CN112210754B

CN112210754B - Preparation method of electrochromic film system and preparation method of electrochromic device

Info

Publication number: CN112210754B
Application number: CN202010896429.9A
Authority: CN
Inventors: 周钧; 程银兵; 庄志杰
Original assignee: Gemch Material Technology Suzhou Co ltd
Current assignee: Gemch Material Technology Suzhou Co ltd
Priority date: 2020-08-31
Filing date: 2020-08-31
Publication date: 2022-12-06
Anticipated expiration: 2040-08-31
Also published as: CN112210754A

Abstract

The invention relates to a preparation method of an electrochromic film system and a preparation method of an electrochromic device. The preparation method of the electrochromic film system comprises the following steps: forming a first conductive thin film layer on the first transparent protective layer by adopting a vapor deposition technology, wherein the first conductive thin film layer is made of metal oxide; forming an ion storage layer on the first conductive thin film layer by adopting a vapor deposition technology, wherein the material of the ion storage layer is lithium alloy or lithium metal oxide; forming an ion conduction and transportation layer on the ion storage layer by adopting a vapor deposition technology, wherein the material of the ion conduction and transportation layer is a polyanion compound containing lithium; forming an ion discoloring layer on the ion conduction conveying layer by adopting a vapor deposition technology, wherein the ion discoloring layer is made of metal oxide; forming a second conductive thin film layer on the ion discoloring layer by adopting a vapor deposition technology, wherein the second conductive thin film layer is made of metal oxide; and forming a second transparent protective layer on the second conductive thin film layer by using a vapor deposition technique.

Description

Preparation method of electrochromic film system and preparation method of electrochromic device

Technical Field

The invention relates to the technical field of display, in particular to a preparation method of an electrochromic film system and a preparation method of an electrochromic device.

Background

The electrochromic phenomenon is a phenomenon that the optical performance of the material is continuously and reversibly changed under the action of an external electric field, and is visually represented as a process that the color and the transparency of the material are reversibly changed. The material with the special function is called electrochromic material, and the novel material has many excellent characteristics, the transmissivity can be continuously changed in a large range and can be adjusted by manpower at will; no viewing angle difference exists; the driving color change requires low voltage, the power supply is simple, and the power consumption is saved; also has the function of memory storage; less influenced by environmental conditions in use, etc. The electrochromic film system and electrochromic device can be made by utilizing electrochromic phenomenon and materials. In a traditional electrochromic scheme, metal lithium is generally adopted as a storage material of ions, however, the metal lithium itself needs to be stored in a special environment, a target of the metal lithium has special requirements on magnetron sputtering deposition equipment and a magnetron sputtering deposition process, a thin film of the metal lithium cannot be kept consistent and continuous in working in an electrochromic device, and the metal lithium and other materials have an interface matching problem. This results in a conventional electrochromic scheme which is disadvantageous for the application.

Disclosure of Invention

In view of the above, it is necessary to provide a method for manufacturing an electrochromic film system and a method for manufacturing an electrochromic device, which are advantageous for application.

A preparation method of an electrochromic film system comprises the following steps:

forming a first conductive thin film layer on the first transparent protective layer by adopting a vapor deposition technology, wherein the first conductive thin film layer is made of metal oxide;

forming an ion storage layer on the first conductive thin film layer by adopting a vapor deposition technology, wherein the material of the ion storage layer is lithium alloy or lithium metal oxide;

forming an ion conduction and transportation layer on the ion storage layer by adopting a vapor deposition technology, wherein the material of the ion conduction and transportation layer is a polyanion compound containing lithium;

forming an ion discoloring layer on the ion conduction conveying layer by adopting a vapor deposition technology, wherein the ion discoloring layer is made of metal oxide;

forming a second conductive thin film layer on the ion discoloring layer by adopting a vapor deposition technology, wherein the second conductive thin film layer is made of metal oxide; and

and forming a second transparent protective layer on the second conductive thin film layer by adopting a vapor deposition technology to obtain the electrochromic film system.

The preparation method of the electrochromic film system in the technical scheme of the invention is simple, can realize the free combination and matching of functional materials such as a plurality of different first conductive film layers, ion storage layers, ion conduction and transmission layers, ion discoloring layers, second conductive film layers and the like, and improves the interface stability among the functional layers, so that the long-time stability of an electrochromic device can be ensured under lower working voltage, and the application is facilitated.

In one embodiment, before forming the second conductive thin film layer on the ion-discoloring layer, the method further comprises the following steps:

and forming an ion color storage layer on the ion color changing layer by adopting a vapor deposition technology, wherein the ion color storage layer is made of lithium metal oxide.

In one embodiment, the operation of forming the ion storage layer on the ion discoloring layer by using the vapor deposition technology is as follows: and (3) pumping the vacuum degree to a set value, then heating to 370-430 ℃, introducing inert gas of 260-380 sccm and oxygen of 30-38 sccm, and carrying out sputtering deposition under a vacuum condition to obtain an ion color storage layer, wherein the thickness of the ion color storage layer is 250-360 nm.

