nickel oxide layer by adopting a magnetron sputtering technology and taking a zinc tin oxide target as a target material, thereby obtaining the nickel oxide electrochromic composite film.
The embodiment of the invention also provides application of the nickel oxide electrochromic composite film in preparation of an electrochromic device.
The embodiment of the invention also provides a flexible electrochromic device which comprises an anode ion storage layer, wherein the anode ion storage layer comprises the nickel oxide electrochromic composite film.
Compared with the prior art, the invention has the beneficial effects that:
(1) the nickel oxide electrochromic composite film prepared by the invention has good Ni3+The ratio of Ni to Ni ensures that the nickel oxide electrochromic composite film has good optical modulation amplitude;
(2) the nickel oxide layer in the nickel oxide electrochromic composite film prepared by the invention is in a crystalline state, and the amorphous zinc tin oxide buffer layer is in an amorphous state, so that the nickel oxide electrochromic composite film can be ensured to have good stability; meanwhile, the composite film has excellent cycling stability, and is beneficial to the stability of the electrochromic film;
(3) the nickel oxide layer in the nickel oxide electrochromic composite film prepared by the invention has a columnar structure, so that more lithium ion binding sites in the electrochromic film can be kept, and the optical modulation amplitude of the film can be improved;
(4) the nickel oxide electrochromic composite film prepared by the invention can obviously reduce the transmittance of the nickel oxide in a coloring state and enlarge the optical modulation amplitude;
(5) the nickel oxide electrochromic composite film prepared by the invention can obviously inhibit the color attenuation of the nickel oxide in a coloring state in the electrochemical cycle process and improve the optical modulation amplitude;
(6) the nickel oxide electrochromic composite film prepared by the invention has higher charge capacity and is suitable for flexible electrochromic devices;
(7) the nickel oxide electrochromic composite film prepared by the invention has good bending resistance;
(8) the method provided by the invention adopts the metal oxide target to replace the traditional metal target direct current reactive sputtering, is beneficial to providing the sputtering stability, and is suitable for future large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD pattern of a nickel oxide electrochromic composite film in example 1 of the present invention and a nickel oxide film in comparative example 1;
FIG. 2 is an XPS spectrum of a nickel oxide electrochromic composite film prepared in example 1 of the present invention;
FIGS. 3a to 3d are surface topography diagrams before and after electrochemical cycle treatment of the nickel oxide electrochromic composite film prepared in the embodiment 1 and the nickel oxide film prepared in the comparative example 1;
FIGS. 4a to 4d are sectional views of the nickel oxide electrochromic composite film prepared in the embodiment 1 and the nickel oxide film prepared in the comparative example 1 before and after electrochemical cycle treatment;
FIGS. 5a to 5b are optical transmittance maps of the nickel oxide electrochromic composite film prepared in example 1 and the nickel oxide film prepared in comparative example 1 in different color changing states;
FIGS. 6a to 6b are light modulation curves at 550nm for the nickel oxide electrochromic composite film prepared in example 1 and the nickel oxide film prepared in comparative example 1, respectively;
FIG. 7 is a charge capacity curve of the nickel oxide electrochromic composite film prepared in example 1 versus the nickel oxide film prepared in comparative example 1 at different cycle numbers;
FIG. 8 is a graph showing the change in charge capacity between the nickel oxide electrochromic composite film prepared in example 1 and the nickel oxide film prepared in comparative example 1 after being bent 2000 times (bending radius 2cm) before and after electrochemical cycle treatment; FIG. 9 is a schematic structural diagram of a nickel oxide electrochromic composite film in an exemplary embodiment of the invention;
description of the drawings: 1-PET substrate, 2-transparent conductive film, 3-NiO film and 4-zinc tin oxide film.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As one aspect of the technical scheme of the invention, the nickel oxide electrochromic composite film comprises a nickel oxide layer and an amorphous zinc tin oxide buffer layer which are arranged in a laminated manner; wherein the nickel oxide layer has a crystallized nano-columnar structure, and the diameter of the crystallized nano-columnar structure is 10-100 nm; the charge capacity of the nickel oxide electrochromic composite film is 6.0-12.0 mC-cm-2。
Specifically, the section of the nickel oxide film in the nickel oxide electrochromic composite film is of a crystalline nano columnar structure, and the diameter of a column is 10-100 nm; an amorphous zinc tin oxide film with a thickness of 3-50 nm is deposited on the nickel oxide film to form a double-layer film structure of nickel oxide and amorphous zinc tin oxide, as shown in fig. 9, which comprises (1) a PET substrate, (2) a transparent conductive film, (3) a nickel oxide film, and (4) a Zinc Tin Oxide (ZTO) film.
