Photothermal electric device, method for manufacturing a photothermal electric device, and array device

Abstract

The present invention provides a photothermal electrical device, a method for manufacturing the photothermal electrical device, and an array device, which can be applied to the field of photothermal-electric integrated devices. The photothermal electrical device includes: an insulating substrate; a patterned metal electrode layer disposed on the insulating substrate; a photocatalyst film layer disposed on the central electrode; a patterned thermoelectric electrode layer disposed on the insulating substrate; wherein, when the photocatalyst film layer is irradiated with light, heat energy is provided to the first ends of the first thermoelectric electrode and the second thermoelectric electrode, so that a thermoelectric potential is generated between the first thermoelectric electrode and the second thermoelectric electrode due to the temperature gradient between the first end and the second end, thereby generating an electrical signal corresponding to the optical signal in the series circuit to achieve light detection, and an electric field is formed on the lower surface of the photocatalyst film layer, whereby the separation efficiency of the photo-generated carriers of the photocatalyst film layer can be effectively improved, thus improving the catalytic ability of the photothermal electrical device.

Description

Technical Field

[0001] The present invention relates to the field of optothermal-electric integrated devices, and particularly to an optothermal-electric device, a method for manufacturing an optothermal-electric device, and an array device. Background Art

[0002] Optothermal-electric detectors are a new type of detection mode based on the optothermal effect and the thermoelectric effect. Their working principle is that a thermoelectric material or a light absorption layer disposed on the surface of the thermoelectric material converts the optical signal to be detected into a temperature difference on both sides of the thermoelectric electrode through the optothermal effect, and then converts the optical signal into an electrical signal through the thermoelectric effect. This self-powered energy conversion process can achieve optical signal detection without a bias voltage assistance. In addition, such detectors can break through the limitation of the bandgap of functional materials in traditional photodetectors on the wavelength to be detected, thereby realizing wide-spectrum detection. For a determined thermoelectric electrode material, improving the optothermal conversion ability of the composite device is of great significance for improving the optical responsivity of the device.

[0003] Thermoelectric photocatalysis technology uses the light energy not fully absorbed by the photocatalyst and the harmful heat on its surface as the heat source of the thermoelectric material, and further converts it into an electrical signal through the thermoelectric effect for improving the photocatalytic efficiency of the photocatalyst. At present, in the thermoelectric photocatalysis system, low-dimensional thermoelectric materials such as nanoparticles, nanorods, and nanosheets are still directly compounded with the catalyst, and the distribution structure difference of the thermoelectric material in the composite system is used to induce a real-time temperature gradient in the thermoelectric material under light illumination, and then enhance the photocatalytic reaction through thermoelectricity. However, in the case of enhancing the photocatalytic reaction through thermoelectricity, there is still a problem of low photocatalytic effect of the device.

[0004] In addition, how to effectively integrate an optothermal-electric detection module and a photocatalytic module on a single device to achieve dual-functional applications still poses a great challenge. Summary of the Invention

[0005] In view of this, the present invention provides an optothermal-electric device, a method for manufacturing an optothermal-electric device, and an array device.

[0006] According to a first aspect of the present invention, there is provided a photothermal electrical device, comprising: an insulating substrate; a patterned metal electrode layer disposed on the insulating substrate; wherein the patterned metal electrode layer includes a central electrode located at the center of the insulating substrate, a plurality of central region electrodes located in the central region of the insulating substrate, surrounding the central electrode and spaced apart from each other, and a first lead-out electrode, a second lead-out electrode, and a plurality of edge region electrodes located in the edge region of the insulating substrate and spaced apart from each other; the plurality of edge region electrodes are spaced apart from each other; one of the first lead-out electrode and the second lead-out electrode is connected to the central electrode; a photocatalyst film layer disposed on the central electrode; a patterned thermoelectric electrode layer disposed on the insulating substrate; wherein the thermoelectric electrode layer includes a plurality of first thermoelectric electrodes and a plurality of second thermoelectric electrodes; each first thermoelectric electrode and each second thermoelectric electrode has a first end located in the central region and a second end located in the edge region, wherein the first end of the first first thermoelectric electrode or the first second thermoelectric electrode in the thermoelectric electrode layer is lapped on the central electrode, the second end is lapped on the edge region electrode, the first end of the last first thermoelectric electrode or the last second thermoelectric electrode is lapped on the central region electrode, the second end is lapped on the other of the first lead-out electrode and the second lead-out electrode, the first ends of the remaining first thermoelectric electrodes and second thermoelectric electrodes in the thermoelectric electrode layer are lapped on the central region electrodes, the second ends are lapped on the edge region electrodes, and the first thermoelectric electrodes and the second thermoelectric electrodes are alternately arranged, so that the plurality of first thermoelectric electrodes and the plurality of second thermoelectric electrodes are connected in series in an alternating manner of the first thermoelectric electrodes and the second thermoelectric electrodes through the plurality of central region electrodes and the plurality of edge region electrodes, wherein, when the photocatalyst film layer is irradiated with light, heat energy is provided to the first ends of the first thermoelectric electrodes and the first ends of the second thermoelectric electrodes, so that a thermoelectric potential is generated in the first thermoelectric electrodes and the second thermoelectric electrodes due to the temperature gradient between the first end and the second end, thereby generating an electrical signal in the series circuit and forming an electric field on the lower surface of the photocatalyst film layer.

[0007] According to an embodiment of the present invention, the first thermoelectric electrode is an N-type thermoelectric electrode, and the second thermoelectric electrode is a P-type thermoelectric electrode; in the alternately connected electrodes, the number of the first thermoelectric electrodes is one more than the number of the second thermoelectric electrodes, so that the photothermal electrical device is convenient for realizing the catalysis of the reduction reaction; or in the alternately connected electrodes, the number of the second thermoelectric electrodes is one more than the number of the first thermoelectric electrodes, so that the photothermal electrical device is convenient for realizing the catalysis of the oxidation reaction.

[0008] According to an embodiment of the present invention, the photocatalyst film layer has oxygen defects.

[0009] According to an embodiment of the present invention, the photothermal electric device further includes: an insulating reflective layer disposed on the metal electrode layer and the thermoelectric electrode layer and exposing the photocatalyst film layer; wherein, the insulating reflective layer is a structure composed of a single material layer or a structure composed of a plurality of material layers stacked, and the plurality of material layers include an insulating dielectric layer and a metal reflective layer stacked on the insulating dielectric layer.

