Flexible thermoelectric materials for use in semiconductor devices and manufacturing methods

Abstract

In the present invention, a flexible thermoelectric material for use in a semiconductor device includes silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) coated around the silver sulfide nanoparticles, the chemical formula of the silver sulfide nanoparticles being Ag x A flexible thermoelectric material and a manufacturing method thereof are disclosed, which is TeS (wherein x=3.9-4.1) and is used in semiconductor devices in the technical field of thermoelectric materials. In the present invention, poly(3,4-ethylenedioxythiophene) has delocalized π bonds, and therefore has a certain conductive ability and can be used as an organic polymer semiconductor. The manufactured silver sulfide nanoparticles have good thermoelectric performance, and the synergistic effect of electrical conductivity and thermal conductivity is achieved, thereby realizing the effect of improving thermoelectric conversion efficiency. By putting silver sulfide nanoparticles into the organic skeleton of poly(3,4-ethylenedioxythiophene), the structure becomes compact, and the electron transfer rate is improved. The flexible thermoelectric material of the present invention has high electrical conductivity and Seebeck coefficient, and therefore the power coefficient of the material is improved.

Description

[Technical Field]

[0001] The present invention relates to the technical field of thermoelectric materials, and more particularly to flexible thermoelectric materials used in semiconductor devices and methods for manufacturing them. [Background technology]

[0002] Thermoelectric materials are functional materials that realize the direct conversion of thermal energy into electrical energy and vice versa through the movement of carriers inside a solid, and the Seebeck effect, discovered in 1823, and the Peltier effect, discovered in 1834, provided the theoretical basis for the applications of thermoelectric energy converters and thermoelectric cooling. Flexible thermoelectric materials can be broadly divided into three types: conductive polymers, composites of conductive polymers and inorganic semiconductor fillers, and inorganic semiconductor thin films.

[0003] As the pace of global industrialization accelerates, global energy shortages and depletion have become issues that cannot be ignored by any country, severely restricting the long-term stable development of society, and the research and development of new energy sources has become a global trend in energy development. Therefore, the research and development of flexible thermoelectric materials and manufacturing methods for use in semiconductor devices is of great significance, but conventional flexible thermoelectric materials and their manufacturing methods have the following disadvantages: China's research into flexible thermoelectric materials is lagging behind and still lags far behind developed countries in Europe and the United States. With the development of flexible thermoelectric materials, the thermoelectric conversion efficiency of flexible thermoelectric materials remains low, necessitating an urgent need to improve the thermoelectric conversion efficiency of flexible thermoelectric materials. Flexible thermoelectric materials manufactured using conventional technology have poor electrical conductivity, making it imperative to find suitable flexible thermoelectric materials with improved electrical conductivity. Currently manufactured flexible thermoelectric materials are expensive, have complex manufacturing processes, and have low market value. Summary of the Invention

[0004] To overcome the drawbacks of the prior art, the present invention provides a flexible thermoelectric material for semiconductor devices and a manufacturing method thereof. To address the problems of poor electrical conductivity and low thermoelectric conversion efficiency of conventional flexible thermoelectric materials, the present invention prepares silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) coated around the silver sulfide nanoparticles. Poly(3,4-ethylenedioxythiophene) has delocalized π bonds, which provide a certain level of conductivity and allows it to be used as an organic polymer semiconductor. The resulting silver sulfide nanoparticles themselves have excellent thermoelectric performance, allowing direct conversion of thermal energy and electrical energy, achieving a synergistic effect between electrical conductivity and thermal conductivity, thereby improving thermoelectric conversion efficiency. Specifically, by incorporating silver sulfide nanoparticles into the organic framework of poly(3,4-ethylenedioxythiophene), the hollow structure is filled with a flocculent structure, resulting in a compact structure and improving electron transfer rate. Secondly, the flexible thermoelectric material of the present invention has high electrical conductivity and Seebeck coefficient, which improves the power coefficient of the material and ultimately leads to excellent thermoelectric performance.