In one embodiment, the operation of forming the first conductive thin film layer on the first transparent protective layer by using the vapor deposition technology is as follows: and (3) pumping the vacuum degree to a set value, then heating to 170-230 ℃, introducing 220-300 sccm inert gas and 35-48 sccm oxygen, and performing sputtering deposition under a vacuum condition to obtain a first conductive thin film layer, wherein the thickness of the first conductive thin film layer is 200-280 nm, and the square resistance value of the first conductive thin film layer is 10 omega/□ -12 omega/□.

In one embodiment, the operation of forming the ion storage layer on the first conductive thin film layer by using the vapor deposition technique is as follows: and (3) pumping the vacuum degree to a set value, then heating to 370-430 ℃, introducing 240-370 sccm of inert gas and 30-38 sccm of oxygen, and performing sputtering deposition under a vacuum condition to obtain an ion storage layer, wherein the thickness of the ion storage layer is 200-250 nm.

In one embodiment, the operation of forming the ion-conducting transport layer on the ion storage layer by using the vapor deposition technique is as follows: and (3) pumping the vacuum degree to a set value, heating to 370-430 ℃, introducing inert gas of 260-380 sccm and oxygen of 30-38 sccm, and performing sputtering deposition under a vacuum condition to obtain the ion conduction transport layer, wherein the thickness of the ion conduction transport layer is 850-1280 nm.

In one embodiment, the operation of forming the ion-discoloring layer on the ion-conducting transport layer using vapor deposition techniques is: and (3) pumping the vacuum degree to a set value, heating to 370-430 ℃, introducing 240-370 sccm of inert gas and 30-38 sccm of oxygen, and performing sputtering deposition under a vacuum condition to obtain an ion discoloring layer, wherein the thickness of the ion discoloring layer is 250-360 nm.

In one embodiment, the operation of forming the second conductive thin film layer on the ion-discoloring layer by using the vapor deposition technique is as follows: and (3) pumping the vacuum degree to a set value, then heating to 170-230 ℃, introducing 220-300 sccm inert gas and 35-48 sccm oxygen, and performing sputtering deposition under a vacuum condition to obtain a second conductive thin film layer, wherein the thickness of the second conductive thin film layer is 200-280 nm, and the square resistance value of the second conductive thin film layer is 10 omega/□ -12 omega/□.

In one embodiment, the operation of forming the second transparent protection layer on the second conductive thin film layer by using the vapor deposition technique is as follows: and (3) pumping the vacuum degree to a set value, then heating to 170-230 ℃, introducing 220-300 sccm inert gas and 35-48 sccm oxygen, and performing sputtering deposition under a vacuum condition to obtain a second transparent protective layer, wherein the thickness of the second transparent protective layer is 50-120 nm.

The method for manufacturing an electrochromic device according to an embodiment includes any one of the above methods for manufacturing an electrochromic film system.

The preparation method of the electrochromic device is simple, can realize free combination and matching of functional materials such as a plurality of different first conductive thin film layers, ion storage layers, ion conduction conveying layers, ion discoloring layers and second conductive thin film layers, and perfects the interface stability among the functional layers, so that the long-time stability of the electrochromic device can be ensured under lower working voltage, and the application is facilitated.

Drawings

FIG. 1 is a schematic view of an electrochromic film system according to an embodiment of the present invention;

fig. 2 is a flowchart of a method for preparing an electrochromic film system according to an embodiment of the present invention.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Referring to fig. 1, an electrochromic film system 100 according to an embodiment of the present invention includes a first transparent protection layer 110, a first conductive thin film layer 120, an ion storage layer 130, an ion conduction transport layer 140, an ion discoloration layer 150, a second conductive thin film layer 170, and a second transparent protection layer 180, which are sequentially stacked, wherein the first conductive thin film layer 120 is made of a metal oxide, the ion storage layer 130 is made of a lithium alloy or a lithium metal oxide, the ion conduction transport layer 140 is made of a lithium-containing polyanion, the ion discoloration layer 150 is made of a metal oxide, and the second conductive thin film layer 170 is made of a metal oxide.

The first transparent protection layer 110 and the second transparent protection layer 180 are located on two sides of other functional layers, and protect the other functional layers. The first transparent protection layer 110 and the second transparent protection layer 180 may be transparent films such as glass, respectively.

The first conductive thin film layer 120 and the second conductive thin film layer 170 are conductive. The first conductive thin film layer 120 and the second conductive thin film layer 170 are made of metal oxide, and can be well matched with materials of other functional layers, so that the interface stability between the functional layers is ensured, and the performance of a subsequent electrochromic device is ensured.

Wherein the ion storage layer 130 is used to store, for example, li ⁺ And the like. The material of the ion storage layer 130 of the invention is lithium alloy or lithium metal oxide, which overcomes various disadvantages of using metal lithium as the storage material of ions in the traditional electrochromic scheme, the lithium alloy or lithium metal oxide does not need to be stored in special environment, no special requirements are required for magnetron sputtering deposition equipment and process, the operation can be kept consistent and continuous in the electrochromic device, and the interface matching between the ion storage layer 130 and the adjacent functional layer is good because the material of the adjacent first conductive thin film layer 120 is metal oxide and the material of the ion conduction transport layer 140 is polyanion compound containing lithium.

The ion-conducting transport layer 140 can isolate the ion storage layer from the ion-discoloring layer, thereby ensuring consistent and stable switching effect of the electrochromic function.

