CN110923667A - Efficient and simple preparation method of secondary electron emission thin film material - Google Patents

Efficient and simple preparation method of secondary electron emission thin film material Download PDF

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CN110923667A
CN110923667A CN201911306771.2A CN201911306771A CN110923667A CN 110923667 A CN110923667 A CN 110923667A CN 201911306771 A CN201911306771 A CN 201911306771A CN 110923667 A CN110923667 A CN 110923667A
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precursor solution
test tube
furnace
temperature
substrate material
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王金淑
王蕊
周帆
梁轩铭
杨韵斐
骆凯捷
李世磊
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Beijing University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4481—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
    • C23C16/4482—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material by bubbling of carrier gas through liquid source material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4486—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by producing an aerosol and subsequent evaporation of the droplets or particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment

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Abstract

A high-efficiency simple preparation method of a secondary electron emission thin film material belongs to the technical field of thin film material preparation. The preparation method comprises the steps of taking a silicon wafer, a silver sheet and FTO glass with smooth and flat surfaces as substrate materials, taking magnesium acetate and zinc acetate as main precursor substances, taking nitrogen as carrier gas, and preparing the MgO/MgO-ZnO film by combining aerogel chemical vapor deposition with high-temperature annealing under the condition of heating the substrate. The method for preparing the secondary emission thin film material has the advantages of simple preparation process, low cost, controllable doping elements and film thickness, uniform components, high secondary emission coefficient, electron bombardment resistance, stable emission performance and the like. Is expected to be applied to various devices such as photomultiplier tubes, image intensifiers and plasma displays.

Description

Efficient and simple preparation method of secondary electron emission thin film material
Technical Field
The invention relates to an efficient and simple preparation method of a secondary electron emission thin film material, in particular to a preparation method of a magnesium oxide thin film and a doped magnesium oxide thin film with good secondary electron emission performance by an aerogel assisted chemical vapor deposition method, and belongs to the technical field of functional thin film material preparation.
Background
With the development of electronic technology, higher requirements are put on secondary electron emission materials for vacuum electronic devices, so that the invention of a preparation method of the secondary electron emission material with higher secondary emission coefficient, longer service life and simple process is of great importance. The insulating solid material magnesium oxide (MgO) with a cubic crystal structure has the advantages of good chemical stability, high-temperature stability, low electron affinity, high secondary emission coefficient and the like, is one of ideal secondary emission materials, and is applied to devices such as a photomultiplier, an electron multiplier tube in a cesium atomic clock, a plasma display and the like. However, magnesium oxide (MgO) has poor conductivity, a charging effect is generated on the surface of the thin film under the bombardment of electron beams/ion beams, surface charges are difficult to neutralize, and secondary electron emission is inhibited, and the magnesium oxide is decomposed under the continuous bombardment of high-energy electron beams/ion beams, so that the secondary emission coefficient is reduced, and the device is failed. The alloy type secondary emission material is prepared for scientific research workers for improving the emission performance of the film, and the conductivity of the film is improved by doping elements with high conductivity, so that the performance is improved. The secondary emission cathode material applied in the traditional electron multiplier tube is an alloy of Ag-Mg, Al-Mg, Cu-Mg and the like, an MgO film is formed on the surface after certain oxygen-containing atmosphere heat activation treatment, and when the primary electron energy is 150-900 eV, the secondary electron emission coefficient is 3.5-12.0, so that the actual working requirements of most vacuum electronic devices can be met. However, the preparation process of the traditional alloy type emitting material needs precisely controlled thermal activation, a single MgO film is formed on the surface of the alloy, and the decomposition is easy to occur after long-time work, so that the performance is attenuated. In addition, scholars at home and abroad prepare the magnesium oxide/gold composite film by adopting methods such as magnetron sputtering and the like. The introduction of the gold nanoparticles in the magnesium oxide film relieves the adverse effect of the surface charge effect of the magnesium oxide film to a certain extent, thereby improving the secondary electron emission performance of the magnesium oxide film. However, the addition of gold particles reduces the denseness of the magnesium oxide film, and the problem of faster decay of secondary emission is common. Different preparation methods and processes have direct influence on the shape, structure, surface roughness and film thickness of the MgO film, so that the difference of the secondary emission performance of the film is large.
