Radial type thin film thermoelectric device and preparation method and application thereof

Abstract

The invention relates to a radial thin-film thermoelectric device and a preparation method and application thereof. The radial thin-film thermoelectric device comprises a substrate, a thermoelectric arm array layer, an anti-diffusion layer and an electrode layer which are stacked in the peripheral area of the surface of the substrate, and a laser absorption layer located in the central area of the substrate. The thermoelectric arm array layer, the anti-diffusion layer and the electrode layer are all located on the periphery of the laser absorption layer in the horizontal direction, the thermoelectric arm array layer comprises thermoelectric arms, and the thermoelectric arms are radially arranged around the periphery of the laser absorption layer; the electrode layer and the anti-diffusion layer are located on the edges of the two sides of the thermoelectric arm array layer, and the thermoelectric arms, the electrode layer and the anti-diffusion layer are in contact connection. In the radial thin film thermoelectric device provided by the invention, the laser absorption layer can absorb heat generated by laser, the heat is transferred through the substrate, and thermoelectric conversion can be performed on radial energy of laser beams through the synergistic effect of all the parts, so that transmission of laser wireless energy is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of semiconductor devices, and in particular to a radial thin-film thermoelectric device and a preparation method and application thereof. Background Art

[0002] In recent years, laser wireless energy transmission technology has received widespread attention and attention due to its high energy density and long-distance transmission advantages, as well as its ability to provide continuous power supply / recharge for in-orbit satellites, drones, mobile terminals and other equipment. The high energy density of lasers causes a large amount of heat to be generated during its photoelectric conversion, resulting in some energy loss. A thermoelectric conversion device is a device that directly converts thermal energy into electrical energy using the Seebeck effect principle. Direct thermal power generation using thermoelectric conversion devices has the advantages of long system service life, no noise, and green environmental protection. It is mostly used in industrial waste heat recovery, space probe range extender generators and other fields.

[0003] Compared with traditional larger thermoelectric modules, thin-film thermoelectric devices have a thinner structure, usually micrometer- or nanometer-scale films. These thin-film thermoelectric devices have the characteristics of excellent performance, small size, integration, and simple preparation. Therefore, they have great application potential in laser wireless energy transmission systems. In addition, compared with traditional thermoelectric conversion systems that use radioisotope heaters and industrial waste heat as heat sources, thermoelectric conversion systems that use lasers as heat sources have the characteristics of highly concentrated heat sources, precise control, and the ability to accurately project heat to the surface of thermoelectric conversion devices at predetermined values, making them more suitable for use in small portable terminal devices. By combining thermoelectric devices with laser wireless energy transmission systems, there is great potential.

[0004] Thermoelectric devices or components actually used are usually composed of many rigid block thermoelectric elements connected in electrical series and thermal parallel. According to different application environments and special service performance requirements, the structure of thermoelectric devices is mainly divided into traditional rigid flat plate structure and tubular structure. When the thermoelectric assembly works in the environment of planar cold and hot sources, the flat thermoelectric device design is more suitable. Its structure is that the Π-shaped thermoelectric element composed of rectangular N-type and P-type thermoelectric arms is integrated in two electrically insulating but thermally conductive ceramic plates in an electrical series and thermal parallel manner. The heat flow is transmitted in a direction perpendicular to the ceramic plate, which is mainly suitable for the working environment of planar heat sources. In the preparation process of flat-plate thermoelectric devices, the rigid block thermoelectric arm is first prepared by hot pressing and cutting, and then the thermoelectric arm is pressed into the ceramic substrate by pressurization. Finally, the P-type and N-type thermoelectric arms are connected in series with the thermoelectric elements in a sandwich structure using traditional welding technology.

[0005] The flat-plate thermoelectric device structure is suitable for flat-plate heat sources and is mainly manufactured using traditional welding methods. Due to the limitation of the melting point of solder, the operating temperature of the device is usually below 200°C. In addition, the use of ceramic insulating sheets makes the device fragile and has poor mechanical impact resistance. In addition, the preparation cost is high, the weight is large, and it is difficult to use in miniaturized portable devices.

[0006] Tubular thermoelectric devices are mainly suitable for working in non-planar or fluid medium cold and heat source environments (such as automobile exhaust, steam). N-type and P-type annular thermoelectric materials are coaxially arranged alternately along the columnar heat source, and a layer of annular isolation material is placed between each annular thermoelectric arm to achieve electrical insulation between adjacent thermoelectric arms. Metal ring electrodes are set on the outer and inner walls of the thermoelectric arm, and the outer and inner metal rings are alternately arranged in the axial direction to achieve the connection of adjacent thermoelectric arms and the electrical series connection of all PN thermoelectric elements.

[0007] CN203721772U discloses a thermoelectric device with an annular structure, comprising: a plurality of annular P-type thermoelectric elements and N-type thermoelectric elements arranged alternately in sequence along the axial direction; an annular isolation layer arranged between each of the P-type thermoelectric elements and the N-type thermoelectric elements; a high-temperature terminal electrode connected to the outer side wall of each pair of the P-type thermoelectric elements and the N-type thermoelectric elements; a low-temperature terminal electrode connected to the inner side wall of an adjacent pair of the P-type thermoelectric elements and the N-type thermoelectric elements; and wires respectively connected to the high-temperature terminal electrode or the low-temperature terminal electrode at both ends of the thermoelectric device. The thermoelectric device can overcome the limitation that the traditional π-shaped thermoelectric device is not suitable for non-flat heat source environments, and can greatly improve the thermal utilization rate and thermoelectric conversion efficiency of the thermoelectric device with an annular structure.

[0008] The design of tubular thermoelectric devices makes it easy to integrate the device with the heat collection / heat dissipation components. However, the radial transmission characteristics of heat flow and current make it difficult to optimize the design of temperature and electric field. At the same time, the welding and device integration between the annular thermoelectric material and the metal electrode are difficult, and the manufacturing cost is extremely high.

[0009] At present, more importantly, both the flat-plate and tubular thermoelectric device designs are difficult to meet the thermoelectric conversion requirements of radial laser beam heat sources.

[0010] Therefore, providing a thermoelectric device that has the advantages of low cost, light weight, and easy integration, and at the same time can realize the thermoelectric conversion of radial laser heat sources and can be applied to laser wireless energy transmission in miniaturized portable devices has become an urgent problem to be solved. Summary of the invention

[0011] In order to solve the above technical problems, the purpose of the present invention is to provide a radial thin-film thermoelectric device and its preparation method and application. In the radial thin-film thermoelectric device provided by the present invention, the laser absorption layer arranged in the central area can absorb the heat generated by the laser, and transfer the heat to the surrounding area through the substrate to reach the thermoelectric arm array layer, anti-diffusion layer and electrode layer located around the laser absorption layer. Through the mutual synergy of various components, the radial energy of the laser beam can be converted into thermoelectricity to realize the transmission of laser wireless energy. In addition, the radial thin-film thermoelectric device provided by the present invention is easy to integrate, simple in structure, low in preparation cost, and more suitable for application in small portable terminal devices.

[0012] To achieve this object, the present invention adopts the following technical solutions:

[0013] In a first aspect, the present invention provides a radial thin-film thermoelectric device, the radial thin-film thermoelectric device comprising a substrate, a thermoelectric arm array layer, an anti-diffusion layer and an electrode layer stacked in the peripheral area of ​​the substrate surface, and a laser absorption layer located in the central area of ​​the substrate;

[0014] The thermoelectric arm array layer, the anti-diffusion layer and the electrode layer are all located around the laser absorption layer in the horizontal direction, and the thermoelectric arm array layer includes thermoelectric arms, and the thermoelectric arms are arranged radially around the laser absorption layer;

[0015] The electrode layer and the anti-diffusion layer are located at the edges of both sides of the thermoelectric arm array layer, and the thermoelectric arms, the electrode layer and the anti-diffusion layer are in contact and connection.

[0016] In the present invention, the “horizontal direction” refers to a direction parallel to the upper and lower surfaces of the substrate.

[0017] In the radial thin-film thermoelectric device provided by the present invention, the laser absorption layer arranged in the central area can absorb the heat generated by the laser, transfer the heat to the surrounding area through the substrate, and reach the thermoelectric arm array layer, anti-diffusion layer and electrode layer located around the laser absorption layer. Through the mutual cooperation of various components, the radial energy of the laser beam can be thermoelectrically converted to realize the transmission of laser wireless energy. In addition, the radial thin-film thermoelectric device provided by the present invention is easy to integrate, has a simple structure, and has a low preparation cost, and is more suitable for application in small portable terminal devices.

[0018] Among them, the function of the thermoelectric arm array layer is to convert the radially conducted temperature gradient between the central area of ​​the substrate and the periphery of the substrate into electrical energy through the Seebeck effect (thermoelectric effect, when there is a temperature gradient in a closed loop composed of two different metals or alloy materials, an electromotive force will be generated in the loop), and the heat generated by the laser absorbed by the laser absorption layer is converted into electrical energy. The arrangement is radially arranged, which can effectively utilize the heat conducted from the laser absorption layer to the periphery of the substrate under laser irradiation; the function of the anti-diffusion layer is to prevent diffusion, prevent the diffusion of elements between the thermoelectric arm array layer and the electrode layer in the vertical direction at high temperature, and improve the stability of the device; the function of the electrode layer is to connect the thermoelectric arms in series electrically and collect and transmit carriers.

[0019] Preferably, the substrate is any one of a circular sheet structure and a polygonal sheet structure.

[0020] Preferably, in the horizontal direction of the radial thin-film thermoelectric device, blank areas of the substrate are reserved on both sides of the thermoelectric arm array layer in the radial direction.

[0021] Preferably, the thermoelectric arm array layer, the anti-diffusion layer and the electrode layer are spaced apart from the laser absorption layer.

[0022] In the present invention, blank areas are reserved on both sides of the thermoelectric arm array layer because the materials that can be used as the laser absorption layer have a certain degree of electrical conductivity, and the reserved blank areas can prevent the device from short-circuiting. If the side surfaces of the laser absorption layer are in direct contact with the inner side surfaces of the stacked thermoelectric arms, the anti-diffusion component and the first electrode, it will cause a short circuit between the functional layers, affecting the performance of the device.

[0023] Preferably, in the vertical direction of the radial thin film thermoelectric device, the electrode layer and the thermoelectric arm array layer are separated by the anti-diffusion layer.

[0024] In the present invention, the “vertical direction” refers to a direction perpendicular to the upper and lower surfaces of the substrate.

[0025] Preferably, the anti-diffusion layer includes at least four anti-diffusion components.

[0026] Preferably, in the horizontal direction of the radial thin film thermoelectric device, the side of the anti-diffusion layer close to the central area of ​​the substrate is a first anti-diffusion component, and the side away from the central area of ​​the substrate is a second anti-diffusion component.

[0027] Preferably, the electrode layer includes at least two first electrodes and at least two second electrodes.

[0028] Preferably, in the horizontal direction of the radial thin film thermoelectric device, the side of the electrode layer close to the central area of ​​the substrate is the first electrode, and the side away from the central area of ​​the substrate is the second electrode.

[0029] Preferably, the thermoelectric arm array layer includes at least two thermoelectric arms.

[0030] Preferably, the thermoelectric arms are arranged at equal angles to form a fan-shaped structure.

[0031] Preferably, in the vertical direction of the radial thin film thermoelectric device, the first anti-diffusion component, the first electrode and the thermoelectric arm are stacked at an edge of one side close to the central area of ​​the substrate.

[0032] Preferably, inner side surfaces of the first anti-diffusion component and the first electrode close to the central region of the substrate are aligned with inner side surfaces of the thermoelectric arm.

[0033] In the present invention, the “inner side surface” refers to the side surface close to the central area of ​​the substrate in the horizontal direction.

[0034] Preferably, in the vertical direction of the radial thin film thermoelectric device, the second anti-diffusion component, the second electrode and the edge of the thermoelectric arm away from the central area of ​​the substrate are stacked.

[0035] Preferably, outer side surfaces of the second anti-diffusion component and the second electrode away from the central region of the substrate are aligned with outer side surfaces of the thermoelectric arm.

[0036] In the present invention, the “outer side surface” refers to the side surface close to the edge region of the substrate in the horizontal direction.

[0037] Preferably, in the radial direction of the radial thin-film thermoelectric device, the radial length of the thermoelectric arm is greater than the sum of the radial length of the first electrode and the radial length of the second electrode.

