KR101456168B1 - Flexible electrochromic device and method of manufacturing the same - Google Patents

Abstract

The present invention suggests a flexible electrochromic device and a manufacturing method thereof. The flexible electrochromic device includes: first and second substrates which are separated, a plurality of first and second grooves which are formed on the facing sides of the first and second substrates respectively, first and second electrodes which are formed on the sides of the first and second substrates respectively, and a plurality of electrochromic structures which are formed between the first and second electrodes by interposing the first and second grooves.

Description

[0001] Flexible electrochromic device and method for manufacturing same [0002]

The present invention relates to an electrochromic device, and more particularly, to a flexible electrochromic device capable of improving flexibility and a method of manufacturing the same.

An electrochromic device is a device in which a discoloration substance is stimulated by an external stimulus such as electricity, a chemical change occurs physically in a molecular structure, and a discoloring effect occurs visually. The electrochromic device is provided such that a first electrode formed on a first substrate and a second electrode formed on a second substrate face each other, and an ion storage layer, an electrolyte layer and an electrochromic layer are laminated between the first and second electrodes . When a potential difference is generated between the first electrode and the second electrode, the electrochromic device moves ions or electrons contained in the electrolyte layer to the inside of the electrochromic layer to perform an oxidation / reduction reaction, thereby changing the color visibly or changing the color Is used. For example, when an electric current flows from the electrochromic layer to the ion storage layer, the electrochromic layer is colored, and when an electric current flows in the opposite direction, discoloration may occur in the electrochromic layer. Of course, depending on the material of the electrochromic layer, the coloring and decoloring reaction may occur in the current flow in the opposite direction.

Such an electrochromic device is widely used as a smart sindow that utilizes light transmission characteristics, a room mirror for an automobile, and a display device. In addition, the electrochromic device needs to be manufactured so as to be flexible in consideration of the speed at which discoloration or discoloration occurs, that is, the response speed is important, and the usability and ease of use are taken into consideration. An example of a flexible electrochromic device is disclosed in Korean Patent No. 10-1109253.

However, the conventional electrochromic device has a disadvantage in that the response speed is slow because a plurality of layers are formed between the first and second substrates to have a size corresponding to the size of the substrate. Further, since a plurality of layers are formed over the entire surface between the first and second substrates, flexibility is low.

The present invention provides a flexible electrochromic device capable of improving flexibility and response speed and a method of manufacturing the same.

The present invention provides a flexible electrochromic device capable of improving flexibility and response speed by processing a substrate and forming a plurality of layers between the substrates in a predetermined pattern spaced apart from each other by a predetermined distance, and a method of manufacturing the same.

According to one aspect of the present invention, a flexible electrochromic device includes: first and second substrates spaced apart from each other; A plurality of first and second grooves respectively formed on one surface of the first substrate and the second substrate facing each other; First and second electrodes respectively formed on the one surface of the first and second substrates; And a plurality of electrochromic structures of a cell structure formed between the first and second electrodes and sandwiching the first and second grooves.

The first and second grooves are respectively formed at the same position on one surface of the first and second substrates.

The first and second grooves are formed in a line shape in at least one direction or in a dot shape at a predetermined distance.

The first and second grooves are formed to a depth of 2% to 60% of the thickness of the first and second substrates.

The electrochromic structure includes an ion storage layer, an electrolyte layer, and an electrochromic layer.

And an air gap formed between the electrochromic structures.

According to another aspect of the present invention, there is provided a method of manufacturing a flexible electrochromic device, comprising: providing a first substrate and a second substrate; Forming a plurality of first and second grooves on one surface of each of the first and second substrates, respectively; Forming first and second electrodes on the first surface of each of the first and second substrates, respectively; Forming a plurality of electrochromic structures spaced apart from each other on at least one of the first and second electrodes by a predetermined distance; And aligning and bonding the first and second substrates.

The first and second grooves are formed at the same position on one surface of the first and second substrates and are formed in a line shape spaced apart from each other by a predetermined distance in at least one direction or in a dot shape spaced apart by a predetermined distance.

