CN112234137B - Large-area flexible thermoelectric refrigeration thin film cascade device and preparation method thereof - Google Patents
Large-area flexible thermoelectric refrigeration thin film cascade device and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a large-area flexible thermoelectric refrigeration film cascade device and a preparation method thereof. The invention has the advantages of simple process, high processing speed, less material waste, high manufacturing precision and the like, and the manufactured large-area flexible thermoelectric refrigeration thin film cascade device has good refrigeration performance, can effectively reduce the temperature of a heat source, and is expected to be applied to the fields of efficient heat dissipation, bidirectional accurate temperature control, heat-sensitive sensors and the like of electronic devices.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a large-area flexible thermoelectric refrigeration thin film cascade device and a preparation method thereof.
Background
With the rapid development of microelectronic integration technology, the performance of the processor is higher and the size is smaller, and meanwhile, the heating value of the processor is also increased, so that development of an efficient thermal management scheme is urgently needed. The thermoelectric material is a new energy material capable of realizing the mutual conversion of heat energy and electric energy, and the thermoelectric device prepared by the thermoelectric material has the advantages of small volume, high reliability, quick response, no pollution, no noise, no moving parts and the like, and is applied to the fields of deep space power supply, automobile exhaust power generation, micro temperature difference power generation, refrigeration and the like. The flexible refrigeration device based on the thermoelectric film also has the advantages of high power density, high efficiency, small volume, flexibility, low cost and the like, and is expected to be applied to the fields of high-efficiency heat dissipation, bidirectional accurate temperature control, heat-sensitive sensors and the like of electronic devices.
At present, the preparation technology of the thermoelectric refrigeration thin film device mainly comprises a mask plate auxiliary magnetron sputtering and evaporation coating technology and a photoetching auxiliary magnetron sputtering and evaporation coating technology. The mask plate auxiliary magnetron sputtering and evaporation coating technology has the problems of extremely low material utilization rate and the like, and the technical precision is limited by the precision of the mask plate. Although the photoetching auxiliary magnetron sputtering and evaporation coating technology can realize micro-nano processing of the thermoelectric element, the precision of the technology depends on the precision of a light source and a mask plate, and the problems of complex etching process, serious waste of raw materials, performance deterioration caused by the etching process and the like exist. In addition, magnetron sputtering and evaporation coating technologies can only ensure uniformity of a small-area film, and are only used for preparing films with an area smaller than 1-2cm at present 2 Is a thermoelectric refrigeration thin film device. Therefore, development of a large-area thermoelectric refrigeration thin film device and a high-precision manufacturing technique thereof is urgently required.
The screen printing method has the advantages of simple process, short time consumption, no need of precise and complex equipment and the like, and is a method for efficiently preparing the thermoelectric film in large area and scale. The stability and printability of the printing paste can be ensured by adding high molecular resin into the thermoelectric paste for printing in the prior art, but organic matters are decomposed and volatilized by the subsequent heat treatment process, so that defects such as holes, cracks and the like are formed in the film, and meanwhile, the organic matters remained in the thermoelectric film can block carrier transportation, so that the electrical property of the thermoelectric film is deteriorated. Around the difficult problem, a new technology for realizing the in-situ preferred orientation of crystal grains by the hot-pressing solidification of epoxy resin for preparing high-performance flexible thermoelectric film by adopting a screen printing method is developed in advance, and the electric transport performance is obviously improvedHigh (250% improvement in power factor) Bi 0.5 Sb 1.5 Te 3 The power factor of the epoxy flexible thermoelectric film is 223% higher than the best result reported at present for the thermoelectric film of the same type. However, the hot press curing process can squeeze the film, so that the edge of the film is widened and even stuck, the structural accuracy of the device is seriously affected, and the refrigeration performance is deteriorated.
