阅读说明：本技术 一种着色深度可调的电致变色器件及其制备方法 (Electrochromic device with adjustable coloring depth and preparation method thereof ) 是由 王群华 刘江 吉顺青 于 2020-05-11 设计创作，主要内容包括：本发明公开了一种电致变色器件,涉及电致变色领域,包括：基底、第一导电层、电致变色层、离子传导层、离子存储层和第二导电层；所述第一导电层被堆叠在所述基底上,所述电致变色层被堆叠在所述第一导电层上,所述离子传导层被堆叠在所述电致变色层上,所述离子存储层被堆叠在所述离子传导层上,所述第二导电层被堆叠在所述离子存储层上；其中,还包括：嵌入层,所述嵌入层被平铺在所述电致变色层或所述离子存储层的至少一个之中；所述嵌入层包括多个缺陷区,所述缺陷区内富集传输离子。本发明的技术效果在于：在电致变色层中形成局部锂含量的高浓度,提升了电致变色器件的着色对比度和稳定性。(The invention discloses an electrochromic device, which relates to the field of electrochromic and comprises: a substrate, a first conductive layer, an electrochromic layer, an ion conducting layer, an ion storage layer, and a second conductive layer; the first electrically conductive layer is stacked on the substrate, the electrochromic layer is stacked on the first electrically conductive layer, the ion conductive layer is stacked on the electrochromic layer, the ion storage layer is stacked on the ion conductive layer, the second electrically conductive layer is stacked on the ion storage layer; wherein, still include: an embedding layer tiled within at least one of the electrochromic layer or the ion storage layer; the embedded layer includes a plurality of defect regions enriched in transport ions. The invention has the technical effects that: the high concentration of local lithium content is formed in the electrochromic layer, and the coloring contrast and stability of the electrochromic device are improved.)

1. An electrochromic device with adjustable coloring depth, which is characterized by comprising: a substrate, a first conductive layer, an electrochromic layer, an ion conducting layer, an ion storage layer, and a second conductive layer;

the first electrically conductive layer is stacked on the substrate, the electrochromic layer is stacked on the first electrically conductive layer, the ion conductive layer is stacked on the electrochromic layer, the ion storage layer is stacked on the ion conductive layer, the second electrically conductive layer is stacked on the ion storage layer;

wherein, still include: an embedding layer tiled within at least one of the electrochromic layer or the ion storage layer; the embedded layer includes a plurality of defect regions enriched in transport ions.

2. The tunable coloration depth electrochromic device according to claim 1, wherein the thickness of the embedding layer is 0.2 to 5 nanometers.

3. The tunable coloration depth electrochromic device according to claim 1, wherein at least one of the electrochromic layer or the ion storage layer comprises a plurality of the embedded layers.

4. The tunable coloring depth electrochromic device according to claim 3, wherein a spacing between a plurality of the embedded layers is 10 to 200 nm.

5. The tunable color depth electrochromic device according to claim 1, wherein the transport ions are lithium ions.

6. The electrochromic device with adjustable coloring depth according to claim 1, wherein the material of the embedded layer has a crystal form different from that of the functional layer where the embedded layer is located; the functional layer is an electrochromic layer or an ion storage layer.

7. The electrochromic device with adjustable coloring depth according to claim 1, wherein the particle size of the material of the embedding layer is different from that of the functional layer where the embedding layer is located, and the functional layer is an electrochromic layer or an ion storage layer.

8. The tunable tint depth electrochromic device of claim 1, wherein the embedding layer comprises at least one of the following materials: carbon, silicon, germanium.

9. The tunable tint depth electrochromic device of claim 1, wherein the embedding layer comprises an oxide of at least one of the following materials: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium.

10. The tunable tint depth electrochromic device of claim 1, wherein the embedding layer comprises a nitride of at least one of the following materials: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium.

11. The tunable color depth electrochromic device according to claim 1, wherein the embedding layer comprises a group consisting of hydroxides of at least one of the following materials: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium.

12. The tunable tint depth electrochromic device of claim 1, wherein at least one of the electrochromic layer and the ion storage layer is a metal oxide deposited coating comprising polycrystalline structured channel walls and an amorphous structured channel core, the channel walls extending along the electrochromic layer in a direction toward the ion storage layer.

13. The tunable coloration depth electrochromic device according to claim 1, wherein the electrochromic layer comprises a cathodic coloration material and the ion storage layer comprises an anodic coloration material.

14. Electrochromic device with adjustable coloration depth according to claim 13, characterized in that the cathodic coloration material is chosen from one or more of the following materials: tungsten oxynitride, molybdenum oxynitride, niobium oxynitride, titanium oxynitride, tantalum oxynitride; the anodic colouring material is selected from one or more of the following materials: nickel oxynitride, iridium oxynitride, manganese oxynitride, cobalt oxynitride, tungsten nickel oxynitride, tungsten iridium oxynitride, tungsten manganese oxynitride, tungsten cobalt oxynitride.

15. The tunable coloration depth electrochromic device according to claim 1, wherein at least one of the electrochromic layer and the ion storage layer further comprises hydrogen.