[0010] According to an embodiment of the present invention, the material of the single material layer includes one of Al2O3, MgO2, SiO2, and TiO2; the material of the insulating dielectric layer includes one of SiO2, Al2O3, HfO2, and TiO2; the thickness range of the insulating dielectric layer is 20 to 200 nm; the material of the metal reflective layer includes one of Al, Ag, Au, Pt, and Ti; the thickness range of the metal reflective layer is 50 to 500 nm.

[0011] According to an embodiment of the present invention, the material of the metal electrode layer includes at least one of an Au layer, an Ag layer, a Pt layer, a Cu layer, and a Cr layer; the thickness range of the metal electrode layer is 10 to 100 nm; the material of the photocatalyst film layer is one of ZnO, TiO2, and Fe2O3; the thickness range of the photocatalyst film layer is 50 to 200 nm; the material of the first thermoelectric electrode includes one of Bi2Te3, PbTe, SnSe, and Zn4Sb3; the thickness range of the first thermoelectric electrode is 100 to 200 nm; the material of the second thermoelectric electrode includes one of Sb2Te3, Cu2Se, and Ag2Se; the thickness range of the second thermoelectric electrode is 100 to 200 nm.

[0012] According to a second aspect of the present invention, there is provided a method for manufacturing any one of the above-mentioned photothermal electric devices, comprising: forming a patterned metal electrode layer on an insulating substrate; wherein the patterned metal electrode layer includes a central electrode located at the center of the insulating substrate, a plurality of central region electrodes located in the central region of the insulating substrate, surrounding the central electrode and spaced apart from each other, and a first lead-out electrode, a second lead-out electrode and a plurality of edge region electrodes located in the edge region of the insulating substrate and spaced apart from each other; the plurality of edge region electrodes are spaced apart from each other; one of the first lead-out electrode and the second lead-out electrode is connected to the central electrode; forming an initial photocatalyst film layer on the central electrode; annealing the initial photocatalyst film layer to obtain a photocatalyst film layer; forming a patterned thermoelectric electrode layer on the insulating substrate; wherein the thermoelectric electrode layer includes a plurality of first thermoelectric electrodes and a plurality of second thermoelectric electrodes; each first thermoelectric electrode and each second thermoelectric electrode has a first end located in the central region and a second end located in the edge region, wherein the first end of the first first thermoelectric electrode or the first second thermoelectric electrode in the thermoelectric electrode layer overlaps with the central electrode, the second end overlaps with the edge region electrode, the first end of the last first thermoelectric electrode or the last second thermoelectric electrode overlaps with the central region electrode, the second end overlaps with the other of the first lead-out electrode and the second lead-out electrode, and the first ends of the remaining first thermoelectric electrodes and second thermoelectric electrodes in the thermoelectric electrode layer overlap with the central region electrodes, the second ends overlap with the edge region electrodes, and the first thermoelectric electrodes and the second thermoelectric electrodes are arranged alternately, so that the plurality of first thermoelectric electrodes and the plurality of second thermoelectric electrodes are connected in series in an alternating manner of the first thermoelectric electrodes and the second thermoelectric electrodes through the plurality of central region electrodes and the plurality of edge region electrodes.

[0013] According to an embodiment of the present invention, the above manufacturing method further includes: forming an insulating reflective layer exposing the photocatalyst film layer on the metal electrode layer and the thermoelectric electrode layer; wherein the insulating reflective layer is a structure composed of a single material layer or a structure composed of a plurality of material layers vertically stacked, and the plurality of material layers include an insulating dielectric layer and a metal reflective layer vertically stacked on the insulating dielectric layer.

[0014] According to an embodiment of the present invention, annealing the initial photocatalyst film layer to obtain a photocatalyst film layer includes: inducing oxygen defects in the initial photocatalyst film layer by annealing the initial photocatalyst film layer in an oxygen-free atmosphere to obtain a photocatalyst film layer.

[0015] According to a third aspect of the present invention, there is provided an array device, including any one of the above-mentioned photothermal electric devices arranged in an array.

[0016] According to an embodiment of the present invention, by disposing a photocatalyst film layer on the upper surface of the central electrode, when the photocatalyst film layer generates heat due to illumination, the first ends of the first thermoelectric electrode and the second thermoelectric electrode are located in the central region, so they will receive the heat energy from the photocatalyst film layer. And the second ends of the first thermoelectric electrode and the second thermoelectric electrode are located in the edge region, so they will maintain a lower temperature relative to the first ends. Thus, the first thermoelectric electrode and the second thermoelectric electrode respectively generate thermoelectric potentials due to the temperature gradient, and further an electric signal corresponding to the optical signal is generated in the series circuit, realizing optical detection. On this basis, the thermoelectric potential generated by the thermoelectric electrode layer will form an electric field on the lower surface of the photocatalyst film layer via the central electrode, thereby effectively improving the separation efficiency of the photo-generated carriers of the photocatalyst film layer, and thus enhancing the catalytic ability of the photothermal electric device. Description of the Drawings

[0017] The above and other objects, features, and advantages of the present invention will become more apparent from the following description of the embodiments of the present invention with reference to the accompanying drawings.

[0018] Figure 1 Schematically shows a schematic diagram of a photothermal electric device according to an embodiment of the present invention.

[0019] Figure 2 Schematically shows a flowchart of a method for manufacturing a photothermal electric device according to an embodiment of the present invention.

[0020] Figure 3 Schematically shows a manufacturing flowchart of a photothermal electric device according to an embodiment of the present invention.

[0021] Figure 4a Schematically shows a schematic diagram of the overall structure of an array device according to an embodiment of the present invention.

[0022] Figure 4b Schematically shows an optical photograph of an array device according to an embodiment of the present invention.

[0023] Figure 4c Schematically shows an optical photograph of a single response unit at the first magnification according to an embodiment of the present invention.

[0024] Figure 4d Schematically shows an optical photograph of a single response unit at the second magnification according to an embodiment of the present invention.

[0025] Figure 5 Schematically shows the responsivity, detectivity, and equivalent power density detection results of an array device according to an embodiment of the present invention for multi-spectral light to be measured (355, 475, 535, 650, 850 nm).

