Photo-thermal electric device, method of manufacturing photo-thermal electric device, and array device

Abstract

The invention provides a photo-thermal electric device, a method for manufacturing the photo-thermal electric device and an array device, which can be applied to the field of photo-thermal-electric integrated devices. The photo-thermal electric device comprises an insulating substrate; the patterned metal electrode layer is arranged on the insulating substrate; the photocatalyst film layer is arranged on the central electrode; the patterned thermoelectric electrode layer is arranged on the insulating substrate; under the condition that the photocatalyst film layer is illuminated, heat energy is provided for 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 force due to the temperature gradient between the first end and the second end; therefore, an electric signal corresponding to the optical signal is generated in the series circuit, optical detection is realized, and an electric field is formed on the lower surface of the photocatalyst film layer, so that the separation efficiency of photon-generated carriers of the photocatalyst film layer can be effectively improved, and the catalytic capability of the photo-thermal electric device is improved.

Description

Technical Field

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

[0002] Photothermoelectric detector is a new detection mode based on photothermal effect and thermoelectric effect. Its working principle is that thermoelectric material or light absorption layer arranged on the surface of thermoelectric material converts the optical signal to be measured into the temperature difference on both sides of thermoelectric electrode through photothermal effect, and then converts the optical signal into electrical signal through thermoelectric effect. This self-generated energy conversion process can realize optical signal detection without the assistance of bias voltage. In addition, this type of detector can break the limitation of band gap of functional materials in traditional photodetectors on the wavelength to be measured, thereby realizing wide spectrum detection. For a certain thermoelectric electrode material, improving the photothermal conversion ability of the composite device is of great significance to improving the light response of the device.

[0003] Thermoelectric photocatalytic technology uses the light energy that is not completely 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 to improve the catalytic efficiency of the photocatalyst. At present, the thermoelectric photocatalytic system still directly combines low-dimensional thermoelectric materials such as nanoparticles, nanorods, nanosheets, etc. with catalysts, and uses the distribution structure differences of thermoelectric materials in the composite system to induce the thermoelectric material to produce a real-time temperature gradient under light conditions, thereby enhancing the photocatalytic reaction through thermoelectricity. However, in the case of enhancing the photocatalytic reaction through thermoelectricity, there is still the problem of low photocatalytic effect of the device.

[0004] In addition, how to effectively integrate the photothermoelectric detection module and the photocatalytic module on a single device to achieve dual-function applications remains a major challenge. Summary of the invention

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

[0006] According to a first aspect of the present invention, a photothermoelectric device is provided, comprising: an insulating substrate; a patterned metal electrode layer arranged 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, 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 arranged on the central electrode; a patterned thermoelectric electrode layer arranged on the insulating substrate; wherein the thermoelectric electrode layer comprises 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 first thermoelectric electrode or the first second thermoelectric electrode in the thermoelectric electrode layer The first end of the thermoelectric electrode 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 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. The first thermoelectric electrodes and the second thermoelectric electrodes are arranged alternately, so that multiple first thermoelectric electrodes and multiple 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 multiple central area electrodes and multiple edge area electrodes, wherein the photocatalyst film layer provides thermal energy to the first end of the first thermoelectric electrode and the first end of the second thermoelectric electrode when exposed to light, 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.

[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 photothermoelectric device is convenient for catalyzing 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 is convenient for catalyzing 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 photothermoelectric device also includes: an insulating reflective layer arranged 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 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.

[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 material layer includes one of SiO2, Al2O3, HfO2 and TiO2; the thickness range of the insulating material layer is 20~200nm; 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 50~500nm.

[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 10~100 nm; the material of the photocatalyst film layer is one of ZnO, TiO2 and Fe2O3; the thickness range of the photocatalyst film layer is 50~200 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 100~200 nm; the material of the second thermoelectric electrode includes one of Sb2Te3, Cu2Se and Ag2Se; the thickness range of the second thermoelectric electrode is 100~200 nm.

