WO2021029561A1

WO2021029561A1 - Electrochromic device

Info

Publication number: WO2021029561A1
Application number: PCT/KR2020/009689
Authority: WO
Inventors: 박중원
Original assignee: 박중원
Priority date: 2019-08-13
Filing date: 2020-07-23
Publication date: 2021-02-18
Also published as: KR102201636B1

Abstract

An electrochromic device according to an embodiment comprises: a first transparent electrode layer; a second transparent electrode layer disposed above the first transparent electrode layer; an electrochromic laminate disposed between the first transparent electrode layer and the second transparent electrode layer; and a protective coating layer covering the second transparent electrode layer.

Description

Electrochromic element

The present invention relates to an electrochromic device, and more particularly, to an electrochromic device having low power consumption and excellent processability and reliability.

An electrochromic device is a device that uses a reversible color change that occurs when an electrochromic substance electrochemically causes an oxidation or reduction reaction. The electrochromic element can be used in a smart window for a building, a mirror (rear mirror, side mirror, etc.) for an automobile, a sunroof or a display device for an automobile.

Compared to, for example, polymer-dispersed liquid crystal (PDLC) or suspended particle display (SPD), the electrochromic device has an advantage of having low power consumption and being able to manufacture a device with a large area at low cost.

Meanwhile, an electrochromic element generally includes a counter electrode layer, an ion conductive layer, and an electrochromic layer disposed between transparent electrode layers. Ions are supplied from the counter electrode layer to the electrochromic layer through the ion conductive layer to cause electrochromic discoloration.

As the ion conductive layer, a gel type polymer electrolyte may be used. However, since the gel-type polymer electrolyte is formed using a dispenser, it is difficult to form an ion conductive layer having a uniform thickness over a large area, and since the gel-type polymer electrolyte flows down by gravity, it is difficult to use for a long time. Accordingly, a technology for using a solid electrolyte as an ion conductive layer has been recently developed. When a solid electrolyte is used, a memory effect of electrochromic can be expected, and power consumption can be reduced compared to an electrochromic device using a gel-type polymer electrolyte that must continuously supply power for electrochromic discoloration.

On the other hand, each layer of the electrochromic device is laminated on the substrate using different techniques. Accordingly, it takes a lot of time to form each layer. In addition, in the electrochromic device, two glass substrates are bonded using a sealing technique, and since there is no means to protect the device other than sealing, it is easily damaged by an external environment, especially moisture. Moreover, the cost of product production increases with the use of two glass substrates.

The problem to be solved by the present invention is to provide an electrochromic device having excellent processability and reliability while reducing cost.

Another problem to be solved by the present invention is to provide an electrochromic device with low power consumption by enhancing a memory effect.

Another problem to be solved by the present invention is to provide an electrochromic device with improved electrochromic efficiency.

Another problem to be solved by the present invention is to provide an electrochromic device that can be manufactured by an in-line process.

An electrochromic device according to an embodiment of the present invention includes: a first transparent electrode layer; A second transparent electrode layer disposed on the first transparent electrode layer; An electrochromic laminate disposed between the first transparent electrode layer and the second transparent electrode layer; And a protective coating layer covering the second transparent electrode layer, wherein the protective coating layer has a single layer or multilayer structure formed using a sputtering technique or a chemical vapor deposition technique.

An electrochromic device manufacturing method according to an embodiment of the present invention includes depositing an electrochromic layer on a substrate, depositing an ion conductive layer on the electrochromic layer, depositing a counter electrode layer on the ion conductive layer, And depositing a transparent electrode layer on the counter electrode layer, and depositing a protective coating layer on the transparent electrode layer.

According to embodiments of the present invention, by adopting a protective coating layer covering the second transparent electrode layer, bonding of the glass substrate may be omitted, and the electrochromic laminate may be efficiently protected from an external environment. Further, since all the layers on the substrate are formed using a deposition technique, an electrochromic device can be manufactured using an in-line deposition apparatus, and thus, productivity can be improved.

