Smart mirror device using surface roughness difference of dry laminated thin film, and manufacturing method therefor

Abstract

A smart mirror device is provided. The smart mirror device comprises: a first electrode and a second electrode disposed to be opposite to each other; an electrochromic layer which is disposed between the first electrode and the second electrode and which includes an antimony-doped tin oxide (ATO); and an electrolyte which is disposed between the second electrode and the electrochromic layer, and in which a first base electrolyte including silver (Ag), a second base electrolyte including bromine (Br) and a solvent are mixed, wherein voltage applied to the electrochromic layer is controlled such that the movement of silver ions (Ag+) in the electrolyte is controlled, and thus any one mode from among a transparent mode for transmitting incident light, a black mode for blocking incident light and a mirror mode for reflecting incident light can be selectively implemented.

Description

Smart mirror element utilizing the difference in surface roughness of dry laminated thin film and its manufacturing method.

[0001] The present invention relates to a smart mirror device utilizing the difference in surface roughness of a dry-laminated thin film and a method for manufacturing the same.

[0002] Electrochromism is a phenomenon in which the color of a material changes reversibly depending on the direction of the electric field when a voltage is applied. A material whose optical properties can be reversibly changed by an electrochemical redox reaction with this characteristic is called an electrochromic material. These electrochromic materials have the characteristic of not showing color when no electrical signal is applied from the outside, but showing color when an electrical signal is applied, or conversely, showing color when no signal is applied from the outside, but disappearing color when a signal is applied.

[0003] Electrochromic devices utilize the phenomenon of reversible color changes in electrochromic materials due to an oxidation-reduction reaction triggered by an externally applied voltage. These electrochromic devices not only ensure visibility but also allow users to actively adjust their transmittance, enabling a variety of color variations. This has broad applications, including smart windows, car rearview mirrors, laptops, mobile phones, and decorative designs. Accordingly, various technologies related to electrochromic devices are being researched.

[0004] For example, Korean Patent Publication No. 10-2017-0142473 (Application No. 10-2016-0075980, Applicant: Jeong Sun-seong) discloses a conductive structure including a substrate, a first metal oxide layer provided on the substrate, a first metal layer provided on the first metal oxide layer and including silver, a second metal oxide layer provided on the first metal layer, and a second metal layer provided on the second metal oxide layer, wherein the metal of the second metal layer has a lower oxidation level than silver, and a conductive structure including the same and an electrochromic element including the same. In addition, various technologies related to electrochromic elements are continuously being researched and developed.

[0005] The technical problem to be solved by the present invention is to provide a smart mirror device and a manufacturing method thereof in which the surface roughness of an electrochromic layer is controlled according to the size of ATO powder used in manufacturing the electrochromic layer.

[0006] Another technical problem to be solved by the present invention is to provide a smart mirror device and a manufacturing method thereof in which electrochemical characteristics and transmittance to incident light are controlled according to the surface roughness of an electrochromic layer.

[0007] Another technical problem to be solved by the present invention is to provide a smart mirror device and a method for manufacturing the same in which the problem of cracks occurring inside the electrochromic layer is significantly reduced.

[0008] Another technical problem that the present invention seeks to solve is to provide a smart mirror device and a method for manufacturing the same, which significantly reduces environmental pollution problems.

[0009] Another technical problem that the present invention seeks to solve is to provide a smart mirror element and a manufacturing method thereof that are easily applicable to large-area processes.

[0010] The technical problems to be solved by the present invention are not limited to those described above.

[0011] To solve the above-described technical problems, the present invention provides a smart mirror device.

[0012] According to one embodiment, the smart mirror element comprises a first electrode and a second electrode disposed opposite to each other, an electrochromic layer disposed between the first electrode and the second electrode and including antimony-doped tin oxide (ATO), and an electrolyte disposed between the second electrode and the electrochromic layer and including a first base electrolyte including silver (Ag), a second base electrolyte including bromine (Br), and a solvent, wherein a voltage applied to the electrochromic layer is controlled to cause silver ions (Ag) in the electrolyte to be mixed. + ) can be selectively implemented in one of the following modes: a transparent mode that transmits incident light, a black mode that blocks incident light, and a mirror mode that reflects incident light.

[0013] According to one embodiment, when a negative voltage is applied to the electrochromic layer, silver ions (Ag) in the electrolyte + ) can be implemented in the black mode by moving to the electrochromic layer.

[0014] According to one embodiment, when a positive (+) voltage is applied to the electrochromic layer, silver ions (Ag) in the electrolyte + ) can be implemented in the mirror mode by moving to the second electrode.

[0015] According to one embodiment, when no voltage is applied to the electrochromic layer, silver ions (Ag) in the electrolyte + ) can be implemented in the above transparent mode by not moving.

[0016] According to one embodiment, the electrochemical characteristics and transmittance to incident light of the smart mirror element may be selectively controlled depending on the surface roughness of the electrochromic layer.

[0017] According to one embodiment, when the surface roughness of the electrochromic layer has an Ra value of 85 nm or more, the electrochemical characteristics of the smart mirror element may be improved.

[0018] According to one embodiment, when the surface roughness of the electrochromic layer has an Ra value of 20 nm or less, the transmittance of the smart mirror element to incident light may be improved.

[0019] According to one embodiment, when implemented in either of the black mode and the mirror mode, the transmittance for incident light in the wavelength range of 300 nm to 1200 nm may be 0%.

[0020] According to one embodiment, the electrochromic layer may have a thickness of 400 nm to 500 nm.

[0021]

[0022] To solve the above-described technical problems, the present invention provides a method for manufacturing a smart mirror element.

[0023] According to one embodiment, the method for manufacturing the smart mirror element may include the steps of preparing a first electrode, forming an electrochromic layer including antimony-doped tin oxide (ATO) on the first electrode, joining the first electrode and a second electrode on which the electrochromic layer is formed so that the electrochromic layer is disposed therebetween, preparing an electrolyte in which a first base electrolyte including silver (Ag), a second base electrolyte including bromine (Br), and a solvent are mixed, and injecting the electrolyte between the second electrode and the electrochromic layer.