The laser etching technology irradiates high-energy laser beam to the surface of the etched workpiece, and forms high power density at the focus to enable the material to be vaporized and evaporated instantaneously. The technology has the advantages of small heat affected zone, high processing speed, no noise and the like, can obtain good dimensional accuracy and processing quality, and is widely applied to the fields of solar cells, electronic semiconductor materials and the like with higher requirements on processing accuracy and process control. Therefore, the invention creatively proposes that the high-performance thin film thermoelectric arm is prepared by adopting screen printing and hot-pressing curing technology, and then the edge of the thermoelectric arm is precisely patterned by adopting laser etching high-precision processing technology, so that the material waste is reduced, and the high-precision manufacturing of the thermoelectric device is realized.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a preparation method of a large-area flexible thermoelectric refrigeration thin film cascade device, which mainly comprises the following steps: (a) Preparing thermoelectric slurry by taking thermoelectric materials, high polymer resin and solvent as raw materials; (b) Screen printing the thermoelectric slurry on a flexible substrate, and hot-pressing to obtain a thermoelectric film; (c) And preparing thermoelectric arms and electrodes on the thermoelectric thin film to obtain the large-area flexible thermoelectric refrigeration thin film cascade device.
Further, the thermoelectric material is selected from p-type or n-type Bi 2 Te 3 Base thermoelectric material, sb 2 Te 3 At least one of the base thermoelectric materials is crushed into powder with the particle size not exceeding 120 mu m before use.
Further, the polymer resin is at least one selected from the group consisting of epoxy resin, acrylic resin, polyurethane resin, and cellulose resin, preferably epoxy resin, more preferably bisphenol F diglycidyl ether epoxy resin.
Further, the solvent is at least one selected from absolute ethyl alcohol, acetone, toluene and butyl glycidyl ether.
Further, the weight ratio of the thermoelectric material, the high polymer resin and the solvent in the slurry is 1:0.05-0.2:0.1-0.5.
Further, the raw materials for preparing the slurry also comprise a curing agent, a catalyst and a surface auxiliary agent, wherein the mass fractions of the curing agent, the catalyst and the surface auxiliary agent in the slurry are respectively 2% -5%, 0.5% -1% and 2% -5%.
Further, the curing agent is at least one selected from methyl hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride, the catalyst is specifically 2-ethyl-4-methylimidazole, and the surface auxiliary agent is specifically graphene.
Further, the specific process of step (a) is as follows: grinding and sieving the thermoelectric material to obtain powder, adding a solvent, fully ball-milling under a protective atmosphere, centrifuging, collecting lower-layer slurry, and fully drying to obtain thermoelectric powder; mixing polymer resin and solvent in certain proportion, adding thermoelectric powder and stirring to obtain thermoelectric slurry.
Furthermore, a surface auxiliary agent is added in the process of preparing the thermoelectric powder, and raw materials such as a curing agent, a catalyst and the like are also added in the process of preparing the thermoelectric slurry by mixing and stirring.
Further, the flexible substrate in the step (b) is specifically a polyimide substrate, which needs to be sufficiently washed and dried before being used.
Further, the specific process of step (b) is as follows: printing electrode slurry on a flexible substrate in a single or multiple screen printing mode, and performing hot-pressing sintering after the electrode slurry is naturally leveled and dried, wherein the hot-pressing sintering process parameters are as follows: the temperature is 150-450 ℃ and the pressure is 1-20MPa.
Further, in the step (c), a thermoelectric leg is first prepared on the thermoelectric film by using a laser etching method, and then an electrode is prepared on the thermoelectric film by using a vacuum coating method.
Furthermore, the laser used in the laser etching method is specifically an ultraviolet laser with the power of 2-20W.
Further, the electrode is made of at least one material selected from Al, cu, ni, ag, ti.
Furthermore, the side length of the manufactured large-area flexible thermoelectric refrigeration film cascade device is 10mm-200mm, and the thickness of the thermoelectric legs is 10 mu m-500 mu m.
The invention also aims to provide a large-area flexible thermoelectric refrigeration film cascade device manufactured according to the method, which has at least two stages, wherein the first stage is a refrigeration area, and the rest stages are heat dissipation areas.
Compared with the prior art, the invention has the following beneficial effects: (1) By introducing the surface auxiliary agent graphene, the electric transport performance of the film is greatly improved, and the refrigerating capacity of the device is improved; (2) By optimizing the formula of the thermoelectric slurry, defects formed in the hot pressing treatment of the thermoelectric film are avoided to the greatest extent, and further electrical property degradation is avoided; (3) After the high-performance thermoelectric film is prepared, a laser etching method and a vacuum coating method are sequentially adopted to prepare thermoelectric arms and electrodes on the thermoelectric film, so that a large-area flexible thermoelectric refrigeration film cascade device is prepared, the internal resistance of the device is reduced, the refrigeration performance of the device is improved, heat of a heat source is transmitted from a refrigeration end to a heat dissipation end, and the temperature of the heat source is effectively reduced; (4) Compared with the magnetron sputtering and evaporation coating technology, the method can only prepare the film with the area of 1-2cm 2 The inventive method enables the production of devices having an area of up to 400cm 2 The flexible thermoelectric refrigeration thin film cascade device has the advantages of simple process, high material utilization rate, high processing precision, good material performance and the like.
