CN-122013139-A - High-temperature stable wide-forbidden-band metal oxide semiconductor electrothermal film and manufacturing method thereof

Abstract

The invention relates to the technical field of electrothermal films, in particular to a high-temperature stable wide-forbidden-band metal oxide semiconductor electrothermal film and a manufacturing method thereof, wherein a semiconductor precursor liquid is sprayed on the surface of a substrate heated to the surface temperature reaching the pyrolysis deposition temperature of the semiconductor precursor liquid by adopting a two-fluid atomization pyrolysis spraying process, two fluids in the two-fluid atomization pyrolysis spraying process are carrier gas and atomizing gas, and then step annealing is carried out after pyrolysis deposition is completed, so that the semiconductor electrothermal film is manufactured; the semiconductor precursor liquid adopts an inorganic acid-organic complex acid dual-stabilization system, and an inorganic silica sol auxiliary agent is added into the semiconductor precursor liquid. The invention forms stable sol with uniform particle size through controllable hydrolysis-polycondensation reaction, so that the crystal lattice growth after film formation is more uniform and orderly, the electrothermal radiation rate is more than 70%, the electrothermal conversion efficiency is up to more than 98.5%, the heating is uniform, the power attenuation is less than minus 5% after long-term use at 500 ℃, the service life is more than 10000 hours, and the invention is suitable for high-temperature heating scenes.

Inventors

• LI YUCHUN
• ZHOU YULU
• Chen Renta
• ZENG JINGWEN
• Huang Xinta
• DANG XIULI
• LI JINCHUN

Assignees

• 福建傲顿科技有限公司

Dates

Publication Date

20260512

Application Date

20260410

Claims (9)

1. 1. The manufacturing method of the high-temperature stable wide-bandgap metal oxide semiconductor electrothermal film is characterized by comprising the following steps: spraying a semiconductor precursor solution on the surface of a substrate heated to the surface temperature reaching the pyrolysis deposition temperature of the semiconductor precursor solution by adopting a two-fluid atomization pyrolysis spraying process, wherein two fluids in the two-fluid atomization pyrolysis spraying process are carrier gas and atomizing gas; step two, step annealing is carried out after pyrolysis deposition is completed, and a semiconductor electrothermal film is prepared; The semiconductor precursor solution comprises, by weight, 50-70 parts of tin tetrachloride pentahydrate, 0.8-4.0 parts of doped metal chloride, 1-3 parts of inorganic acid, 1-4 parts of organic complex acid, 0.2-1 part of inorganic silica sol auxiliary agent, 15-25 parts of alcohol solvent and 0-30 parts of deionized water, wherein metal ions in the doped metal chloride are antimony and one or more of manganese, iron, nickel, copper, zinc, titanium, bismuth, platinum, chromium, cobalt and yttrium, and the organic complex acid is ethylenediamine tetraacetic acid, citric acid, glycine or diethylenetriamine pentaacetic acid.
2. 2. The method for manufacturing the high-temperature stable wide-bandgap metal oxide semiconductor electrothermal film according to claim 1, wherein the two-fluid atomization pyrolysis spraying process adopts multi-pass thin coating, the single-pass film thickness is less than or equal to 50nm, and the total thickness is 0.05-3 μm.
3. 3. The method for manufacturing a high-temperature stable wide bandgap metal oxide semiconductor electrothermal film according to claim 1, wherein the ratio of the atomization gas pressure to the carrier gas pressure in the two-fluid atomization pyrolysis spray coating process is=2.5-3:1.
4. 4. The method of claim 1, wherein the substrate is a rectangular, square or round insulating material substrate, the precursor liquid pushing flow is 12.8-19.2 mL/min, the flow rate is 0.8-1.2 m/s, the overlapping rate is 60-80%, and the axis traversing speed is controlled to be 50-350 mm/s.
5. 5. The method of claim 1, further comprising the steps of screen printing insulating oil on the surface of the substrate before step heating and cleaning the insulating oil after step annealing.
6. 6. The method of manufacturing a high temperature stable wide bandgap metal oxide semiconductor electrothermal film according to claim 1, further comprising the step of preparing an electrode on the semiconductor electrothermal film.
7. 7. The method of claim 1, wherein the substrate is heated by a step, and the step annealing is performed in three steps, namely 600-650 ℃, 300-400 ℃ and 100-150 ℃.
8. 8. The method for manufacturing the high-temperature stable wide-bandgap metal oxide semiconductor electrothermal film according to claim 1, wherein the preparation process of the semiconductor precursor solution comprises the steps of S1, adding organic complexing acid into an alcohol solvent under stirring at room temperature, stirring until the organic complexing acid is completely dissolved, dropwise adding inorganic acid, adjusting the pH value, S2, adding tin tetrachloride pentahydrate into a system of the step S1, stirring until the tin tetrachloride pentahydrate is completely dissolved, adding doped metal chloride in batches after stirring until the tin tetrachloride pentahydrate is completely dissolved, adding deionized water into the system of the step S2, adding an inorganic silica sol auxiliary agent after stirring, stirring to uniformly disperse silica sol in the complexing sol, and S4, filtering at constant temperature for use or packaging for later use.
9. 9. A high temperature stable wide bandgap metal oxide semiconductor electrothermal film manufactured by the manufacturing method according to any one of claims 1 to 8.

