WO2019172133A1 - Electrochromic element and smart window - Google Patents

Electrochromic element and smart window Download PDF

Info

Publication number
WO2019172133A1
WO2019172133A1 PCT/JP2019/008157 JP2019008157W WO2019172133A1 WO 2019172133 A1 WO2019172133 A1 WO 2019172133A1 JP 2019008157 W JP2019008157 W JP 2019008157W WO 2019172133 A1 WO2019172133 A1 WO 2019172133A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal oxide
oxide nanoparticles
transparent electrode
nanocrystal layer
layer
Prior art date
Application number
PCT/JP2019/008157
Other languages
French (fr)
Japanese (ja)
Inventor
知輝 鴻池
佐藤　英次
伸之 伊藤
Original Assignee
シャープ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by シャープ株式会社 filed Critical シャープ株式会社
Priority to JP2020504988A priority Critical patent/JPWO2019172133A1/en
Publication of WO2019172133A1 publication Critical patent/WO2019172133A1/en

Links

Images

Classifications

    • 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

Definitions

  • This disclosure relates to an electrochromic device and a smart window.
  • An electrochromic element whose optical properties reversibly change when a voltage is applied is known.
  • a smart window capable of electrically controlling light transmittance.
  • Patent Document 1 discloses an electrochromic element used for an infrared type smart window.
  • An electrochromic device 900 shown in FIG. 20 includes a first substrate 911, a second substrate 912, a first transparent electrode 901, a second transparent electrode 902, a nanocrystal layer 903, an electrolytic solution 905, a power source 906, a seal portion 907, and a spacer 908. Is provided.
  • the first substrate 911 and the second substrate 912 are provided so as to face each other. Each of the first substrate 911 and the second substrate 912 is transparent.
  • the first transparent electrode 901 is provided on the surface of the first substrate 911 on the second substrate 912 side.
  • the second transparent electrode 902 is provided on the surface of the second substrate 912 on the first substrate 911 side.
  • the nanocrystal layer 903 is provided on the first transparent electrode 901.
  • the nanocrystal layer 903 includes metal oxide nanoparticles having a particle size of several nanometers to several tens of nanometers.
  • the electrolytic solution 905 is enclosed in a region surrounded by the seal portion 907 and is located between the nanocrystal layer 903 and the second transparent electrode 902.
  • the power source 906 is electrically connected to the first transparent electrode 901 and the second transparent electrode 902, and can apply a predetermined voltage between the first transparent electrode 901 and the second transparent electrode 902.
  • the spacer 908 is provided between the nanocrystal layer 903 and the second transparent electrode 902 and defines the height of the region in which the electrolytic solution 905 is enclosed.
  • the nanocrystal layer 903 of the electrochromic device 900 expresses electrochromism using localized surface plasmon resonance (LSPR).
  • LSPR localized surface plasmon resonance
  • Non-Patent Document 1 discloses various nanocrystals used as electrochromic materials.
  • the nanocrystal layer 903 is provided only on one side of the pair of transparent electrodes (specifically, on the first transparent electrode 901).
  • the inventor of the present application examined providing a further nanocrystal layer on the other side of the pair of transparent electrodes.
  • the surface area of the metal oxide nanoparticles is increased as compared with the case where the nanocrystal layer is provided only on one side. Therefore, it is considered that more charges can be stored in the nanocrystal layer when voltage is applied, and the desired transmission spectrum can be maintained for a long time even when the circuit is shut off (that is, suitable memory properties can be provided). It is done.
  • the present disclosure has been made in view of the above problems, and an object thereof is to provide an electrochromic device and a smart window that include two nanocrystal layers and can operate suitably.
  • An electrochromic device includes a first transparent electrode and a second transparent electrode facing each other, and a surface of the first transparent electrode on the second transparent electrode side, and a plurality of first metal oxides
  • An electrolyte layer provided between the first nanocrystal layer and the second nanocrystal layer, wherein the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles are configured
  • the elements are the same, and the thickness of the first nanocrystal layer is different from the thickness of the second nanocrystal layer.
  • the thickness of the second nanocrystal layer is not less than 1% and not more than 30% of the thickness of the first nanocrystal layer.
  • an average particle size of the plurality of first metal oxide nanoparticles is different from an average particle size of the plurality of second metal oxide nanoparticles.
  • An electrochromic device includes a first transparent electrode and a second transparent electrode facing each other, and a surface of the first transparent electrode on the second transparent electrode side, and a plurality of first metal oxides
  • An electrolyte layer provided between the first nanocrystal layer and the second nanocrystal layer, wherein the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles are configured
  • the elements are the same, and the average particle size of the plurality of first metal oxide nanoparticles is different from the average particle size of the plurality of second metal oxide nanoparticles.
  • an average particle diameter of the plurality of second metal oxide nanoparticles is 5 nm to 100 nm larger than an average particle diameter of the plurality of first metal oxide nanoparticles.
  • the composition ratio of the plurality of first metal oxide nanoparticles is different from the composition ratio of the plurality of second metal oxide nanoparticles.
  • An electrochromic device includes a first transparent electrode and a second transparent electrode facing each other, and a surface of the first transparent electrode on the second transparent electrode side, and a plurality of first metal oxides
  • An electrolyte layer provided between the first nanocrystal layer and the second nanocrystal layer, wherein the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles are configured
  • the elements are the same, and the composition ratio of the plurality of first metal oxide nanoparticles is different from the composition ratio of the plurality of second metal oxide nanoparticles.
  • the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles are each a plurality of antimony-doped tin oxide nanoparticles.
  • the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles are each a plurality of tin-doped indium oxide nanoparticles.
  • the electrochromic device further includes a first substrate that supports the first transparent electrode, and a second substrate that supports the second transparent electrode, and the first substrate and the second substrate.
  • a first substrate that supports the first transparent electrode
  • a second substrate that supports the second transparent electrode
  • Each of these is a flexible resin substrate.
  • each of the first transparent electrode and the second transparent electrode is divided into a plurality of electrically independent sub-electrodes.
  • a smart window according to an embodiment of the present invention includes an electrochromic device having any one of the above-described configurations.
  • the smart window further includes a translucent plate, and the electrochromic element is bonded to the translucent plate.
  • a transmission spectrum of each of the first nanocrystal layer and the second nanocrystal layer changes according to a change in applied voltage, and the first nanocrystal layer and the second nanocrystal layer
  • the nanocrystal layer having a relatively large change in the transmission spectrum in accordance with the change in the applied voltage is positioned between the relatively small nanocrystal layer and the light transmitting plate.
  • the smart window further includes a glazing channel disposed to surround a peripheral edge of the translucent plate and a peripheral edge of the electrochromic element, and the electrochromic element surrounds the electrolyte layer.
  • the sealing portion is further provided, and the sealing portion overlaps the glazing channel when viewed from the normal direction of the light transmitting plate.
  • the smart window further includes a first light-transmitting plate and a second light-transmitting plate disposed so as to face the first light-transmitting plate with a predetermined gap therebetween.
  • the chromic element is bonded to the second light transmitting plate side of the first light transmitting plate, and an intermediate layer having a predetermined thickness is located between the electrochromic element and the second light transmitting plate. .
  • the smart window is provided between the electrochromic element and the second light transmitting plate, a spacer that defines a thickness of the intermediate layer, a peripheral portion of the first light transmitting plate, A glazing channel disposed so as to surround a peripheral edge of the electrochromic element and a peripheral edge of the second light-transmitting plate, and the electrochromic element is provided to surround the electrolyte layer
  • the spacer further overlaps the glazing channel, and the seal portion overlaps the spacer and the glazing channel when viewed from the normal direction of the first light transmission plate.
  • the smart window is provided between the electrochromic element and the second light transmitting plate, a spacer that defines a thickness of the intermediate layer, a peripheral portion of the first light transmitting plate, A glazing channel disposed so as to surround a peripheral edge of the electrochromic element and a peripheral edge of the second light-transmitting plate, and the electrochromic element is provided to surround the electrolyte layer
  • the spacer is overlapped with the glazing channel, the seal portion is overlapped with the glazing channel, and when viewed from the normal direction of the first light transmission plate, and more than the spacer Located inside.
  • the smart window further includes a first light-transmitting plate and a second light-transmitting plate disposed so as to face the first light-transmitting plate with a predetermined gap therebetween.
  • the chromic element is disposed between the first light transmissive plate and the second light transmissive plate, and a first intermediate layer having a predetermined thickness between the first light transmissive plate and the electrochromic element. And a second intermediate layer having a predetermined thickness is located between the electrochromic element and the second light transmitting plate.
  • the electrochromic element includes a pair of antireflection films positioned on the outermost surface on the first light transmitting plate side and the outermost surface on the second light transmitting plate side.
  • the smart window is provided between the first light-transmitting plate and the electrochromic device, and defines a first spacer that defines a thickness of the first intermediate layer, the electrochromic device, and the electrochromic device.
  • a second spacer provided between the second light-transmitting plate and defining a thickness of the second intermediate layer; a peripheral portion of the first light-transmitting plate; a peripheral portion of the electrochromic element; and the second transparent member.
  • a glazing channel disposed so as to surround a peripheral portion of the optical plate, wherein the electrochromic element further includes a seal portion provided so as to surround the electrolyte layer, and the first translucent plate When viewed from the normal direction, the first spacer and the second spacer overlap the glazing channel, and the seal portion includes the first spacer and the second spacer. It overlaps the over support and the glazing channel.
  • the smart window is provided between the first light-transmitting plate and the electrochromic device, and defines a first spacer that defines a thickness of the first intermediate layer, the electrochromic device, and the electrochromic device.
  • a second spacer provided between the second light-transmitting plate and defining a thickness of the second intermediate layer; a peripheral portion of the first light-transmitting plate; a peripheral portion of the electrochromic element; and the second transparent member.
  • a glazing channel disposed so as to surround a peripheral portion of the optical plate, wherein the electrochromic element further includes a seal portion provided so as to surround the electrolyte layer, and the first translucent plate When viewed from the normal direction, the first spacer and the second spacer overlap the glazing channel, and the seal portion includes the glazing channel. It overlaps in, and, is located inside the first spacer and the second spacer.
  • an electrochromic device and a smart window that include two nanocrystal layers and can operate suitably.
  • FIG. 2 is a cross-sectional view schematically showing an electrochromic device 100 including a spacer 8.
  • FIG. It is a figure which shows the example of the other structure of the seal part. It is sectional drawing which shows typically the electrochromic element 200 in embodiment of this indication. It is a graph which shows the transmission spectrum of the light control cell D, E, and F. It is sectional drawing which shows typically the electrochromic element 300 in embodiment of this indication. It is sectional drawing which shows typically the electrochromic element 400 in embodiment of this indication.
  • FIG. 3 is a block diagram schematically illustrating a smart window 500 according to an embodiment of the present disclosure. (A) And (b) is sectional drawing and the top view which show the light control part 20 of the smart window 500 typically.
  • FIG. 10 is a cross-sectional view schematically showing an electrochromic element 900 of Patent Document 1.
  • FIG. 10 is a cross-sectional view schematically showing an electrochromic element 900 of Patent Document 1.
  • the inventor of the present application has found that in a configuration in which a nanocrystal layer is provided only on one of a pair of transparent electrodes, the deterioration of the transparent electrode and the electrolytic solution can occur. In addition, it has been found that the same problem can occur in the configuration in which the nanocrystal layer is provided not only on one side of the pair of transparent electrodes but also on the other side.
  • the inventor of the present application has conducted a more detailed study, and by using metal oxide nanoparticles having the same constituent elements as the materials of the two nanocrystal layers, an electrochemical balance can be obtained, and the transparent electrode and the electrolyte can be deteriorated. It has been found that can be suppressed.
  • the use of metal oxide nanoparticles having the same constituent elements is advantageous in terms of production cost, simplification of the production process, and the like.
  • FIG. 1 is a cross-sectional view schematically showing an electrochromic device 100.
  • the electrochromic element 100 includes a first transparent electrode 1 and a second transparent electrode 2, a first nanocrystal layer 3 and a second nanocrystal layer 4, and an electrolyte layer 5.
  • the first transparent electrode 1 and the second transparent electrode 2 are arranged so as to face each other.
  • the first transparent electrode 1 and the second transparent electrode 2 are each transparent and substantially colorless.
  • the first transparent electrode 1 and the second transparent electrode 2 are electrically connected to a power source 6.
  • the first transparent electrode 1 is supported on the first substrate 11.
  • the second transparent electrode 2 is supported on the second substrate 12.
  • the first substrate 11 and the second substrate 12 are each transparent and substantially colorless.
  • the first nanocrystal layer 3 is provided on the surface of the first transparent electrode 1 on the second transparent electrode 2 side.
  • the first nanocrystal layer 3 includes a plurality of metal oxide nanoparticles (hereinafter referred to as “first metal oxide nanoparticles”).
  • the second nanocrystal layer 4 is provided on the surface of the second transparent electrode 2 on the first transparent electrode 1 side.
  • the second nanocrystal layer 4 includes a plurality of metal oxide nanoparticles (hereinafter referred to as “second metal oxide nanoparticles”).
  • the first metal oxide nanoparticles and the second metal oxide nanoparticles are particulate crystals (nanocrystals) each having a particle size of several nm to several tens of nm.
  • the electrolyte layer 5 is provided between the first nanocrystal layer 3 and the second nanocrystal layer 4.
  • the electrolyte layer 5 is surrounded by the seal portion 7.
  • the first metal oxide nanoparticles contained in the first nanocrystal layer 3 and the second metal oxide nanoparticles contained in the second nanocrystal layer 4 are electrochromic materials. Therefore, the transmission spectra of the first nanocrystal layer 3 and the second nanocrystal layer 4 change according to the voltage applied between the first transparent electrode 1 and the second transparent electrode 2. This change in the transmission spectrum is accompanied by a change in transmittance in the near infrared region. Therefore, the electrochromic element 100 of this embodiment can control the transmittance of near infrared light.
  • the near-infrared region refers to a wavelength range of about 800 nm or more and about 2500 nm or less.
  • the acquisition rate of solar heat from sunlight can be controlled by controlling the transmittance of the near-infrared light. For example, near-infrared light can be prevented from entering the room in summer, and near-infrared light can be taken into the room in winter.
  • first metal oxide nanoparticles and the second metal oxide nanoparticles for example, antimony-doped tin oxide (ATO) nanoparticles and tin-doped indium oxide nanoparticles are used. It can be used suitably.
  • ATO antimony-doped tin oxide
  • the principle that the first nanocrystal layer 3 and the second nanocrystal layer 4 exhibit electrochromism will be described later.
  • the change in the transmission spectrum of the first nanocrystal layer 3 and the second nanocrystal layer 4 is not only the change in the transmittance in the near infrared region, but also the change in the transmittance in the visible region (a range from about 400 nm to about 800 nm). May be accompanied.
  • the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements (that is, contain the same elements).
  • the thickness t1 of the first nanocrystal layer 3 is different from the thickness t2 of the second nanocrystal layer 4.
  • the thickness t2 of the second nanocrystal layer 4 is smaller than the thickness t1 of the first nanocrystal layer 3.
  • the thickness t2 of the second nanocrystal layer 4 is not less than 1% and not more than 30% of the thickness t1 of the first nanocrystal layer 3.
  • the electrochromic device 100 includes a pair of nanocrystal layers (first electrodes) provided on one side and the other side of a pair of transparent electrodes (first transparent electrode 1 and second transparent electrode 2).
  • a nanocrystal layer 3 and a second nanocrystal layer 4 thereby, the total surface area of the metal oxide nanoparticles is increased as compared with the case where the nanocrystal layer is provided only on one side of the pair of transparent electrodes. Therefore, more charge can be stored in the nanocrystal layer when a voltage is applied, and a desired transmission spectrum can be maintained for a long time even in a state where the circuit is shut off (a state where power supply from the power source 6 is stopped). That is, a suitable memory property can be realized.
  • the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements. Thereby, since electrochemical balance is taken on both sides of the electrolyte layer 5, the deterioration of the first transparent electrode 1, the second transparent electrode 2, and the electrolyte layer 5 can be suppressed. Further, the fact that the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements is advantageous in terms of manufacturing cost, simplification of the manufacturing process, and the like.
  • the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are different. As a result, the operation shift range of the transmission spectrum can be sufficiently widened, as will be described in detail later with the verification results.
  • Non-Patent Document 1 by injecting electrons into a transparent conductive oxide (TCO) nanostructure such as an ITO (Tin-doped Indium-Oxide) nanocrystal layer, near-infrared It is known that the transmission spectrum of a region can be changed. In short, the principle is to shift the absorption wavelength by localized surface plasmon resonance (LSPR) of the TCO nanostructure by applying a voltage. This will be described in more detail below.
  • TCO transparent conductive oxide
  • ITO Tin-doped Indium-Oxide
  • the resonance frequency of LSPR is proportional to the plasma frequency ⁇ p .
  • N is the electron density
  • e is the charge of the electron
  • m is the effective mass of the electron
  • ⁇ 0 is the dielectric constant of the vacuum. Therefore, when a negative voltage is applied to the TCO nanostructure to increase the electron density, the plasma frequency ⁇ p increases, and the resonance frequency of the LSPR also increases. Therefore, the resonance wavelength of LSPR becomes short (that is, shifts to the short wavelength side).
  • the resonance wavelength of the LSPR can be set in the near infrared region, so that the transmission spectrum in the near infrared region can be changed.
  • the function of changing the transmission spectrum in this way is not unique to the ITO nanocrystal layer containing ITO nanoparticles.
  • the above-described functions can be achieved if the nanoparticles are sized so as to cause LSPR (for example, 100 nm or less), and the nanocrystal layer can inject electrons from the transparent electrode.
  • nanoparticles nanoparticles of various metal oxides such as ATO, PTO (phosphorus-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide) can be used.
  • an electrochromic element 800 shown in FIG. 2 was produced.
  • the electrochromic element 800 shown in FIG. 2 is different from the electrochromic element 100 shown in FIG. 1 in that the second nanocrystal layer 4 is omitted.
  • the nanocrystal layer 3 of the electrochromic element 800 includes ATO nanoparticles having an average particle diameter of 20 nm.
  • the firing temperature when forming the nanocrystal layer 3 is 200 ° C.
  • Three electrochromic devices 800 having nanocrystal layer 3 with thicknesses t1 of 840 mm, 4650 mm, and 7620 mm were fabricated (referred to as “light control cell A”, “light control cell B”, and “light control cell C”, respectively). ).
  • the thickness t1 of the nanocrystal layer 3 is an average value obtained by measuring the thicknesses at three locations from the center to the outer periphery of the nanocrystal layer 3 formed on the first transparent electrode 1 with a stylus step meter. It is.
  • the average particle diameter of a nanoparticle is a biaxial average meter of 100 nanoparticles observed using a transmission electron microscope (TEM).
  • FIG. 3 shows transmission spectra of the light control cells A, B and C when the potential of the second transparent electrode 2 is 0 V and DC voltages of ⁇ 3 V and +3 V are applied to the first transparent electrode 1.
  • Table 1 shows the transmittance of light having a wavelength of 2000 nm when the DC voltages of ⁇ 3 V and +3 V are applied to the first transparent electrode 1 for the light control cells A, B, and C.
  • Table 1 also shows the operation shift range.
  • the “operation shift range” is the difference between the transmittance of light with a wavelength of 2000 nm when +3 V is applied and the transmittance of light with a wavelength of 2000 nm when -3 V is applied.
  • the operation shift range of the light control cell C (the thickness of the nanocrystal layer 3 is 7620 mm) is 56.6%
  • the light control cell B the thickness of the nanocrystal layer 3 is 4650 mm.
  • the operation shift ranges of the light control cell A (the thickness of the nanocrystal layer 3 is 840 mm) are 45.5% and 15.6%, respectively. That is, the dimming cell A has a narrower operation shift range of 41.0% than the dimming cell C.
  • the reason why the operation shift range becomes narrower as the thickness t1 of the nanocrystal layer 3 is smaller is that the optical path length of the light transmitted through the nanocrystal layer 3 becomes shorter as the thickness t1 of the nanocrystal layer 3 becomes smaller. Conceivable.
  • the operation shift range can be varied by adjusting the thickness of the nanocrystal layer, by using a combination of a pair of nanocrystal layers having different thicknesses, the transmission spectrum of the electrochromic device can be reduced.
  • the operation shift range can be sufficiently widened. Specifically, by making the operation shift range of one nanocrystal layer less than or equal to half of the operation shift range of the other nanocrystal layer, the operation shift range of the entire electrochromic device can be sufficiently widened. .
  • a prototype example (Example 1) of the electrochromic element 100 was manufactured as follows, and the optical characteristics thereof were verified.
  • glass substrates were prepared as the first substrate 11 and the second substrate 12, respectively.
  • titanium-doped indium oxide Tianium-doped Indium Oxide: InTiO
  • InTiO titanium-doped Indium Oxide
  • the second transparent electrode 2 was formed on the second substrate 12.
  • a dispersion of ATO nanoparticles is applied on the first transparent electrode 1 by spin coating, dried on a hot plate at 140 ° C. for 1 minute, and then fired at 200 ° C. for 60 minutes, A first nanocrystal layer 3 having a thickness of 7620 mm was formed.
  • the ATO nanoparticle dispersion used contains ATO nanoparticles with an average particle size of 20 nm, and the dispersion medium is a 2: 1 mixture of methyl isobutyl ketone and isobutanol.
  • a dispersion of ATO nanoparticles is applied on the second transparent electrode 2 by spin coating, dried on a hot plate at 140 ° C. for 1 minute, and then fired at 200 ° C. for 60 minutes, A second nanocrystal layer 4 having a thickness of 840 mm was formed.
  • the ATO nanoparticle dispersion used contains ATO nanoparticles with an average particle size of 20 nm, and the dispersion medium is a 2: 1 mixture of methyl isobutyl ketone and isobutanol.
  • an electrochromic element of Comparative Example 1 was produced in the same manner as Example 1 except that the second nanocrystal layer 4 was not formed.
  • FIG. 4 shows the transmission spectrum of Example 1 and Comparative Example 1 when the potential of the second transparent electrode 2 is 0 V and DC voltages of ⁇ 3 V and +3 V are applied to the first transparent electrode 1.
  • Table 2 shows the transmittance of light with a wavelength of 2000 nm and the operation shift range when DC voltages of ⁇ 3 V and +3 V are applied to the first transparent electrode 1 for Example 1 and Comparative Example 1.
  • the operation shift range of Comparative Example 1 is 56.6%, whereas the operation shift range of Example 1 is 49.6%, and the decrease in the operation shift range is 7%. 0.0%.
  • Comparative Example 2 an electrochromic device was fabricated in the same manner as in Example 1 except that the thickness of both the first nanocrystal layer 3 and the second nanocrystal layer 4 was 9780 mm. Further, as Comparative Example 3, an electrochromic element was produced in the same manner as Comparative Example 2 except that the second nanocrystal layer 4 was not formed.
  • FIG. 5 shows transmission spectra of Comparative Example 2 and Comparative Example 3 when the potential of the second transparent electrode 2 is 0 V and DC voltages of ⁇ 3 V and +3 V are applied to the first transparent electrode 1.
  • Table 3 shows the transmittance and operation shift range of light having a wavelength of 2000 nm when DC voltages of ⁇ 3 V and +3 V are applied to the first transparent electrode 1 for Comparative Example 2 and Comparative Example 3.
  • the operation shift range of Comparative Example 3 is 56.8%, whereas the operation shift range of Comparative Example 2 is 0.3%. 3 is as narrow as 55.5% (49.3% for the first embodiment). This is because the transmission spectrum shifts of the first nanocrystal layer 3 and the second nanocrystal layer 4 are opposite to each other.
  • first nanocrystal layer 3 and second nanocrystal layer 4 prevents the operation shift range from being narrowed. it can.
  • Table 4 shows the results of visually observing the occurrence of bubbles in the electrolyte layer 5 for Example 1 and Comparative Examples 1, 2, and 3. As shown in Table 4, it can be seen that in Comparative Examples 1 and 3, bubbles were generated and the electrolyte was deteriorated. On the other hand, in Example 1 (and Comparative Example 2), it can be seen that bubbles are not generated and the deterioration of the electrolytic solution is suppressed.
  • the electrochromic device 100 including two nanocrystal layers and capable of operating appropriately.
  • the operation shift range for light having a wavelength of 2000 nm in the transmission spectrum of the second nanocrystal layer 4 is the operation for light having a wavelength of 2000 nm in the transmission spectrum of the first nanocrystal layer 3. It is preferably less than half of the shift range.
  • the thickness t2 of the second nanocrystal layer 4 is preferably 1% or more and 30% or less of the thickness t1 of the first nanocrystal layer 3. In Example 1, the thickness t2 of the second nanocrystal layer 4 is about 11% of the thickness t1 of the first nanocrystal layer 3.
  • the metal oxide used as the material for the metal oxide nanoparticles is not limited to the exemplified ATO and ITO.
  • a substantially transparent material such as AZO (Aluminum-doped Zinc Oxide) or GZO (Gallium-doped Zinc Oxide) can be used.
  • a material that absorbs light in the visible region such as a composite tungsten oxide or lanthanum hexaboride represented by CsxWyO 3 (x and y indicate composition ratios), can also be used.
  • the average particle diameter of the metal oxide nanoparticles is typically 0.1 nm or more and 1000 nm or less. However, if the average particle size of the metal oxide nanoparticles is too large, it may become difficult to operate. From the viewpoint of ease of operation, the average particle size of the metal oxide nanoparticles is 30 nm or less. It is preferable.
  • each of the first nanocrystal layer 3 and the second nanocrystal layer 4 is typically 100 mm or more and 50000 mm or less. From the viewpoint of the transparency of visible light and the operation shift range of the transmission spectrum, the thickness of each of the first nanocrystal layer 3 and the second nanocrystal layer 4 is preferably 1000 to 15000 mm.
  • the formation method of the first nanocrystal layer 3 and the second nanocrystal layer 4 is not particularly limited.
  • a liquid or semi-solid in which metal oxide nanoparticles are dispersed is applied onto the first substrate 11 or the second substrate 12 and baked to form the first nanocrystal layer 3 and the second nanocrystal layer 4.
  • the dispersion of metal oxide nanoparticles may be applied by a spin coating method, or may be applied by a printing method using a paste to which a vehicle is appropriately added. Further, the coating may be performed by a bar coating method, a slit coating method, a gravure coating method or a die coating method.
  • the firing temperature is such that organic components on the nanocrystal surface are removed and sintering is suitably performed, sufficient solvent resistance can be obtained. However, if the firing temperature is too high and the sintering proceeds excessively, there is a possibility that an LSPR having a desired wavelength cannot be obtained.
  • firing is performed at a temperature of 200 ° C. or higher and 300 ° C. or lower for 60 minutes, for example.
  • first nanocrystal layer 3 and the second nanocrystal layer 4 are made of a solvent system such as polyvinylidene fluoride (PVDF) as a binder in order to improve the binding property with the first substrate 11 and the second substrate 12.
  • PVDF polyvinylidene fluoride
  • a binder, an aqueous binder such as styrene / butadiene rubber, a photo-curing resin, a thermosetting resin, or the like may also be included.
  • the first substrate 11 and the second substrate 12 for example, glass substrates can be used.
  • the plastic substrate formed from resin materials such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), and a polyimide, may be sufficient.
  • These illustrated substrates may be provided with a gas barrier layer formed from an inorganic material or an organic material.
  • the step of forming the nanocrystal layer includes a baking step, it is preferable to use a polyimide substrate with high heat resistance as the plastic substrate.
  • the thickness may be reduced by etching after the two substrates are bonded together.
  • Transparent electrode As the material of the first transparent electrode 1 and the second transparent electrode 2, in addition to InTiO, a material that transmits near-infrared light such as tantalum-substituted tin oxide using anatase-type titanium dioxide as a seed layer or ITO with adjusted carrier density Can be used.
  • the first transparent electrode 1 and the second transparent electrode 2 can be formed by depositing these materials on the first substrate 1 and the second substrate 2 by sputtering, vapor deposition, coating, or the like.
  • the material of the first transparent electrode 1 and the second transparent electrode 2 has a characteristic of reflecting far-infrared light.
  • Infrared light radiated from the room is classified as far-infrared light having a wavelength of about 10 ⁇ m. Therefore, if the first transparent electrode 1 and the second transparent electrode 2 have the characteristic of reflecting far-infrared light, the state of the nanocrystal layer is controlled so that the transmittance of near-infrared light is increased.
  • the indoor heat does not escape to the outdoors as radiant heat, and an ideal state can be realized. Further, even when control is performed so that the transmittance of near-infrared light is lowered in summer, it is possible to prevent the far-infrared light from the outside from entering the room, so that an ideal state can be realized.
  • the electrode extraction (connection to the external wiring) of the first transparent electrode 1 may be performed at one place or at a plurality of places. .
  • the assembly process of the electrochromic element 100 can be simplified and the routing of the wiring can be simplified.
  • a partial response speed delay can be prevented even when there is a resistance component between the first transparent electrode 1 and the second transparent electrode 2, that is, when a current flows.
  • the first transparent electrode 1 may be divided into a plurality of electrically independent sub-electrodes.
  • the transmission spectrum can be changed for each region corresponding to the sub-electrodes.
  • 6A and 6B show an example of a configuration in which the first transparent electrode 1 is divided into a plurality of sub-electrodes 1a.
  • the electrode lead-out portions EP are gathered at one place by routing the plurality of sub-electrodes 1a. An unnecessary voltage drop can be prevented by disposing the lead-out portion of the sub-electrode 1a away from the operation portion of the electrochromic element 100 such as the outside of the seal portion 7 or under the seal portion 7.
  • the plurality of sub-electrodes 1a are directly connected to the wiring without being routed. That is, the electrode extraction part EP is dispersed in a plurality of places.
  • the second transparent electrode 2 may be divided into a plurality of electrically independent sub-electrodes or may not be divided.
  • the electrolyte layer 5 is made of, for example, an electrolytic solution.
  • an electrolytic solution a material that is easily ionized such as lithium hexafluorophosphate (LiPF 6 ), sodium hexafluorophosphate (NaPF 6 ), lithium borofluoride (LiBF 4 ), or the like can be used.
  • ethylene carbonate (EC), diethyl carbonate (DEC), a mixture of EC and DC, propylene carbonate, or the like can be used.
  • an ionic liquid composed of a cyclic quaternary ammonium cation and an imide anion may be used.
  • the electrolyte layer 5 may be composed of a solid electrolyte.
  • a solid electrolyte such as polyethylene oxide containing a lithium salt may be used, or a plastic crystal may be used.
  • the electrochromic element 100 defines the distance (cell thickness) between the first substrate 11 and the second substrate 12 as shown in FIG. It is preferable to provide a spacer 8 for the purpose.
  • the spacer 8 is provided between the first nanocrystal layer 3 and the second nanocrystal layer 4.
  • the spacer 8 can be formed by a photolithography process using a photosensitive resin material.
  • the spacer 8 is, for example, 10 ⁇ m square and 10 ⁇ m high.
  • the formation method of the spacer 8 is not limited to the photolithography process, but may be, for example, a screen printing method.
  • the electrolyte layer 5 is composed of a solid electrolyte, it is not necessary to provide the spacer 8 if the solid electrolyte has appropriate elasticity.
  • seal portion 7 As a material of the seal portion 7, for example, a UV curable resin material can be used.
  • FIG. 8 shows an example of another configuration of the seal portion 7.
  • the seal portion 7 has two regions 7 a and 7 b formed from different materials (seal materials).
  • the area 7a positioned relatively inside is referred to as “inside area”
  • the area 7b positioned relatively outside is referred to as “outside area”.
  • the inner region 7a is formed from a sealing material having higher solvent resistance than the sealing material forming the outer region 7b.
  • the outer region 7b is formed of a sealing material having a stronger adhesive force than the sealing material forming the inner region 7a.
  • the inner region 7a that is in contact with the electrolyte layer 5 is formed of a highly solvent-resistant sealing material
  • the outer region 7b is formed of a sealing material having a strong adhesive force. High reliability and strong adhesion can be achieved at the same time.
  • FIG. 9 is a cross-sectional view schematically showing the electrochromic element 200. Below, it demonstrates centering on the point from which the electrochromic element 200 differs from the electrochromic element 100 of Embodiment 1.
  • FIG. 9 is a cross-sectional view schematically showing the electrochromic element 200. Below, it demonstrates centering on the point from which the electrochromic element 200 differs from the electrochromic element 100 of Embodiment 1.
  • the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are different.
  • the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are substantially the same.
  • the average particle diameter of the 1st metal oxide nanoparticle contained in the 1st nanocrystal layer 3, and the average particle diameter of the 2nd metal oxide nanoparticle contained in the 2nd nanocrystal layer 4 Is different.
  • the average particle diameter of the second metal oxide nanoparticles is larger than the average particle diameter of the first metal oxide nanoparticles.
  • the average particle diameter of the second metal oxide nanoparticles is 5 nm to 100 nm larger than the average particle diameter of the first metal oxide nanoparticles.
  • the electrochromic element 200 of the present embodiment is also the same as the electrochromic element 100 of the first embodiment, on one side and the other side of the pair of transparent electrodes (first transparent electrode 1 and second transparent electrode 2).
  • first transparent electrode 1 and second transparent electrode 2 are provided with a pair of nanocrystal layers (first nanocrystal layer 3 and second nanocrystal layer 4).
  • the total surface area of the metal oxide nanoparticles is increased as compared with the case where the nanocrystal layer is provided only on one side of the pair of transparent electrodes. Therefore, more charges can be stored in the nanocrystal layer when a voltage is applied, and a desired transmission spectrum can be maintained for a long time even when the circuit is shut off. That is, a suitable memory property can be realized.
  • the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements. Thereby, since electrochemical balance is taken, deterioration of the 1st transparent electrode 1, the 2nd transparent electrode 2, and the electrolyte layer 5 can be controlled. Further, the fact that the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements is advantageous in terms of manufacturing cost, simplification of the manufacturing process, and the like.
  • the average particle diameter of the first metal oxide nanoparticles is different from the average particle diameter of the second metal oxide nanoparticles.
  • an electrochromic element 800 shown in FIG. 2 was produced.
  • the nanocrystal layer 3 of the produced electrochromic device 800 includes ITO nanoparticles.
  • the firing temperature when forming the nanocrystal layer 3 is 200 ° C.
  • FIG. 10 shows transmission spectra of the light control cells D, E, and F when the potential of the second transparent electrode 2 is 0 V and DC voltages of ⁇ 3 V and +3 V are applied to the first transparent electrode 1.
  • Table 5 also shows the transmittance and operation shift range of light having a wavelength of 2000 nm when a DC voltage of ⁇ 3 V and +3 V is applied to the first transparent electrode 1 for the dimming cells D, E, and F. It is shown.
  • the dimming cell F has an operation shift range of 55.3% narrower than that of the dimming cell D.
  • the larger the average particle size of the metal oxide nanoparticles the narrower the operation shift range.
  • the larger the average particle size the smaller the specific surface area of the metal oxide nanoparticles and the presence of sufficient electrolyte ions around the nanoparticles. It is thought that it is because it becomes impossible.
  • the operation shift range can be varied by adjusting the average particle diameter of the metal oxide nanoparticles, a pair of nanocrystal layers having different average particle diameters of the metal oxide nanoparticles are used in combination.
  • the operation shift range of the transmission spectrum of the electrochromic device can be sufficiently widened.
  • the operation shift range of one nanocrystal layer less than or equal to half of the operation shift range of the other nanocrystal layer, the operation shift range of the entire electrochromic device can be sufficiently widened. .
  • the average particle diameter of the second metal oxide nanoparticles is set to It is preferable that the average particle diameter of one metal oxide nanoparticle be 5 nm or more and 100 nm or less.
  • FIG. 11 is a cross-sectional view schematically showing the electrochromic element 300.
  • the electrochromic element 300 will be described focusing on differences from the electrochromic element 100 of the first embodiment.
  • the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are different.
  • the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are substantially the same.
  • composition ratio of the first metal oxide nanoparticles is different from the composition ratio of the second metal oxide nanoparticles.
  • the electrochromic element 300 of the present embodiment is also a pair provided on one side and the other side of the pair of transparent electrodes (first transparent electrode 1 and second transparent electrode 2).
  • These nanocrystal layers (first nanocrystal layer 3 and second nanocrystal layer 4) are provided.
  • the total surface area of the metal oxide nanoparticles is increased as compared with the case where the nanocrystal layer is provided only on one side of the pair of transparent electrodes. Therefore, more charges can be stored in the nanocrystal layer when a voltage is applied, and a desired transmission spectrum can be maintained for a long time even when the circuit is shut off. That is, a suitable memory property can be realized.
  • the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements. Thereby, since electrochemical balance is taken, deterioration of the 1st transparent electrode 1, the 2nd transparent electrode 2, and the electrolyte layer 5 can be controlled. Further, the fact that the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements is advantageous in terms of manufacturing cost, simplification of the manufacturing process, and the like.
  • the composition ratio of the first metal oxide nanoparticles is different from the composition ratio of the second metal oxide nanoparticles. Therefore, the operation shift range of the transmission spectrum can be sufficiently widened.
  • the composition ratio of the first metal oxide nanoparticles is different from the composition ratio of the second metal oxide nanoparticles.
  • the operation shift range of the transmission spectrum can be widened. Specifically, the operation density of the first nanocrystal layer 3 is increased by relatively increasing the carrier density of the first metal oxide nanoparticles and relatively decreasing the carrier density of the second metal oxide nanoparticles. The range can be made wider than the operation shift range of the second nanocrystal layer 4, and the operation shift range of the transmission spectrum in the electrochromic device 300 can be widened.
  • the first metal oxide nanoparticles and the second metal oxide nanoparticles are ITO nanoparticles
  • the first metal oxide nanoparticles have an Sn content of 10 wt% to 20 wt%
  • the second metal oxide nanoparticles In the product nanoparticles the Sn content is preferably 1 wt% or more and 5 wt% or less.
  • the electrochromic elements 100, 200, and 300 of Embodiments 1, 2, and 3 have the following configurations (A), (B), and (C), respectively.
  • A The thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are different.
  • B The average particle diameter of the first metal oxide nanoparticles is different from the average particle diameter of the second metal oxide nanoparticles.
  • C The composition ratio of the first metal oxide nanoparticles is different from the composition ratio of the second metal oxide nanoparticles.
  • the configuration (A) is most preferable among the configurations (A), (B), and (C).
  • the electrochromic device of the embodiment of the present disclosure may have the configurations (A) and (B), may have the configurations (A) and (C), and (B ) And (C). Furthermore, the electrochromic device of the embodiment of the present disclosure may have all the configurations of (A), (B), and (C).
  • FIG. 12 is a cross-sectional view schematically showing the electrochromic element 400.
  • the description will be focused on the points where the electrochromic element 400 is different from the electrochromic element 100 of the first embodiment.
  • the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are different from the electrochromic element 100 of the first embodiment.
  • each of the first substrate 11 ′ supporting the first transparent electrode 1 and the second substrate 12 ′ supporting the second transparent electrode 2 is a flexible resin substrate. It is. Since the first substrate 11 ′ and the second substrate 12 ′ are flexible resin substrates, the electrochromic element 400 can be flexible. Therefore, installation of the electrochromic element 400 on a window glass or the like can be performed more easily.
  • the electrochromic element 400 can be manufactured, for example, as follows.
  • a PET film having a thickness of 25 ⁇ m is prepared as the first substrate 11 ′ and the second substrate 12 ′.
  • ITO that becomes transparent in the near-infrared region was deposited by sputtering to form the first transparent electrode 1.
  • the second transparent electrode 2 is formed on the second substrate 12 '.
  • a dispersion of ITO nanoparticles is applied onto the first transparent electrode 1 by spin coating, dried on a hot plate at 140 ° C. for 1 minute, and then fired at 200 ° C. for 60 minutes, A first nanocrystal layer 3 is formed.
  • the used ITO nanoparticle dispersion contains ITO nanoparticles having an average particle size of 10 nm, and the dispersion medium is toluene.
  • a second nanocrystal layer 4 containing ITO nanoparticles is formed on the second transparent electrode 2.
  • the configuration (B) and / or (C) is included in addition to (or instead of) the configuration (A). May be.
  • Embodiment 5 The electrochromic elements 100 to 400 of Embodiments 1 to 4 can be suitably used for, for example, a smart window (light control window).
  • a smart window light control window
  • the transmission spectrum in the near infrared region from the outside can be switched while maintaining the transmittance in the visible light region.
  • the solar heat gain rate can be controlled.
  • FIG. 13 is a block diagram schematically showing the smart window 500.
  • the smart window 500 includes a light control unit 20, a control unit 30, a switch unit 32, a communication unit 34, and a power supply unit 36 as shown in FIG.
  • the light control unit 20 is a window-like portion including an electrochromic element, which is a main body of the smart window 500. A specific configuration of the light control unit 20 will be described in detail later.
  • the control unit 30 controls the operation of the light control unit 20 based on the signal transmitted from the switch unit 32 or the communication unit 34.
  • the control unit 30 is, for example, a circuit board including a calculation unit such as a CPU (Central Processing Unit) or a dedicated processor and a storage unit such as a RAM (Random Access Memory) or a ROM (Read Only Memory).
  • a calculation unit such as a CPU (Central Processing Unit) or a dedicated processor
  • a storage unit such as a RAM (Random Access Memory) or a ROM (Read Only Memory).
  • the power supply unit 36 is a power supply circuit that supplies power to the control unit 30 and the light control unit 20.
  • the power supply unit 36 may include a removable primary battery, a secondary battery, and the like.
  • the switch unit 32 accepts input from the user.
  • the switch unit 32 includes a changeover switch operated by a user, for example, and transmits a signal (operation input signal) corresponding to the operation of the changeover switch to the control unit 30.
  • the communication unit 34 includes a receiving unit that receives a signal from the external communication device 40.
  • the communication unit 34 is connected to the communication device 40 by, for example, wireless communication.
  • wireless communication infrared communication, Wi-Fi (registered trademark), Z-Wave (registered trademark), or the like can be used.
  • the communication device 40 is a terminal device such as a remote controller.
  • the communication between the communication unit 34 and the communication device 40 may be unidirectional communication in which a signal related to the control of the light control unit 20 is unilaterally transmitted from the communication device 40 to the communication unit 34, or bidirectional communication. It may be.
  • bidirectional communication for example, an error signal of the dimming unit 20 can be sent to the communication device 40 and the contents can be displayed on the communication device 40.
  • the communication unit 34 includes a transmission unit in addition to the reception unit.
  • Control of the light control unit 20 can be performed manually from the switch unit 32 or the communication device 40 as described above. Or you may switch the state of the light control part 20 automatically and / or regularly. For example, by providing a timer unit (for example, a clock) in the smart window 500, the state of the dimming unit can be switched periodically without providing the switch unit 32 and the communication unit 34. Moreover, you may control taking in of near infrared light indoors using the information on the internet regarding the weather and temperature of each area. Specifically, for example, weather and temperature information corresponding to the address where the smart window 400 is installed is distributed as a service, which is received by the communication device 40 or the direct communication unit 34 and used to control the light control unit 20. can do.
  • a timer unit for example, a clock
  • the communication device 40 or the communication unit 34 is connected to a HEMS (Home Energy Management System) to manage the indoor temperature, outdoor temperature, power consumption, etc. in combination with a temperature sensor or the like. Alternatively, it may be reflected in the operation of the light control unit 20.
  • HEMS Home Energy Management System
  • FIGS. 14 (a) and 14 (b) a specific configuration of the light control unit 20 will be described with reference to FIGS. 14 (a) and 14 (b).
  • the case where the light control part 20 contains the electrochromic element 100 of Embodiment 1 is illustrated.
  • FIG. 14A the laminated structure of the first transparent electrode 1, the first nanocrystal layer 3, the electrolyte layer 5, the second nanocrystal layer 4, and the second transparent electrode 2 is shown as one dimming layer 9. ing.
  • the light control unit 20 includes an electrochromic element 100, a glass plate (translucent plate) 21, and a glazing channel (sometimes referred to as “Grechan”) 22.
  • the glass plate 21 is typically rectangular as illustrated.
  • the glass plate 21 is illustrated here as a translucent plate, a translucent plate is not limited to this, What is necessary is just a plate-shaped member which has translucency.
  • an acrylic plate may be used as the translucent plate.
  • the electrochromic element 100 is bonded to the glass plate 21 via the adhesive layer 23.
  • the adhesive layer 23 is formed from a paste, a UV curable resin, or the like.
  • the electrochromic element 100 typically has substantially the same outer shape as the glass plate 21. In the illustrated example, the electrochromic element 100 is disposed on the indoor side of the glass plate 21. In other words, the glass plate 21 is disposed on the outdoor side of the electrochromic element 100.
  • the electrochromic element 100 is electrically connected to the power supply unit 36 described above via the wiring 24.
  • the glazing channel 22 is disposed so as to surround (pinch) the peripheral edge of the glass plate 21 and the peripheral edge of the electrochromic element 100.
  • FIGS. 15A and 15B show a state in which the collar 28 is disposed.
  • the ridge 28 is a frame-like support that supports the glass plate 21, the electrochromic element 100, and the glazing channel 22.
  • the glass plate, the electrochromic element 100, and the glazing channel 22 are integrally assembled to the flange 28.
  • the glazing channel 22 is located between the glass plate 21 and the electrochromic element 100 and the flange 28 and closes the gap between the glass plate 21 and the electrochromic element 100 and the flange 28 to ensure airtightness and watertightness. doing.
  • the solar heat gain rate can be controlled by adjusting the transmittance of near-infrared light incident on the indoor side through the glass plate 21 from the outside with the electrochromic element 100.
  • the seal portion 7 of the electrochromic element 100 When viewed from the normal direction of the glass plate (translucent plate) 21, the seal portion 7 of the electrochromic element 100 does not protrude from the glazing channel 22 as shown in FIGS. 14 (a) and 15 (a). (Ie, it overlaps the glazing channel 22). Thereby, since the seal
  • the transmission spectra of the first nanocrystal layer 3 and the second nanocrystal layer 4 of the electrochromic element 100 change according to the change of the applied voltage.
  • the nanocrystal layer here, the first nanocrystal layer 3 having a relatively large change in the transmission spectrum according to the change in the applied voltage is It is preferable that it is located between the relatively smaller nanocrystal layer (here, the second nanocrystal layer 4 and the glass plate (translucent plate) 21 (that is, the outdoor side). Since near-infrared light can be efficiently blocked before entering the electrolyte layer 5, the durability of the smart window 500 can be improved.
  • FIG. 16 is a cross-sectional view schematically showing the light control unit 20A.
  • the dimmer 20A will be described with a focus on differences from the dimmer 20 illustrated in FIG.
  • the light control unit 20 ⁇ / b> A is a first glass plate (first translucent plate) 21 ⁇ / b> A and a second glass plate disposed so as to face the first glass plate 21 ⁇ / b> A via a predetermined gap. (Second translucent plate) 21B.
  • first glass plate 21A is disposed on the outdoor side
  • second glass plate 21B is disposed on the indoor side.
  • the electrochromic element 100 is bonded to the second glass plate 21B side of the first glass plate 21A. That is, the electrochromic element 100 is located between the first glass plate 21A and the second glass plate 21B.
  • An intermediate layer 29 having a predetermined thickness is located between the electrochromic element 100 and the second glass plate 21B.
  • the intermediate layer 29 is, for example, an air layer or an argon layer.
  • the light control unit 20A further includes a spacer 25 provided between the electrochromic element 100 and the second glass plate 21B.
  • the spacer 25 defines the thickness of the intermediate layer 29.
  • various spacers for double-glazed glass can be used.
  • an aluminum spacer containing a desiccant or a resin spacer can be used.
  • the glazing channel 22 is disposed so as to surround the peripheral edge of the first glass plate 21A, the peripheral edge of the electrochromic element 100, and the peripheral edge of the second glass plate 21B.
  • the electrochromic element 100 is provided between the first glass plate 21A and the second glass plate 21B, the electrochromic element 100 is prevented from being damaged by an external impact. be able to. Moreover, since the electrochromic element 100 is bonded to the first glass plate 21A located on the outdoor side, near infrared light from the sun can be blocked before entering the intermediate layer 29. High heat shielding effect can be obtained.
  • the spacer 25 overlaps the glazing channel 22 and the seal portion 7 overlaps the spacer 25 and the glazing channel 22 when viewed from the normal direction of the first glass plate 21A.
  • the pressure of the spacer 25 and the glazing channel 22 can be applied to the region of the electrochromic element 100 where the high-strength seal portion 7 exists.
  • FIG. 17 is a cross-sectional view schematically showing the light control unit 20B. Below, it demonstrates centering on the point from which the light control part 20B differs from the light control part 20A shown in FIG.
  • the spacer 25 overlaps the glazing channel 22 when viewed from the normal direction of the first glass plate 21A. Further, when viewed from the normal direction of the first glass plate 21A, the seal portion 7 overlaps with the glazing channel 22 and is on the inner side than the spacer 25 (the inner side in the in-plane direction of the first glass plate 21). positioned.
  • the size of the second substrate 12 is slightly smaller than the size of the first substrate 11, and the end of the spacer 25 on the outdoor side is in contact with the first substrate 11.
  • the seal part 7 since the seal part 7 is disposed inside the spacer 25, the pressure of the spacer 25 and the glazing channel 22 can be prevented from being applied to the light control layer 9.
  • the wiring 24 and the flexible substrate for wiring may be located in the area
  • FIG. 18 is a cross-sectional view schematically showing the light control unit 20C.
  • the dimming unit 20C will be described with a focus on differences from the dimming unit 20A illustrated in FIG.
  • the light control unit 20C includes a first glass plate (first translucent plate) 21A and a second glass plate (second translucent plate) disposed so as to face the first glass plate 21A with a predetermined gap therebetween. 21B.
  • the electrochromic element 100 is disposed between the first glass plate 21A and the second glass plate 21B.
  • the electrochromic element 100 is not bonded to either the first glass plate 21A or the second glass plate 21B.
  • a first intermediate layer 29A is located between the first glass plate 21A and the electrochromic element 100
  • a second intermediate layer 29B is located between the electrochromic element 100 and the second glass plate 21B. ing. That is, in the light control unit 20C, the electrochromic element 100 is used in place of the central glass plate among the three glass plates constituting the double glass having a so-called triple glass structure.
  • the dimmer 20C includes a first spacer 25A provided between the first glass plate 21A and the electrochromic element 100, and a second spacer 25B provided between the electrochromic element 100 and the second glass plate 21B. And further.
  • the first spacer 25A defines the thickness of the first intermediate layer 29A
  • the second spacer 25B defines the thickness of the second intermediate layer 29B.
  • the electrochromic element 100 of the light control unit 20C includes a pair of antireflection films 13 and 14 located on the outermost surface on the first glass plate 21A side and the outermost surface on the second glass plate 21B side.
  • the electrochromic element 100 includes the pair of antireflection films 13 and 14 as described above, a decrease in transmittance can be suppressed.
  • an AR (Anti-Reflective) film, an LR (Low-Reflective) film, a moth-eye film, or the like can be used as the antireflection films 13 and 14.
  • the first spacer 25A and the second spacer 25B overlap the glazing channel 22, and the seal section 7 includes the first spacer 25A, It should overlap the second spacer 25B and the glazing channel 22.
  • the pressure of the first spacer 25 ⁇ / b> A, the second spacer 25 ⁇ / b> B, and the glazing channel 22 can be applied to the region of the electrochromic element 100 where the high-strength seal portion 7 exists.
  • FIG. 19 is a cross-sectional view schematically showing the light control unit 20D. Below, it demonstrates centering on the point from which the light control part 20D differs from the light control part 20C shown in FIG.
  • the first spacer 25A and the second spacer 25B overlap the glazing channel 22 when viewed from the normal direction of the first glass plate 21A. Further, when viewed from the normal direction of the first glass plate 21A, the seal portion 7 overlaps with the glazing channel 22 and is located on the inner side of the first spacer 25A and the second spacer 25B (of the first glass plate 21). It is located on the inner side in the in-plane direction.
  • the size of the second substrate 12 is slightly smaller than the size of the first substrate 11, and the end on the indoor side of the first spacer 25A and the end on the outdoor side of the second spacer 25B are the first It is in contact with the substrate 11.
  • the seal portion 7 is disposed on the inner side of the first spacer 25A and the second spacer 25B, the pressure of the first spacer 25A, the second spacer 25B, and the glazing channel 22 is applied to the light control layer 9. It can be avoided.
  • the wiring 24 and the flexible substrate for wiring may be located in the area
  • the electrochromic device according to the embodiment of the present disclosure may be installed on something other than the window glass, and may be installed in an agricultural greenhouse, for example.
  • an electrochromic device and a smart window that include two nanocrystal layers and can operate suitably.