[0012] According to a second aspect of the present invention, there is provided a method for manufacturing any of the above-mentioned photothermoelectric devices, comprising: forming a patterned metal electrode layer on an 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, 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; an initial photocatalyst film layer is formed on the central electrode; the initial photocatalyst film layer is annealed to obtain a photocatalyst film layer; a patterned thermoelectric electrode layer is formed on the insulating substrate; wherein the thermoelectric electrode layer comprises a plurality of first thermoelectric electrodes and a plurality of second thermoelectric electrodes. The thermoelectric electrodes are provided with a first end located in a central region and a second end located in an edge region, wherein the first end of the 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 region electrode, the first end of the last first thermoelectric electrode or the last second thermoelectric electrode is overlapped with the central region 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 region electrode and the second ends are overlapped with the edge region electrode, and the first thermoelectric electrodes and the second thermoelectric electrodes are alternately arranged so that the multiple first thermoelectric electrodes and the multiple 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 multiple central region electrodes and the multiple edge region electrodes.

[0013] According to an embodiment of the present invention, the above-mentioned manufacturing method also 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 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.

[0014] According to an embodiment of the present invention, the initial photocatalyst film layer is annealed to obtain the photocatalyst film layer, including: in an oxygen-free atmosphere, by annealing the initial photocatalyst film layer to induce oxygen defects in the initial photocatalyst film layer to obtain the photocatalyst film layer.

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

[0016] According to an embodiment of the present invention, by setting the photocatalyst film layer on the upper surface of the central electrode, when the photocatalyst film layer generates heat due to light, the first end of each of the first thermoelectric electrode and the second thermoelectric electrode will receive heat energy from the photocatalyst film layer because they are located in the central area, and the second end of each of the first thermoelectric electrode and the second thermoelectric electrode will maintain a lower temperature than the first end because they are located in the edge area, so that the first thermoelectric electrode and the second thermoelectric electrode will each generate a thermoelectric potential due to the temperature gradient, and then an electrical signal corresponding to the optical signal is generated in the series circuit, thereby realizing light 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 photogenerated carriers of the photocatalyst film layer, thereby improving the catalytic ability of the photothermoelectric device. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0018] Figure 1 The schematic diagram of a photothermoelectric device according to an embodiment of the present invention is schematically shown.

[0019] Figure 2 The flowchart of the method for manufacturing a photothermoelectric device according to an embodiment of the present invention is schematically shown.

[0020] Figure 3 The manufacturing process of the photothermoelectric device according to the embodiment of the present invention is schematically shown.

[0021] Figure 4a The overall structural diagram of the array device according to the embodiment of the present invention is schematically shown.

[0022] Figure 4b An optical photograph of an array device according to an embodiment of the present invention is schematically shown.

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

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

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

[0026] Figure 6Schematically illustrates the response potential (a-c) of each unit of the array device according to an embodiment of the present invention when illuminated by P, T, and E-shaped light sources and the corresponding imaging images (d-f).

[0027] Figure 7a The photocatalytic H2O2 production rate and stability test results of the array device according to an embodiment of the present invention are schematically shown.

[0028] Figure 7b A schematic diagram schematically shows the photocatalytic production of H2O2 yield by a ZnO-based photocatalyst in the related art. DETAILED DESCRIPTION

[0029] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings.

[0030] The terms used herein are only for describing specific embodiments and are not intended to limit the present invention. The terms "comprise", "include", etc. used herein indicate the existence of the features, steps, operations and / or components, but do not exclude the existence 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] When using expressions such as "at least one of A, B, and C, etc.", it should generally be interpreted as the meaning of the expression generally understood by those skilled in the art. For example, "a system having at least one of A, B, and C" should include but not be limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc. When using expressions such as "at least one of A, B, or C, etc.", it should generally be interpreted as the meaning of the expression generally understood by those skilled in the art. For example, "a system having at least one of A, B, or C" should include but not be limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.

[0033] It should also be noted that the directional terms mentioned in the embodiments, such as "upper", "lower", "front", "back", "left", "right", etc., are only reference directions of the drawings and are not intended to limit the scope of protection of the present invention. Throughout the drawings, the same elements are represented by the same or similar reference numerals. Conventional structures or configurations will be omitted when they may cause confusion in the understanding of the present invention.

[0034] In the process of realizing the concept of the present invention, the inventors found that thermoelectric potential can be generated by thermoelectric materials and directly supplied to photocatalysts, thereby regulating the energy band structure of photocatalysts to enhance photocatalytic reactions. Thermoelectric potential can also be used as an electric field to enhance the separation of photogenerated electron-hole pairs in photocatalysts, thereby enhancing photocatalytic reactions.

