Light controlling element and method for manufacturing the same

Abstract

To provide a light controlling element which can control light for a partial region.SOLUTION: A light controlling element 1 includes: a pair of transparent electrode substrates 10 each having a transparent electrode 12 opposed to form an electrode pair with a gap therebetween; an electrolyte 20 filled in the gap of the electrode pair, the electrolyte 20 including at least silver ions as metal ions of a metal salt in the composition of the electrolyte 20; and a sealing material 30 for sealing the electrolyte 20 in the gap of the electrode pair. A part of the transparent electrode 12 includes a translucent insulating layer 13.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a metal salt deposition electrochromic light control element for partially controlling light, and a method for manufacturing the same. [Background technology]

[0002] In recent years, a metal salt deposition electrochromic dimming element that changes light transmittance in a stepless manner has been disclosed (see Patent Document 1). This dimming element is configured by providing an electrolyte layer in which metal salts, silver and copper, are dissolved in methanol in the gap between an electrode pair, which consists of glass substrates with a transparent conductive film formed on each substrate, facing each other with the transparent conductive film side facing each other. This dimming element then reversibly repeats the deposition or reduction of the metal salt in response to changes in the electric field of the electrode pair, thereby changing the light transmittance in a stepless manner across almost the entire area of ​​the element. Also, a prototype example of a filter that is specialized for applying a light control element with variable transmittance to a television camera has been disclosed (see Non-Patent Document 1).

[0003] Furthermore, when a dimming element is used as a filter for a television camera, the filter may be attached to a component called a turret (see Patent Documents 2 and 3). In this case, the opening structure through which light passes through the filter varies in shape and size, such as round or square. Conventional filters are designed to operate over almost the entire area of ​​the element, so filters with an area larger than the area of ​​the opening through which light passes in the turret are used.

[0004] Also, a dimming element has been disclosed that has two electrolyte layers made of the same material and a pair of transparent electrode films made of the same material sandwiching each electrolyte layer, and that shortens the response time by commonly driving the two electrolyte layers with a pulsed voltage (see Non-Patent Document 2). Furthermore, a light-control element with variable transmittance has been disclosed that can improve the light control response and change the brightness partially (see Patent Document 4). This light-control element achieves partial light control by dividing the transparent electrode on the metal salt deposition side into an even number of parts, such as four. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6402113 [Patent Document 2] Patent No. 7300328 [Patent Document 3] Patent No. 7300329 [Patent Document 4] Patent Publication No. 2021-26178 [Non-patent literature]

[0006] [Non-Patent Document 1] Miyagawa et al., NHK Science & Technology Research Laboratories, Murakami Kaimeido Co., Ltd., "Prototype of Metal Salt Precipitation-Type Dimming Device," ITE Annual Convention 2016, 15B-1 [Non-patent document 2] Miyagawa et al., NHK Science & Technology Research Laboratories, Murakami Kaimeido Co., Ltd., "Improvement of Response of Metal Salt Precipitation-Type Photochromic Devices," ITE Annual Convention 2017, 23D-1 Summary of the Invention [Problem to be solved by the invention]

[0007] Conventionally, in the variable transmittance dimming elements described in Patent Document 1 and Non-Patent Document 1, the area in which the light transmittance is changed is the entire element. Therefore, in order to shorten the dimming response time, a partial dimming operation that does not involve deposition or reduction of metal salts in areas where dimming is not required is required. For example, in the case of the dimming elements described in Patent Documents 2 and 3, a dimming element having an area larger than the area of ​​the opening in the turret section through which light passes is used, so light is irradiated onto areas that do not contribute to dimming, which causes poor dimming response. Even if two electrolyte layers are provided to improve the response of dimming, as in the dimming element described in Non-Patent Document 2, the area that changes the light transmittance is the entire element, so there is a need for a way to prevent light from being irradiated onto areas that do not contribute to dimming.

[0008] Furthermore, even if the element is divided like the light control element described in Patent Document 4, there is a problem that there are limitations on how the element can be divided because a voltage must be applied to the transparent electrodes from the outside for the light control operation. For example, even if an attempt is made to divide the element into 3 x 3, it is not possible to apply a voltage to the central light control element, which places limitations on the shape of the area where the light control operation is performed.

[0009] The present invention has been made in consideration of the above problems and demands, and has an object to provide a light control element capable of controlling light in a partial region, and a method for manufacturing the same. [Means for solving the problem]

[0010] In order to solve the above problems, the light control element of the present invention is a metal salt precipitation electrochromic light control element that performs partial light control, and is characterized by comprising a pair of transparent electrode substrates in which transparent electrodes that form an electrode pair are opposed to each other with a gap between them, an electrolyte solution that is filled in the gap and contains at least silver ions as metal ions of the metal salt, and a sealant that seals the electrolyte in the gap, and in which a translucent insulating layer is disposed in a partial region of the transparent electrodes where the metal salt is precipitated in response to voltage control of the electrode pair.