Abstract

This electrochromic element is provided with: first and second transparent electrodes which face each other; a first nanocrystalline layer which is provided on a second transparent electrode-side surface of the first transparent electrode, and which contains a plurality of first metal oxide nanoparticles; a second nanocrystalline layer which is provided on a first transparent electrode-side surface of the second transparent electrode, and which contains a plurality of second metal oxide nanoparticles; and an electrolyte layer which is provided between the first and second nanocrystalline layers. The first metal oxide nanoparticles and the second metal oxide nanoparticles are composed of the same constituent elements. The thickness of the first nanocrystalline layer and the thickness of the second nanocrystalline layer are different from each other.

Description

エレクトロクロミック素子およびスマートウィンドウElectrochromic devices and smart windows
　本開示は、エレクトロクロミック素子およびスマートウィンドウに関する。 This disclosure relates to an electrochromic device and a smart window.
　電圧の印加によりその光学的性質が可逆的に変化するエレクトロクロミック素子が知られている。エレクトロクロミック素子を用いた製品の１つとして、電気的に光透過率を制御することができるスマートウィンドウが挙げられる。 An electrochromic element whose optical properties reversibly change when a voltage is applied is known. As one of products using an electrochromic element, there is a smart window capable of electrically controlling light transmittance.
　スマートウィンドウの一種として、赤外光の透過率を制御可能なタイプ（以下では「赤外タイプ」と呼ぶこともある。）が提案されている。特許文献１は、赤外タイプのスマートウィンドウに用いられるエレクトロクロミック素子を開示している。 As a kind of smart window, a type capable of controlling the transmittance of infrared light (hereinafter sometimes referred to as “infrared type”) has been proposed. Patent Document 1 discloses an electrochromic element used for an infrared type smart window.
　特許文献１に開示されているエレクトロクロミック素子では、電圧の印加により光の透過スペクトルが変化するエレクトロクロミック層として、ナノ結晶層が設けられている。ここで、図２０を参照しながら、特許文献１のエレクトロクロミック素子の構造を簡単に説明する。 In the electrochromic element disclosed in Patent Document 1, a nanocrystal layer is provided as an electrochromic layer in which a light transmission spectrum is changed by application of a voltage. Here, the structure of the electrochromic element of Patent Document 1 will be briefly described with reference to FIG.
　図２０に示すエレクトロクロミック素子９００は、第１基板９１１、第２基板９１２、第１透明電極９０１、第２透明電極９０２、ナノ結晶層９０３、電解液９０５、電源９０６、シール部９０７およびスペーサ９０８を備える。 An electrochromic device 900 shown in FIG. 20 includes a first substrate 911, a second substrate 912, a first transparent electrode 901, a second transparent electrode 902, a nanocrystal layer 903, an electrolytic solution 905, a power source 906, a seal portion 907, and a spacer 908. Is provided.
　第１基板９１１および第２基板９１２は、互いに対向するように設けられている。第１基板９１１および第２基板９１２のそれぞれは、透明である。 The first substrate 911 and the second substrate 912 are provided so as to face each other. Each of the first substrate 911 and the second substrate 912 is transparent.
　第１透明電極９０１は、第１基板９１１の第２基板９１２側の表面上に設けられている。第２透明電極９０２は、第２基板９１２の第１基板９１１側の表面上に設けられている。 The first transparent electrode 901 is provided on the surface of the first substrate 911 on the second substrate 912 side. The second transparent electrode 902 is provided on the surface of the second substrate 912 on the first substrate 911 side.
　ナノ結晶層９０３は、第１透明電極９０１上に設けられている。ナノ結晶層９０３は、粒径が数ｎｍ～数十ｎｍの金属酸化物ナノ粒子を含んでいる。 The nanocrystal layer 903 is provided on the first transparent electrode 901. The nanocrystal layer 903 includes metal oxide nanoparticles having a particle size of several nanometers to several tens of nanometers.
　電解液９０５は、シール部９０７によって包囲された領域に封入されており、ナノ結晶層９０３と第２透明電極９０２との間に位置している。電源９０６は、第１透明電極９０１および第２透明電極９０２に電気的に接続されており、第１透明電極９０１および第２透明電極９０２間に所定の電圧を印加し得る。 The electrolytic solution 905 is enclosed in a region surrounded by the seal portion 907 and is located between the nanocrystal layer 903 and the second transparent electrode 902. The power source 906 is electrically connected to the first transparent electrode 901 and the second transparent electrode 902, and can apply a predetermined voltage between the first transparent electrode 901 and the second transparent electrode 902.
　スペーサ９０８は、ナノ結晶層９０３と第２透明電極９０２との間に設けられており、電解液９０５が封入されている領域の高さを規定する。 The spacer 908 is provided between the nanocrystal layer 903 and the second transparent electrode 902 and defines the height of the region in which the electrolytic solution 905 is enclosed.
　エレクトロクロミック素子９００のナノ結晶層９０３は、局在表面プラズモン共鳴（ＬＳＰＲ）を利用してエレクトロクロミズムを発現する。 The nanocrystal layer 903 of the electrochromic device 900 expresses electrochromism using localized surface plasmon resonance (LSPR).
　非特許文献１は、エレクトロクロミック材料として用いられる種々のナノ結晶を開示している。 Non-Patent Document 1 discloses various nanocrystals used as electrochromic materials.
国際公開第２０１７／１４１５２８号International Publication No. 2017/141528
　上述したように、特許文献１のエレクトロクロミック素子９００では、一対の透明電極の一方側（具体的には第１透明電極９０１上）にのみナノ結晶層９０３が設けられている。本願発明者は、一対の透明電極の他方側にさらなるナノ結晶層を設けることを検討した。両側にナノ結晶層を設けることにより、片側にのみナノ結晶層を設けた場合よりも金属酸化物ナノ粒子の表面積が増大する。そのため、電圧印加時により多くの電荷をナノ結晶層に蓄えることができ、回路を遮断した状態でも所望の透過スペクトルを長時間維持することができる（つまり好適なメモリ性を持たせられる）と考えられる。 As described above, in the electrochromic element 900 of Patent Document 1, the nanocrystal layer 903 is provided only on one side of the pair of transparent electrodes (specifically, on the first transparent electrode 901). The inventor of the present application examined providing a further nanocrystal layer on the other side of the pair of transparent electrodes. By providing the nanocrystal layer on both sides, the surface area of the metal oxide nanoparticles is increased as compared with the case where the nanocrystal layer is provided only on one side. Therefore, it is considered that more charges can be stored in the nanocrystal layer when voltage is applied, and the desired transmission spectrum can be maintained for a long time even when the circuit is shut off (that is, suitable memory properties can be provided). It is done.
　しかしながら、本願発明者がさらに検討を進めたところ、そのような構成を採用すると、後に詳述するような様々な問題が発生することがわかった。 However, when the inventors of the present application further studied, it was found that when such a configuration was adopted, various problems described in detail later occurred.
　本開示は、上記問題に鑑みてなされたものであり、その目的は、２つのナノ結晶層を備え、且つ、好適に動作し得るエレクトロクロミック素子およびスマートウィンドウを提供することにある。 The present disclosure has been made in view of the above problems, and an object thereof is to provide an electrochromic device and a smart window that include two nanocrystal layers and can operate suitably.
　本発明の実施形態によるエレクトロクロミック素子は、互いに対向する第１透明電極および第２透明電極と、前記第１透明電極の前記第２透明電極側の表面上に設けられ、複数の第１金属酸化物ナノ粒子を含む第１ナノ結晶層と、前記第２透明電極の前記第１透明電極側の表面上に設けられ、複数の第２金属酸化物ナノ粒子を含む第２ナノ結晶層と、前記第１ナノ結晶層および前記第２ナノ結晶層の間に設けられた電解質層と、を備え、前記複数の第１金属酸化物ナノ粒子と前記複数の第２金属酸化物ナノ粒子とは、構成元素が同じであり、前記第１ナノ結晶層の厚さと前記第２ナノ結晶層の厚さとが異なっている。 An electrochromic device according to an embodiment of the present invention includes a first transparent electrode and a second transparent electrode facing each other, and a surface of the first transparent electrode on the second transparent electrode side, and a plurality of first metal oxides A first nanocrystal layer including a material nanoparticle, a second nanocrystal layer including a plurality of second metal oxide nanoparticles provided on a surface of the second transparent electrode on the first transparent electrode side, An electrolyte layer provided between the first nanocrystal layer and the second nanocrystal layer, wherein the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles are configured The elements are the same, and the thickness of the first nanocrystal layer is different from the thickness of the second nanocrystal layer.
　ある実施形態において、前記第２ナノ結晶層の厚さは、前記第１ナノ結晶層の厚さの１％以上３０％以下である。 In one embodiment, the thickness of the second nanocrystal layer is not less than 1% and not more than 30% of the thickness of the first nanocrystal layer.
　ある実施形態において、前記複数の第１金属酸化物ナノ粒子の平均粒径と前記複数の第２金属酸化物ナノ粒子の平均粒径とが異なっている。 In one embodiment, an average particle size of the plurality of first metal oxide nanoparticles is different from an average particle size of the plurality of second metal oxide nanoparticles.
　本発明の実施形態によるエレクトロクロミック素子は、互いに対向する第１透明電極および第２透明電極と、前記第１透明電極の前記第２透明電極側の表面上に設けられ、複数の第１金属酸化物ナノ粒子を含む第１ナノ結晶層と、前記第２透明電極の前記第１透明電極側の表面上に設けられ、複数の第２金属酸化物ナノ粒子を含む第２ナノ結晶層と、前記第１ナノ結晶層および前記第２ナノ結晶層の間に設けられた電解質層と、を備え、前記複数の第１金属酸化物ナノ粒子と前記複数の第２金属酸化物ナノ粒子とは、構成元素が同じであり、前記複数の第１金属酸化物ナノ粒子の平均粒径と前記複数の第２金属酸化物ナノ粒子の平均粒径とが異なっている。 An electrochromic device according to an embodiment of the present invention includes a first transparent electrode and a second transparent electrode facing each other, and a surface of the first transparent electrode on the second transparent electrode side, and a plurality of first metal oxides A first nanocrystal layer including a material nanoparticle, a second nanocrystal layer including a plurality of second metal oxide nanoparticles provided on a surface of the second transparent electrode on the first transparent electrode side, An electrolyte layer provided between the first nanocrystal layer and the second nanocrystal layer, wherein the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles are configured The elements are the same, and the average particle size of the plurality of first metal oxide nanoparticles is different from the average particle size of the plurality of second metal oxide nanoparticles.
　ある実施形態において、前記複数の第２金属酸化物ナノ粒子の平均粒径は、前記複数の第１金属酸化物ナノ粒子の平均粒径よりも５ｎｍ以上１００ｎｍ以下大きい。 In one embodiment, an average particle diameter of the plurality of second metal oxide nanoparticles is 5 nm to 100 nm larger than an average particle diameter of the plurality of first metal oxide nanoparticles.
　ある実施形態において、前記複数の第１金属酸化物ナノ粒子の組成比と前記複数の第２金属酸化物ナノ粒子の組成比とが異なっている。 In one embodiment, the composition ratio of the plurality of first metal oxide nanoparticles is different from the composition ratio of the plurality of second metal oxide nanoparticles.
　本発明の実施形態によるエレクトロクロミック素子は、互いに対向する第１透明電極および第２透明電極と、前記第１透明電極の前記第２透明電極側の表面上に設けられ、複数の第１金属酸化物ナノ粒子を含む第１ナノ結晶層と、前記第２透明電極の前記第１透明電極側の表面上に設けられ、複数の第２金属酸化物ナノ粒子を含む第２ナノ結晶層と、前記第１ナノ結晶層および前記第２ナノ結晶層の間に設けられた電解質層と、を備え、前記複数の第１金属酸化物ナノ粒子と前記複数の第２金属酸化物ナノ粒子とは、構成元素が同じであり、前記複数の第１金属酸化物ナノ粒子の組成比と前記複数の第２金属酸化物ナノ粒子の組成比とが異なっている。 An electrochromic device according to an embodiment of the present invention includes a first transparent electrode and a second transparent electrode facing each other, and a surface of the first transparent electrode on the second transparent electrode side, and a plurality of first metal oxides A first nanocrystal layer including a material nanoparticle, a second nanocrystal layer including a plurality of second metal oxide nanoparticles provided on a surface of the second transparent electrode on the first transparent electrode side, An electrolyte layer provided between the first nanocrystal layer and the second nanocrystal layer, wherein the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles are configured The elements are the same, and the composition ratio of the plurality of first metal oxide nanoparticles is different from the composition ratio of the plurality of second metal oxide nanoparticles.
　ある実施形態において、前記複数の第１金属酸化物ナノ粒子および前記複数の第２金属酸化物ナノ粒子は、それぞれ複数のアンチモンドープ酸化錫ナノ粒子である。 In one embodiment, the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles are each a plurality of antimony-doped tin oxide nanoparticles.
　ある実施形態において、前記複数の第１金属酸化物ナノ粒子および前記複数の第２金属酸化物ナノ粒子は、それぞれ複数の錫ドープ酸化インジウムナノ粒子である。 In one embodiment, the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles are each a plurality of tin-doped indium oxide nanoparticles.
　ある実施形態において、前記エレクトロクロミック素子は、前記第１透明電極を支持する第１基板と、前記第２透明電極を支持する第２基板と、をさらに備え、前記第１基板および前記第２基板のそれぞれは、可撓性を有する樹脂基板である。 In one embodiment, the electrochromic device further includes a first substrate that supports the first transparent electrode, and a second substrate that supports the second transparent electrode, and the first substrate and the second substrate. Each of these is a flexible resin substrate.
　ある実施形態において、第１透明電極および第２透明電極のそれぞれは、電気的に独立した複数のサブ電極に分割されている。 In one embodiment, each of the first transparent electrode and the second transparent electrode is divided into a plurality of electrically independent sub-electrodes.
　本発明の実施形態によるスマートウィンドウは、上述したいずれかの構成を有するエレクトロクロミック素子を備える。 A smart window according to an embodiment of the present invention includes an electrochromic device having any one of the above-described configurations.
　ある実施形態において、前記スマートウィンドウは、透光板をさらに備え、前記エレクトロクロミック素子は、前記透光板に貼り合わされている。 In one embodiment, the smart window further includes a translucent plate, and the electrochromic element is bonded to the translucent plate.
　ある実施形態において、前記第１ナノ結晶層および前記第２ナノ結晶層のそれぞれの透過スペクトルは、印加電圧の変化に応じて変化し、前記第１ナノ結晶層および前記第２ナノ結晶層のうちの、印加電圧の変化に応じた透過スペクトルの変化が相対的に大きい方のナノ結晶層が、相対的に小さい方のナノ結晶層と前記透光板との間に位置している。 In one embodiment, a transmission spectrum of each of the first nanocrystal layer and the second nanocrystal layer changes according to a change in applied voltage, and the first nanocrystal layer and the second nanocrystal layer The nanocrystal layer having a relatively large change in the transmission spectrum in accordance with the change in the applied voltage is positioned between the relatively small nanocrystal layer and the light transmitting plate.
　ある実施形態において、前記スマートウィンドウは、前記透光板の周縁部および前記エレクトロクロミック素子の周縁部を囲むように配置されたグレージングチャンネルをさらに備え、前記エレクトロクロミック素子は、前記電解質層を包囲するように設けられたシール部をさらに有し、前記透光板の法線方向から見たとき、前記シール部は前記グレージングチャンネルに重なっている。 In one embodiment, the smart window further includes a glazing channel disposed to surround a peripheral edge of the translucent plate and a peripheral edge of the electrochromic element, and the electrochromic element surrounds the electrolyte layer. The sealing portion is further provided, and the sealing portion overlaps the glazing channel when viewed from the normal direction of the light transmitting plate.
　ある実施形態において、前記スマートウィンドウは、第１透光板と、前記第１透光板に所定の間隙を介して対向するように配置された第２透光板と、をさらに備え、前記エレクトロクロミック素子は、前記第１透光板の前記第２透光板側に貼り合わされており、前記エレクトロクロミック素子と前記第２透光板との間に、所定の厚さの中間層が位置する。 In one embodiment, the smart window further includes a first light-transmitting plate and a second light-transmitting plate disposed so as to face the first light-transmitting plate with a predetermined gap therebetween. The chromic element is bonded to the second light transmitting plate side of the first light transmitting plate, and an intermediate layer having a predetermined thickness is located between the electrochromic element and the second light transmitting plate. .
　ある実施形態において、前記スマートウィンドウは、前記エレクトロクロミック素子と前記第２透光板との間に設けられ、前記中間層の厚さを規定するスペーサと、前記第１透光板の周縁部、前記エレクトロクロミック素子の周縁部および前記第２透光板の周縁部を囲むように配置されたグレージングチャンネルと、をさらに備え、前記エレクトロクロミック素子は、前記電解質層を包囲するように設けられたシール部をさらに有し、前記第１透光板の法線方向から見たとき、前記スペーサは前記グレージングチャンネルに重なっており、前記シール部は前記スペーサおよび前記グレージングチャンネルに重なっている。 In one embodiment, the smart window is provided between the electrochromic element and the second light transmitting plate, a spacer that defines a thickness of the intermediate layer, a peripheral portion of the first light transmitting plate, A glazing channel disposed so as to surround a peripheral edge of the electrochromic element and a peripheral edge of the second light-transmitting plate, and the electrochromic element is provided to surround the electrolyte layer The spacer further overlaps the glazing channel, and the seal portion overlaps the spacer and the glazing channel when viewed from the normal direction of the first light transmission plate.
　ある実施形態において、前記スマートウィンドウは、前記エレクトロクロミック素子と前記第２透光板との間に設けられ、前記中間層の厚さを規定するスペーサと、前記第１透光板の周縁部、前記エレクトロクロミック素子の周縁部および前記第２透光板の周縁部を囲むように配置されたグレージングチャンネルと、をさらに備え、前記エレクトロクロミック素子は、前記電解質層を包囲するように設けられたシール部をさらに有し、前記第１透光板の法線方向から見たとき、前記スペーサは前記グレージングチャンネルに重なっており、前記シール部は前記グレージングチャンネルに重なっており、且つ、前記スペーサよりも内側に位置している。 In one embodiment, the smart window is provided between the electrochromic element and the second light transmitting plate, a spacer that defines a thickness of the intermediate layer, a peripheral portion of the first light transmitting plate, A glazing channel disposed so as to surround a peripheral edge of the electrochromic element and a peripheral edge of the second light-transmitting plate, and the electrochromic element is provided to surround the electrolyte layer The spacer is overlapped with the glazing channel, the seal portion is overlapped with the glazing channel, and when viewed from the normal direction of the first light transmission plate, and more than the spacer Located inside.
　ある実施形態において、前記スマートウィンドウは、第１透光板と、前記第１透光板に所定の間隙を介して対向するように配置された第２透光板と、をさらに備え、前記エレクトロクロミック素子は、前記第１透光板と前記第２透光板との間に配置されており、前記第１透光板と前記エレクトロクロミック素子との間に所定の厚さの第１中間層が位置し、前記エレクトロクロミック素子と前記第２透光板との間に所定の厚さの第２中間層が位置する。 In one embodiment, the smart window further includes a first light-transmitting plate and a second light-transmitting plate disposed so as to face the first light-transmitting plate with a predetermined gap therebetween. The chromic element is disposed between the first light transmissive plate and the second light transmissive plate, and a first intermediate layer having a predetermined thickness between the first light transmissive plate and the electrochromic element. And a second intermediate layer having a predetermined thickness is located between the electrochromic element and the second light transmitting plate.
　ある実施形態において、前記エレクトロクロミック素子は、前記第１透光板側の最表面および前記第２透光板側の最表面に位置する一対の反射防止膜を含む。 In one embodiment, the electrochromic element includes a pair of antireflection films positioned on the outermost surface on the first light transmitting plate side and the outermost surface on the second light transmitting plate side.
　ある実施形態において、前記スマートウィンドウは、前記第１透光板と前記エレクトロクロミック素子との間に設けられ、前記第１中間層の厚さを規定する第１スペーサと、前記エレクトロクロミック素子と前記第２透光板との間に設けられ、前記第２中間層の厚さを規定する第２スペーサと、前記第１透光板の周縁部、前記エレクトロクロミック素子の周縁部および前記第２透光板の周縁部を囲むように配置されたグレージングチャンネルと、をさらに備え、前記エレクトロクロミック素子は、前記電解質層を包囲するように設けられたシール部をさらに有し、前記第１透光板の法線方向から見たとき、前記第１スペーサおよび前記第２スペーサは前記グレージングチャンネルに重なっており、前記シール部は前記第１スペーサ、第２スペーサおよび前記グレージングチャンネルに重なっている。 In one embodiment, the smart window is provided between the first light-transmitting plate and the electrochromic device, and defines a first spacer that defines a thickness of the first intermediate layer, the electrochromic device, and the electrochromic device. A second spacer provided between the second light-transmitting plate and defining a thickness of the second intermediate layer; a peripheral portion of the first light-transmitting plate; a peripheral portion of the electrochromic element; and the second transparent member. A glazing channel disposed so as to surround a peripheral portion of the optical plate, wherein the electrochromic element further includes a seal portion provided so as to surround the electrolyte layer, and the first translucent plate When viewed from the normal direction, the first spacer and the second spacer overlap the glazing channel, and the seal portion includes the first spacer and the second spacer. It overlaps the over support and the glazing channel.
　ある実施形態において、前記スマートウィンドウは、前記第１透光板と前記エレクトロクロミック素子との間に設けられ、前記第１中間層の厚さを規定する第１スペーサと、前記エレクトロクロミック素子と前記第２透光板との間に設けられ、前記第２中間層の厚さを規定する第２スペーサと、前記第１透光板の周縁部、前記エレクトロクロミック素子の周縁部および前記第２透光板の周縁部を囲むように配置されたグレージングチャンネルと、をさらに備え、前記エレクトロクロミック素子は、前記電解質層を包囲するように設けられたシール部をさらに有し、前記第１透光板の法線方向から見たとき、前記第１スペーサおよび前記第２スペーサは前記グレージングチャンネルに重なっており、前記シール部は前記グレージングチャンネルに重なっており、且つ、前記第１スペーサおよび前記第２スペーサよりも内側に位置している。 In one embodiment, the smart window is provided between the first light-transmitting plate and the electrochromic device, and defines a first spacer that defines a thickness of the first intermediate layer, the electrochromic device, and the electrochromic device. A second spacer provided between the second light-transmitting plate and defining a thickness of the second intermediate layer; a peripheral portion of the first light-transmitting plate; a peripheral portion of the electrochromic element; and the second transparent member. A glazing channel disposed so as to surround a peripheral portion of the optical plate, wherein the electrochromic element further includes a seal portion provided so as to surround the electrolyte layer, and the first translucent plate When viewed from the normal direction, the first spacer and the second spacer overlap the glazing channel, and the seal portion includes the glazing channel. It overlaps in, and, is located inside the first spacer and the second spacer.
　本開示の実施形態によると、２つのナノ結晶層を備え、且つ、好適に動作し得るエレクトロクロミック素子およびスマートウィンドウを提供することができる。 According to the embodiment of the present disclosure, it is possible to provide an electrochromic device and a smart window that include two nanocrystal layers and can operate suitably.
