CN112968122B - Manufacturing method of transparent P-type semiconductor nano film for refrigeration - Google Patents
Manufacturing method of transparent P-type semiconductor nano film for refrigeration Download PDFInfo
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- CN112968122B CN112968122B CN202110363016.9A CN202110363016A CN112968122B CN 112968122 B CN112968122 B CN 112968122B CN 202110363016 A CN202110363016 A CN 202110363016A CN 112968122 B CN112968122 B CN 112968122B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
Abstract
The invention discloses a method for manufacturing a transparent P-type semiconductor nano film for refrigeration, wherein a reasonable proportion of boron oxide and cadmium telluride in spray liquid is that a P-type semiconductor is doped with enough holes, so that the concentration of multiple holes is ensured, and the conductivity is strong; the addition of the indium oxide catalyzes the reaction, so that the reaction speed and the transparency of the treatment fluid are greatly improved; the film layer can bear high direct-current voltage, has the characteristics of high light transmittance, oxidation resistance, corrosion resistance and long service life, and can be manufactured into a large-scale refrigerating sheet.
Description
Technical Field
The invention relates to the technical field of P-type semiconductor materials, in particular to a manufacturing method of a transparent P-type semiconductor nano film for refrigeration.
Background
The semiconductor refrigeration is also called electronic refrigeration or thermoelectric refrigeration, is a discipline which is developed from the 50 s and is positioned at the edge of refrigeration technology and semiconductor technology, and utilizes P-N junction formed by special semiconductor material to form thermocouple pair, so that the Peltier effect is produced, namely, a novel refrigeration method by direct current refrigeration, compression refrigeration and absorption refrigeration are adopted, and the refrigeration method is called as three-large world refrigeration mode.
The semiconductor refrigerating plate (TE) is also called thermoelectric refrigerating plate, and is a heat pump, and its advantages are no sliding parts, and high reliability.
The traditional p/n particle refrigeration technology (traditional semiconductor refrigeration technology) is only applicable to small-volume refrigeration sheets; the device can only be used for low-voltage direct current, so that the power is small, the refrigeration efficiency is low, and the maximum temperature difference only reaches 65-68 ℃; the use condition is limited, and the transformer is needed to be loaded in normal use because the transformer can only be used for low-voltage direct current, so that the use cost is greatly increased.
Disclosure of Invention
The invention aims to provide a manufacturing method of a transparent P-type semiconductor nano film for refrigeration, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the invention provides the following technical scheme, which comprises the following raw materials in parts by weight: 3 to 8 parts of boric acid, 0.2 to 0.5 part of boron oxide, 20 to 25 parts of stannic chloride, 3 to 10 parts of stannic oxide, 0.7 to 0.9 part of cadmium telluride, 0.6 to 0.8 part of indium oxide, 10 to 15 parts of ethanol, 8 to 10 parts of hydrochloric acid, 10 to 15 parts of acetic acid, 0.2 to 0.5 part of glycerol and 10 to 20 parts of distilled water.
The preparation process comprises the following steps:
step one: mixing tin chloride, tin oxide and acetic acid to obtain a first component, and mixing boron oxide, boric acid and glycerol to obtain a second component; uniformly stirring the first component and the second component respectively, mixing, heating to 25-45 ℃ after mixing, continuously stirring, slowly adding distilled water according to the mass percent of 15-25 in the stirring process, stirring for 30 minutes, and filtering precipitated solids to obtain a treatment liquid;
step two: mixing cadmium telluride, stannic chloride and hydrochloric acid to prepare a third component, adding the treatment liquid obtained in the step one into the third component, adding 10-15 ethanol in the adding process, slowly stirring, uniformly stirring to obtain a finished liquid spray, and storing in an environment of 10-15 ℃;
step three: selecting a semiconductor nano film substrate, sending the substrate into heating equipment, heating the substrate to 390-800 ℃, sending the substrate to a film spraying section, fully mixing the finished liquid spray obtained in the second step with 3-8 kg of air pressure, then introducing the mixture into a titanium alloy track type movable spray gun, and uniformly spraying and plating the mixture on the substrate to form a nano film;
step four: printing conductive silver paste on the film substrate obtained in the third step by using a 180-250 mesh polyester wire mesh or a stainless steel wire mesh, feeding the film substrate into a drying tunnel furnace after the paste printing is finished, drying for 5-10 minutes at 120-180 ℃, then feeding the film substrate into a high-temperature tunnel furnace, drying for 5-10 minutes at 520-710 ℃, and welding the electric wires on the electrodes after the drying is finished to obtain the P-type semiconductor nano film finished product.