16. A preparation method of an electrochromic device with adjustable coloring depth is characterized by comprising the following steps:

doping a first target material with inert gas and a first reaction gas to perform reactive sputtering on the first conductive layer to form an electrochromic layer;

forming an ion conducting layer on the electrochromic layer;

doping a second target material with the inert gas and the first reaction gas to perform reactive sputtering on the ion conduction layer to form an ion storage layer;

forming a second conductive layer on the ion storage layer;

heating the deposited electrochromic device in vacuum to diffuse the transmitted ions into the defect area;

further comprising the steps of:

and when a functional layer is deposited, carrying out codeposition or staggered deposition on the functional layer and a third target under the inert gas atmosphere, wherein the functional layer comprises the electrochromic layer and the ion storage layer.

17. The method for manufacturing an electrochromic device with adjustable coloring depth according to claim 16, wherein the staggered deposition is a plurality of staggered depositions.

18. The method according to claim 16, wherein a crystal form of the material formed by depositing the third target material is different from a crystal form of the material in the functional layer.

19. The method according to claim 16, wherein the third target material is deposited to produce a material with a particle size different from that of the functional layer.

20. The method according to claim 16, wherein the third target is selected from the group consisting of: carbon, silicon, germanium.

21. The method of claim 16, wherein the first reaction gas comprises oxygen.

22. The method according to claim 16, wherein the first target material comprises a group consisting of the following materials or oxides thereof: tungsten, molybdenum, niobium, titanium, tantalum.

23. The method according to claim 16, wherein the second target material comprises a material selected from the group consisting of: nickel, iridium, cobalt, manganese, tungsten.

24. The method of claim 21, wherein the first reaction gas further comprises a nitrogen-containing gas.

25. The method of claim 21, wherein the first reaction gas further comprises hydrogen.

26. The method of claim 24, wherein the nitrogen-containing gas is selected from one or more of the following gases: nitrogen, ammonia, nitric oxide, nitrogen dioxide, nitrous oxide, nitrogen fluoride.

27. The method for preparing an electrochromic device with adjustable coloring depth according to claim 16, further comprising the steps of: adding an additional gas to the first reactant gas, the additional gas comprising helium.

28. The method according to claim 16, further comprising adding a second reactive gas when the third target is deposited under the inert gas atmosphere, wherein the second reactive gas is selected from the group consisting of: oxygen, hydrogen, nitrogen-containing gases.

29. The method according to claim 28, wherein the third target is selected from the group consisting of: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium.

Technical Field

The invention relates to the field of electrochromism, in particular to an electrochromism device with adjustable coloring depth and a preparation method thereof.

Background

Electrochromism refers to a phenomenon in which optical properties (reflectivity, transmittance, absorption, etc.) undergo a stable, reversible color change under the action of an applied electric field. Electrochromic technology has been developed for more than forty years, and Electrochromic devices (ECDs) have wide application prospects in the fields of intelligent windows, displays, spacecraft temperature control modulation, automobile no-glare rearview mirrors, weapon equipment stealth and the like due to the characteristics of continuous adjustability of transmitted light intensity, low energy loss, open-circuit memory function and the like. The ECD-based glass serving as a brand-new intelligent window can adjust the intensity of incident sunlight according to a comfortable requirement, effectively reduces energy consumption and shows a remarkable energy-saving effect. With the continuous improvement of the requirements of human beings on consumer products, the ECD shows huge market prospects and application values in the fields of automobiles, home appliances, aerospace, rail transit, green buildings and the like, and electrochromic products attract more and more extensive attention and attention at home and abroad and are a new generation of high-efficiency building energy-saving products after heat-absorbing glass, heat-reflecting coated glass and low-radiation glass.

In a traditional electrochromic device, an electrochromic layer and an ion storage layer (also called an ion storage layer) are generally metal oxides and are disordered mixtures of amorphous states or amorphous states/crystalline states, the metal oxides with high crystallinity generally have good stability, but ion embedding is difficult, so that the light transmittance of the electrochromic device in a colored state cannot achieve the effect of completely shielding a light source, namely the light transmittance of the device in the colored state is high and the effect is poor. On the other hand, metal oxides having low crystallinity are relatively easy to intercalate ions, but have poor cycle stability. Therefore, the traditional electrochromic device cannot simultaneously obtain the electrochromic device which has good stability, high coloring depth and ordered ion transmission.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, a technical problem to be solved by the present invention is to controllably adjust the amount of embedded transport ions in an electrochromic device, thereby adjusting the color contrast of the electrochromic device.

To achieve the above object, the present invention provides an electrochromic device with adjustable coloring depth, comprising: a substrate, a first conductive layer, an electrochromic layer, an ion conducting layer, an ion storage layer, and a second conductive layer;

the first electrically conductive layer is stacked on the substrate, the electrochromic layer is stacked on the first electrically conductive layer, the ion conductive layer is stacked on the electrochromic layer, the ion storage layer is stacked on the ion conductive layer, the second electrically conductive layer is stacked on the ion storage layer;

wherein, still include: an embedding layer tiled within at least one of the electrochromic layer or the ion storage layer; the embedded layer includes a plurality of defect regions enriched in transport ions.

Further, the thickness of the embedding layer is 0.2 to 5 nm.

Further, at least one of the electrochromic layer or the ion storage layer includes a plurality of the embedded layers.

Further, the interval between the plurality of embedding layers is 10 to 200 nm.

Further, the transport ions are lithium ions.

Furthermore, the crystal form of the material of the embedding layer is different from that of the functional layer where the embedding layer is located; the functional layer is an electrochromic layer or an ion storage layer.