[0011] With this configuration, the light-controlling element of the present invention can perform light control by switching between a state in which metal ions in the electrolyte are precipitated as metal salts on the cathode-side transparent electrode substrate, thereby reducing light transmittance, and a state in which the precipitated metal salts are reduced as metal ions in the electrolyte, thereby increasing light transmittance. In this case, since the light-controlling element has a translucent insulating layer disposed in a partial region of the transparent electrode, metal salts are not precipitated in this region by voltage control, and thus no metal salt precipitate layer is formed. Furthermore, the planar shape of this insulating layer can be any shape. As a result, the light control element according to the present invention can control light only in a partial region of any shape where no insulating layer is formed.

[0012] In addition, in order to solve the above-mentioned problems, the manufacturing method of the dimming element of the present invention is a manufacturing method of a metal salt precipitation type electrochromic dimming element that performs partial dimming, and includes the steps of: laminating a transparent electrode on a light-transmitting substrate to produce first and second transparent electrode substrates; laminating a light-transmitting insulating layer on a predetermined partial region of the transparent electrode of at least one of the first and second transparent electrode substrates; opposing the first and second transparent electrode substrates, at least one of which has the transparent electrode laminated thereon, to produce an electrode pair separated by a predetermined gap; and filling the gap with an electrolyte solution containing at least silver ions as metal ions of a metal salt.

[0013] By using this procedure, the method for manufacturing a photochromic element according to the present invention can manufacture a photochromic element that does not precipitate metal salts in the partial regions where the insulating layer is laminated, but can perform photochromic control in other regions by precipitating metal salts and reducing metal ions through voltage control. [Effects of the Invention]

[0014] According to the present invention, it is possible to realize a metal salt deposition electrochromic light control element capable of controlling light in a partial region. This allows the light control element according to the present invention to have a higher response rate in light control than when light control is performed by the entire element. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a cross-sectional view showing the structure of a light control element according to an embodiment of the present invention. [Figure 2] 1 is a front view showing the structure of a light control element according to an embodiment of the present invention. [Figure 3] FIG. 2 is an explanatory diagram illustrating a front view of the light control element according to the embodiment of the present invention. [Figure 4A] FIG. 1 is a front view of a transparent electrode substrate in which an insulating layer is laminated in a square-shaped region. [Figure 4B] 4B is a cross-sectional view of the transparent electrode substrate shown in FIG. 4A taken along line IV-IV. [Figure 5A] FIG. 10 is a front view of a transparent electrode substrate in which an insulating layer is laminated on the outer peripheral region of a quadrangular region. [Figure 5B] FIG. 5B is a VV cross-sectional view of the transparent electrode substrate shown in FIG. 5A. [Figure 6A] FIG. 10 is a front view of a transparent electrode substrate on which an insulating layer is laminated in a character-shaped region. [Figure 6B] 6B is a cross-sectional view of the transparent electrode substrate shown in FIG. 6A taken along the line VI-VI. [Figure 7A] FIG. 10 is a front view of a transparent electrode substrate in which an insulating layer is laminated on the outer periphery of a character-shaped region. [Figure 7B] 7B is a cross-sectional view taken along the line VII-VII of the transparent electrode substrate shown in FIG. 7A. [Figure 8] 3 is a flowchart showing the steps of a method for manufacturing a light control element according to an embodiment of the present invention. [Figure 9A] FIG. 10 is an explanatory diagram for explaining a first step of a mask method for forming an insulating layer on a transparent electrode substrate. [Figure 9B] FIG. 10 is an explanatory diagram for explaining a second procedure of the mask method for forming an insulating layer on a transparent electrode substrate. [Figure 9C] FIG. 10 is an explanatory diagram for explaining a third procedure of the mask method for forming an insulating layer on a transparent electrode substrate. [Figure 10A] FIG. 1 is an explanatory diagram for explaining a first step of a resist method for forming an insulating layer on a transparent electrode substrate. [Figure 10B] FIG. 10 is an explanatory diagram for explaining a second procedure of the resist method for forming an insulating layer on a transparent electrode substrate. [Figure 10C] FIG. 10 is an explanatory diagram for explaining a third procedure of the resist method for forming an insulating layer on a transparent electrode substrate. [Figure 10D] FIG. 10 is an explanatory diagram for explaining a fourth procedure of the resist method for forming an insulating layer on a transparent electrode substrate. [Figure 10E] FIG. 10 is an explanatory diagram for explaining a fifth step of the resist method for forming an insulating layer on a transparent electrode substrate. [Figure 11A] 1 is a graph showing the relationship between wavelength and transmittance in an insulating layer using Kapton (registered trademark) tape. [Figure 11B] 1 is a graph showing the relationship between wavelength and transmittance in an insulating layer using aluminum oxide. [Figure 12] FIG. 10 is a cross-sectional view showing the structure of a light control element according to Modification 1 of the present invention. [Figure 13A] FIG. 2 is a front view of the light-adjustable element according to Modification 1 of the present invention, illustrating a state in which a metal salt is deposited on the first transparent electrode substrate. [Figure 13B] FIG. 10 is a front view of the light-adjustable element according to Modification 1 of the present invention, illustrating a state in which a metal salt is deposited on the second transparent electrode substrate. [Figure 14] FIG. 10 is a cross-sectional view showing the structure of a light control element according to Modification 2 of the present invention. [Figure 15A] FIG. 10 is a front view of a light-adjustable element according to Modification 2 of the present invention, illustrating a state in which metal salt is precipitated only in the first electrolyte tank. [Figure 15B] FIG. 10 is a front view of the light-adjustable element according to Modification 2 of the present invention, illustrating a state in which metal salt is precipitated only in the second electrolyte tank. [Figure 15C] FIG. 10 is a front view of a light-adjustable element according to Modification 2 of the present invention, illustrating a state in which metal salts are deposited in the first and second electrolyte tanks to reduce the transmittance. [Figure 15D] FIG. 10 is a front view of the light-adjustable element according to Modification 2 of the present invention, illustrating a state in which metal salts are deposited in the first and second electrolyte tanks to block light. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. <Dimming element> A light control device 1 according to an embodiment of the present invention will be described with reference to FIGS.