The first and second grooves are formed to a depth of 2% to 60% of the thickness of the first and second substrates.

The electrochromic structure includes an ion storage layer, an electrolyte layer, and an electrochromic layer.

The electrochromic structure is formed in one region of the first substrate and in another region of the second substrate except for the one region.

After the first and second substrates are bonded, an air gap is formed between the electrochromic structures.

The flexible electrochromic device according to the embodiments of the present invention can improve the flexibility of the electrochromic device by forming a plurality of grooves in at least one direction on one surface of the two substrates facing each other. Further, since a plurality of electrochromic structures in which the ion storage layer, the electrolyte layer and the electrochromic layer are laminated are formed in a cell form with a plurality of grooves therebetween, flexibility can be further improved and the response speed can be improved. That is, it is possible to shorten the discoloration and discoloration time, and to improve the uniform discoloration and the driving stability.

1 is a cross-sectional view of a flexible electrochromic device according to an embodiment of the present invention.
2 to 5 are cross-sectional views illustrating a method of manufacturing a flexible electrochromic device according to an embodiment of the present invention.
6 to 9 are sectional views for explaining a method of manufacturing a flexible 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. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of other various forms of implementation, and that these embodiments are provided so that this disclosure will be thorough and complete, It is provided to let you know completely.

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

Referring to FIG. 1, there are provided first and second substrates 100 and 200 disposed on opposite sides of each other, a plurality of first and second substrates 100 and 200 spaced apart from each other by a predetermined distance, First and second electrodes 300 and 400 formed on two opposing surfaces of the first and second substrates 100 and 200 and the first and second electrodes 300 and 400, And an electrochromic structure 1000 in which an ion storage layer 500, an electrolyte layer 600, and an electrochromic layer 700 are laminated so as to have a predetermined gap in at least one direction.

The first and second substrates 100 and 200 may be made of a material having transparency and flexibility, for example, in the form of a rectangular plate having a predetermined thickness. The first and second substrates 100 and 200 are not particularly limited as long as they have transparency and flexibility. For example, the first and second substrates 100 and 200 may be formed of a material selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate, polystyrene, polyacrylic, polyethersulfone Polyether sulfone) can be used. A plurality of first and second grooves 110 and 210 having a predetermined depth are formed at predetermined intervals on the first and second substrates 100 and 200. Here, the first and second grooves 110 and 210 may be formed in a line shape in at least one direction, and may be formed in a dot shape while maintaining predetermined intervals. When the first and second grooves 110 and 210 are formed in a line shape, the first and second grooves 110 and 210 may be formed on at least one of the first and second substrates 100 and 200 in one direction and another direction orthogonal thereto. For example, the first and second grooves 110 and 210 are formed on the first and second substrates 100 and 200 at predetermined intervals in a predetermined direction, and are spaced apart from each other by a predetermined distance May be formed. Accordingly, the first and second grooves 110 and 120 are formed on the first and second substrates 100 and 200, for example, in the form of a lattice. At this time, the first and second grooves 110 and 120 are formed on one surface of the first and second substrates 100 and 200 facing each other, and are formed at the same position. An electrochromic structure 1000 in which the ion storage layer 500, the electrolyte layer 600, and the electrochromic layer 700 are laminated is formed in a region where the first and second grooves 110 and 210 are not formed . That is, a plurality of electrochromic structures 1000 may be formed spaced apart from each other by a width of the first and second grooves 110 and 210. The first and second grooves 110 and 210 are formed in the first and second substrates 100 and 200, respectively, thereby improving the flexibility of the first and second substrates 100 and 200. The first and second grooves 110 and 210 may be formed to have a depth of 2% to 60% of the thickness of the first and second substrates 100 and 200, for example. When the first and second grooves 110 and 120 are formed to a depth of less than 2% of the thickness of the first and second substrates 100 and 200, the increase in flexibility is small, and the first and second substrates 100, The first and second substrates 100 and 200 are damaged when the first and second grooves 110 and 120 are formed or the first and second substrates 100 and 200 are damaged after the electrochromic device is manufactured. Breakage problems such as tearing or breaking along the second grooves 110 and 120 may occur. The first and second grooves 110 and 210 may be formed by various methods. For example, the first and second grooves 110 and 210 may be formed by a method such as a photolithography process or a laser process. In addition, the first and second grooves 110 and 210 may have a cross-sectional shape of, for example, a V-shape having an inclination from the top to the bottom, or may be formed in a vertical shape.