[0026] Figure 6Schematically shows the response potentials of each unit of the array device under the illumination of P, T, and E-shaped light sources (a - c) and the corresponding imaging diagrams (d - f) according to an embodiment of the present invention.

[0027] Figure 7a Schematically shows the photocatalytic preparation of H₂O₂ yield and stability test results of the array device according to an embodiment of the present invention.

[0028] Figure 7b Schematically shows a schematic diagram of the photocatalytic preparation of H₂O₂ yield of a ZnO-based photocatalyst in the related art. Detailed Embodiments

[0029] To make the objectives, technical solutions, and advantages of the present invention more clear and understandable, the following further elaborates on the present invention in detail with reference to specific embodiments and the accompanying drawings.

[0030] The terms used herein are merely for describing specific embodiments and are not intended to limit the present invention. The terms "including", "comprising", etc. used herein indicate the presence of the described features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0031] All terms used herein, including technical and scientific terms, have the meanings commonly understood by those skilled in the art, unless otherwise defined. It should be noted that the terms used herein should be interpreted as having a meaning consistent with the context of this specification and should not be interpreted in an idealized or overly rigid manner.

[0032] In cases where expressions similar to "at least one of A, B, and C, etc." are used, generally, it should be interpreted according to the meaning commonly understood by those skilled in the art. For example, "a system having at least one of A, B, and C" should include, but is not limited to, a system having only A, only B, only C, having A and B, having A and C, having B and C, and / or having A, B, and C, etc. In cases where expressions similar to "at least one of A, B, or C, etc." are used, generally, it should be interpreted according to the meaning commonly understood by those skilled in the art. For example, "a system having at least one of A, B, or C" should include, but is not limited to, a system having only A, only B, only C, having A and B, having A and C, having B and C, and / or having A, B, and C, etc.

[0033] It should also be noted that the directional terms mentioned in the embodiments, such as "upper", "lower", "front", "rear", "left", "right", etc., are only references to the directions in the accompanying drawings and are not used to limit the protection scope of the present invention. Throughout the accompanying drawings, the same elements are denoted by the same or similar reference numerals. When it may cause confusion in the understanding of the present invention, conventional structures or configurations will be omitted.

[0034] In the process of implementing the inventive concept, the inventors found that a thermoelectric potential can be generated by a thermoelectric material and directly supplied to a photocatalyst to regulate the energy band structure of the photocatalyst, thereby enhancing the photocatalytic reaction. The thermoelectric potential can also be used as an electric field to enhance the separation of photo-generated electron-hole pairs of the photocatalyst, thereby enhancing the photocatalytic reaction.

[0035] However, due to the size limitation of low-dimensional thermoelectric materials and the disordered distribution state of thermoelectric materials in the composite system, it is difficult to effectively establish a temperature gradient at both ends of the thermoelectric material. At the same time, there is a phenomenon of mutual cancellation of thermoelectric electric fields in different directions. On this basis, it is difficult for the thermoelectric electric field to effectively promote the catalytic performance of the photocatalyst.

[0036] Based on this, it is of great significance to explore a simple and non-destructive method to improve the light absorption efficiency of the optothermoelectric composite device, effectively increase the temperature gradient of the thermoelectric material in the thermoelectric photocatalytic system and the uniformity of the output direction of the thermoelectric electric field, and realize the dual-functional applications of light detection and photocatalysis on a single device.

[0037] In view of this, the embodiments of the present invention provide an optothermoelectric device, which can effectively increase the temperature gradient of the thermoelectric material in the thermoelectric photocatalytic system and the uniformity of the output direction of the thermoelectric electric field, and realize the dual-functional applications of light detection and photocatalysis on a single device.

[0038] Figure 1 A schematic diagram of the optothermoelectric device according to the embodiment of the present invention is schematically shown.

[0039] As Figure 1 shown, the optothermoelectric device of this embodiment includes: an insulating substrate 100. A patterned metal electrode layer disposed on the insulating substrate 100. A patterned thermoelectric electrode layer disposed on the insulating substrate 100. A photocatalyst film layer 310 disposed on the central electrode 210 of the metal electrode layer.

[0040] In an embodiment of the present invention, the insulating substrate 100 serves as the substrate support part of the device. The insulating substrate 100 can avoid the short - circuit problem between the thermoelectric electrode signals in the thermoelectric electrode layer during the operation of the device. The substrate can be selected from, but not limited to, glass, silicon wafers with oxide layers, silicon carbide, alumina, mica, and polymer solid materials. Glass is preferably selected as the insulating substrate 100. The polymer solid material can be PI (Polyimide) or PET (Polyethyleneterephthalate), etc.

[0041] The patterned metal electrode layer includes a central electrode 210 located at the center of the insulating substrate 100, a plurality of central - area electrodes 220 located in the central area of the insulating substrate 100, surrounding the central electrode 210 and spaced apart from each other, and a first lead - out electrode 230, a second lead - out electrode 240, and a plurality of edge - area electrodes 250 located in the edge area of the insulating substrate 100 and spaced apart from each other. The plurality of edge - area electrodes 250 are spaced apart from each other. In an embodiment of the present invention, the first lead - out electrode 230 and the second lead - out electrode 240 can be used to lead out the electrical signals transmitted within the photothermal electric device. For example, one of the first lead - out electrode 230 and the second lead - out electrode 240 can be used as the positive electrode for signal lead - out, and the other can be used as the negative electrode for signal lead - out. The central electrode 210 can be electrically connected to the edge - area electrode 250 via a thermoelectric electrode. The edge - area electrode 250 and the central - area electrode 220 can be electrically connected via a thermoelectric electrode. Based on this, in an embodiment of the present invention, the first lead - out electrode 230, the second lead - out electrode 240, the central electrode 210, the edge - area electrode 250, the central - area electrode 220, and the thermoelectric electrode form a series circuit, and the first lead - out electrode 230 and the second lead - out electrode 240 are located at both ends of the series circuit. The central electrode 210 can be directly connected to the first lead - out electrode 230 or the second lead - out electrode 240, or the central electrode 210 can be electrically connected to the first lead - out electrode 230 or the second lead - out electrode 240 via a thermoelectric electrode, thereby improving the promoting effect of the thermoelectric potential generated by the thermoelectric electrode on the catalytic performance of the photocatalyst film layer 310 located on the central electrode 210.