[0017] The light control element 1 is a metal salt deposition electrochromic element that controls light partially. The light-adjusting element 1 includes a pair of transparent electrode substrates 10A and 10B in which transparent electrodes 12A and 12B, which form an electrode pair, face each other with a gap therebetween, an electrolyte solution 20 filled in the gap between the electrode pair, and a sealant 30 that seals the electrolyte solution 20 in the gap between the electrodes. In addition, the transparent electrode substrate 10A on the metal salt deposition side has a translucent insulating layer 13 formed in a predetermined partial region of the transparent electrode 12A. As a result, the area of ​​the transparent electrodes 12 (12A, 12B) where the insulating layer 13 is not formed is exposed to the electrolyte solution 20.

[0018] The light-adjusting element 1 is driven by a driving power supply 2 applying a voltage to a pair of transparent electrode substrates 10 (10A, 10B). That is, when a voltage is applied to the light-adjusting element 1 by the driving power supply 2 and the transparent electrode 12A becomes the cathode (-), the metal ions (here, silver ions (Ag+)) in the electrolyte 20 are precipitated as metal salts (silver) on the surface of the transparent electrode 12A on the cathode (-) side, forming a precipitate layer 14. At this time, by applying a voltage of about 2.0 V to 2.5 V, a coloring action occurs on the surface of the transparent electrode 12A.

[0019] 3, when the light-adjusting element 1 is viewed from the front, light is transmitted through the region where the insulating layer 13 is formed, but the transmittance is reduced or light is blocked in the region where the deposition layer 14 is formed. Note that, since no potential difference occurs in the region where the insulating layer 13 is formed, metal salts are not deposited on the insulating layer 13. This allows the light-adjusting device 1 to adjust the light transmittance in the region other than the insulating layer 13.

[0020] After the deposition layer 14 is formed, in order to improve the transmittance or to achieve a completely transparent state by reducing the metal salt of the deposition layer 14 into metal ions in the electrolyte solution 20, the polarity of the voltage applied to the light-adjusting element 1 is reversed. That is, the transparent electrode 12A on the deposition side is set as the anode (+) and the opposing transparent electrode 12B is set as the cathode (-) by the driving power supply 2. In this case, by applying a voltage of about 0.4 V to 0.7 V, a bleaching operation occurs in the transparent electrode 12A. The dimming element 1 achieves reversible dimming operation by repeating this polarity reversal.

[0021] <Drive power source> The driving power supply 2 is a DC power supply that applies a voltage to the pair of transparent electrodes 12 (12A, 12B). One terminal of the driving power source 2 is electrically connected to the transparent electrode 12A, and the other terminal is electrically connected to the transparent electrode 12B. When depositing metal salts, the driving power supply 2 applies a DC voltage of about 2.0 V to 2.5 V to the transparent electrode 12A as the cathode (-) and the transparent electrode 12B as the anode (+). However, even in this case, metal salts are not deposited on the insulating layer 13.

[0022] When the deposited metal salt is reduced to metal ions, the driving power supply 2 applies a DC voltage of about 0.4V to 0.7V to the transparent electrode 12A as the anode (+) and the transparent electrode 12B as the cathode (-). The driving power supply 2 can change the light transmittance of the light control element 1 by changing the voltage applied thereto in a stepwise or stepless manner. The configuration of the light control element 1 will be described in detail below.

[0023] <Transparent electrode substrate> The transparent electrode substrates 10 (10A, 10B) are transparent electrode substrates. A pair of the transparent electrode substrates 10 are arranged opposite each other and connected to the respective electrodes of the driving power source 2, thereby forming an electrode pair. The transparent electrode substrate 10 (10A, 10B) includes a light-transmitting substrate 11 and a transparent electrode 12 formed on the surface thereof.

[0024] The light-transmitting substrate 11 (11A, 11B) is a substrate that transmits light, and is, for example, a glass substrate, a resin substrate, etc. The light-transmitting substrates 11A, 11B may be made of the same type of material or different types of materials.