本開示の実施形態におけるエレクトロクロミック素子１００を模式的に示す断面図である。It is sectional drawing which shows typically the electrochromic element 100 in embodiment of this indication. ナノ結晶層の厚さや金属酸化物ナノ粒子の平均粒径による透過スペクトルの違いを検証するために作製したエレクトロクロミック素子８００を示す断面図である。It is sectional drawing which shows the electrochromic element 800 produced in order to verify the difference in the transmission spectrum by the thickness of a nanocrystal layer, and the average particle diameter of a metal oxide nanoparticle. 調光セルＡ、ＢおよびＣの透過スペクトルを示すグラフである。It is a graph which shows the transmission spectrum of the light control cells A, B, and C. 実施例１および比較例１の透過スペクトルを示すグラフである。3 is a graph showing transmission spectra of Example 1 and Comparative Example 1. 比較例２および３の透過スペクトルを示すグラフである。It is a graph which shows the transmission spectrum of the comparative examples 2 and 3. （ａ）および（ｂ）は、第１透明電極１が複数のサブ電極１ａに分割された構成の例を示す図である。(A) And (b) is a figure which shows the example of the structure by which the 1st transparent electrode 1 was divided | segmented into the some sub electrode 1a. スペーサ８を備えるエレクトロクロミック素子１００を模式的に示す断面図である。2 is a cross-sectional view schematically showing an electrochromic device 100 including a spacer 8. FIG. シール部７の他の構成の例を示す図である。It is a figure which shows the example of the other structure of the seal part. 本開示の実施形態におけるエレクトロクロミック素子２００を模式的に示す断面図である。It is sectional drawing which shows typically the electrochromic element 200 in embodiment of this indication. 調光セルＤ、ＥおよびＦの透過スペクトルを示すグラフである。It is a graph which shows the transmission spectrum of the light control cell D, E, and F. 本開示の実施形態におけるエレクトロクロミック素子３００を模式的に示す断面図である。It is sectional drawing which shows typically the electrochromic element 300 in embodiment of this indication. 本開示の実施形態におけるエレクトロクロミック素子４００を模式的に示す断面図である。It is sectional drawing which shows typically the electrochromic element 400 in embodiment of this indication. 本開示の実施形態におけるスマートウィンドウ５００を模式的に示すブロック図である。FIG. 3 is a block diagram schematically illustrating a smart window 500 according to an embodiment of the present disclosure. （ａ）および（ｂ）は、スマートウィンドウ５００の調光部２０を模式的に示す断面図および平面図である。(A) And (b) is sectional drawing and the top view which show the light control part 20 of the smart window 500 typically. （ａ）および（ｂ）は、スマートウィンドウ５００の調光部２０を模式的に示す断面図および平面図である。(A) And (b) is sectional drawing and the top view which show the light control part 20 of the smart window 500 typically. スマートウィンドウ５００に用いられる他の調光部２０Ａを模式的に示す断面図である。It is sectional drawing which shows typically the other light control part 20A used for the smart window 500. FIG. スマートウィンドウ５００に用いられるさらに他の調光部２０Ｂを模式的に示す断面図である。It is sectional drawing which shows typically the other light control part 20B used for the smart window 500. FIG. スマートウィンドウ５００に用いられるさらに他の調光部２０Ｃを模式的に示す断面図である。It is sectional drawing which shows typically other light control part 20C used for the smart window 500. FIG. スマートウィンドウ５００に用いられるさらに他の調光部２０Ｄを模式的に示す断面図である。It is sectional drawing which shows typically other light control part 20D used for the smart window. 特許文献１のエレクトロクロミック素子９００を模式的に示す断面図である。10 is a cross-sectional view schematically showing an electrochromic element 900 of Patent Document 1. FIG.
　実施形態の説明に先立ち、本願発明者が見出した知見を説明する。 Prior to the description of the embodiment, the knowledge found by the inventors will be described.
　まず、本願発明者は、一対の透明電極の一方上にのみナノ結晶層が設けられている構成において、透明電極や電解液の劣化が発生し得ることを見出した。また、一対の透明電極の一方側にだけでなく、他方側にもナノ結晶層を設ける構成においても、同様の問題が発生し得ることがわかった。 First, the inventor of the present application has found that in a configuration in which a nanocrystal layer is provided only on one of a pair of transparent electrodes, the deterioration of the transparent electrode and the electrolytic solution can occur. In addition, it has been found that the same problem can occur in the configuration in which the nanocrystal layer is provided not only on one side of the pair of transparent electrodes but also on the other side.
　本願発明者は、さらに詳細な検討を行い、２つのナノ結晶層の材料として、構成元素が同じ金属酸化物ナノ粒子を用いることにより、電気化学的なバランスがとれ、透明電極や電解液の劣化を抑制し得ることを見出した。また、構成元素が同じ金属酸化物ナノ粒子を用いることは、製造コストや製造工程の簡略化等の点でも有利である。 The inventor of the present application has conducted a more detailed study, and by using metal oxide nanoparticles having the same constituent elements as the materials of the two nanocrystal layers, an electrochemical balance can be obtained, and the transparent electrode and the electrolyte can be deteriorated. It has been found that can be suppressed. In addition, the use of metal oxide nanoparticles having the same constituent elements is advantageous in terms of production cost, simplification of the production process, and the like.
　しかしながら、ナノ結晶層を両側に配置すると、一方側のみに配置する場合に比べ、透過スペクトルの動作シフト範囲が狭まってしまうという新たな問題が発生する。同じエレクトミック材料を両側に配置した場合、電圧印可時に両側のエレクトロクロミック材料の透過スペクトルがお互い逆の方向にシフトするためである。 However, when the nanocrystal layer is arranged on both sides, a new problem arises that the operation shift range of the transmission spectrum is narrowed compared to the case where the nanocrystal layer is arranged only on one side. This is because when the same electrochromic material is arranged on both sides, the transmission spectra of the electrochromic materials on both sides shift in opposite directions when voltage is applied.
　以下、図面を参照しながら本開示の実施形態を説明する。なお、本開示の実施形態は、以下に例示する構成に限定されるものではない。 Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. Note that the embodiments of the present disclosure are not limited to the configurations exemplified below.
　（実施形態１）
　図１を参照しながら、本実施形態におけるエレクトロクロミック素子１００を説明する。図１は、エレクトロクロミック素子１００を模式的に示す断面図である。 (Embodiment 1)
With reference to FIG. 1, an electrochromic device 100 according to this embodiment will be described. FIG. 1 is a cross-sectional view schematically showing an electrochromic device 100.
　エレクトロクロミック素子１００は、図１に示すように、第１透明電極１および第２透明電極２と、第１ナノ結晶層３および第２ナノ結晶層４と、電解質層５とを備える。 As shown in FIG. 1, the electrochromic element 100 includes a first transparent electrode 1 and a second transparent electrode 2, a first nanocrystal layer 3 and a second nanocrystal layer 4, and an electrolyte layer 5.
　第１透明電極１および第２透明電極２は、互いに対向するように配置されている。第１透明電極１および第２透明電極２は、それぞれ透明であり、実質的に無色である。第１透明電極１および第２透明電極２は、電源６に電気的に接続されている。第１透明電極１は、第１基板１１に支持されている。第２透明電極２は、第２基板１２に支持されている。第１基板１１および第２基板１２は、それぞれ透明であり、実質的に無色である。 The first transparent electrode 1 and the second transparent electrode 2 are arranged so as to face each other. The first transparent electrode 1 and the second transparent electrode 2 are each transparent and substantially colorless. The first transparent electrode 1 and the second transparent electrode 2 are electrically connected to a power source 6. The first transparent electrode 1 is supported on the first substrate 11. The second transparent electrode 2 is supported on the second substrate 12. The first substrate 11 and the second substrate 12 are each transparent and substantially colorless.
　第１ナノ結晶層３は、第１透明電極１の第２透明電極２側の表面上に設けられている。第１ナノ結晶層３は、複数の金属酸化物ナノ粒子（以下では「第１金属酸化物ナノ粒子」と呼ぶ）を含む。 The first nanocrystal layer 3 is provided on the surface of the first transparent electrode 1 on the second transparent electrode 2 side. The first nanocrystal layer 3 includes a plurality of metal oxide nanoparticles (hereinafter referred to as “first metal oxide nanoparticles”).
　第２ナノ結晶層４は、第２透明電極２の第１透明電極１側の表面上に設けられている。第２ナノ結晶層４は、複数の金属酸化物ナノ粒子（以下では「第２金属酸化物ナノ粒子」と呼ぶ）を含む。 The second nanocrystal layer 4 is provided on the surface of the second transparent electrode 2 on the first transparent electrode 1 side. The second nanocrystal layer 4 includes a plurality of metal oxide nanoparticles (hereinafter referred to as “second metal oxide nanoparticles”).
　第１金属酸化物ナノ粒子および第２金属酸化物ナノ粒子は、それぞれ数ｎｍ～数十ｎｍの粒径を有する粒子状の結晶体（ナノ結晶）である。 The first metal oxide nanoparticles and the second metal oxide nanoparticles are particulate crystals (nanocrystals) each having a particle size of several nm to several tens of nm.
　電解質層５は、第１ナノ結晶層３と第２ナノ結晶層４との間に設けられている。電界質層５は、シール部７によって包囲されている。 The electrolyte layer 5 is provided between the first nanocrystal layer 3 and the second nanocrystal layer 4. The electrolyte layer 5 is surrounded by the seal portion 7.
　第１ナノ結晶層３に含まれる第１金属酸化物ナノ粒子および第２ナノ結晶層４に含まれる第２金属酸化物ナノ粒子は、エレクトロクロミック材料である。そのため、第１ナノ結晶層３および第２ナノ結晶層４のそれぞれの透過スペクトルは、第１透明電極１と第２透明電極２との間に印加された電圧に応じて変化する。この透過スペクトルの変化は、近赤外領域における透過率変化を伴っている。従って、本実施形態のエレクトロクロミック素子１００は、近赤外光の透過率を制御することができる。本願明細書において、近赤外領域は、波長が約８００ｎｍ以上約２５００ｎｍ以下の範囲を指す。太陽から放射される赤外光の大部分は近赤外光であるので、近赤外光の透過率を制御することにより、太陽光による日射熱の取得率を制御することができる。例えば、夏期には近赤外光の室内への入射を防ぐことができ、冬期には近赤外光を室内に取り込むことができる。 The first metal oxide nanoparticles contained in the first nanocrystal layer 3 and the second metal oxide nanoparticles contained in the second nanocrystal layer 4 are electrochromic materials. Therefore, the transmission spectra of the first nanocrystal layer 3 and the second nanocrystal layer 4 change according to the voltage applied between the first transparent electrode 1 and the second transparent electrode 2. This change in the transmission spectrum is accompanied by a change in transmittance in the near infrared region. Therefore, the electrochromic element 100 of this embodiment can control the transmittance of near infrared light. In the specification of the present application, the near-infrared region refers to a wavelength range of about 800 nm or more and about 2500 nm or less. Since most of the infrared light radiated from the sun is near-infrared light, the acquisition rate of solar heat from sunlight can be controlled by controlling the transmittance of the near-infrared light. For example, near-infrared light can be prevented from entering the room in summer, and near-infrared light can be taken into the room in winter.
　第１金属酸化物ナノ粒子および第２金属酸化物ナノ粒子としては、例えば、アンチモンドープ酸化錫（Antimony-doped Tin Oxide：ＡＴＯ）ナノ粒子や、錫ドープ酸化インジウム（Tin doped Indium Oxide）ナノ粒子を好適に用いることができる。第１ナノ結晶層３および第２ナノ結晶層４がエレクトロクロミズムを示す原理については後述する。 As the first metal oxide nanoparticles and the second metal oxide nanoparticles, for example, antimony-doped tin oxide (ATO) nanoparticles and tin-doped indium oxide nanoparticles are used. It can be used suitably. The principle that the first nanocrystal layer 3 and the second nanocrystal layer 4 exhibit electrochromism will be described later.
　なお、第１ナノ結晶層３および第２ナノ結晶層４の透過スペクトルの変化は、近赤外領域における透過率変化だけでなく、可視領域（約４００ｎｍ以上約８００ｎｍ以下の範囲）における透過率変化を伴っていてもよい。 The change in the transmission spectrum of the first nanocrystal layer 3 and the second nanocrystal layer 4 is not only the change in the transmittance in the near infrared region, but also the change in the transmittance in the visible region (a range from about 400 nm to about 800 nm). May be accompanied.
　本実施形態では、第１金属酸化物ナノ粒子と第２金属酸化物ナノ粒子とは、構成元素が同じである（つまり同じ元素を含んでいる）。また、本実施形態では、第１ナノ結晶層３の厚さｔ１と、第２ナノ結晶層４の厚さｔ２とが異なっている。具体的には、第２ナノ結晶層４の厚さｔ２が、第１ナノ結晶層３の厚さｔ１よりも小さい。好ましくは、第２ナノ結晶層４の厚さｔ２は、第１ナノ結晶層３の厚さｔ１の１％以上３０％以下である。 In the present embodiment, the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements (that is, contain the same elements). In the present embodiment, the thickness t1 of the first nanocrystal layer 3 is different from the thickness t2 of the second nanocrystal layer 4. Specifically, the thickness t2 of the second nanocrystal layer 4 is smaller than the thickness t1 of the first nanocrystal layer 3. Preferably, the thickness t2 of the second nanocrystal layer 4 is not less than 1% and not more than 30% of the thickness t1 of the first nanocrystal layer 3.
　上述したように、本実施形態のエレクトロクロミック素子１００は、一対の透明電極（第１透明電極１および第２透明電極２）の一方側および他方側に設けられた一対のナノ結晶層（第１ナノ結晶層３および第２ナノ結晶層４）を備える。これにより、一対の透明電極の一方側にのみナノ結晶層を設けた場合よりも金属酸化物ナノ粒子の総表面積が増大する。そのため、電圧印加時により多くの電荷をナノ結晶層に蓄えることができ、回路を遮断した状態（電源６からの電力供給が停止した状態）でも所望の透過スペクトルを長時間維持することができる。つまり、好適なメモリ性を実現することができる。 As described above, the electrochromic device 100 according to the present embodiment includes a pair of nanocrystal layers (first electrodes) provided on one side and the other side of a pair of transparent electrodes (first transparent electrode 1 and second transparent electrode 2). A nanocrystal layer 3 and a second nanocrystal layer 4). Thereby, the total surface area of the metal oxide nanoparticles is increased as compared with the case where the nanocrystal layer is provided only on one side of the pair of transparent electrodes. Therefore, more charge can be stored in the nanocrystal layer when a voltage is applied, and a desired transmission spectrum can be maintained for a long time even in a state where the circuit is shut off (a state where power supply from the power source 6 is stopped). That is, a suitable memory property can be realized.
　また、本実施形態では、第１金属酸化物ナノ粒子と第２金属酸化物ナノ粒子とは、構成元素が同じである。これにより、電解質層５の両側で電気化学的なバランスが取れるので、第１透明電極１、第２透明電極２および電解質層５の劣化を抑制することができる。さらに、第１金属酸化物ナノ粒子と第２金属酸化物ナノ粒子とで構成元素が同じであることは、製造コストや製造工程の簡略化等の点でも有利である。 In the present embodiment, the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements. Thereby, since electrochemical balance is taken on both sides of the electrolyte layer 5, the deterioration of the first transparent electrode 1, the second transparent electrode 2, and the electrolyte layer 5 can be suppressed. Further, the fact that the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements is advantageous in terms of manufacturing cost, simplification of the manufacturing process, and the like.
　また、本実施形態では、第１ナノ結晶層３の厚さｔ１と、第２ナノ結晶層４の厚さｔ２とが異なっている。これにより、後に検証結果を交えて詳述するように、透過スペクトルの動作シフト範囲を十分に広くすることができる。 Further, in the present embodiment, the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are different. As a result, the operation shift range of the transmission spectrum can be sufficiently widened, as will be described in detail later with the verification results.
　［ナノ結晶層の動作原理］
　ここで、ナノ結晶層（第１ナノ結晶層３および第２ナノ結晶層４）がエレクトロクロミズムを示す原理を説明する。 [Principle of operation of nanocrystal layer]
Here, the principle that the nanocrystal layers (the first nanocrystal layer 3 and the second nanocrystal layer 4) exhibit electrochromism will be described.
　非特許文献１に記載されているように、ＩＴＯ（Tin doped Indium Oxide）ナノ結晶層などの透明導電性酸化物（Transparent Conducting Oxide：ＴＣＯ）ナノ構造体に電子を注入することによって、近赤外領域の透過スペクトルを変化させ得ることが知られている。その原理は、端的に言えば、ＴＣＯナノ構造体の局在表面プラズモン共鳴（ＬＳＰＲ）による吸収波長を、電圧印加によってシフトさせることである。以下、より詳細に説明する。 As described in Non-Patent Document 1, by injecting electrons into a transparent conductive oxide (TCO) nanostructure such as an ITO (Tin-doped Indium-Oxide) nanocrystal layer, near-infrared It is known that the transmission spectrum of a region can be changed. In short, the principle is to shift the absorption wavelength by localized surface plasmon resonance (LSPR) of the TCO nanostructure by applying a voltage. This will be described in more detail below.
　ＬＳＰＲの共鳴周波数は、プラズマ周波数ωpに比例する。プラズマ周波数ωpは、下記式で表わされる。
　ωp ２＝Ｎ・ｅ２／（ｍ・ε０） The resonance frequency of LSPR is proportional to the plasma frequency ω p . The plasma frequency ω p is expressed by the following equation.
ω p 2 = N · e 2 / (m · ε 0 )
　ここで、Ｎは電子密度、ｅは電子の電荷、ｍは電子の有効質量、ε０は真空の誘電率である。従って、ＴＣＯナノ構造体に負電圧を印加して電子密度を高くすると、プラズマ周波数ωpが大きくなるので、ＬＳＰＲの共鳴周波数も大きくなる。そのため、ＬＳＰＲの共鳴波長は短くなる（つまり短波長側にシフトする）。ＴＣＯナノ構造体のキャリア密度を調整することにより、ＬＳＰＲの共鳴波長を近赤外領域に設定できるので、近赤外領域における透過スペクトルを変化させることが可能となる。 Here, N is the electron density, e is the charge of the electron, m is the effective mass of the electron, and ε 0 is the dielectric constant of the vacuum. Therefore, when a negative voltage is applied to the TCO nanostructure to increase the electron density, the plasma frequency ω p increases, and the resonance frequency of the LSPR also increases. Therefore, the resonance wavelength of LSPR becomes short (that is, shifts to the short wavelength side). By adjusting the carrier density of the TCO nanostructure, the resonance wavelength of the LSPR can be set in the near infrared region, so that the transmission spectrum in the near infrared region can be changed.
　なお、このように透過スペクトルを変化させる機能は、ＩＴＯナノ粒子を含むＩＴＯナノ結晶層だけに特有のものではない。ナノ粒子が、ＬＳＰＲが生じるようなサイズ（例えば１００ｎｍ以下）であり、且つ、ナノ結晶層が透明電極からの電子を注入され得るような構成であれば、原理的には上述した機能を奏し得る。ナノ粒子としては、ＡＴＯ、ＰＴＯ（リンドープ酸化錫）、ＡＺＯ（アルミニウムドープ酸化亜鉛）、ＧＺＯ（ガリウムドープ酸化亜鉛）等の種々の金属酸化物のナノ粒子を用いることができる。 Note that the function of changing the transmission spectrum in this way is not unique to the ITO nanocrystal layer containing ITO nanoparticles. In principle, the above-described functions can be achieved if the nanoparticles are sized so as to cause LSPR (for example, 100 nm or less), and the nanocrystal layer can inject electrons from the transparent electrode. . As nanoparticles, nanoparticles of various metal oxides such as ATO, PTO (phosphorus-doped tin oxide), AZO (aluminum-doped zinc oxide), GZO (gallium-doped zinc oxide) can be used.
　［ナノ結晶層の厚さによる透過スペクトルの違い］
　ナノ結晶層の厚さによる透過スペクトルの違いを検証した結果を説明する。 [Difference in transmission spectrum depending on nanocrystal layer thickness]
The result of verifying the difference in the transmission spectrum depending on the thickness of the nanocrystal layer will be described.
　検証のため、図２に示すエレクトロクロミック素子８００を作製した。図２に示すエレクトロクロミック素子８００は、第２ナノ結晶層４が省略されている点において、図１に示したエレクトロクロミック素子１００と異なる。 For verification, an electrochromic element 800 shown in FIG. 2 was produced. The electrochromic element 800 shown in FIG. 2 is different from the electrochromic element 100 shown in FIG. 1 in that the second nanocrystal layer 4 is omitted.
　エレクトロクロミック素子８００のナノ結晶層３は、平均粒径が２０ｎｍのＡＴＯナノ粒子を含む。ナノ結晶層３を形成する際の焼成温度は、２００℃である。ナノ結晶層３の厚さｔ１がそれぞれ８４０Å、４６５０Å、７６２０Åである３つのエレクトロクロミック素子８００を作製した（それぞれ「調光セルＡ」、「調光セルＢ」、「調光セルＣ」と呼ぶ）。なお、ナノ結晶層３の厚さｔ１は、第１透明電極１上に形成されたナノ結晶層３の中心から外周部にかけての３か所の厚さを触針式段差計で測定した平均値である。また、ナノ粒子の平均粒径は、透過型電子顕微鏡（ＴＥＭ）を用いて観察したナノ粒子１００個の２軸平均計である。 The nanocrystal layer 3 of the electrochromic element 800 includes ATO nanoparticles having an average particle diameter of 20 nm. The firing temperature when forming the nanocrystal layer 3 is 200 ° C. Three electrochromic devices 800 having nanocrystal layer 3 with thicknesses t1 of 840 mm, 4650 mm, and 7620 mm were fabricated (referred to as “light control cell A”, “light control cell B”, and “light control cell C”, respectively). ). In addition, the thickness t1 of the nanocrystal layer 3 is an average value obtained by measuring the thicknesses at three locations from the center to the outer periphery of the nanocrystal layer 3 formed on the first transparent electrode 1 with a stylus step meter. It is. Moreover, the average particle diameter of a nanoparticle is a biaxial average meter of 100 nanoparticles observed using a transmission electron microscope (TEM).
　図３に、調光セルＡ、ＢおよびＣについて、第２透明電極２の電位を０Ｖとし、第１透明電極１に－３Ｖおよび＋３ＶのＤＣ電圧を印加したときの透過スペクトルを示す。また、表１に、調光セルＡ、ＢおよびＣについて、第１透明電極１に－３Ｖおよび＋３ＶのＤＣ電圧を印加したときの、波長２０００ｎｍの光の透過率を示す。表１には、動作シフト範囲が併せて示されている。ここで、「動作シフト範囲」は、＋３Ｖ印加時の波長２０００ｎｍの光の透過率と、－３Ｖ印加時の波長２０００ｎｍの光の透過率との差である。 FIG. 3 shows transmission spectra of the light control cells A, B and C when the potential of the second transparent electrode 2 is 0 V and DC voltages of −3 V and +3 V are applied to the first transparent electrode 1. Table 1 shows the transmittance of light having a wavelength of 2000 nm when the DC voltages of −3 V and +3 V are applied to the first transparent electrode 1 for the light control cells A, B, and C. Table 1 also shows the operation shift range. Here, the “operation shift range” is the difference between the transmittance of light with a wavelength of 2000 nm when +3 V is applied and the transmittance of light with a wavelength of 2000 nm when -3 V is applied.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　図３および表１からわかるように、ナノ結晶層３の厚さｔ１が小さくなるほど、印加電圧を切り換えたときの透過スペクトルの変化が小さくなる。具体的には、調光セルＣ（ナノ結晶層３の厚さが７６２０Å）の動作シフト範囲が５６．６％であるのに対し、調光セルＢ（ナノ結晶層３の厚さが４６５０Å）および調光セルＡ（ナノ結晶層３の厚さが８４０Å）の動作シフト範囲はそれぞれ４５．５％および１５．６％である。つまり、調光セルＡは、調光セルＣに比べ、動作シフト範囲が４１．０％も狭い。ナノ結晶層３の厚さｔ１が小さいほど動作シフト範囲が狭くなるのは、ナノ結晶層３の厚さｔ１が小さくなるほどナノ結晶層３内を透過する光の光路長が短くなるためであると考えられる。 As can be seen from FIG. 3 and Table 1, the smaller the thickness t1 of the nanocrystal layer 3, the smaller the change in the transmission spectrum when the applied voltage is switched. Specifically, the operation shift range of the light control cell C (the thickness of the nanocrystal layer 3 is 7620 mm) is 56.6%, whereas the light control cell B (the thickness of the nanocrystal layer 3 is 4650 mm). The operation shift ranges of the light control cell A (the thickness of the nanocrystal layer 3 is 840 mm) are 45.5% and 15.6%, respectively. That is, the dimming cell A has a narrower operation shift range of 41.0% than the dimming cell C. The reason why the operation shift range becomes narrower as the thickness t1 of the nanocrystal layer 3 is smaller is that the optical path length of the light transmitted through the nanocrystal layer 3 becomes shorter as the thickness t1 of the nanocrystal layer 3 becomes smaller. Conceivable.
　このように、ナノ結晶層の厚さを調整することにより動作シフト範囲を異ならせることができるので、厚さが互いに異なる一対のナノ結晶層を組み合わせて用いることにより、エレクトロクロミック素子の透過スペクトルの動作シフト範囲を十分に広くすることができる。具体的には、一方のナノ結晶層の動作シフト範囲を、他方のナノ結晶層の動作シフト範囲の半分以下にすることにより、エレクトロクロミック素子全体としての動作シフト範囲を十分に広くすることができる。 As described above, since the operation shift range can be varied by adjusting the thickness of the nanocrystal layer, by using a combination of a pair of nanocrystal layers having different thicknesses, the transmission spectrum of the electrochromic device can be reduced. The operation shift range can be sufficiently widened. Specifically, by making the operation shift range of one nanocrystal layer less than or equal to half of the operation shift range of the other nanocrystal layer, the operation shift range of the entire electrochromic device can be sufficiently widened. .
　［エレクトロクロミック素子の光学特性の検証結果］
　エレクトロクロミック素子１００の試作例（実施例１）を以下のようにして作製し、その光学特性を検証した。 [Verification results of optical characteristics of electrochromic devices]
A prototype example (Example 1) of the electrochromic element 100 was manufactured as follows, and the optical characteristics thereof were verified.
　まず、第１基板１１および第２基板１２としてそれぞれガラス基板を用意した。次に、第１基板１１上に、近赤外領域において透明となるようなチタンドープ酸化インジウム（Titanium-doped Indium Oxide：ＩｎＴｉＯ）をスパッタ法により堆積し、第１透明電極１を形成した。同様にして、第２基板１２上に第２透明電極２を形成した。 First, glass substrates were prepared as the first substrate 11 and the second substrate 12, respectively. Next, titanium-doped indium oxide (Titanium-doped Indium Oxide: InTiO), which becomes transparent in the near infrared region, was deposited on the first substrate 11 by sputtering to form the first transparent electrode 1. Similarly, the second transparent electrode 2 was formed on the second substrate 12.
　続いて、第１透明電極１上に、ＡＴＯナノ粒子の分散液をスピンコート法により塗布し、ホットプレート上で１４０℃で１分間乾燥させた後、２００℃で６０分間焼成を行うことにより、厚さ７６２０Åの第１ナノ結晶層３を形成した。使用したＡＴＯナノ粒子分散液は、平均粒径が２０ｎｍのＡＴＯナノ粒子を含んでおり、分散媒は、メチルイソブチルケトンとイソブタノールとの２：１混合液である。 Subsequently, a dispersion of ATO nanoparticles is applied on the first transparent electrode 1 by spin coating, dried on a hot plate at 140 ° C. for 1 minute, and then fired at 200 ° C. for 60 minutes, A first nanocrystal layer 3 having a thickness of 7620 mm was formed. The ATO nanoparticle dispersion used contains ATO nanoparticles with an average particle size of 20 nm, and the dispersion medium is a 2: 1 mixture of methyl isobutyl ketone and isobutanol.
　次に、第２透明電極２上に、ＡＴＯナノ粒子の分散液をスピンコート法により塗布し、ホットプレート上で１４０℃で１分間乾燥させた後、２００℃で６０分間焼成を行うことにより、厚さ８４０Åの第２ナノ結晶層４を形成した。使用したＡＴＯナノ粒子分散液は、平均粒径が２０ｎｍのＡＴＯナノ粒子を含んでおり、分散媒は、メチルイソブチルケトンとイソブタノールとの２：１混合液である。 Next, a dispersion of ATO nanoparticles is applied on the second transparent electrode 2 by spin coating, dried on a hot plate at 140 ° C. for 1 minute, and then fired at 200 ° C. for 60 minutes, A second nanocrystal layer 4 having a thickness of 840 mm was formed. The ATO nanoparticle dispersion used contains ATO nanoparticles with an average particle size of 20 nm, and the dispersion medium is a 2: 1 mixture of methyl isobutyl ketone and isobutanol.
