JP2006337635A - Photoelectrochromic element, light-controlling glass, transmittance adjusting glass, heat ray cut glass, and image display device - Google Patents

Photoelectrochromic element, light-controlling glass, transmittance adjusting glass, heat ray cut glass, and image display device Download PDF

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JP2006337635A
JP2006337635A JP2005161098A JP2005161098A JP2006337635A JP 2006337635 A JP2006337635 A JP 2006337635A JP 2005161098 A JP2005161098 A JP 2005161098A JP 2005161098 A JP2005161098 A JP 2005161098A JP 2006337635 A JP2006337635 A JP 2006337635A
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film
oxide
photoelectrochromic
device according
transparent
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Yoshinori Iwabuchi
Shingo Ono
Shinichiro Sugi
Masahito Yoshikawa
雅人 吉川
信吾 大野
芳典 岩淵
信一郎 杉
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Bridgestone Corp
株式会社ブリヂストン
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Abstract

【Task】
To provide a photoelectrochromic element that can arbitrarily switch between coloring and decoloring even without an external power source.
[Solution]
An electrode film including a transparent substrate, a transparent electrode film laminated thereon, an electrochromic film, and a metal oxide semiconductor electrode film adsorbing an organic dye, a transparent substrate, and a transparent electrode film and a catalyst thin film laminated thereon A photoelectrochromic device comprising a counter electrode film and an electrolyte sandwiched between the two electrode films.
[Selection] Figure 1

Description

  The present invention relates to a light control glass, a transmittance adjusting glass, a heat ray cut glass, and a photoelectrochromic element that can be advantageously used in an image display device.

  In buildings, such as buildings, it is well known that windows are places where large amounts of heat come and go. For example, there is a report that the rate of heat flowing out of the window during winter heating is about 48%, and the rate of heat entering from the window during cooling in summer reaches 71%. Therefore, it is clear that enormous energy saving can be achieved if the flow of light and heat can be appropriately controlled in such a window.

  Glass capable of performing such light and heat flow control is known as light control glass. A typical example is one using an electrochromic material whose transmittance is reversibly changed by application of an electric current. For example, an electrochromic glass using a tungsten oxide thin film is known.

In such an electrochromic light control glass, transparent electrode films (ITO (indium / tin-oxide), SnO 2 is generally known) attached on a glass plate are arranged to face each other. An electrode (a conductive paste such as silver or copper, a foil, or a plate is generally known) is provided around the inner side surface (attachment surface of the transparent electrode film) of the two glass plates. Tungsten oxide is further deposited on the transparent electrode film of one of the two glass plates, the periphery between the two glass plates is sealed with a sealing agent, and an electrolyte is provided on the inner peripheral side of the sealing agent. Is enclosed. By energizing this electrolyte through the electrodes installed on the respective glass plates, the electrolyte and tungsten oxide are colored and decolored by the reaction between the electrolyte and tungsten oxide. Such an electrochromic light control glass is described in, for example, Japanese Patent Application Laid-Open No. 2003-344876.

JP 2003-344876 A

  As described above, in the electrochromic light control glass, electric wires and electrodes are joined so that electricity can be supplied from an external power source through the electric wires in order to drive. The conductor used for the electrode is an electrically low resistance material such as silver or copper, and its resistance value is lower than the resistance value of the transparent electrode film adhering to almost the entire surface of the glass plate. It can be energized, and the transparent electrode film can be energized from the entire circumference of the electrode. As described above, in the electrochromic light control glass, an external power source is required for coloring and decoloring, and thus there are problems such as restrictions in use or increase in electricity charges.

  On the other hand, a photochromic material, which is a material whose color and the like change with light, is also known, but no practical material is known that can control the transmittance to an appropriate brightness. Also, it is not possible to arbitrarily switch between coloring and decoloring.

  Accordingly, an object of the present invention is to provide a photoelectrochromic element that can be arbitrarily switched between coloring and decoloring even without an external power source.

  Another object of the present invention is to provide a light control glass capable of arbitrarily switching between coloring and decoloring even without an external power source.

  Furthermore, an object of the present invention is to provide a transmittance adjusting glass capable of arbitrarily switching between coloring and decoloring even without an external power source.

  It is another object of the present invention to provide a heat ray cut glass that can be arbitrarily switched between coloring and decoloring even without an external power source.

  Furthermore, an object of the present invention is to provide an image display device that can arbitrarily switch between coloring and decoloring even without an external power source.