[0025] The transparent electrodes 12 (12A, 12B) are thin films that are both transparent and conductive. The transparent electrodes 12 are preferably made of indium tin oxide (ITO), but may be made of other transparent conductive films such as tin oxide or zinc oxide. The transparent electrodes 12A and 12B may be made of the same material or different materials. The transparent electrode 12 can be formed on the surface of the light-transmitting substrate 11 by a general sputtering film formation method.

[0026] Furthermore, on the transparent electrode substrate 10 (10A in this example) on the side where the metal salt is deposited, an insulating layer 13 having light-transmitting properties is laminated on only a predetermined partial region of the transparent electrode 12. The method for laminating this insulating layer 13 will be described later. The transparent electrode substrates 10A and 10B are arranged so that the transparent electrodes 12A and 12B face each other with a gap therebetween.

[0027] <Insulating layer> The insulating layer 13 transmits light and blocks current. The insulating layer 13 has a volume resistivity of 10 8 It is preferable to use a material with a resistivity of Ω·cm or higher. For the insulating layer 13, for example, silicon oxide, gallium oxide, cerium oxide, silicon nitride, carbon nitride, silicon carbide, or the like can be used as an insulating film. When an insulating film is used as the insulating layer 13, the insulating film may be laminated on the transparent electrode substrate 10 by a semiconductor process. Examples of the semiconductor process that can be used include a CVD (Chemical Vapor Deposition) method and an ALD (Atomic Layer Deposition) method.

[0028] Furthermore, the insulating layer 13 can be made of an insulating material such as glass, a resin material (Teflon (registered trademark), film, stencil mask, plastic, etc.), a light-transmitting tape (Kapton (registered trademark) tape), or a light-transmitting paper (cellulose nanofiber). When an insulator is used as the insulating layer 13, the insulator may be attached to the transparent electrode substrate 10. The size and area of ​​the insulating layer 13 laminated (attached) to the transparent electrode substrate 10 are arbitrary. For example, the shape of the insulating layer 13 may be any shape, such as a square, a circle, a polygon, a letter, a pattern, or the like.

[0029] Here, examples of lamination of insulating layer 13 will be described with reference to FIGS. 4A is a front view of the transparent electrode substrate 10, and FIG. 4B is a cross-sectional view of the transparent electrode substrate 10 taken along line IV-IV in FIG. 4A. As shown in Figures 4A and 4B, by laminating an insulating layer 13 in a rectangular shape in the center of the transparent electrode substrate 10, dimming is not performed in the rectangular area, and dimming is performed only in the rectangular peripheral area.

[0030] FIG. 5A is a front view of the transparent electrode substrate 10, and FIG. 5B is a VV cross-sectional view of the transparent electrode substrate 10 of FIG. 5A. As shown in Figures 5A and 5B, by laminating an insulating layer 13 on the rectangular peripheral region of the transparent electrode substrate 10, light control is performed only in the rectangular region, and light control is not performed in the rectangular peripheral region. Here, the insulating layer 13 has a rectangular shape, but it may have any other shape such as a circle, a triangle, etc. Also, a plurality of insulating layers 13 may be provided to form a plurality of shapes.

[0031] 6A is a front view of the transparent electrode substrate 10, and FIG. 6B is a cross-sectional view of the transparent electrode substrate 10 taken along the line VI-VI in FIG. 6A. As shown in Figures 6A and 6B, by laminating an insulating layer 13 in the shape of a letter (letter "A") in the center of the transparent electrode substrate 10, dimming is not performed in the area of ​​the letter shape, and dimming is performed only in the outer peripheral area of ​​the letter shape.

[0032] 7A is a front view of the transparent electrode substrate 10, and FIG. 7B is a cross-sectional view of the transparent electrode substrate 10 taken along line VII-VII of FIG. 7A. As shown in Figures 7A and 7B, by laminating an insulating layer 13 on the outer peripheral area of ​​the character shape (character "A") of the transparent electrode substrate 10, light control is performed only in the character shape area, and light control is not performed in the outer peripheral area of ​​the character shape. Here, the insulating layer 13 is shaped like the letter "A," but may be shaped like other letters. Also, a plurality of insulating layers 13 may be provided to form a plurality of letter shapes. In this way, dimming can be performed in an area of ​​any shape simply by changing the area of ​​the insulating layer 13. In addition, since the area other than the dimming area is insulated, dimming response can be improved. Returning to FIG. 1, the configuration of the light control element 1 will be further described.

[0033] <Electrolyte> The electrolyte 20 is an electrically conductive solution in which a metal salt is dissolved. For example, the electrolyte 20 is a solution in which a silver salt such as silver nitrate (AgNO3) is dissolved in a non-aqueous solvent containing an ester solvent such as propylene carbonate and an alcohol such as methanol so as to contain silver ions. The electrolyte 20 may also contain copper ions, which have a smaller weight content than the silver ions. In this case, a copper salt such as cupric chloride (CuCl2) may be dissolved in the non-aqueous solvent. The electrolyte 20 is nearly colorless and transparent.