　その後、粒径が３０μｍの樹脂スペーサを３ｗｔ％含むＵＶ硬化型樹脂材料を、第１ナノ結晶層３の外周上に、部分的に注入口が存在するように塗布する。続いて、両基板を重ね合せ、紫外線を照射することによってシール部７を形成した。次に、注入口から電解液として、１ｍｏｌ／ＬのＬｉＢＦ４を含むＥＣ（Ethylene carbonate）・ＤＥＣ（Diethyl Carbonate）混合液（ＥＣ：ＤＥＣ＝１：２）を注入し、その後、ＵＶ硬化型樹脂材料で封止を行って電解質層５を形成した。このようにして、実施例１のエレクトロクロミック素子１００が得られた。 Thereafter, a UV curable resin material containing 3 wt% of a resin spacer having a particle size of 30 μm is applied on the outer periphery of the first nanocrystal layer 3 so that the injection port partially exists. Subsequently, both the substrates were overlapped and irradiated with ultraviolet rays to form the seal portion 7. Next, an EC (Ethylene carbonate) / DEC (Diethyl Carbonate) mixed solution (EC: DEC = 1: 2) containing 1 mol / L LiBF 4 is injected from the injection port as an electrolytic solution, and then UV curable resin is used. The electrolyte layer 5 was formed by sealing with a material. Thus, the electrochromic element 100 of Example 1 was obtained.
　また、第２ナノ結晶層４を形成しない点以外は実施例１と同様にして、比較例１のエレクトロクロミック素子を作製した。 Further, an electrochromic element of Comparative Example 1 was produced in the same manner as Example 1 except that the second nanocrystal layer 4 was not formed.
　図４に、実施例１および比較例１について、第２透明電極２の電位を０Ｖとし、第１透明電極１に－３Ｖおよび＋３ＶのＤＣ電圧を印加したときの透過スペクトルを示す。また、表２に、実施例１および比較例１について、第１透明電極１に－３Ｖおよび＋３ＶのＤＣ電圧を印加したときの波長２０００ｎｍの光の透過率および動作シフト範囲を示す。 FIG. 4 shows the transmission spectrum of Example 1 and Comparative Example 1 when the potential of the second transparent electrode 2 is 0 V and DC voltages of −3 V and +3 V are applied to the first transparent electrode 1. Table 2 shows the transmittance of light with a wavelength of 2000 nm and the operation shift range when DC voltages of −3 V and +3 V are applied to the first transparent electrode 1 for Example 1 and Comparative Example 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　図４および表２に示すように、比較例１の動作シフト範囲が５６．６％であるのに対し、実施例１の動作シフト範囲は４９．６％であり、動作シフト範囲の低下が７．０％に抑えられている。 As shown in FIG. 4 and Table 2, the operation shift range of Comparative Example 1 is 56.6%, whereas the operation shift range of Example 1 is 49.6%, and the decrease in the operation shift range is 7%. 0.0%.
　比較例２として、第１ナノ結晶層３および第２ナノ結晶層４の両方の厚さを９７８０Åとする点以外は実施例１と同様にしてエレクトロクロミック素子を作製した。また、比較例３として、第２ナノ結晶層４を形成しない点以外は比較例２と同様にしてエレクトロクロミック素子を作製した。 As Comparative Example 2, an electrochromic device was fabricated in the same manner as in Example 1 except that the thickness of both the first nanocrystal layer 3 and the second nanocrystal layer 4 was 9780 mm. Further, as Comparative Example 3, an electrochromic element was produced in the same manner as Comparative Example 2 except that the second nanocrystal layer 4 was not formed.
　図５に、比較例２および比較例３について、第２透明電極２の電位を０Ｖとし、第１透明電極１に－３Ｖおよび＋３ＶのＤＣ電圧を印加したときの透過スペクトルを示す。また、表３に、比較例２および比較例３について、第１透明電極１に－３Ｖおよび＋３ＶのＤＣ電圧を印加したときの波長２０００ｎｍの光の透過率および動作シフト範囲を示す。 FIG. 5 shows transmission spectra of Comparative Example 2 and Comparative Example 3 when the potential of the second transparent electrode 2 is 0 V and DC voltages of −3 V and +3 V are applied to the first transparent electrode 1. Table 3 shows the transmittance and operation shift range of light having a wavelength of 2000 nm when DC voltages of −3 V and +3 V are applied to the first transparent electrode 1 for Comparative Example 2 and Comparative Example 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　図５および表３に示すように、比較例３の動作シフト範囲が５６．８％であるのに対し、比較例２の動作シフト範囲は０．３％であり、比較例２は、比較例３に対して動作シフト範囲が５５．５％（実施例１に対しては４９．３％）も狭くなっている。これは、第１ナノ結晶層３および第２ナノ結晶層４の透過スペクトルのシフトが互いに逆方向であるためである。 As shown in FIG. 5 and Table 3, the operation shift range of Comparative Example 3 is 56.8%, whereas the operation shift range of Comparative Example 2 is 0.3%. 3 is as narrow as 55.5% (49.3% for the first embodiment). This is because the transmission spectrum shifts of the first nanocrystal layer 3 and the second nanocrystal layer 4 are opposite to each other.
　上述した検証結果からわかるように、厚さが互いに異なる一対のナノ結晶層（第１ナノ結晶層３および第２ナノ結晶層４）を組み合わせて用いることによって、動作シフト範囲が狭くなることを抑制できる。 As can be seen from the verification results described above, the use of a combination of a pair of nanocrystal layers having different thicknesses (first nanocrystal layer 3 and second nanocrystal layer 4) prevents the operation shift range from being narrowed. it can.
　なお、動作シフト範囲が狭くなることを防止するために、一方のナノ結晶層を遮蔽物により覆うことが考えられる。ただし、その場合、当然ながら、エレクトロクロミック素子が全体として透明ではなくなるので、スマートウィンドウのような用途には用いることができなくなる。 In order to prevent the operation shift range from becoming narrow, it is conceivable to cover one nanocrystal layer with a shielding material. However, in that case, of course, the electrochromic element as a whole is not transparent, and thus cannot be used for applications such as smart windows.
　表４に、実施例１、比較例１、２および３について、目視により電解質層５中の気泡の発生の有無を観察した結果を示す。表４に示すように、比較例１および３では、気泡が発生しており、電解液の劣化が発生していることがわかる。これに対し、実施例１（および比較例２）では、気泡が発生しておらず、電解液の劣化が抑制されていることがわかる。 Table 4 shows the results of visually observing the occurrence of bubbles in the electrolyte layer 5 for Example 1 and Comparative Examples 1, 2, and 3. As shown in Table 4, it can be seen that in Comparative Examples 1 and 3, bubbles were generated and the electrolyte was deteriorated. On the other hand, in Example 1 (and Comparative Example 2), it can be seen that bubbles are not generated and the deterioration of the electrolytic solution is suppressed.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　上述したように、本開示の実施形態によれば、２つのナノ結晶層を備え、且つ、好適に動作し得るエレクトロクロミック素子１００が得られる。 As described above, according to the embodiment of the present disclosure, it is possible to obtain the electrochromic device 100 including two nanocrystal layers and capable of operating appropriately.
　十分に動作シフト範囲を広くする観点からは、第２ナノ結晶層４の透過スペクトルの波長２０００ｎｍの光に対する動作シフト範囲が、第１ナノ結晶層３の透過スぺクトルの波長２０００ｎｍの光に対する動作シフト範囲の半分以下であることが好ましい。具体的には、第２ナノ結晶層４の厚さｔ２が、第１ナノ結晶層３の厚さｔ１の１％以上３０％以下であることが好ましい。実施例１では、第２ナノ結晶層４の厚さｔ２は、第１ナノ結晶層３の厚さｔ１の約１１％である。 From the viewpoint of sufficiently widening the operation shift range, the operation shift range for light having a wavelength of 2000 nm in the transmission spectrum of the second nanocrystal layer 4 is the operation for light having a wavelength of 2000 nm in the transmission spectrum of the first nanocrystal layer 3. It is preferably less than half of the shift range. Specifically, the thickness t2 of the second nanocrystal layer 4 is preferably 1% or more and 30% or less of the thickness t1 of the first nanocrystal layer 3. In Example 1, the thickness t2 of the second nanocrystal layer 4 is about 11% of the thickness t1 of the first nanocrystal layer 3.
　続いて、エレクトロクロミック素子１００の各構成要素の具体例や好ましい構成を説明する。 Subsequently, specific examples and preferred configurations of each component of the electrochromic element 100 will be described.
　［ナノ結晶層］
　金属酸化物ナノ粒子の材料として用いられる金属酸化物は、例示したＡＴＯおよびＩＴＯに限定されるものではない。例えば、ＡＺＯ（Aluminum-doped Zinc Oxide：アルミニウムドープ酸化亜鉛）やＧＺＯ（Gallium-doped Zinc Oxide：ガリウムドープ酸化亜鉛）等の可視領域においてほぼ透明な材料を用いることができる。また、ＣｓｘＷｙＯ３（ｘ、ｙは組成比を示す）で表されるような複合タングステン酸化物や六ホウ化ランタンなどのような、可視領域の光を吸収する材料を用いることもできる。 [Nanocrystalline layer]
The metal oxide used as the material for the metal oxide nanoparticles is not limited to the exemplified ATO and ITO. For example, a substantially transparent material such as AZO (Aluminum-doped Zinc Oxide) or GZO (Gallium-doped Zinc Oxide) can be used. Alternatively, a material that absorbs light in the visible region, such as a composite tungsten oxide or lanthanum hexaboride represented by CsxWyO 3 (x and y indicate composition ratios), can also be used.
　金属酸化物ナノ粒子の平均粒径は、典型的には、０．１ｎｍ以上１０００ｎｍ以下である。ただし、金属酸化物ナノ粒子の平均粒径が大きすぎると、動作しにくくなるおそれがあるので、動作のしやすさの観点からは、金属酸化物ナノ粒子の平均粒径は、３０ｎｍ以下であることが好ましい。 The average particle diameter of the metal oxide nanoparticles is typically 0.1 nm or more and 1000 nm or less. However, if the average particle size of the metal oxide nanoparticles is too large, it may become difficult to operate. From the viewpoint of ease of operation, the average particle size of the metal oxide nanoparticles is 30 nm or less. It is preferable.
　第１ナノ結晶層３および第２ナノ結晶層４のそれぞれの厚さは、典型的には、１００Å以上５００００Å以下である。可視光の透明性と透過スペクトルの動作シフト範囲の観点からは、第１ナノ結晶層３および第２ナノ結晶層４のそれぞれの厚さは、１０００Å以上１５０００Å以下であることが好ましい。 The thickness of each of the first nanocrystal layer 3 and the second nanocrystal layer 4 is typically 100 mm or more and 50000 mm or less. From the viewpoint of the transparency of visible light and the operation shift range of the transmission spectrum, the thickness of each of the first nanocrystal layer 3 and the second nanocrystal layer 4 is preferably 1000 to 15000 mm.
　第１ナノ結晶層３および第２ナノ結晶層４の形成方法に特に限定はない。金属酸化物ナノ粒子が分散された液体または半固体を第１基板１１または第２基板１２上に塗布し、焼成を行うことによって、第１ナノ結晶層３および第２ナノ結晶層４を形成することができる。金属酸化物ナノ粒子の分散液をスピンコート法により塗布してもよいし、ビヒクルを適度に添加されたペーストを用いた印刷法により塗布してもよい。また、バーコート法、スリットコート法、グラビアコート法またはダイコート法により塗布を行ってもよい。焼成温度が、ナノ結晶表面にある有機成分が除去されて焼結が好適に生じる温度であれば、十分な耐溶剤性が得られる。ただし、焼成温度が高すぎ、焼結が過度に進むと、所望の波長のＬＳＰＲが得られないおそれがある。ＩＴＯナノ粒子を含むナノ結晶層をスピンコート法により形成する場合、焼成は、例えば、２００℃以上３００℃以下の温度で６０分間行われる。 The formation method of the first nanocrystal layer 3 and the second nanocrystal layer 4 is not particularly limited. A liquid or semi-solid in which metal oxide nanoparticles are dispersed is applied onto the first substrate 11 or the second substrate 12 and baked to form the first nanocrystal layer 3 and the second nanocrystal layer 4. be able to. The dispersion of metal oxide nanoparticles may be applied by a spin coating method, or may be applied by a printing method using a paste to which a vehicle is appropriately added. Further, the coating may be performed by a bar coating method, a slit coating method, a gravure coating method or a die coating method. If the firing temperature is such that organic components on the nanocrystal surface are removed and sintering is suitably performed, sufficient solvent resistance can be obtained. However, if the firing temperature is too high and the sintering proceeds excessively, there is a possibility that an LSPR having a desired wavelength cannot be obtained. In the case where a nanocrystal layer containing ITO nanoparticles is formed by a spin coating method, firing is performed at a temperature of 200 ° C. or higher and 300 ° C. or lower for 60 minutes, for example.
　また、第１ナノ結晶層３および第２ナノ結晶層４は、第１基板１１および第２基板１２との結着性を向上させるために、バインダーとして、ポリフッ化ビニリデン（ＰＶＤＦ）等の溶剤系バインダーやスチレン・ブタジエンゴム等の水系バインダー、光硬化樹脂、熱硬化樹脂等を含んでもよい。 Further, the first nanocrystal layer 3 and the second nanocrystal layer 4 are made of a solvent system such as polyvinylidene fluoride (PVDF) as a binder in order to improve the binding property with the first substrate 11 and the second substrate 12. A binder, an aqueous binder such as styrene / butadiene rubber, a photo-curing resin, a thermosetting resin, or the like may also be included.
　［基板］
　第１基板１１および第２基板１２としては、例えばガラス基板を用いることができる。また、ＰＥＴ（ポリエチレンテレフタレート）やＰＥＮ（ポリエチレンナフタレート）、ポリイミドなどの樹脂材料から形成されたプラスチック基板であってもよい。例示したこれらの基板に、無機材料または有機材料から形成されたガスバリア層が設けられたものを用いてもよい。ナノ結晶層を形成する工程が焼成工程を含む場合、プラスチック基板としては、耐熱性が高いポリイミド基板を用いることが好ましい。また、ガラス基板を用いる場合、両基板を貼り合わせた後にエッチング処理により薄型化してもよい。 [substrate]
As the first substrate 11 and the second substrate 12, for example, glass substrates can be used. Moreover, the plastic substrate formed from resin materials, such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), and a polyimide, may be sufficient. These illustrated substrates may be provided with a gas barrier layer formed from an inorganic material or an organic material. When the step of forming the nanocrystal layer includes a baking step, it is preferable to use a polyimide substrate with high heat resistance as the plastic substrate. In the case where a glass substrate is used, the thickness may be reduced by etching after the two substrates are bonded together.
　［透明電極］
　第１透明電極１および第２透明電極２の材料としては、ＩｎＴｉＯの他、アナターゼ型二酸化チタンをシード層としたタンタル置換酸化スズやキャリア密度を調整したＩＴＯ等の近赤外光を透過する材料を用いることができる。これらの材料を、スパッタ法や蒸着法、塗布法などにより第１基板１および第２基板２上に堆積することによって、第１透明電極１および第２透明電極２を形成することができる。 [Transparent electrode]
As the material of the first transparent electrode 1 and the second transparent electrode 2, in addition to InTiO, a material that transmits near-infrared light such as tantalum-substituted tin oxide using anatase-type titanium dioxide as a seed layer or ITO with adjusted carrier density Can be used. The first transparent electrode 1 and the second transparent electrode 2 can be formed by depositing these materials on the first substrate 1 and the second substrate 2 by sputtering, vapor deposition, coating, or the like.
　また、第１透明電極１および第２透明電極２の材料は、遠赤外光を反射する特性を有することが好ましい。冬期に室内の温度を高く保つためには、室内から屋外に赤外光が出ることを防ぐ必要がある。室内から輻射される赤外光は、波長が１０μｍ程度の、遠赤外光に分類されるものである。そのため、第１透明電極１および第２透明電極２が遠赤外光を反射する特性を有していると、近赤外光の透過率が高くなるようにナノ結晶層の状態を制御しても、室内の熱は輻射熱として屋外に逃げない、理想的な状態を実現することができる。また、夏期に近赤外光の透過率が低くなるように制御したときも、屋外からの遠赤外光が室内に入ることを防止できるので、やはり理想的な状態を実現できる。 Moreover, it is preferable that the material of the first transparent electrode 1 and the second transparent electrode 2 has a characteristic of reflecting far-infrared light. In order to keep the room temperature high in winter, it is necessary to prevent infrared light from being emitted from the room to the outdoors. Infrared light radiated from the room is classified as far-infrared light having a wavelength of about 10 μm. Therefore, if the first transparent electrode 1 and the second transparent electrode 2 have the characteristic of reflecting far-infrared light, the state of the nanocrystal layer is controlled so that the transmittance of near-infrared light is increased. However, the indoor heat does not escape to the outdoors as radiant heat, and an ideal state can be realized. Further, even when control is performed so that the transmittance of near-infrared light is lowered in summer, it is possible to prevent the far-infrared light from the outside from entering the room, so that an ideal state can be realized.
　エレクトロクロミック素子１００が表示を目的としないものである場合、第１透明電極１の電極取り出し（外部配線への接続）は、１箇所で行われてもよいし、複数箇所で行われてもよい。１箇所の場合、エレクトロクロミック素子１００の組み立て工程が簡略化されるとともに配線の引き回しを簡素にすることができる。複数箇所の場合、第１透明電極１と第２透明電極２との間に抵抗成分がある、すなわち電流が流れるような場合にも部分的な応答速度の遅延を防ぐことができる。 When the electrochromic element 100 is not intended for display, the electrode extraction (connection to the external wiring) of the first transparent electrode 1 may be performed at one place or at a plurality of places. . In the case of one place, the assembly process of the electrochromic element 100 can be simplified and the routing of the wiring can be simplified. In the case of a plurality of locations, a partial response speed delay can be prevented even when there is a resistance component between the first transparent electrode 1 and the second transparent electrode 2, that is, when a current flows.
　第１透明電極１は、電気的に独立した複数のサブ電極に分割されていてもよい。第１透明電極１が複数のサブ電極に分割されていると、サブ電極に対応する領域ごとに透過スペクトルを変化させることができる。図６（ａ）および（ｂ）に、第１透明電極１が複数のサブ電極１ａに分割された構成の例を示す。 The first transparent electrode 1 may be divided into a plurality of electrically independent sub-electrodes. When the first transparent electrode 1 is divided into a plurality of sub-electrodes, the transmission spectrum can be changed for each region corresponding to the sub-electrodes. 6A and 6B show an example of a configuration in which the first transparent electrode 1 is divided into a plurality of sub-electrodes 1a.
　図６（ａ）に示す例では、複数のサブ電極１ａの引き回しによって、電極取り出し部ＥＰが１箇所に集約されている。サブ電極１ａの引き回し部分を、シール部７の外側やシール部７の下など、エレクトロクロミック素子１００の動作部から外して配置することによって、不要な電圧降下を防止することができる。 In the example shown in FIG. 6A, the electrode lead-out portions EP are gathered at one place by routing the plurality of sub-electrodes 1a. An unnecessary voltage drop can be prevented by disposing the lead-out portion of the sub-electrode 1a away from the operation portion of the electrochromic element 100 such as the outside of the seal portion 7 or under the seal portion 7.
　図６（ｂ）に示す例では、複数のサブ電極１ａが引き回されることなく、直接配線に接続される。つまり、電極取り出し部ＥＰは、複数箇所に分散されている。 In the example shown in FIG. 6B, the plurality of sub-electrodes 1a are directly connected to the wiring without being routed. That is, the electrode extraction part EP is dispersed in a plurality of places.
　第２透明電極２は、第１透明電極１と同様、電気的に独立した複数のサブ電極に分割されていてもよいし、分割されていなくてもよい。 As with the first transparent electrode 1, the second transparent electrode 2 may be divided into a plurality of electrically independent sub-electrodes or may not be divided.
　［電解質層］
　電解質層５は、例えば電解液で構成される。電解液の電解質としては、ヘキサフルオロリン酸リチウム（ＬｉＰＦ６）やヘキサフルオロリン酸ナトリウム（ＮａＰＦ６）、ホウフッ化リチウム（ＬｉＢＦ４）等のイオン化しやすい材料を用いることができる。電解液の溶媒としては、炭酸エチレン（ＥＣ）、炭酸ジエチル（ＤＥＣ）、ＥＣとＤＣとの混合物、炭酸プロピレン等を用いることができる。また、これらにポリビニルブチラール等を溶解させたゲルを用いてもよい。さらに、例えば環状四級アンモニウムカチオンとイミドアニオンからなるイオン液体を用いてもよい。 [Electrolyte layer]
The electrolyte layer 5 is made of, for example, an electrolytic solution. As the electrolyte of the electrolytic solution, a material that is easily ionized such as lithium hexafluorophosphate (LiPF 6 ), sodium hexafluorophosphate (NaPF 6 ), lithium borofluoride (LiBF 4 ), or the like can be used. As the solvent for the electrolytic solution, ethylene carbonate (EC), diethyl carbonate (DEC), a mixture of EC and DC, propylene carbonate, or the like can be used. Moreover, you may use the gel which melt | dissolved polyvinyl butyral etc. in these. Further, for example, an ionic liquid composed of a cyclic quaternary ammonium cation and an imide anion may be used.
　電解質層５は、固体電界質から構成されてもよい。例えば、リチウム塩を含むポリエチレンオキサイドのような固体電解質を用いてもよいし、柔粘性結晶を用いてもよい。 The electrolyte layer 5 may be composed of a solid electrolyte. For example, a solid electrolyte such as polyethylene oxide containing a lithium salt may be used, or a plastic crystal may be used.
　［スペーサ］
　電解質層５が、電解液等の低粘度材料から構成される場合、エレクトロクロミック素子１００は、図７に示すように、第１基板１１と第２基板１２との距離（セル厚）を規定するためのスペーサ８を備えることが好ましい。図７に例示する構成では、スペーサ８は、第１ナノ結晶層３と第２ナノ結晶層４との間に設けられている。スペーサ８は、感光性樹脂材料を用いてフォトリソ工程により形成することができる。スペーサ８は、例えば１０μｍ角で１０μｍの高さを有する。スペーサ８の形成方法は、フォトリソ工程に限定されず、例えばスクリーン印刷法であってもよい。 [Spacer]
When the electrolyte layer 5 is made of a low-viscosity material such as an electrolytic solution, the electrochromic element 100 defines the distance (cell thickness) between the first substrate 11 and the second substrate 12 as shown in FIG. It is preferable to provide a spacer 8 for the purpose. In the configuration illustrated in FIG. 7, the spacer 8 is provided between the first nanocrystal layer 3 and the second nanocrystal layer 4. The spacer 8 can be formed by a photolithography process using a photosensitive resin material. The spacer 8 is, for example, 10 μm square and 10 μm high. The formation method of the spacer 8 is not limited to the photolithography process, but may be, for example, a screen printing method.
　電解質層５が固体電解質から構成される場合、固体電解質が適度な弾性を有していれば、スペーサ８を設ける必要はない。 When the electrolyte layer 5 is composed of a solid electrolyte, it is not necessary to provide the spacer 8 if the solid electrolyte has appropriate elasticity.
　［シール部］
　シール部７の材料としては、例えばＵＶ硬化型の樹脂材料を用いることができる。 [Seal part]
As a material of the seal portion 7, for example, a UV curable resin material can be used.
　図８に、シール部７の他の構成の例を示す。図８に示す例では、シール部７は、異なる材料（シール材）から形成された２つの領域７ａおよび７ｂを有する。以下では、相対的に内側に位置する領域７ａを「内側領域」と呼び、相対的に外側に位置する領域７ｂを「外側領域」と呼ぶ。 FIG. 8 shows an example of another configuration of the seal portion 7. In the example shown in FIG. 8, the seal portion 7 has two regions 7 a and 7 b formed from different materials (seal materials). Hereinafter, the area 7a positioned relatively inside is referred to as “inside area”, and the area 7b positioned relatively outside is referred to as “outside area”.
　内側領域７ａは、外側領域７ｂを形成するシール材よりも耐溶剤性の高いシール材から形成されている。これに対し、外側領域７ｂは、内側領域７ａを形成するシール材よりも接着力の強いシール材から形成されている。 The inner region 7a is formed from a sealing material having higher solvent resistance than the sealing material forming the outer region 7b. On the other hand, the outer region 7b is formed of a sealing material having a stronger adhesive force than the sealing material forming the inner region 7a.
　このように、電解質層５（電解液）に接触する内側領域７ａを耐溶剤性の高いシール材で形成するとともに、外側領域７ｂを接着力の強いシール材で形成することにより、シール部７の高い信頼性および強い接着力を両立させることができる。 As described above, the inner region 7a that is in contact with the electrolyte layer 5 (electrolytic solution) is formed of a highly solvent-resistant sealing material, and the outer region 7b is formed of a sealing material having a strong adhesive force. High reliability and strong adhesion can be achieved at the same time.
　［製造方法］
　エレクトロクロミック素子１００を製造する際、液晶パネルや色素増感型太陽電池等の製造に用いられる種々の方法・工程を用いることができる。第１基板１１および第２基板１２としてプラスチック基板（樹脂基板）を用いる場合には、ロール・ツー・ロール法によって貼り合せ工程を連続的に行うことができるので、製造コストを低減することが可能である。また、一連の工程を脱酸素乾燥雰囲気下で行うことにより、エレクトロクロミック素子１００の信頼性を向上させることができる。 [Production method]
When manufacturing the electrochromic element 100, various methods and processes used for manufacturing a liquid crystal panel, a dye-sensitized solar cell, and the like can be used. When a plastic substrate (resin substrate) is used as the first substrate 11 and the second substrate 12, the bonding process can be continuously performed by a roll-to-roll method, so that the manufacturing cost can be reduced. It is. Further, the reliability of the electrochromic device 100 can be improved by performing a series of steps in a deoxygenated dry atmosphere.
　（実施形態２）
　図９を参照しながら、本実施形態におけるエレクトロクロミック素子２００を説明する。図９は、エレクトロクロミック素子２００を模式的に示す断面図である。以下では、エレクトロクロミック素子２００が実施形態１のエレクトロクロミック素子１００と異なる点を中心に説明を行う。 (Embodiment 2)
With reference to FIG. 9, the electrochromic element 200 in the present embodiment will be described. FIG. 9 is a cross-sectional view schematically showing the electrochromic element 200. Below, it demonstrates centering on the point from which the electrochromic element 200 differs from the electrochromic element 100 of Embodiment 1. FIG.
　実施形態１のエレクトロクロミック素子１００では、第１ナノ結晶層３の厚さｔ１と第２ナノ結晶層４の厚さｔ２とが異なっている。これに対し、本実施形態のエレクトロクロミック素子２００では、第１ナノ結晶層３の厚さｔ１と第２ナノ結晶層４の厚さｔ２とは、実質的に同じである。 In the electrochromic device 100 of Embodiment 1, the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are different. On the other hand, in the electrochromic element 200 of the present embodiment, the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are substantially the same.