The present invention
An electrode film comprising a transparent substrate, a transparent electrode film laminated thereon, an electrochromic film, and a metal oxide semiconductor electrode film in which an organic dye (spectral sensitizing dye) is adsorbed on a metal oxide semiconductor;
A counter electrode film comprising a transparent substrate, a transparent electrode film and a catalyst thin film laminated thereon, and an electrolyte sandwiched between these two electrode films,
A photoelectrochromic device including

  In the photoelectrochromic device of the present invention, preferred embodiments are as follows.

  1) A switching element is provided between both transparent electrodes.

  2) Between the transparent electrodes, an external circuit capable of switching that can be connected to an external power source is provided. This is convenient when driving with a solar cell becomes impossible, or when driving with an external power source is desired.

  3) A direct current is applied by an external circuit.

  4) The transparent substrate is a transparent resin film. Since it is flexible, it can be applied in various shapes. As a material for the transparent resin film, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, polyether sulfide (PES) or fluororesin is preferable.

  5) At least one of a transparent electrode film, an electrochromic film, a metal oxide semiconductor film, and a catalyst thin film is formed by a vapor deposition method. It is preferable to form all the films by a vapor deposition method.

  6) Examples of the vapor deposition method include physical vapor deposition, vacuum vapor deposition, sputtering, ion plating, CVD or plasma CVD, and particularly reactive sputtering, plasma emission feedback or A high-speed film formation method using impedance feedback or a dual cathode sputtering method is preferable.

  7) Titanium oxide, zinc oxide, tin oxide, antimony oxide, niobium oxide, tungsten oxide or indium oxide, or a metal oxide semiconductor film doped with other metals or other metal oxides Formed from. In particular, it is preferably formed from titanium oxide, zinc oxide or tin oxide. This is advantageous in that power can be generated efficiently even with a small amount of pigment, and that power can be generated efficiently even if the amount of light is small.

  8) The electrochromic film was doped with hydrogen, lithium, sodium or potassium in tungsten oxide, tantalum oxide, molybdenum oxide, titanium oxide, vanadium oxide, rhodium oxide, niobium oxide, nickel oxide, iridium oxide or their oxides. Formed from things. The use of these materials, in particular tungsten oxide, or tungsten oxide doped with alkali metals (preferably Li or K) or hydrogen is advantageous because of the large change in transmittance during coloring and decoloring.

The present invention also provides:
A light control glass comprising the photoelectrochromic element;
A transmittance adjusting glass comprising the photoelectrochromic element;
There is also an image display device including the above-described photoelectrochromic element; and a heat ray cut glass including the above-described photoelectrochromic element.

  The image display device can be produced by, for example, providing a patterned transparent electrode on the element of the present invention. The heat ray cut glass can be obtained by appropriately changing the material and thickness of the electrochromic film because the electrochromic film absorbs and reflects heat rays (IR).

  In the photoelectrochromic device of the present invention, an electrochromic film is incorporated in a conventional organic dye-sensitized solar cell. For this reason, since an electric current can be introduced into the element without an external power supply, the coloring or decoloring of the electrochromic element can be arbitrarily switched without providing an external circuit for supplying the external power supply. . In addition, when an external circuit is provided, it is easy to control coloring / decoloring in the absence of light such as at night, and the degree of coloring / decoloring can be greatly improved. . Therefore, the use of the element is greatly expanded by providing the external electrode.

  In particular, each layer (film) of the element of the present invention can be formed at a low temperature by using a vapor phase film forming method such as sputtering, so that a flexible element using a polymer substrate can be produced. Is possible. In addition, when a high-speed film formation method using plasma emission feedback or impedance feedback or a dual cathode sputtering method is used as a vapor phase film formation method, a film formation at a particularly high speed is possible, and device productivity is improved. Greatly improved.

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

  FIG. 1 is a cross-sectional view showing an example of an embodiment of the photoelectrochromic device of the present invention.