The first and second electrodes 300 and 400 are formed on opposite surfaces of the first and second substrates 100 and 200, respectively. That is, the first and second electrodes 300 and 400 are formed on the first and second grooves 110 and 210 of the first and second substrates 100 and 200, respectively. Also, the first and second electrodes 300 and 400 may be formed along the step of the first and second grooves 110 and 210. That is, the first and second electrodes 300 and 400 may be formed to have a predetermined thickness so that the first and second grooves 110 and 210 are not embedded. The first and second electrodes 100 and 200 may be formed using a transparent conductive material such as indium tin oxide (ITO), florine-doped tin oxide (FTO), ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O ₃ , SnO ₂ -Sb ₂ O ₃ , and polythiophene-based materials.

The electrochromic structure 1000 includes a stacked ion storage layer 500, an electrolyte layer 600 and a electrochromic layer 700 and is formed to contact the first and second electrodes 300 and 400. That is, the electrochromic structure 1000 is formed between the first and second electrodes 300 and 400. For example, the ion storage layer 500 is in contact with the first electrode 300, 700 may be formed in contact with the second electrode 400. Of course, the electrochromic layer 700 may be in contact with the first electrode 300 and the ion storage layer 500 may be in contact with the second electrode 400. In addition, the electrochromic structure 1000 may be formed in an area where the first and second grooves 110 and 210 are not formed. For example, when a plurality of the first and second grooves 110 and 210 are formed on the first and second substrates 100 and 200 in one direction and the other direction orthogonal to each other, And 210 may be formed in a region where the plurality of electrochromic structures 1000 are spaced apart from each other. That is, the adjacent at least two electrochromic structures 1000, for example, four electrochromic structures 1000, are spaced apart from each other by a predetermined distance. Since the plurality of electrochromic structures 1000 are formed in the regions where the first and second grooves 110 and 210 are not formed, the response speed can be improved. In addition, an air gap 800 is formed between the electrochromic structures 1000. That is, an air gap 800 is formed between the first and second grooves 110 and 210 in the vertical direction between the electrochromic structures 1000 adjacent in the horizontal direction. Here, the width of the air gap 800 may correspond to the width of the first and second grooves 110 and 210. However, if the width of the air gap 800 is too large, that is, if the widths of the first and second grooves 110 and 210 are too large, an uncolored line or dot shape when the electrochromic structure 1000 is colored Can be seen. In addition, if the width of the air gap 800 is too small, the electrochromic structure 1000 of the adjacent cell structure can contact the electrochromic device when the electrochromic device is bent or rolled. Therefore, even when the electrochromic structure 1000 is colored, the uncolored area is not visible to the eye, and when the electrochromic structure 1000 is bent, the air gap 800, that is, 1 and the second grooves 110 and 210 may be formed. For example, the air gap 800 may be formed with a width of 30% or less with respect to the width of the electrochromic structure 1000.

The ion storage layer 500 is formed in contact with the first electrode 300 and stores ions having a polarity opposite to that of ions involved in the electrochromic reaction. In the ion storage layer 500, an ion storage material or an oxidation / reduction coloring material may be used to store a plurality of cations such as hydrogen ions, lithium ions, and the like. For example, the ion storage layer 500 may be formed using at least one selected from NiO, Cr ₂ O ₃ , MnO ₂ , Rh ₂ O ₃ , CoOx, Ir (OH) x and Fe ₂ O ₃ .