[0038] In the present invention, the “radial direction” refers to a direction passing through the center of the substrate in the horizontal direction.

[0039] Preferably, in the radial direction of the radial thin film thermoelectric device, the radial length of the thermoelectric arm is greater than the sum of the radial length of the first anti-diffusion component and the radial length of the second anti-diffusion component. Preferably, the laser absorption layer includes any one of a cylinder, a polygonal columnar structure and a composite structure of their combination.

[0040] Preferably, the thermoelectric arm array layer includes one or two types of thermoelectric arms.

[0041] In the present invention, in the thermoelectric arm array layer, a PN-type thermoelectric arm, a single N-type thermoelectric arm, or a single P-type thermoelectric arm may be used.

[0042] Preferably, the thermoelectric arms are connected in series via a first electrode and a second electrode at both ends of the thermoelectric arms.

[0043] Preferably, the thermoelectric arm array layer includes two types of thermoelectric arms, and the thermoelectric arms are P-type thermoelectric arms and N-type thermoelectric arms that are alternately arranged.

[0044] Preferably, the thermoelectric arm array layer includes two types of thermoelectric arms, the first electrode connects the P-type thermoelectric arm and its adjacent N-type thermoelectric arm through a first anti-diffusion component, and the second electrode connects adjacent pairs of the P-type thermoelectric arm and the N-type thermoelectric arm through a second anti-diffusion component in an alternating form with the first electrode.

[0045] Preferably, the thermoelectric arm array layer includes two types of thermoelectric arms, and any second electrode is divided according to the interval area of ​​the connected adjacent thermoelectric arms and extended outward to the outer edge of the substrate to form two outer edge electrodes.

[0046] Preferably, the thermoelectric arm array layer includes a thermoelectric arm, and the thermoelectric arm includes any one of a P-type thermoelectric arm and an N-type thermoelectric arm.

[0047] Preferably, the thermoelectric arm array layer includes a thermoelectric arm, the first electrode at the inner edge of one thermoelectric arm and the second electrode at the outer edge of the adjacent thermoelectric arm are connected to each other through a third electrode, and the second electrode at the outer edge of the same thermoelectric arm and the first electrode at the inner edge of the adjacent thermoelectric arm on the other side are connected to each other through a third electrode, so as to obtain a thermoelectric arm array layer in which the thermoelectric arms are connected in series.

[0048] Preferably, the first electrode, the connected second electrode and the third electrode for connection form a Z-shape in the horizontal direction.

[0049] Preferably, the thermoelectric arm array includes a thermoelectric arm, wherein the second electrode at the edge of any thermoelectric arm is extended outward to the outer edge of the substrate, and the first electrode at the edge of an adjacent thermoelectric arm is extended outward to the outer edge of the substrate through a connected third electrode, and the second electrode and the third electrode are divided and not connected to form two outer edge electrodes.

[0050] The outer edge electrodes provided in the present invention are used in the subsequent radial thin film thermoelectric device integration process, and the radial thin film thermoelectric devices are connected in series by welding the outer edge electrodes of the radial thin film thermoelectric devices through solder.

[0051] Preferably, the horizontal cross-sectional shapes of the thermoelectric arm, the first anti-diffusion component, the second anti-diffusion component, the first electrode and the second electrode can be independently selected from any one of an arc shape and a trapezoid shape.

[0052] More preferably, the cross-sections of the thermoelectric arms, the first anti-diffusion component, the second anti-diffusion component, the first electrode and the second electrode in the horizontal direction are in the shape of arcs.

[0053] Among them, in the horizontal direction, the inner diameter of the cross-section of the first anti-diffusion component and the first electrode is the same as the inner diameter of the cross-section of the thermoelectric arm; the outer diameter of the cross-section of the second anti-diffusion component and the second electrode is the same as the outer diameter of the cross-section of the thermoelectric arm; the inner diameter of the cross-section of the second anti-diffusion component and the second electrode is larger than the outer diameter of the cross-section of the first anti-diffusion component and the first electrode.

[0054] Preferably, when the thermoelectric arm includes alternately arranged P-type thermoelectric arms and N-type thermoelectric arms, the curvature of the first electrode and the second electrode are both greater than the curvature of the P-type thermoelectric arm or the sum of the curvature of the adjacent N-type thermoelectric arm and the curvature of the spacing area between the P-type thermoelectric arm and the adjacent N-type thermoelectric arm.

[0055] Preferably, when the thermoelectric arm includes a P-type thermoelectric arm, the curvature of the first electrode and the second electrode are both greater than the curvature of the P-type thermoelectric arm, and less than the sum of the curvature of the P-type thermoelectric arm and the curvature of the spacing area between the P-type thermoelectric arms.

[0056] Preferably, when the thermoelectric arm includes an N-type thermoelectric arm, the curvature of the first electrode and the second electrode is greater than the curvature of the N-type thermoelectric arm, and less than the sum of the curvature of the N-type thermoelectric arm and the curvature of the spacing area between the N-type thermoelectric arms.

[0057] Preferably, the substrate comprises any one of metal, semiconductor, oxide ceramic or organic flexible material.

[0058] Preferably, the substrate includes metal or semiconductor, and insulation treatment is required on the surface of the substrate.

[0059] Preferably, the material of the thermoelectric arm includes any one of BiTe-based thermoelectric material, PbX-based thermoelectric material, CuSe-based thermoelectric material, Half-Heusler-based thermoelectric material (half-Heusler alloy thermoelectric material), skutterudite-based thermoelectric material or oxide-based thermoelectric material; wherein X in the PbX-based thermoelectric material includes any one of Se, Sn, Te or S.

[0060] Preferably, the material of the diffusion prevention layer includes any one of Ni, Cr, Ti, Cu or Mo, or at least two of them.

[0061] Preferably, the material of the electrode layer includes any one of Cu, Ag or Au, or a combination of at least two of them.

[0062] Preferably, the material of the laser absorption layer includes carbon nanotubes, graphene, Cs 2 O 4 W, SiC or Al 2 O 3 Any one or at least two of the following.

[0063] In the present invention, the size of each component is not specifically limited, and those skilled in the art can select it according to needs.

[0064] As a preferred technical solution of the present invention, the electrode layer and the anti-diffusion layer are sequentially stacked on the upper surfaces of the edges of both sides of the thermoelectric arm array layer from top to bottom.

[0065] The present invention provides a radial thin-film thermoelectric device, in which an electrode layer and an anti-diffusion layer are stacked on the upper surface of the edges of both sides of the thermoelectric arm array layer. This arrangement can prevent the diffusion of elements between the electrode and the thermoelectric arm under high-temperature use, thereby preventing the reliability of the device from decreasing.

[0066] Preferably, in the vertical direction of the radial thin film thermoelectric device, a first insulating heat conducting layer is further provided between the laser absorption layer and the substrate.

[0067] Preferably, the radial length of the first insulating heat-conducting layer is greater than the radial length of the laser absorption layer.

[0068] Preferably, in the vertical direction of the radial thin film thermoelectric device, the first insulating heat conductive layer is partially located between the substrate and the thermoelectric arm array layer.

[0069] In the present invention, the first insulating heat-conducting layer is mainly used to better transfer the heat generated by the laser absorption layer absorbing the laser to the surroundings, reaching the thermoelectric arm array layer, the anti-diffusion layer and the electrode layer located around the laser absorption layer, so as to realize the thermoelectric conversion of the radial energy of the laser beam. In the present invention, if the first insulating heat-conducting layer only contacts the lower surface of the laser absorption layer and does not contact the thermoelectric arm part, it will result in the inability to efficiently conduct the heat of the heat absorption layer to the hot end of the thermoelectric arm.

[0070] As another preferred technical solution of the present invention, the electrode layer and the anti-diffusion layer are stacked in sequence from bottom to top on the lower surfaces of the two side edges of the thermoelectric arm array layer, and the two side edges of the thermoelectric arm array layer are covered on the stacked anti-diffusion layer and electrode layer, and the lower surface of the edge of the thermoelectric arm array layer is in contact and connected with the upper surface of the anti-diffusion layer.

[0071] The present invention provides a radial thin-film thermoelectric device, in which an electrode layer and an anti-diffusion layer are stacked on the lower surface of the two side edges of the thermoelectric arm array layer. The thermal conductivity of the material used in the electrode part is relatively high. The electrodes are arranged on the lower surface of the two side edges of the thermoelectric arm array layer, so that the heat on the substrate can be more easily transferred to the hot end of the thermoelectric arm.

[0072] Preferably, in the vertical direction of the radial thin film thermoelectric device, a first insulating heat-conducting layer is further provided in the central area of ​​the upper surface of the substrate.

[0073] Preferably, in the radial direction of the radial thin film thermoelectric device, the radial length of the first insulating thermal conductive layer is greater than the radial length of the laser absorption layer, the upper surface of the first insulating thermal conductive layer is in contact with the lower surface of the laser absorption layer and the lower surface of the electrode layer, and the side surface of the first insulating thermal conductive layer is in contact with the thermoelectric arm.

[0074] As a further preferred technical solution of the present invention, the laser absorption layer is a cylindrical and / or composite cylindrical structure with an overall closed configuration.

[0075] As a further preferred technical solution of the present invention, the laser absorption layer is a composite cylindrical structure of an overall closed configuration, and the cross-sectional shape of the laser absorption layer in the vertical direction is T-shaped.

[0076] The present invention further configures the laser absorption layer into a composite cylindrical structure with a T-shaped overall closed configuration in the vertical direction, which can cover the insulating heat-conducting layer and the thermoelectric arm array layer near the central area of ​​the substrate and the stacked electrode layer and anti-diffusion layer, and can more efficiently conduct heat to the hot end of the thermoelectric arm, thereby establishing an effective high-quality temperature difference for the thermoelectric device.

[0077] Preferably, the composite cylindrical structure of the laser absorption layer comprises a first end and a second end, wherein a diameter of the first end is greater than a diameter of the second end.

[0078] Preferably, the lower bottom surface of the first end, the side surface of the second end and the bottom surface of the second end are all covered with a continuous second insulating heat-conducting layer.

[0079] In the present invention, a second insulating heat-conducting layer is used to wrap part of the surface of the composite cylindrical structure of the laser absorption layer, mainly to prevent the laser absorption layer from contacting the electrode layer and the thermoelectric arm of the radial thin-film thermoelectric device, causing a short circuit inside the device. At the same time, it is beneficial for the heat absorbed by the laser absorption layer to be better conducted to other components, thereby improving the heat transfer effect.

[0080] Preferably, when the thermoelectric arms in the thermoelectric arm array layer are arc-shaped structures, the diameter of the first end in the composite cylindrical structure of the laser absorption layer is larger than the inner diameter of the thermoelectric arm array layer.

[0081] Preferably, the second insulating thermally conductive layer is partially located in the spacing area between the thermoelectric arm array layer, the anti-diffusion layer and the electrode layer and the laser absorption layer, partially located at the lower bottom surface of the first end of the laser absorption layer, and partially located on the surface of the first insulating thermally conductive layer on the substrate.

[0082] In the present invention, the second insulating heat-conducting layer continuously covers the upper surface of the inner edge of the peripheral region of the radial thin-film thermoelectric device.

[0083] The laser layer of the composite cylindrical structure in the present invention can also be replaced by a composite polygonal cylindrical structure, wherein the upper and lower surfaces of the first end and the second end of the composite cylindrical structure can be replaced by polygonal shapes.

[0084] As a further preferred technical solution of the present invention, the uppermost layer in the vertical direction of the radial thin film thermoelectric device is also provided with a laser reflection layer.

[0085] The radial thin-film thermoelectric device of the present invention introduces a laser reflection layer, which can reflect the laser at the periphery of the device under the irradiation of a laser spot larger than the size of the radial thin-film thermoelectric device, so that the central area of ​​the device maintains a high temperature, thereby forming an effective temperature difference in the device.

[0086] Preferably, a horizontal cross section of the laser reflective layer is in a closed annular shape.

[0087] Preferably, the laser reflection layer is located on an upper surface of an outer edge of the radial thin film thermoelectric device.

[0088] Preferably, in the vertical direction of the radial thin film thermoelectric device, the laser reflection layer overlaps and / or partially overlaps with the thermoelectric arm array layer, the anti-diffusion layer, the electrode layer and the substrate in the radial direction.

