WO2020137328A1 - Transistor électrochromique, rideau électronique, dispositif d'affichage/stockage d'informations et miroir anti-éblouissement - Google Patents

Transistor électrochromique, rideau électronique, dispositif d'affichage/stockage d'informations et miroir anti-éblouissement Download PDF

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WO2020137328A1
WO2020137328A1 PCT/JP2019/046479 JP2019046479W WO2020137328A1 WO 2020137328 A1 WO2020137328 A1 WO 2020137328A1 JP 2019046479 W JP2019046479 W JP 2019046479W WO 2020137328 A1 WO2020137328 A1 WO 2020137328A1
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electrochromic
transparent conductive
conductive film
transistor
active layer
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PCT/JP2019/046479
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English (en)
Japanese (ja)
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太田　裕道
尚記 小野里
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国立大学法人北海道大学
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Publication of WO2020137328A1 publication Critical patent/WO2020137328A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details
    • G02F1/155—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film

Definitions

  • the present invention relates to an electrochromic transistor, an electronic curtain, an information display storage device, and an antiglare mirror, and relates to, for example, antiglare windows of aircrafts, automobiles, buildings, etc., or displaying/storing information on these windows. It is suitable for application to antiglare of automobile rearview mirrors.
  • Electrochromism is a phenomenon in which the color of a material is reversibly changed from colorless transparent to black by electrochemically oxidizing and reducing a substance called electrochromic material that contains metal ions. Electrochromism can be used as an electronic curtain for passenger planes and residential windows because the color of the glass can be switched from colorless transparent to black and the transmittance of outside light can be adjusted. It has begun to be applied as an anti-glare mirror to reduce the glare of the headlights of the following vehicles reflected in the mirror. Its market size is 1.5 billion dollars in 2016 (about 160 billion yen) and 4 billion dollars in 2023 ( It is expected to exceed JPY 430 billion).
  • Tungsten oxide (WO 3 ), which has been known as an electrochromic material since the 1970s, is an insulator that is colorless and transparent and does not conduct electricity. However, it is a metal that is black and conducts electricity well due to electrochemical inclusion of hydrogen. The electrochromism of returning to the original colorless and transparent insulator by drawing out hydrogen is shown.
  • electrochromic transistor a new information display storage device can be realized by using this electrochromic transistor.
  • a transparent source electrode and a drain electrode made of a tin (Sn)-doped indium oxide (ITO) film are formed on a glass substrate, and the transparent source electrode and the drain electrode are formed on the glass substrate so as to extend over these source electrode and drain electrode.
  • a WO 3 layer serving as an active layer is formed on the WO 3 layer, and a water-containing cement thin film made of calcium aluminate having a large number of nanopores is formed as a gate insulating film on the WO 3 layer. It has a structure in which a transparent gate electrode made of an ITO film is sequentially formed.
  • the state of the insulator in which the WO 3 layer does not conduct electricity is information “0”, and the state of the metal through which electricity easily passes is information “1”. It is possible to electrically store and read the information "0” and “1” in addition to the captured color change information "transparent" and "black”.
  • This electrochromic transistor or information display memory device can be manufactured at low cost at room temperature, and it is easy to increase the area.
  • Non-Patent Document 1 in order to protonate the WO 3 layer of the active layer (WO 3 ⁇ H x WO 3 ), it is necessary to apply +3 V to the gate electrode with respect to the source electrode for 300 seconds. For protonation (H x WO 3 ⁇ WO 3 ), it is necessary to apply ⁇ 3 V to the gate electrode with respect to the source electrode for 100 seconds. That is, at a practical operation switching voltage of 3V, the time required for switching is about 100 to 300 seconds. Therefore, it has been desired to reduce the time required for switching.
  • the problem to be solved by the present invention is that the time required for switching is significantly shortened as compared with the electrochromic transistor described in Non-Patent Document 1 even with a practical operating switching voltage of 3V.