The electrolyte layer 600 may be formed by contacting one surface of the electrolyte layer 600 with the ion storage layer 500 and the other surface of the electrolyte layer 600 being in contact with the electrochromic layer 700 and using an ion-containing substance involved in the electrochromic reaction. For example, the electrolyte layer 600 is _{Ta 2 O 5, LiClO 4,} LiNbO 3, Li 3 + x PO 4 - x N x (LiPON), LiVO 3 / SiO 2 / Li 4 SiO 4 -Li 3 VO 4 (LVSO), LiPF ₆ , Li ₃ PO ₄ , and the like.

The electrochromic layer 700 may be formed by contacting one surface of the electrochromic layer 700 with the electrolyte layer 600 and contacting the other surface of the electrochromic layer 700 with the second electrode 400. The electrochromic layer 700 may be formed using an electrochromic material that changes color according to an electrical signal, and the electrochromic material may include an inorganic material and an organic material. As the inorganic material, a transition metal oxide which is deposited in a thin film form can be used. For example, at least one selected from WO ₃ , ZnO, NbO ₅ , V ₂ O ₅ , TiO ₂ , MoO ₃ and the like can be used. Organic electrochromic materials include viologen compounds, diphtalocyanine compounds, tetrathiafulvalene compounds, and the like. On the other hand, although organic compounds are disadvantageous in that they are decomposed into sunlight and can shorten their service life, they can be widely used because they can produce a desired color by appropriately mixing them.

As described above, in the electrochromic device according to the embodiment of the present invention, the plurality of grooves 110 and 210 are formed on one surface of the two substrates 100 and 200 facing each other, It is possible to improve flexibility. The electrochromic structure 1000 in which the ion storage layer 500, the electrolyte layer 600 and the electrochromic layer 700 are laminated is formed into a plurality of cells separated by a plurality of grooves 110 and 210 therebetween The flexibility can be further improved and the response speed can be improved. That is, since a plurality of the electrochromic structures 1000 are formed so as to be spaced apart from each other in a cell form, the response speed can be improved as compared with the case where the electrochromic structure is formed over the entire area of the substrate.

FIGS. 2 to 5 are sequentially sectional views illustrating a method of manufacturing a flexible electrochromic device according to an embodiment of the present invention. Referring to FIG.

Referring to FIG. 2, first and second substrates 100 and 200 having transparency and flexibility are provided. For this purpose, the first and second substrates 100 and 200 may be formed of, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate, polystyrene, polyacrylic, Polyether sulfone (PES), and the like. Here, the first and second substrates 100 and 200 may be made of the same material or may be made of different materials. First and second grooves 110 and 210 having a predetermined depth are formed at predetermined intervals on the first and second substrates 100 and 200, respectively. Here, the first and second grooves 110 and 210 may extend in at least one direction to form a line, or may be formed in a dot shape at a predetermined interval. When the first and second grooves 110 and 210 are formed in a line shape, the first and second grooves 110 and 210 are spaced apart from each other by a predetermined distance on one surface of the first and second substrates 100 and 200, And are formed in a plurality of directions orthogonal to each other. Accordingly, the first and second grooves 110 and 120 are formed on the first and second substrates 100 and 200, for example, in the form of a lattice. At this time, the first and second grooves 110 and 120 are formed at the same position when the first and second substrates 100 and 200 face each other. The first and second grooves 110 and 210 may be formed to a depth of 2% to 60% of the thickness of the first and second substrates 100 and 200, for example. The first and second grooves 110 and 210 may have a predetermined width and may have a width of 30% or less of the width of the region where the first and second grooves 110 and 210 are not formed. . Meanwhile, the first and second grooves 110 and 210 can be formed by various methods. For example, the first and second grooves 110 and 210 can be formed by a method such as a photolithography process or a laser process. When a photolithography process is used, a photoresist film is formed on the first and second substrates 110 and 210, and then a photolithography process using a predetermined mask is performed to form the first and second substrates 110 and 210, for example, The first and second substrates 110 and 210 are etched to a predetermined depth by using a predetermined etchant or etching gas so that the first and second grooves 110 and 210 are exposed Respectively.