1 is a schematic cross-sectional view illustrating an electrochromic device according to an embodiment of the present invention.

2 is a schematic cross-sectional view of an in-line sputtering apparatus for manufacturing an electrochromic device according to an embodiment of the present invention.

3 is a schematic cross-sectional view of an in-line sputtering apparatus for manufacturing an electrochromic device according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The following embodiments are provided as examples in order to sufficiently convey the idea of the present invention to those skilled in the art to which the present invention pertains. Accordingly, the present invention is not limited to the embodiments described below and may be embodied in other forms. In addition, in the drawings, the width, length, and thickness of the component may be exaggerated for convenience. In addition, when one component is described as "above" or "on" another component, not only when each part is "directly above" or "directly" of another component, as well as each component and other components It includes a case where another component is interposed. The same reference numbers throughout the specification denote the same elements.

By adopting the protective coating layer, there is no need to bond the substrate on the second transparent electrode layer, and accordingly, the productivity of the electrochromic element can be improved, and the manufacturing cost can be reduced. Further, it is possible to improve the reliability of the electrochromic device by adopting a protective coating layer suitable for protecting the electrochromic laminate from the external environment. In addition, since the protective coating layer has a single layer or multilayer structure formed using sputtering technology or chemical vapor deposition technology, it is possible to provide an electrochromic device that can be manufactured in an in-situ process using in-line deposition technology. .

The protective coating layer may include at least one oxide film selected from the group consisting of a silicon nitride film, a silicon oxide film, a silicon oxynitride film, an aluminum oxide film, a hafnium oxide film, or a manganese oxide film, for example, polyimide.

Meanwhile, the electrochromic device may further include a substrate in contact with the first transparent electrode layer. The substrate may be a transparent substrate, for example, a glass substrate or a polymer substrate.

The electrochromic laminate may include an electrochromic layer; A counter electrode layer; And an ion conductive layer disposed between the electrochromic layer and the counter electrode layer.

When a voltage is applied to the first transparent electrode layer and the second transparent electrode layer, electric charges move through the ion conductive layer between the counter electrode layer and the electrochromic layer, and thus, electrochromic discoloration occurs. The electrochromic layer and the counter electrode layer may exhibit electrochromic colors by a reduction reaction and an oxidation reaction, or an oxidation reaction and a reduction reaction, respectively. For example, when the electrochromic layer undergoes a reduction reaction, the counter electrode layer undergoes an oxidation reaction, and vice versa.

Materials used for the electrochromic layer include, for example, WO ₃ , NiO, NiWO, NIWNbO, MoO ₃ , Nb ₂ O ₅ , TiO ₂ , CuO, Ir ₂ O ₃ , Cr ₂ O ₃ , MnO ₂ , Mn ₂ O ₃ , V ₂ O ₅ , Ni ₂ O ₃ , Co ₂ O ₃ , SiO ₂ , Ta ₂ O ₅ , ZrO ₂ , or CeO ₂ . Materials used as counter electrode layers include, for example, WO ₃ , NiO, NiWO, NiWNBO, MoO ₃ , Nb ₂ O ₅ , TiO ₂ , CuO, Ir ₂ O ₃ , Cr ₂ O ₃ , MnO ₂ , Mn ₂ O ₃ , V ₂ O ₅ , Ni ₂ O ₃ , Co ₂ O ₃ , SiO ₂ , Ta ₂ O ₅ , ZrO ₂ , or CeO ₂ . Here, the stoichiometric ratio of each material is described, but it should be understood as including materials of non-stoichiometric ratio.

Meanwhile, the ion conductive layer includes ions moving to the electrochromic layer. The ions may include, for example, H+, Li+, D+, alkali metal ions or alkaline earth metal ions. In particular, the ion conducting layer may include hydrogen ions together with lithium ions. The ion conducting layer may be formed of, for example, LiWOx containing hydrogen ions.