[0042] The materials of the metal electrode layer include at least one of an Au layer, an Ag layer, a Pt layer, a Cu layer, and a Cr layer. For example, the metal material layer can be an Au layer, an Ag layer, a Pt layer, a Cu layer, or a Cr layer, or the metal material layer can be obtained by laminating at least two of the Au layer, Ag layer, Pt layer, Cu layer, and Cr layer. The laminated material layers are preferably a Cr layer and a Cu layer laminated in sequence from bottom to top. The thickness range of the metal material layer having one material is 10 to 100 nm. For example, the thickness values are 10 nm, 20 nm, 40 nm, 60 nm, or 80 nm. Also, the thickness range of the metal electrode layer formed due to the lamination of the material layers is 10 to 100 nm. For example, the thickness values are 10 nm, 20 nm, 40 nm, 60 nm, or 80 nm.

[0043] The photocatalyst film layer can be used to generate heat energy corresponding to the optical signal when receiving the optical signal, and at the same time, the photo-thermal electric device can be used as a catalyst. For example, it can be a catalyst for oxidation reaction or a catalyst for reduction reaction. The photocatalyst film layer 310 has oxygen defects, which enable the photocatalyst film layer 310 to have a specific lattice structure, improving the photo-thermal conversion ability of the photocatalyst film layer 310, and thus improving the response degree to the optical signal. However, the embodiments of the present invention are not limited thereto. In another embodiment of the present invention, the above specific lattice structure can also be achieved by doping the photocatalyst film layer 310. In yet another embodiment of the present invention, the surface of the photocatalyst film layer 310 can also be modified with a metal to enable the photocatalyst film layer 310 to achieve the above specific lattice structure. The material of the photocatalyst film layer 310 can be, but is not limited to, an oxide catalyst. For example, the material of the photocatalyst film layer 310 is one of ZnO, TiO2, and Fe2O3, preferably ZnO. The thickness range of the photocatalyst film layer is 50 to 200 nm. For example, the thickness values are 50 nm, 75 nm, 100 nm, 125 nm, 150 nm, 175 nm, or 200 nm. It should be noted that in the embodiments of the present invention, the photocatalyst film layer 310 is only disposed on the central electrode 210 and does not contact the central region electrode 220 to avoid the short-circuit problem.

[0044] The thermoelectric electrode layer includes a plurality of first thermoelectric electrodes 410 and a plurality of second thermoelectric electrodes 420. The first thermoelectric electrodes 410 and the second thermoelectric electrodes 420 have different conduction types from each other. For example, the first thermoelectric electrodes 410 are N-type thermoelectric electrodes, and the second thermoelectric electrodes 420 are P-type thermoelectric electrodes. Alternatively, in another embodiment of the present invention, the first thermoelectric electrodes 410 are P-type thermoelectric electrodes, and the second thermoelectric electrodes 420 are N-type thermoelectric electrodes. Hereinafter, the case where the first thermoelectric electrodes 410 are N-type thermoelectric electrodes and the second thermoelectric electrodes 420 are P-type thermoelectric electrodes is taken as an example. The material of the first thermoelectric electrodes includes one of Bi2Te3, PbTe, SnSe, and Zn4Sb3. The material of the second thermoelectric electrodes 420 includes one of Sb2Te3, Cu2Se, and Ag2Se. The thickness range of the first thermoelectric electrodes 410 is 100-200 nm. For example, the thickness values are 100 nm, 125 nm, 150 nm, 175 nm, or 200 nm. The thickness range of the second thermoelectric electrodes 420 is 100-200 nm. For example, the thickness values are 100 nm, 125 nm, 150 nm, 175 nm, or 200 nm.

[0045] In an embodiment of the present invention, each first thermoelectric electrode 410 and each second thermoelectric electrode 420 have a first end located in the central region and a second end located in the edge region. The above-mentioned central electrode 210 is connected to one of the first lead electrode 230 and the second lead electrode 240.

[0046] For example, the first end of the first thermoelectric electrode in the thermoelectric electrode layer is lapped on the central electrode 210, and the second end is lapped on the edge region electrode 250. This first thermoelectric electrode can be a first thermoelectric electrode or a second thermoelectric electrode; the first end of the last thermoelectric electrode in the thermoelectric electrode layer is lapped on the central region electrode 220, and the second end is lapped on the other one of the first lead electrode 230 and the second lead electrode 240. This last thermoelectric electrode can be a first thermoelectric electrode or a second thermoelectric electrode.

[0047] For example, the first end of the first first thermoelectric electrode 410 or the first second thermoelectric electrode 420 in the thermoelectric electrode layer is lapped on the central electrode 210, and the second end is lapped on the edge region electrode 250. The first end of the last first thermoelectric electrode 410 or the last second thermoelectric electrode 420 is lapped on the central region electrode 220, and the second end is lapped on the other one of the first lead electrode 230 and the second lead electrode 240. The first ends of the remaining first thermoelectric electrodes 410 and second thermoelectric electrodes 420 in the thermoelectric electrode layer are lapped on the central region electrode 220, and the second ends are lapped on the edge region electrode 250. Moreover, the first thermoelectric electrodes 410 and the second thermoelectric electrodes 420 are arranged alternately, so that a plurality of first thermoelectric electrodes 410 and a plurality of second thermoelectric electrodes 420 are connected in series in an alternating manner of the first thermoelectric electrodes 410 and the second thermoelectric electrodes 420 through a plurality of central region electrodes 220 and a plurality of edge region electrodes 250.

[0048] In an embodiment of the present invention, when the second lead electrode 240 is directly connected to the N-type thermoelectric electrode, the first lead electrode 230 directly connected to the central electrode 210 serves as the positive electrode for signal extraction. In another embodiment of the present invention, when the second lead electrode 240 is directly connected to the P-type thermoelectric electrode, the first lead electrode 230 directly connected to the central electrode 210 serves as the negative electrode for signal extraction.