[0089] Preferably, in the radial direction of the radial thin film thermoelectric device, the radial length of the laser reflection layer is greater than the sum of the radial length of the electrode layer and the radial length of the outer edge blank area of ​​the substrate.

[0090] Preferably, an outer side surface of the laser reflection layer away from the central area of ​​the substrate is aligned with a side surface of an outer edge of the substrate.

[0091] In the present invention, there is no specific limitation on the thickness of the thermoelectric arm array layer, electrode layer, anti-diffusion layer, laser absorption layer, first insulating thermal conductive layer, second insulating thermal conductive layer and laser reflection layer, and a radial thin film thermoelectric device can be selected in which the thickness of each layer is consistent at any position.

[0092] In a second aspect, the present invention provides a method for preparing the radial thin film thermoelectric device according to the first aspect, the preparation method comprising:

[0093] A thermoelectric arm array layer, an anti-diffusion layer, an electrode layer and a laser absorption layer are deposited on a substrate respectively by using a mask technology, wherein the thermoelectric arm array layer, the anti-diffusion layer and the electrode layer are stacked in a peripheral area on the surface of the substrate, and the laser absorption layer is located in a central area on the surface of the substrate;

[0094] The thermoelectric arm array layer, the anti-diffusion layer and the electrode layer are all located around the laser absorption layer in the horizontal direction, and the thermoelectric arm array layer includes thermoelectric arms, which are arranged radially around the laser absorption layer.

[0095] The electrode layer and the anti-diffusion layer are located at the edges of both sides of the thermoelectric arm array layer, and the thermoelectric arms, the electrode layer and the anti-diffusion layer are in contact and connection.

[0096] The present invention combines and deposits the materials of various components according to specific positions and structures through mask technology to prepare radial thin-film thermoelectric devices. The preparation method has simple steps, high reliability, and can achieve low-cost and large-scale production.

[0097] Preferably, the preparation method further includes depositing a first insulating thermally conductive layer on the substrate before depositing the thermoelectric arm array layer, the anti-diffusion layer, the electrode layer and the laser absorption layer, and / or the preparation method further includes depositing the second insulating thermally conductive layer in the spacing area between the thermoelectric arm array layer, the anti-diffusion layer and the electrode layer and the laser absorption layer, on the lower bottom surface of the first end of the laser absorption layer, and on the surface of the first insulating thermally conductive layer.

[0098] Preferably, the preparation method further comprises depositing a laser reflection layer after depositing the thermoelectric arm array layer, the anti-diffusion layer, the electrode layer and the laser absorption layer.

[0099] Preferably, the mask technology uses a hollow mask, and the hollow mask is placed on the surface of the substrate for depositing various components in the radial thin film thermoelectric device.

[0100] Preferably, the hollow mask has a wedge-shaped structure.

[0101] Preferably, the material of the hollow mask includes metal nickel.

[0102] Preferably, the thickness of the hollow mask is 0.2-0.5 mm, for example, 0.2 mm, 0.3 mm, 0.4 mm or 0.5 mm.

[0103] Preferably, the hollow mask is prepared by laser etching metal.

[0104] Preferably, in the mask technology, a substrate holder is used to position the hollow mask.

[0105] Preferably, the substrate holder is made of 304 stainless steel.

[0106] Preferably, a limiting groove is provided on the substrate holder, and the notch of the limiting groove is aligned with the wedge-shaped structure on the hollow mask to position the hollow mask.

[0107] Preferably, the thickness of the substrate holder is 0.5-1.5 mm, such as 0.5 mm, 0.7 mm, 0.9 mm, 1.1 mm, 1.3 mm or 1.5 mm, and the thickness of the limiting groove is 2-3 mm, such as 2 mm, 2.2 mm, 2.4 mm, 2.6 mm, 2.7 mm or 3 mm.

[0108] Preferably, the substrate is placed on the substrate holder.

[0109] Preferably, the hollow mask includes a first mask, a second mask, a third mask, a fourth mask, a fifth mask and a sixth mask (for specific hollow structures, see Figure 1-Figure 6 ).

[0110] Preferably, the hollow shape in the first mask is consistent with the shape of a horizontal cross section of the thermoelectric arm array layer including two types of thermoelectric arms.

[0111] Preferably, the hollow shape in the second mask is consistent with the shape of a horizontal cross section of a thermoelectric arm array layer including a thermoelectric arm.

[0112] Preferably, the hollow shape in the third mask is consistent with the shape of the horizontal cross section of the electrode layer and the anti-diffusion layer connecting the two thermoelectric arms.

[0113] Preferably, the hollow shape in the fourth mask is consistent with the shape of a horizontal cross section of an electrode layer and an anti-diffusion layer connecting a thermoelectric arm.

[0114] Preferably, the hollow shape in the fifth mask is consistent with the shape of the horizontal cross section of the insulating heat-conducting layer and / or the laser absorption layer.

[0115] In the present invention, the hollow shape in the fifth mask is consistent with the shape of the horizontal cross section of the insulating heat-conducting layer and the shape of the horizontal cross section of the first end of the laser absorption layer of the composite cylindrical structure.

[0116] Preferably, the hollow shape in the sixth mask is consistent with the shape of the cross section of the laser absorption layer in the horizontal direction.

[0117] In the present invention, the hollow shape in the sixth mask is consistent with the cross-sectional shape of the laser absorption layer located in the middle of the radially arranged thermoelectric arm array layer, or is consistent with the horizontal cross-sectional shape of the second end of the laser absorption layer of the composite cylindrical structure.

[0118] Preferably, the first mask is used to prepare a thermoelectric arm array layer of two types of thermoelectric arms.

[0119] Preferably, the second mask is used to prepare a thermoelectric arm array layer of a thermoelectric arm.

[0120] Preferably, the third mask is used to prepare electrode layers and anti-diffusion layers of two thermoelectric arms.

[0121] Preferably, the fourth mask is used to prepare an electrode layer and an anti-diffusion layer of a thermoelectric arm.

[0122] Preferably, the fifth mask is used to prepare an insulating heat-conducting layer and / or a laser absorption layer.

[0123] Preferably, the sixth mask is used to prepare a laser absorption layer.

[0124] The present invention does not limit the deposition process of each component, including but not limited to magnetron sputtering, electron beam deposition or screen printing, etc. Those skilled in the art can choose according to needs.

[0125] As a preferred technical solution of the present invention, the preparation method of the radial thin film thermoelectric device is as follows:

[0126] ① Preparation process of the first insulating thermal conductive layer:

[0127] The substrate was placed in the substrate holder, and the substrate holder was tightened to the sample stage with screws. Then, the wedge-shaped structure on the fifth mask was aligned with the notch of the limiting groove of the substrate holder. The magnetic sheet under the substrate pressed the fifth mask to the substrate tightly. The magnetron sputtering process was used to deposit the insulating thermal conductive layer target material. The chamber pressure was maintained at 6.0×10 -4 -9.0×10 -4Pa, the chamber pressure during deposition is 0.1-0.5 Pa, the substrate is not heated, the high-purity argon flow rate is 20-40sscm; the RF power supply power is 200-300W, and the deposition time is 3000-4000s; wherein the material of the insulating thermal conductive layer target includes boron nitride.

[0128] ②Preparation process of thermoelectric arm array layer:

[0129] Preparation of N-type thermoelectric arm: fix it with the first mask or the second mask, use the first sputtering target and the second sputtering target for interval magnetron sputtering or co-sputtering preparation, set the parameters of the magnetron sputtering process, and the chamber pressure before deposition is 6.0×10 -4 -9.0×10 -4 Pa, the chamber pressure during sputtering is 0.1-0.5Pa, the high-purity argon flow rate is 20-40sscm, the power supply power used by the first sputtering target is 50-400W, the power supply power used by the second sputtering target is 50-400W, the power supply can be a combination of two of a DC power supply, a radio frequency power supply or a high-power high-pulse power supply, and the magnetron sputtering method includes interval magnetron sputtering or co-sputtering; the specific process of the interval magnetron sputtering includes: the deposition of the first sputtering target and the second sputtering target is carried out alternately, and the alternating frequency is: every 600-1200s of the first sputtering target deposition time, the second sputtering target deposition of 100-1200s is started until the deposition is completed; the specific process of the co-sputtering includes: the first sputtering target and the second sputtering target are deposited simultaneously at their respective set power supplies until the deposition is completed;

[0130] Preparation of P-type thermoelectric arm: fix it with the first mask or the second mask, use the third sputtering target and the fourth sputtering target for interval magnetron sputtering or co-sputtering preparation, set the parameters of the magnetron sputtering process, and the chamber pressure before deposition is 6.0×10 -4 -9.0×10 -4 Pa, the chamber pressure during sputtering is 0.1-0.5Pa, the high-purity argon flow rate is 20-40sscm, the power of the third sputtering target is 50-400W, the power of the fourth sputtering target is 50-400W, the power supply can be a combination of two of a DC power supply, a radio frequency power supply or a high-power high-pulse power supply, and the magnetron sputtering method includes interval magnetron sputtering or co-sputtering; the specific process of the interval magnetron sputtering includes: the deposition of the third sputtering target and the fourth sputtering target is carried out alternately, and the alternating frequency is: every 600-1200s of the third sputtering target deposition time, the fourth sputtering target deposition of 100-1200s is started until the deposition is completed; the specific process of the co-sputtering includes: the third sputtering target and the fourth sputtering target are deposited simultaneously at their respective set power supplies until the deposition is completed;

[0131] Wherein, the first sputtering target and the third sputtering target independently include but are not limited to BiTe, PbX (X = S, Te, Sn, Sb, Se), CoSb 3 , FeVSb, ZrNiSn, GeSi or Ca 3 Co 4 O 9 Any one or a combination of at least two of them, which is an alloy target or an oxide target capable of magnetron sputtering; the second sputtering target and the fourth sputtering target independently include but are not limited to metal targets of any one or a combination of at least two of Ti, Sn, Fe, In, Yb, Ce or Y, and the purity of the target materials is (99.9-99.99%); the first sputtering target, the second sputtering target, the third sputtering target and the fourth sputtering target are any one or a combination of at least two of the above target materials according to the requirements of preparing thermoelectric devices.

[0132] The substrate with the thermoelectric arms deposited thereon is placed in an argon atmosphere and annealed at 300-400° C. for 0.5-2 h to obtain a thermoelectric arm array layer.

[0133] ③Preparation process of anti-diffusion layer:

[0134] The third mask or the fourth mask is used for fixing, and the fifth sputtering target is used as the raw material for deposition through the magnetron sputtering process. The chamber pressure before deposition is 6.0×10 -4 -9.0×10 -4 Pa, the chamber pressure during sputtering is 0.1-0.5Pa, the high-purity argon gas flow rate is 20-40sscm, the DC power supply power is 50-250W, and the deposition time is 1600-2000s to obtain an anti-diffusion layer; wherein the fifth sputtering target includes any one or at least two of Ni, Cr, Ti, Cu or Mo.

[0135] ④ Preparation process of electrode layer:

[0136] The third mask or the fourth mask is used for fixing, and the sixth sputtering target is used as the raw material for deposition through the magnetron sputtering process. The chamber pressure before deposition is 6.0×10 -4 -9.0×10 -4 Pa, the chamber pressure during sputtering is 0.1-0.5Pa, the high-purity argon flow rate is 20-40sscm, the DC power supply power is 100-300W, and the deposition time is 3500-4000s to obtain an electrode layer; wherein the sixth sputtering target includes any one or at least two of Cu, Ag or Au.

[0137] ⑤Preparation process of laser absorption layer:

[0138] The sixth mask is used for fixing, and the material of the laser absorption layer is coated on the central area of ​​the radial thin film thermoelectric device by manual coating to obtain the laser absorption layer; wherein the material of the laser absorption layer includes carbon nanotubes, graphene, Cs 2 O 4 W, SiC or Al 2 O 3 Any one or at least two of the following.

[0139] ⑥Preparation process of laser reflection layer:

[0140] The laser reflection layer was prepared by magnetron sputtering. A circular sticker was pasted on the central area of ​​the radial thin film thermoelectric device. The diameter of the sticker was smaller than the diameter of the substrate and larger than the radial length of the laser absorption layer. The seventh target material was used as the raw material. The chamber pressure before deposition was 6.0×10 -4 -9.0×10 -4 Pa, the chamber pressure during sputtering is 0.1-0.5Pa, the high-purity argon gas flow rate is 20-40sscm, the RF power is 100-400W, and the deposition time is 500-4000s to obtain a laser reflection layer;

[0141] The circular sticker is a PVC sticker with double-sided adhesive on the back; the seventh target material is a material with a high refractive index, including TiO 2 、 2 O 3 , HfO 2 or ZrO 2 Any one of .