In some more specific embodiments, the nickel oxide layer is formed by a plurality of nano-columnar structures arranged along the vertical direction and closely arranged in sequence.
In some specific embodiments, the thickness of the nickel oxide layer is 80 to 300 nm.
Further, the nickel oxide layer is a nickel oxide film.
Further, the thickness of the amorphous zinc tin oxide buffer layer is 3-50 nm.
Furthermore, the amorphous zinc tin oxide buffer layer is a zinc tin oxide film.
Further, the thickness of the nickel oxide electrochromic composite film is 83-350 nm.
Another aspect of the present invention further provides a method for preparing the above nickel oxide electrochromic composite film, including:
providing a substrate provided with a transparent conductive layer;
depositing a nickel oxide layer on the surface of the transparent conductive layer by adopting a magnetron sputtering technology and taking a nickel oxide target as a target material;
and depositing an amorphous zinc tin oxide buffer layer on the surface of the nickel oxide layer by adopting a magnetron sputtering technology and taking a zinc tin oxide target as a target material, thereby obtaining the nickel oxide electrochromic composite film.
In some more specific embodiments, the nickel oxide target comprises a pure nickel oxide target or a co-doped nickel oxide target, and is not limited thereto.
Further, the co-doped nickel oxide target includes Li, Si co-doped nickel oxide targets or Sn, Ta, Nb, etc. co-doped nickel oxide targets with W, respectively, and is not limited thereto.
In some specific embodiments, the mass ratio of zinc oxide to tin oxide in the zinc oxide tin target is 100: (50-200).
Further, the sputtering mode adopted by the magnetron sputtering technology comprises radio frequency sputtering or intermediate frequency sputtering.
In some more specific embodiments, the preparation method specifically comprises: placing the substrate provided with the transparent conducting layer in a magnetron sputtering coating cavity by adopting a magnetron sputtering technology, and depositing and forming a nickel oxide layer on the surface of the transparent conducting layer by taking a nickel oxide target as a target material and inert gas as working gas, wherein the sputtering pressure value adopted by the magnetron sputtering technology is 0.4-3.0 Pa, and the sputtering power density is 2.0-7.0W/cm2The substrate temperature is 25-150 ℃, and the vacuum degree of the coating cavity is 0.10 multiplied by 10-2～10×10-2Pa, the introduction amount of inert gas is 30-50 sccm, and the thickness of the nickel oxide layer is 80-300 nm.
In some more specific embodiments, the preparation method specifically comprises: depositing an amorphous zinc tin oxide buffer layer on the surface of the nickel oxide layer by adopting a magnetron sputtering technology, taking a zinc tin oxide target as a target material and taking inert gas as working gas, wherein the sputtering pressure value adopted by the magnetron sputtering technology is 0.8-2.5 Pa, and the sputtering power density is 1.5-5.0W/cm2The substrate temperature is 25-150 ℃, and the vacuum degree of the reaction cavity is 0.10 multiplied by 10-2～10×10-2pa, the introduction amount of the inert gas is 20-40 sccm, and the thickness of the amorphous zinc tin oxide buffer layer is 3-50 nm.
Further, the inert gas includes argon gas, and is not limited thereto.
In some more specific embodiments, the substrate comprises a flexible substrate or a rigid substrate, and is not limited thereto.
Further, the material of the flexible substrate includes PET, PI, PVC or ultra-thin flexible glass, and is not limited thereto.
Further, the material of the rigid substrate includes glass, and is not limited thereto.
Further, the material of the transparent conductive layer includes ITO, AZO, or FTO, but is not limited thereto.
In some more specific embodiments, the method for preparing the nickel oxide electrochromic composite film comprises the following steps:
(1) magnetron sputtering deposition of nickel oxide films
And placing the co-doped nickel oxide target material in magnetron sputtering coating equipment, and depositing a nano columnar nickel oxide film on the PET substrate covered with the ITO transparent conducting layer. The parameters during sputtering were as follows: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is pure argon; the temperature of the substrate is 25-150 ℃; the degree of vacuum is (0.1-10) × 10-2Pa; the sputtering air pressure value is 0.4-3.0 Pa; the power density of sputtering is 2.0-7.0W/cm2(ii) a The thickness of the nickel oxide film is 80-300 nm; target compositions include, but are not limited to: pure nickel oxide, Li and Si co-doped nickel oxide targets or Sn, Ta, Nb and other nickel oxide targets co-doped with W respectively.
