Thermal insulation device, thermal insulation film and thermal insulation composition

Abstract

The present invention is a heat shielding device (101) having a heat shielding film (10) containing particles that absorb infrared rays to generate electrons and holes, and an acceptor that receives electrons or holes from the particles, and a charge carrier selected from the electrons and holes is released from the heat shielding film (10) to the outside of the device. The heat shielding device (101) can function as a "heat dissipating" device. The heat shielding film (10) can be a single layer or a multilayer film.

Description

Technical Field

[0001] This invention relates to heat insulation devices, heat insulation films, and heat insulation compositions that use infrared-absorbing particles. Background Technology

[0002] Infrared-absorbing particles (hereinafter sometimes referred to as "infrared absorbing particles") have been proposed for use in heat insulation applications. For example, Patent Document 1 discloses a heat insulation composition comprising tin-doped indium tin oxide (ITO) particles and a transparent resin. Patent Document 2 discloses a heat insulation composition comprising infrared absorbing particles, silica particles, and polymer emulsion particles. In Patent Document 2, in addition to ITO, antimony-doped tin oxide (ATO) and zinc oxide are disclosed as materials constituting the infrared absorbing particles. The heat insulation composition comprising infrared absorbing particles is suitable for suppressing incoming heat while allowing a portion of the incident light to pass through. The heat insulation composition is coated onto a substrate such as a glass plate or resin film to form a heat insulation film, which is then used together with the substrate as a heat insulation device.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2016 / 185951

[0006] Patent Document 2: Japanese Patent Application Publication No. 2011-181636 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] Improvements to heat-insulating compositions and materials containing infrared-absorbing particles are primarily aimed at increasing transmittance in a specified wavelength range, particularly the visible region, while suppressing incoming infrared radiation. Patent documents 1 and 2 also attempt to improve compositions based on essentially the same viewpoint: improving wavelength selectivity.

[0009] This invention, from a novel perspective, aims to improve heat insulation devices that utilize infrared-absorbing particles. Another object of this invention is to provide heat insulation films and compositions suitable for such heat insulation devices.

[0010] Methods for solving problems

[0011] In existing thermal insulation devices that use infrared-absorbing particles, a portion of the energy absorbed by the particles flows into the side where infrared radiation should be limited, such as the indoor side, through heat conduction such as radiation.

[0012] The inventors derived a new idea, namely, to suppress the energy absorbed by infrared absorbing particles from being released as heat to the side where energy inflow should be restricted, and based on this, they conducted repeated research, thus completing the present invention.

[0013] This invention provides a heat insulation device that blocks at least a portion of irradiated infrared radiation, wherein...

[0014] A heat-insulating film comprising particles that absorb the infrared radiation to generate electrons and holes, and acceptors that receive the electrons or holes from the particles.

[0015] At least a portion of the charge carriers selected from the electrons and holes are released from the heat insulation film to the outside of the heat insulation device.

[0016] In addition, the present invention provides a heat insulation film that blocks at least a portion of the irradiated infrared rays, wherein,

[0017] It includes electron and hole particles generated by absorbing the infrared radiation, and an acceptor capable of receiving the electron or hole from the particles.

[0018] The heat insulation film i) comprises a charge generating layer containing the particles and a charge receiving layer containing the acceptors, wherein the charge generating layer and the charge receiving layer are in contact with each other; or

[0019] ii) is a monolayer membrane containing the particle and the acceptor.

[0020] Furthermore, the present invention provides a heat-insulating composition for forming a heat-insulating film, wherein,

[0021] It includes particles that absorb infrared radiation to generate electrons and holes, and acceptors capable of receiving the electrons or holes from the particles.

[0022] The heat insulation composition iii) comprises a first composition containing the particles and a second composition containing the acceptor; or

[0023] iv) is a composition comprising the particle and the acceptor.

[0024] Invention Effects

[0025] According to the present invention, a novel device suitable for suppressing the release of energy absorbed by infrared-absorbing particles as heat can be provided. In the present invention, at least a portion of the charge carriers generated by the absorption of infrared radiation move to acceptors and are further released to the outside of the device, thereby suppressing recombination, resulting in the suppression of thermal energy release. According to the present invention, membranes and compositions suitable for manufacturing the device can be provided. Attached Figure Description

[0026] Figure 1A This is a schematic diagram illustrating the temperature rise of a heat absorber caused by infrared radiation without the use of a heat insulation device.

[0027] Figure 1B This is a schematic diagram illustrating the mechanism of heat insulation using conventional devices.

[0028] Figure 1C This is a schematic diagram illustrating the mechanism of heat insulation using another conventional device.

[0029] Figure 1D This is a schematic diagram illustrating the heat insulation mechanism of the device utilizing the present invention.

[0030] Figure 2A This figure shows a cross-section of one embodiment of the device of the present invention together with an overview of the conductive portion.

[0031] Figure 2B For illustrative purposes Figure 2A A diagram illustrating an example of charge carrier release in the device shown.

[0032] Figure 3 This figure shows a cross-section of another embodiment of the device of the present invention together with an overview of the conductive part.

[0033] Figure 4 This figure shows a cross-section of the device of the present invention along with an overview of the conductive portion, in another embodiment.

[0034] Figure 5 This diagram shows a cross-section of the photoelectric conversion device together with the circuitry connected to the device.

[0035] Figure 6 This figure shows a cross-section of the device of the present invention along with an overview of the conductive portion, in another embodiment.

[0036] Figure 7 This figure shows a cross-section of the device of the present invention along with an overview of the conductive portion, in another embodiment.

[0037] Figure 8 An example of a result obtained to determine the relaxation time excited by local surface plasmons.

[0038] Figure 9 A diagram (left) showing the composite particles formed by the binding of infrared absorbing particles with acceptors, and a diagram (right) illustrating the separation of charges generated in the composite particles during infrared irradiation.

[0039] Figure 10 The figure illustrates an application example of the device of the present invention.

[0040] Figure 11 The figure illustrates another application example of the device of the present invention.

[0041] Figure 12 The figure illustrates another application example of the device of the present invention.

[0042] Figure 13 A diagram illustrating an example of temperature change in the device of the present invention.

[0043] Figure 14 A figure illustrating an example of the intensity change of the absorption spectrum accompanying the fading reaction of methylene blue caused by charge carriers supplied by the heat insulation film.

[0044] Figure 15 The graph shows the results obtained by measuring the time-varying intensity of the absorption peak of methylene blue using a heat-insulating film as a laminated film (CuS / CdS) and a heat-insulating film as a monolayer mixed film (CuS-CdS mixed film). Detailed Implementation

[0045] In this specification, "infrared radiation" refers to electromagnetic waves with wavelengths ranging from 0.7 μm to 1000 μm. "Semiconductor" includes not only conventional semiconductors but also half-metals and degenerate semiconductors. Half-metals are materials with a band structure in which the lower portion of the conduction band and the upper portion of the valence band slightly overlap across the Fermi level due to strain in the crystal structure, interlayer interactions, etc. "Degenerate semiconductors" are materials in which the Fermi level is located in the conduction or valence band through doping. "Nanoparticles" refer to particles with a minimum diameter of less than 1 μm, for example, in the range of 0.1 nm or more but less than 1 μm. Nanoparticles typically refer to particles with a maximum size of 5 μm or less, further in the range of 3 nm to 2 μm. It should be noted that the "minimum diameter" is determined by the minimum size passing through the particle's center of gravity, and the "maximum size" is determined by the longest line segment that can be set within the particle. "Functional group" is used as a term that also includes halogen atoms. "Charge carriers" are electrons and / or holes. The "main surface" of a membrane is the membrane surface that extends in a direction orthogonal to the thickness direction of the membrane.

[0046] In a photoelectric conversion device, at least a portion of the charge carriers generated in the photoelectric conversion section are supplied to a conductive section, which, together with the device, constitutes a circuit including at least one of an inverter, a storage device, a voltmeter, and an ammeter. In contrast, in this invention, the external location to which at least a portion of the charge carriers generated in the membrane is released may not correspond to the conductive section that constitutes the aforementioned circuit together with the heat insulation device. The external location to which the charge carriers are released may be anything other than the circuit including at least one of the inverter, the storage device, the voltmeter, and the ammeter. In one embodiment of the invention, the heat insulation device is connected to a conductive section other than the circuit including at least one of the inverter, the storage device, the voltmeter, and the ammeter, and releases at least a portion of the charge carriers to that conductive section.