[0034] The non-aqueous solvent may further contain a supporting electrolyte such as lithium bromide (LiBr) to increase conductivity. The non-aqueous solvent may further contain a thickener to distribute the metal ions evenly. Examples of the thickener include polymers such as polypropylene, polyvinyl butyral, and polymethyl methacrylate.

[0035] The electrolyte solution 20 is sealed in the gap between the pair of transparent electrodes 12 (12A, 12B) by a sealant 30. When a voltage is applied, the electrolyte solution 20 deposits metal salts on the cathode (-) side transparent electrode 12A to form a deposit layer 14, and when the polarity is reversed, the deposit layer 14 is reduced to metal ions.

[0036] <Sealing material> The sealing material 30 is a sealant that seals the electrolyte solution 20 in the space between the pair of transparent electrodes 12 (12A, 12B). The material of the sealing material 30 is not particularly limited, but may be, for example, glass, resin, or the like. The sealing material 30 seals the electrolyte 20 between the pair of transparent electrodes 12 (12A, 12B) so as to maintain a gap of about 0.3 mm in thickness between the pair of transparent electrodes 12. This forms an electrolyte tank SP.

[0037] With the above-described configuration, the light control device 1 can control light in a partial region excluding the region where the insulating layer 13 is laminated. For example, when the dimming element 1 is used as a filter for a television camera, an insulating layer 13 is laminated in advance in the area corresponding to the turret, so that the reversible precipitation and reduction of metal salts can be performed only in the area where dimming is actually performed, thereby improving the responsiveness of the dimming operation. Furthermore, the light-adjusting element 1 can be used as a button for displaying characters or the like, a window material for displaying graphics, or the like, by forming the insulating layer 13 into any shape.

[0038] <Manufacturing method of light-adjusting element> A method for manufacturing the light control device 1 according to the embodiment of the present invention will be described with reference to FIG. 8 (and also with reference to FIG. 1 where appropriate). The manufacturing method of the photochromic device 1 includes a substrate forming step S1, an insulating layer laminating step S2, an electrode pair forming step S3, and an electrolyte filling step S4. Note that, except for the insulating layer laminating step S2, the manufacturing process is the same as that of a conventional metal salt precipitation photochromic device, so only an outline will be explained.

[0039] <Substrate generation process> The substrate producing step S1 is a step of producing a transparent electrode substrate 10. In this substrate producing step S1, a transparent electrode 12 (for example, ITO) is laminated on a light-transmitting substrate 11 (for example, a glass substrate) by a sputtering film formation method, thereby producing the transparent electrode substrate 10. Here, a transparent electrode substrate 10A (first transparent electrode substrate) and a transparent electrode substrate 10B (second transparent electrode substrate) are produced.

[0040] <Insulating layer lamination process> The insulating layer laminating step S2 is a step of laminating and arranging a light-transmitting insulating layer 13 in a predetermined partial region of the transparent electrode 12 of at least one of the first and second transparent electrode substrates 10A and 10B. Here, in the insulating layer laminating step S2, the insulating layer 13 is laminated on the transparent electrode 12A. For example, in the insulating layer laminating step S2, an insulating material (such as tape) is attached to a predetermined partial region where the dimming operation is not performed. Also, for example, in the insulating layer laminating step S2, areas other than a predetermined region where light control operation is not performed are masked, and an insulating film is laminated by a CVD method, an ALD method, etc. An example of the laminating step of the insulating layer 13 using this semiconductor process will be described with reference to FIGS.

[0041] (Example 1) 9A to 9C show a first example (mask method) of the lamination process of insulating layer 13. FIG. 9A, in the insulating layer laminating step S2, a mask 50 is placed in close contact with an area (area for light control) on the transparent electrode 12 side of the transparent electrode substrate 10 where the insulating layer 13 is not laminated. The mask 50 is a metal mask made of, for example, SUS302 (stainless steel) or the like. Then, as shown in FIG. 9B, in the insulating layer laminating step S2, an insulating film is formed as the insulating layer 13 by a CVD method, an ALD method, or the like. Then, as shown in FIG. 9C, in the insulating layer laminating step S2, the mask 50 is removed, leaving only the insulating layer 13 laminated on the transparent electrode 12.

[0042] (Example 2) 10A to 10E show a second example (photolithography (resist method)) of the lamination process of insulating layer 13. FIG. As shown in FIG. 10A, in the insulating layer laminating step S2, a resist material 60 is applied to the entire transparent electrode 12 side of the transparent electrode substrate 10. 10B, in the insulating layer laminating step S2, a mask 50 is formed in the region where the insulating layer 13 is to be laminated (region where light control is not performed), and then exposed to light. Here, the mask 50 is formed by adhering a light-opaque metal such as chromium along the region where the insulating layer 13 is to be laminated, and exposure to ultraviolet light 100 is performed. After exposure, the mask 50 is peeled off.