(2) Magnetron sputtering deposition of zinc tin oxide films
Putting a zinc tin oxide target material into magnetron sputtering coating equipment, and depositing a zinc tin oxide film on the nickel oxide film deposited in the step (1), wherein the main parameters in the sputtering process are as follows: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is pure argon; the temperature of the substrate is 25-150 ℃; vacuum degree of 0.10X 10-2～10×10-2Pa; the sputtering air pressure value is 0.8-2.5 Pa; the power density of sputtering is 1.5-5.0W/cm2(ii) a The thickness of the zinc tin oxide film is 3-50 nm; the mass ratio of zinc oxide to tin oxide in the components of the zinc oxide tin target is 100: 50-200.
In another aspect of the technical scheme of the invention, the application of the nickel oxide electrochromic composite film in preparing an electrochromic device is also provided.
Further, the electrochromic device comprises a flexible electrochromic device.
In another aspect of the technical solution of the present invention, a flexible electrochromic device is further provided, which includes the nickel oxide electrochromic composite film as an anode ion storage layer.
Further, in the flexible electrochromic device, the nickel oxide electrochromic composite film is disposed on a substrate comprising a transparent conductive layer.
Furthermore, the flexible electrochromic device also comprises an electrolyte layer, a cathode electrochromic film, a transparent conducting layer and a substrate.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Magnetron sputtering deposition of nickel oxide films
And placing the Li and Si co-doped nickel oxide target in magnetron sputtering coating equipment, and depositing a nano columnar nickel oxide film on the PET substrate covered with the ITO transparent conductive layer. The parameters during sputtering were as follows: the sputtering mode is intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 80 ℃; vacuum degree of 5X 10-2Pa; the sputtering air pressure value is 2.0 Pa; the power density of sputtering is 4.5W/cm2(ii) a The thickness of the nickel oxide film is 140 nm;
(2) magnetron sputtering deposition of zinc tin oxide films
Putting a zinc tin oxide target material into magnetron sputtering coating equipment, and depositing a zinc tin oxide film on the nickel oxide film deposited in the step (1), wherein the main parameters in the sputtering process are as follows: the sputtering mode is intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 80 ℃; vacuum degree of 5X 10-2Pa; the sputtering air pressure value is 1.5 Pa; the power density of sputtering is 3.0W/cm2(ii) a The thickness of the zinc tin oxide film is 20 nm; the mass ratio of zinc oxide to tin oxide in the components of the zinc oxide tin target is 100: 100; thereby obtaining the nickel oxide electrochromic composite film.
Comparative example 1
Putting the Li and Si co-doped nickel oxide target material into a magnetic controlIn the sputtering coating equipment, a nano columnar nickel oxide film is deposited on a PET substrate covered with an ITO transparent conducting layer. The parameters during sputtering were as follows: the sputtering mode is intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 80 ℃; vacuum degree of 5X 10-2Pa; the sputtering air pressure value is 2.0 Pa; the power density of sputtering is 4.5W/cm2(ii) a The thickness of the nickel oxide film was 140nm, thereby obtaining a nickel oxide film.
And (3) performance characterization:
the method comprises the following steps of observing the phase structure of the film by using an X-ray diffractometer (XRD), observing the valence state of an element by using a photoelectron spectrum (XPS), observing the surface and section morphology of the film by using a Scanning Electron Microscope (SEM), measuring the optical modulation amplitude and electrochromic response time of the film by using an ultraviolet-visible spectrophotometer, and measuring the electrochromic properties such as electrochemical property, cycle stability and the like of the film by using an electrochemical workstation.