Furthermore, the counter electrode layer or the electrochromic layer may include hydrogen ions together with lithium ions.

The electrochromic layer, the ion conductive layer, the counter electrode layer, the transparent electrode layer, and the protective coating layer are all formed using a vapor deposition technique, and techniques such as dispensing or bonding of a glass substrate are omitted.

The electrochromic layer, the ion conductive layer, the counter electrode layer, the transparent electrode layer, and the protective coating layer may be deposited in-situ using an in-line sputtering deposition equipment. Since the layers are deposited without vacuum breaking, defects in each layer can be reduced and productivity can be improved.

In an embodiment, the method of manufacturing an electrochromic device may further include depositing a transparent electrode layer on the substrate before depositing the electrochromic layer.

In another embodiment, the substrate may include a transparent electrode layer, and the electrochromic layer may be deposited on the transparent electrode layer.

Meanwhile, the method of manufacturing the electrochromic device may further include heat-treating the substrate on which the transparent electrode layer is deposited after depositing the transparent electrode layer. By heat treatment of the transparent electrode layer, the specific resistance of the transparent electrode layer can be lowered.

The method of manufacturing an electrochromic device may further include heat-treating the substrate after depositing the counter electrode layer and before depositing the transparent electrode layer. By heat-treating the counter electrode layer, pinholes in the counter electrode layer can be reduced, and accordingly, the memory effect can be improved.

Further, when depositing the counter electrode layer, a bias voltage may be applied to the substrate side. Accordingly, the counter electrode layer can be formed with high density, and pinholes in the counter electrode layer can be reduced.

Meanwhile, when depositing the ion conductive layer, H2 gas is supplied together with a carrier gas, and a flow rate ratio (carrier gas/H2 gas) of the carrier gas and the H2 gas may be in the range of 90/10 to 98/2.

By supplying H2 gas together with the carrier gas, hydrogen ions can be introduced into the ion conductive layer through a deposition process, and thus, hydrogen ions can be used as additional ions for electrochromic, thereby improving electrochromic efficiency.

Meanwhile, the counter electrode layer may include a Li layer inside or on the surface of the layer. Li ions can be replenished by including the Li layer in the counter electrode layer.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

Referring to FIG. 1, the electrochromic device may include a substrate 21, a first transparent electrode layer 23, an electrochromic laminate 30, a second transparent electrode layer 31, and a protective coating layer 33. The electrochromic laminate 30 may include an electrochromic layer 25, an ion conductive layer 27 and a counter electrode layer 29.

The substrate 21 is a transparent substrate and is not particularly limited as long as it is a substrate on which the electrochromic laminate 30 can be deposited. For example, the substrate 21 may be a glass substrate, but is not limited thereto.

The first transparent electrode layer 23 may be formed of a transparent conductive oxide film, for example, an indium tin oxide film (ITO). The first transparent electrode layer 23 may be deposited on the substrate 21 using a sputtering device, and may be heat treated by a heater after being deposited on the substrate 21. The first transparent electrode layer 23 may be deposited to a thickness of, for example, 500 to 5000 Å.

The electrochromic layer 25 is converted from a colorless layer to a colored layer by an oxidation or reduction reaction. As a material having such an electrochromic property, for example, WO ₃ , NiO, NiWO, NIWNbO, MoO ₃ , Nb ₂ O ₅ , TiO ₂ , CuO, Ir ₂ O ₃ , Cr ₂ O ₃ , MnO ₂ , Mn ₂ O ₃ , V ₂ O ₅ , Ni ₂ O ₃ , Co ₂ O ₃ , SiO ₂ , Ta ₂ O ₅ , ZrO ₂ , or CeO ₂ . Here, the stoichiometric ratio of each material is described, but it should be understood as including materials of non-stoichiometric ratio.