  • PROBLEM TO BE SOLVED To provide an electrochromic transistor, a high-performance electron curtain using the electrochromic transistor, a high-performance information display storage device using the electrochromic transistor, and a high-performance antiglare mirror using the electrochromic transistor. Is.
  • the present invention provides An active layer comprising at least an electrochromic material and an electrolyte containing water; It is an electrochromic transistor having a first transparent conductive film and a second transparent conductive film provided so as to sandwich the active layer.
  • the electrochromic transistor is a three-terminal element having a thin film transistor structure that uses an electrochromic material for an active layer and has a source electrode, a drain electrode, and a gate electrode.
  • the active layer may have any form as long as it contains at least an electrochromic material and an electrolyte containing water, and is designed as necessary.
  • the active layer has a structure in which a first layer made of an electrochromic material and a second layer made of an electrolyte are laminated on each other. At least a part or the whole of the active layer may have a structure in which a fine particle electrochromic material and a fine particle electrolyte are mixed.
  • the active layer is provided so as to make electrical contact with the source electrode and the drain electrode.
  • the first transparent conductive film and the second transparent conductive film constitutes a gate electrode, the other is integrated with the active layer, and the sheet resistance of the channel is reduced by making electrical contact with the source electrode and the drain electrode.
  • the first transparent conductive film and the second transparent conductive film are made of, for example, a transparent conductive oxide (TCO), a transparent metal such as ultra-thin gold (Au), or the like, and are selected as necessary.
  • the transparent conductive oxide is generally an oxide containing at least one metal selected from the group consisting of indium (In), zinc (Zn), gallium (Ga) and tin (Sn). ..
  • the transparent conductive oxide is, for example, In 2 O 3 (ITO) doped with tin (Sn), ZnO doped with gallium (Ga), aluminum (Al), or the like, and doped with fluorine (F). Tin oxide (SnO 2 ) and the like.
  • ITO In 2 O 3
  • the electric conductivity of the first transparent conductive film and the second transparent conductive film is generally 0.01 S/cm or more and 100000 S/cm or less.
  • the thickness and electric conductivity (or electric conductivity) of the second transparent conductive film located on the first layer side are selected as follows. That is, the thickness of the first layer is t 1 , the electrical conductivity is ⁇ 1 , and the thickness of one of the first transparent conductive film and the second transparent conductive film located on the side of the first layer is t 2. , And the electrical conductivity is ⁇ 2 .
  • Log (on/off ratio) Log(t 1 / t 1 , ⁇ 1 , t 2 , and ⁇ 2 are selected so that t 2 )+Log( ⁇ 1 / ⁇ 2 ) holds.
  • the electrochromic material may be an inorganic material, an organic material, or an organic-inorganic composite material, and is selected as necessary.
  • the inorganic electrochromic material is typically an oxide electro containing at least one metal selected from the group consisting of tungsten (W), vanadium (V), niobium (Nb) and titanium (Ti). Examples include, but are not limited to, chromic materials.
  • the oxide electrochromic material is, in one typical example, an amorphous or crystalline simple oxide represented by the composition formula AO x (A is tungsten, vanadium, niobium or titanium, and x is in the range of 1 to 3). Is. A representative example of AO 3 is WO 3 .
  • Examples of the organic electrochromic material include, but are not limited to, various conductive polymer compounds, viologen compounds, leuco dye compounds, and terephthalic acid compounds.
  • the electrolyte is not particularly limited as long as it contains water, and is selected as necessary.
  • the electrolyte is preferably, but not limited to, an oxide dielectric containing 1% or more and 50% or less by volume of water.
  • Oxide dielectrics are generally various metal oxides (including complex oxides and glasses) that can be made porous and contain water. Specific examples of such metal oxides include TaO x , NbO x , ZrO x , HfO x , AlO x , SiO x , and GaO x .
  • water-containing cement composed of calcium aluminate having a large number of nanopores described in Non-Patent Document 1 may be used.
  • the transparent substrate is, for example, a transparent glass substrate or a transparent plastic substrate.
  • the transparent substrate is configured flexibly as needed.