The electrochromic film is an all-solid-state film, can realize free combination and matching of functional materials such as a plurality of different first conductive thin film layers, ion storage layers, ion conduction conveying layers, ion electrochromic layers and second conductive thin film layers, and improves the interface stability among the functional layers, so that the long-time stability of an electrochromic device can be ensured under lower working voltage, and the application is facilitated.

In addition to the foregoing embodiments, the electrochromic film system 100 further includes an ion color storage layer 160 located between the ion color storage layer 150 and the second conductive thin film layer 170, and the material of the ion color storage layer 160 is lithium metal oxide.

In addition to the foregoing embodiments, the material of the ion color storage layer 160 is selected from at least one of tungsten lithium oxide (LWO), nickel lithium oxide (LNO), tungsten molybdenum lithium oxide (LWMO), and vanadium lithium oxide (LVO), and the thickness of the ion color storage layer 160 is 250nm to 360nm. The ion color storage layer of the above kind can realize the free combination of the functions of the electrochromic device.

It should be noted that the ion color storage layer 160 may be a single layer or a mixture of multiple thin films, and when the ion color storage layer is a mixture of multiple thin films, the materials between two adjacent layers may be the same or different.

In addition to the foregoing embodiments, the material of the first conductive thin film layer 120 is selected from Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), and tin oxide (SnO) ₂ ) The thickness of the first conductive thin film layer 120 is 200nm to 280nm.

In addition to the above embodiments, the material of the ion storage layer 130 is selected from at least one of Lithium Titanate (LTO), lithium Cobaltate (LCO), lithium Cobalt Nickel Oxide (LCNO), lithium Nickel Oxide (LNO), lithium iron phosphate (LFPO), lithium Cobalt Manganese Oxide (LCMO), lithium Nickel Manganese Oxide (LNMO), tin-lithium alloy (LSn), and silicon-lithium alloy (LSi), and the thickness of the ion storage layer 130 is 200nm to 250nm. The ion storage layer of the above kind has good interface matching performance and stability, and can ensure that reversible ion insertion and ion extraction are always stable and uniform under the action of an external electric field.

It should be noted that the ion storage layer 130 may be a single layer or a mixture of multiple thin films, and when the mixture of multiple thin films is formed, the materials between two adjacent layers may be the same or different.

In addition to the foregoing embodiments, the material of the ion transport layer 140 is selected from at least one of titanium lanthanum lithium oxide (LLTO), titanium lanthanum aluminum lithium oxide (LLATO), zirconium lanthanum lithium oxide (LLZO), zirconium lanthanum aluminum lithium oxide (LLAZO), nitrogen phosphorus lithium oxide (LPON), phosphorus lithium sulfide oxide (LPSO), nitrogen phosphorus lithium sulfide (LPNS), and niobium lithium oxide (LNO), and the thickness of the ion transport layer 140 is 850nm to 1280nm. The ion conduction and transmission layer with the type and the thickness realizes the complete isolation of the ion storage layer and the ion discoloring layer, and ensures the consistent and stable switching effect of the electrochromic function.

It should be noted that the ion conducting transport layer 140 may be a single layer or a mixture of multiple thin films, and when the ion conducting transport layer is a mixture of multiple thin films, the materials between two adjacent layers may be the same or different.

In addition to the above embodiments, the material of the electrochromic layer 150 is selected from at least one of tungsten oxide (WO), nickel Oxide (NO), tungsten molybdenum oxide (WMO), and Vanadium Oxide (VO), and the thickness of the electrochromic layer 150 is 250nm to 360nm.

It should be noted that the ionochromic layer 150 may be a single layer or a mixture of multiple layers of films, and when the mixture of multiple layers of films is formed, the materials between two adjacent layers may be the same or different.

In addition to the foregoing embodiments, the material of the second conductive thin film layer 170 is selected from Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), and tin oxide (SnO) ₂ ) The thickness of the second conductive thin film layer 170 is 200nm to 280nm.

In addition to the foregoing embodiments, the materials of the first transparent protection layer 110 and the second transparent protection layer 180 are independently selected from Alumina (AO), zirconia (ZO), aluminum Chromium (ACO), and silicon oxide (SiO) ₂ ) The thicknesses of the first transparent protection layer 110 and the second transparent protection layer 180 are both 50nm to 120nm.

By applying the electrochromic film system of the technical scheme of the invention, the free combination and matching of functional materials such as a plurality of different first conductive thin film layers, ion storage layers, ion conduction transport layers, ion discoloring layers, second conductive thin film layers and the like can be realized, and the interface stability among the functional layers is improved, so that the long-time stability of an electrochromic device can be ensured under lower working voltage, and the application is facilitated.

Referring to fig. 2, a method for preparing an electrochromic film system according to an embodiment of the present invention includes the following steps:

s10, forming a first conductive thin film layer on the first transparent protective layer by adopting a vapor deposition technology, wherein the first conductive thin film layer is made of metal oxide.