　また、本実施形態では、第１ナノ結晶層３に含まれる第１金属酸化物ナノ粒子の平均粒径と、第２ナノ結晶層４に含まれる第２金属酸化物ナノ粒子の平均粒径とが異なっている。具体的には、第２金属酸化物ナノ粒子の平均粒径が、第１金属酸化物ナノ粒子の平均粒径よりも大きい。好ましくは、第２金属酸化物ナノ粒子の平均粒径は、第１金属酸化物ナノ粒子の平均粒径よりも５ｎｍ以上１００ｎｍ以下大きい。 Moreover, in this embodiment, the average particle diameter of the 1st metal oxide nanoparticle contained in the 1st nanocrystal layer 3, and the average particle diameter of the 2nd metal oxide nanoparticle contained in the 2nd nanocrystal layer 4 Is different. Specifically, the average particle diameter of the second metal oxide nanoparticles is larger than the average particle diameter of the first metal oxide nanoparticles. Preferably, the average particle diameter of the second metal oxide nanoparticles is 5 nm to 100 nm larger than the average particle diameter of the first metal oxide nanoparticles.
　上述したように、本実施形態のエレクトロクロミック素子２００も、実施形態１のエレクトロクロミック素子１００と同様に、一対の透明電極（第１透明電極１および第２透明電極２）の一方側および他方側に設けられた一対のナノ結晶層（第１ナノ結晶層３および第２ナノ結晶層４）を備える。これにより、一対の透明電極の一方側にのみナノ結晶層を設けた場合よりも金属酸化物ナノ粒子の総表面積が増大する。そのため、電圧印加時により多くの電荷をナノ結晶層に蓄えることができ、回路を遮断した状態でも所望の透過スペクトルを長時間維持することができる。つまり、好適なメモリ性を実現することができる。 As described above, the electrochromic element 200 of the present embodiment is also the same as the electrochromic element 100 of the first embodiment, on one side and the other side of the pair of transparent electrodes (first transparent electrode 1 and second transparent electrode 2). Are provided with a pair of nanocrystal layers (first nanocrystal layer 3 and second nanocrystal layer 4). Thereby, the total surface area of the metal oxide nanoparticles is increased as compared with the case where the nanocrystal layer is provided only on one side of the pair of transparent electrodes. Therefore, more charges can be stored in the nanocrystal layer when a voltage is applied, and a desired transmission spectrum can be maintained for a long time even when the circuit is shut off. That is, a suitable memory property can be realized.
　また、本実施形態では、第１金属酸化物ナノ粒子と第２金属酸化物ナノ粒子とは、構成元素が同じである。これにより、電気化学的なバランスが取れるので、第１透明電極１、第２透明電極２および電解質層５の劣化を抑制することができる。さらに、第１金属酸化物ナノ粒子と第２金属酸化物ナノ粒子とで構成元素が同じであることは、製造コストや製造工程の簡略化等の点でも有利である。 In the present embodiment, the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements. Thereby, since electrochemical balance is taken, deterioration of the 1st transparent electrode 1, the 2nd transparent electrode 2, and the electrolyte layer 5 can be controlled. Further, the fact that the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements is advantageous in terms of manufacturing cost, simplification of the manufacturing process, and the like.
　また、本実施形態では、第１金属酸化物ナノ粒子の平均粒径と、第２金属酸化物ナノ粒子の平均粒径とが異なっている。これにより、後に検証結果を交えて詳述するように、透過スペクトルの動作シフト範囲を十分に広くすることができる。 In this embodiment, the average particle diameter of the first metal oxide nanoparticles is different from the average particle diameter of the second metal oxide nanoparticles. As a result, the operation shift range of the transmission spectrum can be sufficiently widened, as will be described in detail later with the verification results.
　［金属酸化物ナノ粒子の平均粒径による透過スペクトルの違い］
　金属酸化物ナノ粒子の平均粒径による透過スペクトルの違いを検証した結果を説明する。 [Difference in transmission spectrum due to average particle diameter of metal oxide nanoparticles]
The result of having verified the difference of the transmission spectrum by the average particle diameter of a metal oxide nanoparticle is demonstrated.
　検証のため、図２に示したエレクトロクロミック素子８００を作製した。作製したエレクトロクロミック素子８００のナノ結晶層３は、ＩＴＯナノ粒子を含む。ナノ結晶層３を形成する際の焼成温度は、２００℃である。ここでは、ＩＴＯナノ粒子の平均粒径がそれぞれ１３ｎｍ、１７ｎｍ、２４ｎｍである３つのエレクトロクロミック素子８００を作製した（それぞれ「調光セルＤ」、「調光セルＥ」、「調光セルＦ」と呼ぶ）。 For verification, an electrochromic element 800 shown in FIG. 2 was produced. The nanocrystal layer 3 of the produced electrochromic device 800 includes ITO nanoparticles. The firing temperature when forming the nanocrystal layer 3 is 200 ° C. Here, three electrochromic elements 800 having average particle diameters of ITO nanoparticles of 13 nm, 17 nm, and 24 nm, respectively, were prepared (“light control cell D”, “light control cell E”, and “light control cell F”, respectively). Called).
　図１０に、調光セルＤ、ＥおよびＦについて、第２透明電極２の電位を０Ｖとし、第１透明電極１に－３Ｖおよび＋３ＶのＤＣ電圧を印加したときの透過スペクトルを示す。また、表５には、調光セルＤ、ＥおよびＦについて、第１透明電極１に－３Ｖおよび＋３ＶのＤＣ電圧を印加したときの、波長２０００ｎｍの光の透過率および動作シフト範囲が併せて示されている。 FIG. 10 shows transmission spectra of the light control cells D, E, and F when the potential of the second transparent electrode 2 is 0 V and DC voltages of −3 V and +3 V are applied to the first transparent electrode 1. Table 5 also shows the transmittance and operation shift range of light having a wavelength of 2000 nm when a DC voltage of −3 V and +3 V is applied to the first transparent electrode 1 for the dimming cells D, E, and F. It is shown.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　図１０および表５からわかるように、金属酸化物ナノ粒子の平均粒径が大きくなるほど、印加電圧を切り換えたときの透過スペクトルの変化が小さくなる。具体的には、調光セルＤ（金属酸化物ナノ粒子の平均粒径が１３ｎｍ）の動作シフト範囲が６０．４％であるのに対し、調光セルＥ（金属酸化物ナノ粒子の平均粒径が１７ｎｍ）および調光セルＦ（金属酸化物ナノ粒子の平均粒径が２４ｎｍ）の動作シフト範囲はそれぞれ１７．０％、５．１％である。つまり、調光セルＦは、調光セルＤに比べ、動作シフト範囲が５５．３％も狭い。金属酸化物ナノ粒子の平均粒径が大きくなるほど動作シフト範囲が狭くなるのは、平均粒径が大きくなるほど金属酸化物ナノ粒子の比表面積が小さくなってナノ粒子の周囲に十分な電解質イオンが存在できなくなるためであると考えられる。 As can be seen from FIG. 10 and Table 5, as the average particle size of the metal oxide nanoparticles increases, the change in the transmission spectrum when the applied voltage is switched decreases. Specifically, while the operation shift range of the light control cell D (average particle diameter of metal oxide nanoparticles is 13 nm) is 60.4%, the light control cell E (average particle diameter of metal oxide nanoparticles) The operation shift ranges of the light control cell F (the diameter of the metal oxide nanoparticles are 24 nm) are 17.0% and 5.1%, respectively. That is, the dimming cell F has an operation shift range of 55.3% narrower than that of the dimming cell D. The larger the average particle size of the metal oxide nanoparticles, the narrower the operation shift range. The larger the average particle size, the smaller the specific surface area of the metal oxide nanoparticles and the presence of sufficient electrolyte ions around the nanoparticles. It is thought that it is because it becomes impossible.
　このように、金属酸化物ナノ粒子の平均粒径を調整することにより動作シフト範囲を異ならせることができるので、金属酸化物ナノ粒子の平均粒径が互いに異なる一対のナノ結晶層を組み合わせて用いることにより、エレクトロクロミック素子の透過スペクトルの動作シフト範囲を十分に広くすることができる。具体的には、一方のナノ結晶層の動作シフト範囲を、他方のナノ結晶層の動作シフト範囲の半分以下にすることにより、エレクトロクロミック素子全体としての動作シフト範囲を十分に広くすることができる。 As described above, since the operation shift range can be varied by adjusting the average particle diameter of the metal oxide nanoparticles, a pair of nanocrystal layers having different average particle diameters of the metal oxide nanoparticles are used in combination. As a result, the operation shift range of the transmission spectrum of the electrochromic device can be sufficiently widened. Specifically, by making the operation shift range of one nanocrystal layer less than or equal to half of the operation shift range of the other nanocrystal layer, the operation shift range of the entire electrochromic device can be sufficiently widened. .
　第２ナノ結晶層４の動作シフト範囲を、第１ナノ結晶層３の動作シフト範囲の半分以下にするためには、具体的には、第２金属酸化物ナノ粒子の平均粒径を、第１金属酸化物ナノ粒子の平均粒径よりも５ｎｍ以上１００ｎｍ以下大きくすることが好ましい。 In order to make the operation shift range of the second nanocrystal layer 4 equal to or less than half of the operation shift range of the first nanocrystal layer 3, specifically, the average particle diameter of the second metal oxide nanoparticles is set to It is preferable that the average particle diameter of one metal oxide nanoparticle be 5 nm or more and 100 nm or less.
　（実施形態３）
　図１１を参照しながら、本実施形態におけるエレクトロクロミック素子３００を説明する。図１１は、エレクトロクロミック素子３００を模式的に示す断面図である。以下では、エレクトロクロミック素子３００が実施形態１のエレクトロクロミック素子１００と異なる点を中心に説明を行う。 (Embodiment 3)
The electrochromic element 300 in the present embodiment will be described with reference to FIG. FIG. 11 is a cross-sectional view schematically showing the electrochromic element 300. In the following description, the electrochromic element 300 will be described focusing on differences from the electrochromic element 100 of the first embodiment.
　実施形態１のエレクトロクロミック素子１００では、第１ナノ結晶層３の厚さｔ１と第２ナノ結晶層４の厚さｔ２とが異なっている。これに対し、本実施形態のエレクトロクロミック素子３００では、第１ナノ結晶層３の厚さｔ１と第２ナノ結晶層４の厚さｔ２とは、実質的に同じである。 In the electrochromic device 100 of Embodiment 1, the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are different. On the other hand, in the electrochromic element 300 of the present embodiment, the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are substantially the same.
　また、本実施形態では、第１金属酸化物ナノ粒子の組成比と、第２金属酸化物ナノ粒子の組成比とが異なっている。 Further, in the present embodiment, the composition ratio of the first metal oxide nanoparticles is different from the composition ratio of the second metal oxide nanoparticles.
　本実施形態のエレクトロクロミック素子３００も、実施形態１のエレクトロクロミック素子１００と同様に、一対の透明電極（第１透明電極１および第２透明電極２）の一方側および他方側に設けられた一対のナノ結晶層（第１ナノ結晶層３および第２ナノ結晶層４）を備える。これにより、一対の透明電極の一方側にのみナノ結晶層を設けた場合よりも金属酸化物ナノ粒子の総表面積が増大する。そのため、電圧印加時により多くの電荷をナノ結晶層に蓄えることができ、回路を遮断した状態でも所望の透過スペクトルを長時間維持することができる。つまり、好適なメモリ性を実現することができる。 Similarly to the electrochromic element 100 of the first embodiment, the electrochromic element 300 of the present embodiment is also a pair provided on one side and the other side of the pair of transparent electrodes (first transparent electrode 1 and second transparent electrode 2). These nanocrystal layers (first nanocrystal layer 3 and second nanocrystal layer 4) are provided. Thereby, the total surface area of the metal oxide nanoparticles is increased as compared with the case where the nanocrystal layer is provided only on one side of the pair of transparent electrodes. Therefore, more charges can be stored in the nanocrystal layer when a voltage is applied, and a desired transmission spectrum can be maintained for a long time even when the circuit is shut off. That is, a suitable memory property can be realized.
　また、本実施形態では、第１金属酸化物ナノ粒子と第２金属酸化物ナノ粒子とは、構成元素が同じである。これにより、電気化学的なバランスが取れるので、第１透明電極１、第２透明電極２および電解質層５の劣化を抑制することができる。さらに、第１金属酸化物ナノ粒子と第２金属酸化物ナノ粒子とで構成元素が同じであることは、製造コストや製造工程の簡略化等の点でも有利である。 In the present embodiment, the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements. Thereby, since electrochemical balance is taken, deterioration of the 1st transparent electrode 1, the 2nd transparent electrode 2, and the electrolyte layer 5 can be controlled. Further, the fact that the first metal oxide nanoparticles and the second metal oxide nanoparticles have the same constituent elements is advantageous in terms of manufacturing cost, simplification of the manufacturing process, and the like.
　また、本実施形態では、第１金属酸化物ナノ粒子の組成比と、第２金属酸化物ナノ粒子の組成比とが異なっている。これにより、透過スペクトルの動作シフト範囲を十分に広くすることができる。 Further, in the present embodiment, the composition ratio of the first metal oxide nanoparticles is different from the composition ratio of the second metal oxide nanoparticles. Thereby, the operation shift range of the transmission spectrum can be sufficiently widened.
　例えば、ＩＴＯナノ粒子では、キャリア密度が増加すると吸収波長が短波長側にシフトし、且つ、動作シフト範囲が増加する傾向がある。そのため、第１金属酸化物ナノ粒子および第２金属酸化物ナノ粒子がＩＴＯナノ粒子である場合、第１金属酸化物ナノ粒子の組成比と第２金属酸化物ナノ粒子の組成比とを異ならせて第１金属酸化物ナノ粒子のキャリア密度と第２金属酸化物ナノ粒子のキャリア密度とを異ならせることにより、透過スペクトルの動作シフト範囲を広くすることができる。具体的には、第１金属酸化物ナノ粒子のキャリア密度を相対的に高くし、第２金属酸化物ナノ粒子のキャリア密度を相対的に低くすることにより、第１ナノ結晶層３の動作シフト範囲を、第２ナノ結晶層４の動作シフト範囲よりも広くすることができ、エレクトロクロミック素子３００における透過スペクトルの動作シフト範囲を広くすることができる。 For example, in the case of ITO nanoparticles, when the carrier density increases, the absorption wavelength tends to shift to the short wavelength side and the operation shift range tends to increase. Therefore, when the first metal oxide nanoparticles and the second metal oxide nanoparticles are ITO nanoparticles, the composition ratio of the first metal oxide nanoparticles is different from the composition ratio of the second metal oxide nanoparticles. By making the carrier density of the first metal oxide nanoparticles different from the carrier density of the second metal oxide nanoparticles, the operation shift range of the transmission spectrum can be widened. Specifically, the operation density of the first nanocrystal layer 3 is increased by relatively increasing the carrier density of the first metal oxide nanoparticles and relatively decreasing the carrier density of the second metal oxide nanoparticles. The range can be made wider than the operation shift range of the second nanocrystal layer 4, and the operation shift range of the transmission spectrum in the electrochromic device 300 can be widened.
　第１金属酸化物ナノ粒子および第２金属酸化物ナノ粒子がＩＴＯナノ粒子である場合、例えば、第１金属酸化物ナノ粒子ではＳｎ含有量が１０ｗｔ％以上２０ｗｔ％以下であり、第２金属酸化物ナノ粒子ではＳｎ含有量が１ｗｔ％以上５ｗｔ％以下であることが好ましい。 When the first metal oxide nanoparticles and the second metal oxide nanoparticles are ITO nanoparticles, for example, the first metal oxide nanoparticles have an Sn content of 10 wt% to 20 wt%, and the second metal oxide nanoparticles In the product nanoparticles, the Sn content is preferably 1 wt% or more and 5 wt% or less.
　［実施形態１～３の組み合わせ］
　実施形態１、２、３のエレクトロクロミック素子１００、２００、３００は、それぞれ下記（Ａ）、（Ｂ）、（Ｃ）の構成を有する。
　（Ａ）第１ナノ結晶層３の厚さｔ１と第２ナノ結晶層４の厚さｔ２とが異なる。
　（Ｂ）第１金属酸化物ナノ粒子の平均粒径と第２金属酸化物ナノ粒子の平均粒径とが異なる。
　（Ｃ）第１金属酸化物ナノ粒子の組成比と第２金属酸化物ナノ粒子の組成比とが異なる。 [Combination of Embodiments 1 to 3]
The electrochromic elements 100, 200, and 300 of Embodiments 1, 2, and 3 have the following configurations (A), (B), and (C), respectively.
(A) The thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are different.
(B) The average particle diameter of the first metal oxide nanoparticles is different from the average particle diameter of the second metal oxide nanoparticles.
(C) The composition ratio of the first metal oxide nanoparticles is different from the composition ratio of the second metal oxide nanoparticles.
　製造コストや製造工程の簡略化の観点からは、構成（Ａ）、（Ｂ）および（Ｃ）のうち、構成（Ａ）がもっとも好ましい。 From the viewpoint of simplifying the manufacturing cost and the manufacturing process, the configuration (A) is most preferable among the configurations (A), (B), and (C).
　また、これら（Ａ）、（Ｂ）および（Ｃ）の構成は、任意に組み合わされてもよい。つまり、本開示の実施形態のエレクトロクロミック素子は、（Ａ）および（Ｂ）の構成を有してもよいし、（Ａ）および（Ｃ）の構成を有してもよく、また、（Ｂ）および（Ｃ）の構成を有してもよい。さらに、本開示の実施形態のエレクトロクロミック素子は、（Ａ）、（Ｂ）および（Ｃ）の構成をすべて有してもよい。 Further, these configurations (A), (B), and (C) may be arbitrarily combined. That is, the electrochromic device of the embodiment of the present disclosure may have the configurations (A) and (B), may have the configurations (A) and (C), and (B ) And (C). Furthermore, the electrochromic device of the embodiment of the present disclosure may have all the configurations of (A), (B), and (C).
　（実施形態４）
　図１２を参照しながら、本実施形態におけるエレクトロクロミック素子４００を説明する。図１２は、エレクトロクロミック素子４００を模式的に示す断面図である。以下では、エレクトロクロミック素子４００が実施形態１のエレクトロクロミック素子１００と異なる点を中心に説明を行う。 (Embodiment 4)
The electrochromic element 400 in this embodiment is demonstrated referring FIG. FIG. 12 is a cross-sectional view schematically showing the electrochromic element 400. In the following, the description will be focused on the points where the electrochromic element 400 is different from the electrochromic element 100 of the first embodiment.
　エレクトロクロミック素子４００では、実施形態１のエレクトロクロミック素子１００と同様、第１ナノ結晶層３の厚さｔ１と、第２ナノ結晶層４の厚さｔ２とが異なっている。 In the electrochromic element 400, the thickness t1 of the first nanocrystal layer 3 and the thickness t2 of the second nanocrystal layer 4 are different from the electrochromic element 100 of the first embodiment.
　また、本実施形態のエレクトロクロミック素子４００では、第１透明電極１を支持する第１基板１１’および第２透明電極２を支持する第２基板１２’のそれぞれが、可撓性を有する樹脂基板である。第１基板１１’および第２基板１２’が可撓性を有する樹脂基板であることにより、エレクトロクロミック素子４００に可撓性を与えることができる。そのため、エレクトロクロミック素子４００の窓ガラス等への設置をより容易に行うことができる。 In the electrochromic element 400 of the present embodiment, each of the first substrate 11 ′ supporting the first transparent electrode 1 and the second substrate 12 ′ supporting the second transparent electrode 2 is a flexible resin substrate. It is. Since the first substrate 11 ′ and the second substrate 12 ′ are flexible resin substrates, the electrochromic element 400 can be flexible. Therefore, installation of the electrochromic element 400 on a window glass or the like can be performed more easily.
　エレクトロクロミック素子４００は、例えば以下のようにして作製することができる。 The electrochromic element 400 can be manufactured, for example, as follows.
　まず、第１基板１１’および第２基板１２’としてそれぞれ厚さ２５μｍのＰＥＴフィルムを用意する。次に、第１基板１１’上に、近赤外領域において透明となるようなＩＴＯをスパッタ法により堆積し、第１透明電極１を形成した。同様にして、第２基板１２’上に第２透明電極２を形成する。 First, a PET film having a thickness of 25 μm is prepared as the first substrate 11 ′ and the second substrate 12 ′. Next, on the first substrate 11 ′, ITO that becomes transparent in the near-infrared region was deposited by sputtering to form the first transparent electrode 1. Similarly, the second transparent electrode 2 is formed on the second substrate 12 '.
　続いて、第１透明電極１上に、ＩＴＯナノ粒子の分散液をスピンコート法により塗布し、ホットプレート上で１４０℃で１分間乾燥させた後、２００℃で６０分間焼成を行うことにより、第１ナノ結晶層３を形成する。使用したＩＴＯナノ粒子分散液は、平均粒径が１０ｎｍのＩＴＯナノ粒子を含んでおり、分散媒は、トルエンである。同様にして、第２透明電極２上に、ＩＴＯナノ粒子を含む第２ナノ結晶層４を形成する。 Subsequently, a dispersion of ITO nanoparticles is applied onto the first transparent electrode 1 by spin coating, dried on a hot plate at 140 ° C. for 1 minute, and then fired at 200 ° C. for 60 minutes, A first nanocrystal layer 3 is formed. The used ITO nanoparticle dispersion contains ITO nanoparticles having an average particle size of 10 nm, and the dispersion medium is toluene. Similarly, a second nanocrystal layer 4 containing ITO nanoparticles is formed on the second transparent electrode 2.
　その後、粒径が３０μｍの樹脂スペーサを３ｗｔ％含むＵＶ硬化型樹脂材料を、第１ナノ結晶層３の外周上に、部分的に注入口が存在するように塗布する。続いて、両基板を重ね合せ、紫外線を照射することによってシール部７を形成する。次に、注入口から電解液として、１ｍｏｌ／ＬのＬｉＢＦ４を含むＥＣ（Ethylene carbonate）・ＤＥＣ（Diethyl Carbonate）混合液（ＥＣ：ＤＥＣ＝１：２）を注入し、その後、ＵＶ硬化型樹脂材料で封止を行って電解質層５を形成する。このようにして、エレクトロクロミック素子４００が得られる。 Thereafter, a UV curable resin material containing 3 wt% of a resin spacer having a particle size of 30 μm is applied on the outer periphery of the first nanocrystal layer 3 so that the injection port partially exists. Subsequently, the two substrates are overlapped and irradiated with ultraviolet rays to form the seal portion 7. Next, an EC (Ethylene carbonate) / DEC (Diethyl Carbonate) mixed solution (EC: DEC = 1: 2) containing 1 mol / L LiBF 4 is injected from the injection port as an electrolytic solution, and then UV curable resin is used. The electrolyte layer 5 is formed by sealing with a material. Thus, the electrochromic element 400 is obtained.
　なお、ここではエレクトロクロミック素子４００が上述した構成（Ａ）を有する場合を例示したが、構成（Ａ）に加えて（あるいは代えて）、構成（Ｂ）および／または（Ｃ）を有していてもよい。 In addition, although the case where the electrochromic element 400 has the configuration (A) described above is illustrated here, the configuration (B) and / or (C) is included in addition to (or instead of) the configuration (A). May be.
　（実施形態５）
　実施形態１～４のエレクトロクロミック素子１００～４００は、例えばスマートウィンドウ（調光窓）に好適に用いることができる。エレクトロクロミック素子１００～４００を、窓の透光板（ガラス板やアクリル板）に重ねて設置することにより、可視光域の透過率を保持したまま、室外からの近赤外域の透過スペクトルを切り替えて日射熱取得率を制御することができる。 (Embodiment 5)
The electrochromic elements 100 to 400 of Embodiments 1 to 4 can be suitably used for, for example, a smart window (light control window). By switching the electrochromic elements 100 to 400 on the window translucent plate (glass plate or acrylic plate), the transmission spectrum in the near infrared region from the outside can be switched while maintaining the transmittance in the visible light region. The solar heat gain rate can be controlled.
　以下、図１３を参照しながら、本実施形態におけるスマートウィンドウ５００を説明する。図１３は、スマートウィンドウ５００を模式的に示すブロック図である。 Hereinafter, the smart window 500 in the present embodiment will be described with reference to FIG. FIG. 13 is a block diagram schematically showing the smart window 500.
　スマートウィンドウ５００は、図１３に示すように、調光部２０、制御部３０、スイッチ部３２、通信部３４および電源部３６を備える。 The smart window 500 includes a light control unit 20, a control unit 30, a switch unit 32, a communication unit 34, and a power supply unit 36 as shown in FIG.
　調光部２０は、エレクトロクロミック素子を含む窓状の部分であり、いわばスマートウィンドウ５００の本体部である。調光部２０の具体的な構成については後に詳述する。 The light control unit 20 is a window-like portion including an electrochromic element, which is a main body of the smart window 500. A specific configuration of the light control unit 20 will be described in detail later.
　制御部３０は、スイッチ部３２または通信部３４から送信された信号に基づいて、調光部２０の動作を制御する。制御部３０は、例えば、ＣＰＵ（Central Processing Unit）や専用プロセッサ等の演算部と、ＲＡＭ（Random Access Memory）、ＲＯＭ（Read Only Memory）等の記憶部とを備えた回路基板である。 The control unit 30 controls the operation of the light control unit 20 based on the signal transmitted from the switch unit 32 or the communication unit 34. The control unit 30 is, for example, a circuit board including a calculation unit such as a CPU (Central Processing Unit) or a dedicated processor and a storage unit such as a RAM (Random Access Memory) or a ROM (Read Only Memory).
　電源部３６は、制御部３０および調光部２０に電力を供給する電源回路である。電源部３６は、脱着可能な一次電池、二次電池等を含み得る。 The power supply unit 36 is a power supply circuit that supplies power to the control unit 30 and the light control unit 20. The power supply unit 36 may include a removable primary battery, a secondary battery, and the like.
　スイッチ部３２は、ユーザによる入力を受け付ける。スイッチ部３２は、例えばユーザによって操作される切替えスイッチを含み、切替えスイッチの操作に応じた信号（操作入力信号）を制御部３０に送信する。 The switch unit 32 accepts input from the user. The switch unit 32 includes a changeover switch operated by a user, for example, and transmits a signal (operation input signal) corresponding to the operation of the changeover switch to the control unit 30.
　通信部３４は、外部の通信装置４０からの信号を受信する受信部を含んでいる。通信部３４は、通信装置４０と例えば無線通信により接続されている。無線通信としては、赤外線通信や、Ｗｉ－Ｆｉ（登録商標）、Ｚ―Ｗａｖｅ（登録商標）などを用いることができる。通信装置４０は、リモートコントローラ等の端末装置である。通信部３４と通信装置４０との間の通信は、通信装置４０から通信部３４に、調光部２０の制御に関する信号が一方的に送られる片方向通信であってもよいし、双方向通信であってもよい。双方向通信の場合、例えば、調光部２０のエラー信号を通信装置４０に送り、その内容を通信装置４０で表示可能とすることができる。双方向通信を行う場合、通信部３４は、受信部に加えて送信部を含む。 The communication unit 34 includes a receiving unit that receives a signal from the external communication device 40. The communication unit 34 is connected to the communication device 40 by, for example, wireless communication. As the wireless communication, infrared communication, Wi-Fi (registered trademark), Z-Wave (registered trademark), or the like can be used. The communication device 40 is a terminal device such as a remote controller. The communication between the communication unit 34 and the communication device 40 may be unidirectional communication in which a signal related to the control of the light control unit 20 is unilaterally transmitted from the communication device 40 to the communication unit 34, or bidirectional communication. It may be. In the case of bidirectional communication, for example, an error signal of the dimming unit 20 can be sent to the communication device 40 and the contents can be displayed on the communication device 40. When performing bidirectional communication, the communication unit 34 includes a transmission unit in addition to the reception unit.