  • the transparent plastic constituting the transparent plastic substrate include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramids, polyimides, polystyrene. , Polyarylates, polysulfones, polyolefins and the like can be used.
  • the present invention is A transparent substrate, Having one or more electrochromic transistors provided on the transparent substrate,
  • the electrochromic transistor is An active layer comprising at least an electrochromic material and an electrolyte containing water; It is an electronic curtain having a first transparent conductive film and a second transparent conductive film provided so as to sandwich the active layer.
  • the present invention is A transparent substrate, Having a plurality of electrochromic transistors provided on the transparent substrate,
  • the electrochromic transistor is An active layer comprising at least an electrochromic material and an electrolyte containing water;
  • An information display storage device having a first transparent conductive film and a second transparent conductive film provided so as to sandwich the active layer.
  • the information display storage device displays color information "colorless and transparent” and “black” when the electrochromic transistor is off and on, and electrical conduction information “0" and “1” when the electrochromic transistor is off and on. It can be stored and read.
  • the arrangement of the electrochromic transistors on the transparent substrate is selected as necessary, but typically, a plurality of electrochromic transistors are arranged in a matrix.
  • the present invention is A transparent substrate provided on the surface of the mirror, Having one or more electrochromic transistors provided on the transparent substrate,
  • the electrochromic transistor is An active layer comprising at least an electrochromic material and an electrolyte containing water; It is an antiglare mirror having a first transparent conductive film and a second transparent conductive film provided so as to sandwich the active layer.
  • the use of the anti-glare mirror is not particularly limited, but it is, for example, an automobile rearview mirror.
  • the transparent conductive film is provided in contact with the active layer containing at least the electrochromic material and the electrolyte containing water, the effective sheet resistance of the channel can be significantly reduced.
  • a high performance electrochromic transistor with an active layer that is colorless and transparent and has an extremely high electrical and optical on/off ratio between an insulator state and a black state and a metal state and a switching speed. be able to.
  • this high-performance electrochromic transistor it is possible to realize an electronic curtain capable of controlling light transmission at high speed, and at the same time, information display capable of displaying/storing/reading information at high speed.
  • a storage device can be realized.
  • this high-performance electrochromic transistor it is possible to realize an antiglare mirror capable of effective antiglare even at night.
  • FIG. 1 is a sectional view showing an electrochromic transistor according to a first embodiment of the present invention.
  • 1 is a plan view showing an electrochromic transistor according to a first embodiment of the present invention.
  • FIG. 3 is a sectional view showing a first example of a structure of an active layer of the electrochromic transistor according to the first embodiment of the present invention.
  • FIG. 6 is a sectional view showing a second example of the structure of the active layer of the electrochromic transistor according to the first embodiment of the present invention.
  • FIG. 3 is a schematic diagram showing the relationship between the electrical on/off ratio and the thickness ratio t 1 /t 2 of the electrochromic transistor according to the first embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing an electrochromic transistor according to an example.
  • FIG. 6 is a plan view showing an electrochromic transistor according to an example. 8 is a drawing-substituting photograph showing an electrochromic transistor according to an example.
  • FIG. 6 is a cross-sectional view showing an electrochromic transistor according to a comparative example.
  • FIG. 6 is a schematic diagram showing a time change of sheet resistance due to protonation of an electrochromic transistor according to an example and an electrochromic transistor according to a comparative example.
  • FIG. 6 is a schematic diagram showing a change over time in sheet resistance with deprotonation of an electrochromic transistor according to an example and an electrochromic transistor according to a comparative example.
  • FIG. 6 is a schematic diagram showing transmission spectra of an electrochromic transistor according to an example and an electrochromic transistor according to a comparative example in an initial state and a state in which +3V is applied to a gate electrode.
  • It is a top view which shows the electronic curtain by the 2nd Embodiment of this invention.
  • It is a front view which shows the example which applied the electronic curtain by the 2nd Embodiment of this invention to the window of an aircraft.