Disclosure of Invention
Aiming at the problems that the magnesium oxide film has poor conductivity and is not resistant to electron beam bombardment, the traditional alloy type emitting material has complex preparation process and is difficult to control, and the like, the invention adopts aerogel-assisted chemical vapor deposition, has simple process and controllable film thickness, and is convenient for doping other elements to regulate and control the electronic structure of the film material. Magnesium acetate and zinc acetate are used as source materials, a film is deposited on the surface of semiconductor and conductor substrate materials such as a silicon wafer, FTO glass, a silver sheet, an aluminum sheet and the like, and then the MgO or ZnO-doped MgO film is obtained through high-temperature annealing. The secondary emission thin film material with excellent performance is prepared by adjusting the process parameters such as substrate temperature, gas flow rate, annealing temperature, solution volume and the like. The element doping proportion can be regulated and controlled by regulating the precursor proportion, the film thickness can be regulated and controlled by changing the volume of the precursor solution, and the regulation and the control of the element doping proportion and the film thickness can be simply and quickly regulated and controlled. The invention mainly prepares the ZnO-MgO film formed by doping Zn, reduces the forbidden bandwidth of the film, improves the escape capability of electrons, and has similar crystal lattice radii of Zn and Mg without causing crystal lattice distortion.
The preparation method of the secondary emission material provided by the invention is realized by the following modes:
an apparatus for preparing single or doped magnesium oxide film comprises a chemical vapor reaction test tube ① and a CVD furnace ②, wherein a precursor solution is contained in the chemical vapor reaction test tube ② 1, the chemical vapor reaction test tube ① is arranged in an ultrasonic oscillator ③, a carrier gas inlet pipe extends into the precursor solution of the chemical vapor reaction test tube ① to carry out bubbling carrier gas, the precursor solution generates uniform mist under the action of an ultrasonic oscillator ③, an air outlet arranged on the chemical vapor reaction test tube ① is connected with the CVD furnace ② 2 through a pipeline, a heat-conducting copper plate is arranged in the CVD furnace ②, a prepared substrate material ② 0 is fixed on a common glass plate and placed on the heat-conducting copper plate in the CVD furnace, a heating device is arranged in the CVD furnace or outside the CVD furnace to heat to a certain temperature, and the mist generated by the precursor solution is carried by the carrier gas in the chemical vapor reaction test tube ① to enter the CVD furnace ② to carry out deposition on the substrate material.
The method for preparing the single or doped magnesium oxide film by adopting the device equipment is characterized by comprising the following steps:
fixing the ultrasonically cleaned base material on a glass sheet by using high-temperature-resistant glue, putting the glass sheet on a heat-conducting copper plate in a CVD furnace, setting the heating temperature of the CVD furnace to 350-500 ℃, and starting heating to raise the temperature; simultaneously introducing nitrogen; preparing a precursor solution, increasing the nitrogen flow rate when the temperature in the furnace rises to 350-500 ℃, dropping the precursor solution into a reaction test tube, adjusting the angle between the reaction test tube and an ultrasonic sprayer so that uniform mist appears in the test tube, allowing the mist to flow into a CVD furnace under the action of carrier gas, performing decomposition reaction under the action of high temperature, and depositing the mist on the surface of a substrate material; when the fog is obviously weakened, continuously measuring the precursor solution, dripping the precursor solution into the test tube, and repeating the above operations until the deposition is completed; adjusting the gas flow rate to be small, turning off a heating power supply, and taking out the glass sheet and the substrate material on the glass sheet after the glass sheet and the substrate material are cooled to room temperature along with the furnace; and (3) placing the CVD deposited substrate material into a corundum boat, placing the corundum boat into a tube furnace for annealing treatment, keeping the annealing temperature at 500-1000 ℃ for 0.5-4 h, introducing argon for protection in the annealing process, and taking out a sample after the furnace body is cooled to room temperature after annealing is finished.
Further: the CVD furnace is a normal pressure CVD furnace; adopting high-purity nitrogen gas with the purity not lower than 99.9 percent as carrier gas;
the precursor solution is formed by fully dissolving salts such as magnesium, zinc and the like which can be dissolved in methanol into the methanol; the concentration of the precursor solution is 0.05-0.3mol/L, the molar ratio of zinc to magnesium is (0-2) to (9-10), and the sum of the two is 10;
the methanol soluble salts of magnesium and zinc are selected from magnesium acetate and zinc acetate;
the substrate material may be selected from conductors, semiconductors, and the like; such as silver sheet, copper sheet, aluminum sheet or FTO conductive glass with good conductivity, and can also be quartz glass sheet or semiconductor monocrystalline silicon sheet with smooth surface, low roughness and no conductivity. After the silver sheet, the copper sheet and the aluminum sheet are cut into small squares, grinding and polishing are needed, and 1200#, 2000#, and 3000# SiC sand papers are used for rough grinding in sequence to remove surface adsorbates and oxide layers. Then, the diamond polishing agent with the grade of 2.5 mu m and 1 mu m is used for carrying out fine polishing treatment on the diamond polishing agent, so that the surface roughness is reduced as much as possible.
