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CN-121972384-A - Apparatus and method for making crystal lattice oxygen vacancies in oxides using electric field assistance

CN121972384ACN 121972384 ACN121972384 ACN 121972384ACN-121972384-A

Abstract

The invention belongs to the technical field of oxide films/coatings, and particularly relates to a device and a method for manufacturing crystal lattice oxygen vacancies in an oxide by utilizing electric field assistance. The device comprises a tube furnace, a quartz tube penetrating through a heating cavity of the tube furnace, a coating sample clamping unit arranged in the quartz tube, a power supply and a monitoring loop. Both ends of the quartz tube are sealed by vacuum sealing flanges. When the device is used, a sample with an oxide coating is fixed in a clamping unit, the sample is placed in a constant temperature area of a tube furnace for heating, and meanwhile, current is applied through a wire, so that oxygen in an oxide crystal lattice is promoted to escape under the synergistic effect of a thermal field and an electric field, and high-concentration crystal lattice oxygen vacancies are formed in the coating. The method has simple process and controllable conditions, and can effectively regulate and control the physical and chemical properties of the oxide film/coating on the premise of not introducing foreign matters and not damaging the integrity of the coating.

Inventors

  • LI HEPING
  • WANG WENCHUAN
  • WANG XINYUN
  • ZHOU HUAMIN

Assignees

  • 华中科技大学

Dates

Publication Date
20260505
Application Date
20260305

Claims (8)

  1. 1. An apparatus for creating crystal lattice oxygen vacancies in an oxide using electric field assistance, comprising: a tube furnace (1); The quartz tube (2) axially penetrates through the heating cavity of the tube furnace (1), and two ends of the quartz tube (2) are sealed through vacuum sealing flanges (3); the coating sample clamping unit is arranged in the quartz tube (2) and positioned in the constant temperature area of the tube furnace (1) and is used for clamping and fixing a coating sample (10); A power supply (6) for providing an applied electric field; The lead (7) passes through an opening on the vacuum sealing flange (3) to be connected into the quartz tube (2), and is connected in series with the coating sample clamping unit and the power supply (6) to form a current loop; and the universal meter (5) is connected in series in the current loop and is used for monitoring loop current in real time.
  2. 2. The apparatus of claim 1, wherein the coating specimen holding unit comprises: a pair of insulating spacers (8); a pair of metal clamps (9) which are respectively positioned at two sides of the coating sample (10) and are used for clamping and fixing the insulating gasket (8), the coating sample (10) and the electrode sheet (11); And an electrode sheet (11) which is arranged between the coating sample (10) and the metal clamp (9) and is electrically contacted with the conductive paste coated on the surface of the coating sample (10).
  3. 3. The device according to claim 1, characterized in that a gasket (4) is arranged between the vacuum sealing flange (3) and the quartz tube (2), and an opening through which a wire can pass is arranged on the vacuum sealing flange (3).
  4. 4. A method of making crystal lattice oxygen vacancies using the apparatus of any one of claims 1-3, comprising the steps of: Step S1, preparing a coating sample, namely preparing an oxide coating on the surface of a substrate by adopting a coating process or a deposition process to obtain a coating sample (10), wherein the coating process comprises a sol-gel method, a spraying method, a spin-coating method and a dipping and pulling method, and the deposition process comprises a chemical vapor deposition method, a physical vapor deposition method and an atomic layer deposition method; S2, assembling a sample unit, namely coating conductive paste on the surfaces of two ends of the coating sample (10), and clamping and fixing the insulating gasket (8), the coating sample (10) and the electrode plate (11) through a metal clamp (9) to form a coating sample clamping unit; S3, connecting a current loop, namely placing the coating sample clamping unit in a quartz tube (2), and connecting a metal clamp (9) with a power supply (6) and a universal meter (5) outside the tube in series by utilizing a lead (7) to form the current loop; Step S4, heating treatment, namely placing the quartz tube (2) in a tube furnace (1), setting the temperature of the tube furnace to be 300-1200 ℃, and heating to a set temperature at a heating rate of 5-50 ℃ per minute; s5, heat preservation and electric field auxiliary treatment, namely heat preservation is carried out for 3-12 hours at a set temperature, a power supply (6) is started, 0.5A-50A of current is applied to a coating sample (10), and lattice oxygen in the oxide escapes through the coupling effect of an electric field and a thermal field to form lattice oxygen vacancies; And S6, after the treatment is finished, the power supply (6) and the tube furnace (1) are sequentially turned off, so that the coating sample (10) is cooled to room temperature along with the furnace at a speed of 5-30 ℃ per minute.
  5. 5. The method according to claim 4, wherein the oxide coating prepared in the step S1 is ZrO 2 、TiO 2 、CeO 2 、ZnO、Cr 2 O 3 or Al 2 O 3 various metal oxides or composite oxides.
  6. 6. The method according to claim 4, wherein the temperature of the tube furnace in the step S4 is 300-1200 ℃ and the temperature rising rate is 5-50 ℃ per minute.
  7. 7. The method according to claim 4, wherein the heat preservation time in the step S5 is 3-12 hours, and the applied current is 0.5A-50A.
  8. 8. The method according to claim 4, wherein the cooling rate in step S6 is 5-30 ℃.

