阅读说明：本技术 一种全无机固态电致变色器件及其制备方法 (All-inorganic solid electrochromic device and preparation method thereof ) 是由 李晨 贾鹏宇 洪应平 熊继军 于 2019-09-29 设计创作，主要内容包括：本发明公开了一种全无机固态电致变色器件,包括两侧设置的透明玻璃基板A和透明玻璃基板B,设置于透明玻璃基板A上靠近于中部的透明导电薄膜层I,设置于透明玻璃基板B上靠近于中部的透明导电薄膜层II,设置于透明导电薄膜层I内侧的电致变色层,设置于透明导电薄膜层II内侧的离子储存层,设置于电致变色层内侧的电子阻挡层I,设置于离子储存层内侧的电子阻挡层II；设置于电子阻挡层I和电子阻挡层II中间的离子传输层；所述电致变色层采用WO<Sub>3</Sub>掺杂TiO<Sub>2</Sub>薄膜,所述离子传输层采用锂磷氧氮(LiPON)薄膜,所述离子储存层采用V<Sub>2</Sub>O<Sub>5</Sub>薄膜本发明解决了电致变色器件循环使用过程中一直存在的变色性能不稳定,循环寿命差的缺陷。(The invention discloses an all-inorganic solid electrochromic device, which comprises a transparent glass substrate A and a transparent glass substrate B, wherein the transparent glass substrate A and the transparent glass substrate B are arranged on two sides, a transparent conductive thin film layer I is arranged on the transparent glass substrate A and is close to the middle part, a transparent conductive thin film layer II is arranged on the transparent glass substrate B and is close to the middle part, an electrochromic layer arranged on the inner side of the transparent conductive thin film layer I, an ion storage layer arranged on the inner side of the transparent conductive thin film layer II, an electron blocking layer I arranged on the inner side of the electrochromic layer and an electron blocking layer II arranged on the inner side of; the ion transmission layer is arranged between the electron blocking layer I and the electron blocking layer II; the electrochromic layer adopts WO 3 Doped TiO 2 2 The ion transmission layer adopts a lithium phosphorus oxygen nitrogen (LiPON) film, and the ion storage layer adopts V 2 O 5 The film solves the problems of unstable color-changing performance and cycle existing in the recycling process of the electrochromic deviceThe life is poor.)

1. An all-inorganic solid-state electrochromic device is characterized by comprising a transparent glass substrate A and a transparent glass substrate B which are arranged on two sides, a transparent conductive thin film layer I which is arranged on the transparent glass substrate A and is close to the middle part, a transparent conductive thin film layer II which is arranged on the transparent glass substrate B and is close to the middle part, an electrochromic layer arranged on the inner side of the transparent conductive thin film layer I, an ion storage layer arranged on the inner side of the transparent conductive thin film layer II, an electron blocking layer I arranged on the inner side of the electrochromic layer and an electron blocking layer II arranged on the inner side of the ion storage layer; the ion transmission layer is arranged between the electron blocking layer I and the electron blocking layer II; the electrochromic layer adopts WO₃Doped TiO 2₂The ion transmission layer is a lithium phosphorus oxygen nitrogen (LiPON) film.

2. The all-inorganic solid electrochromic device according to claim 1, wherein the transparent conductive thin film layer I is formed on the transparent glass substrate a and is formed on a side near the middle portion, and the transparent conductive thin film layer II is formed on the transparent glass substrate B and is formed on a side near the middle portion.

3. The all-inorganic solid electrochromic device according to claim 2, wherein the thickness of the transparent conductive thin film layer I and the transparent conductive thin film layer II is 200nm to 300 nm.

4. The all-inorganic solid electrochromic device according to claim 1, wherein said WO is₃Doped TiO 2₂The thickness of the film is 400nm-500nm, WO₃Doped TiO 2₂The method adopts a magnetron multi-target co-sputtering method, a sputtering target material adopts a tungsten target and a titanium target with the diameter of 6cm and the thickness of 6mm, the sputtering is carried out in the atmosphere with a certain oxygen-argon flow ratio, the target base distance is 15-20cm, and the working pressure is 2Pa to 3 Pa.

5. The all-inorganic solid electrochromic device according to claim 1, wherein said ion storage layer employs V₂O₅An ion storage layer with electrochromic characteristics of negative and positive, and a crystal structure similar to WO₃The open structure has stronger ion storage capacity, and the film layer is prepared by using a magnetron sputtering method.