[0035] However, due to the size limitation of low-dimensional thermoelectric materials and the disordered distribution of thermoelectric materials in the composite system, it is difficult to effectively establish the temperature gradient at both ends of the thermoelectric material. At the same time, the thermoelectric fields in different directions cancel each other out. On this basis, it is difficult for the thermoelectric 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 photothermoelectric composite devices, effectively improve the temperature gradient of thermoelectric materials in the thermoelectric photocatalytic system and the uniformity of the output direction of the thermoelectric electric field, and realize the dual-functional application of light detection and photocatalysis on a single device.

[0037] In view of this, an embodiment of the present invention provides a photothermoelectric device that can effectively improve the uniformity of the temperature gradient of thermoelectric materials and the output direction of the thermoelectric electric field in a thermoelectric photocatalytic system, and realize the dual-function application of light detection and photocatalysis on a single device.

[0038] Figure 1 The schematic diagram of a photothermoelectric device according to an embodiment of the present invention is schematically shown.

[0039] like Figure 1 As shown, the photothermoelectric 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, and a photocatalyst film layer 310 disposed on the central electrode 210 of the metal electrode layer.

[0040] In the embodiment of the present invention, the insulating substrate 100 is used as the base 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 when the device is in operation. The substrate can be selected from, but not limited to: glass, silicon wafer with an oxide layer, silicon carbide, aluminum oxide, mica and polymer solid materials, preferably glass 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 extraction electrode 230, a second extraction 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 extraction electrode 230 and the second extraction electrode 240 can be used to extract the electrical signal transmitted in the photothermoelectric device. For example, one of the first extraction electrode 230 and the second extraction electrode 240 can be used as a positive electrode for signal extraction, and the other can be used as a negative electrode for signal extraction. 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 the embodiment of the present invention, the first extraction electrode 230, the second extraction electrode 240, the central electrode 210, the edge region electrode 250, the central region electrode 220, and the thermoelectric electrode constitute a series circuit, and the first extraction electrode 230 and the second extraction electrode 240 are located at both ends of the series circuit. The central electrode 210 can be directly connected to the first extraction electrode 230 or the second extraction electrode 240, or the central electrode 210 can be electrically connected to the first extraction electrode 230 or the second extraction electrode 240 via a thermoelectric electrode, thereby improving 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 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. For example, the metal material layer may be an Au layer, an Ag layer, a Pt layer, a Cu layer or a Cr layer, or the metal material layer may be obtained by stacking at least two material layers of an Au layer, an Ag layer, a Pt layer, a Cu layer and a Cr layer. The stacked material layers are preferably Cr layers and Cu layers stacked in sequence from bottom to top. The thickness of the metal material layer having one material ranges from 10 to 100 nm, for example, a thickness value of 10 nm, 20 nm, 40 nm, 60 nm or 80 nm. And, the thickness of the metal electrode layer formed by stacking the material layers ranges from 10 to 100 nm, for example, a thickness value of 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 light signal when receiving the light signal, and at the same time, the photothermoelectric device can be used as a catalyst. For example, it can be used as a catalyst for oxidation reaction, or it can be used as a catalyst for reduction reaction. The photocatalyst film layer 310 has oxygen defects, and the oxygen defects make the photocatalyst film layer 310 have a specific lattice structure, which improves the light-to-heat conversion ability of the photocatalyst film layer 310, thereby improving the response to the light signal. However, the embodiment of the present invention is not limited to this. In another embodiment of the present invention, the photocatalyst film layer 310 can also be doped to achieve the above-mentioned specific lattice structure. In another embodiment of the present invention, the photocatalyst film layer 310 can also be surface modified with a metal to enable the photocatalyst film layer 310 to achieve the above-mentioned specific lattice structure. The material of the photocatalyst film layer 310 can be and 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 of the photocatalyst film layer ranges from 50 to 200 nm, for example, the thickness is 50 nm, 75 nm, 100 nm, 125 nm, 150 nm, 175 nm or 200 nm. It should be noted that in the embodiment 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, so as to avoid short circuit problems.

[0044] The thermoelectric electrode layer includes a plurality of first thermoelectric electrodes 410 and a plurality of second thermoelectric electrodes 420. The first thermoelectric electrode 410 and the second thermoelectric electrode 420 have different conductivity types from each other. For example, the first thermoelectric electrode 410 is an N-type thermoelectric electrode, and the second thermoelectric electrode 420 is a P-type thermoelectric electrode. Alternatively, in another embodiment of the present invention, the first thermoelectric electrode 410 is a P-type thermoelectric electrode, and the second thermoelectric electrode 420 is an N-type thermoelectric electrode. The following example is taken as an example of 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. The material of the first thermoelectric electrode includes one of Bi2Te3, PbTe, SnSe and Zn4Sb3. The material of the second thermoelectric electrode 420 includes one of Sb2Te3, Cu2Se and Ag2Se. The thickness of the first thermoelectric electrode 410 ranges from 100 to 200 nm, for example, the thickness value is 100 nm, 125 nm, 150 nm, 175 nm or 200 nm. The second thermoelectric electrode 420 has a thickness ranging from 100 nm to 200 nm, for example, a thickness of 100 nm, 125 nm, 150 nm, 175 nm or 200 nm.