Referring to FIG. 3, first and second electrodes 300 and 400 are formed on one surface of a first substrate 100 and a second substrate 200, respectively, where first and second grooves 110 and 210 are formed, respectively . At this time, the first and second electrodes 300 and 400 may be formed using a transparent conductive material, for example. Also, the first and second electrodes 300 and 400 may be formed along the step of the first and second grooves 110 and 210. That is, the first and second electrodes 300 and 400 may be formed so that the first and second grooves 110 and 210 are not embedded. Then, the electrochromic structure 1000 is formed on the first and second electrodes 300 and 400. [ The electrochromic structure 1000 may include an ion storage layer 500, an electrolyte layer 600, and a electrochromic layer 700. At this time, the electrochromic structure 1000 is formed on the first and second electrodes 300 and 400 in the reverse order. That is, an electrochromic structure 1000 is formed on the first electrode 300 in the order of the ion storage layer 500, the electrolyte layer 600, and the electrochromic layer 700, and on the second electrode 400, The electrochromic structure 1000 is formed in the order of the layer 700, the electrolyte layer 600, and the ion storage layer 500. Since the second substrate 200 is bonded on the first substrate 100 after the bonding, the ion storage layer 500, the electrolyte layer 600, and the electrochromic layer 700 are bonded from the first substrate 100 on the lower side, As shown in FIG. Then, the electrochromic structure 1000 is patterned to form a plurality of cells spaced apart from each other. That is, a photoresist film (not shown) is formed on the electrochromic structure 1000 and patterned so as to expose at least regions corresponding to the first and second trenches 110 and 210 by a photolithography and a development process using a predetermined mask The electrochromic structure 1000 can be etched. In addition, the electrochromic structure 1000 may be formed on the first and second substrates 100 and 200 in at least one region and in two different regions. For example, an electrochromic structure 1000 is formed on an odd-numbered line on a first substrate 100 in one direction, and an electrochromic structure 1000 is formed on an even-numbered line on a second substrate 200. At this time, the electrochromic structures 1000 formed on the odd-numbered and even-numbered lines in one direction on the first and second substrates 100 and 200 are formed in a cell shape with the adjacent electrochromic structures 1000 spaced apart from each other by a predetermined distance .

Referring to FIG. 4, a conductive adhesive (not shown) is applied to at least one of the first and second substrates 100 and 200. For example, a conductive adhesive is applied to the first electrode 300 and the electrochromic layer 700 of the first substrate 100. The second substrate 200 is formed on the first substrate 100 so that one surface of the second substrate 200 on which the electrochromic structure 1000 is formed faces the first surface of the first substrate 100 on which the electrochromic structure 1000 is formed. 200). At this time, the first grooves 110 formed on the first substrate 100 and the second grooves 210 formed on the second substrate 200 align with each other.

Referring to FIG. 5, the first substrate 100 and the second substrate 200 are bonded. A plurality of electrochromic structures 1000 are formed in a cell shape between the first and second grooves 110 and 210 and an electrochromic device in which an air gap 800 is formed between the electrochromic structures 1000 .

6 to 9 are sectional views sequentially illustrating a method of manufacturing a flexible electrochromic device according to another embodiment of the present invention.

Referring to FIG. 6, first and second substrates 100 and 200 having transparency and flexibility are provided, and first and second grooves 110 and 200 having a predetermined depth are formed on the first and second substrates 100 and 200, 210 are formed at predetermined intervals. For example, the first and second grooves 110 and 210 may be formed on one surface of the first and second substrates 100 and 200 at a predetermined interval in one direction and the other direction perpendicular to each other. The first and second grooves 110 and 210 may be formed to a depth of 2% to 60% of the thickness of the first and second substrates 100 and 200, for example. The first and second grooves 110 and 210 may have a predetermined width and may have a width of 30% or less of the width of the region where the first and second grooves 110 and 210 are not formed. .