Furthermore, the particle size of the material of the embedding layer is different from that of the functional layer where the embedding layer is located, and the functional layer is an electrochromic layer or an ion storage layer.

Further, the embedding layer includes a group consisting of at least one of the following materials: carbon, silicon, germanium.

Further, the embedding layer comprises an oxide of at least one of the following materials: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium.

Further, the embedding layer comprises a nitride of at least one of the following materials: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium.

Further, the intercalation layer includes a group consisting of hydroxides of at least one of the following materials: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium.

Further, at least one of the electrochromic layer and the ion storage layer is a metal oxide deposition coating film comprising a polycrystalline structure channel wall and an amorphous structure channel core, wherein the channel wall extends along the electrochromic layer to the direction of the ion storage layer.

Further, a cathodic coloring material is included in the electrochromic layer and an anodic coloring material is included in the ion storage layer.

Further, the cathodic coloring material is selected from one or more of the following materials: tungsten oxynitride, molybdenum oxynitride, niobium oxynitride, titanium oxynitride, tantalum oxynitride; the anodic colouring material is selected from one or more of the following materials: nickel oxynitride, iridium oxynitride, manganese oxynitride, cobalt oxynitride, tungsten nickel oxynitride, tungsten iridium oxynitride, tungsten manganese oxynitride, tungsten cobalt oxynitride.

Further, at least one of the electrochromic layer and the ion storage layer further comprises hydrogen.

The invention also discloses a preparation method of the electrochromic device with adjustable coloring depth, which comprises the following steps:

doping a first target material with inert gas and a first reaction gas to perform reactive sputtering on the first conductive layer to form an electrochromic layer;

forming an ion conducting layer on the electrochromic layer;

doping a second target material with the inert gas and the first reaction gas to perform reactive sputtering on the ion conduction layer to form an ion storage layer;

forming a second conductive layer on the ion storage layer;

heating the deposited electrochromic device in vacuum to diffuse the transmitted ions into the defect area;

further comprising the steps of:

and when a functional layer is deposited, carrying out codeposition or staggered deposition on the functional layer and a third target under the inert gas atmosphere, wherein the functional layer comprises the electrochromic layer and the ion storage layer.

Further, the staggered deposition is a plurality of staggered depositions.

Further, the crystal form of the material generated during deposition of the third target material is different from the crystal form of the material in the functional layer.

Further, the grain size of the material generated when the third target material is deposited is different from the grain size of the material in the functional layer.

Further, the third target is selected from the group consisting of one of the following materials: carbon, silicon, germanium.

Further, the first reactant gas includes oxygen.

Further, the first target comprises a material selected from the group consisting of: tungsten, molybdenum, niobium, titanium, tantalum.

Further, the second target comprises a material selected from the group consisting of: nickel, iridium, cobalt, manganese, tungsten.

Further, the first reaction gas further comprises a nitrogen-containing gas.

Further, the first reaction gas further comprises hydrogen.

Further, the nitrogen-containing gas is selected from one or more of the following gases: nitrogen, ammonia, nitric oxide, nitrogen dioxide, nitrous oxide, nitrogen fluoride.

Further, the method also comprises the following steps: adding an additional gas to the first reactant gas, the additional gas comprising helium.

Further, when the deposition is performed under the inert gas atmosphere by using the third target, the method further comprises the step of adding a second reaction gas, wherein the second reaction gas is selected from the group consisting of: oxygen, hydrogen, nitrogen-containing gases.

Further, the third target is selected from the group consisting of: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium.

The invention has the technical effects that: lithium ions with controllable positions are embedded in the electrochromic layer and high concentration of local lithium content is formed, so that the coloring contrast and stability of the electrochromic device are further improved.

The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.

Drawings

Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments made with reference to the following drawings:

FIG. 1 is a schematic structural diagram of an embodiment of the present invention;

FIG. 2 is a scanning electron microscope image of the film structure of the examples and comparative examples of the present invention;

FIG. 3 is a schematic diagram of the channel walls and channel core structure according to one embodiment of the present invention;

FIG. 4 is a scanning electron microscope image of a channel wall and a channel core according to an embodiment of the invention;

FIG. 5 is a flowchart of a method according to an embodiment of the invention.

Description of reference numerals: 100-a substrate; 105-a first conductive layer; 110-an electrochromic layer; 115-ion conducting layer; 120-an ion storage layer; 125-a second conductive layer; 300-channel walls; 301-channel core; 400-an embedding layer; 500-defect area.

Detailed Description

The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.

In the drawings, structurally identical elements are represented by like reference numerals, and structurally or functionally similar elements are represented by like reference numerals throughout the several views. The size and thickness of each component shown in the drawings are arbitrarily illustrated, and the present invention is not limited to the size and thickness of each component. The thickness of the components may be exaggerated where appropriate in the figures to improve clarity.

For the purposes of this brief description, the "nitrogen content" as referred to herein is defined as the atomic mole fraction of nitrogen as a percentage of the individual functional layers of the electrochromic device. The lithium content is the percentage of the atomic mole number of lithium in the functional layer to the single functional layer of the electrochromic device.