FIG. 1 is an XRD pattern of a nickel oxide electrochromic composite film in example 1 of the present invention and a nickel oxide film in comparative example 1; it can be seen that the nickel oxide thin film in the nickel oxide electrochromic composite film and the nickel oxide thin film in comparative example 1 are crystalline and have (111), (200), and (220) peaks, while the zinc tin oxide layer is amorphous, so that no diffraction peak of zinc tin oxide is observed;
FIG. 2 is an XPS spectrum of the nickel oxide electrochromic composite film prepared in example 1 of the present invention, and it can be seen that the nickel oxide electrochromic composite film has good Ni content3+A ratio of Ni, wherein Ni3+the/Ni stoichiometric ratio can be determined by Ni3+And Ni2+And Ni3The sum of the ratios was calculated as 0.47, Ni3+Is an active material participating in electrochromic reaction, and more Ni3+Presence means a larger optical modulation amplitude;
FIGS. 3 a-3 b are surface topography diagrams of the nickel oxide electrochromic composite film prepared in example 1 and the nickel oxide film prepared in comparative example 1, respectively, and it can be seen that both have porous nanostructures; after 600 cycles of electrochemical cycles, the nickel oxide electrochromic composite film prepared in example 1 can slow down damage to the surface topography of the color-changing layer film caused by the insertion and extraction of lithium ions in the cycle process, and maintain the surface topography (as shown in fig. 3 c), while the nickel oxide film in comparative example 1 has serious surface deterioration and cracks after 600 cycles of electrochemical cycles (as shown in fig. 3 d). The stability of the microstructure of the nickel oxide electrochromic composite film prepared in the embodiment 1 is improved, which is beneficial to improving the stability of the electrochromic film;
FIGS. 4a to 4b are sectional views of the electrochromic composite nickel oxide film prepared in the embodiment 1 and the electrochromic nickel oxide film prepared in the comparative example 1, respectively, with a diameter of about 20 to 30 nm; the diameter of the columnar structure of the nickel oxide electrochromic composite film prepared in the embodiment 1 is always maintained at about 20-30 nm (as shown in fig. 4 c) before and after 600 circles of electrochemical cycles, while the structure of the nickel oxide film prepared in the comparative example 1 is deteriorated after 600 circles of electrochemical cycles, the columnar structure in the film is gradually densified and coarsened, the columnar structure is not obvious, and the diameter of the nickel oxide film is changed to about 50nm (as shown in fig. 4 d), so that the stable columnar structure of the nickel oxide electrochromic composite film prepared in the embodiment 1 can be seen, more lithium ion binding sites in the electrochromic film can be kept, and the optical modulation amplitude of the film can be improved.
FIGS. 5a to 5b are optical transmittance maps of the nickel oxide electrochromic composite film prepared in example 1 and the nickel oxide film prepared in comparative example 1 in different color changing states; as can be seen from FIGS. 5a to 5b, in the wavelength range of 300nm to 1100nm, the colored state transmittance of example 1 is lower, and the optical modulation amplitude is larger, both of which are better than those of comparative example 1;
FIGS. 6a to 6b are light modulation curves at 550nm for the nickel oxide electrochromic composite film prepared in example 1 and the nickel oxide film prepared in comparative example 1, respectively; as can be seen from FIGS. 6a to 6b, the transmittance in the colored state of example 1 after 600 cycles of electrochemical cycling at a wavelength of 550nm is 50%, the optical modulation amplitude is 35.5% (as shown in FIG. 6 a), and is better than 61.9% and 22.8% (as shown in FIG. 6 b) of comparative example 1, which indicates that the nickel oxide electrochromic composite film in example 1 significantly inhibits the color fading in the colored state of nickel oxide during electrochemical cycling and improves the optical modulation amplitude.
FIG. 7 isThe charge capacity curve of the nickel oxide electrochromic composite film prepared in the embodiment 1 and the nickel oxide film prepared in the comparative example 1 under different cycle numbers is that after 600 CV cycles, the charge capacity of the embodiment 1 is 8.0mC cm-2Much higher than 4.0mC cm for comparative example 1-2It is demonstrated that the nickel oxide electrochromic composite film in example 1 has a higher charge capacity.
Fig. 8 is a charge capacity change diagram before and after the nickel oxide electrochromic composite film prepared in example 1 and the nickel oxide film prepared in comparative example 1 are respectively bent for 2000 times (bending radius 2cm) before and after electrochemical cycle treatment, and after 2000 times of bending, the charge capacity decline of the composite film covered with the amorphous tin zinc oxide layer is only 5-6%, and the charge capacity decline of the sample not covered with the amorphous tin zinc oxide layer is as high as 18-20%, which indicates that the nickel oxide electrochromic composite film in example 1 has good bending resistance.