Referring to FIG. 7, first and second electrodes 300 and 400 are formed on one surface of a first substrate 100 and a second substrate 200, respectively, where first and second grooves 110 and 210 are formed, respectively . At this time, the first and second electrodes 300 and 400 may be formed using a transparent conductive material, for example. Also, the first and second electrodes 300 and 400 may be formed along the step of the first and second grooves 110 and 210. Next, an electrochromic structure 1000 is formed on one of the first and second electrodes 300 and 400. For example, the electrochromic structure 1000 can be formed by laminating the ion storage layer 500, the electrolyte layer 600, and the electrochromic layer 700 on the first electrode 300. Then, the electrochromic structure 1000 is patterned to form a plurality of cells spaced apart from each other. That is, a photoresist film (not shown) is formed on the electrochromic structure 1000 and patterned so as to expose at least a region corresponding to the first groove 110 in a photolithography process using a predetermined mask, ) Can be etched.

Referring to FIG. 8, a conductive adhesive (not shown) is applied to at least one of the first and second substrates 100 and 200. For example, a conductive adhesive is applied on the second electrode 400 of the second substrate 200. A second substrate 400 is formed on the second substrate 200 so as to face the first surface of the first substrate 100 on which the electrochromic structure 1000 of the first substrate 100 is formed. 200). At this time, the first grooves 110 formed on the first substrate 100 and the second grooves 210 formed on the second substrate 200 align with each other.

Referring to FIG. 9, the first substrate 100 and the second substrate 200 are bonded. A plurality of electrochromic structures 1000 are formed in a cell shape between the first and second grooves 110 and 210 and an electrochromic device in which an air gap 800 is formed between the electrochromic structures 1000 .

Although the technical idea of the present invention has been specifically described according to the above embodiments, it should be noted that the above embodiments are for explanation purposes only and not for the purpose of limitation. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention.

100, 200: first and second substrates 110, 210: first and second grooves
300, 400: first and second electrodes 500: ion storage layer
600: electrolyte layer 700: electrochromic layer
800: air gap 1000: electrochromic structure

Claims (12)

First and second substrates spaced apart from each other;
A plurality of first and second grooves respectively formed on one surface of the first substrate and the second substrate facing each other;
First and second electrodes respectively formed on the one surface of the first and second substrates; And
And a plurality of electrochromic structures of a cell structure formed between the first and second electrodes and sandwiching the first and second grooves therebetween.
The flexible electrochromic device of claim 1, wherein the first and second grooves are respectively formed at the same position on one surface of the first and second substrates.
The flexible electrochromic device according to claim 2, wherein the first and second grooves are formed in a line shape in at least one direction or are formed in a dot shape at a predetermined interval.
4. The flexible electrochromic device of claim 3, wherein the first and second grooves are formed at a depth of 2% to 60% of the thickness of the first and second substrates.
The flexible electrochromic device of claim 1, wherein the electrochromic structure comprises an ion storage layer, an electrolyte layer, and an electrochromic layer.
The flexible electrochromic device of claim 1, further comprising an air gap formed between the electrochromic structures.
Providing a first substrate and a second substrate, respectively;
Forming a plurality of first and second grooves on one surface of each of the first and second substrates, respectively;
Forming first and second electrodes on the first surface of each of the first and second substrates, respectively;
Forming a plurality of electrochromic structures spaced apart from each other on at least one of the first and second electrodes by a predetermined distance; And
And aligning the first and second substrates after the first and second substrates are aligned.
[7] The method of claim 7, wherein the first and second grooves are formed at the same position on one surface of the first and second substrates, respectively, and are formed in a line shape spaced apart from each other by a predetermined distance in at least one direction, Wherein the flexible electrochromic device is formed of a flexible electrochromic device.
9. The method of claim 8, wherein the first and second grooves are formed to a depth of 2% to 60% of the thickness of the first and second substrates.
8. The method of claim 7, wherein the electrochromic structure comprises an ion storage layer, an electrolyte layer, and an electrochromic layer.
11. The method of claim 10, wherein the electrochromic structure is formed in one region of the first substrate and is formed in another region of the second substrate except for the one region.
8. The method of claim 7, wherein an air gap is formed between the first and second substrates and between the electrochromic structures.

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