As shown in fig. 1, the present invention discloses an electrochromic device with adjustable coloring depth, comprising: substrate 100, first conductive layer 105, electrochromic layer 110, ion conducting layer 115, ion storage layer 120, and second conductive layer 125;

a first conductive layer 105 is stacked on the substrate 100, an electrochromic layer 110 is stacked on the first conductive layer 105, an ion conductive layer 115 is stacked on the electrochromic layer 110, an ion storage layer 120 is stacked on the ion conductive layer 115, and a second conductive layer 115 is stacked on the ion storage layer 120;

wherein, still include: an embedded layer 400, the embedded layer 400 tiled within at least one of the electrochromic layer 110 or the ion storage layer 120, the embedded layer 400 including a plurality of defective regions 500, the defective regions 500 being enriched in transport ions. The transport ions are typically lithium ions, or other ions that can produce an electrochromic reaction with the electrochromic layer 110 and the ion storage layer. In the following description, the "lithium ion" is sometimes taken as an example to explain the principles of the present invention.

The first conductive layer 105 and the second conductive layer 125 are conventional conductive layers, and the material includes one or more of Indium Tin Oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), and fluorine-doped tin oxide (FTO). Electrochromic layer 110, ion conducting layer 115, and ion storage layer 120 are sequentially covered between first conductive layer 105 and second conductive layer 125.

The thickness of the embedding layer 400 is 0.2 nm to 5 nm, preferably also 0.5 nm to 1 nm, and also 2 nm to 4 nm. Since the particle size of the particles in the embedding layer 400 is different from the particle size of the electrochromic layer 110 and the film layer of the ion storage layer 120, thus causing discontinuities in crystallinity, defect density, stress, composition of the materials in the deposited electrochromic layer 110 and the ion storage layer 120, relative changes in particle-to-particle porosity and distance, i.e., a plurality of defective regions 500 are created at the interface between the electrochromic layer 110 or the ion storage layer 120, where the transported ions tend to collect with the defective regions 500, thereby resulting in a high concentration of locally transported particles inside the electrochromic layer 110 and the ion storage layer 120, thereby increasing the content of transmitted ions when the electrochromic device enters the electrochromic layer or the functional layer containing the cathode electrochromic material when being electrified and colored, thereby generating more color-changing compounds and leading the electrochromic device to obtain higher color contrast. Moreover, after the content of the basic transport ions in the electrochromic layer 110 and the ion storage layer 120 is increased, that is, after the basic transport ions are increased, when the electrochromic device is powered on, the electrochromic layer 110 only needs to obtain less transport ions than that of the traditional electrochromic device, and the coloring process can be completed, so that the color change speed of the electrochromic device is further increased.

In addition, the stability of the electrochromic device is also improved. Generally, the electrochromic layer 110 and the ion storage layer 120 having higher crystallinity may have higher stability. However, in this case, when the electrochromic device is powered on, the transmission particles are more difficult to embed, thereby causing disadvantages of lighter color in a colored state and excessively high light transmittance. Thus, conventional electrochromic devices typically have a compromise between ease of transport ion intercalation and film layer stability. In the electrochromic device disclosed by the invention, the defect area 500 is introduced into the electrochromic layer 110 and the ion storage layer 120 to enrich and transmit ions, so that the crystallinity of the electrochromic layer 110 and the ion storage layer 120 can be selectively improved during deposition, the embedding process of transmitting ions is not influenced, the original light transmittance range of the electrochromic device is not influenced under the high crystallinity of the electrochromic layer 110 and the ion storage layer 120, the electrochromic device with a more stable structure is obtained, and the service life of the electrochromic device is prolonged.

In the conventional electrochromic device, since the electrochromic layer and the ion storage layer have uniform compositions, the distances between pores and particles are uniformly distributed, and thus the transport ions are uniformly distributed in the pores in the electrochromic layer 110 and the ion storage layer 120, a high concentration of transport particles in a local portion inside the layer cannot be formed.

Further, the embedding layer 400 may be plural, and each of the embedding layers may have a spacing of 10 to 200 nm, or may have a spacing of 50 to 75 nm, or may have a spacing of 100 to 150 nm in the corresponding functional layer, i.e., the electrochromic layer or the ion storage layer. By increasing or decreasing the number and spacing of the intercalation layers 400, the lithium content or lithium concentration in the vicinity of the intercalation layers 400 can be regulated, and thereby the coloring contrast and stability of the electrochromic device can be regulated.

Further, since the embedding layer 400 only needs to make a discontinuity at the interface of the electrochromic layer 110 or the ion storage layer 120 to generate the defective region 500, it is also necessary that the material of the embedding layer 400 has a different crystal form from that of the materials used for the electrochromic layer 110 and the ion storage layer 120. In addition, to meet the ion transport speed in electrochromic devices, the material selected for the embedding layer 400 should also be suitable for ion transport.

Based on the above material selection criteria, the embedding layer 400 may include a group consisting of: carbon, silicon, germanium. Wherein the carbon, silicon, germanium may be polycrystalline or amorphous, resulting in discontinuity of crystallinity, defect density, stress, composition of the materials in the deposited electrochromic layer 110 and the ion storage layer 120.

Further, the embedding layer 400 includes a group consisting of oxides of the following materials: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium to facilitate the ion transport rate.

Further, the embedding layer 400 includes a group consisting of nitrides of the following materials: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium, cause crystal distortion, increase the stability of the film and promote ion transport rates.

Further, the insertion layer 400 includes a group consisting of hydroxides of the following materials: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium. Due to the addition of the hydrogen atoms, the dangling bonds of the oxygen atoms on the interface of the film layer are terminated, and the stability of the film layer is improved. Generally, the hydrogen content of the film does not exceed 4%, and beyond this, the water absorption of the film is increased.