6. The method for preparing an all-inorganic solid-state electrochromic device according to claim 1, comprising the steps of:

coating a transparent glass substrate a with ZnO: sputtering an AZO film by using the AI block as a sputtering target to form a transparent conductive film layer I;

the transparent conductive film layer I is taken as a substrate, the W target and the Ti target are taken as target materials, and the magnetic control multi-target co-sputtering process is adopted to prepare WO₃Doped TiO 2₂A thin film forming an electrochromic layer;

sputtering S on the electrochromic layer₃N₄A thin film forming an electron blocking layer I;

with Li on the electron-blocking layer I₃PO₄Sputtering a target material to prepare a lithium phosphorus oxygen nitrogen (LiPON) film to form an ion transport layer;

sputtering S on lithium phosphorus oxynitride (LiPON) film₃N₄A thin film forming an electron blocking layer II;

sputtering V on the electron barrier layer II by taking a vanadium target as a target material₂O₅A thin film forming an ion storage layer;

and coating the ion storage layer with ZnO: the AI block is a sputtering target material to sputter an AZO film to form a transparent conductive film layer II on the other side;

curing the prepared multi-film layer and another transparent glass substrate into an integrated electrochromic device in an autoclave by a method of laminating multi-film layers;

and butting the transparent conductive thin film layer I and the transparent conductive thin film layer II with the anode and the cathode of an external power supply respectively to obtain the conductive film.

Technical Field

The invention relates to the field of electrochromic devices, in particular to an all-inorganic solid-state electrochromic device and a preparation method thereof.

Background

The electrochromic film can realize coloring and bleaching effects under the action of an external electric field, and the excellent display effect of the electrochromic film is widely applied to the fields of electronic information, sensors, intelligent windows, military, national defense and the like. The traditional electrochromic device has the defects of short cycle life, low color change response speed, unstable performance, high manufacturing cost, complex process and the like due to the defects of the performance of each film layer. The domestic electrochromic research mainly focuses on the performance improvement of single-layer electrochromic film materials, the preparation of small-size semi-solid devices and a small number of all-solid devices, and the like, and the cycle life of the devices can only reach about thousands of times and can not reach 10 times of the requirement of industrial application⁴The above steps are repeated. Therefore, how to improve the cycle life of the electrochromic device to realize large-scale industrial application thereof is a major research hotspot and direction at present.

Disclosure of Invention

In order to solve the problems, the invention provides an all-inorganic solid-state electrochromic device structure and a preparation method thereof.

In order to achieve the purpose, the invention adopts the technical scheme that:

an all-inorganic solid-state electrochromic device comprises a transparent glass substrate A and a transparent glass substrate B which are arranged on two sides, a transparent conductive thin film layer I which is arranged on the transparent glass substrate A and is close to the middle part, a transparent conductive thin film layer II which is arranged on the transparent glass substrate B and is close to the middle part, an electrochromic layer arranged on the inner side of the transparent conductive thin film layer I, an ion storage layer arranged on the inner side of the transparent conductive thin film layer II, an electron blocking layer I arranged on the inner side of the electrochromic layer and an electron blocking layer II arranged on the inner side of the ion storage layer; the ion transmission layer is arranged between the electron blocking layer I and the electron blocking layer II; the electrochromic layer adopts WO₃Doped TiO 2₂The ion transmission layer is a lithium phosphorus oxygen nitrogen (LiPON) film.

Furthermore, the transparent conductive thin film layer I is located on the transparent glass substrate A and close to one side of the middle part, the transparent conductive thin film layer I is made of aluminum-doped zinc oxide AZO, the transparent conductive thin film layer II is located on the transparent glass substrate B and close to one side of the middle part, and the transparent conductive thin film layer II is made of aluminum-doped zinc oxide AZO.

Further, the thickness of the transparent conductive thin film layer I and the transparent conductive thin film layer II is 200nm-300 nm.

Further, the WO₃Doped TiO 2₂The thickness of the film is 400nm-500nm, WO₃Doped TiO 2₂The method adopts a magnetron multi-target co-sputtering method, a sputtering target material adopts a tungsten target and a titanium target with the diameter of 6cm and the thickness of 6mm, the sputtering is carried out in the atmosphere with a certain oxygen-argon flow ratio, the target base distance is 15-20cm, and the working pressure is 2Pa to 3 Pa.