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

[0046] For example, the first end of the first thermoelectric electrode in the thermoelectric electrode layer is overlapped with the central electrode 210, and the second end is overlapped with the edge area electrode 250. The first thermoelectric electrode can be the first thermoelectric electrode or the second thermoelectric electrode. The first end of the last thermoelectric electrode in the thermoelectric electrode layer is overlapped with the central area electrode 220, and the second end is overlapped with the other of the first lead-out electrode 230 and the second lead-out electrode 240. The last thermoelectric electrode can be the first thermoelectric electrode or the 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 overlapped with the central electrode 210, and the second end is overlapped with the edge area electrode 250, the first end of the last first thermoelectric electrode 410 or the last second thermoelectric electrode 420 is overlapped with the central area electrode 220, and the second end is overlapped with the other of the first lead-out electrode 230 and the second lead-out electrode 240, the first ends of the remaining first thermoelectric electrodes 410 and the second thermoelectric electrodes 420 in the thermoelectric electrode layer are overlapped with the central area electrode 220, and the second ends are overlapped with the edge area electrode 250, and the first thermoelectric electrodes 410 and the second thermoelectric electrodes 420 are alternately arranged, so that multiple first thermoelectric electrodes 410 and multiple second thermoelectric electrodes 420 are connected in series in a manner in which the first thermoelectric electrodes 410 and the second thermoelectric electrodes 420 alternate with each other through multiple central area electrodes 220 and multiple edge area electrodes 250.

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

[0049] The first end of each of the first thermoelectric electrode 410 and the second thermoelectric electrode 420 can be used as a photothermal end, and the second end of each of the first thermoelectric electrode 410 and the second thermoelectric electrode 420 can be used as a cold end, thereby achieving a temperature gradient at each end of the first thermoelectric electrode 410 and the second thermoelectric electrode 420. Through the temperature gradient, the first thermoelectric electrode 410 and the second thermoelectric electrode 420 can generate a thermoelectric potential, thereby achieving the conversion of thermal energy into an electrical signal. Based on this, the photocatalyst film layer 310 provides thermal energy to the first end of the first thermoelectric electrode 410 and the first end of the second thermoelectric electrode 420 when exposed to light, so that the first thermoelectric electrode 410 and the second thermoelectric electrode 420 generate a 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 310.

[0050] Moreover, in 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 along the direction of the series circuit, thereby improving the uniformity of the output direction of the thermoelectric 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 the number of the second thermoelectric electrodes 420, so that the photothermoelectric device is easy to achieve catalysis of the reduction reaction. Or in the alternately connected electrodes, the number of the second thermoelectric electrodes 420 is one more than the number of the first thermoelectric electrodes 410, so that the photothermoelectric device is easy to achieve catalysis of the oxidation reaction.

[0052] According to an embodiment of the present invention, by setting the photocatalyst film layer 310 on the upper surface of the central electrode 210, when the photocatalyst film layer 310 generates heat due to light, the first end of each of the first thermoelectric electrode 410 and the second thermoelectric electrode 420 will receive heat energy from the photocatalyst film layer 310 because they are located in the central area, and the second end of each of the first thermoelectric electrode 410 and the second thermoelectric electrode 420 will maintain a lower temperature than the first end because they are located in the edge area, so that the first thermoelectric electrode 410 and the second thermoelectric electrode 420 will respectively generate thermoelectric potential due to the temperature gradient, and then an electrical signal corresponding to the optical signal is generated in the series circuit, thereby realizing light 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 photogenerated carriers of the photocatalyst film layer 310, thereby improving the catalytic ability of the photothermoelectric device.

[0053] According to an embodiment of the present invention, 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 310. 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.

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

[0055] For example, the material of the single material layer may 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 of the single material layer may range from 70 to 700 nm, such as a thickness of 70 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, or 700 nm.