Further, referring to fig. 1, the operation of forming the first conductive thin film layer 120 on the first transparent passivation layer 110 by using the vapor deposition technique is as follows: and (3) pumping the vacuum degree to a set value, then heating to 170-230 ℃, introducing 220-300 sccm inert gas and 35-48 sccm oxygen, and performing sputtering deposition under a vacuum condition to obtain the first conductive thin film layer 120, wherein the thickness of the first conductive thin film layer 120 is 200-280 nm, and the square resistance value of the first conductive thin film layer 120 is 10 omega/□ -12 omega/□. Wherein, the vacuum condition is the conventional condition for sputtering deposition in the field, namely the vacuum degree is about 0.1 Pa.

Further, the material of the first transparent protection layer 110 is selected from Alumina (AO), zirconia (ZO), aluminum Chromium (ACO) and silicon oxide (SiO) ₂ ) The thickness of the first transparent protective layer 110 is 50nm to 120nm.

Further, the material of the first conductive thin film layer 120 is selected from Indium Tin Oxide (ITO), zinc aluminum oxide (AZO), and tin oxide (SnO) ₂ ) At least one of (1).

And S20, forming an ion storage layer on the first conductive thin film layer by adopting a vapor deposition technology, wherein the material of the ion storage layer is lithium alloy or lithium metal oxide.

Further, referring to fig. 1, the operation of forming the ion storage layer 130 on the first conductive thin film layer 120 by using the vapor deposition technique is as follows: and pumping the vacuum degree to a set value, heating to 370-430 ℃, introducing 240-370 sccm of inert gas and 30-38 sccm of oxygen, and performing sputtering deposition under a vacuum condition to obtain the ion storage layer 130, wherein the thickness of the ion storage layer 130 is 200-250 nm. Wherein, the vacuum condition is the conventional condition for sputtering deposition in the field, namely the vacuum degree is about 0.1 Pa.

Further, the material of the ion storage layer 130 is selected from at least one of Lithium Titanate (LTO), lithium Cobaltate (LCO), lithium Cobalt Nickel Oxide (LCNO), lithium Nickel Oxide (LNO), lithium iron phosphate (LFPO), lithium Cobalt Manganese Oxide (LCMO), lithium nickel oxide (LNMO), tin-lithium alloy (LSn), and silicon-lithium alloy (LSi). The ion storage layer of the above kind has good interface matching performance and stability, and can ensure that reversible ion insertion and ion extraction are always stable and uniform under the action of an external electric field.

And S30, forming an ion conduction and transport layer on the ion storage layer by adopting a vapor deposition technology, wherein the material of the ion conduction and transport layer is a polyanion compound containing lithium.

Further, referring to fig. 1, the operation of forming the ion conducting transport layer 140 on the ion storage layer 130 by using the vapor deposition technique is as follows: and (3) pumping the vacuum degree to a set value, heating to 370-430 ℃, introducing inert gas of 260-380 sccm and oxygen of 30-38 sccm, and performing sputtering deposition under a vacuum condition to obtain the ion conduction transport layer 140, wherein the thickness of the ion conduction transport layer 140 is 850-1280 nm. Wherein, the vacuum condition is the conventional condition for sputtering deposition in the field, namely the vacuum degree is about 0.1 Pa.

Further, the material of the ion conducting transport layer 140 is selected from at least one of titanium lanthanum lithium oxide (LLTO), titanium lanthanum aluminum lithium oxide (LLATO), zirconium lanthanum lithium oxide (LLZO), zirconium lanthanum aluminum lithium oxide (LLAZO), nitrogen phosphorus lithium oxide (LPON), phosphorus sulfur lithium oxide (LPSO), nitrogen phosphorus lithium sulfide (LPNS), and niobium lithium oxide (LNO). The ion conduction and transmission layer with the type and the thickness realizes the complete isolation of the ion storage layer and the ion discoloring layer, and ensures the consistent and stable switching effect of the electrochromic function.

S40, forming an ion discoloring layer on the ion conduction conveying layer by adopting a vapor deposition technology, wherein the ion discoloring layer is made of metal oxide.

Further, referring to fig. 1, the operation of forming the ion-discoloring layer 150 on the ion-conducting transport layer 140 by using the vapor deposition technique is as follows: and (3) pumping the vacuum degree to a set value, then heating to 370-430 ℃, introducing 240-370 sccm of inert gas and 30-38 sccm of oxygen, and performing sputtering deposition under a vacuum condition to obtain the ion discoloring layer 150, wherein the thickness of the ion discoloring layer 150 is 250-360 nm. Wherein, the vacuum condition is the conventional condition for sputtering deposition in the field, namely the vacuum degree is about 0.1 Pa.

Further, the material of the electrochromic layer 150 is selected from at least one of tungsten oxide (WO), nickel Oxide (NO), tungsten molybdenum oxide (WMO), and Vanadium Oxide (VO).

And S50, forming a second conductive thin film layer on the ion discoloring layer by adopting a vapor deposition technology, wherein the second conductive thin film layer is made of metal oxide.

Further, referring to fig. 1, before forming the second conductive thin film layer 170 on the ion-discoloring layer 150, the method further includes the following steps:

an ion color storage layer 160 is formed on the ion color changing layer 150 by a vapor deposition technique, and the material of the ion color storage layer 160 is lithium metal oxide.