Further, the ion storage layer adopts V₂O₅An ion storage layer with a thickness of 300-400nm and having electrochromic characteristics of both cathode and anode, and the crystal structure of the ion storage layer is similar to that of WO₃The open structure has stronger ion storage capacity, and is prepared by a magnetron sputtering method.

The invention also provides a specific preparation method of the all-inorganic solid electrochromic device, which comprises the following steps:

sputtering an AZO film on a transparent glass substrate A by taking a ZnO/Al block as a sputtering target to form a transparent conductive film layer I;

the transparent conductive film layer I is taken as a base layer, the W target and the Ti target are taken as target materials, and the magnetic control multi-target co-sputtering process is adopted to prepare WO₃Doped TiO 2₂A thin film forming an electrochromic layer;

sputtering Si on electrochromic layer₃N₄Forming a film in a chamber atmosphere of nitrogen and argon to form an electron blocking layer I;

with Li on the electron-blocking layer I₃PO₄Preparing a lithium phosphorus oxygen nitrogen (LiPON) film for the target material by radio frequency sputtering to form an ion transmission layer;

sputtering S on lithium phosphorus oxynitride (LiPON) film₃N₄A thin film forming an electron blocking layer II;

sputtering V on the electron barrier layer II by taking a vanadium target as a target material₂O₅A thin film forming an ion storage layer;

sputtering an AZO film on the ion storage layer by taking ZnO and Al blocks as sputtering targets to form a transparent conductive film layer II;

curing the prepared film layer and another transparent glass substrate into an integrated electrochromic device in an autoclave by a method of laminating a plurality of films;

and butting the transparent conductive thin film layer l and the transparent conductive thin film layer II with the anode and the cathode of an external power supply respectively to obtain the conductive film.

The proposal utilizes TiO₂High cycle characteristics of and WO₃The stability of the method reduces the dissolution of related oxidation phases caused by the self-discharge phenomenon of a cathode layer in the circulating process, solves the defects of unstable color-changing performance and poor circulating life of the electrochromic device in the circulating application process, and the circulating life of the electrochromic device prepared by the method can reach more than ten thousand times without obvious color-changing and color-fading cyclic attenuation phenomena. In addition, electron blocking layers Si are introduced on two sides of the ion transmission layer₃N₄The defect of unstable color change performance caused by the leakage current phenomenon in the electrochromic process is greatly reduced. Meanwhile, the electrochromic ion transport layer adopts nitrogenous lithium phosphate-LiPON with excellent electrochemical stability and ionic conductivity combined with V₂O₅The method has the characteristic of higher ion storage capacity, is beneficial to the ion transportation in the device so as to expand the optical modulation range of electrochromism, and finally can ensure that the optical modulation range can reach over 75 percent. The preparation process adopts a magnetron sputtering method, has simple process and mature technology and is suitable for industrial production.

Drawings

FIG. 1 is a schematic structural diagram of an all-inorganic solid-state electrochromic device according to an embodiment of the present invention;

in the figure: 1-a transparent glass substrate a; 2-transparent conductive thin film layer I; 3-an electrochromic layer; 4-electron blocking layer I; 5-electron blocking layer II; 6-an ion storage layer; 7-transparent conductive thin film layer II; 8-transparent glass substrate B; 9-external power supply; 10-ion transport layer.

Fig. 2 is a flow chart of a process for manufacturing an all-inorganic solid electrochromic device according to an embodiment of the present invention.

Fig. 3 is a microscopic reaction schematic diagram of an all-inorganic solid electrochromic device according to an embodiment of the present invention.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.

