WO2018188154A1 - Structure of full-solid-state thin-film electrochromic device and preparation method therefor - Google Patents

Abstract

A structure of a full-solid-state thin-film electrochromic device and a preparation method therefor, belonging to the field of electrochromic processing. The electrochromic device comprises in sequence from top to bottom a metal reflection layer or a transparent conductive layer, an electrochromic layer, a medium layer, a lithium alloy layer, an ion storage layer and a transparent conductive layer. The solid state electrochromic device comprises multiple layers of composite film layers, and has the advantages of a concise process, fast coating speed, good component control and good weather resistance. With the present invention, a breakthrough is made in device film layer design, the property wherein the effective unit volume lithium content of metal lithium or lithium alloy is much higher than that of lithium compounds is utilized, and the characteristic of the sputtering speed of metal lithium alloy being much higher than that of lithium oxide is also used. The aims of improving the production efficiency of the device, reducing equipment cost and prolonging cycle life are achieved, the electrochromic response speed of the device is high, and the market competitiveness is good.

Description

 Structure and preparation method of solid full-film electrochromic device

Technical field

 The invention belongs to the field of electrochromic processing, and in particular relates to a structure and a preparation method of a solid full-film electrochromic device.

Background technique

Electrochromism refers to the phenomenon that the optical properties (reflectance, transmittance, absorptivity, etc.) of a material undergo a stable and reversible color change under the action of an applied electric field, and the appearance is a reversible change in color and transparency. The electrochromic smart glass has the adjustability of light absorption and transmission under the action of an electric field, and can selectively absorb or reflect the external heat radiation and the internal heat diffusion, thereby improving the natural light level and preventing peek. Therefore, electrochromic devices have a wide use value in the field of construction, anti-glare for vehicles, and sun-discoloring glasses.

The working area of the electrochromic device generally consists of a layer of color changing material, an ion conductor layer, and an ion storage layer. In existing electrochromic devices, the color-changing material layer, the ion conductor layer, and the ion storage layer are often required to be formed by various processes, and then need to be processed through a complicated packaging process. All solid state devices employing inorganic ion storage layers can withstand longer solar radiation than all solid state devices of organic ion storage layers. The lithium source in the inorganic all solid state device is derived from a lithium oxide ion conducting layer or a lithium oxide ion storage layer. The prior art adopts a direct sputtering lithium oxide ion conductive layer or a lithium oxide ion storage layer, and has a low effective lithium content per unit volume in lithium oxide, difficulty in controlling the consistency of lithium oxide film layer composition, and a low sputtering rate. The resulting equipment is costly and expensive.

Summary of the invention

Therefore, the technical problem to be solved by the present invention is to overcome the bottleneck of the consistency control of the composition of the electrochromic device and the slow deposition of the lithium source compound in the prior art, thereby proposing the structure and preparation of a solid full-film electrochromic device. method.

In order to solve the above technical problem, the present invention discloses an all-solid-state electrochromic device (as shown in FIG. 1 ), and the electrochromic device is sent up to the next by a metal reflective layer or a transparent conductive layer, an electrochromic layer. The dielectric layer, the lithium alloy layer, the ion storage layer, and the transparent conductive layer are composed.

Preferably, the metal reflective layer is one of silver and aluminum.

Preferably, the transparent conductive layer is one of indium tin oxide, aluminum-doped zinc oxide, and fluorine-doped tin oxide.

Preferably, the electrochromic layer may be a transition metal oxide.

Preferably, the transition metal oxide is one of tungsten oxide, vanadium pentoxide, ruthenium oxide, titanium oxide, ruthenium oxide, cobalt oxide, and molybdenum oxide.

Preferably, the dielectric layer is one of silicon oxide and silicon oxynitride.

Preferably, the lithium alloy layer is one of a lithium aluminum alloy and a lithium magnesium aluminum alloy.

Preferably, the dielectric layer has a thickness of 10 to 500 nm; the lithium alloy layer has a thickness of 5 to 100 nm; the ion storage layer has a thickness of 300 to 1000 nm; and the electrochromic layer has a thickness of 300 to 1000 nm; The metal reflective layer has a thickness of 20 to 500 nm.