  • It is a top view which shows an example which displays and memorize
  • Electrode 1 and 2 show an electrochromic transistor according to a first embodiment, FIG. 1 is a sectional view, and FIG. 2 is a plan view.
  • a transparent conductive film 12 is provided on a transparent substrate 11.
  • a transparent source electrode 13 and a transparent drain electrode 14 are provided on the transparent conductive film 12 so as to face each other.
  • An active layer 15 is provided on the transparent conductive film 12 so that both ends thereof are electrically contacted over the source electrode 13 and the drain electrode 14.
  • the active layer 15 contains at least an electrochromic material and an electrolyte containing water, and may contain a material other than the electrochromic material and the electrolyte as necessary, but typically, the electrochromic material and the electrolyte. It consists of and.
  • the electrochromic material forming the active layer 15 is a colorless and transparent insulator when it is not protonated, and in the electrochromic transistor, the active layer 15 becomes non-conductive and a current flows between the source electrode 13 and the drain electrode 14. However, when the electrochromic material is protonated, it changes to a black metal. At that time, in the electrochromic transistor, the active layer 15 becomes conductive and a current flows between the source electrode 13 and the drain electrode 14 to turn it on. Become.
  • An absorption layer 16 that also serves as a gate insulating film is provided on the active layer 15.
  • a gate electrode 17 made of a transparent conductive film is provided on the absorption layer 16. Therefore, this electrochromic transistor has a structure in which the active layer 15 is sandwiched between the transparent conductive film and the transparent conductive film 12 which form the gate electrode 17.
  • the transparent substrate 11 is a transparent glass substrate or a transparent plastic substrate made of the transparent plastic already mentioned.
  • the transparent substrate 11 is configured flexibly as needed.
  • the thickness and material of the transparent substrate 11 are selected as needed within a range in which required transparency and strength can be obtained.
  • the planar shape of the transparent substrate 11 is rectangular, but the planar shape of the transparent substrate 11 is selected as necessary depending on the application of the electrochromic transistor and other polygons (triangle, pentagon, hexagon, etc.). Besides, it may have a circular shape, an elliptical shape, or a shape obtained by modifying these shapes.
  • the transparent conductive film forming the transparent conductive film 12 and the gate electrode 17 is made of, for example, various kinds of transparent conductive oxide (TCO) or an ultrathin Au film.
  • TCO transparent conductive oxide
  • the thickness and electric conductivity of the transparent conductive film 12 will be described later.
  • the source electrode 13 and the drain electrode 14 are made of, for example, a transparent conductive film such as various transparent conductive oxides (TCO) or an ultrathin Au film, and are selected as needed.
  • the planar shapes of the source electrode 13 and the drain electrode 14 are generally rectangular, but are not limited to this.
  • the electrochromic material and the electrolyte forming the active layer 15 are selected from those already mentioned as needed.
  • the electrolyte consists of an oxide dielectric containing water and is transparent.
  • the active layer 15 has a structure in which a first layer made of an electrochromic material and a second layer made of an electrolyte are laminated on each other, and at least a part or all of the active layer 15 is a fine particle electrochromic material and fine particles. There is a case where it has a mixed structure with a solid electrolyte. An example of the former is shown in FIG. 3 and an example of the latter is shown in FIG. As shown in FIG.
  • the lower layer of the active layer 15 is a first layer 15a made of an electrochromic material and the upper layer is a second layer 15b made of an electrolyte.
  • FIG. 4 has a structure in which a large number of fine particle electrochromic materials 15c and fine particle electrolytes 15d are mixed.
  • the fine particle electrochromic material 15c is drawn larger than the fine particle electrolyte 15d in order to distinguish between the fine particle electrochromic material 15c and the fine particle electrolyte 15d. Is not limited to this, and is selected as needed. Further, in FIG.
  • the fine particle-shaped electrochromic material 15c and the fine particle-shaped electrolyte 15d are drawn in a spherical shape, but the shape is not limited to this, and other shapes may be used.
  • the planar shape of the active layer 15 is generally rectangular, but is not limited to this and may be selected as necessary.