As shown in fig. 1, an embodiment of the present invention provides an all-inorganic solid-state electrochromic device, including a transparent glass substrate A1 and a transparent glass substrate B8 disposed at two sides, a transparent conductive thin film layer I2 disposed on the transparent glass substrate A1 near the middle, a transparent conductive thin film layer II7 disposed on the transparent glass substrate B near the middle, an electrochromic layer 3 disposed at the inner side of the transparent conductive thin film layer I, an ion storage layer 6 disposed at the inner side of the transparent conductive thin film layer II, an electron blocking layer I4 disposed at the inner side of the electrochromic layer 3, and an electron blocking layer II5 disposed at the inner side of the ion storage layer; an ion transport layer 10 disposed between the electron blocking layer I4 and the electron blocking layer II 5; the electrochromic layer adopts WO₃Doped TiO 2₂Film with thickness of 400nm-500nm, WO₃Doped TiO 2₂The method is characterized in that a magnetron multi-target co-sputtering method is adopted, a tungsten target and a titanium target with the diameter of 6cm and the thickness of 6mm are adopted as sputtering targets, sputtering is carried out in an atmosphere with a certain oxygen-argon flow ratio, the target base distance is 15-20cm, and the working pressure is 2-3 Pa; the ion transmission layer adopts a lithium phosphorus oxygen nitrogen (LiPON) film; has better ion conductivity and light transmission, and the value of the ion conductivity can reach 10 at normal temperature^-6S/cm, light transmittance up to 80%. The thickness of the transparent conductive film layer I and the transparent conductive film layer II is 200nm-300nm, and the material is aluminum-doped zinc oxide AZO; the ion storage layer adopts V₂O₅An ion storage layer with electrochromic characteristics of both positive and negative ions and a crystal structure similar to that of WO₃The open structure has stronger ion storage capacity, and is prepared by a magnetron sputtering method.

As shown in fig. 2, an embodiment of the present invention further provides a method for preparing an all-inorganic solid electrochromic device, which adopts a magnetron sputtering method, and includes the following steps:

s1, sputtering an AZO film on the transparent glass substrate A by taking ZnO and Al blocks as sputtering targets to form a transparent conductive film layer I; when in preparation, firstly, Al is weighed according to the mass ratio of 1: 50₂O₃Grinding and drying ZnO powder, adding 1mol of PVA as an adhesive, placing the mixture into a mould, sintering the mixture for 3 hours at 1500 ℃, and cooling the mixture in the air along with a furnace to obtain a target material; then putting the transparent glass substrate A into a magnetron sputtering furnace, sputtering an AZO film on the surface of the transparent glass substrate A by adopting radio frequency magnetron sputtering, wherein the air pressure is 2.5Pa, the Ar flow is 25sccm, the sputtering power is 150W, the substrate temperature is 250 ℃, and the deposition time is 1 h;

s2, preparing WO by taking the transparent conductive film layer I as a base layer, taking the W target and the Ti target as targets and adopting a magnetron multi-target co-sputtering process₃Doped TiO 2₂A thin film forming an electrochromic layer; during preparation, the AZO film is taken as a substrate, the target material is W/Ti, two targets are sputtered and deposited on the substrate simultaneously, and direct current magnetron sputtering is adopted, Ar: O₂The sputtering power is 140W, the substrate temperature is 200 ℃, and the deposition time is 1h under the condition of 40: 1.

S3, sputtering S on the electrochromic layer in the atmosphere of nitrogen and argon₃N₄A thin film forming an electron blocking layer I;

s4 application of Li on the electron blocking layer I₃PO₄Sputtering a target material to prepare a lithium phosphorus oxygen nitrogen (LiPON) film to form an ion transport layer; during preparation, the target material is Li₃PO₄The sputtering atmosphere is N₂Mixed gas of Ar, N₂Ar (sccm) is 30: 70, the sputtering mode is radio frequency magnetron sputtering, the power is 140W, the substrate temperature is 200 ℃, the deposition time is 1h, and the film thickness is 400 nm;

s5 sputtering S on the lithium phosphorus oxygen nitrogen (LiPON) film₃N₄A thin film forming an electron blocking layer II;

s6 sputtering V on the electron barrier layer II by using a vanadium target as a target₂O₅A thin film forming an ion storage layer; the material is prepared by direct current magnetron sputtering, the target material is vanadium metal, the sputtering mode is direct current magnetron sputtering, and the flow ratio of oxygen to argon is O₂Ar (sccm) is 30: 70, the power is 160W, the substrate temperature is 200 ℃, the deposition time is 0.5h, and the film thickness is 300 nm;

s7, sputtering an AZO film on the ion storage layer by taking ZnO and Al blocks as sputtering targets to form a transparent conductive film layer II;

s8, curing the prepared film layer and another transparent glass substrate into an integrated electrochromic device in an autoclave by a method of laminating a plurality of films;

and S9, butting the transparent conductive film layer I and the transparent conductive film layer II with the anode and the cathode of the external power supply 9 respectively to obtain the conductive film.

The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.