  In FIG. 1, a transparent substrate 11A, a transparent electrode film 12A is provided on the surface thereof, and a catalyst thin layer 13 is formed on the surface of the transparent electrode film, thereby forming an electrode film 1A. A transparent electrode film 12B is formed on the surface, an electrochromic film 16 is formed on the surface of the transparent electrode film, and a metal oxide semiconductor electrode film 15 having a spectral sensitizing dye adsorbed on the metal oxide semiconductor is formed on the transparent electrode film 12B. 1B is configured. These two electrode films 1A and 1B are stacked with the transparent electrode films facing each other, and an electrolyte 14 is enclosed between them. Further, the transparent electrode film 12A and the transparent electrode film 12B are connected on one side, and a switch Sw1 for conducting electricity is provided in the middle. Thus, when the switch Sw1 is turned on, the potential difference between the two electrode films becomes zero. The transparent electrode film 12A is also connected to the transparent electrode film 12B on the other side, and an external circuit 17 connected to an external power source and a switch Sw2 for conducting electricity are provided in the middle. The circuit 17 may be omitted, but the control of the element is limited in the absence of light. Although the switch Sw1 is generally provided, coloring and decoloring can be performed by irradiating light and releasing electricity without the switch.

  The connection between the switch Sw1 or the switch Sw2 including the external circuit 17 connected to the external power source and the transparent electrode film is generally as follows. Wiring of electrically low resistance material such as silver and copper around the transparent electrode film adhering to almost the entire surface of the transparent substrate so that electricity can be supplied (or interrupted by electricity) from an external power source. Electrode). The wiring material is an electrically low resistance material such as silver or copper as described above, and its resistance value is lower than the resistance value of the transparent electrode film. Can escape.

  In the photoelectrochromic device of the present invention, the layers (films) are preferably laminated in the order as described above, but even if the order is slightly changed (for example, the electrochromic layer is a transparent electrode film of a counter electrode) (It may be provided above.) It may be usable. An auxiliary layer such as an adhesive layer may be provided between these layers (films).

  In the photoelectrochromic device of the present invention shown in FIG. 1 above, when an external power supply is not used, the switch Sw2 of the external circuit 17 connected to the external power supply is normally turned off and used so that the solar cell works. . Specifically, when the switch Sw1 is turned off under the condition that light such as sunlight is irradiated when an external power source is not used, due to excitation due to light absorption of the spectral sensitizing dye of the semiconductor electrode film, Between the transparent electrode film 12A and the transparent electrode film 12B, electricity flows by the electrolyte 14, and therefore electricity also flows through the electrochromic film 16, and charges and ions are injected into the electrochromic material to be colored (the transmittance decreases). To do). Similarly, when the switch Sw1 is turned on under the condition of irradiation with light such as sunlight, the charge injected into the electrochromic film 16 passes through the external circuit (external circuit including Sw1) via Sw1. Flow out to the transparent electrode film 12A. For this reason, the electrochromic film 16 loses charge and ions and is decolored (the transmittance is improved).

  On the other hand, when the switch Sw1 is turned off under the condition that the light such as sunlight is not irradiated, the charges and ions injected into the electrochromic film 16 are held in the film 16, so that the electrochromic film 16 In the state, that is, in the colored state, the coloring is maintained. When the switch Sw1 is turned on without light irradiation, the potential difference between the transparent electrode film 12A and the transparent electrode film 12B becomes 0, so that the electrochromic film 16 is decolored (transmittance is improved).

  Therefore, in the photoelectrochromic device of the present invention, the coloring and decoloring of the electrochromic film 16 can be freely selected, particularly during light irradiation, without an external circuit having a power source. In addition, for example, since it is usually not necessary to change the coloring / decoloring of the electrochromic film 16 after the sunlight is no longer irradiated at night, the photoelectrochromic element of the present invention has an external circuit. It can be said that it is sufficiently practical even without it.

  When the external circuit 17 connected to the external power source is used under the condition of no light irradiation (Sw1 is turned off so that electricity does not escape), when the switch Sw2 is turned on, the transparent electrode film 12A and the transparent electrode film 12B During this period, electricity flows through the electrochromic film 16 and is colored (the transmittance is reduced). When the switch Sw2 is turned off and the switch Sw1 is turned on, the charge and ions flow out from the electrochromic film 16 until the potential difference between the transparent electrode 12A and the transparent electrode 12B disappears. (Transmittance is improved).

  As described above, in the photoelectrochromic device of the present invention, when the external circuit is included, the coloring and decoloring can be freely controlled even under the condition where no light is irradiated at night or the like, and it is used for a wide range of applications. can do.