[0047] The external environment to which charge carriers are released is not limited to a solid. The external environment can contain gas or liquid. The insulating film can have a main surface exposed to the gas or liquid. In contrast, in a photoelectric conversion device, the two main surfaces of the photoelectric conversion film, which performs the power generation function, are in contact with the layer that carries the charge carriers.

[0048] One way charge carriers are released to the outside of the device is through conduction to the outside, but it is not limited to this. At least a portion of the charge carriers can be released by oxidizing or reducing chemical species outside the device at the surface of the device. In other words, the release process of charge carriers can be a process in which the amount of charge carriers decreases as chemical species outside the device are oxidized or reduced. This reaction typically takes place at the interface between the insulation device and the outside, for example on the main surface of the insulation film that is exposed.

[0049] Charge carriers can be released by conduction alone, by oxidation or reduction reactions alone, or by a combination of reactions and conduction. In one aspect of the invention, the external environment to which charge carriers are released comprises a first external environment that is a gas or liquid and a second external environment that is a solid. At least a portion of the charge carriers selected from either electrons or holes is released by oxidation or reduction of a chemical species of the first external environment, and at least a portion of the charge carriers selected from either electrons or holes is released by conduction to the second external environment.

[0050] The aforementioned external component can be a conductive part of a solid that can have a ground (GND) potential. The ground potential can be the earth potential. The external component can be a circuit that converts the energy of the released charge carriers only into Joule heat. The circuit does not need to have active components such as transistors. The circuit can have only resistors as passive components. The resistor can be a resistive element designed to have a predetermined resistance value, or it can be a resistor other than that. The resistor can be a component designed for a purpose other than applying resistance. Such a component is, for example, a component designed to support a device. The aforementioned circuit can also have only resistive elements as components, except for switching elements.

[0051] At least a portion of the charge carriers released from the membrane are released, for example, to the outside having a ground potential, particularly a ground potential, and their energy is converted into Joule heat in the resistor, for example.

[0052] The thermal insulation device may also include a conductive portion for releasing charge carriers to the outside. The conductive portion inside the device may include, for example, at least one selected from conductive wires and connection terminals for connecting to external conductive portions. The conductive portion included in the thermal insulation device can be electrically connected to an external circuit, which is any circuit other than one of an inverter, an energy storage device, a voltmeter, and an ammeter.

[0053] The conductive part may have a switching element. The switching element can be a manual element or an element configured to be controlled by an external input signal. The switching element can control the electrical connection between the thermal insulation device and the outside world. For example, the switching element can start, stop, or regulate the release of charge carriers from the thermal insulation device by controlling the conduction of charge carriers. By regulating the amount of charge carriers released from the thermal insulation device, the re-radiation of infrared radiation from the thermal insulation device can also be controlled by controlling the recombination of charge carriers.

[0054] The heat insulation device may include electrodes for connecting to conductive parts or to external conductive parts. The electrodes may be light-transmitting electrodes, such as transparent electrodes, or non-light-transmitting electrodes such as metal electrodes.

[0055] The heat insulation device may also include opaque electrodes. The area forming the opaque electrodes may be less than 50% of the area of ​​the device where infrared light is incident. This ratio may be more than 1% and less than 50%, and further more than 5% and less than 50%.

[0056] The conductive part of the heat insulation device may include an electrode that receives charge carriers from the heat insulation film. Furthermore, the conductive part may include a first electrode and a second electrode arranged in a manner that sandwiches the heat insulation film. The first electrode and the second electrode may be a combination of a transparent electrode and a non-transparent electrode, a combination of transparent electrodes, or a combination of non-transparent electrodes. However, the conductive part may only include the first electrode or the second electrode; that is, it may only include one or more electrodes formed by contacting only one of the surfaces of the barrier film.

[0057] The thermal insulation device may also include a resistive element. In the resistive element, at least a portion of the energy of the charge carriers released from the membrane is converted into Joule heat. For example, the conductive portion of the thermal insulation device may include a resistive element designed to have a specified resistance value. In this case, the charge carriers can also be released to the outside of the device via the resistive element within the device.

[0058] In heat insulation devices, the transmittance of the heat insulation film at a wavelength of 700nm can be 24% or higher, 25% or higher, and further 30% or higher, and may also be 40% or higher depending on the situation. The transmittance of the heat insulation film at a wavelength of 600nm can be 18% or higher, 20% or higher, and further 30% or higher, and may also be 40% or higher depending on the situation.

[0059] In a heat insulation device, at least 50% of the light-receiving area where infrared radiation is incident can be a light-transmitting area. In this light-transmitting area, at least a portion of visible light is transmitted. The proportion of the light-transmitting area can be 50% or more, further 70% or more, and particularly 95% or more. The light-transmitting area can be an area where at least a portion of the visible light incident along with the infrared radiation is transmitted. A heat insulation film can be disposed in the light-transmitting area. Metal components such as connecting terminals, non-transparent electrodes, etc., can be disposed in non-light-transmitting areas outside the light-transmitting area.

[0060] In a heat insulation device, the heat insulation film may comprise a charge-generating layer containing particles that absorb infrared radiation and generate electrons and holes, and a charge-receiving layer containing acceptors, wherein the charge-generating layer and the charge-receiving layer may be in contact with each other. In the heat insulation device of the present invention, the heat insulation film may be a single-layer film comprising the aforementioned particles and acceptors. The heat insulation film may be formed on a substrate directly or in between other films. An example of other films is an electrode, particularly a transparent electrode.

[0061] The heat insulation device may also include an adhesive layer for fixing the heat insulation device. The heat insulation device may also include a first light-transmitting substrate and a second light-transmitting substrate disposed separately from each other, with a heat-insulating film disposed on the surface of the first light-transmitting substrate on the second light-transmitting substrate side and / or on the surface of the second light-transmitting substrate on the first light-transmitting substrate side.

[0062] Particles that absorb infrared radiation to generate electrons and holes can include materials capable of absorbing infrared radiation through localized surface plasmon resonance. These particles can be inorganic.

[0063] Hereinafter, embodiments of the present invention will be further described with reference to the accompanying drawings; however, the following description is not intended to limit the present invention to the specific embodiments. In the drawings, the same reference numerals are used to denote the same components and parts, and repeated descriptions are omitted. Unless there is obvious contradiction, matters described with reference to one drawing may also be applied to the manner shown in other drawings.

[0064] [Using the device for heat insulation]

[0065] like Figure 1A As shown, infrared radiation 400 radiated from heat source 200 reaches heat absorber 300, causing the temperature of heat absorber 300 to rise by ΔT. O .exist Figure 1B In this configuration, a heat insulation device 500 with infrared absorption characteristics is disposed between the heat source 200 and the heat absorber 300. The heat insulation device 500 allows a portion of the infrared radiation 400 to pass through and absorbs a portion of it. The heat insulation device 500 can, to a certain extent, suppress the temperature rise ΔT of the heat absorber 300. A (ΔT A <ΔT O However, the infrared radiation 400 absorbed by the heat insulation device 500 is re-radiated from the heat insulation device 500 in the form of infrared radiation 410 through radiation, etc., and a portion of it reaches the heat absorber 300. It should be noted that the infrared radiation is also re-radiated from the heat insulation device 500 towards the heat source 200, but in Figure 1B The illustration of infrared radiation directed towards the heat source 200 is omitted. This is in... Figure 1C and Figure 1D The same applies to China.