[0142] In a third aspect, the present invention provides an application of the radial thin film thermoelectric device as described in the first aspect, wherein the radial thin film thermoelectric device is used for laser wireless energy transmission.

[0143] Compared with the prior art, the present invention has at least the following beneficial effects:

[0144] (1) In the radial thin-film thermoelectric device provided by the present invention, the laser absorption layer arranged in the central area can absorb the heat generated by the laser, transfer the heat to the surrounding area through the substrate, and reach the thermoelectric arm array layer, anti-diffusion layer and electrode layer located around the laser absorption layer. Through the mutual cooperation of various components, the radial energy of the laser beam can be converted into thermoelectricity to realize the transmission of laser wireless energy. In addition, the radial thin-film thermoelectric device provided by the present invention is easy to integrate, has a simple structure, and has a low preparation cost, and is more suitable for application in small portable terminal devices.

[0145] (2) The present invention uses mask technology to deposit the materials of various components in combination according to specific positions and structures to prepare radial thin film thermoelectric devices. The preparation method has simple steps, high reliability, and can achieve low-cost and large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0146] Figure 1 4 is a schematic top view of the first mask of the present invention.

[0147] Figure 2 4 is a schematic top view of the second mask of the present invention.

[0148] Figure 3 4 is a schematic top view of the third mask of the present invention.

[0149] Figure 4 4 is a schematic top view of the fourth mask of the present invention.

[0150] Figure 5 4 is a schematic top view of the fifth mask of the present invention.

[0151] Figure 6 4 is a schematic top view of the sixth mask of the present invention.

[0152] Figure 7 It is a top view schematic diagram of the distribution of the limiting grooves on the substrate holder in the present invention.

[0153] Figure 8 It is a schematic diagram of the top view of the radial thin film thermoelectric device of Example 1-1 of the present invention.

[0154] Fig. 9 It is a schematic diagram of the top view of the structure of the radial thin film thermoelectric device of Example 1-2 of the present invention.

[0155] Fig.10 It is a schematic diagram of the radial cross-sectional front view of the radial direction of the radial thin film thermoelectric device of Example 1-1 and Example 1-2 of the present invention.

[0156] Fig.11 It is a schematic diagram of the top view of the radial thin film thermoelectric device of Example 2-1 of the present invention.

[0157] Fig.12 It is a schematic diagram of the top view of the structure of the radial thin film thermoelectric device of Example 2-2 of the present invention.

[0158] Fig.13 It is a schematic diagram of the radial cross-sectional front view of the radial thin film thermoelectric device of Example 2-1 and Example 2-2 of the present invention.

[0159] Fig.14 It is a schematic diagram of the preparation process of the radial thin film thermoelectric device of Example 2-2 of the present invention.

[0160] Fig.15 This is a physical picture of the radial thin-film thermoelectric device of Example 2-2 of the present invention.

[0161] Fig.16 It is a schematic diagram of the top view of the radial thin film thermoelectric device of Example 3-1 of the present invention.

[0162] Fig.17 It is a schematic diagram of the top view of the radial thin film thermoelectric device of Example 3-2 of the present invention.

[0163] Fig.18 It is a schematic diagram of the radial cross-sectional front view of the radial thin-film thermoelectric device of Example 3-1 and Example 3-2 of the present invention.

[0164] Fig.19 It is a schematic diagram of the top view of the radial thin film thermoelectric device of Example 4-1 of the present invention.

[0165] Fig. 20 It is a schematic diagram of the top view of the structure of the radial thin film thermoelectric device of Example 4-2 of the present invention.

[0166] Fig.21 It is a schematic diagram of the radial cross-sectional front view of the radial thin film thermoelectric device of Example 4-1 and Example 4-2 of the present invention.

[0167] Fig. 22 It is a schematic diagram of the top view of the radial thin film thermoelectric device of Example 5-1 of the present invention.

[0168] Fig.23 It is a schematic diagram of the top view of the radial thin film thermoelectric device of Example 5-2 of the present invention.

[0169] Fig.24 It is a schematic diagram of the radial cross-sectional front view of the radial thin-film thermoelectric device of Example 5-1 and Example 5-2 of the present invention.

[0170] Among them, 1-substrate, 2-laser absorption layer, 3-thermoelectric arm array layer, 4-anti-diffusion layer, 5-electrode layer, 501-first electrode, 502-second electrode, 503-outer edge electrode, 504-third electrode, 6-insulating thermal conductive layer, 601-first insulating thermal conductive layer, 602-second insulating thermal conductive layer, 7-laser reflecting layer.

[0171] Fig.25 4 is a graph showing the wavelength-absorption rate of the laser absorption layer in the radial thin film thermoelectric device of Example 2-2 of the present invention.

[0172] Fig.26 This is a thermal imaging image of the radial thin film thermoelectric device of Example 2-2 of the present invention under a 25W laser power test.

[0173] Fig. 27 A graph showing the relationship between laser power and temperature of the radial thin film thermoelectric device of Example 2-2 of the present invention.

[0174] Fig.28 A relationship diagram between the open circuit voltage and short circuit current of the radial thin film thermoelectric device of Example 2-2 of the present invention at different laser power densities. DETAILED DESCRIPTION

[0175] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and through specific implementation methods. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0176] The parameters of the mask manufacturing, shape and size used in the following embodiments are as follows:

[0177] Preparation of the mask: The mask used in the following embodiments has a wedge-shaped structure, and its material is nickel metal with a thickness of 0.3 mm. The hollow mask is prepared by laser etching a metal nickel sheet according to the required shape:

[0178] The first mask is used to prepare the thermoelectric arm array layer of the two thermoelectric arms. The top view schematic diagram of the hollow mask is shown in FIG. Figure 1 shown.

[0179] The second mask is used to prepare a thermoelectric arm array layer of a thermoelectric arm, and the top view schematic diagram of the hollow mask is as shown in FIG. Figure 2 shown.

[0180] The third mask is used to prepare the electrode layer and anti-diffusion layer of the two thermoelectric arms. The schematic top view of the hollow mask is shown in FIG. Figure 3 shown.

[0181] The fourth mask is used to prepare an electrode layer and an anti-diffusion layer of a thermoelectric arm. The schematic top view of the hollow mask is as follows: Figure 4 shown.

[0182] The fifth mask is used to prepare the second end of the insulating heat-conducting layer and the laser absorption layer of the composite cylindrical structure. The schematic top view of the hollow mask is as shown in FIG. Figure 5 shown.

[0183] The sixth mask is used to prepare a laser absorption layer of a cylindrical structure and a laser absorption layer of a composite cylindrical structure. The top view of the hollow mask is as follows: Figure 6 shown.

[0184] Figure 7A top view schematic diagram of the substrate holder and the limit groove distribution used in the present invention is given, the internal annular limit groove plays a positioning role for the hollow mask component, the substrate holder and the limit groove bracket thereon are combined together through a welding process, the wedge-shaped structure on the hollow mask is aligned with the notch of the limit groove on the substrate holder, and the hollow mask is positioned. The substrate holder and the limit groove on the substrate holder are made of 304 stainless steel, the thickness of the substrate holder is 1mm, and the thickness of the limit groove is 2.5mm.

[0185] in, Figure 1-Figure 7 The specific size parameter values ​​of the symbols marked in the displayed mask top view schematic diagram are shown in Table 1.

[0186] Table 1

[0187] symbol parameter symbol parameter symbol parameter symbol parameter <![CDATA[R 1 ]]> 22mm <![CDATA[R 10 ]]> 75mm <![CDATA[a 9 ]]> 5.89mm <![CDATA[L 3 ]]> 14.01mm <![CDATA[R 2 ]]> 6mm <![CDATA[a 1 ]]> 6.48mm <![CDATA[a 10 ]]> 7.48mm <![CDATA[L 4 ]]> 14.07mm <![CDATA[R 3 ]]> 25.4mm <![CDATA[a 2 ]]> 1.77mm <![CDATA[a 11 ]]> 23.88mm <![CDATA[L 5 ]]> 19.4mm <![CDATA[R 4 ]]> 20mm <![CDATA[a 3 ]]> 8.64mm <![CDATA[a 12 ]]> 13.12mm <![CDATA[L 6 ]]> 2.5mm <![CDATA[R 5 ]]> 8mm <![CDATA[a 4 ]]> 2.36mm <![CDATA[a 13 ]]> 11.05mm <![CDATA[L 7 ]]> 5mm <![CDATA[R 6 ]]> 8mm <![CDATA[a 5 ]]> 15.12mm <![CDATA[a 14 ]]> 3.81mm <![CDATA[θ 1 ]]> 28° <![CDATA[R 7 ]]> 5mm <![CDATA[a 6 ]]> 13.74mm <![CDATA[a 15 ]]> 3.53mm <![CDATA[θ 2 ]]> 45° <![CDATA[R 8 ]]> 2.5mm <![CDATA[a 7 ]]> 5.5mm <![CDATA[L 1 ]]> 5.4mm <![CDATA[θ 3 ]]> 23° <![CDATA[R 9 ]]> 30.4mm <![CDATA[a 8 ]]> 4.12mm <![CDATA[L 2 ]]> 5mm <![CDATA[θ 4 ]]> 6°

[0188] In the radial thin film thermoelectric device provided in the following embodiments, in the horizontal direction of the radial thin film thermoelectric device, the centers of the circles and arc shapes involved in the substrate, laser absorption layer, thermoelectric arm array layer, anti-diffusion layer and electrode layer are the same.

[0189] The Al used in the following examples 2 O 3 The substrate needs to be pretreated. The pretreatment process includes: first, ultrasonic cleaning in acetone for 10 minutes, then blowing the surface dry with nitrogen, and then ultrasonic cleaning with ethanol for 10 minutes, drying with nitrogen, and the pretreatment is completed.

[0190] The water-based graphene coating used in the following examples is derived from the graphene heat dissipation coating of Suzhou Tanfeng Technology, model TF-18621.

[0191] Example 1-1

[0192] This embodiment provides a radial thin film thermoelectric device, and its top view structural diagram is as follows: Figure 8 As shown, the schematic diagram of the main view of the cross-section in the radial direction is as follows Fig.10 As shown, it includes a substrate 1, a laser absorption layer 2 located in the central area of ​​the substrate 1, and a stacked thermoelectric arm array layer 3, an anti-diffusion layer 4 and an electrode layer 5 located in the peripheral area of ​​the substrate 1, and the three are located around the laser absorption layer 2 in the horizontal direction; the electrode layer 5 and the anti-diffusion layer 4 are stacked on the upper surfaces of the two side edges of the thermoelectric arm array layer 3 from top to bottom, and in the vertical direction of the device, the anti-diffusion layer 4 separates the electrode layer 5 and the thermoelectric arm array layer 3, and the anti-diffusion layer 4 is in contact and connected with the electrode layer 5 and the thermoelectric arm array layer 3 respectively.

[0193] Among them, the substrate 1 is a circular sheet structure, made of Al 2 O 3 Ceramic, thickness 0.5mm;

[0194] The laser absorption layer 2 is a cylindrical structure, made of graphene, and has a thickness of 10 μm;

[0195] The thermoelectric arm array layer 3 is composed of 8 pairs of N-type thermoelectric arms and P-type thermoelectric arms arranged alternately, and its structure is a fan-shaped structure. The thermoelectric arms are distributed at equal angles and arranged radially around the laser absorption layer 2. The N-type thermoelectric arms and the P-type thermoelectric arms have the same shape, and their cross-sections are both arc-shaped, with an arc of 17° and a thickness of 2μm. The material of the N-type thermoelectric arm is Yb 0.06 oeLh 3 , the material of the P-type thermoelectric arm is Ti 0.08 oeLh 3 Blank areas of the substrate 1 are reserved on both sides of the N-type thermoelectric arm and the P-type thermoelectric arm in the radial direction, and there are gaps between the thermoelectric arm array layer 3, the anti-diffusion layer 4 and the electrode layer 5 and the laser absorption layer 2.