  The photoelectrochromic device of the present invention is produced using a flexible transparent resin film on a transparent substrate, and this is affixed to a glass plate or the like as necessary, and light control glass, transmittance adjustment glass, image It may be used as a display device or heat ray cut glass, or a glass plate is used for one or both of the transparent substrates, and the obtained element is used as it is for light control glass, transmittance adjustment glass, image display device or heat ray cut glass. May be used as

  Further, on the inner side surfaces of the two transparent substrates, a dark color concealing layer such as a black ceramic paste may be provided around each of them. Further, a peripheral adhesive sealant may be provided around the periphery of the two transparent substrates. Generally, an electrolyte is sealed on the inner peripheral side of the peripheral adhesive sealant. The black ceramic paste hides the peripheral terminal of the electrolyte, which is a part of the structure responsible for driving, and the peripheral electrode so that they cannot be seen in appearance.

  Each material used for the photoelectrochromic device of the present invention will be described.

  As the transparent substrates 11 </ b> A and 11 </ b> B, various transparent organic resin substrates or glass substrates that can ensure visible light transmittance can be used. In the case of an organic resin substrate, the thickness is generally 25 μm to 10 mm, preferably 0.1 to 10 mm. Examples of organic resins include polyesters such as polyethylene terephthalate, acrylic resins such as polymethyl methacrylate, fluororesins such as polycarbonate, PTFE (polytetrafluoroethylene) and ETFE (ethylene / tetrafluoroethylene copolymer). Can do. In the case of a glass substrate, the thickness is generally 25 μm to 10 mm, preferably 0.5 to 5 mm.

  On the organic resin substrate, it is preferable to provide an adhesive layer for adhering to other materials, and in that case, it is preferable to provide a release film for protection on the adhesive layer. As the release film, a polycarbonate film, a PET film, or the like is used. In general, the thickness is preferably 1 to 1000 μm and 10 to 500 μm. Examples of the resin used for the adhesive layer include an ethylene / vinyl acetate copolymer and an adhesive acrylic resin (eg, butyl acrylate polymer). These resins may be crosslinked by heating or the like. In general, the thickness is preferably 1 to 1000 μm and 10 to 500 μm.

As the transparent electrode films 12A and 12B, a substrate formed of a conductive metal oxide thin film of In 2 O 3 or SnO 2 or a substrate made of a conductive material such as metal is used. Preferred examples of the conductive metal oxide include In 2 O 3 : Sn (ITO), SnO 2 : Sb (ATO), SnO 2 : F (FTO), ZnO: Al, ZnO: F, and CdSnO 4. Can do. ITO, ATO, and FTO are particularly preferable.

A catalyst thin film 13 is provided on one of the transparent electrode films 12A. As will be described later, the catalyst thin film has a function of causing a reduction reaction of oxidized redox ions such as I 3 ions at a sufficient speed. Examples of the material include metals such as platinum, gold, silver, copper, rhodium, and ruthenium, ruthenium oxide, and carbon. In particular, platinum is preferable. The thickness is generally 0.1 to 1000 nm, particularly 0.5 to 10 nm.
An electrochromic film 16 is provided on the other 12B of the transparent electrode. For the electrochromic film, a material that shows a change in transmittance including a change in color or the like when energized is generally used. It is preferable to use a material used for a conventional toning glass or the like. Examples of the material include tungsten oxide, tantalum oxide, molybdenum oxide, titanium oxide, vanadium oxide, niobium oxide, nickel oxide, iridium oxide, or oxides thereof doped with hydrogen, lithium, sodium, or potassium. be able to. These materials (particularly tungsten oxide or tungsten oxide doped with hydrogen or lithium, sodium or potassium (preferably Li or K) are preferable, and tungsten oxide is particularly preferable). Is advantageous because it is large. The thickness is generally preferably 10 to 5000 nm and 50 to 1000 nm.

  On the electrochromic film 16, a metal oxide semiconductor electrode film 15, which is a semiconductor for a photoelectric conversion material, is formed by adsorbing a spectral sensitizing dye to a metal oxide semiconductor. Examples of the metal oxide semiconductor of the present invention include one or more known semiconductors such as titanium oxide, zinc oxide, tungsten oxide, antimony oxide, niobium oxide, indium oxide, barium titanate, strontium titanate, cadmium sulfide. Can be used. In particular, titanium oxide, zinc oxide, or tin oxide is preferable. Among these, titanium oxide is preferable from the viewpoint of stability and safety. Examples of titanium oxide include anatase-type titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, various titanium oxides such as metatitanic acid, orthotitanic acid, titanium hydroxide, and hydrous titanium oxide. In the present invention, anatase type titanium oxide is preferable. The film thickness of the metal oxide semiconductor is generally 10 nm or more, and preferably 100 to 10,000 nm.