[0066] exist Figure 1C In this configuration, instead of the heating device 500, a heat insulation device 600 is provided to enhance the infrared reflection characteristics of the device 500. In this case, the temperature rise ΔT of the heat absorber 600 can be further suppressed. R (ΔT R <ΔT A However, the infrared radiation 420 reflected by the insulation device 600 can sometimes hinder temperature reduction in the heat source 200 or in a highly enclosed space containing the heat source 200. Sometimes, the heat source 200, located in a highly enclosed space, is an artificial heat source, such as an industrial furnace. Even in poorly enclosed spaces, strong reflected infrared radiation 420 can have undesirable effects on the surrounding environment. An example of such infrared radiation 420 is reflected sunlight that is reflected off the exterior walls of a building and reaches adjacent buildings.

[0067] Figure 1D The heat insulation device 100 of this type illustrates discharges a portion of the energy of the absorbed infrared radiation to the outside in the form of charge carriers. Therefore, it suppresses the temperature rise (ΔT) of the heat absorber 300 caused by the re-radiated infrared radiation 410. I <ΔT A By using the heat insulation device 100, the suppression of infrared re-emission can be implemented without relying on an increase in infrared radiation reflected from the device 100. At least a portion of the charge carriers generated by absorbing a portion of the energy of the infrared radiation 400 are released, for example, through conduction to an external conductive portion. Unlike the release of energy from reflected light, the release destination can be easily controlled as a result of the release of charge carrier energy. As described above, charge carriers can also be released, for example, by participating in a chemical reaction on the surface of the heat insulation device 100.

[0068] [Structure of the device]

[0069] exist Figure 2A In the illustrated configuration, the heat insulation device 101 includes a substrate 5 and a heat insulation film 10 formed on the substrate 5. One of the main surfaces of the heat insulation film 10 is an exposed surface, in contact with external gas. The heat insulation film 10 includes infrared absorbing particles that absorb incident infrared radiation to generate electrons and holes, and acceptors capable of receiving electrons or holes as charge carriers from the infrared absorbing particles. The heat insulation device 101 includes an electrode 8 disposed in contact with a portion of the heat insulation film 10. The electrode 8 is formed on the periphery of the surface of the heat insulation film 10. The electrode 8 may be, for example, a metal film, which is substantially opaque, but may also be a transparent film. One end of a conductive portion 11 is connected to the electrode 8. The other end of the conductive portion 11 is connected to a charge carrier release destination 19. The release destination 19 is a charge receiving portion located outside the device. The conductive portion 11 has a switching element 12 between the electrode 8 and the release destination 19.

[0070] refer to Figure 2B right Figure 2A An example of charge carrier release in this manner will be illustrated. In this example, electrons generated in the heat insulation film 10 reduce external chemical species 70 on the main surface of the heat insulation film 10, resulting in their release from the heat insulation device 101. In this example, the heat insulation film 10 acts as a photocatalyst, promoting the reaction of chemical species 70. On the other hand, holes are led out to the release destination 19 through the electrode 8 and the conductive part 11. However, Figure 2BThe release of charge carriers shown is just one example of the many ways in which charge carriers can be released. The release of charge carriers can occur through chemical reactions involving the redox reaction of charge carriers with external chemical species, the export of charge carriers to the outside, or a combination thereof. Reactions such as the oxidation of external chemical species can be accompanied by the decomposition or modification of that chemical species.

[0071] The release destination 19 can be a ground wire, particularly a ground wire; however, it may not be a ground wire as long as it can provide a specified potential. The specified potential can be either ground potential or ground potential. The release destination 19 can be, for example, a window frame or a car body. They can function fully as ground wires even without grounding. Depending on the opening and closing of the switching element 12, the electrode 8 is disconnected from or connected to the release destination 19, for example, which is a ground wire. The switching element 12 can be a manual element or an element whose opening and closing can be controlled by a switch control unit (controller) (not shown). It should be noted that the switching element 12 is not mandatory. In the absence of the switching element 12, the electrode 8 is directly connected to the release destination 19 via the conductive part 11, and its potential is, for example, fixed at a ground potential.

[0072] The conductive part 11 may be a conductive wire, but is not limited to it; it may be a conductive adhesive, solder, conductive component, etc., or may be composed of multiple of these. Conductive adhesives and solders are used, for example, to fix the conductive wire to the electrode. The conductive component may be a connecting terminal for connecting the conductive wire to the electrode, or it may be a component for fixing the entire device. The connecting terminal for connecting the conductive wire to the electrode may be a known terminal for supplying power to an antenna for vehicle glass. Such connecting terminals are disclosed in Japanese Patent Application Publication No. 2001-313513 and Japanese Patent Application Publication No. 2000-151247, etc. The connecting terminal may be electrically connected to the heat insulation device 101 simply by physically pressing in an external conductive wire. As a component for fixing the entire device, a component for supporting the periphery of the device while placing it inside a window frame can be exemplified.

[0073] The conductive part 11 can be pre-installed on the heat insulation device 101 or on the outside of the heat insulation device 101. The conductive part pre-installed on the heat insulation device 101 can be connected to the external conductive part to form the conductive part 11 as a whole.

[0074] The heat insulation device 101 has a light-receiving area capable of receiving incident light 50 containing infrared radiation. The light source of the incident light 50 can be the sun or an artificial light source. The artificial light source includes a high-temperature heat source, such as a high-temperature furnace. The light-receiving area includes a translucent area 41 in which at least a portion of the visible light contained in the incident light 50 is transmitted, and a non-translucent area 42 in which the visible light contained in the incident light 50 is substantially not transmitted. In the non-translucent area 42 of the heat insulation device 101, an electrode 8 made of metal blocks the transmission of the incident light 50. The ratio of the translucent area 41 in the entire light-receiving area can be 50% or more, 70% or more, or further 90% or more. The visible light transmittance in the translucent area 41 is, for example, 20% or more, or further 30% or more.

[0075] In the heat insulation device 101, since the substrate 5 is translucent, there is a translucent region 41. When the substrate 5 is opaque, the entire light-receiving area becomes an opaque region 42. In this case, the device 101 is configured such that the heat insulation film 10 is located closer to the incident light side than the substrate 5. However, in this case, it is also preferable that the opaque electrode 8 disposed on the light-receiving side is formed only within the range limited by the light-receiving region, specifically in a region less than 50%, less than 30%, and further less than 10% of the light-receiving region. The region where the opaque electrode 8 is formed can be more than 1%, more than 3%, and further more than 5% of the light-receiving region.

[0076] like Figure 3 and Figure 4 As shown, the heat insulation devices 102 and 103 can replace electrode 8 by having a transparent electrode 3, or have both electrode 8 and transparent electrode 3. Figure 3 In the heat insulation device 102 shown, a transparent electrode 3 is formed between the heat insulation film 10 and the light-transmitting substrate 5. A portion of the surface of the transparent electrode 3 becomes an exposed area 31 not covered by the heat insulation film 10. The exposed area 31 is used as a connection area with the conductive part 11. The connection between the transparent electrode 3 and the conductive part 11 can be implemented in the same way as the connection between the electrode 8 and the conductive part 11.

[0077] Thermal insulation devices 101 and 102 are connected to release destination 19 via switching element 12. Conversely, thermal insulation device 103 forms part of circuit 20 with resistor 13. Alternatively, conductive portions forming part of circuit 20 exist outside thermal insulation device 103. Resistor 13 can be a passive element designed to display a specified resistance value, or it can be a resistor not designed to be passive. When resistor 13 is present outside the device, circuit 20 is formed by connecting the two conductive portions 11 of thermal insulation device 103 to the ends of resistor 13.

[0078] As shown in the figure, circuit 20 may not be connected to either the inverter or the energy storage device. Circuit 20 may not be connected to the measuring device that functions as an ammeter and / or voltmeter. Circuit 20 may also not include a power source. The same applies to the conductive part 11. In other words, charge carriers are released to the release destination 19 or converted into heat energy in the resistor 13 without passing through any of the inverter, energy storage device, ammeter, and voltmeter.

[0079] In the heat insulation devices 101, 102, and 103, the heat insulation film 101 has a main surface exposed to the outside. The exposed main surface may be more than 50% and further more than 70% of its area exposed to the outside. The outside that the exposed main surface contacts may be a gas phase or a liquid phase.