[0049] The first ends of the first thermoelectric electrode 410 and the second thermoelectric electrode 420 can be used as the photothermic ends, and the second ends of the first thermoelectric electrode 410 and the second thermoelectric electrode 420 can be used as the cold ends, thereby realizing a temperature gradient across the two ends of the first thermoelectric electrode 410 and the second thermoelectric electrode 420 respectively. Through this temperature gradient, the first thermoelectric electrode 410 and the second thermoelectric electrode 420 can generate thermoelectric potentials respectively, thereby realizing the conversion of thermal energy into electrical signals. Based on this, when the photocatalyst film layer 310 is irradiated with light, it provides thermal energy to the first ends of the first thermoelectric electrode 410 and the second thermoelectric electrode 420, so that the first thermoelectric electrode 410 and the second thermoelectric electrode 420 generate thermoelectric potentials due to the temperature gradient between the first ends and the second ends, thereby generating electrical signals in the series circuit and forming an electric field on the lower surface of the photocatalyst film layer 310.

[0050] Moreover, among the alternately connected electrodes, since the first thermoelectric electrodes 410 and the second thermoelectric electrodes 420 with different conductive properties are arranged alternately, the thermoelectric potentials generated by the first thermoelectric electrodes 410 and the second thermoelectric electrodes 420 are both in the direction of the series circuit, improving the unity of the output direction of the thermoelectric electric field.

[0051] Further, taking the case where the first thermoelectric electrode 410 is an N-type thermoelectric electrode and the second thermoelectric electrode 420 is a P-type thermoelectric electrode as an example, in the alternately connected electrodes, the number of the first thermoelectric electrodes 410 is one more than that of the second thermoelectric electrodes 420, so that the optothermal electric device is convenient for realizing the catalysis of the reduction reaction. Or in the alternately connected electrodes, the number of the second thermoelectric electrodes 420 is one more than that of the first thermoelectric electrodes 410, so that the optothermal electric device is convenient for realizing the catalysis of the oxidation reaction.

[0052] According to an embodiment of the present invention, by disposing the photocatalyst film layer 310 on the upper surface of the central electrode 210, when the photocatalyst film layer 310 generates heat due to being irradiated by light, the first ends of the first thermoelectric electrode 410 and the second thermoelectric electrode 420 will receive the heat energy from the photocatalyst film layer 310 because they are located in the central region, while the second ends of the first thermoelectric electrode 410 and the second thermoelectric electrode 420 will maintain a temperature lower than that of the first ends because they are located in the edge region. Thus, the first thermoelectric electrode 410 and the second thermoelectric electrode 420 respectively generate thermoelectric potentials due to the temperature gradient, and further an electric signal corresponding to the optical signal is generated in the series circuit, realizing optical detection. On this basis, the thermoelectric potential generated by the thermoelectric electrode layer will form an electric field on the lower surface of the photocatalyst film layer 310 via the central electrode 210, thereby effectively improving the separation efficiency of the photo-generated carriers of the photocatalyst film layer 310, and thus improving the catalytic ability of the optothermal electric device.

[0053] According to an embodiment of the present invention, the optothermal electric device further includes an insulating reflective layer disposed on the metal electrode layer and the thermoelectric electrode layer and exposing the photocatalyst film layer 310. The insulating reflective layer is a structure composed of a single material layer or a structure composed of a plurality of material layers stacked, and the plurality of material layers include an insulating dielectric layer and a metal reflective layer stacked on the insulating dielectric layer.

[0054] According to an embodiment of the present invention, the insulating reflective layer can be used to form a temperature distribution decreasing from the center to the edge along the direction of the thermoelectric electrode under illumination. In the embodiment of the present invention, the insulating reflective layer can be formed by stacking an insulating dielectric layer and a metal reflective layer. The metal reflective layer can be used to form a temperature distribution decreasing from the center to the edge along the direction of the thermoelectric electrode under illumination. The insulating dielectric layer can be used to prevent the short circuit of the thermoelectric electrode due to the metal reflective layer.

[0055] For example, the material of the single-material layer can be a material with a high dielectric constant and a high light reflectivity. The material of the single-material layer includes but is not limited to one of Al2O3, MgO2, SiO2, and TiO2. For example, the thickness range of the single-material layer can be 70~700 nm, such as thickness values of 70 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, or 700 nm.

[0056] The material of the insulating dielectric layer can be a high-dielectric material. The material of the insulating dielectric layer includes but is not limited to one of SiO2, Al2O3, HfO2, and TiO2, and is preferably SiO2. The thickness range of the insulating dielectric layer is 20~200 nm. The metal reflective layer can be a material with a high light reflectivity. For example, the material of the metal reflective layer includes but is not limited to one of Al, Ag, Au, Pt, and Ti. The thickness range of the metal reflective layer is 50~500 nm, such as thickness values of 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, or 500 nm.

[0057] According to an embodiment of the present invention, by providing an insulating reflective layer to reflect the light incident on the thermoelectric electrode, only the photocatalyst film layer 310 in the central region generates heat when absorbing light energy, so that only the first end of the thermoelectric electrode close to the photocatalyst film layer 310 is heated, while the photothermal conversion efficiency of the second end covered by the insulating reflective layer is reduced and remains at a low temperature, enhancing the temperature gradient between the first end and the second end of the thermoelectric electrode and improving the response degree of the thermoelectric electrode to the heat generated by the photocatalyst film layer 310.

[0058] Figure 2 A flowchart schematically showing a method for manufacturing a photothermal electric device according to an embodiment of the present invention is shown.

[0059] As Figure 2 shown, the method for manufacturing a photothermal electric device in this embodiment includes operations S210~S240.

[0060] In operation S210, a patterned metal electrode layer is formed on an insulating substrate.

[0061] In operation S220, an initial photocatalyst film layer is formed on the central electrode.

[0062] In operation S230, the initial photocatalyst film layer is annealed to obtain a photocatalyst film layer.

[0063] In operation S240, a patterned thermoelectric electrode layer is formed on the insulating substrate.

[0064] Figure 3Schematically shows a manufacturing flow chart of a photothermal electric device according to an embodiment of the present invention.

[0065] As Figure 3 shown, the manufacturing process of this embodiment includes steps a to h. Among them, step a is to deposit a Cr layer; step b is to deposit a Cu layer; step c is to deposit an initial ZnO photocatalyst film layer; step d is to anneal to prepare ZnO x photocatalyst film layer; step e is to deposit an n-type Bi2Te3 thermoelectric electrode; step f is to deposit a p-type Sb2Te3 thermoelectric electrode; step g is to deposit a SiO2 insulating dielectric layer; step h is to deposit an Al metal reflective layer.