Drawings
FIG. 1 is a schematic diagram of a large-area flexible thermoelectric refrigeration film five-stage cascade device manufactured in embodiments 1-3 of the present invention;
FIG. 2 is a physical diagram of a five-stage cascade device of a large-area flexible thermoelectric refrigeration film, which is prepared in embodiment 2 of the invention;
FIG. 3 is a schematic structural diagram of a five-stage cascade device of a large-area flexible thermoelectric refrigeration film prepared in example 4 of the present invention;
FIG. 4 is a physical diagram of a five-stage cascade device of a large-area flexible thermoelectric refrigeration film, which is prepared in example 4 of the present invention;
FIG. 5 is a graph showing the relationship between the temperature and time in the central refrigeration zone of the five-stage cascade device of the large-area flexible thermoelectric refrigeration film prepared in examples 1 to 4 of the present invention.
Detailed Description
In order to make the technical scheme and the beneficial effects of the present invention fully understood by those skilled in the art, the following description is further made with reference to specific embodiments and drawings.
Example 1
The structure of the large-area flexible thermoelectric refrigeration film five-stage cascade device manufactured by the embodiment is shown in figure 1 (black area is thermoelectric arm, gray area is electrode), and the whole size of the device is 68 multiplied by 57mm 2 The first stage is a refrigerating area, and the remaining four stages are heat dissipation areas. The preparation method of the device specifically comprises the following steps:
to p-type Bi 0.5 Sb 1.5 Te 3 Crushing and grinding the crystal bar, and sieving the crushed crystal bar with a 120-mesh screen to obtain standby powder with the particle size smaller than 120 mu m;
weighing the Bi according to the calculated mass percentage 0.5 Sb 1.5 Te 3 9.9g of powder and 0.1g of graphene are added into a high-energy ball milling tank (ball-material ratio is 55:1), 50mL of absolute ethyl alcohol is added as a ball milling medium, and after sealing, the ball milling is started after vacuumizing and Ar gas protection are carried out. Ball milling process parameters: ball milling rotation speed is 200r/min, ball milling is carried out for 2h;
centrifuging the ball-milled powder at 4000r/min for 10min, taking down the slurry, placing the slurry in a vacuum drying oven, heating to 60 ℃, and then preserving heat and vacuum drying for 3h to obtain thermoelectric powder for later use;
weighing 0.613g of bisphenol F diglycidyl ether epoxy resin, 0.521g of methyl hexahydrophthalic anhydride, 0.123g of 2-ethyl-4-methylimidazole, 3.543g of butyl glycidyl ether, uniformly mixing to obtain an epoxy resin solution, adding 9.85g of thermoelectric powder, fully mixing and stirring to obtain uniform and stable Bi 0.5 Sb 1.5 Te 3 A base thermoelectric slurry;
cutting 10X 10cm 2 Placing the polyimide substrate with the size in absolute ethyl alcohol, ultrasonically cleaning for 5min, and drying to obtain a substrate to be used; using a single sheetPrinting the thermoelectric slurry on a substrate by a secondary screen printing method to obtain a large-area thermoelectric wet film; and (3) leveling and drying the printed wet film, and then placing the wet film into a hot press for hot pressing and sintering, wherein the hot pressing process parameters are as follows: the temperature is 340 ℃, the pressure is 16MPa, and the time is 4 hours;
performing accurate patterning treatment on the thermoelectric film obtained by hot pressing by using a laser etching machine to obtain a thermoelectric arm, wherein specific etching parameters are as follows: the wavelength of the light beam is 355nm, the average power of the light beam intensity is more than 5W, and the diameter of the light beam is 0.02mm;
and carrying out vacuum evaporation on Ni, cu and Al electrodes on the sample subjected to laser etching, and connecting all thermoelectric arms in series or in parallel to obtain the flexible thermoelectric film five-stage cascade refrigerating device.