[0080] In heat insulation devices 101 and 102, charge carriers generated within the heat insulation film 10 can be released to the outside through participation in a chemical reaction, or released to a release destination 19 via electrode 3 or electrode 8 and conductive part 11. This release significantly reduces the amount of electrons and holes recombining within the device. This suppression of recombining leads to suppression of heat radiated from the device again, in other words, suppression of the temperature rise of the device itself. It should be noted that in heat insulation device 103, the charges generated within the heat insulation film 10 recombine in the resistance 13 outside the device, generating Joule heat. However, in this case, the amount of electrons and holes recombining within the device is also significantly reduced, and the heat released from the device 103 itself is suppressed.

[0081] Therefore, compared to conventional heat-insulating films that directly absorb infrared radiation, heat re-radiated in the form of infrared radiation is suppressed in heat-insulating devices 101, 102, and 103. For example, by using heat-insulating devices in building materials, heating of buildings, roads, etc., can be suppressed, helping to reduce the so-called heat island phenomenon. Heat-insulating devices can also be used to suppress heating of electronic devices such as LED displays that emit infrared radiation, and heating of light sources such as headlights that emit infrared radiation. In these light-emitting bodies, the reduction in luminous efficiency can also be suppressed. Heat-insulating devices may also contain light sources that include light in the infrared region.

[0082] Although it was to illustrate the way charge is released... Figures 2A to 4 While simplified, the heat insulation devices 101-103 may also include components not shown. For example, heat insulation devices 101 and 102 may include two or more electrodes 8 disposed separately on the heat insulation film 10, and may be connected to two or more release destinations 19 via two or more conductive parts 11. The same applies to heat insulation device 103.

[0083] Here, refer to Figure 5A typical photoelectric conversion device will be described. In circuit 120 connected to photoelectric conversion device 110, charge / discharge controller 115, inverter 118, and load 113 are connected to each other via conductive line 111, and controller 115 is further connected to battery 116. It should be noted that in circuit 120, the wiring between devices 113, 115, 116, and 118 is simplified and represented by a single line. If load 113 is a DC load, inverter 118 is not required, but battery 116 is still provided in this case. When circuit 120 is connected to a power system facing a power company, battery 116 can be omitted, but a power conditioner with inverter function is required between photoelectric conversion device 110 and the power system. Unlike circuit 20 illustrated above, at least one of inverter and energy storage device is provided in circuit 120. In the laboratory, to understand the characteristics of photoelectric conversion device, measuring devices such as voltmeters are also connected to the photoelectric conversion device. Unlike the heat insulation device illustrated above, the photoelectric conversion device is connected to at least one of the inverter, energy storage device, voltmeter, and ammeter.

[0084] The photoelectric conversion device 110 has, in sequence, a transparent electrode 153, an electron transport layer 157, a power generation layer 151, a hole transport layer 159, and a back electrode 158 on a light-transmitting substrate 155. The back electrode 158 is also a reflective layer, used to extract current and confine a portion of the incident light 150 within the device. Therefore, unlike the heat insulation devices 101-103, in order to improve photoelectric conversion efficiency, in the photoelectric conversion device 110, the two electrodes 155 and 158 are typically formed substantially over their entire area, with no light-transmitting area, or if present, a very limited area. Furthermore, unlike heat insulation devices that may only have a single layer of electrode 3 or electrode 8 (see [reference]...), this is a significant improvement. Figure 2A and Figure 3 In the photoelectric conversion device 110, electrodes 153 and 158 of the power generation layer 151 need to be divided into multiple layers and sandwiched between them.

[0085] In the photoelectric conversion device 110, the two main surfaces of the power generation layer 151 are completely covered by adjacent layers 157 and 159 and are not exposed to the outside.

[0086] As described above, it can be understood that the heat insulation devices 101 to 103 have a heat insulation film 10 as an infrared absorbing film, and can also be connected to the outside of the device in a manner that makes at least one of the group consisting of v) and vi) below true.

[0087] Based on these embodiments, a method of using an infrared absorbing device as a heat insulation device can be understood. The infrared absorbing device includes an infrared absorbing film comprising particles that absorb infrared rays and generate electrons and holes, and acceptors that receive electrons or holes from the particles. In the method of use, the infrared absorbing device is configured in such a manner that at least one of the following (v) to (vii) is formed.

[0088] v) At least a portion of the charge carriers in the electrons and holes generated in the infrared absorption film by infrared irradiation are released by oxidizing or reducing chemical species outside the infrared absorption device, wherein the outside of the infrared absorption device is in contact with the main surface of the infrared absorption film and is in the gas or liquid phase.

[0089] vi) At least a portion of the electrons and holes generated in the infrared absorption film by infrared irradiation recombine outside the infrared device, wherein the outside of the infrared device is a circuit excluding at least one of an inverter, a storage device, a voltmeter, and an ammeter.

[0090] vii) Selected at least a portion of the charge carriers in the electrons and holes generated in the infrared absorption film by infrared irradiation are released to the outside of the infrared device having a ground potential.

[0091] However, as mentioned above, the device itself can have resistive elements. In this case, in vi), electrons and holes recombine not only outside the device but also inside the device, generating Joule heating. In vi), the device does not have any of the following external components: an inverter, an energy storage device, a voltmeter, or an ammeter.

[0092] Return to Figure 2A , Figure 2B , Figure 3 and Figure 4The relationship between the opening and closing of the switching element 12 and re-radiation will be explained. If the switching element 12 is closed, the amount of electrons and holes recombining within devices 101-103 is significantly reduced, and the heat re-radiated from devices 101-103 is suppressed. If the switching element 12 is opened, the amount of charge released to the outside decreases, resulting in an increase in the temperature of the heat insulation film 10 and an increase in the heat released from the heat insulation film 10. When the heat insulation device is used as a window, there may be situations where heat entering from the outside should be suppressed in summer. In this case, it is appropriate to close the switching element 102. On the other hand, there are situations such as winter when heat loss from the indoors to the outside is undesirable. In this case, it is appropriate to keep the switching element 102 open. The switching element 102 can be operated manually or automatically controlled by a controller. Inputs such as the temperature detected by indoor and outdoor temperature sensors and the light intensity detected by an outdoor light sensor can be given to the controller.

[0093] The heat insulation film 10 can be a single-layer film or a multi-layer film composed of multiple layers. Figure 6 and Figure 7 An example of a heat insulation device with multiple layers of heat insulation film is shown. In heat insulation devices 105 and 106, heat insulation film 10 has a charge generating layer 1 and a charge receiving layer 2. The charge generating layer 1 contains particles that absorb infrared radiation and generate electrons and holes. The charge receiving layer 2 contains acceptors capable of receiving electrons or holes from the particles. The positions of the charge generating layer 1 and the charge receiving layer 2 may be reversed as shown in the figure. It should be noted that... Figure 6 The example shown is a release destination 19 as the ground wire.

[0094] like Figure 6 and Figure 7 As shown, the heat insulation device may include only a single charge receiving layer or two or more charge receiving layers. In the latter case, a charge receiving layer for receiving electrons can be arranged on one side and a charge receiving layer for receiving holes can be arranged on the other side, sandwiching the charge generating layer. However, the heat insulation device can function fully even with only a single charge receiving layer for receiving electrons or holes. Furthermore, although not shown, the heat insulation device may also be... Figure 2A The structure shown directly connects the heat-insulating film 10 to the conductive part 11 without the electrode 8. Alternatively, the heat-insulating device may include an electron transport layer or a hole transport layer between the heat-insulating film and the electrode. For example, the electron or hole transport layer may be disposed between the charge receiving layer and an electrode such as a transparent electrode or a metal electrode.

[0095] [Heat insulation film]

[0096] The following describes the materials and layers that can form a heat insulation film.

[0097] (Infrared absorbing particles)

[0098] There are no particular restrictions on infrared absorbing particles, as long as they absorb infrared radiation and generate electrons and holes. Infrared absorbing particles can generate charge carriers with higher energies based on Fermi level charge carriers. The infrared absorbing materials that infrared absorbing particles can contain are described below.

[0099] Infrared absorbing materials may contain at least one selected from the group consisting of oxides, phosphides, sulfides, selenides, and tellurides. However, for applications requiring durability such as heat resistance, materials containing oxides are generally suitable. Infrared absorbing materials can be semiconductors or may be doped. Examples of doping include doping with different elements, self-doping, and defect doping.