Description

Apparatus and method for making crystal lattice oxygen vacancies in oxides using electric field assistance Technical Field The invention belongs to the technical field of oxide films/coatings, and particularly relates to a device and a method for manufacturing crystal lattice oxygen vacancies in an oxide by utilizing electric field assistance. Background Oxide films/coatings (e.g., zrO 2、TiO2、CeO2, znO, etc.) are used in the fields of photoelectrocatalysis, gas sensors, solid oxide fuel cells, resistive random access memories, etc., due to their chemical stability and dielectric properties. The crystal lattice oxygen vacancies are used as a key point defect in the oxide material, and can regulate and control the energy band structure of the material and improve the carrier concentration, thereby effectively regulating the conductivity, the optical absorption characteristic and the surface catalytic activity of the material. Therefore, the realization of the manufacture and regulation of crystal lattice oxygen vacancies in the oxide coating is an important means for improving the performance of the oxide coating. Currently, the conventional methods for lattice oxygen vacancy formation in oxide production mainly include a heterovalent element doping method and a high-energy particle impact method, wherein oxygen vacancies are generated by introducing low-valent metal cations instead of high-valent cations in the lattice. The method needs to greatly increase the doping amount for obtaining high-concentration oxygen vacancies, which is extremely easy to cause component segregation, lattice distortion or second-phase impurity precipitation. The high-energy particle impact method is to bombard the surface of the oxide film/coating by using high-energy particles such as plasma, ion beam or electron beam, and peel off lattice oxygen atoms through physical collision. But the bombardment of the energetic particles tends to damage the film/coating surface, resulting in a significant increase in surface roughness and even causing microcracking or spalling of the coating, compromising the structural integrity of the film/coating. In summary, how to develop a device and a method for manufacturing lattice oxygen vacancies in oxide thin films/coatings with high efficiency and controllability without introducing foreign atoms and without damaging the structural integrity of the thin films/coatings is a technical problem to be solved in the field of oxide thin films/coatings. Disclosure of Invention The invention provides a device and a method for manufacturing crystal lattice oxygen vacancies in oxide by utilizing electric field assistance, wherein a coating sample is fixed in a quartz tube by a coating sample clamping unit, the coating sample is heated to a preset temperature by a tube furnace, then a power supply is started, current is applied to two ends of the surface of the coating, and under the coupling effect of the electric field and a thermal field, crystal lattice oxygen in the oxide escapes, so that crystal lattice oxygen vacancies are generated in the film/coating. An apparatus for creating crystal lattice oxygen vacancies in an oxide using electric field assistance, comprising: A tube furnace; The quartz tube axially penetrates through the heating cavity of the tube furnace, and two ends of the quartz tube are sealed through vacuum sealing flanges; The coating sample clamping unit is arranged in the quartz tube and positioned in the constant temperature area of the tube furnace and used for clamping and fixing a coating sample; the power supply is used for providing an external electric field; The lead passes through the opening on the vacuum sealing flange to be connected into the quartz tube, and is connected with the coating sample clamping unit and the power supply in series to form a current loop; and the universal meter is connected in series in the current loop and is used for monitoring loop current in real time. Further, the coating sample holding unit includes: A pair of insulating spacers; The metal clamps are respectively positioned at two sides of the coating sample and are used for clamping and fixing the insulating gasket, the coating sample and the electrode plate; And the electrode plate is arranged between the coating sample and the metal clamp and is electrically contacted with the conductive paste coated on the surface of the coating sample. Further, a gasket is arranged between the vacuum sealing flange and the quartz tube, and an opening for a wire to pass through is arranged on the vacuum sealing flange. A method of making crystal lattice oxygen vacancies using the apparatus, comprising the steps of: S1, preparing a coating sample, namely preparing an oxide coating on the surface of a substrate by adopting a coating process or a deposition process to obtain the coating sample, wherein the coating process comprises a sol-gel method, a spraying method, a spin-coating method and a dip-coati