As a preferable technical scheme of the invention, the spray gun spray liquid quantity is digitally controlled, and the error range is
±0.5％。
Compared with the prior art, the invention has the beneficial effects that: the reasonable proportion of the boron oxide and the cadmium telluride is that the p-type semiconductor is doped with enough holes, so that the concentration of multiple electrons (holes) is ensured, and the conductivity is strong; the addition of the indium oxide catalyzes the reaction, so that the reaction speed and the transparency of the treatment fluid are greatly improved; the film layer can bear high direct-current voltage, has the characteristics of high light transmittance, oxidation resistance, corrosion resistance and long service life, and can be manufactured into a large-scale refrigerating sheet.
Drawings
FIG. 1 is a graph showing various index data of the present invention;
FIG. 2 is a table of comparative test results according to the present invention;
Detailed Description
Example 1
As shown in fig. 1 to 2, the invention discloses a manufacturing method of a transparent P-type semiconductor nano film for refrigeration, which comprises the following raw materials in parts by weight: 3 parts of boric acid, 0.2 part of boron oxide, 20 parts of stannic chloride, 3 parts of stannic oxide, 0.7 part of cadmium telluride, 0.6 part of indium oxide, 10 parts of ethanol, 8 parts of hydrochloric acid, 10 parts of acetic acid, 0.2 part of glycerol and 10 parts of distilled water.
The preparation method comprises the following steps:
step one: mixing tin chloride, tin oxide and acetic acid to obtain a first component, and mixing boron oxide, boric acid and glycerol to obtain a second component; uniformly stirring the first component and the second component respectively, mixing, heating to 30 ℃ after mixing, continuously stirring, slowly adding distilled water according to the mass percent of 15 in the stirring process, stirring for 30 minutes, and filtering precipitated solids to obtain a treatment liquid;
step two: mixing cadmium telluride, stannic chloride and hydrochloric acid to prepare a third component, adding 10 parts of ethanol into the treatment solution obtained in the step one, slowly stirring, uniformly stirring to obtain a finished liquid spray, and storing at 10 ℃;
step three: selecting a semiconductor nano film substrate, sending the substrate into heating equipment, heating the substrate to 390 ℃, sending the substrate to a film spraying section, fully mixing the finished liquid spray obtained in the second step with 3 kg of air pressure, then introducing the mixture into a titanium alloy track type movable spray gun, and then uniformly spraying and plating the mixture on the substrate to form a nano film;
step four: printing conductive silver paste on the film substrate obtained in the third step by using a 180-mesh polyester wire mesh or a stainless steel wire mesh, sending the film substrate into a drying tunnel furnace after finishing the paste printing, drying at 120 ℃ for 5 minutes, then sending the film substrate into a high-temperature tunnel furnace, drying at 520 ℃ for 5 minutes, and welding a wire on an electrode after finishing the drying, thus obtaining the P-type semiconductor nano film finished product.
Example 2
The material comprises the following raw materials in parts by weight: 6 parts of boric acid, 0.4 part of boron oxide, 22 parts of stannic chloride, 7 parts of stannic oxide, 0.8 part of cadmium telluride, 0.7 part of indium oxide, 13 parts of ethanol, 9 parts of hydrochloric acid, 12 parts of acetic acid, 0.4 part of glycerol and 15 parts of distilled water.