The electrochromic layer 25 may be deposited on the first transparent electrode layer 23 using a deposition technique, for example, a sputtering technique. The electrochromic layer 25 may be deposited to a thickness of, for example, 1000 to 10000 Å. During deposition of the electrochromic layer 25 using a sputtering technique, H2 gas may be supplied with a carrier gas such as Ar, and thus hydrogen ions may be introduced into the electrochromic layer 25. Further, a layer of a material used as a mobile ion, for example, a Li layer may be added to the surface of the electrochromic layer 25.

On the other hand, the ion conductive layer 27 is a layer that conducts ions between the electrochromic layer 25 and the counter electrode layer 29 when a voltage is applied to both ends of the electrochromic laminate 30. The ion conductive layer 27 may be formed of a material containing mobile ions. The mobile ions may include, for example, H+, Li+, D+, alkali metal ions or alkaline earth metal ions. The ion conductive layer 27 may be formed of, for example, LiWOx, for example, Li2WO4, and further, may include hydrogen ions.

The ion conductive layer 27 may be deposited using a deposition technique, such as a sputtering technique. The ion conductive layer 27 may be formed to a thickness of, for example, 300 to 3000 Å. During deposition of the ion conductive layer 27 using a sputtering technique, H2 gas may be supplied with a carrier gas such as Ar, and thus hydrogen ions may be introduced into the ion conductive layer 27. The flow ratio (Ar/H2) of Ar and H2 gas may be in the range of 90/10 to 98/2.

The counter electrode layer 29 is converted from a colorless layer to a colored layer by an oxidation or reduction reaction. The counter electrode layer 29 has electrochromic characteristics through a reaction opposite to that of the electrochromic layer 25. Materials used as the counter electrode layer 29 include, for example, WO ₃ , NiO, NiWO, NIWNbO, MoO ₃ , Nb ₂ O ₅ , TiO ₂ , CuO, Ir ₂ O ₃ , Cr ₂ O ₃ , MnO ₂ , Mn ₂ O ₃ , V ₂ O ₅ , Ni ₂ O ₃ , Co ₂ O ₃ , SiO ₂ , Ta ₂ O ₅ , ZrO ₂ , or CeO ₂ . Here, the stoichiometric ratio of each material is described, but it should be understood as including materials of non-stoichiometric ratio.

The counter electrode layer 29 may be deposited on the ion conductive layer 27 using a deposition technique, for example, a sputtering technique. The counter electrode layer 29 may be deposited to a thickness of, for example, about 500 to 5000 Å. When depositing the counter electrode layer 29, a bias voltage may be applied to the substrate 21 in addition to the voltage applied to the target. By applying a bias voltage to the substrate 21 side, a high-density counter electrode layer 29 can be formed, and accordingly, pinholes in the counter electrode layer can be reduced.

On the other hand, the pinhole in the counter electrode layer 29 reduces the memory effect of the electrochromic element. Accordingly, by depositing the counter electrode layer 29 at a high density to reduce pinholes, the memory effect of the electrochromic device can be improved. Further, in order to reduce pinholes in the counter electrode layer 29, the counter electrode layer 29 may be deposited at a relatively high temperature, and after the counter electrode layer 29 is deposited, heat treatment may be performed at a temperature of about 100 to 300°C. May be.

During deposition of the counter electrode layer 29 using a sputtering technique, H2 gas may be supplied along with a carrier gas such as Ar, and thus hydrogen ions may be introduced into the counter electrode layer 29. Introduction of hydrogen ions improves the electrochromic efficiency.

Further, a layer of a material used as moving ions, for example, a Li layer may be added when the counter electrode layer 29 is deposited. In addition, a layer of a material used as moving ions, for example, a Li layer, may be added to the surface of the counter electrode layer 29. The Li layer increases the life of the electrochromic device by supplying Li ions.

Meanwhile, the second transparent electrode layer 31 may be formed of a transparent conductive oxide film, for example, an indium tin oxide film (ITO) or an indium gallium zinc oxide film (IGZO). The second transparent electrode layer 31 may be deposited on the counter electrode layer 29 using a sputtering device, and may be heat treated by a heater. The second transparent electrode layer 31 may be deposited to a thickness of, for example, 500 to 5000 Å.