[0043] 10C, in the insulating layer laminating step S2, the resist material 60 that has been irradiated with ultraviolet light 100 due to the mask 50 (FIG. 10B) is left, and the resist material 60 that has been irradiated with ultraviolet light is peeled off to form openings. Note that in this example, a positive resist is used as the resist material 60, and the unexposed portion that has not been irradiated with ultraviolet light 100 is peeled off by a developer. Thereafter, as shown in FIG. 10D, in the insulating layer laminating step S2, an insulating film is formed as the insulating layer 13 in the region opened in FIG. 10C by a CVD method, an ALD method, or the like. Finally, as shown in FIG. 10E, in the insulating layer laminating step S2, the resist material 60 (FIG. 10D) is removed using a remover, so that only the insulating layer 13 remains laminated on the transparent electrode 12. The method using the resist material 60 described in Figure 10 (resist method) is superior to the method described in Figure 9 (mask method) in that it allows for the insulating layer 13 to be formed finely on the transparent electrode 12. Returning to FIG. 8, the method for manufacturing the light control element 1 will be described further.

[0044] <Electrode pair generation process> The electrode pair forming step S3 is a step of forming an electrode pair by opposing the first and second transparent electrode substrates 10A and 10B and spaced apart by a predetermined distance. In this electrode pair generation step S3, the transparent electrode substrates 10A and 10B are arranged with a gap (e.g., 0.3 mm) between them, with the sealing material 30 as a spacer, so that the transparent electrodes 12A and 12B face each other. The sealing material 30 is arranged so as to surround all four sides of the gap. The transparent electrodes 12A and 12B and the sealing material 30 may be bonded together with an adhesive or the like.

[0045] <Electrolyte filling process> The electrolyte filling step S4 is a step of filling the space formed by the sealing material 30 of the electrode pair generated in the electrode pair generation step S3 with an electrolyte 20 containing at least silver ions as the metal ions of the metal salt. In the electrolyte filling step S4, for example, a fine injection needle is used to fill the electrolyte 20. In this way, an electrolyte tank SP is formed. By applying a voltage to the transparent electrodes 12A and 12B of the light control element 1 produced by the above process, the light control element 1 can control light in a partial area excluding the area where the insulating layer 13 is laminated.

[0046] <Transmittance experiment results> Next, with reference to FIGS. 11A and 11B (and also with reference to FIG. 1 as needed), the results of experiments on the light transmittance of the light control element 1 depending on the material of the insulating layer 13 will be described. 11A is a graph showing the results of Experiment 1 below, which was measured using Kapton (registered trademark) tape as insulating layer 13, and FIG. 11B is a graph showing the results of Experiment 2 below, which was measured using aluminum oxide as insulating layer 13. In both graphs, the horizontal axis represents wavelength (nm) and the vertical axis represents the transmittance (%) of insulating layer 13.

[0047] <Experiment 1> In Experiment 1, in the light-controlling element 1 shown in FIG. 1, a transparent electrode 12 (material: crystalline ITO, film thickness: 150 nm, film resistance: 9.1×10 Ω / cm ) was formed on the surface of a light-transmitting substrate 11 (thickness: 0.7 mm, size: 50 mm × 34 mm). 2 ) was formed, and Kapton (registered trademark) tape was used as the insulating layer 13 on the surface of the transparent electrode 12A on the metal salt deposition side. Here, the applied voltage of the driving power supply 2 was set to 2.8 V. This was to confirm that metal salts would not be deposited on the insulating layer 13 by applying a voltage higher than that in normal operation (2.0 V to 2.5 V). Even after 120 seconds had passed since the voltage application, the transmittance of insulating layer 13 remained almost unchanged regardless of the passage of time, as shown in the graph in Fig. 11A. In this experiment, metal salts were instantly deposited in the region where insulating layer 13 was not stacked.

[0048] <Experiment 2> In Experiment 2, the light-control element 1 shown in Fig. 1 was used, with aluminum oxide layered as the insulating layer 13 in the lamination process described with reference to Fig. 9A on the transparent electrode substrate 10, which was composed of the same light-transmitting substrate 11 and transparent electrode 12 as in Experiment 1. An ALD apparatus was used to deposit the aluminum oxide layer, and TMA (trimethylaluminum) was oxidized using plasma to form a film with a thickness of 20 nm. Here, the voltage applied to the driving power supply 2 is set to 2.2 V, which is the same as that in normal operation. Even after 180 seconds had passed since the voltage application, the transmittance of insulating layer 13 remained almost unchanged regardless of the passage of time, as shown in the graph in Fig. 11B. In this experiment, too, metal salts were instantly deposited in the areas where insulating layer 13 was not stacked.

[0049] The above experimental results demonstrate that the dimming element 1 can maintain a nearly constant transmittance in the region where the insulating layer 13 is laminated, regardless of the applied voltage, and that the transmittance can be variably controlled in other partial regions. Although the light control element 1 according to the embodiment of the present invention has been described above, the present invention is not limited to this embodiment. Modifications of the light control element 1 will be described below.

[0050] <Modification of dimming element> <Variation 1> In the light-adjusting element 1 of FIG. 1, of the pair of transparent electrodes 12A and 12B that make up the electrode pair, deposition of metal salt is carried out only on the surface of the transparent electrode 12A. However, the deposition of the metal salt may be carried out on the surfaces of both of the pair of transparent electrodes 12A and 12B.