Example 2
(1) Magnetron sputtering deposition of nickel oxide films
And placing the pure nickel oxide target material in magnetron sputtering coating equipment, and depositing the nano columnar nickel oxide film on the PET substrate covered with the ITO transparent conductive layer. The parameters during sputtering were as follows: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 25 ℃; vacuum degree of 0.1X 10-2Pa; the sputtering air pressure value is 0.4 Pa; the power density of sputtering is 2.0W/cm2(ii) a The thickness of the nickel oxide film is 80 nm;
(2) magnetron sputtering deposition of zinc tin oxide films
Putting a zinc tin oxide target material into magnetron sputtering coating equipment, and depositing a zinc tin oxide film on the nickel oxide film deposited in the step (1), wherein the main parameters in the sputtering process are as follows: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 25 ℃; vacuum degree of 0.1X 10-2Pa; the sputtering air pressure value is 0.8 Pa; the power density of the sputtering is 1.5W/cm2(ii) a The thickness of the zinc tin oxide film is 3 nm; the mass ratio of zinc oxide to tin oxide in the components of the zinc oxide tin target is 100: 50, so that the nickel oxide electrode is obtainedPhotochromic composite films.
Example 3
(1) Magnetron sputtering deposition of nickel oxide films
Placing the Sn and W co-doped nickel oxide target material in magnetron sputtering coating equipment, and depositing a nano columnar nickel oxide film on a PET substrate covered with the ITO transparent conducting layer. The parameters during sputtering were as follows: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 150 ℃; vacuum degree of 10X 10-2Pa; the sputtering air pressure value is 3.0 Pa; the power density of sputtering is 7.0W/cm2(ii) a The thickness of the nickel oxide film is 300 nm;
(2) magnetron sputtering deposition of zinc tin oxide films
Putting a zinc tin oxide target material into magnetron sputtering coating equipment, and depositing a zinc tin oxide film on the nickel oxide film deposited in the step (1), wherein the main parameters in the sputtering process are as follows: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 150 ℃; vacuum degree of 10X 10-2Pa; the sputtering air pressure value is 2.5 Pa; the power density of sputtering is 5.0W/cm2(ii) a The thickness of the zinc tin oxide film is 50 nm; the mass ratio of zinc oxide to tin oxide in the components of the zinc oxide tin target is 100: 200, so that the nickel oxide electrochromic composite film is obtained.
Example 4
(1) Magnetron sputtering deposition of nickel oxide films
Placing the Nb and W co-doped nickel oxide target material in magnetron sputtering coating equipment, and depositing a nano columnar nickel oxide film on a PET substrate covered with an ITO transparent conductive layer. The parameters during sputtering were as follows: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 50 ℃; vacuum degree of 8X 10-2Pa; the sputtering air pressure value is 1.0 Pa; the power density of sputtering is 5.0W/cm2(ii) a The thickness of the nickel oxide film is 150 nm;
(2) magnetron sputtering deposition of zinc tin oxide films
Putting the zinc tin oxide target material into a magnetron sputtering coating device, and depositing oxidation on the nickel oxide film deposited in the step (1)The main parameters of the zinc-tin film in the sputtering process are as follows: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 80 ℃; vacuum degree of 8X 10-2Pa; the sputtering air pressure value is 1.0 Pa; the power density of sputtering is 4.0W/cm2(ii) a The thickness of the zinc tin oxide film is 30 nm; the mass ratio of zinc oxide to tin oxide in the components of the zinc oxide tin target is 100: 150, so that the nickel oxide electrochromic composite film is obtained.
Example 5
(1) Magnetron sputtering deposition of nickel oxide films
And placing the pure nickel oxide target material in magnetron sputtering coating equipment, and depositing a nano columnar nickel oxide film on the glass substrate covered with the ITO transparent conductive layer. The parameters during sputtering were as follows: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 25 ℃; vacuum degree of 0.1X 10-2Pa; the sputtering air pressure value is 0.4 Pa; the power density of sputtering is 2.0W/cm2(ii) a The thickness of the nickel oxide film is 80 nm;
(2) magnetron sputtering deposition of zinc tin oxide films
Putting a zinc tin oxide target material into magnetron sputtering coating equipment, and depositing a zinc tin oxide film on the nickel oxide film deposited in the step (1), wherein the main parameters in the sputtering process are as follows: the sputtering mode is radio frequency sputtering or intermediate frequency sputtering, and the working gas is pure argon; the substrate temperature is 25 ℃; vacuum degree of 0.1X 10-2Pa; the sputtering air pressure value is 0.8 Pa; the power density of the sputtering is 1.5W/cm2(ii) a The thickness of the zinc tin oxide film is 3 nm; the mass ratio of zinc oxide to tin oxide in the components of the zinc oxide tin target is 100: 50, so that the nickel oxide electrochromic composite film is obtained.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.