To fully understand the performance of the thermoelectric device manufactured in this example, a refrigeration performance test was performed to obtain a graph of the temperature versus time of the central refrigeration zone as shown in fig. 5-a. As can be seen from the figure, when the thermoelectric refrigeration device is loaded with an operating current of 0.3A, the temperature of the heat source can be reduced from 41.8 ℃ to 41.4 ℃ with a temperature reduction range of 0.4 ℃.
Example 2
The schematic structural diagram and the physical photo of the large-area flexible thermoelectric refrigeration film five-stage cascade device manufactured by the embodiment are shown in fig. 1-2 respectively, and the device manufacturing method specifically comprises the following steps:
to p-type Bi 0.5 Sb 1.5 Te 3 Crushing and grinding the crystal bar, and sieving the crushed crystal bar with a 120-mesh screen to obtain standby powder with the particle size smaller than 120 mu m;
weighing the Bi according to the calculated mass percentage 0.5 Sb 1.5 Te 3 9.9g of powder and 0.1g of graphene are added into a high-energy ball milling tank (ball-material ratio is 55:1), 50mL of absolute ethyl alcohol is added as a ball milling medium, and after sealing, the ball milling is started after vacuumizing and Ar gas protection are carried out. Ball milling process parameters: ball milling rotation speed is 200r/min, ball milling is carried out for 2h;
centrifuging the ball-milled powder at 4000r/min for 10min, taking down the slurry, placing the slurry in a vacuum drying oven, heating to 60 ℃, and then preserving heat and vacuum drying for 3h to obtain thermoelectric powder for later use;
weighing bisphenol F diglycidylGlycerin ether epoxy resin 0.613g, methyl hexahydrophthalic anhydride 0.521g, 2-ethyl-4-methylimidazole 0.123g, butyl glycidyl ether 3.543g, and uniformly mixing to obtain an epoxy resin solution; adding 9.85g of the thermoelectric powder, fully mixing and stirring to obtain uniform and stable Bi 0.5 Sb 1.5 Te 3 A base thermoelectric slurry;
cutting 10X 10cm 2 Placing the polyimide substrate with the size in absolute ethyl alcohol, ultrasonically cleaning for 5min, and drying to obtain a substrate to be used; printing the thermoelectric slurry on a substrate by adopting a multi-time screen printing method to obtain a large-area thermoelectric wet film; and (3) leveling and drying the printed wet film, and then placing the wet film into a hot press for hot pressing and sintering, wherein the hot pressing process parameters are as follows: the temperature is 340 ℃, the pressure is 10MPa, and the time is 4 hours;
performing accurate patterning treatment on the thermoelectric film obtained by hot pressing by using a laser etching machine to obtain a thermoelectric arm, wherein specific etching parameters are as follows: the wavelength of the light beam is 355nm, the average power of the light beam intensity is more than 5W, and the diameter of the light beam is 0.02mm;
and carrying out vacuum evaporation on Ni, cu and Al electrodes on the sample subjected to laser etching, and connecting all thermoelectric arms in series or in parallel to obtain the flexible thermoelectric film five-stage cascade refrigerating device.
The thermoelectric device manufactured in this example was tested for refrigerating performance by the same method, and the result is shown in fig. 5-b. As shown in the figure, when the working current of the thermoelectric refrigeration device is 0.6A, the temperature of the heat source can be reduced from 41.2 ℃ to 40.4 ℃ and the temperature reduction amplitude reaches 0.8 ℃.