[0196] The anti-diffusion layer 4 includes a first anti-diffusion component and a second anti-diffusion component respectively located on the upper surfaces of the two side edges of the thermoelectric arm array layer 3, and the material is made of Cu-Mo alloy (atomic ratio 1:1, purity 99.9%), wherein the side close to the central area of ​​the substrate 1 is the first anti-diffusion component, and the side away from the central area of ​​the substrate 1 is the second anti-diffusion component, and the cross-section shape of all anti-diffusion components is arc-shaped, with an arc of 39° and a thickness of 500nm. The inner side surface of the first anti-diffusion component close to the central area of ​​the substrate 1 is aligned with the inner side surface of the thermoelectric arm array layer 3, and the outer side surface of the second anti-diffusion component away from the central area of ​​the substrate 1 is aligned with the outer side surface of the thermoelectric arm array layer 3.

[0197] The electrode layer 5 includes a first electrode 501, a second electrode 502 and an edge electrode 503 located on the upper surface of the diffusion prevention layer. The material is Cu (purity is 99.99%). The lower surface of the electrode layer 5 is completely in contact with and overlaps with the upper surface of the diffusion prevention layer 4. The cross-sections of the first electrode 501 and the second electrode 502 are both arc-shaped, with an arc of 39° and a thickness of 1.5 μm. The first electrode 501 connects the P-type thermoelectric arm and its adjacent N-type thermoelectric arm through the first diffusion prevention component. The second electrode 502 connects the adjacent pairs of P-type thermoelectric arms and N-type thermoelectric arms through the second diffusion prevention component in an interlaced manner with the first electrode 501. The inner side surface of the first electrode 501 close to the central area of ​​the substrate 1 is aligned with the inner side surface of the thermoelectric arm array layer, and the outer side surface of the second electrode 502 away from the central area of ​​the substrate 1 is aligned with the outer side surface of the thermoelectric arm array layer. The two edge electrodes 503 are obtained by dividing a second electrode 502 according to the interval area between adjacent thermoelectric arms and extending outward to the outer edge of the substrate.

[0198] This embodiment also provides a method for preparing the radial thin film thermoelectric device, comprising:

[0199] (1) The pretreated Al 2 O 3 The ceramic substrate 1 is placed in the substrate holder, and the substrate holder is tightened to the sample stage with screws. Then the wedge-shaped structure on the first mask is aligned with the notch of the limiting groove of the substrate holder. The magnetic sheet under the substrate 1 presses the first mask to the substrate tightly. CoSb 3 Target and Yb rare earth target in Al 2 O 3 The ceramic layer substrate was subjected to interval magnetron sputtering. The parameters of the magnetron sputtering process were set. The chamber pressure before deposition was 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2Pa, the high-purity argon gas flow rate is 30sscm, CoSb 3 The DC power supply used for the target is 100W, the RF power used for the Yb target is 60W, and the CoSb 3 The total deposition time of the target is 7200s, and the Yb target is deposited on CoSb 3 The target was deposited for 100 s after every 1200 s of deposition until the deposition was completed, and an N-type thermoelectric arm structure was obtained;

[0200] Continue to use the first mask and rotate it to use CoSb 3 Target and Ti metal target in Al 2 O 3 The deposition was carried out on the ceramic layer substrate in the alternate areas with the N-type thermoelectric arms. The parameters of the magnetron sputtering process were set. The chamber pressure before deposition was 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2Pa, the high-purity argon gas flow rate is 30sscm, CoSb 3 The DC power supply used for the target is 100W, the RF power used for the Ti target is 150W, and the CoSb 3 The total deposition time of the target is 7200s, and the Ti target is deposited on CoSb 3 The target was deposited for 100 seconds after every 1200 seconds of deposition until the deposition was completed to obtain a P-type thermoelectric arm structure; then the substrate with the N-type and P-type thermoelectric arms deposited was annealed at 350°C for 1 hour in an argon atmosphere to allow the doping elements in the thermoelectric arms to diffuse evenly.

[0201] (II) The third mask was used and fixed to the substrate holder. Mo-Cu alloy (atomic number 1:1, purity 99.99%) was used as the target material. The chamber pressure before deposition was 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2 Pa, the high-purity argon gas flow rate is 30 sscm, the DC power supply power is 50 W, and the deposition time is 1800 s to obtain the diffusion-resistant layer 4;

[0202] (III) Continue to use the third mask, use Cu (purity 99.99%) as the target material, and the chamber pressure before deposition is 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2 Pa, the high-purity argon gas flow rate is 30 sscm, the DC power supply power is 200 W, and the deposition time is 3600 s, to obtain an electrode layer 5 consisting of a first electrode 501, a second electrode 502 and an outer edge electrode 503;

[0203] (IV) The sixth mask is used and fixed to the substrate holder, and the water-based graphene paint is dipped into a paint pen and manually coated on the central area of ​​the radial thin-film thermoelectric device to obtain the laser absorption layer 2, thereby preparing a radial thin-film thermoelectric device.

[0204] Example 1-2

[0205] The difference between this embodiment and embodiment 1-1 is that in the radial thin-film thermoelectric device provided in this embodiment, the N-type thermoelectric arms and the P-type thermoelectric arms alternately arranged in embodiment 1 are replaced by 8 N-type thermoelectric arms, and each N-type thermoelectric arm is also arranged at equal angles to form a fan-shaped structure. The top view of the specific structure is shown in FIG. Fig. 9 As shown, the schematic diagram of the main view of the cross-section in the radial direction is as follows Fig.10 As shown; N-type thermoelectric arms are connected in series with each other, and the connection method is: the first electrode 501 at the inner edge of the N-type thermoelectric arm and the second electrode 502 at the outer edge of the adjacent N-type thermoelectric arm are connected to each other through the third electrode 504, and the second electrode 502 at the outer edge of the same N-type thermoelectric arm and the first electrode 501 at the inner edge of the adjacent N-type thermoelectric arm on the other side are connected to each other through the third electrode 504, so as to obtain a thermoelectric arm array layer 3 in which the N-type thermoelectric arms are connected in series, and the first electrode 501, the connected second electrode 502 and the third electrode 504 used for connection form a Z-type structure to realize the series connection between the thermoelectric arms; and, the second electrode 501 at the edge of any N-type thermoelectric arm is extended outward to the outer edge 503 of the substrate, and the first electrode 501 at the edge of the adjacent N-type thermoelectric arm is extended outward to the outer edge of the substrate through the connected third electrode 504, and the outward second electrode 502 and the third electrode 504 are divided and not connected to form an outer edge electrode 503. The cross-sectional shape and arrangement of the anti-diffusion layer 5 and the electrode layer 5 in the horizontal direction are exactly the same. The lower surface of the electrode layer 5 is completely in contact with and overlaps with the upper surface of the anti-diffusion layer 4. The lower surface of the anti-diffusion component in the anti-diffusion layer 4 is partially in contact with and connected to the upper surface of the thermoelectric arm, and partially connected to the upper surface of the substrate.

[0206] Accordingly, the preparation method of the radial thin film thermoelectric device provided in this embodiment is adjusted as follows: Step (I) uses a second mask and a substrate holder for fixing, and uses CoSb 3Target and Yb rare earth target in Al 2 O 3 A magnetron sputtering process is performed on the ceramic layer substrate 1 to deposit an N-type thermoelectric arm; steps (II) and (III) are both fixed with a fourth mask and a substrate holder, and an anti-diffusion layer 4 and an electrode layer 5 are deposited in sequence.

[0207] The remaining parameters and contents are the same as those in Example 1-1.

[0208] Example 2-1

[0209] The difference between this embodiment and embodiment 1-1 is that the radial thin film thermoelectric device provided in this embodiment further includes an insulating heat conductive layer 6, which is located on the upper surface of the substrate 1 and is connected to the bottom surfaces of the laser absorption layer 2 and the thermoelectric arm array layer 3 by contact. The insulating heat conductive layer 6 is a cylinder, and the center of the bottom surface is co-pointed with the center of the substrate surface. The top view of the specific structure is shown in FIG. Fig.11 As shown, the schematic diagram of the main view of the cross-section in the radial direction is as follows Fig.13 shown.

[0210] Accordingly, the method for preparing the radial thin film thermoelectric device provided in this embodiment further includes, before depositing the N-type thermoelectric arm and the P-type thermoelectric arm on the substrate 1, first fixing the substrate 1 with a fifth mask, using BN (boron nitride, purity of 99.9%) as a target material, and the chamber pressure before deposition is 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2 Pa, the substrate is not heated, the high-purity argon flow rate is 30sscm, the RF power supply power is 250W, the deposition time is 3600s, and an insulating thermal conductive layer 6 is obtained.

[0211] The remaining parameters and contents are the same as those in Example 1-1.

[0212] Example 2-2

[0213] The difference between this embodiment and embodiment 1-2 is that the radial thin film thermoelectric device provided in this embodiment further includes an insulating heat conductive layer 6, which is located on the upper surface of the substrate 1 and is connected to the bottom surface of the laser absorption layer 2 and the thermoelectric arm array layer 3 by contact. The insulating heat conductive layer 6 is a cylinder, and the center of the bottom surface is co-pointed with the center of the substrate surface. The top view of the specific structure is shown in FIG. Fig.12 As shown, the schematic diagram of the main view of the cross-section in the radial direction is as follows Fig.13 shown.

[0214] Accordingly, the method for preparing the radial thin film thermoelectric device provided in this embodiment further includes, before depositing the N-type thermoelectric arm and the P-type thermoelectric arm on the substrate 1, first fixing the substrate 1 with a fifth mask, using BN (boron nitride, purity of 99.9%) as a target material, and the chamber pressure before deposition is 8.0×10 -4Pa, the chamber pressure during sputtering is 0.2 Pa, the substrate is not heated, the high-purity argon gas flow rate is 30sscm, the RF power supply power is 250W, the deposition time is 3600s, and the insulating thermal conductive layer 6 is obtained. The specific preparation method is shown in the flow diagram Fig.14 The actual picture of the prepared radial thin film thermoelectric device is shown in Fig.15 shown.

[0215] The remaining parameters and contents are the same as those in Example 1-2.

[0216] Example 3-1

[0217] This embodiment provides a radial thin film thermoelectric device, the top view of the specific structure is as follows Fig.16 As shown, the schematic diagram of the main view of the cross-section in the radial direction is as follows Fig.18 As shown, it includes a substrate 1, an insulating heat-conducting layer 6 and a laser absorption layer 2 located in the central area of ​​the substrate, and a stacked thermoelectric arm array layer 3, an anti-diffusion layer 4 and an electrode layer 5 located in the peripheral area of ​​the substrate, and the three are located around the laser absorption layer 2 in the horizontal direction; the electrode layer 5 and the anti-diffusion layer 4 are stacked on the lower surfaces of the two side edges of the thermoelectric arm array layer 3 from bottom to top, in the vertical direction of the device, the anti-diffusion layer 4 separates the electrode layer 5 and the thermoelectric arm array layer 3, and the anti-diffusion layer 4 is in contact with and connected to the electrode layer 5 and the thermoelectric arm array layer 3 respectively, the lower surface of the insulating heat-conducting layer 6 is in contact with and connected to the upper surface of the substrate, its upper surface is in contact with the bottom surface of the laser absorption layer 2 and the bottom surface of the electrode layer 5, and its side surface is in contact with and connected to the side surface of the thermoelectric arm array layer 3.

[0218] Among them, the substrate 1 is a cylindrical structure, made of Al 2 O 3 Ceramic, thickness 0.5mm;

[0219] The laser absorption layer 2 is a cylindrical structure, made of graphene, and has a thickness of 10 μm;

[0220] The thermoelectric arm array layer 3 is composed of 8 pairs of N-type thermoelectric arms and P-type thermoelectric arms arranged alternately, and its structure is a fan-shaped structure. The thermoelectric arms are distributed at equal angles and arranged radially around the laser absorption layer 2. The N-type thermoelectric arms and the P-type thermoelectric arms have the same shape, and their cross-sections are all arc-shaped with an arc of 17°. The thickness at all positions is 2μm. The material of the N-type thermoelectric arm is Yb 0.06 oeLh 3 , the material of the P-type thermoelectric arm is Ti 0.08 oeLh 3 Blank areas of the substrate are reserved on both sides of the N-type thermoelectric arm and the P-type thermoelectric arm in the radial direction, and gaps are spaced between the thermoelectric arm array layer 3, the anti-diffusion layer 4 and the electrode layer 5 and the laser absorption layer 2.