[0024] According to one embodiment, the electrochromic layer may be formed by a dry lamination method of spraying antimony-doped tin oxide (ATO) onto the first electrode.

[0025] According to one embodiment, the pressure at which the antimony-doped tin oxide (ATO) is sprayed onto the first electrode may be controlled depending on the size of the antimony-doped tin oxide (ATO).

[0026] According to one embodiment, when the antimony-doped tin oxide (ATO) has a micro (μm) size, it may be sprayed onto the first electrode at a relatively high pressure, and when the antimony-doped tin oxide (ATO) has a nano (nm) size, it may be sprayed onto the first electrode at a relatively low pressure.

[0027] According to one embodiment, the method may include heat-treating the first electrode and spraying the antimony-doped tin oxide (ATO) when the antimony-doped tin oxide (ATO) has a nano (nm) size.

[0028] A smart mirror device according to an embodiment of the present invention may include a first electrode and a second electrode disposed opposite to each other, an electrochromic layer disposed between the first electrode and the second electrode and including antimony-doped tin oxide (ATO), and an electrolyte disposed between the second electrode and the electrochromic layer and including a first base electrolyte including silver (Ag), a second base electrolyte including bromine (Br), and a solvent.

[0029] Accordingly, the smart mirror element, depending on the voltage applied to the electrochromic layer, silver ions (Ag) in the electrolyte +) is controlled, any one of a transparent mode that transmits incident light, a black mode that blocks incident light, and a mirror mode that reflects incident light can be selectively implemented.

[0030] In addition, the electrochemical properties and transmittance to incident light of the smart mirror element can be selectively controlled depending on the size of antimony-doped tin oxide (ATO) used in the process of forming the electrochromic layer.

[0031] Specifically, when the antimony-doped tin oxide (ATO) used in the process of forming the electrochromic layer has a micro (μm) size, the surface roughness of the electrochromic layer is relatively increased, so that the reaction surface area increases, thereby improving the electrochemical characteristics.

[0032] In contrast, when the antimony-doped tin oxide (ATO) used in the process of forming the electrochromic layer has a nano (nm) size, the surface roughness of the electrochromic layer is relatively low, so that scattering of incident light is minimized, and thus the transmittance for incident light can be improved.

[0033] In addition, since a dry lamination method (e.g., Nanoparticle Deposition System) is used in the process of manufacturing the electrochromic layer, the problem of internal crack occurrence and environmental pollution of the electrochromic layer is significantly reduced, and it can be easily applied to a large-area process.

[0034] FIG. 1 is a flowchart illustrating a method for manufacturing a smart mirror element according to an embodiment of the present invention.

[0035] FIG. 2 is a schematic diagram illustrating a manufacturing process of a smart mirror element according to an embodiment of the present invention.

[0036] FIG. 3 is a drawing for explaining the transparent mode of a smart mirror element according to an embodiment of the present invention.

[0037] FIG. 4 is a drawing for explaining a discoloration process for implementing a smart mirror element in black mode according to an embodiment of the present invention.

[0038] FIG. 5 is a drawing for explaining a decolorization process after a smart mirror element according to an embodiment of the present invention is implemented in black mode.

[0039] FIG. 6 is a drawing for explaining a discoloration process for implementing a smart mirror element in mirror mode according to an embodiment of the present invention.

[0040] FIG. 7 is a drawing for explaining a decolorization process after a smart mirror element according to an embodiment of the present invention is implemented in mirror mode.

[0041] Figure 8 is a photograph of the transparent mode, black mode, and mirror mode of the smart mirror device according to Experimental Example 1 of the present invention.

[0042] Fig. 9 is a photograph taken of a smart mirror device according to Experimental Example 1 of the present invention implemented in black mode.

[0043] FIG. 10 is a photograph of ATO powder used in the manufacturing process of a smart mirror element according to Experimental Examples 1 and 2 of the present invention.

[0044] Fig. 11 is a photograph of an electrochromic layer of a smart mirror device according to Experimental Examples 1 and 2 of the present invention.

[0045] FIG. 12 is a photograph of an electrochromic layer of a smart mirror device implemented in black mode according to Experimental Examples 1 and 2 of the present invention.

[0046] FIG. 13 is a drawing for explaining the thickness of the electrochromic layer of the smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0047] FIG. 14 is a drawing for explaining the surface roughness of the electrochromic layer of the smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0048] FIG. 15 is a drawing for explaining the change in surface roughness of an electrochromic layer when a smart mirror element according to Experimental Examples 1 and 2 of the present invention is implemented in black mode.

[0049] FIG. 16 is a drawing for explaining the results of transmittance measurement when the smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention is implemented in transparent mode, black mode, and mirror mode.

[0050] FIG. 17 is a drawing for explaining the results of reflectivity measurements when the smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention is implemented in transparent mode, black mode, and mirror mode.

[0051] FIG. 18 is a drawing for explaining the results of measuring the transmittance and opacity of a smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0052] FIG. 19 is a drawing for explaining the reaction mechanism of a smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0053] FIG. 20 is a drawing for explaining the electrochemical impedance measurement results of a smart mirror element according to Experimental Examples 1 and 2 of the present invention.

[0054] FIG. 21 and FIG. 22 are drawings for explaining the results of cyclic voltage current measurements of a smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0055] FIG. 23 is a drawing for explaining the diffusion coefficient of a smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0056] FIG. 24 is a drawing for explaining the durability of a smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0057] FIG. 25 and FIG. 26 are drawings for explaining the influence of temperature in the process of forming an electrochromic layer of a smart mirror element according to Experimental Example 2 of the present invention.

[0058] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. However, the technical concept of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to sufficiently convey the spirit of the present invention to those skilled in the art.

[0059] In this specification, when a component is referred to as being on another component, it means that it can be formed directly on the other component, or a third component may be interposed between them. In addition, in the drawings, the thicknesses of films and regions are exaggerated for the purpose of effectively explaining the technical contents.