The substrate material is cut into square and rectangular sheets with certain sizes, and the length of the substrate material is 2-5cmx2-5 cm. Ultrasonic cleaning sequentially in acetone, isopropanol, distilled water, and ethanol solution for 15 min. After drying, the glass plate is stuck on a common glass plate by using high temperature resistant glue and is put on a heat conducting copper plate in a normal pressure CVD furnace.
In the deposition process, the flow rate of nitrogen gas is set to be 40l/h in the substrate heating process before deposition is started, and the flow rate is increased to 80-120 l/h during deposition.
The precursor solution is dripped into the reaction test tube each time in an amount which enables the precursor solution to be atomized under the action of ultrasonic waves. About 1ml of the precursor solution was taken each time by a dropper for reaction.
A device for improving the crystallinity of a single or doped magnesium oxide film is characterized in that a tube furnace is used for carrying out high-temperature annealing on a sample, and high-purity argon is introduced to be used as protective gas, so that the magnesium oxide film with better crystallinity is obtained.
The doping proportion and the film thickness of corresponding elements are controlled by adjusting the proportion of source materials and the volume of a solution, and a film with excellent performance is prepared by adjusting the gas flow rate and the substrate temperature; and then annealing is utilized to improve crystallinity, and annealing temperature and heat preservation time are regulated and controlled, so that an oxide thin film material which is compact, controllable in film thickness and doping proportion and good in crystallinity is formed, and the oxide thin film material has excellent performances of high secondary electron emission coefficient and good emission stability.
The invention has the beneficial effects that:
the invention adopts aerogel-assisted vapor deposition combined with annealing post-treatment to obtain the product with high secondary emission coefficient and electron bombardment resistance (the primary electron energy is 600eV, and the current density is 2.5 mA/cm)2The maximum secondary emission coefficient delta is still larger than 4) after the electron beam continuously bombards for 80 hours, and the novel pure MgO film cathode and the ZnO-doped MgO film cathode are obtained. The method has no need of vacuum requirement, and is simple in operationThe film thickness and the doping proportion are conveniently and quickly regulated, the deposited film is uniform and compact, the appearance is regular, and the film thickness is about 100-300 nm.
Drawings
FIG. 1 is a simplified schematic view of a chemical vapor deposition apparatus used in all examples
FIG. 2 is a surface SEM image of the MgO film produced in example 1;
FIG. 3 is a sectional SEM photograph of the MgO film produced in example 1;
FIG. 4 is a graph of the relationship between the energy of primary electrons and the secondary emission coefficient in example 1;
FIG. 5 is a graph of the relationship between the energy of primary electrons and the secondary emission coefficient in example 2;
FIG. 6 is a graph of the relationship between the energy of primary electrons and the secondary emission coefficient in example 3;
FIG. 7 is a surface SEM image of the MgO film produced in example 4;
FIG. 8 is a graph of the relationship between the energy of primary electrons and the secondary emission coefficient in example 4.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
In the following examples, substrate materials such as silicon wafers, FTO glass, silver sheets and the like are sequentially cleaned by acetone, isopropanol and alcohol for 15min by ultrasonic waves, and then dried and placed in a drying oven for standby. The dimensions of the substrate material were 2X 2 cm.