[0100] The infrared absorbing material is preferably an inorganic material as described above. Such infrared absorbing particles are suitable for use in applications where the heat insulation film reaches high temperatures by absorbing large amounts of infrared radiation. It should be noted that, as mentioned above, there are no particular limitations on the infrared absorbing particles as long as they are particles that absorb infrared radiation and generate electrons and holes; they are not limited to inorganic particles.

[0101] Infrared absorbing materials can include transparent conductive oxides. Examples of transparent conductive oxides include indium tin oxide (ITO), indium aluminum oxide, indium cerium oxide, zinc aluminum oxide, zinc gallium oxide, zinc indium oxide, cadmium indium oxide, cadmium indium oxide, cadmium fluoride oxide, cadmium fluoride oxide, cadmium chloride oxide, cadmium bromine oxide, molybdenum oxide, tin antimony oxide (ATO), tin oxide fluoride oxide (FTO), titanium oxide, gallium oxide, and vanadium oxide.

[0102] Infrared absorbing materials may contain at least one selected from the group consisting of copper sulfide, copper phosphide, copper telluride, copper selenide, ruthenium oxide, rhenium oxide, molybdenum oxide, tungsten oxide, tungsten bronze, and delafossite-type copper oxides, and may also contain copper sulfide and / or tungsten oxide.

[0103] As copper sulfide, examples can be made from CuS or Cu. 2-x S(0<x<1) represents copper sulfide, which, as copper phosphide, can be exemplified by Cu 3-x Copper phosphide, represented by P(0 < x < 1) or CuP, can be exemplified as copper telluride by CuTe or Cu... 2-x Copper telluride, represented by Te (0 < x < 1), can be exemplified as copper selenide by CuSe or Cu. 2-x Se(0<x<1) represents copper selenide.

[0104] Ruthenium oxide can be exemplified by RuO2 or RuO 2-x Ruthenium oxide, represented by (0 < x < 1), can be exemplified as rhenium oxide by ReO2 or ReO2. 2-x Rhenium oxide, represented by (0 < x < 1), can be exemplified as molybdenum oxide by MoO3 or MoO2. 3-x Molybdenum oxide represented by (0 < x < 1), as tungsten oxide, can be exemplified as WO3 or WO4. 3-x (0<x<1) represents tungsten oxide.

[0105] Tungsten bronze is a non-stoichiometric compound obtained by the intrusion of alkali metals or other metal atoms into tungsten oxide in a non-stoichiometric ratio. Specifically, examples include CsxWO3 (0 < x < 1; CWO), LiWO3, LiCsWO3, LiRbWO3, and LiKWO3. Examples of copper oxides of the copper-iron type include CuAlO2, CuGaO2, and CuCrO2.

[0106] Infrared absorbing particles can contain materials capable of absorbing infrared radiation through localized surface plasmon resonance (hereinafter, sometimes referred to as "LSPR-IR absorbing materials"). The presence of LSPRs in LSPR-IR absorbing materials can be determined, for example, by explicitly showing that the wavelength of the absorption peak changes linearly with changes in the refractive index of the surrounding medium. LSPR-IR absorbing materials can be semiconductors. However, LSPR-IR materials are not essential in infrared absorbing particles.

[0107] LSPR-IR absorbing materials can be those with a relaxation time of 1 ns or more excited by local surface plasmon resonances. Materials with this property include, for example, at least one selected from the group consisting of copper sulfide, copper selenide, and cesium tungsten oxide (CWO). However, they are not limited to these materials; appropriate materials can be selected by determining the relaxation time excited by local surface plasmon resonances using time-resolved transient absorption spectroscopy.

[0108] exist Figure 8 The image shows an example of results obtained by determining the relaxation time from localized surface plasmon excitation using time-resolved transient absorption spectroscopy. Figure 8 The absorption spectra are shown at 2.5 nanoseconds (ns), 6 ns, and 12.5 ns after localized surface plasmon excitation. Figure 8 In the absorption spectrum shown, bleaching (negative signal) caused by localized surface plasmon excitation can be confirmed in the near-infrared region. Figure 8In the example shown, the negative signal does not disappear even after 2.5 ns, 6 ns, and further after 12.5 ns, therefore the relaxation time is at least 10 ns. Materials that exhibit such a long relaxation time for active carriers after LSPR excitation, regardless of the wavelength and intensity of the pump light, are suitable as LSPR-IR absorbing materials. It should be noted that time-resolved transient absorption spectroscopy can be applied as a direct method that directly measures the entire duration of the phenomenon.

[0109] It should be noted that, in Figure 8 The results for the determination of copper sulfide are shown in the figure. This determination was performed using a pump-probe method, which uses a chloroform solution of copper sulfide as the sample, a picosecond laser with a wavelength of 1064 nm as the pump light, and a supercontinuum source as the probe light. Details of the laser and probe light are described below.

[0110] Picosecond laser (EKSPLA "PL2210A", repetition rate 1kHz, pulse width 25ps, pulse energy 0.9mJ (wavelength 1064nm))

[0111] Supercontinuum light source (Fianium "SC450", repetition frequency 20MHz, pulse width 50-100ps)

[0112] However, this condition is just one example; in the determination of relaxation time excited from local surface plasmons, appropriate conditions corresponding to the material being studied can be set.

[0113] (Subject)

[0114] Regarding the acceptor, there are no particular restrictions on its type, as long as it can receive electrons or holes from the infrared absorbing particles. The acceptor material contained in the acceptor can be appropriately selected based on the infrared absorbing material contained in the infrared absorbing particles. When the infrared absorbing material is copper sulfide, the acceptor may contain cadmium sulfide. When the infrared absorbing material is cesium-doped tungsten oxide, the acceptor may contain at least one selected from, for example, zinc oxide, titanium oxide, tin oxide, and gallium oxide. When the infrared material is ITO, the acceptor may contain tin oxide. The acceptor can be contained in the form of particles or in the form of a layer. The acceptor can be contained in the same layer as the infrared absorbing particles or in an adjacent layer. Furthermore, the acceptor can be a conductive organic material, such as graphene, carbon nanotubes, graphite, or diamond-like carbon.

[0115] (composite particles)

[0116] Infrared absorbing particles and acceptors can be integrated into composite particles. An example of a composite particle is shown below. Figure 9The composite particle consists of ITO particles surrounded by tin oxide (SnO2) particles. The two types of particles can be physically or chemically bonded. For example... Figure 9 As shown in the right figure, the holes and electrons generated by infrared radiation (represented as "radiative heat" in the figure) refer to the movement of electrons towards the SnO2 particles as acceptors, separating them from the holes remaining in the ITO particles. The charge separation achieved through the use of composite particles is advantageous for suppressing recombination and for the efficient release of charge carriers.

[0117] (Adhesive)

[0118] Barrier films may contain adhesives. Adhesives can impart preferred properties such as flexibility. In addition, adhesives can be sandwiched between particles such as infrared absorbing particles, thereby imparting preferred properties to the film or layer.

[0119] The binder may contain functional groups capable of binding with particles, such as at least one selected from fluorine (F), chlorine (Cl), bromine (Br), iodine (I), cyanide (CN), thiocyanate (SCN), isothiocyanate (NCS), hydroxide (OH), mercapto (SH), carbonyl (CO), amino (NR3), nitrosyl (NO), nitrosyl (NO2), phosphine (PR3), carbene (R2C), and pyridine (NC5H5). The functional group may be anionic, such as F... - Anionic functional groups that bind to nanoparticles in various forms. Here, R can be any organic group or hydrogen atom. As can be understood from the above examples, functional groups that can bind to particles can be metal atoms or other functional groups that can function as ligands for anions.

[0120] The binder can be an inorganic compound or an organic compound. The binder can be an ion containing the functional groups exemplified above or composed of functional groups, or a salt composed of such ions and their counterions. The binder can be a compound having multiple of the above functional groups, such as hydrazine (H2NNH2), ethylenediamine (H2NCH2CH2NH2), 1,2-ethylenedithiol (HSCH2CH2SH, EDT), mercaptopropionic acid (HSCH2CH2COOH), acetylacetone (H3CCOCHCOCH3), and aminobenzyl nitrile (NH2C6H4CN).