[0221] The anti-diffusion layer 4 includes a first anti-diffusion component and a second anti-diffusion component respectively located at the two side edges of the lower surface of the thermoelectric arm array layer 3, and the material is made of Cu-Mo alloy (atomic ratio 1:1, purity 99.9%), wherein the side close to the central area of ​​the substrate 1 is the first anti-diffusion component, and the side away from the central area of ​​the substrate 1 is the second anti-diffusion component, and the cross-section shape of all anti-diffusion components is arc-shaped, with an arc of 39° and a thickness of 500nm. In the horizontal direction, the inner side surface of the first anti-diffusion component close to the central area of ​​the substrate 1 is aligned with the inner side surface of the thermoelectric arm array layer 3, and the outer side surface of the second anti-diffusion component away from the central area of ​​the substrate 1 is aligned with the outer side surface of the thermoelectric arm array layer 3.

[0222] The electrode layer 5 is located on the lower surface of the anti-diffusion layer 4 and the upper surface of the two side edges of the substrate 1, including a first electrode 501, a second electrode 502 and an outer edge electrode 503, and is made of copper (purity is 99.99%). The upper surface of the electrode layer 5 is completely in contact with and overlaps with the lower surface of the anti-diffusion layer 4, wherein the cross-sections of the first electrode 501 and the second electrode 502 are both arc-shaped, with an arc of 39° and a thickness of 1.5 μm. The first electrode 501 connects the P-type thermoelectric arm and its adjacent N-type thermoelectric arm through the first anti-diffusion component, and the second electrode 502 connects adjacent pairs of P-type thermoelectric arms and N-type thermoelectric arms through the second anti-diffusion component in an alternating manner with the first electrode 501. The inner side surface of the first electrode 501 close to the central area of ​​the substrate 1 is aligned with the inner side surface of the thermoelectric arm array layer, and the outer side surface of the second electrode 502 away from the central area of ​​the substrate 1 is aligned with the outer side surface of the thermoelectric arm array layer. The two outer edge electrodes 503 are obtained by dividing a second electrode according to the spacing area between adjacent thermoelectric arms and extending outward to the outer edge of the substrate.

[0223] The insulating heat-conducting layer 6 is made of BN (boron nitride) (purity of 99.9%), and has a cylindrical structure, with the center of the bottom surface and the center of the substrate surface being coincident.

[0224] This embodiment also provides a method for preparing the radial thin film thermoelectric device, comprising:

[0225] S1. Pre-treated Al 2 O 3 The ceramic substrate 1 is placed in the substrate holder, and the substrate holder is tightened to the sample stage with screws. Then the wedge-shaped structure on the fifth mask is aligned with the notch of the limiting groove of the substrate holder. The magnetic sheet under the substrate 1 presses the fifth mask to the substrate tightly. BN (boron nitride, purity 99.9%) is used as the target material. The chamber pressure before deposition is 8.0×10 - 4Pa, the chamber pressure during sputtering is 0.2 Pa, the substrate is not heated, the high-purity argon flow rate is 30sscm, the RF power supply power is 250W, the deposition time is 3600s, and an insulating thermal conductive layer 6 is obtained.

[0226] S2. Continue to use the third mask, use Cu (purity 99.99%) as the target material, and the chamber pressure before deposition is 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2 Pa, the high-purity argon gas flow rate is 30 sscm, the DC power supply power is 200 W, and the deposition time is 3600 s, to obtain an electrode layer 5 consisting of a first electrode 501, a second electrode 502 and an outer edge electrode 503;

[0227] S3. The third mask was used and fixed to the substrate holder. Mo-Cu alloy (atomic number 1:1, purity 99.99%) was used as the target material. The chamber pressure before deposition was 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2 Pa, the high-purity argon gas flow rate is 30 sscm, the DC power supply power is 50 W, and the deposition time is 1800 s to obtain the diffusion-resistant layer 4;

[0228] S4. Use the first mask and fix it to the substrate holder, using CoSb 3 Target and Yb rare earth target in Al 2 O 3 The ceramic layer substrate was subjected to interval magnetron sputtering. The parameters of the magnetron sputtering process were set. The chamber pressure before deposition was 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2Pa, the high-purity argon gas flow rate is 30sscm, CoSb 3 The DC power supply used for the target is 100W, the RF power used for the Yb target is 60W, and the CoSb 3 The total deposition time of the target is 7200s, and the Pb target is on CoSb 3 The target was deposited for 100 s after every 1200 s of deposition until the deposition was completed, and an N-type thermoelectric arm structure was obtained;

[0229] Continue using the first mask and rotate the angle to use CoSb 3 Target and Ti metal target in Al 2 O 3 The ceramic layer substrate is alternately deposited with N-type thermoelectric arms, and the parameters of the magnetron sputtering process are set. The chamber pressure before deposition is 8.0×10 - 4 Pa, the chamber pressure during sputtering is 0.2Pa, the high-purity argon gas flow rate is 30sscm, CoSb 3 The DC power supply used for the target is 100W, the RF power used for the Ti target is 150W, and the CoSb 3The total deposition time of the target is 7200s, and the Ti target is deposited on CoSb 3 The target was deposited for 100 seconds after every 1200 seconds of deposition until the deposition was completed, thereby obtaining a P-type thermoelectric arm structure; the obtained device was then annealed at 350° C. for 1 hour in an argon atmosphere to allow the doping elements in the thermoelectric arm to diffuse evenly.

[0230] S5. Use the sixth mask and fix it to the substrate holder, use a paint pen to dip into the water-based graphene paint and manually apply the material of the laser absorption layer 2 on the central area of ​​the radial thin-film thermoelectric device to obtain the laser absorption layer 2, thereby preparing a radial thin-film thermoelectric device.

[0231] Example 3-2

[0232] The difference between this embodiment and embodiment 3-1 is that in the radial thin-film thermoelectric device provided in this embodiment, the alternating arrangement of the N-type thermoelectric arms and the P-type thermoelectric arms in embodiment 1 is replaced by 8 N-type thermoelectric arms, and each N-type thermoelectric arm is also arranged at equal angles. The top view of the specific structure is shown in FIG. Fig.17 As shown, the schematic diagram of the main view of the cross-section in the radial direction is as follows Fig.18 As shown; N-type thermoelectric arms are connected in series, and the connection method is: the first electrode 501 at the inner edge of the thermoelectric arm is connected to the second electrode 502 at the outer edge of the adjacent thermoelectric arm through the third electrode 504, and the second electrode 502 at the outer edge of the same thermoelectric arm is connected to the first electrode 501 at the inner edge of the thermoelectric arm adjacent to the other side through the third electrode 504, so as to obtain a thermoelectric arm layer in which the thermoelectric arms are connected in series, and the first electrode 501, the connected second electrode 502 and the third electrode 504 used for connection form a Z-shaped structure to realize the series connection between the thermoelectric arms; and the second electrode 502 at the edge of any thermoelectric arm is extended outward to the outer edge of the substrate, and the first electrode 501 at the edge of the adjacent thermoelectric arm is extended outward to the outer edge of the substrate through the connected third electrode, and the outward second electrode 502 and the third electrode 504 are divided and not connected to form an outer edge electrode 503. The cross-section shape and arrangement of the anti-diffusion layer 5 and the electrode layer 5 in the horizontal direction are exactly the same, and the upper surface of the electrode layer 5 is completely in contact with and overlaps with the lower surface of the anti-diffusion layer 4.

[0233] Accordingly, the preparation method of the radial thin film thermoelectric device provided in this embodiment is adjusted as follows: Steps S2 and S3 both use the fourth mask and the substrate holder to fix, and deposit the electrode layer 5 and the anti-diffusion layer 4 in sequence; Step S4 uses the second mask and the substrate holder to fix, and only uses CoSb 3 Target and Yb rare earth target in Al 2 O 3 A magnetron sputtering process is performed on the ceramic layer substrate to deposit an N-type thermoelectric arm.

[0234] The remaining parameters and contents are the same as those in Example 3-1.

[0235] Example 4-1

[0236] The difference between this embodiment and embodiment 3-1 is only that: in this embodiment, the laser absorption layer 2 is a composite cylindrical structure of an overall closed configuration, the cross-sectional shape of the laser absorption layer 2 in the vertical direction is T-shaped, the diameter of the cylinder at the first end is 15 mm, the height is 10 μm, the diameter of the cylinder at the second end is 10 mm, the height is 3 μm, the lower surface of the first end, the side surface of the second end, and the bottom surface of the second end are all coated with a second insulating thermal conductive layer 602, the second insulating thermal conductive layer 602 continuously covers the upper surface of the inner edge of the peripheral area of ​​the radial thin film thermoelectric device, the second insulating thermal conductive layer 602 is partially located in the interval area between the thermoelectric arm array layer 3, the anti-diffusion layer 4 and the electrode layer 5 and the laser absorption layer 2, partially located on the lower bottom surface of the first end of the laser absorption layer 2, and partially located on the surface of the first insulating thermal conductive layer 601 on the substrate 1, and the second insulating thermal conductive layer 602 on the bottom surface of the second end is connected to the first insulating thermal conductive layer 601 on the substrate by contact. The top view of the radial thin film thermoelectric device provided in this embodiment is as follows: Fig.19 As shown, the schematic diagram of the main view of the cross-section in the radial direction is as follows Fig.21 shown.

[0237] Accordingly, the method for preparing the radial thin film thermoelectric device provided in this embodiment comprises the following steps:

[0238] S1. Pre-treated Al 2 O 3 The ceramic substrate 1 is placed in the substrate holder, and the substrate holder is tightened to the sample stage with screws. Then the wedge-shaped structure on the fifth mask is aligned with the notch of the limiting groove of the substrate holder. The magnetic sheet under the substrate 1 presses the fifth mask to the substrate tightly. BN (boron nitride, purity 99.9%) is used as the target material. The chamber pressure before deposition is 8.0×10 - 4 Pa, the chamber pressure during sputtering is 0.2 Pa, the substrate is not heated, the high-purity argon flow rate is 30sscm, the RF power supply power is 250W, and the deposition time is 3600s to obtain the first insulating thermal conductive layer 601.

[0239] S2. The third mask is used and fixed to the substrate holder, and Cu (purity 99.99%) is used as the target material. The chamber pressure before deposition is 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2 Pa, the high-purity argon gas flow rate is 30 sscm, the DC power supply power is 200 W, and the deposition time is 3600 s, to obtain an electrode layer 5 consisting of a first electrode 501, a second electrode 502 and an outer edge electrode 503;

[0240] S3. Continue to use the third mask, use Mo-Cu alloy (atomic number is 1:1, purity is 99.99%) as the target material, and the chamber pressure before deposition is 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2 Pa, the high-purity argon gas flow rate is 30 sscm, the DC power supply power is 50 W, and the deposition time is 1800 s to obtain the diffusion-resistant layer 4;

[0241] S4. Use the first mask and fix it to the substrate holder, using CoSb 3 Target and Yb rare earth target in Al 2 O 3 The ceramic layer substrate was subjected to interval magnetron sputtering. The parameters of the magnetron sputtering process were set. The chamber pressure before deposition was 8.0×10 -4 Pa, the chamber pressure during sputtering is 0.2Pa, the high-purity argon gas flow rate is 30sscm, CoSb 3 The DC power supply used for the target is 100W, the RF power used for the Yb target is 60W, and the CoSb 3 The total deposition time of the target is 7200s, and the Pb target is on CoSb 3 The target was deposited for 100 s after every 1200 s of deposition until the deposition was completed, and an N-type thermoelectric arm structure was obtained;

[0242] Continue using the first mask and rotate the angle to use CoSb 3 Target and Ti metal target in Al 2 O 3 The ceramic layer substrate is alternately deposited with N-type thermoelectric arms, and the parameters of the magnetron sputtering process are set. The chamber pressure before deposition is 8.0×10 - 4 Pa, the chamber pressure during sputtering is 0.2Pa, the high-purity argon gas flow rate is 30sscm, CoSb 3 The DC power supply used for the target is 100W, the RF power used for the Ti target is 150W, and the CoSb 3 The total deposition time of the target is 7200s, and the Ti target is deposited on CoSb 3 The target was deposited for 100 seconds after every 1200 seconds of deposition until the deposition was completed, thereby obtaining a P-type thermoelectric arm structure; the obtained device was then annealed at 350° C. for 1 hour in an argon atmosphere to allow the doping elements in the thermoelectric arm to diffuse evenly.