[0005] To achieve the above object, the present invention employs the following technical means: The present invention provides a flexible thermoelectric material for semiconductor devices, which comprises silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) coated around the silver sulfide nanoparticles, and the silver sulfide nanoparticles have a chemical formula of Ag x A flexible thermoelectric material for use in semiconductor devices is provided, which is TeS (wherein x=3.9 to 4.1).

[0006] Preferably, the chemical formula of the silver sulfide nanoparticles is Ag x TeS (where x = 3.95 to 4.0).

[0007] Furthermore, the silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) are prepared in a mass ratio of 2:3.

[0008] Furthermore, the process for producing the silver sulfide nanoparticles includes Step 1 of weighing Ag, Te, and S alone; Step 2, in which the weighed simple substance in step 1 is melted and annealed in a muffle furnace; and Step 3, ball milling the product annealed in Step 2 to obtain the silver sulfide nanoparticles.

[0009] Furthermore, in step 1, the formula for calculating the mass required for Ag, Te, and S alone is:

number

[0010] Furthermore, in step 2, the melting temperature is 900 to 1000°C, and the melting time is 24 to 48 hours; in step 2, the annealing temperature is 500 to 600°C, and the annealing time is 1 to 2 hours; and in step 3, the ball milling rotation speed is 200 to 300 r / min, and the ball milling time is 30 to 60 minutes.

[0011] Furthermore, the purity of the poly(3,4-ethylenedioxythiophene) is 98%.

[0012] The present invention provides a method for producing a silver sulfide nanoparticle-based polymer comprising: Step 1, in which the silver sulfide nanoparticles produced according to claim 3 and poly(3,4-ethylenedioxythiophene) are thoroughly mixed in 20 mL of isopropyl alcohol by mass ratio and reacted; Step 2 is to place the reaction product in a drying box and dry it at 70°C for 60 minutes. Step 3: Put the product of step 2 into a mold and press it into a sheet at room temperature to a thickness of 1 to 2 mm; The present invention further provides a method for manufacturing a flexible thermoelectric material for use in semiconductor devices, including step 4, in which the product of step 3 is placed in a spark plasma sintering system, sintered at a sintering temperature of 400 to 500°C, and then cooled naturally to room temperature to obtain the flexible thermoelectric material.

[0013] The effects obtained by the present invention through the above method are as follows: (1) The present invention produces silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) coated around the silver sulfide nanoparticles. Poly(3,4-ethylenedioxythiophene) has delocalized π bonds, so it has a certain conductive ability and can be used as an organic polymer semiconductor. (2) The produced silver sulfide nanoparticles themselves have good thermoelectric performance, and can directly convert thermal energy into electrical energy and vice versa. The synergistic effect of electrical conductivity and thermal conductivity is achieved, thereby improving the thermoelectric conversion efficiency. (3) In particular, by incorporating silver sulfide nanoparticles into the organic framework of poly(3,4-ethylenedioxythiophene), the hollow structure frame is filled with a cotton-like structure, resulting in a compact structure and improving the electron transfer rate. (4) Secondly, the flexible thermoelectric material of the present invention has high electrical conductivity and Seebeck coefficient, which improves the power coefficient of the material and ultimately leads to excellent thermoelectric performance. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 10 is a scanning electron microscope image of a flexible thermoelectric material used in a semiconductor device manufactured in Example 3 of the present invention.

[0015] The drawings are provided for a further understanding of the present invention, constitute a part of the specification, and are used to explain the present invention together with the embodiments of the present invention, but are not intended to limit the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0016] The following provides a clear and complete description of the technical means in the embodiments of the present invention, with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, and are not all of the embodiments. Based on the embodiments of the present invention, those skilled in the art can obtain other embodiments without creative ingenuity, and all of these embodiments fall within the scope of protection of the present invention.

[0017] In the examples of the present invention, all raw materials or processing techniques are intended to be conventional raw materials or conventional processing techniques commercially available in the art unless otherwise specified.

[0018] Example 1 The present invention provides a flexible thermoelectric material for use in semiconductor devices, which comprises silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) coated around the silver sulfide nanoparticles. The chemical formula of the silver sulfide nanoparticles is Ag x TeS (where x=3.95), i.e., Ag 3.95 It is TeS.