The protective coating layer 33 protects the electrochromic element from the external environment. The protective coating layer 33 protects the electrochromic laminate from moisture, and further protects the electrochromic element from external physical forces to prevent defects such as scratching.

The protective coating layer 33 may be deposited on the second transparent electrode layer 31 using a sputtering technique or a chemical vapor deposition technique. The protective coating layer 33 may include, for example, an oxide film or polyimide of at least one of a silicon nitride film, a silicon oxide film, a silicon oxynitride film, an aluminum oxide film, a hafnium oxide film, or a manganese oxide film.

The protective coating layer 33 may be formed as a single layer, but is not limited thereto, and may be formed as multiple layers. By adopting the protective coating layer 33, it is possible to omit the conventional glass substrate, thereby reducing the weight of the product. Further, since the bonding process of the glass substrate can be omitted, productivity is improved and manufacturing cost can be reduced. Moreover, the protective coating layer 33 does not contain a curable resin that requires a separate curing process other than the deposition process, and thus, a mass production process currently used in the liquid crystal display production process can be used, which is suitable for product enlargement. Furthermore, a flexible electrochromic device may be provided by using a relatively thin protective coating layer 33 instead of a glass substrate.

In the electrochromic device according to the present embodiment, a voltage is applied to the first transparent electrode layer 23 and the second transparent electrode layer 31. When a voltage is applied, charges, in particular, ions move between the counter electrode layer 29 and the electrochromic layer 25 through the ion conducting layer 27, and thus, electrochromic discoloration occurs. The electrochromic layer 25 and the counter electrode layer 29 may exhibit electrochromic discoloration by a reduction reaction and an oxidation reaction, or an oxidation reaction and a reduction reaction, respectively.

The electrochromic element according to the present embodiment may be used in a smart window for a building, a mirror (rear mirror, side mirror, etc.) for an automobile, a sunroof for a vehicle, or a display device, like the conventional electrochromic element. Moreover, the electrochromic device according to the present embodiment may be applied to glasses for vision correction, augmented reality smart glasses, or information smart glasses for information display. That is, the electrochromic element may be applied to eyeglasses for vision correction and used as sunglasses, and may be applied to augmented reality smart glasses or information smart glasses to perform a light shutter function.

The base substrate of glasses for applying the electrochromic element, or the base substrate of smart glasses is a transparent material, for example, glass, or polyethylene naphthalate (PEN), polyimide (PI). , Aryl diglycol carbonate (ADC: allyl diglycol carboanate; ex. CR39) system, Tribex system, acrylic system, polycarbonate (PC: Polycarbonate) system, polyurethane (PU: polyurethane) system, polyethylene It may be a polymer-based material such as terephthalate (PET, polyethylene terephthalate)-based or episulfide-based material.

2, the in-line sputtering apparatus includes a stage 110, a carrier 51, a target holder 120, a plurality of targets T1, T2, T3, T4, T5, and a heater 125. I can.

The stage 110 provides a means of movement through which the carrier 51 can move. The carrier 51 moves through the stage 110 to a chamber in which a deposition process is performed in each process step.

The target holder 120 supports the targets T1 to T5. The target holder 120 may also support the heater 125.

A series of targets T1, T2, T3, T4, T5 are arranged in-line. Five targets T1, T2, T3, T4, T5) are shown in order, but fewer or more targets may be placed in order. Targets (T1, T2, T3, T4, T5) may be disposed in the chamber, respectively, and when sputtering deposition is completed in one target, the substrate 21 is a chamber with the target of the next process by the carrier 51 Moving on to, the following deposition process is carried out continuously. Thus, the in-line sputtering apparatus can deposit thin films in-situ without vacuum breaking.