[0066] A patterned metal electrode layer can be formed on an insulating substrate by means of patterned micro-nano processing technology and physical deposition. Corresponding Figure 3 to steps a to b. The purpose of patterning is for the functional design of the integrated device. In the embodiment of the present invention, the patterned micro-nano processing method can and is not limited to selecting methods such as hard mask masking, photolithography, electron beam exposure, etc. according to the size of the device. Physical deposition can and is not limited to selecting techniques such as magnetron sputtering, electron beam evaporation, thermal evaporation coating, atomic layer deposition, pulsed laser deposition or molecular beam epitaxy, etc. according to the selection of the electrode material. The preferred method for depositing the metal electrode layer is electron beam evaporation deposition. The deposition parameters in the present invention are: the deposition Cr beam current range is 15 - 25 mA, preferably 19 mA, the deposition rate is 0.2 - 0.4 Å / s, preferably 0.3 Å / s, and the deposition thickness is 20 nm; the deposition Cu beam current range is 30 - 40 mA, preferably 36 mA, the deposition rate is 0.1 - 0.3 Å / s, preferably 0.2 Å / s, and the deposition thickness is 20 nm.

[0067] A patterned initial photocatalyst film layer can be formed on the surface of the central electrode in the metal electrode layer by means of patterned micro-nano processing technology and physical deposition, corresponding Figure 3 to step c. The deposition parameters of the initial photocatalyst film layer are: the laser wavelength is 532 nm or 1064 nm, preferably 532 nm. The laser frequency range is 10 - 30 Hz, preferably 20 Hz. The laser intensity is 62 - 82 mJ. The oxygen defects can be introduced into the photocatalyst by annealing in an oxygen-free environment to improve the light absorption efficiency of the catalyst film layer, corresponding Figure 3 to step d. The preferred deposition method for the photocatalyst film layer is pulsed laser deposition technology, and the thickness is preferably 50 - 200 nm.

[0068] A first thermoelectric electrode and a second thermoelectric electrode surrounding the photocatalyst unit can be sequentially formed on the insulating substrate by means of patterned micro-nano processing technology and physical deposition, corresponding Figure 3Steps e - f. The deposition method is preferably magnetron sputtering technology. The sputtering current for depositing the thermoelectric electrode layer is 40 - 60 mA, the deposition pressure is 3 - 6 Pa, preferably 4 Pa.

[0069] In some solutions, the photoinduced surface temperature of the composite device is increased by increasing the number of times the light to be measured is reflected on the surface of the device. For example, by modifying noble metal nanoparticles on the surface of the thermoelectric electrode, the surface photoinduced temperature is increased by inducing the surface plasmon resonance effect, or a photosensitive layer with a complex secondary structure is modified on the electrode surface by electrodeposition. However, these methods all inevitably face the problems of high consumption of manufacturing resources and complex processing steps. Moreover, it is difficult to combine chemical synthesis methods with micro - nano processing technologies to achieve the fabrication of highly integrated patterned devices.

[0070] In this regard, in the present invention, the metal electrode layer, the photocatalyst film layer, and the thermoelectric electrode layer are prepared only by the deposition method and patterned micro - nano processing, thereby manufacturing a photothermal - electric device, reducing the device manufacturing steps and the resources consumed for manufacturing the device. And through the combination of physical deposition methods and micro - nano processing technologies, the fabrication of highly integrated patterned devices is achieved.

[0071] According to an embodiment of the present invention, the initial photocatalyst film layer is annealed to obtain a photocatalyst film layer, including: in an oxygen - free atmosphere, by annealing the initial photocatalyst film layer, oxygen defects are induced in the initial photocatalyst film layer to obtain the photocatalyst film layer.

[0072] In an embodiment of the present invention, the oxygen - free atmosphere can be and is not limited to: vacuum environment, N2 environment, Ar environment and other oxygen - free environments, preferably N2 environment for annealing operation. The annealing temperature range is 300 - 500 °C, such as 300 °C, 350 °C, 400 °C, 450 °C or 500 °C. The annealing duration range is 2 - 4 h, such as 2 h, 2.5 h, 3 h, 3.5 h or 4 h. The N2 flow rate range is 500 - 700 sccm, such as 500 sccm, 550 sccm, 600 sccm, 650 sccm or 700 sccm, preferably 600 sccm.

[0073] According to an embodiment of the present invention, the above - mentioned manufacturing method further includes: forming an insulating reflective layer that exposes the photocatalyst film layer on the metal electrode layer and the thermoelectric electrode layer. Wherein, the insulating reflective layer is a structure composed of a single material layer or a structure composed of multiple material layers vertically stacked, and the multiple material layers include an insulating dielectric layer and a metal reflective layer vertically stacked on the insulating dielectric layer.

[0074] In an embodiment of the present invention, a patterned insulating reflective layer can be formed in the area of the substrate other than the photocatalyst film layer by means of patterned micro-nano processing technology and physical deposition.

[0075] Reference Figure 3 Referring to steps g to h, in an embodiment of the present invention, a patterned insulating dielectric layer and a patterned metal reflective layer can be sequentially formed in the area of the substrate other than the photocatalyst film layer by means of patterned micro-nano processing technology and physical deposition.

[0076] The above-described method for depositing the insulating reflective layer is preferably an electron beam evaporation technique. In the present invention, the deposition parameters are as follows: the deposition SiO2 beam current is 15 mA, the deposition rate is 0.3 Å / s, the deposition thickness is 20 nm, the deposition Al beam current is 55 mA, the deposition rate is 0.3 Å / s, and the deposition thickness is 50 nm.

[0077] Figure 4a Schematically shows a schematic diagram of the overall structure of an array device according to an embodiment of the present invention. Figure 4b Schematically shows an optical photograph of an array device according to an embodiment of the present invention. Figure 4c Schematically shows an optical photograph of a single response unit at a first magnification according to an embodiment of the present invention. Figure 4d Schematically shows an optical photograph of a single response unit at a second magnification according to an embodiment of the present invention. According to an embodiment of the present invention, an array device is provided, including a thermophotovoltaic device arranged in an array form.