    Unlike conventional dye-sensitized solar cells for power generation, the metal oxide semiconductor film of the present invention does not require a large porosity in the film, but rather, when the porosity is too large and a large amount of dye is adsorbed, The transmittance is lowered by the dye, and sufficient transmittance cannot be obtained at the time of decoloring. For this reason, when the porosity of the film is large, it is preferable that the film thickness is reduced, and when the porosity is small, the film thickness is increased and adjusted so as to obtain an optimum dye amount. Accordingly, the porosity of the metal oxide semiconductor film is preferably 5 to 20%, particularly preferably 5 to 15%, and the film thickness is preferably 100 to 5000 nm, particularly 500 to 2000 nm as described above. In particular, the porosity (%) × film thickness (nm) value is preferably in the range of 1000 to 20000, more preferably 3000 to 15000.

  In general, a metal oxide semiconductor film having such a structure can be obtained by various vapor deposition methods.

  The metal oxide semiconductor film may be formed by using, for example, a metal corresponding to the material and / or a metal oxide as a target, a vapor deposition method, for example, a physical vapor deposition method, a vacuum vapor deposition method, a sputtering method, an ion It can be formed by a plating method, a CVD method or a plasma CVD method. As a preferable method for forming the metal oxide semiconductor film 3 of the present invention, it is particularly preferable to employ a reactive sputtering method, a high-speed film formation method using plasma emission feedback or impedance feedback, or a dual cathode sputtering method. .

Particularly preferred method, a sputtering method, 1.3 W / cm 2 or more, further 2.6 W / cm 2 or more, particularly 11W / cm 2 or more target input power density for forming the metal oxide semiconductor film , And 0.6 Pa or more, further 2.0 Pa or more, particularly 2.6 Pa or more. The sputtering method is particularly preferably a dual cathode sputtering method, and a reactive sputtering method. Is also preferable.

  The dual cathode sputtering method is preferably a reactive sputtering method, that is, sputtering a metal or metal oxide while introducing a reactive gas such as oxygen gas. In particular, it is preferable to perform sputtering while supplying oxygen gas by using metal titanium, titanium oxide, particularly conductive titanium oxide as a target.

  It is also preferable to use a high-speed film formation method using plasma emission feedback or impedance feedback instead of the dual cathode sputtering method and reactive sputtering method. This method is a sputtering method using a system that feeds back plasma emission intensity or plasma impedance, and it is preferable to employ a dual cathode reactive sputtering method or a dual cathode magnetron sputtering method as the sputtering.

  As described above, a semiconductor film can be rapidly formed by performing sputtering under conditions more extreme than normal sputtering conditions, thereby obtaining a metal oxide semiconductor film having the specific shape and structure. Can do. Thereby, the adsorption amount of the organic dye can be greatly increased, and a high-efficiency solar cell having high energy conversion efficiency can be obtained.

  The transparent electrode films 12A and 12B, the catalyst thin layer 13, and the electrochromic film 16 can also be generally formed by sputtering in the same manner as the formation of the metal oxide semiconductor film. In particular, reactive sputtering, dual cathode sputtering, reactive sputtering, plasma emission feedback, or high-speed film formation using impedance feedback is preferable.

  Spectral sensitizing dyes have absorption in the visible light region and / or infrared light region, and in the present invention, one or more of various metal complexes and organic dyes can be used. Those having a functional group such as a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfone group, and a carboxyalkyl group in the molecule of the spectral sensitizing dye are preferred in the present invention because of their rapid adsorption to the semiconductor. Moreover, since it is excellent in the effect of spectral sensitization and durability, a metal complex is preferable. As the metal complex, metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine, chlorophyll, hemin, and ruthenium, osmium, iron, and zinc complexes described in JP-A-1-220380 and JP-A-5-504023 are used. be able to. As the organic dye, metal-free phthalocyanine, cyanine dye, merocyanine dye, xanthene dye, and triphenylmethane dye can be used. Specific examples of cyanine dyes include NK1194 and NK3422 (both manufactured by Nippon Sensitive Dye Research Co., Ltd.). Specific examples of merocyanine dyes include NK2426 and NK2501 (both manufactured by Nippon Sensitive Dye Research Laboratories). Specific examples of xanthene dyes include uranin, eosin, rose bengal, rhodamine B, and dibromofluorescein. Specific examples of the triphenylmethane dye include malachite green and crystal violet.