  • the absorption layer 16 plays a role of absorbing OH ⁇ released from the active layer 15 during the operation of the electrochromic transistor.
  • the absorption layer 16 is made of, for example, NiO, but is not limited to this.
  • the thickness of the absorption layer 16 is not particularly limited and is selected as necessary, but is generally 10 nm to 30 nm. The absorption layer 16 can be omitted if necessary.
  • the gate electrode 17 is made of, for example, a transparent conductive film such as various transparent conductive oxides (TCO) or an ultrathin Au film, and is selected as necessary.
  • the planar shape of the gate electrode 17 is generally rectangular, but is not limited to this.
  • the thickness of the gate electrode 17 is not particularly limited and is selected as necessary, but is generally 10 nm to 30 nm.
  • the thickness t of the first layer 15a is t. 1
  • the electric conductivity ⁇ 1 , the thickness t 2 of the transparent conductive film 12 and the electric conductivity ⁇ 2 are selected as follows. That is, in FIG. 5, the vertical axis represents the electrical on/off ratio of the electrochromic transistor, and the horizontal axis represents the thickness ratio t 1 /t 2 . In FIG. 5, the vertical axis represents the electrical on/off ratio of the electrochromic transistor, and the horizontal axis represents the thickness ratio t 1 /t 2 .
  • ⁇ 2 was changed to 0.01 S/cm, 0.1 S/cm, 1 S/cm, 10 S/cm, 100 S/cm, and 1000 S/cm to draw a straight line.
  • the active layer 15 has a structure in which a large number of fine particle electrochromic materials 15c and fine particle electrolytes 15d are mixed as shown in FIG. 4, the total mass of the electrochromic material 15c contained in the active layer 15 is By using the thickness (equivalent thickness) converted to the thickness of the first layer 15a as t 2 , the same handling as above can be approximately performed.
  • the electrochromic material of the active layer 15 is initially not protonated and is assumed to be a colorless and transparent insulator. In this state, the active layer 15 is not conductive and no current flows between the source electrode 13 and the drain electrode 14. A gate voltage V g necessary for electrolysis of water described below is applied between the source electrode 13 and the gate electrode 17. Generally, the source electrode 13 is grounded. When a positive voltage is applied as the gate voltage V g , an electric field is applied from the gate electrode 17 to the transparent conductive film 12 in the thickness direction of the active layer 15. By this electric field, water in the electrolyte contained in the active layer 15 is electrolyzed to generate protons (H + ) and hydroxide ions (OH ⁇ ).
  • H + is taken into the electrochromic material of the active layer 15 by the electric field and protonated, and OH ⁇ penetrates the active layer 15 by the electric field and is taken into the absorption layer 16.
  • the electrochromic material of the active layer 15 is protonated, the electrochromic material becomes a black metal. At this time, the active layer 15 becomes conductive, and a current flows between the source electrode 13 and the drain electrode 14.
  • the source electrode 13 and the drain electrode 14 made of the transparent conductive film are formed thereon.
  • These transparent conductive films can be formed by a conventionally known method and are selected as necessary, and for example, a pulse laser deposition (PLD) method, a vacuum evaporation method or the like is used.
  • PLD pulse laser deposition
  • the source electrode 13 and the drain electrode 14 can be formed by selectively depositing a transparent conductor using a metal mask.
  • the active layer 15 is formed on the transparent conductive film 12 so that both ends thereof straddle the source electrode 13 and the drain electrode 14.
  • the active layer 15 is composed of the first layer 15a and the second layer 15b as shown in FIG. 3, the first layer 15a and the second layer 15b are sequentially formed.
  • the first layer 15a and the second layer 15b can be formed by a conventionally known method and are selected according to need. For example, a PLD method using a metal mask, a vacuum deposition method, or the like is used. ..
  • the active layer 15 is composed of the fine particle electrochromic material 15c and the fine particle electrolyte 15d as shown in FIG.
  • the fine particle electrochromic material 15c and the fine particle electrolyte 15d are prepared in advance, and these are mixed with water or the like.