Fig. 2(a) and 2(b) show scanning electron micrographs of a conventional electrochromic device and an electrochromic device in an embodiment of the present invention, and it can be seen from fig. 2(a) that the layers in the conventional electrochromic device are uniform and continuous layers. While the layered structure, and the defect area 500 due to the non-uniformity of the deposited material, can be clearly seen in fig. 2 (b).

Further, the electrochromic layer 110 is also a metal oxide deposition coating film including a channel wall 300 with a polycrystalline structure and a channel core 301 with an amorphous structure, as shown in fig. 3 and 4, the channel wall 300 is a metal oxide with a polycrystalline structure and extends along the electrochromic layer 110 toward the ion storage layer 120, and the channel core 301 is a metal oxide with an amorphous structure and is filled in the channel wall 300. Thus, lithium ions may rapidly move along the channel walls 300 through the amorphous metal oxide in the channel core 301, i.e., the ion transport rate of the electrochromic layer 110 is increased, since the amorphous metal oxide is more ion conductive.

Further, the electrochromic layer 110 is a metal oxynitride deposited film of a polycrystalline structure, the film thickness is usually 150 to 650nm, and the material used specifically includes tungsten oxynitride (WO)_xN_y) Molybdenum oxynitride (MoO)_xN_y) Niobium oxynitride (NbO)_xN_y) Titanium oxynitride (TiO)_xN_y) Tantalum oxynitride (TaO)_xN_y) Depending on the nitrogen content, the parameters x and y vary accordingly. The molar number of nitrogen atoms in the electrochromic layer 110 is generally 0.05% to 20%, or 0.5% to 5%, or 0.5% to 10% of the total atomic molar number. Generally, the content of nitrogen exceeds 20%, the color of the deposited coating film can be deepened, which is caused by the color of the metal oxynitride, and the deepening of the color of the coating film can influence the light transmittance of the electrochromic glass in a fading state, so that the color change range of a finished device is reduced.

After metal oxide used by a conventional electrochromic layer is replaced by metal oxynitride, according to the difference of nitrogen content, nitrogen ions can replace oxygen ions in the original metal oxide, for example, tungsten is taken as an example, original W-O ionic bonds are partially replaced by W-N ionic bonds, so that the asymmetry of crystal lattices is caused, the acting force balance among original ions is destroyed, adjacent atoms deviate from the balance position, and the crystal distortion is caused. After the crystal is distorted, the interaction around the ion transport channel is reduced, thereby increasing the ion transport speed of the electrochromic layer. The nitrogen element is taken as a relatively stable element, and the stability of the metal compound is not affected by the introduction of the nitrogen element, so that the good stability is still maintained.

Further, at least one of the electrochromic layer 110 or the ion storage layer 120 further includes hydrogen atoms. Due to the addition of the hydrogen atoms, the dangling bonds of the oxygen atoms on the interface of the film layer are terminated, and the stability of the film layer is improved. Generally, the hydrogen content of the film does not exceed 4%, and beyond this, the water absorption of the film is increased.

Ion conducting layer 115 is deposited over electrochromic layer 110 for transporting lithium ions from electrochromic layer 110 or ion storage layer 120 to the other opposing electrochromic layer when first conductive layer 105 and second conductive layer 125 are energized. Similarly, when the current is reversed, lithium ions flow in the opposite direction, cycling the electrochromic device between colored and faded. In the present embodiment, lithium silicon oxynitride (LiSi) may be used for the ion conductive layer 115_zO_xN_y) Lithium tantalum oxynitride (LiTa)_zO_xN_y) Lithium niobium oxynitride (LiNb)_zO_xN_y) Lithium cobalt oxynitride (LiCo)_zO_xN_y) Lithium aluminum oxynitride (LiAl)_zO_xN_y) Lithium phosphorus oxynitride (LiP)_zO_xN_y) Lithium boron oxynitride (LiB)_zO_xN_y) One or more of (a). The parameters of x, y and z are changed according to the nitrogen content. In the film layer of the ion conductive layer 115, the molar number of nitrogen atoms is generally 0.05% to 30% of the total atomic molar number,can also be 0.5 to 5 percent and can also be 10 to 20 percent. Since the oxynitride has two characteristics of ion conductivity and electronic insulation, it can perfectly satisfy that the electrochromic device can transmit ions between the electrochromic layer 110 and the ion storage layer 120, and simultaneously block the electron movement when the first conductive layer 105 and the second conductive layer 125 are electrified, thereby preventing short circuit. Therefore, compared with the ion conducting layer in the conventional electrochromic device, the thickness of the ion conducting layer 115 of the present invention can be made thinner, and can be as thin as 3 nm at most, and meanwhile, the ion conducting layer 115 still has the characteristics of electronic insulation and ion transmission, and can also be 10 nm to 50nm, and can also be 100 nm to 300 nm, and preferably 5 nm to 200 nm, so that the overall thickness of the electrochromic device is reduced, and thus when the electrochromic device is applied to actual products, such as electrochromic glass and electrochromic display screens, the actual products are also thinner and lighter. In the prior art, the ion conducting layer is usually thickened to 600 nm or more to achieve the effect of electronic insulation.