[0060] Also, although terms such as first, second, and third have been used to describe various components in various embodiments of this specification, these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiments. Also, the term "and / or" has been used herein to mean including at least one of the components listed before and after.

[0061] In the specification, singular expressions include plural expressions unless the context clearly dictates otherwise. In addition, terms such as "comprise" or "have" are intended to specify the presence of a feature, number, step, component, or combination thereof described in the specification, and should not be construed as excluding the presence or addition of one or more other features, numbers, steps, components, or combinations thereof. In addition, the term "connection" is used in the present specification to mean both indirectly connecting multiple components and directly connecting them.

[0062] In addition, when describing the present invention below, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

[0063]

[0064] FIG. 1 is a flowchart for explaining a method for manufacturing a smart mirror element according to an embodiment of the present invention, and FIG. 2 is a schematic diagram for explaining a manufacturing process of a smart mirror element according to an embodiment of the present invention.

[0065] Referring to FIGS. 1 and 2, a first electrode (100) may be prepared (S100). According to one embodiment, the first electrode (100) may include FTO glass (Fluorine Tin doped Oxide glass).

[0066] An electrochromic layer (200) may be formed on the first electrode (100) (S200). According to one embodiment, the electrochromic layer (200) may include antimony-doped tin oxide (ATO).

[0067] According to one embodiment, the electrochromic layer (200) may be formed by a dry lamination method. For example, a powder of tin oxide (ATO) doped with antimony may be provided on the first electrode (100) using a Nanoparticle Deposition System (NPDS). In contrast, when the electrochromic layer (200) is formed by a wet lamination method, internal cracks may occur due to evaporation of the solvent in the electrochromic layer, which may cause a problem of deterioration in the performance of the smart mirror element. In addition, in the case of a wet lamination method, an environmental pollution problem may occur. However, as described above, when the electrochromic layer (200) is formed by a dry lamination method, the problem of internal cracks and the problem of environmental pollution can be significantly reduced.

[0068] In addition, as described above, since the electrochromic layer (200) is formed by a dry lamination method, a plurality of antimony-doped tin oxide (ATO) particles can be observed in the electrochromic layer (200).

[0069] According to one embodiment, the surface roughness of the electrochromic layer (200) can be controlled depending on the size of the antimony-doped tin oxide (ATO) sprayed onto the first electrode (100). For example, when the antimony-doped tin oxide (ATO) sprayed onto the first electrode (100) has a micro (μm) size, the electrochromic layer (200) can have a relatively high surface roughness. Specifically, when the antimony-doped tin oxide (ATO) sprayed onto the first electrode (100) has a micro (μm) size, the electrochromic layer (200) can have an Ra value of 85 nm or more. In contrast, when the antimony-doped tin oxide (ATO) sprayed onto the first electrode (100) has a nano (nm) size, the electrochromic layer (200) can have a relatively low surface roughness. Specifically, when the antimony-doped tin oxide (ATO) sprayed on the first electrode (100) has a nano (nm) size, the electrochromic layer (200) can have an Ra value of 20 nm or less.

[0070] In addition, the pressure at which the antimony-doped tin oxide (ATO) is sprayed onto the first electrode (100) can be controlled depending on the size of the antimony-doped tin oxide (ATO) sprayed onto the first electrode (100). For example, when the antimony-doped tin oxide (ATO) has a micro (μm) size, it can be sprayed onto the first electrode (100) at a relatively high pressure. In contrast, when the antimony-doped tin oxide (ATO) has a nano (nm) size, it can be sprayed onto the first electrode (100) at a relatively low pressure. In addition, when the antimony-doped tin oxide (ATO) has a nano (nm) size, the antimony-doped tin oxide (ATO) can be sprayed while heat-treating the first electrode (100).

[0071] That is, when the size of the antimony-doped tin oxide (ATO) is relatively large (e.g., μm size), the electrochromic layer (200) can be formed by spraying at a relatively high pressure, whereas when the size of the antimony-doped tin oxide (ATO) is relatively small (e.g., nm size), the electrochromic layer (200) can be formed by spraying at a relatively low pressure while heat-treating the first electrode (100). Accordingly, the reliability of the electrochromic layer (200) can be improved.

[0072] In contrast, if the first electrode (100) is not heat-treated or sprayed at a relatively high pressure even though the size of the antimony-doped tin oxide (ATO) is relatively small (e.g., nm size), the antimony-doped tin oxide (ATO) may not be deposited on the first electrode (100), which may cause a problem in that the reliability of the electrochromic layer (200) is lowered.

[0073] According to one embodiment, the electrochemical characteristics and transmittance to incident light of the smart mirror element can be selectively controlled depending on the size of the antimony-doped tin oxide (ATO) used to form the electrochromic layer (200).

[0074] For example, when the antimony-doped tin oxide (ATO) used to form the electrochromic layer (200) has a micro (μm) size, the electrochemical characteristics of the smart mirror device can be improved. Specifically, when the antimony-doped tin oxide (ATO) used to form the electrochromic layer (200) has a micro (μm) size, the surface roughness of the electrochromic layer (200) is formed relatively high, so that the reaction surface area of ​​the electrochromic layer (200) increases, and thus the electrochemical characteristics can be improved.

[0075] In contrast, when the antimony-doped tin oxide (ATO) used to form the electrochromic layer (200) has a nano (nm) size, the smart mirror element can have improved transmittance to incident light. Specifically, when the antimony-doped tin oxide (ATO) used to form the electrochromic layer (200) has a nano (nm) size, the surface roughness of the electrochromic layer (200) is formed relatively low, so that scattering of light incident on the electrochromic layer (200) is minimized, and thus the transmittance to incident light can be improved.

[0076] According to one embodiment, when the electrochromic layer (200) is formed over a large area, the size of the antimony-doped tin oxide (ATO) used to form the outer region of the electrochromic layer (200) and the size of the antimony-doped tin oxide (ATO) used to form the central region may be different. Specifically, the antimony-doped tin oxide (ATO) used to form the outer region of the electrochromic layer (200) may have a micro (μm) size, while the antimony-doped tin oxide (ATO) used to form the central region may have a nano (nm) size.