Example 3
The structure of the large-area flexible thermoelectric refrigeration film five-stage cascade device manufactured by the embodiment is shown in fig. 1, and the specific manufacturing method is as follows:
to p-type Bi 0.5 Sb 1.5 Te 3 Crushing and grinding the crystal bar, and sieving the crushed crystal bar with a 120-mesh screen to obtain standby powder with the particle size smaller than 120 mu m;
weighing the Bi according to the calculated mass percentage 0.5 Sb 1.5 Te 3 9.9g of powder and 0.1g of graphene are added into a high-energy ball milling tank (ball-material ratio is 55:1), 50mL of absolute ethyl alcohol is added as a ball milling medium, and the ball milling medium is sealedAnd vacuumizing, and charging Ar gas for protection, and starting ball milling. Ball milling process parameters: ball milling rotation speed is 200r/min, ball milling is carried out for 2h;
centrifuging the ball-milled powder for 10min at the rotating speed of 4000r/min, taking down the layer of slurry, placing the slurry in a vacuum drying oven, heating to 60 ℃, and then preserving heat and vacuum drying for 3h to obtain the thermoelectric powder for standby;
0.613g of bisphenol F diglycidyl ether epoxy resin, 0.521g of methyl hexahydrophthalic anhydride, 0.123g of 2-ethyl-4-methylimidazole and 3.543g of butyl glycidyl ether are weighed and uniformly mixed to obtain an epoxy resin solution; adding 9.85g of the thermoelectric powder, fully mixing and stirring to obtain uniform and stable Bi 0.5 Sb 1.5 Te 3 A base thermoelectric slurry;
cutting 10X 10cm 2 Placing the polyimide substrate with the size in absolute ethyl alcohol, ultrasonically cleaning for 5min, and drying to obtain a substrate to be used; printing the thermoelectric slurry on a substrate by adopting a multi-time screen printing method to obtain a large-area thermoelectric wet film; and (3) leveling and drying the printed wet film, and then placing the wet film into a hot press for hot pressing and sintering, wherein the hot pressing process parameters are as follows: the temperature is 340 ℃, the pressure is 10MPa, and the time is 4 hours;
performing accurate patterning treatment on the thermoelectric film obtained by hot pressing by using a laser etching machine to obtain a thermoelectric arm, wherein specific etching parameters are as follows: the wavelength of the light beam is 355nm, the average power of the light beam intensity is more than 5W, and the diameter of the light beam is 0.02mm;
and carrying out vacuum evaporation on Ni, cu and Al electrodes on the sample subjected to laser etching, and connecting all thermoelectric arms in series or in parallel to obtain the flexible thermoelectric film five-stage cascade refrigerating device.
The thermoelectric device manufactured in this example was tested for its refrigerating performance by the same method, and the result is shown in fig. 5-c. As shown in the figure, when the working current of the thermoelectric refrigeration device is 1.2A, the temperature of the heat source can be reduced from 41.8 ℃ to 40.4 ℃ and the temperature reduction amplitude reaches 1.4 ℃.
Example 4
The structure schematic diagram and the physical photo of the large-area flexible thermoelectric refrigeration film five-stage cascade device manufactured by the embodiment are respectively shown in figures 3-4, and the whole size of the device is 74 multiplied by 135mm 2 . The method comprisesThe preparation method of the device comprises the following steps:
to p-type Bi 0.5 Sb 1.5 Te 3 Crushing and grinding the crystal bar, and sieving the crushed crystal bar with a 120-mesh screen to obtain standby powder with the particle size smaller than 120 mu m;
weighing the Bi according to the calculated mass percentage 0.5 Sb 1.5 Te 3 9.9g of powder and 0.1g of graphene are added into a high-energy ball milling tank (ball-material ratio is 55:1), 50mL of absolute ethyl alcohol is added as a ball milling medium, and after sealing, the ball milling is started after vacuumizing and Ar gas protection are carried out. Ball milling process parameters: ball milling rotation speed is 200r/min, ball milling is carried out for 2h;
centrifuging the ball-milled powder at a rotating speed of 4000r/min for 10min, taking down the layer of slurry, placing the slurry in a vacuum drying oven, heating to 60 ℃, and then preserving heat and drying in vacuum for 3h to obtain the thermoelectric powder for standby;
0.613g of bisphenol F diglycidyl ether epoxy resin, 0.521g of methyl hexahydrophthalic anhydride, 0.123g of 2-ethyl-4-methylimidazole and 3.543g of butyl glycidyl ether are weighed and uniformly mixed to obtain an epoxy resin solution; adding 9.85g of the thermoelectric powder, fully mixing and stirring to obtain uniform and stable Bi 0.5 Sb 1.5 Te 3 A base thermoelectric slurry;
cutting 16X 10cm 2 Placing the polyimide substrate with the size in absolute ethyl alcohol, ultrasonically cleaning for 5min, and drying to obtain a substrate to be used; printing the thermoelectric slurry on a substrate by adopting a multi-time screen printing method to obtain a large-area thermoelectric wet film; and (3) leveling and drying the printed wet film, and then placing the wet film into a hot press for hot pressing and sintering, wherein the hot pressing process parameters are as follows: the temperature is 340 ℃, the pressure is 16MPa, and the time is 4 hours;
performing accurate patterning treatment on the thermoelectric film obtained by hot pressing by using a laser etching machine to obtain a thermoelectric arm, wherein specific etching parameters are as follows: the wavelength of the light beam is 355nm, the average power of the light beam intensity is more than 5W, and the diameter of the light beam is 0.02mm;
and carrying out vacuum evaporation on Ni, cu and Al electrodes on the sample subjected to laser etching, and connecting all thermoelectric arms in series or in parallel to obtain the flexible thermoelectric film five-stage cascade refrigerating device.