In addition, compared with the prior art of silicon lithium oxide, aluminum lithium oxide, cobalt lithium oxide, etc., the ion conducting layer 115 used in the present invention has ion conductivity that can be increased by about one order of magnitude. The nitrogen content of the ion conducting layer 115 is regulated, so that the ion transmission speed of the device can be regulated, the color change speed of the electrochromic device can be further regulated, the requirements of different users on the color change speed can be met, and especially the uniform color change effect under different color change speeds can be realized. For example, the electrochromic device color change speed is proportionally reduced at higher nitrogen content of the film, and increased at lower nitrogen content. In addition, in the deposition process of the conventional electrochromic device, due to defects generated in the conventional deposition process, the local area color changing speeds of the electrochromic device are not the same, so that the color changing uniformity of the electrochromic device is influenced, and the local area color changing speeds of the electrochromic device can be respectively regulated and controlled to be consistent by regulating and controlling the nitrogen content of the local area of the film layer, so that the obtained electrochromic device has more uniform color changing effect. In another embodiment of the present invention, the ion transmission speed of different areas on the electrochromic device can also be regulated to make the color change speed uneven, and the ion transmission speed of some areas on the electrochromic device can be 0 under extreme conditions, so as to achieve the purpose of forming patterns or patterns on the electrochromic device.

The ion storage layer 120 is deposited on the ion transport layer 115 with a film thickness of 150 to 650nm and is selected from nickel oxynitride (NiO)_xN_y) Iridium oxynitride (IrO)_xN_y) Manganese oxynitride (MnO)_xN_y) Cobalt oxynitride (CoO)_xN_y) Tungsten nickel oxynitride (WNi)_zO_xN_y) Iridium oxynitride pigeon (WIr)_zO_xN_y) Tungsten manganese oxynitride (WMn)_zO_xN_y) Tungsten-cobalt oxynitride (WCo)_zO_xN_y) The mole number of nitrogen atoms in the film layer accounts for about 0.05 to 15 percent of the whole mole number of atoms.

Since the metal composition inside the ion storage layer 120 is different from that of the electrochromic layer 110, the ion storage layer 120 is generally in a microcrystalline or amorphous structure, and nitrogen is further introduced into the conventional ion storage layer 120 to convert the conventional nickel oxide or iridium oxide material into a nickel oxynitride, iridium oxynitride or cobalt oxynitride material, thereby improving the stability of the device during the coloring and discoloring process due to the higher binding energy of nitride relative to oxide.

Alternatively, the electrochromic materials in the electrochromic layer 110 and the ion storage layer 120 are a cathode coloring material and an anode coloring material, respectively. For example, the electrochromic layer 110 may employ a cathodically coloring material, such as tungsten oxynitride; the ion storage layer 120 may employ an anodic coloring material, such as nickel oxynitride. That is, after lithium ions are separated from the ion storage layer 120, the ion storage layer also enters a colored state. Thus, the electrochromic layer 110 and the ion storage layer 120 combine and collectively reduce the light transmittance transmitted through the overall electrochromic device.

Further, tungsten may be introduced into the ion storage layer 120, which may further enhance the ion transport performance of the electrochromic device and only have a slight effect on the fading performance of the device itself.

In general, the electrochromic device prepared by the method of the invention has a color change range of 1-69%. In contrast, the existing electrochromic devices, such as those of View, Inc., have a color change range of only about 1% to 58% under the same transparent substrate. This is primarily due to the lower color of the electrochromic nitride relative to the electrochromic oxide, which generally increases the light transmittance of the film layers deposited on the transparent substrate, e.g., electrochromic layer 110, ion storage layer 120.

The device can reversibly cycle between a bleached state and a colored state when in operation. In the bleached state, lithium ions are colored by applying a voltage at the first conductive layer 105 and the second conductive layer 125 through the ion conductive layer 115 and into the electrochromic layer 110 containing the cathode electrochromic material, while the ion storage layer 120 containing the anode electrochromic material is also brought into the colored state together with the electrochromic layer 110 by the exit of the lithium ions. When the voltage potentials applied at first conductive layer 105 and second conductive layer 125 are reversed, lithium ions leave electrochromic layer 110, pass through ion conductive layer 115, and return into ion storage layer 120. Thereby, the device is switched to a bleached state. Depending on the voltage control, the electrochromic device can be switched not only back and forth between the bleached state and the colored state, but also to one or more intermediate color states between the bleached state and the colored state.

Finally, in the preparation process of the conventional electrochromic device, the conventional electrochromic device can contain a part of nitrogen element more or less because the environmental airtightness cannot achieve the effect of absolute vacuum. The inventors herein have clarified that nitrogen in a conventional electrochromic device is merely an environmental error, and the content of the nitrogen atom mole number in the single layer in the conventional electrochromic device is only about 0.004% of the entire atom mole number, and the above-described effects of the nitrogen-containing electrochromic device cannot be obtained.

As shown in fig. 5, the invention also discloses a preparation method of the electrochromic device with adjustable coloring depth, which comprises the following steps:

step S201: doping a first target material with inert gas and a first reaction gas, performing reactive sputtering on the first conductive layer 105 to form an electrochromic layer 110, sputtering the electrochromic layer 110 in an inert gas atmosphere by using a third target material to form an embedded layer 400, and performing codeposition or staggered deposition on the embedded layer 400 and the electrochromic layer 110;

the first conductive layer 105 may be directly deposited on the substrate 100 by vacuum coating, evaporation coating, sol-gel, or the like, or the electrochromic layer 110 may be directly deposited on the substrate 100 having the first conductive layer 105.