[0051] FIG. 12 shows the configuration of a light-adjusting element 1B in which metal salts are deposited on the surfaces of both transparent electrodes 12A and 12B. The light control element 1B has insulating layers 13A and 13B disposed on both surfaces of the transparent electrodes 12A and 12B of the light control element 1. That is, the light control device 1B differs from the light control device 1 only in that the insulating layer 13B is also disposed in a predetermined partial region of the transparent electrode 12B.

[0052] The light control device 1B can achieve a light control operation alternately in a plurality of regions by controlling the voltage applied to the driving power supply 2. Specifically, when the transparent electrode 12A is set as the cathode (-) and the transparent electrode 12B is set as the anode (+) and the driving power supply 2 applies a voltage of about 2.0V to 2.5V, metal salts are deposited on the surface of the transparent electrode 12A to form a deposition layer 14A. In this case, as shown in FIG. 13A, when the dimming element 1B is viewed from the front, light is transmitted through the area where the insulating layer 13A is formed, but the transmittance is reduced or light is blocked in the area where the deposition layer 14A is formed.

[0053] After the deposition layer 14A is formed on the transparent electrode 12A, the polarity of the voltage applied to the dimming element 1B is reversed, with the transparent electrode 12A as the anode (+) and the transparent electrode 12B as the cathode (-), and a voltage of approximately 0.4V to 0.7V is applied from the driving power supply 2, whereby the deposition layer 14A on the transparent electrode 12A is reduced to metal ions. Furthermore, when the voltage of the driving power supply 2 is increased to about 2.0 V to 2.5 V with this polarity maintained, a metal salt is deposited on the surface of the transparent electrode 12B of the light-adjusting element 1B, forming a deposition layer 14B. In this case, as shown in FIG. 13B, when the dimming element 1B is viewed from the front, light is transmitted through the area where the insulating layer 13B is formed, but the transmittance is reduced or light is blocked in the area where the deposition layer 14B is formed.

[0054] After the deposition layer 14B is formed on the transparent electrode 12B, the polarity of the voltage applied to the dimming element 1B is reversed, with the transparent electrode 12A as the cathode (-) and the transparent electrode 12B as the anode (+), and a voltage of approximately 0.4V to 0.7V is applied from the driving power supply 2, whereby the deposition layer 14B on the transparent electrode 12B is reduced to metal ions, causing a decoloring operation. In this way, the light-adjusting device 1B can adjust the transmittance in a plurality of different partial regions by controlling the voltage.

[0055] <Variation 2> In the light-adjusting element 1 of FIG. 1, there is one tank (electrolyte tank SP) of the electrolyte 20 sandwiched between a pair of transparent electrodes 12A and 12B that form an electrode pair. However, the electrolyte tank SP may have two tanks.

[0056] FIG. 14 shows the configuration of a light-adjusting device 1C having two electrolyte tanks (electrolyte tanks SP1 and SP2). The light control element 1C is configured by opposing two light control elements 1. The transparent electrode substrate 10B2 shares the light-transmitting substrate 11B with the two light control elements 1, and transparent electrodes 12 (12B, 12B2) are formed on both sides of the light-transmitting substrate 11B. As a result, there are two tanks of the electrolytic solution 20 (electrolytic solution tanks SP1, SP2). In the light control element 1C, an insulating layer 13A is formed on the surface of a transparent electrode 12A, and a light-transmitting insulating layer 13C is laminated on the surface of a transparent electrode 12C.

[0057] In this case, the light control device 1C can simultaneously achieve light control by controlling the voltages applied to the drive power supplies 2 and 2B. Therefore, the light control device 1C can speed up the response of the light control operation due to the deposition of metal salts. Specifically, when the transparent electrode 12A is set as the cathode (-) and the transparent electrode 12B is set as the anode (+) and the driving power supply 2 applies a voltage of about 2.0V to 2.5V, metal salts are deposited on the surface of the transparent electrode 12A to form a deposition layer 14A.

[0058] After the deposition layer 14A is formed on the transparent electrode 12A, the polarity of the applied voltage is reversed, with the transparent electrode 12A as the anode (+) and the transparent electrode 12B as the cathode (-), and when the driving power supply 2 applies a voltage of approximately 0.4V to 0.7V, the deposition layer 14A on the transparent electrode 12A is reduced to metal ions.

[0059] Similarly, when the driving power supply 2B applies a voltage of about 2.0V to 2.5V with the transparent electrode 12C as the cathode (-) and the transparent electrode 12B2 as the anode (+), metal salts are deposited on the surface of the transparent electrode 12C to form a deposition layer 14C. After the deposition layer 14C is formed on the transparent electrode 12C, the polarity of the applied voltage is reversed, with the transparent electrode 12C as the anode (+) and the transparent electrode 12B2 as the cathode (-), and a voltage of approximately 0.4V to 0.7V is applied from the driving power supply 2B, whereby the deposition layer 14C on the transparent electrode 12C is reduced to metal ions. This allows the light-adjusting device 1C to control the deposition and reduction of metal salts in each of the two electrolyte tanks SP1 and SP2.