Description

High-temperature stable wide-forbidden-band metal oxide semiconductor electrothermal film and manufacturing method thereof Technical Field The invention relates to the technical field of electrothermal films, in particular to a high-temperature stable wide-forbidden-band metal oxide semiconductor electrothermal film and a manufacturing method thereof. Background The electrothermal material is a functional material capable of converting electric energy into heat energy, and is a core component of electric heating equipment. The electrothermal materials can be classified into resistive heating materials, far infrared heating materials, optical wave heating materials, microwave heating and electromagnetic induction heating materials according to heating mechanism. The electrothermal materials can be divided into electrothermal fiber, electrothermal wire (wire), electrothermal belt, electrothermal film, electrothermal foil, electrothermal sheet, electrothermal tube (rod), electrothermal plate, electrothermal disk, electrothermal ring, etc. At present, the mainstream electrothermal materials in the market are resistance heating materials, such as resistance heating wires, resistance heating sheets and resistance heating discs, the electrothermal conversion efficiency is very low and is only about 70%, and the problems of easy damage, easy electricity leakage, easy open flame generation, incapability of directly contacting with liquid and the like exist, so that the application scene is greatly limited. The far infrared heating material remarkably improves the electric heating conversion efficiency by more than 90%, and the heating process is safer and more environment-friendly, thereby meeting more application requirements. The far infrared heating material which is mature at the present stage is an electrothermal film thin film material, mainly comprising a carbon electrothermal film, a metal electrothermal film, a macromolecule electrothermal film and a semiconductor electrothermal film. The carbon electrothermal film and the polymer electrothermal film have the obvious power attenuation problem at high temperature, so that the carbon electrothermal film and the polymer electrothermal film can only be used under the condition of low temperature and cannot meet the high-temperature application requirement, the metal electrothermal film has high cost and the forming process is responsible and is not suitable for large-area popularization and use, the semiconductor electrothermal film has lower cost than the metal electrothermal film, the power attenuation under the condition of high temperature is lower than that of the carbon electrothermal film and the polymer electrothermal film, but the semiconductor electrothermal film has poor high-temperature stability and the power attenuation is as high as more than minus 15 percent in the medium-high-temperature application scene. Disclosure of Invention The invention aims to provide a manufacturing method of a high-temperature stable wide-bandgap metal oxide semiconductor electrothermal film, which can remarkably reduce power attenuation in a medium-high temperature application scene. In order to achieve the aim of the invention, the invention adopts the following technical scheme: the manufacturing method of the high-temperature stable wide-bandgap metal oxide semiconductor electrothermal film comprises the following steps: spraying a semiconductor precursor solution on the surface of a substrate heated to the surface temperature reaching the pyrolysis deposition temperature of the semiconductor precursor solution by adopting a two-fluid atomization pyrolysis spraying process, wherein two fluids in the two-fluid atomization pyrolysis spraying process are carrier gas and atomizing gas; step two, step annealing is carried out after pyrolysis deposition is completed, and a semiconductor electrothermal film is prepared; The semiconductor precursor solution comprises, by weight, 50-70 parts of tin tetrachloride pentahydrate, 0.8-4.0 parts of doped metal chloride, 1-3 parts of inorganic acid, 1-4 parts of organic complex acid, 0.2-1 part of inorganic silica sol auxiliary agent, 15-25 parts of alcohol solvent and 0-30 parts of deionized water, wherein metal ions in the doped metal chloride are antimony and one or more of manganese, iron, nickel, copper, zinc, titanium, bismuth, platinum, chromium, cobalt and yttrium, and the organic complex acid is ethylenediamine tetraacetic acid, citric acid, glycine or diethylenetriamine pentaacetic acid. Preferably, the two-fluid atomization pyrolysis spraying process adopts multi-pass thin coating, the thickness of a single pass film is less than or equal to 50nm, and the total thickness is 0.05-3 mu m. Preferably, the atomization gas pressure and the carrier gas pressure in the two-fluid atomization pyrolysis spray coating process are 2.5-3:1. Preferably, the substrate is a rectangular, square or round insulating material substrate, t