[0121] The binder preferably comprises, for example, a compound with a molecular weight of 280 or less, further 250 or less, preferably 200 or less, more preferably 100 or less, even more preferably 80 or less, and, where applicable, less than 65. There is no particular limitation on the lower limit of the molecular weight, for example, it is 20 or more, further 30 or more. The use of binders with relatively low molecular weights is suitable for controlling the spacing of nanoparticles within a narrow range, and for controlling the resistance of variable resistivity components, infrared absorption characteristics, etc., within appropriate ranges.

[0122] The amount of binder can be appropriately adjusted according to its type, and is expressed as the ratio of the mass of the binder to the total amount of particles and binder. For example, it can be 1% or more, further 2% or more, particularly 3% or more, and depending on the situation, 5% or more, preferably 8% or more. There is no particular upper limit to this content, but it is 30% or less, further 20% or less.

[0123] The aforementioned binders are suitable for coordination or adhesion to particles. The binder can be a material other than such adhesive compounds. Examples of such compounds include various resins, specifically polyvinyl alcohol, polyvinyl acetal, polyvinylpyrrolidone, carboxymethyl cellulose, acrylic resins, polyvinyl acetate, polyethylene terephthalate, polystyrene, polyethylene, etc. Furthermore, depending on the necessity for film formation, application, etc., organic solvents, conductive polymers, conductive particles, pH adjusters, colorants, thickeners, surfactants, etc., can be used.

[0124] A film or layer containing infrared-absorbing particles and a binder can be formed using a thermal insulation composition via spraying, impregnation, or other methods. In this case, the binder can be ligand-mediated to the particles. This liquid-phase film formation method is suitable for increasing the efficiency and scale of device manufacturing. This method is also well-suited for the fabrication of flexible devices using flexible resin substrates. However, it is not limited to this; the thermal insulation film and the layers constituting it can also be formed using other vapor-phase film formation methods such as sputtering.

[0125] In addition, adhesives can be modified through laser treatment or other processes to function as acceptors.

[0126] (Heat insulation film)

[0127] As described above, the heat insulation film, for example, includes infrared absorbing particles that absorb infrared radiation and generate electrons and holes, and acceptors capable of receiving electrons or holes from the particles. The heat insulation film i) comprises a charge generating layer containing the aforementioned particles and a charge receiving layer containing the aforementioned acceptors, the charge generating layer and the charge receiving layer being in contact with each other, or ii) is a monolayer film containing the aforementioned particles and the aforementioned acceptors. As described above, the heat insulation film is formed as a monolayer film or a multilayer film containing infrared absorbing particles, acceptors, and an adhesive. Furthermore, ii) the monolayer film containing the aforementioned particles and the aforementioned acceptors is formed as iia) a hybrid film in which the aforementioned particles and the aforementioned acceptors are simply mixed and formed into a film, or iib) a film containing the aforementioned particles and the aforementioned acceptors integrated by mutual bonding, more specifically by mutual chemical or physical bonding.

[0128] The light transmittance of the heat insulation film at a wavelength of 700nm can be above 25%, further above 30%, and especially above 50%.

[0129] (Composition for thermal insulation)

[0130] The heat-insulating composition used to form a heat-insulating film can be prepared as a single-liquid or multi-liquid type depending on the composition and materials of the heat-insulating film. For example, the heat-insulating composition includes infrared-absorbing particles that absorb infrared radiation and generate electrons and holes, and acceptors capable of receiving electrons or holes from the particles. The heat-insulating composition iii) has a first composition containing the aforementioned particles and a second composition containing the aforementioned acceptors, or iv) is a composition containing both the aforementioned particles and the aforementioned acceptors. Furthermore, iv) the composition containing the aforementioned particles and the aforementioned acceptors is iva) a mixture obtained by simply mixing the aforementioned particles and the aforementioned acceptors, or ivb) a composition obtained by integrating the aforementioned particles and the aforementioned acceptors through mutual bonding, more specifically chemical or physical bonding. In any case, the adhesive can be prepared as another composition, i.e., for example a third composition.

[0131] [Substrate]

[0132] There are no restrictions on the shape and material of the substrate, as long as it can support the barrier film. The barrier film can be transparent or opaque. Transparent substrates can be glass plates, resin plates, or resin films.

[0133] [Application Example]

[0134] Reference Figures 10-12 Examples of actual product applications will be provided. Figure 10 The multilayer glass shown comprises a pair of spaced-apart glass plates 15 and 25, with an insulating film 10 formed on the surface of an intermediate layer 40 on one of the glass plates 15. The intermediate layer 40 is, for example, an air layer that is isolated from the outside. The intermediate layer 40 can be depressurized or can be a layer containing an inactive gas. The glass plates 15 and 25 can be resin plates.

[0135] Figure 11 The heat insulation sheet shown has a light-transmitting resin sheet 35 and a heat insulation film 10, and also has an adhesive layer 30 covering the heat insulation film 10. The resin sheet 35 can be a flexible sheet. The adhesive layer 30 is formed for bonding the heat insulation sheet to other substrates. Figure 12 The image shows the adhesive layer 30 being adhered to the glass plate 15. An advantage of this application example is that the heat-insulating film can be easily fixed in the desired position.

[0136] exist Figures 10-12 An example using a translucent substrate is shown, but the invention can also be applied to non-translucent substrates. Furthermore, the application location is not limited to the openings where multilayer glass is disposed. For example, the partition walls surrounding an industrial furnace that is heated to a high temperature of approximately 1000°C or higher and emits a large amount of infrared radiation are one location where the aforementioned heat-insulating film is desired. Forming a heat-insulating film at such a high temperature location can also be achieved by coating the aforementioned heat-insulating composition.

[0137] The present invention will be further illustrated below by way of examples, but the following description is not intended to limit the present invention to the specific examples.

[0138] (Example 1)

[0139] A tin oxide film was fabricated on an ITO substrate, which served as a transparent electrode with a pre-formed ITO film, using the sol-gel method. A CdS layer with a thickness of 500 nm was then fabricated on the substrate using RF sputtering.

[0140] Next, a solution for forming the charge-generating layer containing CuS nanoparticles was prepared. 0.246 g of copper acetate and 20 ml of oleylamine were added to a three-necked flask A, and a vacuum was applied while stirring. Flask A was then heated in an oil bath to raise the liquid temperature to 160°C and maintained at this temperature for 1 hour. The heating rate was set to 8°C / min. Meanwhile, 0.096 g of sulfur and 30 ml of 1-octadecene were added to another three-necked flask B. While stirring, the solution was repeatedly evacuated and purged with nitrogen, then nitrogen was introduced to maintain the nitrogen atmosphere. Flask B was then heated in an oil bath to raise the liquid temperature to 160°C to dissolve the sulfur. The heating rate was set to 5°C / min. Flask B was left to stand for 1 hour, then nitrogen was introduced to maintain the nitrogen atmosphere.

[0141] The contents of flask A were transferred to a centrifuge tube. The contents of flask B were then added to the centrifuge tube using a syringe and kept in this state for 10 minutes. The heater was then turned off, and the liquid temperature was allowed to drop to 40°C. Approximately 30 ml of hexane was then added to the centrifuge tube. The solid material was visually confirmed to have dissolved. Then, 30 ml of ethanol was added, and the mixture was centrifuged at 2000 rpm for 5 minutes, collecting the precipitate. The precipitate was then dissolved in 5 ml of octane, followed by another 30 ml of ethanol, and centrifuged again at 2000 rpm for 5 minutes, collecting the precipitate once more. The mass of the precipitate was determined, and based on this, octane was added to a concentration of 200 mg / ml to disperse the copper sulfide nanoparticles, yielding the first ink.

[0142] The first precipitate contains copper sulfide nanoparticles and oleylamine, a compound capable of coordinating with the copper sulfide nanoparticles. Thermogravimetric analysis (TGA) of the precipitate showed that the mass ratio of oleylamine to the total mass of the copper sulfide nanoparticles and oleylamine was 10%.