[0077] That is, the surface roughness can be increased in the outer region where the wiring is connected to improve the electrochemical properties, while the surface roughness can be decreased in the central region to improve the transmittance to incident light. Accordingly, even though the electrochromic layer (200) is manufactured over a large area, not only can rapid discoloration and fading be achieved due to the high electrochemical properties, but also aesthetics can be secured due to the high transmittance to incident light.

[0078] According to one embodiment, the electrochromic layer (200) may be formed to have a thickness of 400 nm to 500 nm. To this end, the conditions of a Nanoparticle Deposition System (NPDS) that provides a powder of antimony-doped tin oxide (ATO) on the first electrode (100) may be controlled.

[0079] For example, the electrochromic layer (200) may be formed at a temperature of 150°C or higher. In contrast, when the electrochromic layer (200) is formed at a temperature of less than 150°C, deposition of antimony-doped tin oxide (ATO) may not occur, and thus the electrochromic layer (200) may not be formed or may have an excessively thin thickness.

[0080] In addition, the electrochromic layer (200) may be formed through a number of laminations exceeding 1 time and less than 4 times. Conversely, when the electrochromic layer (200) is formed through a number of laminations exceeding 1 time or 4 times, a problem of excessively thin thickness may occur.

[0081] In addition, the electrochromic layer (200) may be formed at a nozzle scan speed of more than 200 μm / s and less than 1500 μm / s. In contrast, if the electrochromic layer (200) is formed at a nozzle scan speed of less than 200 μm / s, the thickness may become excessively thick, and if the electrochromic layer (200) is formed at a nozzle scan speed of 1500 μm / s or more, the thickness may become excessively thin.

[0082] The first electrode (100) and the second electrode (300) on which the electrochromic layer (200) is formed can be bonded (S300). Specifically, the first electrode (100) and the second electrode (300) can be bonded so that the electrochromic layer (200) is disposed between the first electrode (100) and the second electrode (300). According to one embodiment, the second electrode (300) can include a different material from the first electrode (100). For example, the second electrode (300) can include ITO glass (Indium Tin doped Oxide glass).

[0083] An electrolyte (400) may be prepared (S400) in which a first base electrolyte containing silver (Ag), a second base electrolyte containing bromine (Br), and a solvent are mixed. For example, the first base electrolyte may contain silver nitrate (AgNO3). For example, the second base electrolyte may contain tetra-n-butylammonium bromide (TBABr). For example, the solvent may contain dimethyl sulfoxide (DMSO).

[0084] The electrolyte (400) can be injected between the second electrode (300) and the electrochromic layer (200) (S500). Accordingly, a smart mirror element according to the above embodiment can be manufactured.

[0085] The smart mirror element can control the movement of silver (Ag) ions in the electrolyte (400) according to the voltage applied to the electrochromic layer (200). Accordingly, the smart mirror element can selectively implement any one of a transparent mode that transmits incident light, a black mode that blocks incident light, and a mirror mode that reflects incident light. Hereinafter, the transparent mode, the black mode, and the mirror mode will be described in detail.

[0086] FIG. 3 is a drawing for explaining a transparent mode of a smart mirror element according to an embodiment of the present invention, FIG. 4 is a drawing for explaining a discoloration process for implementing a smart mirror element according to an embodiment of the present invention in black mode, FIG. 5 is a drawing for explaining a decolorization process after a smart mirror element according to an embodiment of the present invention is implemented in black mode, FIG. 6 is a drawing for explaining a discoloration process for implementing a smart mirror element according to an embodiment of the present invention in mirror mode, and FIG. 7 is a drawing for explaining a decolorization process after a smart mirror element according to an embodiment of the present invention is implemented in mirror mode.

[0087] Transparent mode

[0088] Referring to FIG. 3, when no voltage is applied to the electrochromic layer (200), silver ions (Ag) in the electrolyte (400) + ) may not move. Accordingly, the smart mirror element can be implemented in a transparent mode that transmits incident light.

[0089] Black mode

[0090] Referring to FIG. 4, when a negative (-) voltage is applied to the electrochromic layer (200), silver ions (Ag) in the electrolyte (400) + ) can be moved to the electrochromic layer (200). Silver ions (Ag) moved to the electrochromic layer (200) + ) can be deposited on the electrochromic layer (200). In addition, bromine ions (Br) in the electrolyte (400) - ) can be oxidized. Accordingly, the smart mirror element is discolored, and the smart mirror element can be implemented in a black mode that blocks incident light.

[0091] Referring to FIG. 5, when a positive (+) voltage is applied to the electrochromic layer (200) of the smart mirror element implemented in black mode, the smart mirror element may be discolored. Specifically, when a positive (+) voltage is applied to the electrochromic layer (200) of the smart mirror element implemented in black mode, silver ions (Ag) deposited on the electrochromic layer (200) + ) is dissolved in the electrolyte (400), and bromine ions (Br) in the electrolyte (400) - ) is reduced, the smart mirror element may be discolored.

[0092] Mirror mode

[0093] Referring to FIG. 6, when a positive (+) voltage is applied to the electrochromic layer (200), silver ions (Ag) in the electrolyte (400) + ) can be moved to the second electrode (300). The silver ions (Ag) moved to the second electrode (300) + ) can be deposited on the second electrode (300). In addition, bromine ions (Br) in the electrolyte (400) - ) can be oxidized. Accordingly, the smart mirror element is discolored, and the smart mirror element can be implemented in a mirror mode that reflects incident light.

[0094] Referring to FIG. 7, when a negative (-) voltage is applied to the electrochromic layer (200) of the smart mirror element implemented in mirror mode, the smart mirror element may be discolored. Specifically, when a negative (-) voltage is applied to the electrochromic layer (200) of the smart mirror element implemented in mirror mode, silver ions (Ag) deposited on the second electrode (200) + ) is dissolved in the electrolyte (400), and bromine ions (Br) in the electrolyte (400) -) is reduced, the smart mirror element may be discolored.