Further, the operation of forming the ion-storing layer 160 on the ion-discoloring layer 150 using the vapor deposition technique is: and (3) pumping the vacuum degree to a set value, then heating to 370-430 ℃, introducing inert gas of 260-380 sccm and oxygen of 30-38 sccm, and performing sputtering deposition under a vacuum condition to obtain the ion color storage layer 160, wherein the thickness of the ion color storage layer 160 is 250-360 nm. Wherein, the vacuum condition is the conventional condition for sputtering deposition in the field, namely the vacuum degree is about 0.1 Pa.

Furthermore, the material of the ion color storage layer 160 is selected from at least one of tungsten lithium oxide (LWO), nickel lithium oxide (LNO), tungsten molybdenum lithium oxide (LWMO), and vanadium lithium oxide (LVO), and the thickness of the ion color storage layer 160 is 250nm to 360nm. The ion color storage layer of the above kind can realize the free combination of the functions of the electrochromic device.

Further, the operation of forming the second conductive thin film layer 170 on the ion-changing layer 150 or the ion-storing layer 160 using the vapor deposition technique is: and (3) pumping the vacuum degree to a set value, then heating to 170-230 ℃, introducing 220-300 sccm inert gas and 35-48 sccm oxygen, and performing sputtering deposition under a vacuum condition to obtain a second conductive thin film layer 170, wherein the thickness of the second conductive thin film layer 170 is 200-280 nm, and the square resistance value of the second conductive thin film layer 170 is 10 omega/□ -12 omega/□. Wherein, the vacuum condition is the conventional condition for sputtering deposition in the field, namely the vacuum degree is about 0.1 Pa.

Further, the second conductive thin film layer 170 is made of a material selected from Indium Tin Oxide (ITO),Zinc aluminum oxide (AZO) and tin oxide (SnO) ₂ ) At least one of (1).

And S60, forming a second transparent protective layer on the second conductive thin film layer by adopting a vapor deposition technology to obtain the electrochromic film system.

Further, referring to fig. 1, the operation of forming the second transparent protection layer 180 on the second conductive thin film layer 170 by using the vapor deposition technique is as follows: and (3) pumping the vacuum degree to a set value, then heating to 170-230 ℃, introducing 220-300 sccm inert gas and 35-48 sccm oxygen, and performing sputtering deposition under a vacuum condition to obtain a second transparent protective layer 180, wherein the thickness of the second transparent protective layer 180 is 50-120 nm. Wherein, the vacuum condition is the conventional condition for sputtering deposition in the field, namely the vacuum degree is about 0.1 Pa.

Further, the material of the second transparent protection layer 180 is selected from Alumina (AO), zirconia (ZO), aluminum Chromium (ACO) and silicon oxide (SiO) ₂ ) At least one of (1).

An electrochromic device of an embodiment includes any of the electrochromic film systems described above. Among them, the electrochromic device is any device using the above electrochromic film system, and may be, for example, a display device or electrochromic glass.

By applying the electrochromic device of the technical scheme of the invention, the free combination and matching of functional materials such as a plurality of different first conductive thin film layers, ion storage layers, ion conduction conveying layers, ion discoloring layers, second conductive thin film layers and the like can be realized, and the interface stability among the functional layers is perfected, so that the long-time stability of the electrochromic device can be ensured under lower working voltage, and the application is facilitated.

A preparation method of an electrochromic device, which comprises the preparation method of any one of the electrochromic film systems.

The preparation method of the electrochromic device is simple, can realize free combination and matching of functional materials such as a plurality of different first conductive thin film layers, ion storage layers, ion conduction conveying layers, ion discoloring layers and second conductive thin film layers, and improves the interface stability among the functional layers, so that the long-time stability of the electrochromic device can be ensured under lower working voltage, and the application is facilitated.

In order to make the technical solution of the present application more specific, clear and easy to understand, the technical solution of the present application is illustrated by reference to the above implementation contents, but it should be noted that the contents to be protected by the present application are not limited to the following embodiments.

Example 1

Vacuum background to 5.7 x 10 ^-5 Pa, heating the substrate to 170 ℃, introducing 220sccm Ar and 35sccm O ₂ And keeping the vacuum degree at about 0.1Pa, carrying out sputtering deposition on a first conductive thin film layer and scribing, wherein the first conductive thin film layer is made of Indium Tin Oxide (ITO) and has the thickness of 220nm.

Heating the substrate deposited with the first conductive film layer to 370 ℃, and introducing Ar of 240sccm and O of 35sccm ₂ And sputtering and depositing an ion storage layer by keeping the vacuum degree at about 0.1Pa, wherein the material of the ion storage layer is Lithium Titanate (LTO), and the thickness of the ion storage layer is 250nm.

The substrate with the deposited ion storage layer was heated to 370 ℃ and Ar of 240sccm and O of 35sccm were introduced ₂ And sputtering and depositing an ion conduction and transport layer with the vacuum degree kept at about 0.1Pa, wherein the ion conduction and transport layer is made of nitrogen phosphorus lithium oxide (LPON), and the thickness of the ion conduction and transport layer is 950nm.

The substrate with the ion-conducting transport layer deposited thereon was heated to 370 ℃ and Ar of 240sccm and O of 35sccm were introduced ₂ And sputtering and depositing an ion discoloring layer with the vacuum degree of about 0.1Pa, wherein the ion discoloring layer is made of tungsten oxide (WO) and has the thickness of 350nm.