[0143] Then, 50 μl of the first ink was applied to the CdS layer using a spin coater to obtain a coated film. It should be noted that the concentration of the first ink was adjusted to 50 mg / ml during coating.

[0144] A 200 μl solution (second ink) containing EDT (1,2-ethylenedithiol) was coated onto the film using a spin coater to obtain a thin film that functions as a heat-insulating film. The solvent for this solution was octane, and the concentration of EDT (1,2-ethylenedithiol) was set to 0.3% by mass. Through contact with the second ink, at least a portion of the compound coordinated with the copper sulfide nanoparticles was replaced by oleylamine (first compound) with EDT (1,2-ethylenedithiol) (second compound, binder).

[0145] An additional coating film is formed on the coating film using the same film-forming process as described above with the first ink, and then the second ink is used to perform compound substitution in the same manner as described above. This results in a thick-film charge-generating layer.

[0146] Next, gold is deposited onto a portion of the surface of the charge-generating layer to form a metal electrode. The metal electrode forms a film with a thickness of approximately 300 nm in a region less than 5% of the surface of the charge-generating layer. A conductive wire is then fixed to each of the ITO (transparent electrode) and the metal electrode in the resulting heat insulation device using a conductive adhesive. A 1 kΩ resistor is further connected between the two conductive wires to form an external circuit.

[0147] An experiment was conducted to irradiate the heat insulation device with infrared light while it was connected to an external circuit. Light from an AM1.5 simulated solar source (100mW) was passed through a band-channel filter to irradiate the heat insulation device with only wavelengths above 600nm. A blackbody was placed at the location where the light transmitted through the heat insulation device was absorbed, and the temperature changes of the heat insulation device and the blackbody were measured. The temperature changes were measured with the heat insulation device connected to an external circuit, with the heat insulation device not connected to an external circuit, and with the blackbody directly irradiated without a heat insulation device. The temperature rise over the 10-minute period from the start of irradiation is shown in Table 1.

[0148] [Table 1]

[0149] (Example 1) CuS / CdS

[0150]

[0151] It can be confirmed that when the heat insulation device releases charge to the outside, it can effectively block the incoming infrared rays and also suppress the temperature rise of the heat insulation device itself.

[0152] (Example 2)

[0153] Using hydrazine instead of EDT, at least a portion of the compound coordinated with the copper sulfide nanoparticles was replaced from oleylamine (first compound) with hydrazine (second compound, binder). Otherwise, the insulation device was fabricated in the same manner as in Example 1, and measurements were performed under the same conditions. It should be noted that in Example 2, measurements were also performed with the insulation device connected to a grounding wire instead of an external circuit. This measurement was performed with both the ITO and the metal electrode connected to the grounding wire. The results are shown in Table 2.

[0154] [Table 2]

[0155] (Example 2) CuS / CdS

[0156]

[0157] In Example 2, it was also confirmed that when the heat insulation device releases charge to the outside, it can effectively block the incoming infrared rays and suppress the temperature rise of the heat insulation device itself.

[0158] (Example 3)(Comparative Example 1)

[0159] Ga2O3 nanoparticles were prepared using the same method as previously reported (J.AM.CHEM.SOC.2010, 132, 9250-9252). An octane solution (50 mg / mL) of Ga2O3 nanoparticles was spin-coated onto a glass plate, i.e., an FTO substrate, on which an FTO film as a transparent electrode had been pre-formed, and then cleaned with acetonitrile. This process was repeated twice. Then, an octane solution (50 mg / mL) of CWO nanoparticles was spin-coated onto the Ga2O3 nanoparticle film and cleaned with acetonitrile. This process was repeated five times to prepare a CWO nanoparticle / Ga2O3 nanoparticle laminated film. The resulting laminated film was heated at 450°C for 30 minutes under atmospheric conditions to remove ligands. The calcined laminated film was then calcined at 450°C for 2 hours under a reducing atmosphere (argon atmosphere containing 4% hydrogen) to obtain the heat insulation device of Example 3. In addition, except that the membrane containing Ga2O3 nanoparticles was not provided, the same procedure as in Example 3 was followed to obtain the heat insulation device of Comparative Example 1.

[0160] Using the two heat insulation devices described above, the temperature change of the blackbody and the heat insulation devices was measured 5 minutes after the start of irradiation, similar to Example 2. However, in Example 3, only the grounding wire was connected, while the measurement in the case of external connection was omitted in Comparative Example 1. The results are shown in Table 3. It should be noted that, similar to Examples 1 and 2, the temperature rise was further suppressed in Example 3 by connecting to an external circuit.

[0161] [Table 3]

[0162] (Example 3) CWO / Ga2O3; (Comparative Example 1) CWO

[0163]

[0164] (Example 4)(Comparative Example 2)

[0165] Next, a solution for forming the charge-generating layer containing Cu7S4 nanoparticles was prepared. First, 1.891 g of copper acetate, 1.13 g of 1,3-dibutyl-2-thiourea, and 10 ml of oleylamine were added to a three-necked flask, and nitrogen purging was performed while stirring. Then, the liquid temperature was raised to 80°C using a covered resistance heater and maintained for 1 hour. Next, as the liquid temperature decreased to 40°C, 40 ml of chloroform was slowly added to the three-necked flask to dissolve the solid components.

[0166] The contents of the three-necked flask were transferred to a centrifuge tube. After confirming complete dissolution of the solids within the tube, 40 mL of ethanol was added. The mixture was then centrifuged at 2000 rpm for 10 minutes, and the supernatant was immediately discarded. Next, the precipitate was dissolved in 5 mL of octane, followed by the addition of 30 mL of ethanol. The mixture was then centrifuged again at 2000 rpm for 5 minutes, and the precipitate was collected. The mass of the precipitate was determined, and based on this, octane was added to a concentration of 200 mg / mL to disperse the copper sulfide nanoparticles, yielding the first ink.

[0167] The first precipitate contains copper sulfide nanoparticles and oleylamine, a compound capable of coordinating with the copper sulfide nanoparticles. Thermogravimetric analysis (TGA) of the precipitate showed that the mass ratio of oleylamine to the total mass of the copper sulfide nanoparticles and oleylamine was 10%.

[0168] As described in Example 1, a coating film was formed by spin-coating a first ink onto a CdS layer pre-laminated on an ITO substrate with zinc oxide using a high-frequency sputtering method with a CdS target. Then, a 200 μl solution (second ink) containing EDT (1,2-ethylenedithiol) was coated onto the coating film using a spin coater, resulting in a thin film that functions as a heat-insulating film. An additional coating film was formed on this coating film using the same method as described above with the first ink, and then compound substitution was performed using the second ink in the same manner as described above. This formed a thick charge-generating layer, resulting in the heat-insulating device of Example 4. Furthermore, the heat-insulating device of Comparative Example 2 was obtained by operating in the same manner as in Example 4, except that a CdS layer was not provided.

[0169] Using the two heat insulation devices described above, the temperature change of the blackbody and the heat insulation devices was measured 5 minutes after the start of irradiation, similar to Example 2. However, in Example 4 and Comparative Example 2, the measurement in the case of connection with an external circuit was omitted. The results are shown in Table 4. It should be noted that, similar to Example 1, the temperature rise was further suppressed in Example 4 by connecting to an external circuit.

[0170] [Table 4]

[0171] (Example 4) Cu7S4 / CdS; (Comparative Example 2) Cu7S4

[0172]

[0173] It can be confirmed that, compared with Comparative Examples 1 and 2, which consist only of infrared absorbing particles and do not contain acceptors, the temperature rise of the device was effectively suppressed in Examples 3 and 4.

[0174] (Example 5)

[0175] Except that hydrazine was used instead of EDT, the insulation device was fabricated in the same manner as in Example 4, and measurements were performed under the same conditions as in Example 2. In Example 5, measurements were also performed by connecting the insulation device to an external circuit or grounding wire. The results are shown in Table 5.