　調光部２０の制御は、上述したように、スイッチ部３２や通信装置４０から手動で行うことができる。あるいは、調光部２０の状態を自動的および／または定期的に切り替えてもよい。例えば、スマートウィンドウ５００内にタイマ部（例えば時計）を設けることによって、スイッチ部３２や通信部３４を設けずに、調光部の状態を定期的に切り換えることができる。また、各地域の天気や気温に関するインターネット上の情報を利用して、近赤外光の室内への取り込みを制御してもよい。具体的には、例えば、スマートウィンドウ４００を設置する住所に対応する天気や気温の情報をサービスとして配信し、これを通信装置４０または直接通信部３４で受信して調光部２０の制御に利用することができる。また、インターネット上の情報を用いる代わりに、通信装置４０または通信部３４をＨＥＭＳ（Home Energy Management System）に接続し、温度センサ等との組み合わせで室内温度や屋外温度、消費電力等を管理して、調光部２０の動作に反映させてもよい。 Control of the light control unit 20 can be performed manually from the switch unit 32 or the communication device 40 as described above. Or you may switch the state of the light control part 20 automatically and / or regularly. For example, by providing a timer unit (for example, a clock) in the smart window 500, the state of the dimming unit can be switched periodically without providing the switch unit 32 and the communication unit 34. Moreover, you may control taking in of near infrared light indoors using the information on the internet regarding the weather and temperature of each area. Specifically, for example, weather and temperature information corresponding to the address where the smart window 400 is installed is distributed as a service, which is received by the communication device 40 or the direct communication unit 34 and used to control the light control unit 20. can do. Also, instead of using information on the Internet, the communication device 40 or the communication unit 34 is connected to a HEMS (Home Energy Management System) to manage the indoor temperature, outdoor temperature, power consumption, etc. in combination with a temperature sensor or the like. Alternatively, it may be reflected in the operation of the light control unit 20.
　続いて、図１４（ａ）および（ｂ）を参照しながら、調光部２０の具体的な構成を説明する。以下では、調光部２０が実施形態１のエレクトロクロミック素子１００を含む場合を例示する。また、図１４（ａ）では、第１透明電極１、第１ナノ結晶層３、電解質層５、第２ナノ結晶層４および第２透明電極２の積層構造を１つの調光層９として示している。 Next, a specific configuration of the light control unit 20 will be described with reference to FIGS. 14 (a) and 14 (b). Below, the case where the light control part 20 contains the electrochromic element 100 of Embodiment 1 is illustrated. In FIG. 14A, the laminated structure of the first transparent electrode 1, the first nanocrystal layer 3, the electrolyte layer 5, the second nanocrystal layer 4, and the second transparent electrode 2 is shown as one dimming layer 9. ing.
　調光部２０は、図１４（ａ）および（ｂ）に示すように、エレクトロクロミック素子１００と、ガラス板（透光板）２１と、グレージングチャンネル（「グレチャン」と呼ばれることもある）２２とを有する。 As shown in FIGS. 14A and 14B, the light control unit 20 includes an electrochromic element 100, a glass plate (translucent plate) 21, and a glazing channel (sometimes referred to as “Grechan”) 22. Have
　ガラス板２１は、例示しているように典型的には矩形状である。なお、ここでは透光板としてガラス板２１を例示しているが、透光板はこれに限定されるものでなく、透光性を有する板状の部材であればよい。例えば、透光板としてアクリル板を用いてもよい。 The glass plate 21 is typically rectangular as illustrated. In addition, although the glass plate 21 is illustrated here as a translucent plate, a translucent plate is not limited to this, What is necessary is just a plate-shaped member which has translucency. For example, an acrylic plate may be used as the translucent plate.
　エレクトロクロミック素子１００は、接着層２３を介してガラス板２１に貼り合わされている。接着層２３は、糊剤、ＵＶ硬化樹脂等から形成される。エレクトロクロミック素子１００は、典型的には、ガラス板２１と略同じ外形を有している。図示している例では、エレクトロクロミック素子１００は、ガラス板２１の屋内側に配置されている。言い換えると、ガラス板２１はエレクトロクロミック素子１００の屋外側に配置されている。エレクトロクロミック素子１００は、上述した電源部３６に配線２４を介して電気的に接続されている。 The electrochromic element 100 is bonded to the glass plate 21 via the adhesive layer 23. The adhesive layer 23 is formed from a paste, a UV curable resin, or the like. The electrochromic element 100 typically has substantially the same outer shape as the glass plate 21. In the illustrated example, the electrochromic element 100 is disposed on the indoor side of the glass plate 21. In other words, the glass plate 21 is disposed on the outdoor side of the electrochromic element 100. The electrochromic element 100 is electrically connected to the power supply unit 36 described above via the wiring 24.
　グレージングチャンネル２２は、ガラス板２１の周縁部およびエレクトロクロミック素子１００の周縁部を囲む（挟む）ように配置されている。 The glazing channel 22 is disposed so as to surround (pinch) the peripheral edge of the glass plate 21 and the peripheral edge of the electrochromic element 100.
　ガラス板２１、エレクトロクロミック素子１００およびグレージングチャンネル２２は、框（図１４（ａ）および（ｂ）では不図示）によって支持される。図１５（ａ）および（ｂ）に、框２８が配置された状態を示す。 The glass plate 21, the electrochromic element 100, and the glazing channel 22 are supported by a ridge (not shown in FIGS. 14A and 14B). FIGS. 15A and 15B show a state in which the collar 28 is disposed.
　図１５（ａ）および（ｂ）に示すように、框２８は、ガラス板２１、エレクトロクロミック素子１００およびグレージングチャンネル２２を支持する枠状の支持体である。ガラス板、エレクトロクロミック素子１００およびグレージングチャンネル２２は、一体的に框２８に組み付けられている。グレージングチャンネル２２は、ガラス板２１およびエレクトロクロミック素子１００と、框２８との間に位置しており、ガラス板２１およびエレクトロクロミック素子１００と框２８との隙間を塞いで気密性および水密性を確保している。 15 (a) and 15 (b), the ridge 28 is a frame-like support that supports the glass plate 21, the electrochromic element 100, and the glazing channel 22. The glass plate, the electrochromic element 100, and the glazing channel 22 are integrally assembled to the flange 28. The glazing channel 22 is located between the glass plate 21 and the electrochromic element 100 and the flange 28 and closes the gap between the glass plate 21 and the electrochromic element 100 and the flange 28 to ensure airtightness and watertightness. doing.
　スマートウィンドウ５００では、屋外からガラス板２１を介して屋内に入射する近赤外光の透過率をエレクトロクロミック素子１００で調節することにより、日射熱取得率を制御することができる。 In the smart window 500, the solar heat gain rate can be controlled by adjusting the transmittance of near-infrared light incident on the indoor side through the glass plate 21 from the outside with the electrochromic element 100.
　ガラス板（透光板）２１の法線方向から見たとき、エレクトロクロミック素子１００のシール部７は、図１４（ａ）および図１５（ａ）に示すように、グレージングチャンネル２２からはみ出ないように配置される（つまりグレージングチャンネル２２に重なっている）ことが好ましい。これにより、シール部７が外部から見えなくなるので、スマートウィンドウ５００の意匠性を高くすることができる。 When viewed from the normal direction of the glass plate (translucent plate) 21, the seal portion 7 of the electrochromic element 100 does not protrude from the glazing channel 22 as shown in FIGS. 14 (a) and 15 (a). (Ie, it overlaps the glazing channel 22). Thereby, since the seal | sticker part 7 becomes invisible from the exterior, the design property of the smart window 500 can be made high.
　既に説明したように、エレクトロクロミック素子１００の第１ナノ結晶層３および第２ナノ結晶層４のそれぞれの透過スペクトルは、印加電圧の変化に応じて変化する。第１ナノ結晶層３および第２ナノ結晶層４のうちの、印加電圧の変化に応じた透過スペクトルの変化が相対的に大きい方のナノ結晶層（ここでは第１ナノ結晶層３）が、相対的に小さい方のナノ結晶層（ここでは第２ナノ結晶層４とガラス板（透光板）２１との間（つまり屋外側）に位置していることが好ましい。これにより、太陽からの近赤外光を、電解質層５に入射する前に効率よく遮断することができるので、スマートウィンドウ５００の耐久性を向上させることができる。 As already described, the transmission spectra of the first nanocrystal layer 3 and the second nanocrystal layer 4 of the electrochromic element 100 change according to the change of the applied voltage. Of the first nanocrystal layer 3 and the second nanocrystal layer 4, the nanocrystal layer (here, the first nanocrystal layer 3) having a relatively large change in the transmission spectrum according to the change in the applied voltage is It is preferable that it is located between the relatively smaller nanocrystal layer (here, the second nanocrystal layer 4 and the glass plate (translucent plate) 21 (that is, the outdoor side). Since near-infrared light can be efficiently blocked before entering the electrolyte layer 5, the durability of the smart window 500 can be improved.
　［調光部の他の構成］
　図１６を参照しながら、スマートウィンドウ５００に用いられる他の調光部２０Ａを説明する。図１６は、調光部２０Ａを模式的に示す断面図である。以下では、調光部２０Ａが、図１４（ａ）等に示した調光部２０と異なる点を中心に説明を行う。 [Other configurations of light control unit]
With reference to FIG. 16, another dimmer 20A used in the smart window 500 will be described. FIG. 16 is a cross-sectional view schematically showing the light control unit 20A. Hereinafter, the dimmer 20A will be described with a focus on differences from the dimmer 20 illustrated in FIG.
　調光部２０Ａは、図１６に示すように、第１ガラス板（第１透光板）２１Ａと、第１ガラス板２１Ａに所定の間隙を介して対向するように配置された第２ガラス板（第２透光板）２１Ｂとを有する。図示している例では、第１ガラス板２１Ａが屋外側に配置され、第２ガラス板２１Ｂが屋内側に配置されている。 As shown in FIG. 16, the light control unit 20 </ b> A is a first glass plate (first translucent plate) 21 </ b> A and a second glass plate disposed so as to face the first glass plate 21 </ b> A via a predetermined gap. (Second translucent plate) 21B. In the illustrated example, the first glass plate 21A is disposed on the outdoor side, and the second glass plate 21B is disposed on the indoor side.
　エレクトロクロミック素子１００は、第１ガラス板２１Ａの第２ガラス板２１Ｂ側に貼り合わされている。つまり、エレクトロクロミック素子１００は、第１ガラス板２１Ａと第２ガラス板２１Ｂとの間に位置している。エレクトロクロミック素子１００と第２ガラス板２１Ｂとの間には、所定の厚さの中間層２９が位置している。中間層２９は、例えば空気層やアルゴン層である。 The electrochromic element 100 is bonded to the second glass plate 21B side of the first glass plate 21A. That is, the electrochromic element 100 is located between the first glass plate 21A and the second glass plate 21B. An intermediate layer 29 having a predetermined thickness is located between the electrochromic element 100 and the second glass plate 21B. The intermediate layer 29 is, for example, an air layer or an argon layer.
　調光部２０Ａは、エレクトロクロミック素子１００と第２ガラス板２１Ｂとの間に設けられたスペーサ２５をさらに有する。スペーサ２５は、中間層２９の厚さを規定する。スペーサ２５としては、複層ガラス用の種々のスペーサを用いることができ、例えば、乾燥剤入りのアルミスペーサや樹脂スペーサを用いることができる。 The light control unit 20A further includes a spacer 25 provided between the electrochromic element 100 and the second glass plate 21B. The spacer 25 defines the thickness of the intermediate layer 29. As the spacer 25, various spacers for double-glazed glass can be used. For example, an aluminum spacer containing a desiccant or a resin spacer can be used.
　グレージングチャンネル２２は、第１ガラス板２１Ａの周縁部、エレクトロクロミック素子１００の周縁部および第２ガラス板２１Ｂの周縁部を囲むように配置されている。 The glazing channel 22 is disposed so as to surround the peripheral edge of the first glass plate 21A, the peripheral edge of the electrochromic element 100, and the peripheral edge of the second glass plate 21B.
　図１６に示す調光部２０Ａでは、エレクトロクロミック素子１００が第１ガラス板２１Ａと第２ガラス板２１Ｂとの間に設けられているので、外部からの衝撃によるエレクトロクロミック素子１００の破損を防止することができる。また、エレクトロクロミック素子１００が、屋外側に位置する第１ガラス板２１Ａに貼り合わされていることにより、太陽からの近赤外光を中間層２９に入射する前に遮断することができるので、夏季に高い遮熱効果を得ることができる。 In the light control unit 20A shown in FIG. 16, since the electrochromic element 100 is provided between the first glass plate 21A and the second glass plate 21B, the electrochromic element 100 is prevented from being damaged by an external impact. be able to. Moreover, since the electrochromic element 100 is bonded to the first glass plate 21A located on the outdoor side, near infrared light from the sun can be blocked before entering the intermediate layer 29. High heat shielding effect can be obtained.
　また、調光部２０Ａでは、第１ガラス板２１Ａの法線方向から見たとき、スペーサ２５はグレージングチャンネル２２に重なっており、シール部７は、スペーサ２５およびグレージングチャンネル２２に重なっている。これにより、エレクトロクロミック素子１００のうち、強度の高いシール部７が存在している領域に、スペーサ２５およびグレージングチャンネル２２の圧力がかかるようにすることができる。 Further, in the light control portion 20A, the spacer 25 overlaps the glazing channel 22 and the seal portion 7 overlaps the spacer 25 and the glazing channel 22 when viewed from the normal direction of the first glass plate 21A. Thereby, the pressure of the spacer 25 and the glazing channel 22 can be applied to the region of the electrochromic element 100 where the high-strength seal portion 7 exists.
　図１７を参照しながら、スマートウィンドウ５００に用いられるさらに他の調光部２０Ｂを説明する。図１７は、調光部２０Ｂを模式的に示す断面図である。以下では、調光部２０Ｂが、図１６に示した調光部２０Ａと異なる点を中心に説明を行う。 Referring to FIG. 17, another light control unit 20B used for the smart window 500 will be described. FIG. 17 is a cross-sectional view schematically showing the light control unit 20B. Below, it demonstrates centering on the point from which the light control part 20B differs from the light control part 20A shown in FIG.
　調光部２０Ｂでは、図１７に示すように、スペーサ２５は、第１ガラス板２１Ａの法線方向から見たとき、グレージングチャンネル２２に重なっている。また、シール部７は、第１ガラス板２１Ａの法線方向から見たとき、グレージングチャンネル２２に重なっており、且つ、スペーサ２５よりも内側（第１ガラス板２１の面内方向における内側）に位置している。図示している例では、第２基板１２のサイズが第１基板１１のサイズよりもやや小さく、スペーサ２５の屋外側の端部は、第１基板１１に接している。 In the light control unit 20B, as shown in FIG. 17, the spacer 25 overlaps the glazing channel 22 when viewed from the normal direction of the first glass plate 21A. Further, when viewed from the normal direction of the first glass plate 21A, the seal portion 7 overlaps with the glazing channel 22 and is on the inner side than the spacer 25 (the inner side in the in-plane direction of the first glass plate 21). positioned. In the illustrated example, the size of the second substrate 12 is slightly smaller than the size of the first substrate 11, and the end of the spacer 25 on the outdoor side is in contact with the first substrate 11.
　調光部２０Ｂでは、シール部７がスペーサ２５よりも内側に配置されているので、調光層９にスペーサ２５やグレージングチャンネル２２の圧力がかからないようにすることができる。なお、スペーサ２５やグレージングチャンネル２２の圧力がかかる領域に、配線２４や配線用のフレキシブル基板が位置してもよい。 In the light control part 20B, since the seal part 7 is disposed inside the spacer 25, the pressure of the spacer 25 and the glazing channel 22 can be prevented from being applied to the light control layer 9. In addition, the wiring 24 and the flexible substrate for wiring may be located in the area | region where the pressure of the spacer 25 or the glazing channel 22 is applied.
　図１８を参照しながら、スマートウィンドウ５００に用いられるさらに他の調光部２０Ｃを説明する。図１８は、調光部２０Ｃを模式的に示す断面図である。以下では、調光部２０Ｃが、図１６に示した調光部２０Ａと異なる点を中心に説明を行う。 Referring to FIG. 18, still another dimming unit 20C used for the smart window 500 will be described. FIG. 18 is a cross-sectional view schematically showing the light control unit 20C. Hereinafter, the dimming unit 20C will be described with a focus on differences from the dimming unit 20A illustrated in FIG.
　調光部２０Ｃは、第１ガラス板（第１透光板）２１Ａと、第１ガラス板２１Ａに所定の間隙を介して対向するように配置された第２ガラス板（第２透光板）２１Ｂとを有する。エレクトロクロミック素子１００は、第１ガラス板２１Ａと第２ガラス板２１Ｂとの間に配置されている。 The light control unit 20C includes a first glass plate (first translucent plate) 21A and a second glass plate (second translucent plate) disposed so as to face the first glass plate 21A with a predetermined gap therebetween. 21B. The electrochromic element 100 is disposed between the first glass plate 21A and the second glass plate 21B.
　エレクトロクロミック素子１００は、第１ガラス板２１Ａおよび第２ガラス板２１Ｂのいずれにも貼り合わされていない。第１ガラス板２１Ａとエレクトロクロミック素子１００との間には、第１中間層２９Ａが位置しており、エレクトロクロミック素子１００と第２ガラス板２１Ｂとの間には第２中間層２９Ｂが位置している。つまり、調光部２０Ｃでは、いわゆるトリプルガラス構造の複層ガラスを構成する３つのガラス板のうちの中央のガラス板の代わりに、エレクトロクロミック素子１００が用いられている。 The electrochromic element 100 is not bonded to either the first glass plate 21A or the second glass plate 21B. A first intermediate layer 29A is located between the first glass plate 21A and the electrochromic element 100, and a second intermediate layer 29B is located between the electrochromic element 100 and the second glass plate 21B. ing. That is, in the light control unit 20C, the electrochromic element 100 is used in place of the central glass plate among the three glass plates constituting the double glass having a so-called triple glass structure.
　調光部２０Ｃは、第１ガラス板２１Ａとエレクトロクロミック素子１００との間に設けられた第１スペーサ２５Ａと、エレクトロクロミック素子１００と第２ガラス板２１Ｂとの間に設けられた第２スペーサ２５Ｂとをさらに有する。第１スペーサ２５Ａは、第１中間層２９Ａの厚さを規定し、第２スペーサ２５Ｂは、第２中間層２９Ｂの厚さを規定する。第１スペーサ２５Ａおよび第２スペーサ２５Ｂでエレクトロクロミック素子１００を支持することにより、接着層等を用いることなくエレクトロクロミック素子１００を調光部２０Ｃ内に配置することができる。 The dimmer 20C includes a first spacer 25A provided between the first glass plate 21A and the electrochromic element 100, and a second spacer 25B provided between the electrochromic element 100 and the second glass plate 21B. And further. The first spacer 25A defines the thickness of the first intermediate layer 29A, and the second spacer 25B defines the thickness of the second intermediate layer 29B. By supporting the electrochromic element 100 with the first spacer 25A and the second spacer 25B, the electrochromic element 100 can be disposed in the light control unit 20C without using an adhesive layer or the like.
　また、調光部２０Ｃのエレクトロクロミック素子１００は、第１ガラス板２１Ａ側の最表面および第２ガラス板２１Ｂ側の最表面に位置する一対の反射防止膜１３および１４を含む。トリプルガラス構造では、ガラスのような固体と空気のような気体との界面が少なくとも６つ形成され、これらの界面においては、界面反射が起こるので、可視光線を含む光の透過率が低くなる。エレクトロクロミック素子１００が上述したような一対の反射防止膜１３および１４を含むことにより、透過率の低下を抑制できる。反射防止膜１３および１４としては、ＡＲ（Anti Reflective）フィルムやＬＲ（Low Reflective）フィルム、モスアイフィルム等を用いることができる。 Further, the electrochromic element 100 of the light control unit 20C includes a pair of antireflection films 13 and 14 located on the outermost surface on the first glass plate 21A side and the outermost surface on the second glass plate 21B side. In the triple glass structure, at least six interfaces between a solid such as glass and a gas such as air are formed, and interface reflection occurs at these interfaces, so that the transmittance of light including visible light is low. When the electrochromic element 100 includes the pair of antireflection films 13 and 14 as described above, a decrease in transmittance can be suppressed. As the antireflection films 13 and 14, an AR (Anti-Reflective) film, an LR (Low-Reflective) film, a moth-eye film, or the like can be used.
　また、調光部２０Ｃでは、第１ガラス板２１Ａの法線方向から見たとき、第１スペーサ２５Ａおよび第２スペーサ２５Ｂはグレージングチャンネル２２に重なっており、シール部７は、第１スペーサ２５Ａ、第２スペーサ２５Ｂおよびグレージングチャンネル２２に重なっている 。これにより、エレクトロクロミック素子１００のうち、強度の高いシール部７が存在している領域に、第１スペーサ２５Ａ、第２スペーサ２５Ｂおよびグレージングチャンネル２２の圧力がかかるようにすることができる。 Further, in the light control section 20C, when viewed from the normal direction of the first glass plate 21A, the first spacer 25A and the second spacer 25B overlap the glazing channel 22, and the seal section 7 includes the first spacer 25A, It should overlap the second spacer 25B and the glazing channel 22. Thereby, the pressure of the first spacer 25 </ b> A, the second spacer 25 </ b> B, and the glazing channel 22 can be applied to the region of the electrochromic element 100 where the high-strength seal portion 7 exists.
　図１９を参照しながら、スマートウィンドウ５００に用いられるさらに他の調光部２０Ｄを説明する。図１９は、調光部２０Ｄを模式的に示す断面図である。以下では、調光部２０Ｄが、図１８に示した調光部２０Ｃと異なる点を中心に説明を行う。 Referring to FIG. 19, still another light control unit 20D used for the smart window 500 will be described. FIG. 19 is a cross-sectional view schematically showing the light control unit 20D. Below, it demonstrates centering on the point from which the light control part 20D differs from the light control part 20C shown in FIG.
　調光部２０Ｄでは、図１９に示すように、第１スペーサ２５Ａおよび第２スペーサ２５Ｂは、第１ガラス板２１Ａの法線方向から見たとき、グレージングチャンネル２２に重なっている。また、シール部７は、第１ガラス板２１Ａの法線方向から見たとき、グレージングチャンネル２２に重なっており、且つ、第１スペーサ２５Ａおよび第２スペーサ２５Ｂよりも内側（第１ガラス板２１の面内方向における内側）に位置している。図示している例では、第２基板１２のサイズが第１基板１１のサイズよりもやや小さく、第１スペーサ２５Ａの屋内側の端部および第２スペーサ２５Ｂの屋外側の端部は、第１基板１１に接している。 In the light control unit 20D, as shown in FIG. 19, the first spacer 25A and the second spacer 25B overlap the glazing channel 22 when viewed from the normal direction of the first glass plate 21A. Further, when viewed from the normal direction of the first glass plate 21A, the seal portion 7 overlaps with the glazing channel 22 and is located on the inner side of the first spacer 25A and the second spacer 25B (of the first glass plate 21). It is located on the inner side in the in-plane direction. In the illustrated example, the size of the second substrate 12 is slightly smaller than the size of the first substrate 11, and the end on the indoor side of the first spacer 25A and the end on the outdoor side of the second spacer 25B are the first It is in contact with the substrate 11.
　調光部２０Ｄでは、シール部７が第１スペーサ２５Ａおよび第２スペーサ２５Ｂよりも内側に配置されているので、調光層９に第１スペーサ２５Ａ、第２スペーサ２５Ｂおよびグレージングチャンネル２２の圧力がかからないようにすることができる。なお、第１スペーサ２５Ａや第２スペーサ２５Ｂ、グレージングチャンネル２２の圧力がかかる領域に、配線２４や配線用のフレキシブル基板が位置してもよい。 In the light control unit 20D, since the seal portion 7 is disposed on the inner side of the first spacer 25A and the second spacer 25B, the pressure of the first spacer 25A, the second spacer 25B, and the glazing channel 22 is applied to the light control layer 9. It can be avoided. In addition, the wiring 24 and the flexible substrate for wiring may be located in the area | region where the pressure of the 1st spacer 25A, the 2nd spacer 25B, and the glazing channel 22 applies.
　なお、本開示の実施形態によるエレクトロクロミック素子は、窓ガラス以外のものに設置されてもよく、例えば、農業用のビニールハウスに設置されてもよい。 In addition, the electrochromic device according to the embodiment of the present disclosure may be installed on something other than the window glass, and may be installed in an agricultural greenhouse, for example.
　本開示の実施形態によると、２つのナノ結晶層を備え、且つ、好適に動作し得るエレクトロクロミック素子およびスマートウィンドウを提供することができる。 According to the embodiment of the present disclosure, it is possible to provide an electrochromic device and a smart window that include two nanocrystal layers and can operate suitably.
　［援用の記載］
　本国際出願は、２０１８年３月５日に日本国特許庁に出願された特願２０１８－３８７４７号に基づく優先権を主張するものであり、特願２０１８－３８７４７号の開示内容の全てを参照により本国際出願に援用する。  [Description of support]
This international application claims priority based on Japanese Patent Application No. 2018-38747 filed with the Japan Patent Office on March 5, 2018. Refer to the entire disclosure of Japanese Patent Application No. 2018-38747. Is incorporated herein by reference.
　１　　第１透明電極
　１ａ　　サブ電極
　２　　第２透明電極
　３　　第１ナノ結晶層
　４　　第２ナノ結晶層
　５　　電解質層
　６　　電源
　７　　シール部
　７ａ　　内側領域
　７ｂ　　外側領域
　８　　スペーサ
　１１、１１’　　第１基板
　１２、１２’　　第２基板
　１３、１４　　反射防止膜
　２０、２０Ａ、２０Ｂ、２０Ｃ、２０Ｄ　　調光部
　２１　　透光板（ガラス板）
　２１Ａ　　第１透光板（第１ガラス板）
　２１Ｂ　　第２透光板（第２ガラス板）
　２２　　グレージングチャンネル
　２３　　接着層
　２４　　配線
　２５　　スペーサ
　２５Ａ　　第１スペーサ
　２５Ｂ　　第２スペーサ
　２８　　框
　２９　　中間層
　３０　　制御部
　３２　　スイッチ部
　３４　　通信部
　３６　　電源部
　４０　　通信装置
　１００、２００、３００、４００　　エレクトロクロミック素子
　５００　　スマートウィンドウ DESCRIPTION OF SYMBOLS 1 1st transparent electrode 1a Sub electrode 2 2nd transparent electrode 3 1st nanocrystal layer 4 2nd nanocrystal layer 5 Electrolyte layer 6 Power supply 7 Seal part 7a Inner area | region 7b Outer area | region 8 Spacer 11, 11 '1st board | substrate 12, 12 '2nd board | substrate 13, 14 Antireflection film 20, 20A, 20B, 20C, 20D Light control part 21 Light-transmitting plate (glass plate)
21A First translucent plate (first glass plate)
21B Second translucent plate (second glass plate)
22 Grazing channel 23 Adhesive layer 24 Wiring 25 Spacer 25A First spacer 25B Second spacer 28 ２９ 29 Intermediate layer 30 Control unit 32 Switch unit 34 Communication unit 36 Power supply unit 40 Communication device 100, 200, 300, 400 Electrochromic element 500 Smart window