Heating the substrate deposited with the ion discoloring layer to 170 ℃, and introducing 220sccm Ar and 35sccm O ₂ And sputtering and depositing a second conductive thin film layer and scribing while keeping the vacuum degree at about 0.1Pa, wherein the second conductive thin film layer is made of Indium Tin Oxide (ITO) and has a thickness of 220nm.

Heating the substrate deposited with the second conductive film layer to 170 ℃, and introducing Ar of 220sccm and O of 35sccm ₂ And sputtering and depositing a second transparent protective layer with the vacuum degree of about 0.1Pa, wherein the second transparent protective layer is made of Aluminum Oxide (AO) and has the thickness of 50nm.

Example 2

Vacuum background to 5.7 x 10 ^-5 Pa, heating the substrate to 190 deg.C, introducing Ar of 220sccm and O of 35sccm ₂ And sputtering and depositing a first conductive thin film layer and scribing by keeping the vacuum degree at about 0.1Pa, wherein the first conductive thin film layer is made of zinc aluminum oxide (AZO), and the thickness of the first conductive thin film layer is 200nm.

Heating the substrate deposited with the first conductive film layer to 390 ℃, and introducing Ar of 260sccm and O of 35sccm ₂ And keeping the vacuum degree at about 0.1Pa, and performing sputtering deposition on an ion storage layer, wherein the material of the ion storage layer is Lithium Cobalt Manganese Oxide (LCMO), and the thickness of the ion storage layer is 250nm.

Heating the substrate deposited with the ion storage layer to 390 ℃, and introducing Ar of 260sccm and O of 35sccm ₂ And carrying out sputtering deposition on the ion conduction transport layer with the vacuum degree kept at about 0.1Pa, wherein the material of the ion conduction transport layer is nitrogen phosphorus lithium oxide (LPON), and the thickness of the ion conduction transport layer is 900nm.

Heating the substrate deposited with the ion-conducting transport layer to 390 ℃, and introducing 260sccm of Ar and 35sccm of O ₂ And sputtering and depositing an ion discoloring layer with the vacuum degree of about 0.1Pa, wherein the ion discoloring layer is made of tungsten oxide (WO) and has the thickness of 330nm.

Heating the substrate deposited with the ion discoloring layer to 190 ℃, and introducing 220sccm Ar and 35sccm O ₂ Sputtering and depositing under the vacuum degree of about 0.1PaAnd (3) depositing and scribing a second conductive thin film layer, wherein the second conductive thin film layer is made of zinc aluminum oxide (AZO), and the thickness of the second conductive thin film layer is 200nm.

Heating the substrate deposited with the second conductive film layer to 190 ℃, and introducing Ar of 220sccm and O of 35sccm ₂ And keeping the vacuum degree to be about 0.1Pa, and carrying out sputtering deposition on a second transparent protective layer, wherein the second transparent protective layer is made of Aluminum Oxide (AO) and has the thickness of 80nm.

Example 3

Vacuum background to 5.7 x 10 ^-5 Pa, heating the substrate to 200 ℃, introducing 230sccm of Ar and 35sccm of O ₂ Sputtering and depositing a first conductive thin film layer and scribing while keeping the vacuum degree at about 0.1Pa, wherein the first conductive thin film layer is made of tin oxide (SnO) ₂ ) And the thickness of the first conductive thin film layer is 50nm.

Heating the substrate deposited with the first conductive film layer to 400 ℃, and introducing 280sccm of Ar and 35sccm of O ₂ And sputtering and depositing an ion storage layer by keeping the vacuum degree at about 0.1Pa, wherein the material of the ion storage layer is Lithium Cobalt Nickel Oxide (LCNO), and the thickness of the ion storage layer is 230nm.

Heating the substrate deposited with the ion storage layer to 400 ℃, and introducing 280sccm of Ar and 35sccm of O ₂ And sputtering and depositing an ion conduction and transport layer with the vacuum degree kept at about 0.1Pa, wherein the ion conduction and transport layer is made of nitrogen phosphorus lithium sulfide (LPNS) and has the thickness of 1050nm.

Heating the substrate deposited with the ion-conducting transport layer to 400 ℃, and introducing 280sccm of Ar and 35sccm of O ₂ And keeping the vacuum degree to be about 0.1Pa, and carrying out sputtering deposition on an ion discoloring layer, wherein the material of the ion discoloring layer is tungsten oxide (WO), and the thickness of the ion discoloring layer is 360nm.

Heating the substrate deposited with the ion discoloring layer to 200 ℃, and introducing 230sccm of Ar and 35sccm of O ₂ Sputtering and depositing a second conductive film layer and scribing while keeping the vacuum degree at about 0.1Pa, wherein the second conductive film layer is made of tin oxide (SnO) ₂ ) And the thickness of the second conductive thin film layer is 220nm.

Heating the substrate deposited with the second conductive film layer to 200 ℃, and introducing 230sccm of Ar and 35sccm of O ₂ And keeping the vacuum degree to be about 0.1Pa, and performing sputtering deposition on a second transparent protective layer which is made of Aluminum Oxide (AO) and has the thickness of 100nm.