The thermoelectric device manufactured in this example was tested for its refrigerating performance by the same method, and the result is shown in fig. 5-d. As shown in the figure, when the working current of the thermoelectric refrigeration device is 0.25A, the temperature of a heat source can be reduced from 45.0 ℃ to 44.4 ℃ and the temperature reduction amplitude reaches 0.6 ℃.
Claims (9)
1. The preparation method of the large-area flexible thermoelectric refrigeration thin film cascade device is characterized by comprising the following steps of:
(a) Preparing thermoelectric slurry by using thermoelectric materials, high polymer resin, solvent, curing agent, catalyst and surface auxiliary agent as raw materials;
(b) Screen printing the thermoelectric slurry on a flexible substrate, and hot-pressing to obtain a thermoelectric film;
(c) Preparing a thermoelectric arm on the thermoelectric film by adopting a laser etching method, and then preparing an electrode on the thermoelectric film by adopting a vacuum coating method to obtain a large-area flexible thermoelectric refrigeration film cascade device;
the thermoelectric material is selected from p-type or n-type Bi with particle diameter not exceeding 120 μm 2 Te 3 Base thermoelectric material, sb 2 Te 3 At least one of the thermoelectric materials; the high polymer resin is selected from at least one of epoxy resin, acrylic resin, polyurethane resin and cellulose resin; the solvent is at least one of absolute ethyl alcohol, acetone, toluene and butyl glycidyl ether; the curing agent is at least one selected from methyl hexahydrophthalic anhydride and methyl tetrahydrophthalic anhydride, the catalyst is specifically 2-ethyl-4-methylimidazole, and the surface auxiliary agent is specifically graphene.
2. The method of manufacturing according to claim 1, wherein: the weight ratio of the thermoelectric material, the high polymer resin and the solvent in the slurry is 1:0.05-0.2:0.1-0.5.
3. The method of manufacturing according to claim 1, wherein: the mass fractions of the curing agent, the catalyst and the surface auxiliary agent in the slurry are respectively 2% -5%, 0.5% -1% and 2% -5%.
4. The method of claim 1, wherein step (a) comprises the steps of: grinding and sieving the thermoelectric material to obtain powder, adding a solvent, fully ball-milling under a protective atmosphere, centrifuging, collecting lower-layer slurry, and fully drying to obtain thermoelectric powder; mixing polymer resin and solvent in certain proportion, adding thermoelectric powder and stirring to obtain thermoelectric slurry.
5. The method of manufacturing according to claim 4, wherein: adding a surface auxiliary agent in the process of preparing thermoelectric powder, and adding a curing agent and a catalyst in the process of preparing thermoelectric slurry by mixing and stirring.
6. The method of claim 1, wherein step (b) comprises the steps of: printing electrode slurry on a flexible substrate in a single or multiple screen printing mode, and performing hot-pressing sintering after the electrode slurry is naturally leveled and dried, wherein the hot-pressing sintering process parameters are as follows: the temperature is 150-450 ℃ and the pressure is 1-20MPa; the flexible substrate is specifically a polyimide substrate, and is required to be sufficiently washed and dried before use.
7. The method of manufacturing according to claim 1, wherein: the laser selected in the step (c) by the laser etching method is specifically ultraviolet laser with the power of 2-20W; the electrode is made of at least one material selected from Al, cu, ni, ag, ti.
8. The method of manufacturing according to claim 1, wherein: the side length of the manufactured large-area flexible thermoelectric refrigeration film cascade device is 10mm-200mm, and the thickness of a thermoelectric arm is 10 mu m-500 mu m.
9. The large-area flexible thermoelectric refrigeration thin film cascade device prepared by any one of the methods of claims 1-8 is characterized in that: the device has at least two stages, wherein the first stage is a refrigeration area, and the rest stages are heat dissipation areas.
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