Claims (22)

  1. 　互いに対向する第１透明電極および第２透明電極と、
    　前記第１透明電極の前記第２透明電極側の表面上に設けられ、複数の第１金属酸化物ナノ粒子を含む第１ナノ結晶層と、
    　前記第２透明電極の前記第１透明電極側の表面上に設けられ、複数の第２金属酸化物ナノ粒子を含む第２ナノ結晶層と、
    　前記第１ナノ結晶層および前記第２ナノ結晶層の間に設けられた電解質層と、
    を備え、
    　前記複数の第１金属酸化物ナノ粒子と前記複数の第２金属酸化物ナノ粒子とは、構成元素が同じであり、
    　前記第１ナノ結晶層の厚さと前記第２ナノ結晶層の厚さとが異なっている、エレクトロクロミック素子。     A first transparent electrode and a second transparent electrode facing each other;
    A first nanocrystal layer including a plurality of first metal oxide nanoparticles provided on a surface of the first transparent electrode on the second transparent electrode side;
    A second nanocrystal layer provided on a surface of the second transparent electrode on the first transparent electrode side and including a plurality of second metal oxide nanoparticles;
    An electrolyte layer provided between the first nanocrystal layer and the second nanocrystal layer;
    With
    The plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles have the same constituent elements,
    The electrochromic device, wherein a thickness of the first nanocrystal layer is different from a thickness of the second nanocrystal layer.
  2. 　前記第２ナノ結晶層の厚さは、前記第１ナノ結晶層の厚さの１％以上３０％以下である、請求項１に記載のエレクトロクロミック素子。 The electrochromic device according to claim 1, wherein the thickness of the second nanocrystal layer is 1% or more and 30% or less of the thickness of the first nanocrystal layer.
  3. 　前記複数の第１金属酸化物ナノ粒子の平均粒径と前記複数の第２金属酸化物ナノ粒子の平均粒径とが異なっている、請求項１または２に記載のエレクトロクロミック素子。 The electrochromic device according to claim 1 or 2, wherein an average particle size of the plurality of first metal oxide nanoparticles is different from an average particle size of the plurality of second metal oxide nanoparticles.
  4. 　互いに対向する第１透明電極および第２透明電極と、
    　前記第１透明電極の前記第２透明電極側の表面上に設けられ、複数の第１金属酸化物ナノ粒子を含む第１ナノ結晶層と、
    　前記第２透明電極の前記第１透明電極側の表面上に設けられ、複数の第２金属酸化物ナノ粒子を含む第２ナノ結晶層と、
    　前記第１ナノ結晶層および前記第２ナノ結晶層の間に設けられた電解質層と、
    を備え、
    　前記複数の第１金属酸化物ナノ粒子と前記複数の第２金属酸化物ナノ粒子とは、構成元素が同じであり、
    　前記複数の第１金属酸化物ナノ粒子の平均粒径と前記複数の第２金属酸化物ナノ粒子の平均粒径とが異なっている、エレクトロクロミック素子。     A first transparent electrode and a second transparent electrode facing each other;
    A first nanocrystal layer including a plurality of first metal oxide nanoparticles provided on a surface of the first transparent electrode on the second transparent electrode side;
    A second nanocrystal layer provided on a surface of the second transparent electrode on the first transparent electrode side and including a plurality of second metal oxide nanoparticles;
    An electrolyte layer provided between the first nanocrystal layer and the second nanocrystal layer;
    With
    The plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles have the same constituent elements,
    An electrochromic device, wherein an average particle diameter of the plurality of first metal oxide nanoparticles is different from an average particle diameter of the plurality of second metal oxide nanoparticles.
  5. 　前記複数の第２金属酸化物ナノ粒子の平均粒径は、前記複数の第１金属酸化物ナノ粒子の平均粒径よりも５ｎｍ以上１００ｎｍ以下大きい、請求項３または４に記載のエレクトロクロミック素子。 The electrochromic device according to claim 3 or 4, wherein an average particle size of the plurality of second metal oxide nanoparticles is 5 nm or more and 100 nm or less larger than an average particle size of the plurality of first metal oxide nanoparticles.
  6. 　前記複数の第１金属酸化物ナノ粒子の組成比と前記複数の第２金属酸化物ナノ粒子の組成比とが異なっている、請求項１から５のいずれかに記載のエレクトロクロミック素子。 6. The electrochromic device according to claim 1, wherein a composition ratio of the plurality of first metal oxide nanoparticles is different from a composition ratio of the plurality of second metal oxide nanoparticles.
  7. 　互いに対向する第１透明電極および第２透明電極と、
    　前記第１透明電極の前記第２透明電極側の表面上に設けられ、複数の第１金属酸化物ナノ粒子を含む第１ナノ結晶層と、
    　前記第２透明電極の前記第１透明電極側の表面上に設けられ、複数の第２金属酸化物ナノ粒子を含む第２ナノ結晶層と、
    　前記第１ナノ結晶層および前記第２ナノ結晶層の間に設けられた電解質層と、
    を備え、
    　前記複数の第１金属酸化物ナノ粒子と前記複数の第２金属酸化物ナノ粒子とは、構成元素が同じであり、
    　前記複数の第１金属酸化物ナノ粒子の組成比と前記複数の第２金属酸化物ナノ粒子の組成比とが異なっている、エレクトロクロミック素子。     A first transparent electrode and a second transparent electrode facing each other;
    A first nanocrystal layer including a plurality of first metal oxide nanoparticles provided on a surface of the first transparent electrode on the second transparent electrode side;
    A second nanocrystal layer provided on a surface of the second transparent electrode on the first transparent electrode side and including a plurality of second metal oxide nanoparticles;
    An electrolyte layer provided between the first nanocrystal layer and the second nanocrystal layer;
    With
    The plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles have the same constituent elements,
    An electrochromic device, wherein a composition ratio of the plurality of first metal oxide nanoparticles is different from a composition ratio of the plurality of second metal oxide nanoparticles.
  8. 　前記複数の第１金属酸化物ナノ粒子および前記複数の第２金属酸化物ナノ粒子は、それぞれ複数のアンチモンドープ酸化錫ナノ粒子である、請求項１から７のいずれかに記載のエレクトロクロミック素子。 The electrochromic device according to any one of claims 1 to 7, wherein each of the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles is a plurality of antimony-doped tin oxide nanoparticles.
  9. 　前記複数の第１金属酸化物ナノ粒子および前記複数の第２金属酸化物ナノ粒子は、それぞれ複数の錫ドープ酸化インジウムナノ粒子である、請求項１から７のいずれかに記載のエレクトロクロミック素子。 The electrochromic device according to any one of claims 1 to 7, wherein each of the plurality of first metal oxide nanoparticles and the plurality of second metal oxide nanoparticles is a plurality of tin-doped indium oxide nanoparticles.
  10. 　前記第１透明電極を支持する第１基板と、
    　前記第２透明電極を支持する第２基板と、
    をさらに備え、
    　前記第１基板および前記第２基板のそれぞれは、可撓性を有する樹脂基板である、請求項１から９のいずれかに記載のエレクトロクロミック素子。     A first substrate supporting the first transparent electrode;
    A second substrate supporting the second transparent electrode;
    Further comprising
    10. The electrochromic element according to claim 1, wherein each of the first substrate and the second substrate is a resin substrate having flexibility.
  11. 　第１透明電極および第２透明電極のそれぞれは、電気的に独立した複数のサブ電極に分割されている、請求項１から１０のいずれかに記載のエレクトロクロミック素子。 The electrochromic device according to any one of claims 1 to 10, wherein each of the first transparent electrode and the second transparent electrode is divided into a plurality of electrically independent sub-electrodes.
  12. 　請求項１から１１のいずれかに記載のエレクトロクロミック素子を備えたスマートウィンドウ。 A smart window comprising the electrochromic device according to any one of claims 1 to 11.
  13. 　透光板をさらに備え、
    　前記エレクトロクロミック素子は、前記透光板に貼り合わされている、請求項１２に記載のスマートウィンドウ。     It further includes a translucent plate,
    The smart window according to claim 12, wherein the electrochromic element is bonded to the translucent plate.
  14. 　前記第１ナノ結晶層および前記第２ナノ結晶層のそれぞれの透過スペクトルは、印加電圧の変化に応じて変化し、
    　前記第１ナノ結晶層および前記第２ナノ結晶層のうちの、印加電圧の変化に応じた透過スペクトルの変化が相対的に大きい方のナノ結晶層が、相対的に小さい方のナノ結晶層と前記透光板との間に位置している、請求項１３に記載のスマートウィンドウ。     Each of the transmission spectra of the first nanocrystal layer and the second nanocrystal layer changes according to a change in applied voltage,
    Of the first nanocrystal layer and the second nanocrystal layer, a nanocrystal layer having a relatively large change in transmission spectrum according to a change in applied voltage is a nanocrystal layer having a relatively small size. The smart window according to claim 13, wherein the smart window is located between the translucent plates.
  15. 　前記透光板の周縁部および前記エレクトロクロミック素子の周縁部を囲むように配置されたグレージングチャンネルをさらに備え、
    　前記エレクトロクロミック素子は、前記電解質層を包囲するように設けられたシール部をさらに有し、
    　前記透光板の法線方向から見たとき、前記シール部は前記グレージングチャンネルに重なっている、請求項１３または１４に記載のスマートウィンドウ。     Further comprising a glazing channel disposed so as to surround a peripheral edge of the translucent plate and a peripheral edge of the electrochromic element;
    The electrochromic device further includes a seal portion provided so as to surround the electrolyte layer,
    The smart window according to claim 13 or 14, wherein the seal portion overlaps the glazing channel when viewed from the normal direction of the light transmissive plate.
  16. 　第１透光板と、
    　前記第１透光板に所定の間隙を介して対向するように配置された第２透光板と、
    をさらに備え、
    　前記エレクトロクロミック素子は、前記第１透光板の前記第２透光板側に貼り合わされており、
    　前記エレクトロクロミック素子と前記第２透光板との間に、所定の厚さの中間層が位置する、請求項１２に記載のスマートウィンドウ。     A first translucent plate;
    A second light transmissive plate disposed to face the first light transmissive plate with a predetermined gap therebetween;
    Further comprising
    The electrochromic element is bonded to the second light transmitting plate side of the first light transmitting plate,
    The smart window according to claim 12, wherein an intermediate layer having a predetermined thickness is located between the electrochromic element and the second translucent plate.
  17. 　前記エレクトロクロミック素子と前記第２透光板との間に設けられ、前記中間層の厚さを規定するスペーサと、
    　前記第１透光板の周縁部、前記エレクトロクロミック素子の周縁部および前記第２透光板の周縁部を囲むように配置されたグレージングチャンネルと、
    をさらに備え、
    　前記エレクトロクロミック素子は、前記電解質層を包囲するように設けられたシール部をさらに有し、
    　前記第１透光板の法線方向から見たとき、前記スペーサは前記グレージングチャンネルに重なっており、前記シール部は前記スペーサおよび前記グレージングチャンネルに重なっている、請求項１６に記載のスマートウィンドウ。     A spacer provided between the electrochromic element and the second translucent plate and defining a thickness of the intermediate layer;
    A glazing channel disposed so as to surround a peripheral portion of the first light-transmitting plate, a peripheral portion of the electrochromic element, and a peripheral portion of the second light-transmitting plate;
    Further comprising
    The electrochromic device further includes a seal portion provided so as to surround the electrolyte layer,
    The smart window according to claim 16, wherein the spacer overlaps the glazing channel and the seal portion overlaps the spacer and the glazing channel when viewed from the normal direction of the first light transmission plate.
  18. 　前記エレクトロクロミック素子と前記第２透光板との間に設けられ、前記中間層の厚さを規定するスペーサと、
    　前記第１透光板の周縁部、前記エレクトロクロミック素子の周縁部および前記第２透光板の周縁部を囲むように配置されたグレージングチャンネルと、
    をさらに備え、
    　前記エレクトロクロミック素子は、前記電解質層を包囲するように設けられたシール部をさらに有し、
    　前記第１透光板の法線方向から見たとき、前記スペーサは前記グレージングチャンネルに重なっており、前記シール部は前記グレージングチャンネルに重なっており、且つ、前記スペーサよりも内側に位置している、請求項１６に記載のスマートウィンドウ。     A spacer provided between the electrochromic element and the second translucent plate and defining a thickness of the intermediate layer;
    A glazing channel disposed so as to surround a peripheral portion of the first light-transmitting plate, a peripheral portion of the electrochromic element, and a peripheral portion of the second light-transmitting plate;
    Further comprising
    The electrochromic device further includes a seal portion provided so as to surround the electrolyte layer,
    When viewed from the normal direction of the first light-transmitting plate, the spacer overlaps the glazing channel, and the seal portion overlaps the glazing channel and is located on the inner side of the spacer. The smart window according to claim 16.
  19. 　第１透光板と、
    　前記第１透光板に所定の間隙を介して対向するように配置された第２透光板と、
    をさらに備え、
    　前記エレクトロクロミック素子は、前記第１透光板と前記第２透光板との間に配置されており、
    　前記第１透光板と前記エレクトロクロミック素子との間に所定の厚さの第１中間層が位置し、前記エレクトロクロミック素子と前記第２透光板との間に所定の厚さの第２中間層が位置する、請求項１２に記載のスマートウィンドウ。     A first translucent plate;
    A second light transmissive plate disposed to face the first light transmissive plate with a predetermined gap therebetween;
    Further comprising
    The electrochromic element is disposed between the first light transmitting plate and the second light transmitting plate,
    A first intermediate layer having a predetermined thickness is positioned between the first light-transmitting plate and the electrochromic element, and a second layer having a predetermined thickness is disposed between the electrochromic element and the second light-transmitting plate. The smart window of claim 12, wherein the intermediate layer is located.
  20. 　前記エレクトロクロミック素子は、前記第１透光板側の最表面および前記第２透光板側の最表面に位置する一対の反射防止膜を含む、請求項１９に記載のスマートウィンドウ。 The smart window according to claim 19, wherein the electrochromic element includes a pair of antireflection films located on an outermost surface on the first light transmitting plate side and an outermost surface on the second light transmitting plate side.
  21. 　前記第１透光板と前記エレクトロクロミック素子との間に設けられ、前記第１中間層の厚さを規定する第１スペーサと、
    　前記エレクトロクロミック素子と前記第２透光板との間に設けられ、前記第２中間層の厚さを規定する第２スペーサと、
    　前記第１透光板の周縁部、前記エレクトロクロミック素子の周縁部および前記第２透光板の周縁部を囲むように配置されたグレージングチャンネルと、
    をさらに備え、
    　前記エレクトロクロミック素子は、前記電解質層を包囲するように設けられたシール部をさらに有し、
    　前記第１透光板の法線方向から見たとき、前記第１スペーサおよび前記第２スペーサは前記グレージングチャンネルに重なっており、前記シール部は前記第１スペーサ、第２スペーサおよび前記グレージングチャンネルに重なっている、請求項１９または２０に記載のスマートウィンドウ。     A first spacer provided between the first translucent plate and the electrochromic element and defining a thickness of the first intermediate layer;
    A second spacer provided between the electrochromic element and the second translucent plate and defining a thickness of the second intermediate layer;
    A glazing channel disposed so as to surround a peripheral portion of the first light-transmitting plate, a peripheral portion of the electrochromic element, and a peripheral portion of the second light-transmitting plate;
    Further comprising
    The electrochromic device further includes a seal portion provided so as to surround the electrolyte layer,
    When viewed from the normal direction of the first light transmitting plate, the first spacer and the second spacer overlap the glazing channel, and the seal portion overlaps the first spacer, the second spacer, and the glazing channel. The smart window according to claim 19 or 20, wherein the windows overlap.
  22. 　前記第１透光板と前記エレクトロクロミック素子との間に設けられ、前記第１中間層の厚さを規定する第１スペーサと、
    　前記エレクトロクロミック素子と前記第２透光板との間に設けられ、前記第２中間層の厚さを規定する第２スペーサと、
    　前記第１透光板の周縁部、前記エレクトロクロミック素子の周縁部および前記第２透光板の周縁部を囲むように配置されたグレージングチャンネルと、
    をさらに備え、
    　前記エレクトロクロミック素子は、前記電解質層を包囲するように設けられたシール部をさらに有し、
    　前記第１透光板の法線方向から見たとき、前記第１スペーサおよび前記第２スペーサは前記グレージングチャンネルに重なっており、前記シール部は前記グレージングチャンネルに重なっており、且つ、前記第１スペーサおよび前記第２スペーサよりも内側に位置している、請求項１９または２０に記載のスマートウィンドウ。     A first spacer provided between the first translucent plate and the electrochromic element and defining a thickness of the first intermediate layer;
    A second spacer provided between the electrochromic element and the second translucent plate and defining a thickness of the second intermediate layer;
    A glazing channel disposed so as to surround a peripheral portion of the first light-transmitting plate, a peripheral portion of the electrochromic element, and a peripheral portion of the second light-transmitting plate;
    Further comprising
    The electrochromic device further includes a seal portion provided so as to surround the electrolyte layer,
    When viewed from the normal direction of the first light transmitting plate, the first spacer and the second spacer overlap the glazing channel, the seal portion overlaps the glazing channel, and the first The smart window according to claim 19 or 20, wherein the smart window is located inside a spacer and the second spacer.
PCT/JP2019/008157 2018-03-05 2019-03-01 Electrochromic element and smart window WO2019172133A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020504988A JPWO2019172133A1 (en) 2018-03-05 2019-03-01 Electrochromic elements and smart windows