Example 1
Fixing the ultrasonically cleaned silicon wafer on a glass sheet by using high-temperature-resistant glue, putting the glass sheet on a heat-conducting copper plate in a special aerogel auxiliary CVD furnace, setting the heating temperature to be 500 ℃, starting heating, raising the temperature, and introducing nitrogen at the same time, wherein the gas flow rate is 40 l/h. Preparing 0.1mol/L precursor solution, weighing 0.214g of magnesium acetate, dissolving in 10ml of methanol, and fully dissolving the magnesium acetate by using a magnetic stirrer. When the temperature in the furnace rises to 500 ℃, adjusting the nitrogen flow rate to 90l/h, measuring 1ml of precursor solution by using a rubber head dropper, dripping the precursor solution into a reaction test tube, adjusting the angle between the reaction test tube and an ultrasonic sprayer so that uniform fog appears in the test tube, wherein the fog is carried out under the action of carrier gasFlowing into a deposition chamber, and performing decomposition reaction under the action of high temperature to deposit on the surface of the substrate material. When the fog is obviously weakened, continuously measuring 1ml of solution, dripping the solution into a test tube, and repeating the above operation steps until the solution is completely reacted. And (4) reducing the gas flow rate to 40l/h, closing the heating power supply, and taking out the glass sheet and the silicon wafer on the glass sheet after the glass sheet and the silicon wafer are cooled to room temperature along with the furnace. And (3) placing the silicon wafer deposited by the CVD into a corundum boat, placing the corundum boat into a tube furnace for annealing treatment, wherein the annealing temperature is 700 ℃, the heating rate is 10 ℃/min, the heat preservation is carried out for 1h, and argon is introduced for protection in the annealing process. And after the annealing is finished, taking out the sample after the furnace body is cooled to room temperature. Loading the sample into a secondary emission test bench, bombarding the surface of the sample vertically with electron beam generated by a heated barium-tungsten cathode, and measuring the back bottom current of the prepared MgO film sample and the secondary current collected by a collector after full activation to obtain the change curve of the secondary emission coefficient of the silicon substrate MgO film sample along with the primary electron energy, as shown in FIG. 3, wherein the primary electron energy is 600eV, and the current density is 2.5mA/cm2The maximum secondary emission coefficient delta of the electron beam after the electron beam continuously bombards for 80 hours is still larger than 4.
Example 2
Fixing the FTO glass cleaned by ultrasonic on a glass sheet by using high-temperature-resistant glue, putting the glass sheet on a heat-conducting copper plate in a special aerogel auxiliary CVD furnace, setting the heating temperature to 350 ℃, starting heating, raising the temperature, and introducing nitrogen at the same time, wherein the gas flow rate is 40 l/h. 0.1mol/L precursor solution is prepared, 0.214g of magnesium acetate is weighed and dissolved in 10ml of methanol, and the magnesium acetate is fully dissolved by a magnetic stirrer. And (3) when the temperature in the furnace rises to 350 ℃, adjusting the nitrogen flow rate to 90l/h, measuring 1ml of precursor solution by using a rubber head dropper, dripping the precursor solution into a reaction test tube, adjusting the angle between the reaction test tube and an ultrasonic sprayer so that uniform mist appears in the test tube, allowing the mist to flow into a deposition chamber under the action of carrier gas, performing decomposition reaction under the action of high temperature, and depositing the mist on the surface of the substrate material. When the fog is obviously weakened, continuously measuring 1ml of solution, dripping the solution into a test tube, and repeating the above operation steps until the solution is completely reacted. And (4) reducing the gas flow rate to 40l/h, closing the heating power supply, and taking out the glass sheet and the FTO glass on the glass sheet after the glass sheet is cooled to room temperature along with the furnace. Placing the FTO glass deposited by CVD into a corundum boat and placing into a tube furnaceAnnealing at 900 deg.c and heating rate of 10 deg.c/min for 1 hr while introducing argon for protection. And after the annealing is finished, taking out the sample after the furnace body is cooled to room temperature. The sample is loaded into a secondary emission test bench, electron beams generated by a heated barium-tungsten cathode vertically bombard the surface of the sample, the back bottom flow of the prepared MgO film sample and the secondary flow collected by a collector are measured after the sample is fully activated, and the change curve of the secondary emission coefficient of the MgO film sample on the surface of the FTO glass substrate along with the primary electron energy is obtained, which is shown in figure 4, the primary electron energy is 600eV, and the current density is 2.5mA/cm2The maximum secondary emission coefficient delta of the electron beam after the electron beam continuously bombards for 80 hours is still larger than 4.