Claims (10)
1. The nickel oxide electrochromic composite film is characterized by comprising a nickel oxide layer and an amorphous zinc tin oxide buffer layer which are arranged in a laminated manner; wherein the nickel oxide layer has a crystallized nano-columnar structure, and the diameter of the crystallized nano-columnar structure is 10-100 nm; the charge capacity of the nickel oxide electrochromic composite film is 6.0-12.0 mC-cm-2。
2. The nickel oxide electrochromic composite film according to claim 1, characterized in that: the nickel oxide layer is formed by sequentially and tightly arranging a plurality of nano columnar structures arranged along the vertical direction.
3. The nickel oxide electrochromic composite film according to claim 1, characterized in that: the thickness of the nickel oxide layer is 80-300 nm; and/or the nickel oxide layer is a nickel oxide film;
and/or the thickness of the amorphous zinc tin oxide buffer layer is 3-50 nm; and/or the amorphous zinc tin oxide buffer layer is a zinc tin oxide film;
and/or the thickness of the nickel oxide electrochromic composite film is 83-350 nm.
4. The method for producing a nickel oxide electrochromic composite film according to any one of claims 1 to 3, characterized by comprising:
providing a substrate provided with a transparent conductive layer;
depositing a nickel oxide layer on the surface of the transparent conductive layer by adopting a magnetron sputtering technology and taking a nickel oxide target as a target material;
and depositing an amorphous zinc tin oxide buffer layer on the surface of the nickel oxide layer by adopting a magnetron sputtering technology and taking a zinc tin oxide target as a target material, thereby obtaining the nickel oxide electrochromic composite film.
5. The method of claim 4, wherein: the nickel oxide target comprises a pure nickel oxide target or a co-doped nickel oxide target; preferably, the co-doped nickel oxide target comprises a Li and Si co-doped nickel oxide target or a Sn, Ta and Nb respectively and W co-doped nickel oxide target;
and/or the mass ratio of zinc oxide to tin oxide in the zinc oxide tin target is 100: 50-200;
and/or the sputtering mode adopted by the magnetron sputtering technology comprises radio frequency sputtering or intermediate frequency sputtering.
6. The preparation method according to claim 4, characterized by specifically comprising: placing the substrate provided with the transparent conducting layer in a magnetron sputtering coating cavity by adopting a magnetron sputtering technology, and depositing and forming a nickel oxide layer on the surface of the transparent conducting layer by taking a nickel oxide target as a target material and inert gas as working gas, wherein the sputtering pressure value adopted by the magnetron sputtering technology is 0.4-3.0 Pa, and the sputtering power density is 2.0-7.0W/cm2The substrate temperature is 25-150 ℃, and the vacuum degree of the coating cavity is 0.10 multiplied by 1-210×10-2Pa, the introduction amount of inert gas is 30-50 sccm, and the thickness of the nickel oxide layer is 80-300 nm.
7. The preparation method according to claim 4, characterized by specifically comprising: depositing an amorphous zinc tin oxide buffer layer on the surface of the nickel oxide layer by adopting a magnetron sputtering technology, taking a zinc tin oxide target as a target material and taking inert gas as working gas, wherein the sputtering pressure value adopted by the magnetron sputtering technology is 0.8-2.5 Pa, and the sputtering power density is 1.5-5.0W/cm2The substrate temperature is 25-150 ℃, and the vacuum degree of the reaction cavity is 0.10 multiplied by 10-210×10-2Pa, the introduction amount of inert gas is 20-40 sccm, and the thickness of the amorphous zinc tin oxide buffer layer is 3-50 nm.
8. The method of claim 4, wherein: the substrate comprises a flexible substrate or a rigid substrate; preferably, the flexible substrate is made of PET, PI, PVC or ultrathin flexible glass; preferably, the material of the rigid substrate comprises glass;
and/or the material of the transparent conducting layer comprises ITO, AZO or FTO.
9. Use of the nickel oxide electrochromic composite film according to any one of claims 1 to 3 for the preparation of an electrochromic device; preferably, the electrochromic device comprises a flexible electrochromic device.
10. A flexible electrochromic device characterized by comprising an anodic ion storage layer comprising the nickel oxide electrochromic composite film according to claims 1 to 3;
preferably, the flexible electrochromic device further comprises an electrolyte layer, a cathode electrochromic layer, a transparent conductive layer and a substrate.
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