The invention also discloses a method for preparing any of the electrochromic devices, the method steps are as follows:

a. taking a glass or a flexible high polymer as a substrate, and washing it in a furnace;

b. depositing a metal reflective layer or a transparent conductive layer on the surface of the substrate using magnetron sputtering;

c. taking a mask plate over the metal reflective layer to leave a wiring area; subsequently depositing an electrochromic layer by a physical vapor deposition apparatus;

d. subsequently depositing a dielectric layer on the electrochromic layer by magnetron sputtering or thermal evaporation or electron beam evaporation or chemical vapor deposition equipment;

e. physically vapor depositing a layer of metallic lithium or lithium alloy on the dielectric layer.

f. depositing an ion storage layer by magnetron sputtering on the lithium alloy layer;

g. On the ion storage layer, a mask is coated to leave a wiring area, and a second transparent conductive film is plated.

Compared with the prior art, the above technical solution of the present invention has the following advantages: the all-solid electrochromic device provided by the invention is composed of a multi-layer composite film layer, has a simple process, a fast coating rate, good component control, and good weather resistance of the device. The advantage of high cycle stability. The target in the process can use a DC power source, which is 8-11 times higher than the conventional process using a RF power source, which greatly increases the productivity and greatly improves the color change rate of the overall device. The invention breaks through the limitation that the coating rate of the lithium source layer of the existing all-solid-state electrochromic device structure is too slow, and innovatively solves the problem that the magnetic vapor deposition device has low efficiency in sputtering the lithium-lithide ceramic target by the physical vapor deposition device. It is easier to achieve large-scale production. In terms of application prospects, according to the choice of the underlying materials, it can be used in two major industries. For example, the bottom layer uses a metal reflective layer for electrochromic automotive rearview mirrors, and the bottom layer uses a transparent conductive layer for building curtain wall energy-saving glass.

DRAWINGS

In order to make the content of the present invention easier to understand, the present invention will be further described in detail below with reference to the accompanying drawings

1 is a schematic longitudinal sectional view of an electrochromic device for an automobile rear view mirror according to an embodiment;

2 is a front elevational view of an automotive rearview mirror electrochromic device according to an embodiment;

3 is a comparative diagram of the fade color reflectance for an automotive rearview mirror electrochromic device according to an embodiment;

4 is a graph showing the reflectance of a car rearview mirror electrochromic device according to an embodiment as a function of time;

5 is a schematic longitudinal sectional structural view of an electrochromic device for building curtain wall energy-saving glass according to an embodiment;

6 is a comparison diagram of the effect of fading and discoloration state of the electrochromic device for building curtain wall energy-saving glass according to the embodiment;

7 is a view showing an effect of transmittance of an electrochromic device for building curtain wall energy-saving glass according to an embodiment at a wavelength of 850 nm as a function of response time;

 The reference numerals are: 1-all solid state electrochromic device film.

detailed description

Example 1

Embodiment 1 This embodiment discloses an all-solid-state electrochromic device for an automobile rearview mirror (as shown in FIGS. 1 and 2), which is placed in a magnetron sputtering chamber after the mirror-size glass is chamfered. In the body, a device is sequentially formed on the surface of the glass to form a device, and the electrochromic device is sequentially sent to the bottom to include:

A silver reflective layer, a tungsten oxide layer, a silicon oxide layer, a lithium magnesium alloy layer, a titanium-doped lithium iron phosphate layer, and an indium tin oxide layer. Subsequently, the rearview mirror performance characterization test was carried out, as shown in Figures 3 and 4, which has a large amplitude adjustment range and a fast response capability.

The silver reflective layer has a thickness of 60 nm; the tungsten oxide layer has a thickness of 350 nm; the silicon oxide layer has a thickness of 30 nm; the lithium magnesium alloy layer has a thickness of 20 nm; the titanium-doped lithium iron phosphate layer has a thickness of 600 nm; and the indium tin oxide layer has a thickness of 200 nm. ;

Embodiment 2 This embodiment discloses an all-solid-state electrochromic device. The electrochromic device is sequentially provided with an aluminum reflective layer, a tungsten oxide layer, a silicon oxynitride layer, a lithium aluminum alloy layer, and a nickel oxide. , transparent conductive layer.