[0078] For example, based on the above-described patterned micro-nano processing and physical deposition methods, the above thermophotovoltaic device can be extended and manufactured into an arrayed structure device as shown in Figure 4a and Figure 4b The number of response units is 25. It should be noted that the number of response units here is set based on actual needs, and the present invention does not limit this. Each response unit in the arrayed device is the above thermophotovoltaic device, as shown in Figure 4c and Figure 4d A group of response units are formed by sequentially connecting 9 thermoelectric electrodes in series, ZnO xThe photocatalyst film layer is deposited on the surface of the central electrode, and the SiO2 / Al layer covers the part other than the photocatalyst film layer. When the arrayed photothermal-electric device is applied to light detection, the intensity and shape of the light source to be measured can be simultaneously detected by correlating the electrical signals of each response unit with the position coordinates. When the device is applied to photocatalysis, the discrete response units can greatly improve the overall structural stability of the array device. The arrayed structure can be formed in any symmetric or asymmetric shape, preferably a symmetric structure. The number of response units in the array device can also be adjusted without limitation according to the usage requirements, preferably a 5*5 square array.

[0079] In the present invention, relying on the high photothermal conversion efficiency of the photocatalyst film layer, the arrayed photothermal-electric device achieves efficient broad-spectrum detection, and the results are as Figure 5 shown. The array device exhibits excellent light response capabilities under monochromatic light irradiation at 355 nm, 475 nm, 535 nm, 650 nm, and 850 nm respectively. Its responsivities are 64.70, 43.96, 45.59, 50.65, and 52.84 mV W -1 , and the specific detectivities are 7.97*10 7 , 5.41*10 7 , 5.62*10 7 , 6.24*10 7 , and 6.51*10 7 cm Hz 1 / 2 W -1 , and the equivalent power densities are 0.890, 1.309, 1.263, 1.136, 1.089 *10 -8 WHz -1 / 2 , demonstrating that the array device has excellent broad-spectrum detection capabilities.

[0080] Figure 6 Schematically shows the response potentials (a~c) of each unit and the corresponding imaging diagrams (d~f) of the array device under P, T, and E-shaped light source irradiations according to an embodiment of the present invention.

[0081] In the present invention, due to the arrayed structure, the array device achieves accurate imaging of the incident light source. As shown in a of Figure 6 , when a light source with a P shape irradiates the surface of the arrayed device, it can be seen that there is a significant response potential output in the light-irradiated area, and the output potential range is 0.135~0.196 mV, while the output potential in the non-irradiated area is almost 0, showing good light resolution ability. Extract the stable response potential values of each unit and plot them in Figure 6In the imaging diagram shown in d, it can be seen that the array device can accurately present the shape information of the incident light. Similarly, the device can still maintain accurate recognition and imaging capabilities for T- and E-shaped light sources. Among them, Figure 6 b in corresponds to the T-shaped light source, Figure 6 and e in is the imaging diagram of the T-shaped light source. Figure 6 c in corresponds to the E-shaped light source, Figure 6 and f in is the imaging diagram of the E-shaped light source.

[0082] Figure 7a Schematically shows the test results of the photocatalytic production yield and stability of H2O2 of the array device according to an embodiment of the present invention.

[0083] Figure 7b Schematically shows the schematic diagram of the photocatalytic production yield of the ZnO-based photocatalyst in the related art.

[0084] In the present invention, when the array device is applied to the photocatalytic H2O2 preparation reaction, the thermoelectric potential generated by the thermoelectric electrode effectively promotes the separation of photo-generated carriers in the photocatalyst, enabling the composite device to achieve a thermoelectric-enhanced photocatalytic reaction efficiency under illumination conditions. The results are as Figure 7a shown. The actual photocatalytic H2O2 production yield of the array device is 13.39 mmol h -1 m -2 , which is significantly higher than Figure 7b the ZnO-based photocatalyst system in the related art shown. After a total of four reaction cycles of 8 hours, the photocatalytic efficiency of the array device can still maintain 98% of the initial value, showing excellent stability.

[0085] According to the embodiments of the present invention, the arrayed structural units in the present invention enable the array device to effectively image the light source pattern when applied to light detection, and can greatly improve the stability of the overall structure of the device when applied to photocatalysis. Moreover, the arrayed photothermal-electric device in the present invention has successfully achieved the simultaneous combination of light detection and photocatalysis functions on a single device, providing guiding significance for the development of photothermal-electric technology and multifunctional photothermal-electric devices.

[0086] Those skilled in the art can understand that the features described in the various embodiments of the present invention can be combined or combined in various ways, even if such combinations or combinations are not explicitly described in the present invention. In particular, without departing from the spirit and teachings of the present invention, the features described in the various embodiments of the present invention can be combined and / or combined in various ways. All such combinations and / or combinations fall within the scope of the present invention.

[0087] The embodiments of the present invention have been described above. However, these embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. Although the embodiments have been described separately above, this does not mean that the measures in each embodiment cannot be used advantageously in combination. Without departing from the scope of the present invention, those skilled in the art can make various substitutions and modifications, and all such substitutions and modifications should fall within the scope of the present invention.

Claims

1. A photothermoelectric device, characterized in that: include: Insulating substrate; A patterned metal electrode layer is provided on the insulating substrate; wherein the patterned metal electrode layer comprises a central electrode located at the center of the insulating substrate, a plurality of central region electrodes located in the central region of the insulating substrate and surrounding the central electrode and spaced apart from each other, and a first lead-out electrode, a second lead-out electrode and a plurality of edge region electrodes located in the edge region of the insulating substrate and spaced apart from each other; the plurality of edge region electrodes are spaced apart from each other; one of the first lead-out electrode and the second lead-out electrode is connected to the central electrode; A photocatalyst film layer disposed on the central electrode; A patterned thermoelectric electrode layer is arranged on the insulating substrate; wherein the thermoelectric electrode layer includes a plurality of first thermoelectric electrodes and a plurality of second thermoelectric electrodes; each of the first thermoelectric electrodes and each of the second thermoelectric electrodes has a first end located in the central area and a second end located in the edge area, wherein the first end of the first first thermoelectric electrode or the first second thermoelectric electrode in the thermoelectric electrode layer is overlapped with the central electrode, and the second end is overlapped with the edge area electrode, the first end of the last first thermoelectric electrode or the last second thermoelectric electrode is overlapped with the central area electrode, and the second end is overlapped with the other of the first lead-out electrode and the second lead-out electrode, the first ends of the remaining first thermoelectric electrodes and the second thermoelectric electrodes in the thermoelectric electrode layer are overlapped with the central area electrode, and the second ends are overlapped with the edge area electrode, and the first thermoelectric electrodes and the second thermoelectric electrodes are alternately arranged, so that the plurality of first thermoelectric electrodes and the plurality of second thermoelectric electrodes are connected in series in a manner that the first thermoelectric electrodes and the second thermoelectric electrodes are alternately connected through the plurality of central area electrodes and the plurality of edge area electrodes, When the photocatalyst film layer is exposed to light, it provides thermal energy to the first end of the first thermoelectric electrode and the first end of the second thermoelectric electrode, so that the first thermoelectric electrode and the second thermoelectric electrode generate thermoelectric potential due to the temperature gradient between the first end and the second end, thereby generating an electrical signal in the series circuit and forming an electric field on the lower surface of the photocatalyst film layer.