[0095] As a result, a smart mirror device according to an embodiment of the present invention may include a first electrode and a second electrode disposed opposite to each other, an electrochromic layer disposed between the first electrode and the second electrode and including antimony-doped tin oxide (ATO), and an electrolyte disposed between the second electrode and the electrochromic layer and including a first base electrolyte including silver (Ag), a second base electrolyte including bromine (Br), and a solvent.

[0096] Accordingly, the smart mirror element, depending on the voltage applied to the electrochromic layer, silver ions (Ag) in the electrolyte + ) is controlled, any one of a transparent mode that transmits incident light, a black mode that blocks incident light, and a mirror mode that reflects incident light can be selectively implemented.

[0097] In addition, the electrochemical properties and transmittance to incident light of the smart mirror element can be selectively controlled depending on the size of antimony-doped tin oxide (ATO) used in the process of forming the electrochromic layer.

[0098] Specifically, when the antimony-doped tin oxide (ATO) used in the process of forming the electrochromic layer has a micro (μm) size, the surface roughness of the electrochromic layer is relatively increased, so that the reaction surface area increases, thereby improving the electrochemical characteristics.

[0099] In contrast, when the antimony-doped tin oxide (ATO) used in the process of forming the electrochromic layer has a nano (nm) size, the surface roughness of the electrochromic layer is relatively low, so that scattering of incident light is minimized, and thus the transmittance for incident light can be improved.

[0100] In addition, since a dry lamination method (e.g., Nanoparticle Deposition System) is used in the process of manufacturing the electrochromic layer, the problem of internal crack occurrence and environmental pollution of the electrochromic layer is significantly reduced, and it can be easily applied to a large-area process.

[0101]

[0102] Above, a smart mirror device and a manufacturing method thereof according to an embodiment of the present invention have been described. Below, specific experimental examples and characteristic evaluation results of a smart mirror device and a manufacturing method thereof according to an embodiment of the present invention are described.

[0103] Manufacturing of smart mirror elements according to experimental examples

[0104] An electrochromic layer was formed by dry-depositing ATO (Antimony-doped Tin Oxide) powder on the first electrode using a nanoparticle deposition system (NPDS), and the first and second electrodes were bonded so that the electrochromic layer was positioned therebetween. Thereafter, an electrolyte was injected between the electrochromic layer and the second electrode to manufacture a smart mirror element according to the experimental example.

[0105] More specifically, FTO glass (Fluorine Tin doped Oxide glass) was used as the first electrode, and ITO glass (Indium Tin doped Oxide glass) was used as the second electrode. In addition, a mixture of 50 mM AgNO3, 250 mM TBABr (tetra-n-butylammonium bromide), and DMSO (Dimethyl sulfoxide) was used as the electrolyte. In addition, the specific conditions of the NPDS system for forming the electrochromic layer are summarized in below.

[0106] MaterialMicro ATO: 40~50 μm (Nanoshell, USA)Nano ATO: 30 nm (Nanoshell, USA)Nozzle / substrate distance (SoD), Bed flow3 mm, 27.5 L / minNozzle scan speedMicro ATO: 100 μm / sec x 2Nano ATO: 150℃, 1500 μm / sec x 2Compressor pressure0.3 MPaChamber pressure0.01 MPa (Gauge pressure)

[0107] A smart mirror device using micro-sized (μm) ATO to form an electrochromic layer is defined as Experimental Example 1, and a smart mirror device using nano-sized (nm) ATO is defined as Experimental Example 2.

[0108] Figure 8 is a photograph of the transparent mode, black mode, and mirror mode of the smart mirror device according to Experimental Example 1 of the present invention.

[0109] Fig. 8 (a) shows a state in which the smart mirror element according to the above experimental example 1 is implemented in transparent mode by taking a picture, Fig. 8 (b) shows a state in which the smart mirror element according to the above experimental example 1 is implemented in black mode by taking a picture, and Fig. 8 (c) shows a state in which the smart mirror element according to the above experimental example 1 is implemented in mirror mode by taking a picture.

[0110] The transparent mode was implemented by not applying voltage to the electrochromic layer, the black mode was implemented by applying negative (-) voltage to the electrochromic layer, and the mirror mode was implemented by applying positive (+) voltage to the electrochromic layer.

[0111] As can be seen in (a) to (c) of Fig. 8, in transparent mode, it was confirmed that the back of the smart mirror element had a high transmittance that could be seen, in black mode, it was confirmed that the back of the smart mirror element could not be seen, and in mirror mode, it was confirmed that an object was reflected through the smart mirror element.

[0112] Fig. 9 is a photograph taken of a smart mirror device according to Experimental Example 1 of the present invention implemented in black mode.

[0113] Referring to FIG. 9, a TEM (Transmission Electron Microscope) photograph is shown of the area around the electrochromic layer (ATO layer) of the smart mirror device according to Experimental Example 1 implemented in black mode.

[0114] As can be seen in Fig. 9, the smart mirror device according to the above experimental example 1 implemented in black mode has silver ions (Ag) in the electrochromic layer (ATO layer). + ) were reduced and a layer of silver nanoparticles was deposited.

[0115] FIG. 10 is a photograph of ATO powder used in the manufacturing process of a smart mirror element according to Experimental Examples 1 and 2 of the present invention.

[0116] Referring to (a) and (b) of FIG. 10, SEM (Scanning Electron Microscope) photographs of ATO powder used in the manufacturing process of a smart mirror element according to Experimental Example 1 are shown, and referencing (c) and (d) of FIG. 10, SEM (Scanning Electron Microscope) photographs of ATO powder used in the manufacturing process of a smart mirror element according to Experimental Example 2 are shown.

[0117] As can be seen in (a) and (b) of Fig. 10, it can be seen that in the manufacturing process of the smart mirror element according to the experimental example 1, ATO having a micro (μm) size was used, and in the manufacturing process of the smart mirror element according to the experimental example 2, ATO having a nano (nm) size was used.

[0118] Fig. 11 is a photograph of an electrochromic layer of a smart mirror device according to Experimental Examples 1 and 2 of the present invention.