For example, the substrate 21 on which the first transparent electrode layer 23 is deposited may be disposed under the target T1 in the in-line sputtering apparatus. The target T1 is, for example, a target for depositing the electrochromic layer 25, and may be, for example, a tungsten or tungsten oxide target. A tungsten oxide film may be deposited by directly sputtering tungsten oxide, or after sputtering tungsten, oxygen may be supplied to oxidize the deposited tungsten.

During deposition of the electrochromic layer 25, H ₂ gas may be introduced along with a carrier gas. When deposition of the electrochromic layer 25 is completed, the substrate 21 moves to the chamber where the target T2 is located.

The target T2 is for forming the ion conducting layer 27 and may be a target including moving ions. The target T2 may be, for example, a Li or Li ₂ WO ₄ target. When the electrochromic layer 25 is a tungsten oxide film, a thin layer of Li is deposited on the surface of the electrochromic layer 25 to form an ion conductive layer 27 of LiWOx.

The ion conducting layer 27 may be deposited at a relatively higher temperature compared to other layers. Further, a bias voltage may be added to the substrate 21 while depositing the ion conductive layer 27.

After the ion conductive layer 27 is deposited, the substrate 21 is moved to the chamber where the target T3 is located to deposit the counter electrode layer 29. The target T3 may include the same material as the counter electrode layer 29 or may be a metal material of the counter electrode layer 29. For example, the target T3 may be a Ni target, and a Ni layer may be deposited on the ion conductive layer 27 and oxidized to form a counter electrode layer 29 such as NiO.

After the counter electrode layer 29 is formed, the substrate 21 may move to the chamber in which the target T4 is located. The target T4 may be, for example, a Li target, and a Li layer may be added to the surface of the counter electrode layer 29 by using the target T4. In order to form the Li layer inside the counter electrode layer 29, a target for further depositing the counter electrode layer 29 may be added subsequent to the target T4.

After the counter electrode layer 29 is deposited, the substrate 21 may move to the chamber in which the target T5 is located to deposit the second transparent electrode layer 31. The target T5 may be a transparent conductive oxide, for example, an ITO target. After the second transparent electrode layer 31 is deposited, heat treatment may be performed on the substrate 21, and for this purpose, a heater 125 may be used.

Meanwhile, although not shown, a target for depositing the protective coating layer 33 may be provided, and the substrate 21 on which the heat treatment has been performed moves to the chamber for depositing the protective coating layer 33 so that the protective coating layer 33 Can be deposited.

According to the present embodiment, the electrochromic laminate 30, the second transparent electrode layer 31, and the protective coating layer 33 may be collectively deposited using an in-line sputtering device, and accordingly, the electrochromic element Productivity is dramatically improved.

Further, hydrogen ions may be introduced into the electrochromic laminate 30 by supplying hydrogen gas while the electrochromic layer 25, the ion conductive layer 27, or the counter electrode layer 29 is deposited. Source ions induce electrochromic ions together with metal transfer ions such as Li ions, thereby improving electrochromic efficiency.

Further, while depositing the counter electrode layer 29 using an in-line sputtering apparatus, the chamber temperature is relatively high, or a bias voltage is applied to the substrate 21, or after deposition is completed, the counter electrode layer ( By heat treatment 29), pinholes in the counter electrode layer 29 can be reduced, and thus, the memory effect can be improved.

Meanwhile, in the present embodiment, it is described that the substrate 21 on which the first transparent electrode layer 23 is formed is supplied to the in-line sputtering apparatus, but is not limited thereto. For example, a target for depositing the first transparent electrode layer 23 may be disposed, and before the electrochromic layer 23 is deposited, the first transparent electrode layer 23 is in-line on the substrate 21 It may also be deposited in a sputtering device.

Referring to FIG. 3, the in-line sputtering apparatus according to the present embodiment is substantially similar to that described with reference to FIG. 2, except that a heater 135 is additionally disposed between targets.