Example 3
Fixing the ultrasonically cleaned silver sheet on a glass sheet by using high-temperature-resistant glue, putting the glass sheet on a heat-conducting copper plate in a special aerogel auxiliary CVD furnace, setting the heating temperature to 400 ℃, starting heating, raising the temperature, and introducing nitrogen at the same time, wherein the gas flow rate is 40 l/h. Preparing 0.1mol/L precursor solution, weighing 0.214g of magnesium acetate, dissolving in 10ml of methanol, and fully dissolving the magnesium acetate by using a magnetic stirrer. And (3) when the temperature in the furnace rises to 400 ℃, adjusting the nitrogen flow rate to 90l/h, measuring 1ml of precursor solution by using a rubber head dropper, dripping the precursor solution into a reaction test tube, adjusting the angle between the reaction test tube and an ultrasonic sprayer so that uniform spraying appears in the test tube, allowing the spraying to flow into a deposition chamber under the action of carrier gas, performing decomposition reaction under the action of high temperature, and depositing on the surface of the substrate material. When the fog is obviously weakened, continuously measuring 1ml of solution, dripping the solution into a test tube, and repeating the above operation steps until the solution is completely reacted. And (4) reducing the gas flow rate to 40l/h, closing the heating power supply, and taking out the glass sheet and the silicon wafer on the glass sheet after the glass sheet and the silicon wafer are cooled to room temperature along with the furnace. And (3) placing the silicon wafer deposited by the CVD into a corundum boat, placing the corundum boat into a tube furnace for annealing treatment, wherein the annealing temperature is 900 ℃, the heating rate is 10 ℃/min, the heat preservation is carried out for 1h, and argon is introduced for protection in the annealing process. And after the annealing is finished, taking out the sample after the furnace body is cooled to room temperature. Loading the sample into a secondary emission test bench, bombarding the surface of the sample vertically with electron beam generated by a heated barium-tungsten cathode, and measuring the back bottom flow of the prepared MgO film sample and the secondary flow collected by a collector after full activation to obtain silver sheet baseThe change curve of the secondary emission coefficient of the bottom MgO film sample with the primary electron energy is shown in FIG. 5, the primary electron energy is 600eV, and the current density is 2.5mA/cm2The maximum secondary emission coefficient delta of the electron beam is still larger than 10 after the electron beam continuously bombards for 80 hours.
Example 4
Fixing the ultrasonically cleaned silver sheet on a glass sheet by using high-temperature-resistant glue, putting the glass sheet on a heat-conducting copper plate in a special aerogel auxiliary CVD furnace, setting the heating temperature to 400 ℃, starting heating, raising the temperature, and introducing nitrogen at the same time, wherein the gas flow rate is 40 l/h. Preparing a precursor mixed solution with the concentration of 0.1mol/L in the heating process, respectively weighing 0.193g of magnesium acetate and 0.022g of zinc acetate to dissolve in 10ml of methanol, and uniformly mixing the solution by using a magnetic stirrer. And (3) when the temperature in the furnace rises to 400 ℃, adjusting the nitrogen flow rate to 90l/h, measuring 1ml of precursor solution by using a rubber head dropper, dripping the precursor solution into a reaction test tube, adjusting the angle between the reaction test tube and an ultrasonic sprayer so that uniform mist appears in the test tube, allowing the mist to flow into a deposition chamber under the action of carrier gas, performing decomposition reaction under the action of high temperature, and depositing the mist on the surface of the substrate material. When the fog is obviously weakened, continuously measuring 1ml of solution, dripping the solution into a test tube, and repeating the above operation steps until the solution is completely reacted. And (4) reducing the gas flow rate to 40l/h, closing the heating power supply, and taking out the glass sheet and the silver sheet on the glass sheet after the glass sheet and the silver sheet are cooled to room temperature along with the furnace. And (3) placing the silver sheet deposited by the CVD into a corundum boat, placing the corundum boat into a tube furnace for annealing treatment, wherein the annealing temperature is 700 ℃, the heating rate is 10 ℃/min, the heat preservation is 1h, and argon is introduced for protection in the annealing process. And after the annealing is finished, taking out the sample after the furnace body is cooled to room temperature. Loading the sample into a secondary emission test bench, bombarding the surface of the sample vertically with electron beam generated by a heated barium-tungsten cathode, and measuring the back bottom current of the prepared ZnO-doped MgO thin film sample and the secondary current collected by a collector after full activation to obtain the change curve of the secondary emission coefficient of the ZnO-doped MgO thin film sample with the silver sheet substrate along with the primary electron energy, as shown in FIG. 7, wherein the primary electron energy is 600eV, and the current density is 2.5mA/cm2The maximum secondary emission coefficient delta of the electron beam after the electron beam continuously bombards for 80 hours is still larger than 4.
The invention is not limited to the above embodiments, but includes any modifications, equivalents, improvements, etc. without departing from the spirit and scope of the invention.