[0243] S5. The fifth mask is used and fixed to the substrate holder, and BN (boron nitride, purity 99.9%) is used as the target material. The chamber pressure before deposition is 8.0×10 -4Pa, the chamber pressure during sputtering is 0.2Pa, the substrate is not heated, the high-purity argon flow rate is 30sscm, the RF power supply power is 250W, the deposition time is 3600s, and when sputtering the second insulating thermally conductive layer 602 located on the side, it is necessary to continuously change the target position and increase the target height to obtain the second insulating thermally conductive layer 602.

[0244] S6. Use the sixth mask and fix it with the substrate holder, use a paint pen dipped in water-based graphene paint to manually apply the material of the laser absorption layer 2 on the second insulating thermal conductive layer 602 in the central area of ​​the radial thin-film thermoelectric device to obtain the second end of the laser absorption layer 2, and then use the fifth mask and fix it with the substrate holder, continue to use a paint pen dipped in water-based graphene paint to manually apply the material of the laser absorption layer 2 on the second insulating thermal conductive layer 602 in the central area of ​​the radial thin-film thermoelectric device to obtain the first end of the laser absorption layer 2, thereby preparing a radial thin-film thermoelectric device.

[0245] The remaining parameters and contents are the same as those in Example 3-1.

[0246] Example 4-2

[0247] The difference between this embodiment and embodiment 4-1 is that in the radial thin-film thermoelectric device provided in this embodiment, the alternating arrangement of the N-type thermoelectric arms and the P-type thermoelectric arms in embodiment 4-1 is replaced by 8 N-type thermoelectric arms, and each N-type thermoelectric arm is also arranged at equal angles to form a fan-shaped structure. The top view of the specific structure is shown in FIG. Fig. 20 As shown, the schematic diagram of the main view of the cross-section in the radial direction is as follows Fig.21 As shown; N-type thermoelectric arms are connected in series, and the connection method is: the first electrode 501 at the inner edge of the thermoelectric arm and the second electrode 502 at the outer edge of the adjacent thermoelectric arm are connected to each other through the third electrode 504, and the second electrode 502 at the outer edge of the same thermoelectric arm and the first electrode 501 at the inner edge of the thermoelectric arm adjacent to the other side are connected to each other through the third electrode 504, so as to obtain a thermoelectric arm array layer 3 in which the thermoelectric arms are connected in series, and the first electrode 501, the connected second electrode 502 and the third electrode 504 used for connection form a Z-type structure to realize the series connection between the thermoelectric arms; and, the second electrode 501 at the edge of any thermoelectric arm is extended outward to the outer edge of the substrate, and the first electrode 501 at the edge of the adjacent thermoelectric arm is extended outward to the outer edge of the substrate through the connected third electrode 504, and the outward second electrode 502 and the third electrode 504 are divided and not connected to form an outer edge electrode 503. The cross-section shapes and arrangements of the diffusion prevention layer 5 and the electrode layer 5 in the horizontal direction are completely identical, and the upper surface of the electrode layer 5 is in complete contact and overlap with the lower surface of the diffusion prevention layer 4 .

[0248] Accordingly, the preparation method of the radial thin film thermoelectric device provided in this embodiment is adjusted as follows: Steps S2 and S3 both use the fourth mask and the substrate holder to fix, and deposit the electrode layer 5 and the anti-diffusion layer 4 in sequence; Step S4 uses the second mask and the substrate holder to fix, and only uses CoSb 3 Target and Yb rare earth target in Al 2 O 3 A magnetron sputtering process is performed on the ceramic layer substrate to deposit an N-type thermoelectric arm.

[0249] The remaining parameters and contents are the same as those in Example 4-1.

[0250] Example 5-1

[0251] The difference between this embodiment and embodiment 4-1 is that in the radial thin film thermoelectric device provided in this embodiment, a laser reflection layer 7 is also provided on the top layer of the thermoelectric device. The outer diameter of the laser reflection layer 7 is the same as the radius of the substrate, both of which are 25.4 mm, and its inner radius is 17.4 mm. The laser reflection layer 7 covers all parts of the outer edge of the substrate of the radial thin film thermoelectric device. The top view of the radial thin film thermoelectric device provided in this embodiment is shown in FIG. Fig. 22 As shown, the schematic diagram of the main view of the cross-section in the radial direction is as follows Fig.24 shown.

[0252] Accordingly, the method for preparing the radial thin film thermoelectric device provided in this embodiment further includes S6, and the specific process is as follows:

[0253] The laser reflection layer is prepared by laser magnetron sputtering, so that the circular sticker is attached to the central area of ​​the radial thin film thermoelectric device and is co-centered with the entire device. Its radius is 17.4 mm, and the TiO 2 The target (purity 99.99%) was used as the raw material, and the chamber pressure before deposition was 8.0×10 -4 Pa, the chamber pressure during sputtering was 0.2 Pa, the high-purity argon gas flow rate was 30 sscm, the RF power supply power was 250 W, the deposition time was 3600 s, and the laser reflection layer 7 was obtained; finally, the circular sticker was torn off.

[0254] The remaining parameters and contents are the same as those in Example 4-1.

[0255] Example 5-2

[0256] The difference between this embodiment and embodiment 4-2 is that in the radial thin film thermoelectric device provided in this embodiment, a laser reflection layer 7 is also provided on the uppermost layer of the device. The outer diameter of the laser reflection layer 7 is the same as the radius of the substrate, both of which are 25.4 mm, and the inner radius is 17.4 mm. The laser reflection layer 7 covers all parts of the outer edge of the substrate of the radial thin film thermoelectric device. The top view of the radial thin film thermoelectric device provided in this embodiment is shown in FIG. Fig.23As shown, the schematic diagram of the main view of the cross-section in the radial direction is as follows Fig.24 shown.

[0257] Accordingly, the method for preparing the radial thin film thermoelectric device provided in this embodiment further includes S6, and the specific process is as follows:

[0258] The laser reflection layer was prepared by laser magnetron sputtering. A circular sticker was pasted on the central area of ​​the radial thin-film thermoelectric device and was co-centered with the entire device. The radius was 17.4 mm. 2 The target (purity 99.99%) was used as the raw material, and the chamber pressure before deposition was 8.0×10 -4 Pa, the chamber pressure during sputtering was 0.2 Pa, the high-purity argon gas flow rate was 30 sscm, the RF power supply power was 250 W, the deposition time was 3600 s, and the laser reflection layer 7 was obtained; finally, the circular sticker was torn off.

[0259] The remaining parameters and contents are the same as those in Example 4-2.

[0260] Comparative Example 1-1

[0261] The difference between this comparative example and Example 1-1 is that the radial thin-film thermoelectric device provided in this comparative example omits the anti-diffusion layer 4 between the thermoelectric arm array layer 3 and the electrode layer 5. The remaining parameters and contents are the same as those of Example 1-1.

[0262] Comparative Example 1-2

[0263] The difference between this comparative example and Example 1-2 is that the radial thin-film thermoelectric device provided in this comparative example omits the anti-diffusion layer 4 between the thermoelectric arm array layer 3 and the electrode layer 5. The remaining parameters and contents are the same as those of Example 1-2.

[0264] The thermoelectric device of the above embodiment was subjected to laser photothermoelectric test. The test conditions were constant temperature and humidity environment (temperature 25°C, humidity 30%). An 808nm laser with a laser power of 0-100W was used (the spot size was adjustable from 5 to 60mm). During the test, the laser power used in Example 1-1 to Example 4-2 and Comparative Example 1-1 to Comparative Example 1-2 was 25W, the test distance was 20cm, and the spot diameter was 10mm; the laser power used in Examples 5-1 and 5-2 was 100W, the test distance was 140cm, and the spot diameter was 60mm; an annular water cooling was used behind the device to dissipate heat from the outer edge of the device. The test results are shown in Table 2:

[0265] Table 2

[0266]

[0267] From Table 1 we can see that:

[0268] (1) It can be seen from Examples 1-1 to 1-2 that in the radial thin film thermoelectric device provided by the present invention, the laser absorption layer arranged in the central area can absorb the heat generated by the laser, transfer the heat to the surroundings through the substrate, and reach the thermoelectric arm array layer, anti-diffusion layer and electrode layer located around the laser absorption layer. Through the mutual synergy of various components, the radial energy of the laser beam can be converted into thermoelectricity to realize the transmission of laser wireless energy.

[0269] (2) It can be seen from Example 2-1 to Example 2-2 that the present invention can efficiently transfer heat to the surroundings of the device by further providing an insulating thermal conductive layer on the upper surface of the substrate, and establish a larger temperature difference between the inner and outer ends of the thermoelectric arm array layer under the same laser power density, thereby obtaining a larger open circuit voltage and short circuit current.

[0270] (3) It can be seen from Examples 3-1 to 3-2 that the present invention stacks the electrode layer and the anti-diffusion layer on the lower surface of the two side edges of the thermoelectric arm array layer. The high thermal conductivity of the two layers can enable the insulating thermal conductive layer and the electrode layer to have better thermal conduction performance than the insulating thermal conductive layer and the thermoelectric arm array layer, thereby achieving a larger effective temperature difference and thus improving the technical effect of the laser wireless energy transmission efficiency.

[0271] (4) It can be seen from Examples 4-1 to 4-2 that the present invention further configures the laser absorption layer into a composite cylindrical structure with a T-shaped cross-section in the vertical direction and an overall closed configuration, so that a larger area of ​​the laser absorption layer covers the hot end of the device. When the laser is irradiated, the hot end of the device is directly heated, and a large temperature difference is quickly formed between the inside and outside of the device, thereby improving the efficiency of laser wireless energy transmission.

[0272] (5) It can be seen from Examples 5-1 to 5-2 that the present invention further introduces a laser reflection layer into the radial thin film thermoelectric device. When irradiated by a laser larger than the device, the outer edge of the device can reflect the laser, and only the middle hot end absorbs the laser energy, thereby establishing a temperature difference between the inside and outside of the device, thereby realizing laser wireless energy transmission.

[0273] (3) By comparing Example 1-1 with Comparative Example 1-1, and Example 1-2 with Comparative Example 1-2, it can be seen that if the anti-diffusion layer is omitted in the present invention, it will lead to element diffusion between the thermoelectric arm array layer and the electrode layer in the vertical direction at high temperature, thereby causing the internal resistance of the device to increase, and both the open circuit voltage and the short circuit current will decrease under the same laser power irradiation.

[0274] The radial thin film thermoelectric device provided in Example 2-2 was tested using an 808nm laser with a laser power of 0-100W. The test conditions were a constant temperature and humidity environment (temperature 25°C, humidity 30%). During the test, the distance between the laser and the thermoelectric device was 14cm. An annular water cooling was used behind the thermoelectric device to dissipate heat from the outer edge of the device. The test results are shown in Table 3:

[0275] Table 3

[0276]

[0277] From Table 2 we can see that:

[0278] The radial thin-film thermoelectric device provided by the present invention can convert the light energy of the laser into heat and electricity under different laser powers, thereby realizing the application of laser wireless energy transmission.

[0279] Among them, through Fig.25 It can be seen that the absorption rate of the laser absorption layer used in Example 2-2 under 808nm laser is 93.94%.

[0280] Fig.26 This is a thermal imaging picture of the radial thin film thermoelectric device of Example 2-2 under a 25W laser power test. It can be seen from the figure that under laser irradiation, the laser absorption layer can convert the laser into heat and transfer the heat to the surroundings. According to the temperature distribution in the picture, the temperature of the laser absorption layer is 230°C, the temperature of the thermoelectric arm close to the laser absorption layer is 160°C, and the temperature of the thermoelectric arm away from the laser absorption layer is 32°C, which intuitively shows that the device forms an effective temperature difference in the radial direction under laser irradiation, thereby applying laser wireless energy transmission.

[0281] Fig. 27 A graph showing the relationship between laser power and temperature of the radial thin film thermoelectric device of Example 2-2 is given. It can be seen from the graph that the temperature of the laser absorption layer is transferred to the hot end of the radial thin film thermoelectric device (the end of the thermoelectric arm array layer close to the laser receiving layer) through heat conduction, and then to the cold end of the radial thin film thermoelectric device (the end of the thermoelectric arm array layer far from the laser receiving layer). The temperature difference of the thermoelectric device increases with the increase of laser irradiation energy.