  • a paste-like dispersion liquid uniformly dispersed in the solvent is prepared, and the dispersion liquid is applied or printed on the transparent conductive film 12 so as to extend over the source electrode 13 and the drain electrode 14.
  • a conventionally known method can be used.
  • a coating method for example, a dipping method, a spray method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, or the like can be used.
  • a letterpress printing method As a printing method, a letterpress printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method or the like can be used.
  • the fine particle electrochromic material 15c and the fine particle electrolyte 15d are applied or printed on the transparent conductive film 12, the source electrode 13 and the drain electrode 14, and then the solvent is evaporated and removed.
  • firing may be performed in order to improve the mechanical strength of the active layer 15 and improve the adhesion to the transparent conductive film 12 and the like.
  • the firing temperature is selected to be lower than the heat resistant temperature of the transparent substrate 11, and is generally 40 to 200°C.
  • the absorption layer 16 is formed on the active layer 15.
  • the absorption layer 16 can be formed by a conventionally known method and is selected according to need. For example, a PLD method, a vacuum vapor deposition method or the like is used.
  • the gate electrode 17 made of a transparent conductive film is formed on the absorption layer 16.
  • the gate electrode 17 can be formed by a conventionally known method and is selected according to need. For example, a PLD method, a vacuum deposition method or the like is used.
  • the gate electrode 17 can be formed by selectively depositing a transparent conductor using a metal mask.
  • the target electrochromic transistor is manufactured.
  • FIG. 8 shows an optical microscope photograph of this electrochromic transistor.
  • the transparent substrate 11 a glass substrate having a thickness of 0.7 mm and a size of 10 mm ⁇ 10 mm was used.
  • the transparent conductive film 12 a ZnO film having a thickness of 30 nm (electric conductivity is 30 S/cm) was formed.
  • An active layer 15 having a two-layer structure composed of a first layer 15a and a second layer 15b is used, the first layer 15a is a WO 3 layer having a thickness of 100 nm, and the second layer 15b is a layer having a thickness of 250 nm.
  • a TaO x layer was formed.
  • As the absorption layer 16 a NiO layer having a thickness of 20 nm was formed.
  • An ITO film having a thickness of 20 nm was formed as the gate electrode 17.
  • the distance between the source electrode 13 and the drain electrode 14, that is, the channel length is 800 ⁇ m, which is the same as the length of the gate electrode 17 in the channel length direction, that is, the gate length.
  • the length of the active layer 15 in the direction orthogonal to the channel length direction, that is, the channel width is 400 ⁇ m.
  • FIG. 9 shows a sectional view of this electrochromic transistor.
  • the plan view of this electrochromic transistor is similar to that of FIG.
  • the ZnO film as the transparent conductive film 12 is not formed, the WO 3 layer has a thickness of 80 nm, and the cement thin film CAN having a thickness of 300 nm is used instead of the TaO x layer shown in FIG.
  • the formation of (calcium aluminate having a large number of holes with a diameter of about 10 nm (chemical composition 12CaO.7Al 2 O 3 , the main component of alumina cement)) is different from that of the electrochromic transistor according to the embodiment. And the size of each part is the same.
  • FIG. 10 shows the retention time (Retention time) when the first layer 15a of the active layer 15 is protonated by applying +3 V as the gate voltage V g to the gate electrode 17 of the electrochromic transistor according to the example and the comparative example. ) shows the measurement results of the change in the sheet resistance R s with respect to t.
  • the sheet resistance measuring electrodes E 1 to E 4 are formed on the WO 3 layer (first layer 15a made of an electrochromic material) and the ZnO film (transparent conductive film 12). Were contacted with each other and the DC four-terminal method was used. The applied current was about 100 ⁇ A.
  • FIG. 11 shows the retention time t when the first layer 15a of the active layer 15 is deprotonated by applying ⁇ 3 V as the gate voltage V g to the gate electrode 17 of the electrochromic transistor according to the example and the comparative example. shows the results of measuring the change in the sheet resistance R s for.