[0060] For example, when the region of the insulating layer 13A and the region of the insulating layer 13C do not overlap in a plan view, the light control device 1C can control various changes in light control, as shown in FIGS. 15A to 15D. In other words, when metal salts are precipitated in only the electrolyte tank SP1 in the dimming element 1C, as shown in Figure 15A, light is transmitted in the area where the insulating layer 13A is formed, but the transmittance is reduced or light is blocked in the area where the precipitate layer 14A is formed (including the area of ​​the insulating layer 13C).

[0061] Furthermore, when metal salts are precipitated in only the electrolyte tank SP2 in the dimming element 1C, as shown in Figure 15B, light is transmitted through the area where the insulating layer 13C is formed, but the transmittance is reduced or light is blocked in the area where the precipitate layer 14C is formed (including the area of ​​the insulating layer 13A).

[0062] Furthermore, when metal salts are precipitated in both electrolyte tanks SP1 and SP2, the dimming element 1C can reduce the transmittance in the areas where insulating layers 13A and 13C are formed, as shown in Figure 15C, or can block light in the areas where insulating layers 13A and 13C are formed, as shown in Figure 15D, depending on the amount of precipitation. To reduce the precipitate layer 14A to metal ions, the transparent electrode 12A is set as the anode (+), the transparent electrode 12B is set as the cathode (-), and a voltage of about 0.4 V to 0.7 V is applied from the driving power supply 2. Similarly, to reduce the precipitate layer 14C to metal ions, the transparent electrode 12C is set as the anode (+), the transparent electrode 12B2 is set as the cathode (-), and a voltage of about 0.4 V to 0.7 V is applied from the driving power supply 2B.

[0063] In this way, the light-adjusting device 1C can control the deposition and reduction of the deposition layers 14A and 14C simultaneously or individually. As a result, by controlling the voltage and applied polarity, the light control element 1C can adjust the transmittance, display characters, graphics, etc., transition to a non-transparent state, transition to a completely transparent state, etc. For example, by laminating the character string "ON" as the insulating layer 13A and the character string "OFF" as the insulating layer 13C, it is possible to switch between displaying each character string. The light control element 1C may have an insulating layer formed on the transparent electrodes 12B and 12B2.

[0064] The photochromic elements according to the embodiments of the present invention and their variations described above can be used, for example, as camera filters (ND (Neutral Density) filters) that partially adjust the amount of light incident from the outside, anti-glare mirrors, photochromic filters for lighting, window materials, etc. Furthermore, the light control element according to the embodiment of the present invention and its modified examples can be used as a light control element for a display device that displays any characters, patterns, or the like. [Explanation of symbols]

[0065] 1. Dimming element 2. Drive power supply 10 Transparent electrode substrate 11 Translucent substrate 12 Transparent electrode 13 Insulating layer 20 Electrolyte 30 Encapsulating material 50 Mask 60 Resist material 100 UV rays

Claims

1. A metal salt deposition electrochromic light control element that controls light partially, a pair of transparent electrode substrates in which transparent electrodes forming an electrode pair are opposed to each other with a gap therebetween; an electrolyte solution filled in the gap and containing at least silver ions as metal ions of a metal salt; a sealant that seals the electrolyte in the gap, A light-controlling element, characterized in that a light-transmitting insulating layer is disposed in a partial region of the transparent electrode where the metal salt is precipitated in response to voltage control of the electrode pair.

2. 2. The light-adjusting element according to claim 1, wherein the insulating layer is disposed on a partial area of ​​one or both of the transparent electrodes constituting the electrode pair.

3. The insulating layer has a volume resistivity of 10 ８ 2. The light-adjusting element according to claim 1, wherein the resistivity is Ω·cm or more.

4. 2. The light control element according to claim 1, wherein the insulating layer is made of aluminum oxide, silicon oxide, gallium oxide, cerium oxide, silicon nitride, carbon nitride, or silicon carbide.

5. 2. The light control element according to claim 1, wherein the insulating layer is made of glass, a resin material, a light-transmitting tape, or a light-transmitting paper.

6. The light-adjusting element according to claim 1 , wherein the insulating layer has a shape of a square, a circle, a polygon, a letter, or a pattern.

7. A method for manufacturing a metal salt deposition electrochromic light control element for partially controlling light, comprising: laminating a transparent electrode on a light-transmitting substrate to produce first and second transparent electrode substrates; a step of laminating and disposing a light-transmitting insulating layer on a predetermined partial region of the transparent electrode of at least one of the first and second transparent electrode substrates; a step of forming an electrode pair by opposing the first and second transparent electrode substrates, at least one of which has the transparent electrode laminated thereon, and spaced apart by a predetermined distance; a step of filling the gap with an electrolyte solution containing at least silver ions as metal ions of a metal salt; A method for manufacturing a light control element, comprising:

Images