[0282] Fig.28 A relationship diagram between the open circuit voltage and short circuit current of the radial thin film thermoelectric device of Example 2-2 under different laser power densities is given. It can be seen from the figure that under laser irradiation, the radial thin film thermoelectric device has good output performance and can output a maximum of about 6.25μW of energy under 25W laser irradiation.

[0283] In summary, in the radial thin-film thermoelectric device provided by the present invention, the laser absorption layer arranged in the central area can absorb the heat generated by the laser, transfer the heat to the surroundings through the substrate, and reach the thermoelectric arm array layer, anti-diffusion layer and electrode layer located around the laser absorption layer. Through the mutual synergy of various components, the radial energy of the laser beam can be converted into thermoelectricity to realize the transmission of laser wireless energy.

[0284] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A radial thin film thermoelectric device, characterized in that: The radial thin film thermoelectric device comprises a substrate, a thermoelectric arm array layer, an anti-diffusion layer and an electrode layer stacked in the peripheral area of ​​the substrate surface, and a laser absorption layer located in the central area of ​​the substrate; The thermoelectric arm array layer, the anti-diffusion layer and the electrode layer are all located around the laser absorption layer in the horizontal direction, and the thermoelectric arm array layer includes thermoelectric arms, and the thermoelectric arms are arranged radially around the laser absorption layer; The electrode layer and the anti-diffusion layer are located at the edges of both sides of the thermoelectric arm array layer, and the thermoelectric arms, the electrode layer and the anti-diffusion layer are in contact and connection.

2. The radial thin film thermoelectric device according to claim 1, characterized in that: The substrate is any one of a circular sheet structure or a polygonal sheet structure; Preferably, in the horizontal direction of the radial thin-film thermoelectric device, blank areas of the substrate are reserved on both sides of the thermoelectric arm array layer in the radial direction; Preferably, the thermoelectric arm array layer, the anti-diffusion layer and the electrode layer are spaced apart from the laser absorption layer; Preferably, in the vertical direction of the radial thin film thermoelectric device, the electrode layer and the thermoelectric arm array layer are separated by the anti-diffusion layer; Preferably, the anti-diffusion layer comprises at least four anti-diffusion components; Preferably, in the horizontal direction of the radial thin film thermoelectric device, the side of the anti-diffusion layer close to the central area of ​​the substrate is a first anti-diffusion component, and the side away from the central area of ​​the substrate is a second anti-diffusion component; Preferably, the electrode layer comprises at least two first electrodes and at least two second electrodes; Preferably, in the horizontal direction of the radial thin film thermoelectric device, the side of the electrode layer close to the central area of ​​the substrate is the first electrode, and the side away from the central area of ​​the substrate is the second electrode; Preferably, the thermoelectric arm array layer includes at least two thermoelectric arms; Preferably, the thermoelectric arms are arranged at equal angles to form a fan-shaped structure; Preferably, in the vertical direction of the radial thin film thermoelectric device, the first anti-diffusion component, the first electrode and the edge of one side of the thermoelectric arm close to the central area of ​​the substrate are stacked; Preferably, the inner side surfaces of the first anti-diffusion component and the first electrode close to the central area of ​​the substrate are aligned with the inner side surfaces of the thermoelectric arm; Preferably, in the vertical direction of the radial thin film thermoelectric device, the second anti-diffusion component, the second electrode and the edge of the thermoelectric arm away from the central area of ​​the substrate are stacked; Preferably, the outer side surfaces of the second anti-diffusion component and the second electrode away from the central area of ​​the substrate are aligned with the outer side surfaces of the thermoelectric arm; Preferably, in the radial direction of the radial thin-film thermoelectric device, the radial length of the thermoelectric arm is greater than the sum of the radial length of the first electrode and the radial length of the second electrode; Preferably, in the radial direction of the radial thin-film thermoelectric device, the radial length of the thermoelectric arm is greater than the sum of the radial length of the first anti-diffusion component and the radial length of the second anti-diffusion component; Preferably, the laser absorption layer comprises any one of a cylinder, a polygonal columnar structure and a composite structure of their combination.

3. The radial thin film thermoelectric device according to claim 2, characterized in that: The thermoelectric arm array layer includes one or two thermoelectric arms; Preferably, the thermoelectric arms are connected in series via a first electrode and a second electrode at both ends of the thermoelectric arms; Preferably, the thermoelectric arm array layer includes two types of thermoelectric arms, and the thermoelectric arms are P-type thermoelectric arms and N-type thermoelectric arms that are alternately arranged; Preferably, the thermoelectric arm array layer includes two types of thermoelectric arms, the first electrode connects the P-type thermoelectric arm and its adjacent N-type thermoelectric arm through a first anti-diffusion component, and the second electrode connects adjacent pairs of the P-type thermoelectric arm and the N-type thermoelectric arm through a second anti-diffusion component in a staggered manner with the first electrode; Preferably, the thermoelectric arm array layer includes two types of thermoelectric arms, and any one of the second electrodes is divided according to the interval area of ​​the connected adjacent thermoelectric arms and extended outward to the outer edge of the substrate to form two outer edge electrodes; Preferably, the thermoelectric arm array layer includes a thermoelectric arm, and the thermoelectric arm includes any one of a P-type thermoelectric arm or an N-type thermoelectric arm; Preferably, the thermoelectric arm array layer comprises a thermoelectric arm, wherein a first electrode at an inner edge of the thermoelectric arm and a second electrode at an outer edge of an adjacent thermoelectric arm are connected to each other via a third electrode, and a second electrode at an outer edge of the same thermoelectric arm and a first electrode at an inner edge of an adjacent thermoelectric arm on the other side are connected to each other via a third electrode, so as to obtain a thermoelectric arm array layer in which the thermoelectric arms are connected in series. Preferably, the first electrode, the connected second electrode and the third electrode for connection form a Z-shape in the horizontal direction; Preferably, the thermoelectric arm array includes a thermoelectric arm, wherein the second electrode at the edge of any thermoelectric arm is extended outward to the outer edge of the substrate, and the first electrode at the edge of an adjacent thermoelectric arm is extended outward to the outer edge of the substrate through a connected third electrode, and the second electrode and the third electrode are divided and not connected to form two outer edge electrodes.

4. The radial thin film thermoelectric device according to any one of claims 1 to 3, characterized in that: The electrode layer and the anti-diffusion layer are sequentially stacked on the upper surfaces of the edges of both sides of the thermoelectric arm array layer from top to bottom; Preferably, in the vertical direction of the radial thin film thermoelectric device, a first insulating heat conducting layer is further provided between the laser absorption layer and the substrate; Preferably, the radial length of the first insulating heat-conducting layer is greater than the radial length of the laser absorption layer; Preferably, in the vertical direction of the radial thin film thermoelectric device, the first insulating heat conductive layer is partially located between the substrate and the thermoelectric arm array layer.

5. The radial thin film thermoelectric device according to any one of claims 1 to 3, characterized in that: The electrode layer and the anti-diffusion layer are sequentially stacked on the lower surfaces of the two side edges of the thermoelectric arm array layer from bottom to top, the two side edges of the thermoelectric arm array layer are covered on the stacked anti-diffusion layer and the electrode layer, and the lower surface of the edge of the thermoelectric arm array layer is in contact with the upper surface of the anti-diffusion layer; Preferably, a first insulating heat-conducting layer is further provided in the central area of ​​the upper surface of the substrate in the vertical direction of the radial thin-film thermoelectric device; Preferably, in the radial direction of the radial thin-film thermoelectric device, the radial length of the first insulating heat-conducting layer is greater than the radial length of the laser absorption layer, the upper surface of the first insulating heat-conducting layer is in contact with the lower surface of the laser absorption layer and the lower surface of the electrode layer, and the side surface of the first insulating heat-conducting layer is in contact with the thermoelectric arm; Preferably, the laser absorption layer is a cylindrical and / or composite cylindrical structure with an overall closed configuration; Preferably, the laser absorption layer is a composite cylindrical structure of an overall closed configuration, and its vertical cross-sectional shape is T-shaped; Preferably, the composite cylindrical structure of the laser absorption layer comprises a first end and a second end, wherein the diameter of the first end is greater than the diameter of the second end; Preferably, the lower bottom surface of the first end, the side surface of the second end and the bottom surface of the second end are all covered with a continuous second insulating heat-conducting layer; Preferably, the second insulating thermally conductive layer is partially located in the spacing area between the thermoelectric arm array layer, the anti-diffusion layer and the electrode layer and the laser absorption layer, partially located at the lower bottom surface of the first end of the laser absorption layer, and partially located on the surface of the first insulating thermally conductive layer on the substrate.

6. The radial thin film thermoelectric device according to any one of claims 1 to 5, characterized in that: The uppermost layer in the vertical direction of the radial thin film thermoelectric device is also provided with a laser reflection layer; Preferably, the horizontal top view of the laser reflective layer is in a closed annular shape; Preferably, the laser reflection layer is located on the upper surface of the outer edge of the radial thin film thermoelectric device; Preferably, in the vertical direction of the radial thin film thermoelectric device, the laser reflection layer overlaps and / or partially overlaps with the thermoelectric arm array layer, the anti-diffusion layer, the electrode layer and the substrate in the radial direction; Preferably, in the radial direction of the radial thin film thermoelectric device, the radial length of the laser reflection layer is greater than the sum of the radial length of the electrode layer and the radial length of the outer edge blank area of ​​the substrate; Preferably, an outer side surface of the laser reflection layer away from the central area of ​​the substrate is aligned with a side surface of an outer edge of the substrate.

7. A radial thin film thermoelectric device according to any one of claims 1 to 6, characterized in that: The preparation method comprises: A thermoelectric arm array layer, an anti-diffusion layer, an electrode layer and a laser absorption layer are deposited on a substrate respectively by using a mask technology, wherein the thermoelectric arm array layer, the anti-diffusion layer and the electrode layer are stacked in a peripheral area on the surface of the substrate, and the laser absorption layer is located in a central area on the surface of the substrate; The thermoelectric arm array layer, the anti-diffusion layer and the electrode layer are all located around the laser absorption layer in the horizontal direction, and the thermoelectric arm array layer includes thermoelectric arms, which are arranged radially around the laser absorption layer. The electrode layer and the anti-diffusion layer are located at the edges of both sides of the thermoelectric arm array layer, and the thermoelectric arms, the electrode layer and the anti-diffusion layer are in contact and connection.

8. The preparation method according to claim 7, characterized in that: The preparation method further comprises depositing a first insulating heat-conducting layer on the substrate before depositing the thermoelectric arm array layer, the anti-diffusion layer, the electrode layer and the laser absorption layer, and / or the preparation method further comprises depositing the second insulating heat-conducting layer in the interval area between the thermoelectric arm array layer, the anti-diffusion layer and the electrode layer and the laser absorption layer, on the lower bottom surface of the first end of the laser absorption layer, and on the surface of the first insulating heat-conducting layer; Preferably, the preparation method further comprises depositing a laser reflection layer after depositing the thermoelectric arm array layer, the anti-diffusion layer, the electrode layer and the laser absorption layer; Preferably, the mask technology uses a hollow mask, and the hollow mask is placed on the surface of the substrate to deposit various components in the radial thin film thermoelectric device; Preferably, the hollow mask has a wedge-shaped structure; Preferably, in the mask technology, a substrate holder is used to position the hollow mask; Preferably, a limiting groove is provided on the substrate holder, and the notch of the limiting groove is aligned with the wedge-shaped structure on the hollow mask to position the hollow mask.

9. The preparation method according to claim 8, characterized in that: The hollow mask includes a first mask, a second mask, a third mask, a fourth mask, a fifth mask and a sixth mask; Preferably, the first mask is used to prepare a thermoelectric arm array layer of two types of thermoelectric arms; Preferably, the second mask is used to prepare a thermoelectric arm array layer of a thermoelectric arm; Preferably, the third mask is used to prepare the electrode layer and the anti-diffusion layer of the two thermoelectric arms; Preferably, the fourth mask is used to prepare an electrode layer and an anti-diffusion layer of a thermoelectric arm; Preferably, the fifth mask is used to prepare an insulating thermal conductive layer and / or a laser absorption layer; Preferably, the sixth mask is used to prepare a laser absorption layer.

10. An application of the radial thin film thermoelectric device according to any one of claims 1 to 6, characterized in that: The radial thin film thermoelectric device is used for laser wireless energy transmission.

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