Claims (10)

1. An apparatus for preparing single or doped magnesium oxide film is characterized by comprising a chemical vapor reaction test tube ① and a CVD furnace ②, wherein a precursor solution is contained in the chemical vapor reaction test tube ② 1, the chemical vapor reaction test tube ① is placed in an ultrasonic oscillator ③, a carrier gas inlet pipe extends into the precursor solution of the chemical vapor reaction test tube ① to carry out bubbling carrier gas, the precursor solution generates uniform mist under the action of an ultrasonic oscillator ③, an air outlet arranged on the chemical vapor reaction test tube ① is connected with the CVD furnace ② 2 through a pipeline, a heat-conducting copper plate is arranged in the CVD furnace ②, a prepared substrate material ② 0 is fixed on a common glass plate and placed on the heat-conducting copper plate in the CVD furnace, a heating device capable of heating to a certain temperature is arranged in or outside the CVD furnace, and the carrier gas in the chemical vapor reaction test tube ① carries the mist generated by the precursor solution to enter the CVD furnace ② to carry out deposition on the substrate material.
2. A method for preparing a single or doped magnesium oxide thin film using the apparatus of claim 1, characterized by comprising the steps of:
fixing the ultrasonically cleaned base material on a glass sheet by using high-temperature-resistant glue, putting the glass sheet on a heat-conducting copper plate in a CVD furnace, setting the heating temperature of the CVD furnace to 350-500 ℃, and starting heating to raise the temperature; simultaneously introducing nitrogen; preparing a precursor solution, increasing the nitrogen flow rate when the temperature in the furnace rises to 350-500 ℃, dropping the precursor solution into a reaction test tube, adjusting the angle between the reaction test tube and an ultrasonic sprayer so that uniform mist appears in the test tube, allowing the mist to flow into a CVD furnace under the action of carrier gas, performing decomposition reaction under the action of high temperature, and depositing the mist on the surface of a substrate material; when the fog is obviously weakened, continuously measuring the precursor solution, dripping the precursor solution into the test tube, and repeating the above operations until the deposition is completed; adjusting the gas flow rate to be small, turning off a heating power supply, and taking out the glass sheet and the substrate material on the glass sheet after the glass sheet and the substrate material are cooled to room temperature along with the furnace; and (3) placing the CVD deposited substrate material into a corundum boat, placing the corundum boat into a tube furnace for annealing treatment, keeping the annealing temperature at 500-1000 ℃ for 0.5-4 h, introducing argon for protection in the annealing process, and taking out a sample after the furnace body is cooled to room temperature after annealing is finished.
3. The method of claim 2, wherein the CVD furnace is an atmospheric pressure CVD furnace; high purity nitrogen was used as the carrier gas.
4. The method according to claim 2, wherein the precursor solution is formed by dissolving salts such as magnesium and zinc, etc. which are soluble in methanol, sufficiently in methanol; the concentration of the precursor solution is 0.05-0.3mol/L, the molar ratio of zinc and magnesium is (0-2): 9-10), and the sum of the two is 10.
5. The method of claim 2, wherein the methanol-soluble salts of magnesium and zinc are selected from the group consisting of magnesium acetate and zinc acetate.
6. The method of claim 2, wherein the substrate material is selected from the group consisting of conductors and semiconductors.
7. The method according to claim 2, wherein the substrate material is selected from the group consisting of silver flakes, copper flakes, aluminum flakes or FTO conductive glass of good conductivity, or quartz glass flakes or semiconductor monocrystalline silicon pieces; after the silver sheet, the copper sheet and the aluminum sheet are cut into small squares, grinding and polishing are needed, and SiC sand paper 1200#, 2000#, and 3000# is used for rough grinding in sequence to remove surface adsorbates and an oxide layer; then, a diamond polishing agent with the grade of 2.5 mu m and 1 mu m is used for carrying out fine polishing treatment on the diamond, so that the surface roughness is reduced as much as possible; cutting the substrate material into square, rectangular sheets and the like with a certain size, wherein the length is 2-5cmx2-5 cm; ultrasonic cleaning sequentially in acetone, isopropanol, distilled water, and ethanol solution for 15 min.
8. The method of claim 2, wherein the flow rate of the nitrogen gas is set to 40l/h during heating of the substrate before starting deposition, and is increased to 80 to 120l/h during deposition.
9. The method according to claim 2, wherein the amount of the precursor solution added dropwise to the reaction tube at a time is such that the precursor solution can be atomized under the action of the ultrasonic waves; preferably, about 1ml of the precursor solution is taken each time by means of a dropper for the reaction.
10. A single or doped magnesium oxide film prepared by the method of any one of claims 2 to 9.
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