  • the sheet resistance R s was measured in the same manner as above using the sheet resistance measuring electrodes E 1 to E 4 .
  • the electrochromic transistor according to the comparative example in the electrochromic transistor according to the comparative example, it takes about 300 seconds to complete the protonation, whereas in the electrochromic transistor according to the example, the protonation is completed in about 1 second. Further, as is apparent from FIG. 11, in the electrochromic transistor according to the comparative example, it takes about 100 seconds to complete deprotonation, whereas in the electrochromic transistor according to the example, deprotonation is completed in about 1 second. ing. That is, the electrochromic transistor according to the example has a switching time significantly shortened to about 1/300 as compared with the electrochromic transistor according to the comparative example.
  • Figure 12 shows the results of measurement of the transmission spectrum of the entire transistor while applying a + 3V as examples and the initial state (state prior to application of the gate voltage V g) of the electrochromic transistor according to the comparative example and the gate voltage V g.
  • the application time of the gate voltage V g is 1 second
  • the application time of the gate voltage V g is 20 seconds.
  • the light transmittance for a wavelength of about 570 nm is 67% when the electrochromic transistor according to the embodiment is off, 28% when the on/off ratio is about 40% when the on, and 71% when the electrochromic transistor according to the comparative example is off.
  • the on/off ratio is about 10% at 63% when turned on. That is, the electrochromic transistor according to the example has an optical on/off ratio improved by about 4 times as compared with the electrochromic transistor according to the comparative example.
  • the same advantages as those of the electrochromic transistor described in Non-Patent Document 1 can be obtained, and the transparent conductive film is provided between the transparent substrate 11 and the active layer 15.
  • the electrical on/off ratio which is the ratio of the sheet resistance of the on-channel to the sheet resistance of the off-channel
  • the off-color is colorless.
  • the optical on/off ratio which is the ratio of the light transmittance in the black state when turned on to the light transmittance in the transparent state, can be made sufficiently high, and even at a practical operating switching voltage of 3 V, it is extremely high. It is possible to realize a high-performance electrochromic transistor capable of switching at high speed.
  • This electrochromic transistor can be manufactured inexpensively at room temperature and can easily be made large in area.
  • This electrochromic transistor is an electronic curtain used for windows of moving objects such as various aircraft (passenger planes, transport planes, helicopters, etc.) and various automobiles (including electric vehicles and self-driving cars), automobile rearview mirrors.
  • an information display storage device for displaying and storing information in windows, etc., it can be applied to a touch panel and the like.
  • FIG. 13 shows an electronic curtain according to the second embodiment.
  • This electronic curtain uses the electrochromic transistor according to the first embodiment as an optical shutter.
  • This electronic curtain has one or a plurality of electrochromic transistors according to the first embodiment formed on a transparent substrate 11.
  • the electrochromic transistor does not necessarily have to be formed on the entire surface of the transparent substrate 11, and may be formed on a portion of the transparent substrate 11 where light transmission is desired to be controlled.
  • the active layer 15 of a single electrochromic transistor is formed so that the area of the transparent substrate 11 and the total area of the active layer 15 are substantially the same.
  • a plurality of electrochromic transistors are spread over the entire surface of the glass plate 110.
  • the source wiring, the drain wiring, and the gate wiring of the electrochromic transistor can be formed on the transparent substrate 11 using various conductive films such as a transparent conductive film, and can be led out to the outer peripheral portion of the transparent substrate 11. In this way, the power source can be connected to the end portions of the source wiring, the drain wiring, and the gate wiring that are drawn to the outer peripheral portion of the transparent substrate 11.
  • This electronic curtain can be basically installed in any part as long as it is a part where it is desired to control the transmission of light.
  • various types of windows such as aircraft windows, buildings, houses, etc. It can be applied to windows of buildings.
  • FIG. 14 shows an example in which the electronic curtain 200 is applied to the window 110 provided on the wall surface 100 inside the aircraft
  • FIG. 15 shows an example in which the electronic curtain 200 is applied to the window 400 on the wall 300 of the building.