The electrochromic layer 110 is reactively sputtered onto the first conductive layer 105 by plasma vacuum coating with a first target. Reactive sputtering is carried out in particular with an inert gas, preferably argon, doped with a first reactive gas to form the corresponding compound on the first conductive layer 105. The first reaction gas may be oxygen, and the first target may be one or more of tungsten, molybdenum, niobium, titanium, and tantalum, or an oxide of the corresponding metal. During sputtering, the metal on the target is ionized and deposited on the substrate under the action of the magnetic field formed by the N magnet and the S magnet fixed around the target. In order to effectively control the oxidation valence state, the mixed gas in the plasma state and the metal ions can be pumped away by using the pumping channel, and the metal deposited on the substrate can not be kept in the oxygen-containing atmosphere, so that secondary oxidation can not be caused. Meanwhile, the power of the pumping channel should be adjusted accordingly, so that the mixed gas in the plasma state and the metal ions can stay on the periphery of the substrate for a sufficient time, and the metal ions can be deposited on the substrate.

In order to prevent ions sputtered from the first target and the second target in step S203 from being further oxidized by external oxygen during reactive sputtering, which may result in the inability to adjust the specific oxide ratio of the formed film, it is necessary to maintain an oxygen-free inert gas atmosphere outside the sputtering region to prevent external environmental interference and ensure that the oxidation reaction of the ions occurs only in the sputtering region. In this embodiment, a pumping channel is used to pump away oxygen-containing gas that escapes the sputtering zone around the target.

During deposition of the electrochromic layer 110, the third target may be used for sputtering under an inert gas atmosphere to form the embedded layer 400, and co-deposition or staggered deposition with the electrochromic layer 110. According to different times of the staggered deposition, the embedded layer 400 may be a single layer or a multi-layer, and the third target may be carbon, silicon, germanium, or any other material with good ion conductivity and with a crystal growth different from that of the material used for the electrochromic layer 110. This results in discontinuity at the interface of the electrochromic layer 110, forming a defective region 500, which causes lithium ions to tend to concentrate near the intercalation layer 400, thereby increasing the specific color depth of the electrochromic device when colored. Of course, the specific content and arrangement of the lithium ions may be controlled accordingly according to the thickness of the intercalation layer 400 or the number of deposition layers. For example, when the thickness of the embedding layer 400 and the number of times of staggered deposition are small, the coloring state of the electrochromic device becomes lighter, and thus the coloring range of the electrochromic device is adjusted, thereby satisfying the requirement of electrochromic transmittance in different situations.

In a preferred staggered deposition process, one or more deposition steps may be performed between the deposition steps of the electrochromic layer 110. For example, the cycle may be repeated until the electrochromic layer 110 is deposited to a predetermined thickness by first depositing a limited amount of the reactively sputtered compound from the first target, followed by sputter deposition directly from the third target, followed by depositing an additional amount of reactively sputtered compound from the first target.

A third target may also be co-deposited with the first target while depositing the material of the electrochromic layer 110 and the material of the embedding layer 400 on the first conductive layer 105. At this time, the discontinuity of the interface between the electrochromic layer 110 and the embedding layer 400 is increased, thereby increasing the generation of the defective region 500.

Step S202: forming an ion conductive layer 115 on the electrochromic layer 110;

the third target is reactively sputtered by vacuum coating, magnetron sputtering, or the like to form an ion conductive layer 115 on the electrochromic layer 110. The third target material can be selected from conventional targets in the prior art, such as lithium, silicon, cobalt, boron, phosphorus or their mixture.

Furthermore, a nitrogen-containing gas circuit can be additionally added on the conventional magnetron sputtering equipment and is separately introduced into the reaction chamber for reactive sputtering. According to requirements, a plurality of gas circuits containing nitrogen element gas can be added to adjust the concentration of local nitrogen-containing gas in the reactive sputtering process, so as to control the nitrogen content of different areas on the ion conduction layer, thereby regulating and controlling the ion transmission speed of the electrochromic device, further reducing device defects and keeping the ion transmission speed of different areas of the electrochromic device consistent. In another embodiment of the present invention, the ion transmission speed of different areas on the electrochromic device can also be regulated to make the color change speed uneven, and the ion transmission speed of some areas on the electrochromic device can be 0 under extreme conditions, so as to achieve the purpose of forming patterns or patterns on the electrochromic device.

Step S203: doping the first reaction gas with the inert gas to perform reactive sputtering on the ion conduction layer 115 by using the second target material to form an ion storage layer 120, performing sputtering under the inert gas atmosphere by using the third target material when depositing the ion storage layer 120 to form an embedded layer 400, and performing codeposition or staggered deposition on the embedded layer 400 and the ion storage layer 120;

the ion storage layer 120 may use metal nickel, iridium, tungsten, cobalt, manganese, etc. as a second target material, and uses inert gas as a carrier gas to dope the first reaction gas for reactive sputtering, which is similar to the electrochromic layer 110, and the details are not repeated here. In addition, because the pure metal nickel and the metal cobalt have magnetism and interfere the arrangement process of particles in the magnetron sputtering process, the tungsten-containing alloy with the metal can be used to achieve the purpose of demagnetizing the target material.