  In order to adsorb the organic dye (spectral sensitizing dye) to the conductor film, the oxide semiconductor film is attached to the substrate at room temperature or under heating in an organic dye solution formed by dissolving the organic dye in an organic solvent. What is necessary is just to immerse. The solvent of the solution is not particularly limited as long as it can dissolve the spectral sensitizing dye to be used. Specifically, water, alcohol, toluene, and dimethylformamide can be used.

  In this way, an organic dye-sensitized metal oxide semiconductor electrode film (semiconductor for photoelectric conversion material) is obtained.

  Using the thus obtained organic dye-sensitized metal oxide semiconductor electrode in which a transparent electrode and an organic dye-adsorbing metal oxide semiconductor are formed on a substrate, an electric chromic device with a solar cell of the present invention (photo Electrochromic element) is produced. For example, a thin catalyst layer is formed on one transparent organic resin substrate coated with a transparent electrode (transparent conductive film) to form one electrode film (1A), and then the transparent electrode (transparent conductive film) is formed. On the coated transparent organic resin substrate, the electrochromic film 16 and the semiconductor electrode film 15 for photoelectric conversion material are formed to adsorb the dye, and the other electrode film (1B) is formed. These electrode films are bonded with a sealing agent. Then, an electrolyte can be sealed between these electrodes to obtain the element of the present invention. A switch and an external power source (external circuit) are generally attached to this.

  When the spectral sensitizing dye adsorbed on the semiconductor film of the present invention is irradiated with sunlight, the spectral sensitizing dye absorbs light in the visible region and is excited. Electrons generated by this excitation move to the semiconductor and then move to the electrochromic film. Electrons that have moved to the electrochromic film draw ions in the electrolyte into the electrochromic film. On the other hand, the spectral sensitizing dye having electrons transferred to the semiconductor is in an oxidant state, but this oxidant is reduced by the redox system in the electrolyte and returns to its original state. The electrochromic film is colored by electrons (charges) and ions taken into the film. In this way, the photoelectrochromic device of the present invention can function.

Examples of the electrolyte (redox electrolyte) include I / I 3 system, Br / Br 3 system, and quinone / hydroquinone system. Such a redox electrolyte can be obtained by a conventionally known method. For example, an I / I 3 based electrolyte can be obtained by mixing a lithium salt of iodine and iodine. The electrolyte can be a liquid electrolyte or a solid polymer electrolyte containing this in a polymer material. In the liquid electrolyte, an electrochemically inert solvent is used as the solvent, and for example, acetonitrile, propylene carbonate, ethylene carbonate, or the like is used. Any conductive material may be used as the counter electrode, and any conductive material can be used. However, in the present invention, the reduction reaction of oxidized redox ions such as I 3 ions is performed at a sufficiently high rate. A transparent electrode 12B on which the catalyst thin layer 13 having catalytic ability is formed is used.

  The following examples further illustrate the present invention.

[Example 1]
(A) Preparation of catalyst organic thin film and transparent organic resin substrate with transparent electrode film (electrode film (corresponding to 1A in FIG. 1)) A transparent electrode film was formed on the transparent organic resin substrate using a sputtering apparatus.

  Using a 100 mmφ ITO (indium-tin oxide) ceramic target on a 5 × 5 cm polyethylene terephthalate substrate (thickness: 188 μm), argon gas was supplied at 10 cc / min and oxygen gas was supplied at 1.5 cc / min. However, the pressure in the apparatus was set to 5 mTorr, and sputtering was performed for 5 minutes under the condition of a supply power of 500 W to form an ITO film having a thickness of 300 nm. The surface resistance was 10Ω / □.

  On the obtained transparent electrode film, using a Pt target of 100 mmφ, while supplying argon gas at 10 cc / min, the pressure in the apparatus is set to 5 mTorr and sputtering is performed for 20 seconds under the condition of 200 W supply power. And a Pt catalyst thin film having a thickness of 3 nm was formed.

(B) Production of transparent organic resin substrate with metal oxide semiconductor film, electrochromic film and transparent electrode film (electrode film (corresponding to 1B in FIG. 1)) (1) Production of transparent organic resin substrate with transparent electrode Sputtering apparatus A transparent electrode film was formed on the transparent organic resin substrate.