[0056] The material of the insulating material layer may be a high dielectric material. The material of the insulating material layer includes but is not limited to one of SiO2, Al2O3, HfO2 and TiO2, preferably SiO2. The thickness of the insulating material layer ranges from 20 to 200 nm. The metal reflective layer may be a material with 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 of the metal reflective layer ranges from 50 to 500 nm, for example, the thickness value is 50 nm, 100 nm, 200 nm, 300 nm, 400 nm or 500 nm.

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

[0058] Figure 2 The flowchart of the method for manufacturing a photothermoelectric device according to an embodiment of the present invention is schematically shown.

[0059] like Figure 2 As shown, the method for manufacturing a photothermoelectric device in this embodiment includes: operations S210 to 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 an insulating substrate.

[0064] Figure 3The manufacturing process of the photothermoelectric device according to the embodiment of the present invention is schematically shown.

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

[0066] A patterned metal electrode layer can be formed on an insulating substrate by patterned micro-nano processing technology and physical deposition. Figure 3 a~b steps. The purpose of patterning is to be used for the functional design of integrated devices. In the embodiment of the present invention, the patterned micro-nano processing method can be selected according to the size of the device, but is not limited to: hard mask shielding, photolithography, electron beam exposure and other methods. Physical deposition can be selected according to the selection of electrode materials, but is not limited to: magnetron sputtering, electron beam evaporation, thermal evaporation coating, atomic layer deposition, pulsed laser deposition or molecular beam epitaxy and other technologies. The method of depositing the metal electrode layer is preferably a deposition method of electron beam evaporation. The deposition parameters in the present invention are: the beam current range of Cr deposition 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 beam current range of Cu deposition 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 patterned micro-nano processing technology and physical deposition, corresponding to Figure 3 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. 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 to Figure 3 In step d, the deposition method of the photocatalyst film layer is preferably pulsed laser deposition technology, and the thickness is preferably 50-200 nm.

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

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

[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 deposition and patterned micro-nano processing, thereby manufacturing a photothermoelectric device, reducing the device manufacturing steps and the resources consumed in manufacturing the device. And by combining the physical deposition method with micro-nano processing technology, the manufacture 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 the photocatalyst film layer, including: in an oxygen-free atmosphere, by annealing the initial photocatalyst film layer to induce oxygen defects 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 selected from, but not limited to, vacuum environment, N2 environment, Ar environment and other oxygen-free environments, preferably N2 environment for annealing. The annealing temperature ranges from 300 to 500 ° C, for example, 300 ° C, 350 ° C, 400 ° C, 450 ° C or 500 ° C. The annealing time ranges from 2 to 4 h, for example, 2 h, 2.5 h, 3 h, 3.5 h or 4 h. The N2 flow rate ranges from 500 to 700 sccm, for example, 500 sccm, 550 sccm, 600 sccm, 650 sccm or 700 sccm, preferably 600 sccm.

[0073] According to an embodiment of the present invention, the manufacturing method further comprises: 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 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 the embodiment of the present invention, a patterned insulating reflective layer can be formed in the area on the substrate except the photocatalyst film layer by patterned micro-nano processing technology and physical deposition.

[0075] refer to Figure 3 In steps g~h, in an embodiment of the present invention, a patterned insulating dielectric layer and a patterned metal reflective layer can be formed in sequence in the area on the substrate except for the photocatalyst film layer by patterned micro-nano processing technology and physical deposition.

[0076] The above-mentioned method of depositing the insulating reflective layer is preferably electron beam evaporation technology. The deposition parameters in the present invention are: the beam current for depositing SiO2 is 15 mA, the deposition rate is 0.3 Å / s, and the deposition thickness is 20 nm; the beam current for depositing Al is 55 mA, the deposition rate is 0.3 Å / s, and the deposition thickness is 50 nm.

[0077] Figure 4a The overall structural diagram of the array device according to the embodiment of the present invention is schematically shown. Figure 4b An optical photograph of an array device according to an embodiment of the present invention is schematically shown. Figure 4c An optical photograph of a single response unit at a first magnification according to an embodiment of the present invention is schematically shown. Figure 4d The optical photograph of a single response unit at a second magnification according to an embodiment of the present invention is schematically shown. According to an embodiment of the present invention, an array device is provided, comprising photothermoelectric devices arranged in an array.