  • the light transmittance can be controlled at high speed, antiglare can be achieved when applied to a window, and high-performance electronic that can be manufactured at low cost.
  • the curtain can be realized.
  • FIG. 16 shows an information display storage device according to the third embodiment. This information display storage device uses the electrochromic transistor according to the first embodiment.
  • the electrochromic transistors according to the first embodiment are arranged on the transparent substrate 11 in a matrix of n rows and m columns, n ⁇ m in total, vertically and horizontally. It is a thing.
  • These electrochromic transistors T ij can be driven independently.
  • the source wiring, the drain wiring, and the gate wiring of the electrochromic transistor T ij can be formed in the same manner as the wiring of the pixel switching thin film transistor of the liquid crystal display, for example.
  • These source wiring, drain wiring, and gate wiring can be formed on the transparent substrate 11 using various conductive films such as a transparent conductive film, and can be drawn out to the outer peripheral portion of the transparent substrate 11. In this way, the power source can be connected to the end portions of the source wiring, the drain wiring, and the gate wiring that are drawn to the outer peripheral portion of the transparent substrate 11.
  • the electrochromic transistor T ij is driven according to the information to be displayed and stored in the information display storage device, the active layer 15 is colorless and transparent and the state of the insulator is “0” and the active layer 15 is black and the state of the metal is “. 1”.
  • the active layer 15 is colorless and transparent and the state of the insulator is “0” and the active layer 15 is black and the state of the metal is “. 1”.
  • the character “A” is displayed and stored as information
  • the electrochromic transistor T ij necessary for displaying the character “A” is driven, and the electrochromic of the active layer 15 is driven.
  • the material turns black due to protonation. By doing so, the character "A” can be displayed and stored.
  • the electrochromic transistor T ij used for displaying the character “A” is driven to make it colorless and transparent by deprotonating the electrochromic material of the active layer 15.
  • information can be displayed/stored/erased/read out at high speed on windows of various moving bodies such as airplanes and automobiles or windows of buildings, and the manufacturing cost is low. It is possible to realize a high performance information display storage device that can be realized.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Optics & Photonics (AREA)
  • Ceramic Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Thin Film Transistor (AREA)

Abstract

L'invention concerne un transistor électrochromique comprenant : une électrode de grille 17 comprenant une couche active 15 comprenant un électrolyte contenant une résine électrochromique et de l'eau, et un film électroconducteur transparent 12 et un film électroconducteur transparent pourvu de la couche active 15 entre eux ; et une électrode de source 13 et une électrode de drain 14. À partir d'un état dans lequel la résine électrochromique de la couche active 15 est un isolant incolore et transparent, une tension de grille positive est appliquée à l'électrode de grille 17, et par électrolyse de l'eau contenue par l'électrolyte de la couche active 15, des protons sont générés, et la résine électrochromique est protonée et convertie en un métal noir. Une tension de grille négative est appliquée à l'électrode de grille, et des protons sont ainsi déplacés dans la direction inverse, et le matériau électrochromique est déprotoné et renvoyé à l'état d'isolant incolore et transparent.
PCT/JP2019/046479 2018-12-27 2019-11-28 Transistor électrochromique, rideau électronique, dispositif d'affichage/stockage d'informations et miroir anti-éblouissement WO2020137328A1 (fr)

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JP2018243861A JP2020106626A (ja) 2018-12-27 2018-12-27 エレクトロクロミックトランジスタ、電子カーテン、情報表示記憶装置および防眩ミラー
JP2018-243861 2018-12-27

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JP2003007133A (ja) * 2001-06-22 2003-01-10 Nippon Kodoshi Corp 高イオン伝導性固体電解質及び該固体電解質を使用した電気化学システム
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220107540A1 (en) * 2020-10-07 2022-04-07 Tpk Touch Solutions (Xiamen) Inc. Displayed light-adjustment device
US11656520B2 (en) * 2020-10-07 2023-05-23 Tpk Touch Solutions (Xiamen) Inc. Displayed light-adjustment device

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