  Using a 100 mmφ ITO (indium-tin oxide) ceramic target on a 5 × 5 cm polyethylene terephthalate substrate (thickness: 188 μm), argon gas was supplied at 10 cc / min and oxygen gas was supplied at 1.5 cc / min. However, the pressure inside the apparatus was set to 5 mTorr, and sputtering was performed for 5 minutes under the condition of a supply power of 500 W to form an ITO film having a thickness of 3000 mm. The surface resistance was 10Ω / □.

(2) Production of electrochromic film Using a dual cathode magnetron sputtering apparatus with plasma emission feedback, two metallic tungsten (W) targets with a diameter of 100 mm are arranged on the ITO transparent electrode, and argon gas is supplied at 100 cc / min. Supplied with. Oxygen gas was introduced while performing feedback so that the plasma emission intensity was constant. The oxygen flow rate during film formation was 10 to 15 cc / min. Sputtering was performed for 32 minutes under the condition of a supply power of 3 kW (power density 19 W / cm 2 ) to form an electrochromic film of tungsten oxide having a thickness of 300 nm.

(3) Production of metal oxide semiconductor film Using a dual cathode magnetron sputtering apparatus with plasma emission feedback, two metal titanium targets with a diameter of 100 mm are placed on the electrochromic film, and oxygen gas is supplied at 5 cc / min. After the supply, the pressure in the apparatus was set to 5 mTorr (0.7 Pa). Oxygen gas was introduced while performing feedback so that the plasma emission intensity was constant. The oxygen flow rate during film formation was 10 to 15 cc / min. Sputtering was performed for 60 minutes under the condition of a power supply of 3 kW (power density 19 W / cm 2 ) to form a titanium oxide film having a thickness of 800 nm.

  The porosity of the obtained semiconductor film was measured.

Measuring method of porosity:
Each of the following weights was measured and determined from the following formula (measurement was performed in accordance with JISZ8807):
w1: Mass of sample sufficiently containing water (g)
w2: Absolute dry mass of the sample (g)
w3: Buoyancy of sample (g)
Porosity = (w1-w2) / w3 × 100
From the above measurement, the porosity of the semiconductor film was 17%.

(4) Adsorption of spectral sensitizing dye Spectral sensitization represented by cis-di (thiocyanato) -bis (2,2′-bipyridyl-4-dicarboxylate-4′-tetrabutylammonium carboxylate) ruthenium (II) The dye was dissolved in an ethanol solution. The concentration of this spectral sensitizing dye was 3 × 10 −4 mol / l. Next, the substrate on which the film-like titanium oxide was formed was placed in this ethanol liquid and immersed for 18 hours at room temperature to obtain the metal oxide semiconductor electrode of the present invention.

(5) Production of photoelectrochromic device with solar cell An electrolyte was placed between the obtained two electrode films, and this side surface was sealed with resin, and then a lead wire and a switch (Sw1) were attached, and the device of the present invention (Type without Sw2 in FIG. 1) was produced. In addition, as for electrolyte, in the solvent of acetonitrile, lithium iodide, 1,2-dimethyl-3-propyl imidazolium iodide, iodine and t-butyl pyridine, respectively, the concentration is 0.1 mol / l, 0.3 What was melt | dissolved so that it might become a mol / l, 0.05 mol / l, and 0.5 mol / l was used.

When the obtained device was irradiated with light having an intensity of 100 W / m 2 with a solar simulator, it was colored in the Sw-off state and the transmittance was 12% (measured using a spectrophotometer and subjected to visual correction). Met. In the Sw-on state, the color was erased and the transmittance was 72%.

It is sectional drawing which shows an example of embodiment in the photoelectrochromic element of this invention.

Explanation of symbols

1A Electrode film 1B Counter electrode film 11A, 11B Transparent substrate 12A, 12B Transparent electrode film
13 Catalyst Thin Layer 14 Electrolyte 15 Metal Oxide Semiconductor Electrode Film Adsorbed with Spectral Sensitizing Dye 16 Electrochromic Film 17 External Circuit Connected to External Power Supply

Claims (17)