[0176] [Table 5]

[0177] (Example 5) Cu7S4 / CdS

[0178]

[0179] It can also be confirmed in Example 5 that when the heat insulation device releases charge to the outside, it can effectively block the incoming infrared rays and also suppress the temperature rise of the heat insulation device itself.

[0180] (Example 6)

[0181] A mixture of copper sulfide (CuS) nanoparticles dissolved in octane at a concentration of 100 mg / mL and CdS nanoparticles dissolved in octane at a concentration of 100 mg / mL (the third ink) was prepared and used as the third ink. Similar to the first ink in Example 1, the third ink also contained oleylamine.

[0182] As described in Example 1, a coating film was formed by spin-coating a third ink onto a CdS layer pre-laminated with zinc oxide onto an ITO substrate using a high-frequency sputtering method with a CdS target. A 200 μl solution containing hydrazine (fourth ink) was then applied to the coating film using a spin coater, resulting in a thin film functioning as an infrared-responsive sensor. The solvent for this solution was octane, and the concentration of hydrazine was set to 0.3% by mass. Through contact with hydrazine, at least a portion of the compound coordinated to the copper sulfide nanoparticles was replaced by hydrazine (second compound, binder) from the oleylamine (first compound) coordinated during nanoparticle synthesis. The heat insulation device was then fabricated in the same manner as in Example 1, and the same measurements were performed. In Example 6, measurements were also performed by connecting the heat insulation device to an external circuit or grounding wire. The results are shown in Table 6.

[0183] [Table 6]

[0184] (Example 6) CuS-CdS hybrid film

[0185]

[0186] In Example 6, which uses a single-layer film containing infrared absorbing particles and acceptor particles, it was also confirmed that when the heat insulation device releases charge to the outside, it can effectively block the incoming infrared rays and suppress the temperature rise of the heat insulation device itself.

[0187] (Example 7)

[0188] ITO nanoparticles were synthesized using the same method as previously reported (Nano letters, 2019, 19, 11, 8149-8154). Then, tin oxide was grown on the surface of the ITO nanoparticles using a seed-mediated growth method to obtain composite particles of ITO and tin oxide. The composite formation was carried out using ITO nanoparticles as a substrate, following previously reported methods, by growing a SnO2 layer (Materials Chemistry and Physics Volume 166, 15 September 2015, Pages 87-94). Then, using the same ink-based film-forming method as in Example 1, but instead of EDT, hydrazine was used as in Example 2, and an ITO / SnO2 film was formed by spin-coating onto a substrate. The same thermal insulation device was then fabricated as in Example 1, and the same measurements were performed. The results are shown in Table 7.

[0189] [Table 7]

[0190] (Example 7) ITO / SnO2 composite particles, (Comparative Example 3) ITO particles

[0191]

[0192] (Example 8)

[0193] For the heat insulation device obtained in the same manner as in Example 1, the temperature change over time under infrared irradiation was investigated. However, the distance from the filter to the heat insulation device was greater than in Example 1. The results are shown below. Figure 13 In the absence of connection to an external circuit ( Figure 13 When the device is "not connected," its temperature reaches a constant level in approximately 4 minutes, with an increase of 0.7°C to 0.8°C. In contrast, in the device connected to an external circuit (with a resistance of 1kΩ), the temperature rises slowly. In this device, it takes approximately 8 minutes for the temperature to reach a constant level, and the increase stops at 0.5°C.

[0194] It should be noted that the transmittance at a wavelength of 700 nm was measured for each heat insulation film, and the results showed that each of the embodiments was at least greater than 24%. Specifically, the transmittance at a wavelength of 700 nm for the heat insulation film of Embodiment 1 (8) was 52%. Regarding the transmittance at a wavelength of 700 nm for the heat insulation films of other embodiments, Embodiment 2 was 50%, Embodiment 3 was 45%, Embodiment 4 was 25%, Embodiment 5 was 83%, Embodiment 6 was 50%, and Embodiment 7 was 90%. It should be noted that the transmittance at a wavelength of 600 nm for the heat insulation film of Embodiment 1 (8) was 67%. Regarding the transmittance at a wavelength of 600 nm for the heat insulation films of other embodiments, Embodiment 2 was 65%, Embodiment 3 was 57%, Embodiment 4 was 20%, Embodiment 5 was 82%, Embodiment 6 was 65%, and Embodiment 7 was 90%.

[0195] (Example 9)

[0196] The extent of the methylene blue fading reaction promoted by charge carriers was evaluated using a barrier device with a CuS / CdS stacked barrier film of Example 2 and a barrier device containing a CuS-CdS mixed monolayer film of Example 6. This evaluation was performed by irradiating the barrier device with infrared light while it was immersed in a pool containing an aqueous solution of methylene blue and measuring the change in absorbance caused by methylene blue. However, this measurement was performed without connecting the electrodes to an external circuit. Similarly, for the pool, light from an AM1.5 simulated solar source (100 mW) was passed through a band-channel filter to irradiate infrared light with wavelengths above 600 nm. The time-varying absorption spectrum of the barrier device containing the CuS-CdS mixed monolayer film up to 5 hours is shown in the figure. Figure 14 In addition, the time-varying intensity of the absorption peaks using two blocking devices is shown in the figure. Figure 15 As shown in these figures, the holes created in the barrier membrane by infrared irradiation generate reactive species such as hydroxyl radicals, leading to the decomposition of methylene blue.

[0197] Industrial availability

[0198] The device of this invention can be used in a wide range of fields as a heat insulation device, i.e., a so-called "heat dissipation" device, which releases a portion of the energy of absorbed infrared radiation out of the device in the form of electric charge. Electric charge is much easier to control in terms of direction and amount of release than heat. This invention is useful as a solution for providing "heat dissipation" technology, and although not particularly limited, this technology can be used, for example, in the placement of openings in buildings and vehicles, around furnaces heated to high temperatures, or to mitigate temperature rise in electronic equipment.

Claims

1. A heat insulation device that blocks at least a portion of irradiated infrared radiation, wherein, have: A heat-insulating film comprising particles that absorb the infrared radiation to generate electrons and holes, and acceptors that receive the electrons or holes from the particles, and Non-transparent electrodes, The area where the electrode is formed is less than 50% of the light-receiving area of ​​the device where infrared light is incident. The heat insulation film has a main surface exposed to gas or liquid. At least a portion of the charge carriers selected from the electrons and holes are released from the heat insulation film to the outside of the heat insulation device.

2. The heat insulation device according to claim 1, wherein, The external circuitry refers to anything other than the circuitry that includes at least one of an inverter, an energy storage device, a voltmeter, and an ammeter.

3. The heat insulation device according to claim 1, wherein, At least a portion of the charge carriers are released by oxidizing or reducing the external chemical species on the main surface.

4. The heat insulation device according to claim 1, wherein, The external environment includes a first external environment and a second external environment, wherein the first external environment is a gas or liquid, and the second external environment is a solid. At least a portion of the electrons and holes are released by oxidation or reduction of the first external chemical species. At least a portion of the other of the electrons and the holes is released through conduction to the second exterior.

5. The heat insulation device according to claim 2, wherein, It also includes a conductive portion for releasing the charge carriers to the outside. The conductive part is electrically connected to the external environment, which is anything other than the circuit.

6. The heat insulation device according to claim 5, wherein, The conductive part has a switching element that controls the electrical connection between the heat insulation device and the outside.

7. The heat insulation device according to claim 5, wherein, The conductive portion includes a first electrode and a second electrode arranged to be sandwiched within the heat insulation film.

8. The heat insulation device according to claim 5, wherein, The conductive part includes a resistive element.

9. The heat insulation device according to claim 1, wherein, The transmittance of the heat insulation film at a wavelength of 700nm is above 24%.

10. The heat insulation device according to claim 1, wherein, The heat insulation film includes a charge generating layer containing the particles and a charge receiving layer containing the acceptors, the charge generating layer and the charge receiving layer being in contact with each other.

11. The heat insulation device according to claim 1, wherein, The particles contain materials capable of absorbing infrared radiation through localized surface plasmon resonance.

12. The heat insulation device according to claim 11, wherein, The particles are inorganic particles.

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