[0119] Referring to (a) and (b) of FIG. 11, SEM photographs of the electrochromic layer of the smart mirror element according to Experimental Example 1 are shown, and referencing (c) and (d) of FIG. 11, SEM photographs of the electrochromic layer of the smart mirror element according to Experimental Example 2 are shown.

[0120] As can be seen in (a) and (b) of Fig. 11, when ATO having a micro (μm) size was used, a relatively rough surface was obtained, whereas as can be seen in (c) and (d) of Fig. 11, when ATO having a nano (nm) size was used, a relatively smooth surface was obtained.

[0121] FIG. 12 is a photograph of an electrochromic layer of a smart mirror device according to Experimental Examples 1 and 2 of the present invention implemented in black mode.

[0122] Referring to (a) and (b) of FIG. 12, SEM photographs of the electrochromic layer of the smart mirror element according to Experimental Example 1 implemented in black mode are shown, and referencing (c) and (d) of FIG. 12, SEM photographs of the electrochromic layer of the smart mirror element according to Experimental Example 2 implemented in black mode are shown.

[0123] As can be seen in (a) and (b) of Fig. 12, when ATO having a micro (μm) size was used, a relatively rough surface was obtained, whereas as can be seen in (c) and (d) of Fig. 12, when ATO having a nano (nm) size was used, a relatively smooth surface was obtained.

[0124] FIG. 13 is a drawing for explaining the thickness of the electrochromic layer of the smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0125] Referring to (a) of Fig. 13, the thickness of the electrochromic layer of the smart mirror element according to the experimental example 1 is measured and shown, and referring to (b) of Fig. 13, the thickness of the electrochromic layer of the smart mirror element according to the experimental example 2 is measured and shown.

[0126] As can be seen in (a) of Fig. 13, when ATO having a micro (μm) size was used, it was formed with a thickness of 454 nm, and as can be seen in (b) of Fig. 13, when ATO having a nano (nm) size was used, it was formed with a thickness of 490 nm.

[0127] FIG. 14 is a drawing for explaining the surface roughness of the electrochromic layer of the smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0128] Referring to (a) of Fig. 14, the surface roughness Ra value of the electrochromic layer of the smart mirror element according to the experimental example 1 is measured and shown, and referring to (b) of Fig. 14, the surface roughness Ra value of the electrochromic layer of the smart mirror element according to the experimental example 2 is measured and shown.

[0129] As can be seen in (a) of Fig. 14, when ATO having a micro (μm) size was used, it had an Ra value of 85 nm, whereas as can be seen in (b) of Fig. 14, when ATO having a nano (nm) size was used, it had an Ra value of 20 nm.

[0130] FIG. 15 is a drawing for explaining the change in surface roughness of an electrochromic layer when a smart mirror element according to Experimental Examples 1 and 2 of the present invention is implemented in black mode.

[0131] Referring to (a) of Fig. 15, the surface roughness Rq value of the electrochromic layer is measured and shown when the smart mirror element according to the experimental example 1 is implemented in transparent mode, and referring to (b) of Fig. 15, the surface roughness Rq value of the electrochromic layer is measured and shown when the smart mirror element according to the experimental example 1 is implemented in black mode.

[0132] As can be seen in (a) and (b) of Fig. 15, when ATO having a micro (μm) size was used, it was confirmed that the Rq value was 54.87±3.42 nm in transparent mode, while the Rq value was 135.71±37.29 nm in black mode.

[0133] Referring to (c) of Fig. 15, the surface roughness Rq value of the electrochromic layer is measured and shown when the smart mirror element according to the experimental example 2 is implemented in transparent mode, and referring to (d) of Fig. 15, the surface roughness Rq value of the electrochromic layer is measured and shown when the smart mirror element according to the experimental example 2 is implemented in black mode.

[0134] As can be seen in (c) and (d) of Fig. 15, when ATO having a nano (nm) size was used, it was confirmed that the Rq value was 44.36±1.81 nm in transparent mode, while the Rq value was 78.16±12.15 nm in black mode.

[0135] FIG. 16 is a drawing for explaining the results of transmittance measurement when the smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention is implemented in transparent mode, black mode, and mirror mode.

[0136] Referring to (a) of Fig. 16, the smart mirror element according to the experimental example 1 is implemented in transparent mode (Initial), black mode (Black), and mirror mode (Mirror), and then the transmittance is measured and shown in each mode. Referring to (b) of Fig. 16, the smart mirror element according to the experimental example 2 is implemented in transparent mode (Initial), black mode (Black), and mirror mode (Mirror), and then the transmittance is measured and shown in each mode.

[0137] As can be confirmed in (a) and (b) of Fig. 16, it was confirmed that both the smart mirror elements according to Experimental Example 1 and Experimental Example 2 had a transmittance of 0% for incident light in the wavelength range of 300 nm to 1200 nm in black mode and mirror mode.

[0138] FIG. 17 is a drawing for explaining the results of reflectivity measurements when the smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention is implemented in transparent mode, black mode, and mirror mode.

[0139] Referring to (a) of Fig. 17, the smart mirror element according to the experimental example 1 is implemented in transparent mode (Initial), black mode (Black), and mirror mode (Mirror), and then the reflectivity is measured and displayed in each mode. Referring to (b) of Fig. 17, the smart mirror element according to the experimental example 2 is implemented in transparent mode (Initial), black mode (Black), and mirror mode (Mirror), and then the reflectivity is measured and displayed in each mode.

[0140] As can be seen in (a) and (b) of Fig. 17, it was confirmed that both the smart mirror elements according to Experimental Examples 1 and 2 had a reflectivity of 75% or more in mirror mode.

[0141] FIG. 18 is a drawing for explaining the results of measuring the transmittance and opacity of a smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0142] Referring to Fig. 18, the transmittance (Transmittance, %) and opacity (Haze, %) are measured and shown for each of the smart mirror elements according to Experimental Example 1 (micro ATO) and Experimental Example 2 (nano ATO).