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-038747 2018-03-05
JP2018038747 2018-03-05

Publications (1)

Publication Number Publication Date
WO2019172133A1 true WO2019172133A1 (en) 2019-09-12

Family

ID=67847173

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/008157 WO2019172133A1 (en) 2018-03-05 2019-03-01 Electrochromic element and smart window

Country Status (2)

Country Link
JP (1) JPWO2019172133A1 (en)
WO (1) WO2019172133A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021066006A1 (en) * 2019-09-30 2021-04-08 パナソニック液晶ディスプレイ株式会社 Electrochromic device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014525607A (en) * 2011-08-26 2014-09-29 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア Transparent conductive oxide electrochromic devices with nanostructures
US20170219906A1 (en) * 2016-02-01 2017-08-03 Heliotrope Technologies, Inc. Electrochromic system containing a bragg reflector and method for controlling photochromic darkening
JP2017187766A (en) * 2016-04-01 2017-10-12 日東電工株式会社 Electrochromic lighting control member, light transmissive conductive film and electrochromic lighting control element

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014525607A (en) * 2011-08-26 2014-09-29 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア Transparent conductive oxide electrochromic devices with nanostructures
US20170219906A1 (en) * 2016-02-01 2017-08-03 Heliotrope Technologies, Inc. Electrochromic system containing a bragg reflector and method for controlling photochromic darkening
JP2017187766A (en) * 2016-04-01 2017-10-12 日東電工株式会社 Electrochromic lighting control member, light transmissive conductive film and electrochromic lighting control element

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021066006A1 (en) * 2019-09-30 2021-04-08 パナソニック液晶ディスプレイ株式会社 Electrochromic device

Also Published As

Publication number Publication date
JPWO2019172133A1 (en) 2021-01-07

Similar Documents

Publication Publication Date Title
US10564506B2 (en) Electrochromic device and method for making electrochromic device
KR101535100B1 (en) Electrochromic smart window and manufacturing method thereof
US10401701B2 (en) Integrated photovoltaic and electrochromic windows
Granqvist et al. Progress in chromogenics: New results for electrochromic and thermochromic materials and devices
US5604626A (en) Photochromic devices
JP6665210B2 (en) Electrochromic device and smart window with electrochromic device
KR101862200B1 (en) Electrochromic glass system, smart windows glass system using the electrochromic glass system and production method of smart windows glass system
US9904142B2 (en) Light-modulating element and smart glass
US20140175281A1 (en) Mulitple controlled electrochromic devices for visible and ir modulation
CN111624829B (en) Colorful electrochromic structure, preparation method and application thereof
KR20090031915A (en) Glass type electrochemical/electrically controllable device with variable optical and/or energetic characteristic
CN114600247A (en) Non-emissive variable transmission device and light emitting device assembly and method of use thereof
CN104880884A (en) Electrochromic intelligent glass and manufacturing method thereof
EP3260914B1 (en) Smart window
EP3004980B1 (en) An electrophoretic solar control device
JP2017509813A (en) Active building windows
WO2019172133A1 (en) Electrochromic element and smart window
JP2018155796A (en) Electrochromic device and dimming window
KR102470079B1 (en) Chromic nanoparticles, discoloring device including the same and display device including the same
JP2020201339A (en) Electrochromic device and smart window
JP2021001994A (en) Electrochromic element and smart window
Balakrishnan et al. Nanostructured electrochromic materials for smart switchable windows
WO2019189194A1 (en) Electrochromic element, smart window, and method for driving electrochromic element
Granqvist Switchable glazing technology: electrochromic fenestration for energy-efficient buildings
CN204694954U (en) A kind of electrochromic intelligent glass

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19763772

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020504988

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19763772

Country of ref document: EP

Kind code of ref document: A1