The thickness of the aluminum reflective layer is 100 nm; the thickness of the tungsten oxide layer is 400 nm; the thickness of the silicon oxynitride layer is 50 nm; the thickness of the lithium magnesium alloy layer is 25 nm; the thickness of the nickel oxide layer is 650 nm; and the thickness of the indium tin oxide layer is 200 nm;

 Example 3 This embodiment discloses an all-solid-state electrochromic device (the overall longitudinal sectional structure of which is shown in FIG. 5). The electrochromic device is sequentially provided to include an aluminum alloy reflective layer, a tungsten oxide layer, and a silicon nitrogen. An oxide layer, a lithium aluminum alloy layer, and a copper-doped lithium iron phosphate layer.

The thickness of the tungsten oxide is 500 nm; the lithium aluminum alloy layer is 30 nm; the silicon oxynitride layer is 100 nm; and the nickel oxide layer is 500 nm;

 Embodiment 4 This embodiment discloses a preparation process of an all-solid-state electrochromic device for building curtain wall energy-saving glass, and the steps are as follows:

The 1.8 mm glass was plasma-cleaned and placed in a magnetron sputtering coating apparatus.

DC magnetron sputtering transparent conductive layer ITO film: background vacuum degree is 1.8X10 ^-3 Pa, pure argon gas is introduced to the chamber gas pressure 0.3Pa, power is set to 6W/cm ² , glass is heated at 200 ° sputtering The ITO transparent conductive layer having a film thickness of 100 nm.

Subsequently, the mask plate is placed above the silver layer, and the electrochromic tungsten oxide layer is plated by a metal tungsten target by DC reactive sputtering: the background vacuum is 1.8×10 ⁻³ Pa, and the pure argon gas is introduced to the argon partial pressure of 1.3 Pa. A tungsten oxide electrochromic layer having a gas to oxygen partial pressure of 2.2 Pa, a power of 12 W/cm ² , and a sputtered film layer thickness of 600 nm was introduced.

Then, based on the process 3, an intermediate frequency power source magnetron sputtering film is used as the ion conduction layer: the target uses a silicon-aluminum target, the instrument is pumped to a background vacuum of 1.8×10 ^-3 Pa, and the chamber is filled with oxygen to a pressure of 1.3 Pa. The silicon-aluminum oxide ion-conducting layer having a radio frequency power of 2.2 W/cm ² and a sputtered film layer thickness of 50 nm.

On the basis of process 4, a lithium-cobalt co-doped nickel oxide film was used as the ion storage layer by DC power source magnetron sputtering: the target was 7% lithium, 5% titanium doped nickel oxide ceramic target, and the instrument was pumped to the background. A lithium-titanium co-doped nickel oxide film having a vacuum of 1.8×10 ⁻³ Pa, a pure argon gas to 1.3 Pa, a DC power of 5 W/cm ² , and a sputtered film layer thickness of 700 nm.

On the carbon-doped lithium iron phosphate film, a transparent conductive layer ITO film was sputtered by DC magnetron: the background vacuum was 1.8×10 ^-3 Pa, the pure argon gas was introduced to the chamber gas pressure of 0.3 Pa, and the power was set to 6 W/ Cm ² , an ITO transparent conductive layer having a sputtered film layer thickness of 100 nm.

Experimental example

Experimental example 1

The transmission curve of the device before and after discoloration was tested, as shown in Fig. 6. The transmittance of the device before and after discoloration is large, and the maximum can be adjusted from 85% to 5%, which is very suitable for electrochromic building curtain wall.

Experimental example 2

The performance of the device as a function of response time at 850 nm was tested. As shown in Figure 7, the device has fast response capability and can achieve high transmission to high absorption changes in seconds.