The preparation method comprises the following steps:
step one: mixing tin chloride, tin oxide and acetic acid to obtain a first component, and mixing boron oxide, boric acid and glycerol to obtain a second component; uniformly stirring the first component and the second component respectively, mixing, heating to 35 ℃ after mixing, continuously stirring, slowly adding distilled water according to the mass percent of 20 in the stirring process, stirring for 30 minutes, and filtering precipitated solids to obtain a treatment liquid;
step two: mixing cadmium telluride, stannic chloride and hydrochloric acid to prepare a third component, adding the treatment liquid obtained in the step one into the third component, adding 13 ethanol in the adding process, slowly stirring, uniformly stirring to obtain a finished liquid spray, and storing in an environment of 13 ℃;
step three: selecting a semiconductor nano film substrate, sending the substrate into heating equipment, heating the substrate to 600 ℃, sending the substrate to a film spraying section, fully mixing the finished liquid spray obtained in the second step with 6 kg of air pressure, then introducing the mixture into a titanium alloy track type movable spray gun, and uniformly spraying and plating the mixture on the substrate to form a nano film;
step four: printing conductive silver paste on the film substrate obtained in the third step by using a 220-mesh polyester wire mesh or a stainless steel wire mesh, sending the film substrate into a drying tunnel furnace after finishing the paste printing, drying at 160 ℃ for 10 minutes, then sending the film substrate into a high-temperature tunnel furnace, drying at 600 ℃ for 10 minutes, and welding a wire on an electrode after finishing the drying, thus obtaining the P-type semiconductor nano film finished product.
Example 3
The material comprises the following raw materials in parts by weight: 8 parts of boric acid, 0.5 part of boron oxide, 25 parts of tin chloride, 10 parts of tin oxide, 0.9 part of cadmium telluride, 0.8 part of indium oxide, 15 parts of ethanol, 10 parts of hydrochloric acid, 15 parts of acetic acid, 0.5 part of glycerol and 20 parts of distilled water.
The preparation method comprises the following steps:
step one: mixing tin chloride, tin oxide and acetic acid to obtain a first component, and mixing boron oxide, boric acid and glycerol to obtain a second component; uniformly stirring the first component and the second component respectively, mixing, heating to 45 ℃ after mixing, continuously stirring, slowly adding distilled water according to the mass percent of 5 in the stirring process, stirring for 30 minutes, and filtering precipitated solids to obtain a treatment liquid;
step two: mixing cadmium telluride, stannic chloride and hydrochloric acid to prepare a third component, adding the treatment liquid obtained in the step one into the third component, adding 15 ethanol in the adding process, slowly stirring, uniformly stirring to obtain a finished liquid spray, and storing in an environment of 15 ℃;
step three: selecting a semiconductor nano film substrate, sending the substrate into heating equipment, heating the substrate to 800 ℃, sending the substrate to a film spraying section, fully mixing the finished liquid spray obtained in the second step with 8 kg of air pressure, then introducing the mixture into a titanium alloy track type movable spray gun, and then uniformly spraying and plating the mixture on the substrate to form a nano film;
step four: printing conductive silver paste on the film substrate obtained in the third step by using a 250-mesh polyester wire mesh or a stainless steel wire mesh, sending the film substrate into a drying tunnel furnace after finishing the paste printing, drying at 180 ℃ for 10 minutes, then sending the film substrate into a high-temperature tunnel furnace, drying at 710 ℃ for 10 minutes, and welding a wire on an electrode after finishing the drying, thus obtaining the P-type semiconductor nano film finished product.
The three groups of samples are subjected to inspection and test, and the obtained detection results are comprehensively obtained to obtain the figure 1.