Example 4

Vacuum background to 5.7 x 10 ^-5 Pa, heating the substrate to 190 ℃, introducing 220sccm Ar and 35sccm O ₂ And sputtering and depositing a first conductive thin film layer and scribing by keeping the vacuum degree at about 0.1Pa, wherein the first conductive thin film layer is made of zinc aluminum oxide (AZO), and the thickness of the first conductive thin film layer is 200nm.

Heating the substrate deposited with the first conductive film layer to 390 ℃, and introducing Ar of 260sccm and O of 35sccm ₂ And sputtering and depositing an ion storage layer by keeping the vacuum degree at about 0.1Pa, wherein the material of the ion storage layer is tin-lithium alloy (LSn), and the thickness of the ion storage layer is 240nm.

Heating the substrate deposited with the ion storage layer to 390 ℃, and introducing Ar of 260sccm and O of 35sccm ₂ And sputtering and depositing an ion conduction and transmission layer with the vacuum degree of about 0.1Pa, wherein the material of the ion conduction and transmission layer is zirconium lanthanum aluminum lithium oxide (LLAZO), and the thickness of the ion conduction and transmission layer is 1000nm.

Heating the substrate deposited with the ion-conducting transport layer to 390 ℃, and introducing 260sccm of Ar and 35sccm of O ₂ And keeping the vacuum degree to be about 0.1Pa, and performing sputtering deposition on an ion discoloring layer which is made of tungsten molybdenum oxide (WMO) and is 330nm thick.

Heating the substrate deposited with the ion discoloring layer to 190 ℃, and introducing 220sccm Ar and 35sccm O ₂ And sputtering and depositing a second conductive thin film layer and scribing the second conductive thin film layer while keeping the vacuum degree at about 0.1Pa, wherein the second conductive thin film layer is made of zinc aluminum oxide (AZO), and the thickness of the second conductive thin film layer is 200nm.

Heating the substrate deposited with the second conductive film layer to 190 ℃, and introducing Ar of 220sccm and O of 35sccm ₂ Keeping the vacuum degree at about 0.1Pa, and performing sputtering deposition to obtain a second transparent filmThe protective layer, the material of second transparent protective layer is Aluminium Oxide (AO), and the thickness of second transparent protective layer is 80nm.

Example 5

Heating the substrate deposited with the ion storage layer to 390 ℃, and introducing Ar of 260sccm and O of 35sccm ₂ And sputtering and depositing an ion conduction and transport layer with the vacuum degree kept at about 0.1Pa, wherein the material of the ion conduction and transport layer is nitrogen phosphorus lithium oxide (LPON), and the thickness of the ion conduction and transport layer is 900nm.

Heating the substrate deposited with the ion discoloring layer to 400 ℃, and introducing Ar of 300sccm and O of 35sccm ₂ And sputtering and depositing an ion storage layer and scribing lines while keeping the vacuum degree at about 0.1Pa, wherein the material of the ion storage layer is tungsten lithium oxide (LWO), and the thickness of the ion storage layer is 300nm.

Heating the substrate deposited with the ion color storage layer to 190 ℃, and introducing 220sccm Ar and 35sccm O ₂ And sputtering and depositing a second conductive thin film layer and scribing the second conductive thin film layer while keeping the vacuum degree at about 0.1Pa, wherein the second conductive thin film layer is made of zinc aluminum oxide (AZO), and the thickness of the second conductive thin film layer is 200nm.

Heating the substrate deposited with the second conductive film layer to 1Ar of 220sccm and O of 35sccm are introduced at 90 DEG C ₂ And sputtering and depositing a second transparent protective layer with the vacuum degree of about 0.1Pa, wherein the second transparent protective layer is made of Aluminum Oxide (AO) and has the thickness of 80nm.

And (4) performance testing:

the electrochromic film systems of examples 1 to 5 were tested for electrochromic response time (time to change from transparent to colored) and color change as shown in table 1 after applying the voltages shown in table 1, and then the voltages were removed and the time to maintain steady state was recorded, the specific data are shown in table 1.

TABLE 1 Performance test data for examples 1-5

As can be seen from the performance test data in table 1, the electrochromic response times of the electrochromic films of examples 1 to 5 are all shorter at lower voltages, and the color changes are uniform and consistent; after the voltage is removed, the voltage can be maintained for more than 370 min. The electrochromic film system of the technical scheme of the invention can realize quick electrochromic response under lower working voltage, and ensures the long-time stability of the electrochromic device.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The preparation method of the electrochromic film system is characterized by comprising the following steps of:

forming a first conductive thin film layer on the first transparent protective layer by adopting a vapor deposition technology, wherein the first conductive thin film layer is made of metal oxide; the operation of forming the first conductive thin film layer on the first transparent protective layer by adopting the vapor deposition technology comprises the following steps: pumping the vacuum degree to a set value, then heating to 170-230 ℃, introducing 220-300 sccm inert gas and 35-48 sccm oxygen, and performing sputtering deposition under a vacuum condition to obtain a first conductive thin film layer, wherein the thickness of the first conductive thin film layer is 200-280 nm, and the square resistance value of the first conductive thin film layer is 10 omega/□ -12 omega/□;