2. The photothermoelectric device according to claim 1, characterized in that: The first thermoelectric electrode is an N-type thermoelectric electrode, and the second thermoelectric electrode is a P-type thermoelectric electrode; In the alternately connected electrodes, the number of the first thermoelectric electrodes is one more than the number of the second thermoelectric electrodes, so that the photothermoelectric device facilitates catalysis of the reduction reaction; or In the alternately connected electrodes, the number of the second thermoelectric electrodes is one more than the number of the first thermoelectric electrodes, so that the photothermoelectric device facilitates catalysis of the oxidation reaction.

3. The photothermoelectric device according to claim 1 or 2, characterized in that: The photocatalyst film layer has oxygen defects.

4. The photothermoelectric device according to claim 1 or 2, characterized in that: The photothermoelectric device further comprises: An insulating reflective layer disposed on the metal electrode layer and the thermoelectric electrode layer and exposing the photocatalyst film layer; The insulating reflective layer is a structure composed of a single material layer or a structure composed of multiple material layers stacked together, and the multiple material layers include an insulating dielectric layer and a metal reflective layer stacked on the insulating dielectric layer.

5. The photothermoelectric device according to claim 4, characterized in that: The material of the single material layer includes one of Al2O3, MgO2, SiO2 and TiO2; The material of the insulating dielectric layer includes one of SiO2, Al2O3, HfO2 and TiO2; The thickness of the insulating dielectric layer is in the range of 20 to 200 nm; The material of the metal reflective layer includes one of Al, Ag, Au, Pt and Ti; The thickness of the metal reflective layer is in the range of 50-500 nm.

6. The photothermoelectric device according to claim 1 or 2, characterized in that: The material of the metal electrode layer includes at least one of an Au layer, an Ag layer, a Pt layer, a Cu layer and a Cr layer; The thickness of the metal electrode layer is in the range of 10 to 100 nm; The material of the photocatalyst film layer is one of ZnO, TiO2 and Fe2O3; The thickness of the photocatalyst film layer ranges from 50 to 200 nm; The material of the first thermoelectric electrode includes one of Bi2Te3, PbTe, SnSe and Zn4Sb3; The thickness of the first thermoelectric electrode ranges from 100 to 200 nm; The material of the second thermoelectric electrode includes one of Sb2Te3, Cu2Se and Ag2Se; The thickness of the second thermoelectric electrode is in the range of 100-200 nm.

7. A method for manufacturing a photothermoelectric device according to any one of claims 1 to 6, characterized in that: include: The patterned metal electrode layer is formed on the insulating substrate; wherein the patterned metal electrode layer includes a central electrode located at the center of the insulating substrate, a plurality of central region electrodes located in the central region of the insulating substrate and surrounding the central electrode and spaced apart from each other, and a first lead-out electrode, a second lead-out electrode and a plurality of edge region electrodes located in the edge region of the insulating substrate and spaced apart from each other; the plurality of edge region electrodes are spaced apart from each other; one of the first lead-out electrode and the second lead-out electrode is connected to the central electrode; forming an initial photocatalyst film layer on the central electrode; Annealing the initial photocatalyst film layer to obtain the photocatalyst film layer; The patterned thermoelectric electrode layer is formed on the insulating substrate; wherein the thermoelectric electrode layer includes a plurality of first thermoelectric electrodes and a plurality of second thermoelectric electrodes; each of the first thermoelectric electrodes and each of the second thermoelectric electrodes has a first end located in the central area and a second end located in the edge area, wherein the first end of the first first thermoelectric electrode or the first second thermoelectric electrode in the thermoelectric electrode layer is overlapped with the central electrode, and the second end is overlapped with the edge area electrode, the first end of the last first thermoelectric electrode or the last second thermoelectric electrode is overlapped with the central area electrode, and the second end is overlapped with the other of the first lead-out electrode and the second lead-out electrode, the first ends of the remaining first thermoelectric electrodes and the second thermoelectric electrodes in the thermoelectric electrode layer are overlapped with the central area electrode, and the second ends are overlapped with the edge area electrode, and the first thermoelectric electrodes and the second thermoelectric electrodes are alternately arranged so that the plurality of first thermoelectric electrodes and the plurality of second thermoelectric electrodes are connected in series in a manner that the first thermoelectric electrodes and the second thermoelectric electrodes alternate with each other through the plurality of central area electrodes and the plurality of edge area electrodes.

8. The method according to claim 7, characterized in that The method further comprises: On the metal electrode layer and the thermoelectric electrode layer, an insulating reflective layer is formed to expose the photocatalyst film layer; The insulating reflective layer is a structure consisting of a single material layer or a structure consisting of multiple material layers vertically stacked, and the multiple material layers include an insulating dielectric layer and a metal reflective layer vertically stacked on the insulating dielectric layer.

9. The method according to claim 7 or 8, characterized in that: The step of annealing the initial photocatalyst film layer to obtain the photocatalyst film layer comprises: The photocatalyst film layer is obtained by annealing the initial photocatalyst film layer in an oxygen-free atmosphere to induce oxygen defects in the initial photocatalyst film layer.

10. An array device, comprising the photothermoelectric devices according to any one of claims 1 to 6 arranged in an array.

Images