[0019] Among them, silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) were prepared in a mass ratio of 2:3.

[0020] The manufacturing process of silver sulfide nanoparticles consists of Step 1, in which Ag, Te, and S are weighed. Step 2: The weighed simple substance is melted and annealed in a muffle furnace. and step 3, ball milling the product annealed in step 2 to obtain silver sulfide nanoparticles.

[0021] In particular, in step 1, the formula for calculating the mass required for Ag, Te, and S alone is:

number

[0022] Among them, 50 g of Ag, 11 g of Te, and 2 g of S were weighed.

[0023] Among them, in step 2, the melting temperature was 900°C, the melting time was 24 h, the annealing temperature was 500°C, and the annealing time was 1 h, and in step 3, the ball milling rotation speed was 200 r / min, and the ball milling time was 30 min.

[0024] Among them, the purity of poly(3,4-ethylenedioxythiophene) was 98%.

[0025] The present invention provides a method for producing a silver sulfide nanoparticle-based polymer comprising: Step 1, in which the silver sulfide nanoparticles produced according to claim 3 and poly(3,4-ethylenedioxythiophene) are thoroughly mixed in 20 mL of isopropyl alcohol by mass ratio and reacted; Step 2: Place the reaction product in a drying box and dry it at 70°C for 60 minutes. Step 3: Put the product of step 2 into a mold and press it into a piece at room temperature to a thickness of 1-2 mm. The present invention further provides a method for manufacturing a flexible thermoelectric material for use in semiconductor devices, including step 4, in which the product of step 3 is placed in a spark plasma sintering system, sintered at a sintering temperature of 500°C, and then allowed to cool naturally to room temperature to obtain a flexible thermoelectric material.

[0026] Example 2 The present invention provides a flexible thermoelectric material for use in semiconductor devices, which comprises silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) coated around the silver sulfide nanoparticles. The chemical formula of the silver sulfide nanoparticles is Ag x TeS (where x=3.97), i.e., Ag 3.97 It is TeS.

[0027] Among them, silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) were prepared in a mass ratio of 2:3.

[0028] The manufacturing process of silver sulfide nanoparticles consists of Step 1, in which Ag, Te, and S are weighed. Step 2: The weighed simple substance is melted and annealed in a muffle furnace. and step 3, ball milling the product annealed in step 2 to obtain silver sulfide nanoparticles.

[0029] In particular, in step 1, the formula for calculating the mass required for Ag, Te, and S alone is:

number

[0030] Among them, 50.2 g of Ag, 11 g of Te, and 1.9 g of S were weighed.

[0031] Among them, in step 2, the melting temperature was 940°C, the melting time was 36 h, the annealing temperature was 530°C, and the annealing time was 1.4 h, and in step 3, the ball milling rotation speed was 240 r / min, and the ball milling time was 40 min.

[0032] Among them, the purity of poly(3,4-ethylenedioxythiophene) was 98%.

[0033] In particular, see Example 1 for the method for producing a flexible thermoelectric material used in semiconductor devices.

[0034] Example 3 The present invention provides a flexible thermoelectric material for use in semiconductor devices, which comprises silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) coated around the silver sulfide nanoparticles. The chemical formula of the silver sulfide nanoparticles is Ag x TeS (where x=3.99), i.e., Ag 3.99 It is TeS.

[0035] Among them, silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) were prepared in a mass ratio of 2:3.

[0036] The manufacturing process of silver sulfide nanoparticles consists of Step 1, in which Ag, Te, and S are weighed. Step 2: The weighed simple substance is melted and annealed in a muffle furnace. and step 3, ball milling the product annealed in step 2 to obtain silver sulfide nanoparticles.

[0037] In particular, in step 1, the formula for calculating the mass required for Ag, Te, and S alone is:

number

[0038] Among them, 50.3 g of Ag, 10.9 g of Te, and 2 g of S were weighed.