forming an ion storage layer on the first conductive thin film layer by adopting a vapor deposition technology, wherein the material of the ion storage layer is lithium alloy or lithium metal oxide; the operation of forming the ion storage layer on the first conductive thin film layer by using the vapor deposition technology is as follows: pumping the vacuum degree to a set value, then heating to 370-430 ℃, introducing 240-370 sccm of inert gas and 30-38 sccm of oxygen, and carrying out sputtering deposition under a vacuum condition to obtain an ion storage layer, wherein the thickness of the ion storage layer is 200-250 nm;

forming an ion conduction and transportation layer on the ion storage layer by adopting a vapor deposition technology, wherein the material of the ion conduction and transportation layer is a polyanion compound containing lithium; the operation of forming the ion-conducting transport layer on the ion storage layer by using the vapor deposition technology is as follows: pumping the vacuum degree to a set value, heating to 370-430 ℃, introducing inert gas of 260-380 sccm and oxygen of 30-38 sccm, and performing sputtering deposition under a vacuum condition to obtain an ion conduction transport layer, wherein the thickness of the ion conduction transport layer is 850-1280 nm;

forming an ion discoloring layer on the ion conduction conveying layer by adopting a vapor deposition technology, wherein the ion discoloring layer is made of metal oxide; the operation of forming the ion-discoloring layer on the ion-conducting transport layer by adopting the vapor deposition technology comprises the following steps: pumping the vacuum degree to a set value, heating to 370-430 ℃, introducing 240-370 sccm of inert gas and 30-38 sccm of oxygen, and performing sputtering deposition under a vacuum condition to obtain an ion discoloring layer, wherein the thickness of the ion discoloring layer is 250-360 nm;

forming an ion storage layer on the ion discoloring layer by adopting a vapor deposition technology, wherein the ion storage layer is made of lithium metal oxide; the operation of forming the ion color storage layer on the ion color changing layer by adopting the vapor deposition technology comprises the following steps: pumping the vacuum degree to a set value, then heating to 370-430 ℃, introducing inert gas of 260-380 sccm and oxygen of 30-38 sccm, and carrying out sputtering deposition under a vacuum condition to obtain an ion color storage layer, wherein the thickness of the ion color storage layer is 250-360 nm;

forming a second conductive thin film layer on the ion color storage layer by adopting a vapor deposition technology, wherein the second conductive thin film layer is made of metal oxide; the operation of forming the second conductive thin film layer on the ion color storage layer by adopting the vapor deposition technology comprises the following steps: pumping the vacuum degree to a set value, then heating to 170-230 ℃, introducing 220-300 sccm inert gas and 35-48 sccm oxygen, and performing sputtering deposition under a vacuum condition to obtain a second conductive thin film layer, wherein the thickness of the second conductive thin film layer is 200-280 nm, and the square resistance value of the second conductive thin film layer is 10 omega/□ -12 omega/□; and

forming a second transparent protective layer on the second conductive thin film layer by adopting a vapor deposition technology to obtain an electrochromic film system; the operation of forming the second transparent protective layer on the second conductive thin film layer by adopting the vapor deposition technology comprises the following steps: and (3) pumping the vacuum degree to a set value, then heating to 170-230 ℃, introducing 220-300 sccm of inert gas and 35-48 sccm of oxygen, and performing sputtering deposition under a vacuum condition to obtain a second transparent protective layer, wherein the thickness of the second transparent protective layer is 50-120 nm.

2. The method of claim 1, wherein the first transparent protective layer is made of at least one material selected from the group consisting of alumina, zirconia, and silica, and has a thickness of 50nm to 120nm.

3. The method of claim 1, wherein the first conductive thin film layer is made of at least one material selected from the group consisting of indium tin oxide, zinc aluminum oxide, and tin oxide.

4. The method according to claim 1, wherein the material of the ion storage layer is at least one selected from lithium titanate, lithium cobaltate, lithium cobalt nickelate, lithium iron phosphate, lithium cobalt manganite, lithium nickel manganate, tin-lithium alloy and silicon-lithium alloy.

5. The method according to claim 1, wherein the material of the ion-conducting transport layer is at least one selected from the group consisting of lanthanum lithium titanium oxide, lanthanum aluminum lithium titanium oxide, lanthanum lithium zirconium oxide, lanthanum aluminum zirconium oxide, lithium nitrogen phosphorus oxide, lithium phosphorus sulfide oxide, lithium nitrogen phosphorus sulfide, and lithium niobium oxide.

6. The method according to claim 1, wherein the material of the electrochromic layer is at least one selected from the group consisting of tungsten oxide, nickel oxide, tungsten molybdenum oxide, and vanadium oxide.

7. The method of claim 1, wherein the material of the ion-storing layer is at least one selected from the group consisting of lithium tungsten oxide, lithium nickel oxide, lithium molybdenum tungsten oxide, and lithium vanadium oxide.

8. The method of claim 1, wherein the second conductive thin film layer is made of at least one material selected from the group consisting of indium tin oxide, zinc aluminum oxide, and tin oxide.

9. The method of claim 1, wherein the second transparent protective layer is made of at least one material selected from the group consisting of alumina, zirconia, and silica.

10. A method for producing an electrochromic device, comprising the method for producing an electrochromic film system according to any one of claims 1 to 9.