Experimental example 3 The electrochromic device is subjected to the fading rate and the change with the corresponding time. The experimental test results are shown in FIG. 3 and FIG. 4, and it can be seen that the electrochromic device obtained in the embodiment has a fast response speed and can be The state of high penetration to high light absorption is completed in a few seconds.

 Figure 3 is a comparison of the discoloration contrast: the transmittance of the overall device under discoloration and fading. The overall device has a large degree of discoloration and has a high light modulation effect.

 Figure 4 color response time chart: The overall device response speed is very fast, can complete the state of high penetration to high light absorption in a few seconds.

It is apparent that the above-described embodiments are merely illustrative of the examples, and are not intended to limit the embodiments. Other variations or modifications of the various forms may be made by those skilled in the art in light of the above description. There is no need and no way to exhaust all of the implementations. Obvious changes or variations resulting therefrom are still within the scope of the invention.

Claims (9)

An all-solid-state electrochromic device characterized in that the electrochromic device is composed of a metal reflective layer or a transparent conductive layer, an electrochromic layer, a dielectric layer, a lithium alloy layer, an ion storage layer, and a transparent layer from top to bottom. Conductive layer composition, Wherein, the dielectric layer is one of nano amorphous silicon, transparent nano non-metal oxide layer, and transparent nano metal oxide layer; The lithium alloy layer is LiMxNy, and both M and N are aluminum or magnesium or silicon, 0<x<0.8, 0<y<0.8. The all-solid-state electrochromic device according to claim 1, wherein the dielectric layer comprises nano-amorphous silicon, nano-silicon oxide, nano-silicon oxynitride, nano-aluminum oxide, nano-magnesium oxide, and nano-iron oxide. , nano zinc oxide, nano titanium oxide, nano cerium oxide or a nano hybrid compound of these materials, lithium nitrite phosphate. The all-solid-state electrochromic device according to claims 1 and 2, wherein the dielectric layer and the lithium alloy layer are further lithiated to form a corresponding loose lithium ion conductive layer after the device is prepared. The all solid state electrochromic device of claim 3 wherein said electrochromic layer is a transition metal oxide. The all-solid-state electrochromic device according to claim 4, wherein the transition metal oxide is one of tungsten oxide, vanadium pentoxide, ruthenium oxide, titanium oxide, cobalt oxide, and molybdenum oxide. The all-solid-state electrochromic device according to claim 5, wherein the ion storage layer is nickel oxide, nickel tungsten oxide, Prussian blue, cerium oxide, nickel titanium oxide, nickel aluminum oxide, iron phosphate. Lithium, titanium or zinc or copper doped lithium iron phosphate. The all-solid-state electrochromic device according to claim 6, wherein the transparent conductive layer is indium tin oxide, aluminum-doped zinc oxide, and fluorine-doped tin oxide. The all-solid-state electrochromic device according to claim 7, wherein the ion conductive layer has a thickness of 10 to 500 nm; the lithium alloy layer has a thickness of 10 to 100 nm; and the ion storage layer has a thickness of 200 to 1000 nm. The electrochromic layer has a thickness of 200 to 1000 nm, the metal reflective layer has a thickness of 10 to 1000 nm, and the transparent conductive layer has a thickness of 50 to 300 nm. . A method of preparing an electrochromic device according to any one of claims 1-8, wherein the method steps are as follows:  a. taking a glass or a flexible high polymer as a substrate, and washing it in a furnace;  b. depositing a metal reflective layer or a transparent conductive layer on the surface of the substrate using DC power source magnetron sputtering; c. taking a mask plate over the metal reflective layer or transparent conductive layer to leave a wiring area; then depositing an electrochromic layer by physical vapor deposition; d. subsequently depositing an ion conducting layer on the electrochromic layer by physical vapor deposition or chemical vapor deposition equipment; e. plating a lithium alloy layer on the ion conductive layer by physical vapor deposition; f. plating an ion storage layer on the ion conductive layer by magnetron sputtering; g. On the ion storage layer, a second transparent conductive layer is plated by DC power source magnetron sputtering.