[0039] Among them, in step 2, the melting temperature was 970°C, the melting time was 41 h, the annealing temperature was 560°C, and the annealing time was 1.7 h, and in step 3, the ball milling rotation speed was 270 r / min, and the ball milling time was 50 min.

[0040] Among them, the purity of poly(3,4-ethylenedioxythiophene) was 98%.

[0041] In particular, see Example 1 for the method for producing a flexible thermoelectric material used in semiconductor devices.

[0042] Example 4 The present invention provides a flexible thermoelectric material for use in semiconductor devices, which comprises silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) coated around the silver sulfide nanoparticles. The chemical formula of the silver sulfide nanoparticles is Ag x TeS (where x=4.0), i.e., Ag4TeS.

[0043] Among them, silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) were prepared in a mass ratio of 2:3.

[0044] The manufacturing process of silver sulfide nanoparticles consists of Step 1, in which Ag, Te, and S are weighed. Step 2: The weighed simple substance is melted and annealed in a muffle furnace. and step 3, ball milling the product annealed in step 2 to obtain silver sulfide nanoparticles.

[0045] In particular, in step 1, the formula for calculating the mass required for Ag, Te, and S alone is:

number

[0046] Among them, 50.3 g of Ag, 10.8 g of Te, and 2.1 g of S were weighed.

[0047] Among them, in step 2, the melting temperature was 1000°C, the melting time was 48 h, the annealing temperature was 600°C, and the annealing time was 2 h, and in step 3, the ball milling rotation speed was 300 r / min, and the ball milling time was 60 min.

[0048] Among them, the purity of poly(3,4-ethylenedioxythiophene) was 98%.

[0049] In particular, see Example 1 for the method for producing a flexible thermoelectric material used in semiconductor devices.

[0050] Performance measurement The electrical conductivity and Seebeck coefficient were measured using SBA458 in a flowing argon gas (150 ml / min) atmosphere. The sample thickness was 2 mm and the sample diameter was 12.7 mm.

[0051] Table 1. Performance of flexible thermoelectric materials used in semiconductor devices [Table 1] As shown in FIG. 1 and Table 1, the Seebeck coefficient, electrical conductivity, and power coefficient of the flexible thermoelectric material in Example 3 of the present invention, which is manufactured by the method of the present invention, are significantly higher than those of the other examples. The Seebeck coefficient reaches 16.4 μV / K, the electrical conductivity reaches 798.0 S / cm, and the power coefficient is 18.3 μV / mK. 2 It was found that the amount of material introduced must be within a certain range, and that either too much or too little will affect performance. Therefore, considering the overall effect of the flexible thermoelectric material, the electrical conductivity and thermal conductivity of the flexible thermoelectric material of the present invention achieve a synergistic effect, improving thermoelectric conversion efficiency and providing excellent thermoelectric performance.

[0052] Although embodiments of the present invention have been disclosed and described, it will be apparent to those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is limited only by the claims and their equivalents.

[0053] Although the present invention and its embodiments have been described above, this description is not limitative, and what is shown in the drawings is merely one embodiment of the present invention, and actual applications are not limited to this. In other words, any structural schemes and embodiments similar to the technical means designed by a person skilled in the art based on the suggestions thereof, without departing from the spirit of the invention, and without originality, should all fall within the scope of protection of the present invention.

Claims

1. A flexible thermoelectric material for use in a semiconductor device, comprising silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) coated around the silver sulfide nanoparticles, wherein the silver sulfide nanoparticles have a chemical formula of AgTeS (wherein x = 3.9 to 4.1).

2. The flexible thermoelectric material for semiconductor devices according to claim 1, wherein the silver sulfide nanoparticles have a chemical formula of AgxTeS, where x=3.95-4.

0.

3. The flexible thermoelectric material for semiconductor devices according to claim 2, wherein the silver sulfide nanoparticles and poly(3,4-ethylenedioxythiophene) are prepared in a mass ratio of 2:

3.

4. The flexible thermoelectric material for use in semiconductor devices according to claim 3, wherein the purity of the poly(3,4-ethylenedioxythiophene) is 98%.

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