  1. An electrode film comprising a transparent substrate, a transparent electrode film laminated thereon, an electrochromic film, and a metal oxide semiconductor electrode film formed by adsorbing an organic dye on a metal oxide semiconductor;
    A counter electrode film comprising a transparent substrate, a transparent electrode film and a catalyst thin film laminated thereon, and an electrolyte sandwiched between these two electrode films,
    A photoelectrochromic device including:
  2.   The photoelectrochromic device according to claim 1, wherein a switching device is provided between the transparent electrodes.
  3.   The photoelectrochromic device according to claim 1, wherein an external circuit capable of switching that can be connected to an external power source is provided between the transparent electrodes.
  4.   The photoelectrochromic device according to claim 3, wherein a direct current can be applied by an external circuit.
  5.   The photoelectrochromic device according to claim 1, wherein the transparent substrate is a transparent resin film.
  6.   6. The photoelectrochromic device according to claim 5, wherein the material of the transparent resin film is polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, polyether sulfide, or fluororesin.
  7.   The photoelectrochromic device according to claim 1, wherein at least one of a transparent electrode film, an electrochromic film, a metal oxide semiconductor film, and a catalyst thin film is formed by a vapor deposition method. .
  8.   The photoelectrochromic device according to claim 7, wherein the transparent electrode film, the electrochromic film, the metal oxide semiconductor film, and the catalyst thin film are all formed by a vapor deposition method.
  9.   The photoelectrochromic device according to claim 7 or 8, wherein the vapor deposition method is a physical vapor deposition method, a vacuum vapor deposition method, a sputtering method, an ion plating method, a CVD method or a plasma CVD method.
  10.   The photoelectrochromic device according to claim 8 or 9, wherein the vapor phase film formation method is a reactive sputtering method, a high-speed film formation method using plasma emission feedback or impedance feedback, or a dual cathode type sputtering method.
  11.   A metal oxide semiconductor film is formed from titanium oxide, zinc oxide, tin oxide, antimony oxide, niobium oxide, tungsten oxide, or indium oxide, or these metal oxides doped with other metals or other metal oxides. The photoelectrochromic device according to any one of claims 1 to 10.
  12.   The photoelectrochromic device according to any one of claims 1 to 11, wherein the metal oxide semiconductor film is formed of titanium oxide, zinc oxide, or tin oxide.
  13.   The electrochromic film is tungsten oxide, tantalum oxide, molybdenum oxide, titanium oxide, vanadium oxide, rhodium oxide, niobium oxide, nickel oxide, iridium oxide, or these oxides doped with hydrogen, lithium, sodium or potassium The photoelectrochromic device according to claim 1, wherein the photoelectrochromic device is formed from.
  14.   The light control glass containing the photoelectrochromic element of any one of Claims 1-13.
  15.   The transmittance | permeability adjustment glass containing the photoelectrochromic element of any one of Claims 1-13.
  16.   The image display device containing the photoelectrochromic element of any one of Claims 1-13.
  17. Hot-wire cut glass containing the photoelectrochromic element of any one of Claims 1-13.
JP2005161098A 2005-06-01 2005-06-01 Photoelectrochromic element, light-controlling glass, transmittance adjusting glass, heat ray cut glass, and image display device Pending JP2006337635A (en)

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JP2013538359A (en) * 2010-06-01 2013-10-10 レイブンブリック,エルエルシー Multifunctional structural components
US9221573B2 (en) 2010-01-28 2015-12-29 Avery Dennison Corporation Label applicator belt system
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JPH07152050A (en) * 1993-11-29 1995-06-16 Showa Denko Kk All-solid electrochromic element and its production
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JP2010523961A (en) * 2007-03-30 2010-07-15 イー2ヴイ テクノロジーズ (ユーケイ) リミテッド Detection device
US9221573B2 (en) 2010-01-28 2015-12-29 Avery Dennison Corporation Label applicator belt system
US9637264B2 (en) 2010-01-28 2017-05-02 Avery Dennison Corporation Label applicator belt system
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KR20170121673A (en) * 2016-04-25 2017-11-02 한국에너지기술연구원 Self-powering electrochromic devices containing small molecule organic ligand-metal oxide layer
KR20170121670A (en) * 2016-04-25 2017-11-02 한국에너지기술연구원 Self-powering electrochromic devices containing small molecule organic ligand-metal oxide layer
KR101916845B1 (en) * 2016-04-25 2019-01-24 한국에너지기술연구원 Self-powering electrochromic devices containing small molecule organic ligand-metal oxide layer
KR101945434B1 (en) * 2016-04-25 2019-02-08 한국에너지기술연구원 Self-powering electrochromic devices containing small molecule organic ligand-metal oxide layer
KR101959450B1 (en) * 2016-04-25 2019-03-18 한국에너지기술연구원 Self-powering electrochromic devices containing small molecule organic ligand-metal oxide layer

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