[0143] As can be seen in Fig. 18, in terms of transmittance, it was confirmed that the smart mirror device according to Experimental Example 1 exhibited 77% at a visible light wavelength of 600 nm, while the smart mirror device according to Experimental Example 2 exhibited 81%. In addition, in terms of opacity, it was confirmed that in terms of opacity, it was confirmed that the smart mirror device according to Experimental Example 1 exhibited 52% at a visible light wavelength of 600 nm, while the smart mirror device according to Experimental Example 2 exhibited 32%, showing a difference of approximately 20%.

[0144] That is, it was confirmed that when ATO having a micro (μm) size was used, it had relatively low transmittance and relatively high opacity, whereas when ATO having a nano (nm) size was used, it had relatively high transmittance and relatively low opacity.

[0145] FIG. 19 is a drawing for explaining the reaction mechanism of a smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0146] Referring to FIG. 19, the results of CV (cyclic voltammetry) analysis for each of the smart mirror elements according to Experimental Example 1 (micro-sized ATO) and Experimental Example 2 (nano-sized ATO) are shown.

[0147] As can be seen in Figure 19, silver ions (Ag) are absorbed in a relatively rough electrochromic layer (ATO layer). + ) react, a black mode is implemented, and silver ions (Ag) are released from the relatively flat second electrode (ITO electrode). + ) were able to confirm that mirror mode was implemented when they reacted.

[0148] FIG. 20 is a drawing for explaining the electrochemical impedance measurement results of a smart mirror element according to Experimental Examples 1 and 2 of the present invention.

[0149] Referring to Fig. 20, the impedance measurement results for each smart mirror element according to Experimental Example 1 (micro ATO) and Experimental Example 2 (nano ATO) are shown. Specifically, R is measured through EIS (Electrochemical Impedance Spectroscopy) analysis. s (sheet resistance) and R ct (Charge transfer resistance) was measured. The measurement results are summarized in Table 2 below. In addition, Fig. 20 (a) shows the measurement results in the high-frequency range, and Fig. 20 (b) shows the measurement results in the low-frequency range.

[0150] Classification R s R ct Experimental Example 1 (Micro ATO) 29 Ω 38 Ω Experimental Example 2 (Nano ATO) 24 Ω 44 Ω

[0151] As can be seen in Figure 20 and Table 2, R sIt was confirmed that the value was higher for the smart mirror element according to Experimental Example 1. This is believed to be the result of increased resistivity due to electron scattering occurring on a rough surface. On the other hand, the R value was higher due to the increase in the reaction surface area caused by the high surface roughness of the smart mirror element according to Experimental Example 1. ct It was confirmed that the value was lower than that of the smart mirror element according to Experimental Example 2.

[0152] FIG. 21 and FIG. 22 are drawings for explaining the results of cyclic voltage current measurements of a smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0153] Referring to FIGS. 21 and 22, the cyclic voltammetry (CV) measurement results for each of the smart mirror elements according to Experimental Example 1 and Experimental Example 2 are shown. Specifically, (a) of FIG. 21 shows the results of the smart mirror element according to Experimental Example 1, (b) of FIG. 21 shows the results of the smart mirror element according to Experimental Example 2, and FIG. 22 compares and shows the results of the smart mirror elements according to Experimental Example 1 and Experimental Example 2. In addition, the charge capacity (mC / cm) for each of the smart mirror elements according to Experimental Example 1 and Experimental Example 2 is shown. 2 ) was measured, and the measurement results are summarized in below.

[0154] Discriminative charge capacity (mC / cm) 2 )Experimental Example 1109.87Experimental Example 295.59

[0155] As can be seen in , it was confirmed that the charge capacity of the smart mirror element according to the above experimental example 1 was higher than the charge capacity of the smart mirror element according to the above experimental example 2.

[0156] FIG. 23 is a drawing for explaining the diffusion coefficient of a smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0157] Referring to (a) of Fig. 23, the peak current (A) of the smart mirror element according to Experimental Example 1 is measured and shown, and referring to (b) of Fig. 23, the peak current (A) of the smart mirror element according to Experimental Example 2 is measured and shown. In addition, the diffusion coefficients of the smart mirror elements according to Experimental Examples 1 and 2 were calculated using <Mathematical Formula 1> below, and the calculated results are summarized in below.

[0158] <Mathematical Formula 1>

[0159]

[0160] D: Diffusion coefficient (cm 2 / s)

[0161] i p : Peak potential (A)

[0162] C: Concentration of ions (mol / cm) 2 )

[0163] V: Voltage scan rate (V / s)

[0164] A: Area (cm) 2 )

[0165] Diffusion coefficient at 200 mV / sec (10 -7 cm 2 / sec)cathodicanodicExperimental Example 112.311.1Experimental Example 29.226.27

[0166] As can be seen in Fig. 23 and , it was confirmed that the smart mirror element according to Experimental Example 1 had higher electrochemical characteristics than the smart mirror element according to Experimental Example 2.

[0167] FIG. 24 is a drawing for explaining the durability of a smart mirror element according to Experimental Example 1 and Experimental Example 2 of the present invention.

[0168] Referring to Fig. 24, in order to confirm the durability of the smart mirror elements according to Experimental Examples 1 and 2, the change in transmittance in discoloration / bleaching was measured continuously 50 times at a wavelength of 600 nm. Specifically, the black mode was discolored by applying a voltage of -3.0 V for 50 seconds, and then bleached by applying a voltage of +1.0 V for 150 seconds and then applying a voltage of 0 V for 200 seconds. On the other hand, the mirror mode was discolored by applying a voltage of +2.5 V for 50 seconds, and then bleached by applying a voltage of -1.0 V for 150 seconds and then applying a voltage of 0 V for 200 seconds. Fig. 24 (a) shows the result of the smart mirror element according to Experimental Example 1, and Fig. 24 (b) shows the result of the smart mirror element according to Experimental Example 2.

[0169] As can be seen in (a) of Fig. 24, in the case of the smart mirror element according to the experimental example 1, the change in transmittance (ΔT) after 1 and 50 cycles was measured to be 63% from 76%, confirming that the performance was maintained at approximately 82% of the initial performance after 50 cycles.