Through the above steps, the insertion layer 400 may also be formed in the ion storage layer 120 to obtain a local high-concentration lithium content in the ion storage layer 120, so that in a discolored state, the light transmittance of the ion storage layer 120 may be correspondingly improved, which is the same as that in step S201, and is an improvement of lithium ions, and a corresponding light-colored or colorless compound generated by an electrochromic reaction with the material and electrons in the ion storage layer is added, that is, the electrochromic compound generated with lithium ions and electrons in the electrochromic layer 110 is colored, and the electrochromic compound generated with lithium ions and electrons in the ion storage layer 120 is discolored, thereby also increasing the discoloring speed of the ion storage layer 120.

It should be understood that the deposition process of the embedding layer 400 may be performed among the functional layers, i.e., both the electrochromic layer 110 and the ion storage layer 120, to control the performance of the electrochromic device. Preferably, the deposition process of the embedding layer 400 is performed in the functional layers, i.e. in both the electrochromic layer 110 and the ion storage layer 120, so that the performance of the resulting electrochromic device is optimized.

Step S204: forming a second conductive layer 125 on the ion storage layer 120;

the second conductive layer 125 is formed in the same manner as the first conductive layer 105, and is not described herein again.

Step S205: heating the deposited electrochromic device in vacuum to diffuse the transported ions into the defect region 500;

generally, after the deposition process is completed, the deposited electrochromic device needs to be subjected to vacuum heating, i.e., annealing treatment, preferably 200 to 300 ℃. Thus, lithium deposited directly in the electrochromic layer 110 and the ion storage layer 120 is more easily activated to diffuse at high temperature and fill up the pores between the material particles, while annealing allows better contact to be made between the interfaces between the functional layers of the electrochromic device. Whereas in the defect area 500 the discontinuity of the particles around it results in a large amount of pores being included around it, whereby the lithium ions tend to concentrate in the defect area 500, thereby resulting in a high concentration of local lithium ions in the electrochromic layer 110 and the ion storage layer 120.

Further, the embedded layer 400 is deposited by a second reactive gas selected from the group consisting of: oxygen, hydrogen, nitrogen-containing gases. The third target is selected from the group consisting of: silicon, tantalum, niobium, cobalt, aluminum, phosphorus, boron, lithium.

Thus, the ion transport efficiency and stability of the insertion layer 400 are increased, and the functions of hydrogen gas and nitrogen-containing gas will be described later.

Further, the first reaction gas further comprises a nitrogen-containing gas. The nitrogen-containing gas may include: nitrogen (N)₂) Ammonia (NH)₃) Nitrogen monoxide (NO), nitrogen dioxide (NO)₂) Dinitrogen oxide (N)₂O), Nitrogen Fluoride (NF)₃) And other mixed gases containing the aforementioned gases, and the mole ratio of nitrogen element in the mixed gas is required to achieve the objective of the invention. Specifically, in the deposition of the electrochromic layer 110, or the ion conducting layer 115 and the ion storage layer 120 described below, all of the gases, regardless of the means by which they enter the reactor, should contain an inert gas as a carrier gas, and oxygen and nitrogen-containing gases as reactant gases. In the case of the electrochromic layer 110, the mixing ratio of the nitrogen-containing gas in the reaction gas must be sufficient to make the nitrogen element in the deposited first electrochromic layer 110 account for 0.05% to 20% of the whole atomic mole number. In the preferred embodiment, the mixing ratio of nitrogen to oxygen in the reaction gas is (0.1-10) to 1.

In addition, when other nitrogen-containing gases are used, such as ammonia gas, nitrogen fluoride, etc., the impurity elements therein cannot form stable compounds with the metal, and are pumped out by the pumping channel during the sputtering deposition process.

Further, the first reaction gas further comprises hydrogen.

Since oxygen at the interface of the metal oxide crystal on the electrochromic layer 110 has a dangling bond, hydrogen can be introduced, and after the hydrogen is decomposed into hydrogen atoms, the dangling bond of the interface oxygen can be filled to terminate the dangling bond of the interface oxygen atoms, so that the stability of the film layer is increased. In addition, the ratio of hydrogen to oxygen is (0.1-5) to 1, and if the ratio exceeds the above range, the water absorption of the film layer is increased, and the performance of the film layer is affected.

In addition, the hydrogen gas also comprises partial etching effect, and amorphous parts in the film layer can be etched. And the adsorption/desorption process involved in the etching process also plays a positive role in obtaining the crystalline and amorphous separated orientation channel structure.

Further, an additional gas, which is helium, is further included when depositing the electrochromic layer 110 or the ion storage layer 120.

During the reactive sputtering process, helium atoms in helium gas are partially adsorbed on the reaction interface, polycrystalline metal oxide is gradually deposited around the helium atoms as the deposition of the metal oxide proceeds, and since helium itself does not react with the metal, helium atoms are desorbed from the reaction interface again in the process of film deposition and diffuse out of the deposited electrochromic layer film, leaving the channel walls 300 with polycrystalline structure on the electrochromic layer film. Then, during the process of further depositing the metal oxide, the amorphous metal oxide enters the channel walls 300 to form channel cores 301, thereby obtaining a polycrystalline and amorphous separated orientation channel structure. Compared with the conventional electrochromic device, the polycrystalline structure and the amorphous structure in the electrochromic layer are in a disordered state and do not contain a channel structure.

The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.