The film plating technology adopts a tunnel furnace type heating system, so that the size of a film plating substrate can be within the size of the tunnel furnace, and the movable spray gun film plating technology can cover all areas in the tunnel furnace, so that the surface of the substrate can be entirely plated with a P-type semiconductor film, and the film plating technology can be used as a large-scale refrigerating sheet. The defect that the p/n particle refrigeration technology needs to fix solid p/n particles on a matrix is overcome, so that most of the p/n particle refrigeration technology can only be used for small volume, and if the p/n particle refrigeration technology needs to be used for large-volume refrigeration sheets, high cost and complicated manufacturing process are needed. The transparent P-type semiconductor nano film for refrigeration disclosed by the invention absorbs heat uniformly in a planar manner, so that when current passes through a thermocouple pair formed by connecting an N-type semiconductor material and a P-type semiconductor material, heat transfer is generated between two ends, and the heat absorption effect is improved.
The semiconductor nano film substrate is a composite of materials such as stainless steel, aluminum alloy, ceramic, microcrystalline glass, silicon carbide and silicon nitride, the substrate in the first sample is a whole composite, the substrate in the second sample lacks ceramic and microcrystalline glass, the substrate in the third sample lacks silicon carbide and silicon nitride, and the three different substrates are respectively manufactured into P-type semiconductor nano film finished products, and the P-type semiconductor nano film finished products are connected with the same direct current power supply for testing, so that the graph 2 is obtained.
The components not described in detail herein are prior art.
Although the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes and modifications without inventive labor may be made within the scope of the present invention without departing from the spirit of the present invention, which is within the scope of the present invention.
Claims (2)
1. The manufacturing method of the transparent P-type semiconductor nano film for refrigeration is characterized by comprising the following raw materials in parts by weight: 3 to 8 parts of boric acid, 0.2 to 0.5 part of boron oxide, 20 to 25 parts of stannic chloride, 3 to 10 parts of stannic oxide, 0.7 to 0.9 part of cadmium telluride, 0.6 to 0.8 part of indium oxide, 10 to 15 parts of ethanol, 8 to 10 parts of hydrochloric acid, 10 to 15 parts of acetic acid, 0.2 to 0.5 part of glycerol and 10 to 20 parts of distilled water; the manufacturing method comprises the following steps:
step one: mixing tin chloride, tin oxide and acetic acid to obtain a first component, and mixing boron oxide, boric acid and glycerol to obtain a second component; uniformly stirring the first component and the second component respectively, mixing, heating to 25-45 ℃ after mixing, continuously stirring, slowly adding distilled water according to the mass percent of 15-25 in the stirring process, stirring for 30 minutes, and filtering precipitated solids to obtain a treatment liquid;
step two: mixing cadmium telluride, stannic chloride and hydrochloric acid to prepare a third component, adding 10-15 parts of ethanol into the treatment solution obtained in the step one, slowly stirring, uniformly stirring to obtain a finished liquid spray, and storing in an environment of 10-15 ℃;
step three: selecting a semiconductor nano film substrate, sending the substrate into heating equipment, heating the substrate to 390-800 ℃, sending the substrate to a film spraying section, fully mixing the finished liquid spray obtained in the second step with 3-8 kg of air pressure, then introducing the mixture into a titanium alloy track type movable spray gun, and uniformly spraying and plating the mixture on the substrate to form a nano film;
step four: printing conductive silver paste on the film substrate obtained in the third step by using a 180-250 mesh polyester wire mesh or a stainless steel wire mesh, feeding the film substrate into a drying tunnel furnace after the paste printing is finished, drying for 5-10 minutes at 120-180 ℃, then feeding the film substrate into a high-temperature tunnel furnace, drying for 5-10 minutes at 520-710 ℃, and welding the electric wires on the electrodes after the drying is finished to obtain the P-type semiconductor nano film finished product.
2. The method for manufacturing the transparent P-type semiconductor nano film for refrigeration according to claim 1, which is characterized in that: the spray gun spray liquid amount is digitally controlled, and the error range is +/-0.5%.
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