For example, after the electrochromic layer 25 and the ion conductive layer 27 are deposited using the target (T1) and the target (T2), the ion conductive layer 27 is heat-treated using the heater 135. In addition, after the counter electrode layer 29 is deposited using the target T3, heat treatment may be performed using the heater 135. Furthermore, heat treatment may be performed even after the Li layer is deposited on the counter electrode layer 29 using the target T4, and the heat treatment may be performed even after the second transparent electrode layer 31 is deposited. In addition, when a target for depositing the first transparent electrode layer 23 is disposed, heat treatment is performed on the first transparent electrode layer 23 before depositing the electrochromic layer 25 even after the first transparent electrode layer 23 is deposited. Can be done.

Therefore, heat treatment can be performed on each layer using the heater 135, thereby providing thin film layers having good film quality.

In the above-described embodiments, the substrate 21 may be a base substrate of glasses or smart glasses, or after the electrochromic element is formed on the substrate 21, it is peeled off with or from the substrate 21. It can also be attached to the base substrate of glasses or smart glasses.

Although various embodiments of the present invention have been described above, the present invention is not limited to these embodiments.

Claims

A first transparent electrode layer;

A second transparent electrode layer disposed on the first transparent electrode layer;

An electrochromic laminate disposed between the first transparent electrode layer and the second transparent electrode layer; And

Including a protective coating layer (passivation coating layer) covering the second transparent electrode layer,

The protective coating layer is an electrochromic device having a single-layer or multi-layer structure formed using a sputtering technique or a chemical vapor deposition technique.
The method according to claim 1,

The protective coating layer is an electrochromic device comprising at least one oxide film or polyimide selected from the group consisting of a silicon nitride film, a silicon oxide film, a silicon oxynitride film, an aluminum oxide film, a hafnium oxide film, or a manganese oxide film.
The method according to claim 1,

Electrochromic device further comprising a substrate in contact with the first transparent electrode layer.
The method of claim 3,

The electrochromic laminate,

Electrochromic layer;

A counter electrode layer; And

An electrochromic element comprising an ion conductive layer disposed between the electrochromic layer and the counter electrode layer.
The method of claim 4,

The ion conductive layer is an electrochromic device including hydrogen ions together with lithium ions.
The method of claim 5,

The counter electrode layer or the electrochromic layer is an electrochromic device comprising hydrogen ions together with lithium ions.
Depositing an electrochromic layer on the substrate,

Depositing an ion conductive layer on the electrochromic layer,

Depositing a counter electrode layer on the ion conductive layer,

Depositing a transparent electrode layer on the counter electrode layer,

Electrochromic device manufacturing method comprising depositing a protective coating layer on the transparent electrode layer.
The method of claim 7,

The electrochromic layer, the ion conductive layer, the counter electrode layer, the transparent electrode layer, and the protective coating layer are deposited in-situ using an in-line sputtering deposition equipment.
The method of claim 7,

Before depositing the electrochromic layer, the method of manufacturing an electrochromic device further comprising depositing a transparent electrode layer on the substrate.
The method of claim 7,

The substrate includes a transparent electrode layer,

The electrochromic layer is deposited on the transparent electrode layer.
The method of claim 7,

After depositing the transparent electrode layer, an electrochromic device manufacturing method further comprising heat-treating the substrate on which the transparent electrode layer is deposited.
The method of claim 11,

After depositing the counter electrode layer, the method of manufacturing an electrochromic device further comprising heat-treating the substrate before depositing the transparent electrode layer.
The method of claim 7,

When the counter electrode layer is deposited, a bias voltage is applied to the substrate side.
The method of claim 7,

When depositing the ion conductive layer, H2 gas is supplied together with a carrier gas, and the flow rate ratio (carrier gas/H2 gas) of the carrier gas and the H2 gas is in the range of 90/10 to 98/2.
The method of claim 7,

The counter electrode layer includes a Li layer on the surface of the electrochromic device manufacturing method.