[0170] On the other hand, as can be seen in (b) of Fig. 24, in the case of the smart mirror element according to the experimental example 2, degradation occurred at the beginning of the cycle and the discoloration transmittance rapidly decreased, and it was confirmed that the performance was maintained at approximately 75% of the initial performance after 50 cycles.

[0171] That is, it was found that the smart mirror element according to the above experimental example 1 had better durability than the smart mirror element according to the above experimental example 2, and was therefore suitable for long-term use.

[0172] FIG. 25 and FIG. 26 are drawings for explaining the influence of temperature in the process of forming an electrochromic layer of a smart mirror element according to Experimental Example 2 of the present invention.

[0173] Referring to Fig. 25, a smart mirror element according to the above experimental example 2 was prepared, but other process conditions (e.g., nozzle scan speed of 1000 μm / sec, 2-time lamination) were fixed during the electrochromic layer formation process, and multiple samples were prepared at different temperatures (Room Temp, 50°C, 100°C, 150°C), and photographs were taken for each sample.

[0174] As can be seen in Fig. 25, it was confirmed that the electrochromic layer formed at a temperature below 150°C (room temperature, 50°C, 100°C) did not undergo proper deposition of ATO.

[0175] Referring to (a) of Fig. 26, the thickness of the electrochromic layer formed at a temperature of 100°C is measured and shown, and referring to (b) of Fig. 26, the thickness of the electrochromic layer formed at a temperature of 150°C is measured and shown.

[0176] As can be seen in (a) of Fig. 26, the electrochromic layer formed at a temperature of 100°C had a thickness of 490 nm, while as can be seen in (b) of Fig. 26, the electrochromic layer formed at a temperature of 150°C had a thickness of 391 nm.

[0177] Accordingly, it was found that in order to form an electrochromic layer having a thickness of 400 nm to 500 nm, the ATO deposition process temperature must be controlled to 150°C or higher.

[0178]

[0179] While the present invention has been described in detail using preferred embodiments, the scope of the present invention is not limited to the specific embodiments described above, and should be interpreted in accordance with the appended claims. Furthermore, those skilled in the art will appreciate that numerous modifications and variations are possible without departing from the scope of the present invention.

[0180] A smart mirror element and a manufacturing method thereof utilizing the difference in surface roughness of a dry-laminated thin film according to an embodiment of the present invention can be applied to the smart mirror industry.

Claims

1. First electrode and second electrode arranged opposite each other; An electrochromic layer disposed between the first electrode and the second electrode and including antimony-doped tin oxide (ATO); and An electrolyte comprising a first base electrolyte including silver (Ag), a second base electrolyte including bromine (Br), and a solvent, and disposed between the second electrode and the electrochromic layer, By controlling the voltage applied to the electrochromic layer, silver ions (Ag) in the electrolyte + ) by controlling the movement of the light source, a smart mirror element in which one of a transparent mode transmitting incident light, a black mode blocking incident light, and a mirror mode reflecting incident light is selectively implemented.

2. In paragraph 1, When a negative (-) voltage is applied to the above electrochromic layer, silver ions (Ag) in the electrolyte + ) is moved to the electrochromic layer, thereby implementing a smart mirror element in the black mode.

3. In paragraph 1, When a positive (+) voltage is applied to the above electrochromic layer, silver ions (Ag) in the electrolyte + ) is moved to the second electrode, thereby implementing a smart mirror element in the mirror mode.

4. In paragraph 1, When no voltage is applied to the electrochromic layer, silver ions (Ag) in the electrolyte + ) is not moved, thereby implementing a smart mirror element in the above transparent mode.

5. In paragraph 1, A smart mirror device, wherein the electrochemical characteristics and transmittance to incident light of the smart mirror device are selectively controlled according to the surface roughness of the electrochromic layer.

6. In paragraph 5, A smart mirror device including an electrochemical characteristic of the smart mirror device that is improved when the surface roughness of the electrochromic layer has an Ra value of 85 nm or more.

7. In paragraph 5, A smart mirror device including an improved transmittance of incident light of the smart mirror device when the surface roughness of the electrochromic layer has an Ra value of 20 nm or less.

8. In paragraph 1, A smart mirror element having a transmittance of 0% for incident light in the wavelength range of 300 nm to 1200 nm when implemented in any one of the above black mode and the above mirror mode.

9. In paragraph 1, A smart mirror device wherein the electrochromic layer has a thickness of 400 nm to 500 nm.

10. Step of preparing the first electrode; A step of forming an electrochromic layer including antimony-doped tin oxide (ATO) on the first electrode; A step of bonding the first electrode and the second electrode, on which the electrochromic layer is formed, so that the electrochromic layer is disposed therebetween; A step of preparing an electrolyte in which a first base electrolyte containing silver (Ag), a second base electrolyte containing bromine (Br), and a solvent are mixed; and A method for manufacturing a smart mirror element, comprising the step of injecting the electrolyte between the second electrode and the electrochromic layer.

11. In paragraph 10, A method for manufacturing a smart mirror element, wherein the electrochromic layer is formed by a dry lamination method of spraying antimony-doped tin oxide (ATO) onto the first electrode.

12. In paragraph 11, A method for manufacturing a smart mirror element, comprising controlling the pressure at which the antimony-doped tin oxide (ATO) is sprayed onto the first electrode according to the size of the antimony-doped tin oxide (ATO).

13. In paragraph 12, When the above antimony-doped tin oxide (ATO) has a micro (μm) size, it is sprayed at a relatively high pressure onto the first electrode, A method for manufacturing a smart mirror element, comprising spraying the antimony-doped tin oxide (ATO) having a nano (nm) size onto the first electrode at a relatively low pressure.

14. In paragraph 13, A method for manufacturing a smart mirror element, comprising heat-treating the first electrode and spraying the antimony-doped tin oxide (ATO) when the antimony-doped tin oxide (ATO) has a nano (nm) size.

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