[0078] For example, based on the above-mentioned patterned micro-nano processing and physical deposition method, the above-mentioned photothermoelectric device can be expanded and manufactured into Figure 4a and Figure 4b The arrayed structure device shown has 25 response units. 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-mentioned photothermoelectric device, such as Figure 4c and Figure 4d As shown in the figure, a group of response units is formed by connecting 9 thermoelectric electrodes in series. xThe photocatalyst film layer is deposited on the surface of the central electrode, and the SiO2 / Al layer covers the portion other than the photocatalyst film layer. When the arrayed photothermoelectric device is used for light detection, the intensity and shape of the light source to be measured can be detected simultaneously by associating the electrical signal of each response unit with the position coordinates. When the device is used for photocatalysis, the discrete response units can greatly improve the overall structural stability of the array device. The arrayed structure can be of any symmetrical or asymmetrical shape, preferably a symmetrical structure. The number of response units in the array device can also be adjusted without restriction according to usage requirements, preferably a 5*5 square array.

[0079] In the present invention, by means of the efficient photothermal conversion efficiency of the photocatalyst film layer, the arrayed photothermal device achieves efficient broad spectrum detection. Figure 5 The array device exhibited excellent photoresponse ability under 355 nm, 475 nm, 535 nm, 650 nm and 850 nm monochromatic light irradiation, and its photoresponse was 64.70, 43.96, 45.59, 50.65 and 52.84 mV W, respectively. -1 , the detection ratios 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 The equivalent power densities are 0.890, 1.309, 1.263, 1.136, and 1.089 *10 respectively. -8 WHz -1 / 2 , proving that the array device has excellent broad spectrum detection capabilities.

[0080] Figure 6 Schematically illustrates the response potential (a-c) of each unit of the array device according to an embodiment of the present invention when illuminated by P, T, and E-shaped light sources and the corresponding imaging images (d-f).

[0081] In the present invention, thanks to the array structure, the array device achieves accurate imaging of the incident light source. Figure 6 As shown in Figure a, when a P-shaped light source is irradiated onto the surface of the arrayed device, the irradiated area has a significant response potential output, with an output potential range of 0.135~0.196 mV, while the output potential of the unirradiated area is almost 0, showing good light resolution. The stable response potential values ​​of each unit are extracted and plotted 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. Figure 6 b in the figure corresponds to a T-type light source. Figure 6 Figure e in the figure is the imaging image of the T-type light source. Figure 6 The c in the middle corresponds to the E-type light source, Figure 6 The image f in the figure is the imaging image of type E light source.

[0082] Figure 7a The photocatalytic H2O2 production rate and stability test results of the array device according to an embodiment of the present invention are schematically shown.

[0083] Figure 7b A schematic diagram schematically shows the photocatalytic production of H2O2 yield by a ZnO-based photocatalyst in the related art.

[0084] In the present invention, the array device is applied to the photocatalytic H2O2 preparation reaction. The thermoelectric potential generated by the thermoelectric electrode effectively promotes the separation of photogenerated carriers in the photocatalyst, so that the composite device achieves thermoelectrically enhanced photocatalytic reaction efficiency under light conditions. The results are as follows Figure 7a The actual photocatalytic H2O2 production rate of the array device is 13.39 mmol h -1 m -2 , significantly higher than Figure 7b The ZnO-based photocatalyst system in the related art shown in the figure can still maintain 98% of the initial photocatalytic efficiency of the array device after four reaction cycles totaling 8 hours, showing excellent stability.

[0085] According to the embodiments of the present invention, the arrayed structural unit in the present invention enables the array device to achieve effective imaging of 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. In addition, the arrayed photothermoelectric device in the present invention successfully achieves both light detection and photocatalysis functions on a single device, providing guidance for the development of photothermoelectric technology and multifunctional photothermoelectric devices.

[0086] It will be appreciated by those skilled in the art that the features described in the various embodiments of the present invention may be combined and / or combined in various ways, even if such combinations and / 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 may be combined and / or combined in various ways. All of these combinations and / or combinations fall within the scope of the present invention.

[0087] The embodiments of the present invention are described above. However, these embodiments are only for the purpose of illustration, and are not intended to limit the scope of the present invention. Although each embodiment is described above, it does not mean that the measures in each embodiment cannot be used in combination advantageously. Without departing from the scope of the present invention, those skilled in the art may make various substitutions and modifications, which should all 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 oxidation reactions.

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 material layer includes one of SiO2, Al2O3, HfO2 and TiO2; The thickness of the insulating material 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 ranges from 50 to 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.

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