阅读说明：本技术 一种具有低密度氧空位缺陷的氧化镓外延材料的制备方法 (Preparation method of gallium oxide epitaxial material with low-density oxygen vacancy defects ) 是由 胡继超 李丹 李连碧 臧源 王曦 蒲红斌 于 2020-04-15 设计创作，主要内容包括：本发明公开了一种具有低密度氧空位缺陷的氧化镓外延材料的制备方法,首先将金属镓源放入石英舟内,石英舟放入双温区石英管式炉内温区1中；然后将清洗、吹干后的衬底放在衬底托上,将载有衬底片的衬底托放入石英管式炉内温区2中；将反应腔抽真空,抽真空后腔体压强为1pa；向石英反应腔内通入作为载气的惰性气体；同时加热管式炉内温区1中载有金属镓源的石英舟和温区2中的衬底；通过设置升温时间使温区1的工作温度和温区2中的工作温度同时达到相应设置的温度,打开氧气气路,让惰性气体携带氧气进入石英反应管,在衬底上沉积氧化镓薄膜,完成氧化镓薄膜制备,本发明解决了现有技术中存在的氧化镓材料中极易出现氧空位缺陷的问题。(The invention discloses a preparation method of a gallium oxide epitaxial material with low-density oxygen vacancy defects, which comprises the following steps of firstly, putting a metal gallium source into a quartz boat, and putting the quartz boat into a double-temperature-zone quartz tube type furnace inner temperature zone 1; then the cleaned and dried substrate is placed on a substrate holder, and the substrate holder carrying the substrate slice is placed in a temperature zone 2 in the quartz tube furnace; vacuumizing the reaction cavity, wherein the pressure of the cavity is 1pa after vacuumizing; introducing inert gas serving as carrier gas into the quartz reaction chamber; simultaneously heating a quartz boat loaded with a metal gallium source in a temperature zone 1 in the heat pipe furnace and a substrate in the temperature zone 2; the method comprises the steps of setting the temperature rise time to enable the working temperature of the temperature area 1 and the working temperature of the temperature area 2 to reach the correspondingly set temperatures at the same time, opening the oxygen gas circuit, enabling inert gas to carry oxygen into the quartz reaction tube, depositing a gallium oxide film on a substrate, and completing preparation of the gallium oxide film.)

1. A preparation method of a gallium oxide epitaxial material with low-density oxygen vacancy defects is characterized by comprising the following steps:

step 1, putting a metal gallium source into a quartz boat, and putting the quartz boat into a double-temperature-zone quartz tube type furnace inner temperature zone 1;

step 2: placing the cleaned and dried substrate on a substrate holder, and placing the substrate holder carrying the substrate sheet into a quartz tube type furnace inner temperature zone 2; vacuumizing the reaction cavity, wherein the pressure of the cavity is 1pa after vacuumizing;

and step 3: introducing inert gas serving as carrier gas into the quartz reaction chamber;

and 4, step 4: simultaneously heating a quartz boat loaded with a metal gallium source in a temperature zone 1 in the heat pipe furnace and a substrate in the temperature zone 2; setting the temperature rise time to enable the working temperature of the temperature zone 1 and the working temperature of the temperature zone 2 to reach the corresponding set temperatures at the same time, wherein the working temperature of the metal gallium source in the temperature zone 1 is 550-650 ℃; the working temperature of the substrate in the temperature zone 2 is 700-1050 ℃;

and 5: when the working temperature of the reaction boat in the temperature zone 1 and the working temperature of the substrate in the temperature zone 2 in the quartz tube reach set temperatures, opening an oxygen gas path to allow inert gas to carry oxygen into the quartz reaction tube; setting growth time, and depositing a gallium oxide film on the substrate;

step 6: after the growth of the gallium oxide film is finished, closing an oxygen source gas path, and keeping the temperature of the temperature zone 1 and the temperature zone 2 and the flow of the inert gas unchanged for a period of time;

and 7: and after the holding time is over, repeating the step 5 and the step 6, and then closing the gas and reducing the temperature to finish the preparation of the gallium oxide film.

2. The method for preparing gallium oxide epitaxial material with low-density oxygen vacancy defects according to claim 1, wherein the metal gallium source in step 1 is metal gallium particles with a purity of 99.99% -99.99999%.

3. The method of claim 1, wherein the substrate in step 2 is one of silicon, sapphire, silicon carbide, gallium nitride, gallium oxide, or diamond.

4. The method for preparing a gallium oxide epitaxial material with low density oxygen vacancy defects according to claim 1, wherein the distance between the metallic gallium source and the substrate in step 2 is set to 5-25 cm.

5. The method for preparing gallium oxide epitaxial material with low density oxygen vacancy defects according to claim 1, wherein the inert gas in step 3 is one or more of argon, nitrogen, helium and neon.

6. The method for preparing the gallium oxide epitaxial material with the low-density oxygen vacancy defect according to claim 1, wherein the purity of the oxygen carried by the inert gas in the step 5 is 99.999% -99.99999%, the flow rate of the oxygen is controlled to be 5-100 sccm, and the growth time is set to be 10-300 s.

7. The method for preparing a gallium oxide epitaxial material with low density oxygen vacancy defects according to claim 1, wherein the temperature of temperature zone 1, temperature zone 2 and inert gas flow rate are maintained for a period of time of 60s to 600s in step 6.

Technical Field

The invention belongs to the technical field of semiconductor devices, and particularly relates to a preparation method of a gallium oxide epitaxial material with low-density oxygen vacancy defects.

Background

When the ultraviolet light with the wave band of 200-280nm passes through the atmosphere, the photon target signal is strongly reacted with the ozone layer and is absorbed completely, so that the ultraviolet light with the wave band is almost nonexistent in the atmosphere. Based on the advantage that the solar blind ultraviolet light is almost zero background signals in the atmosphere, the solar blind ultraviolet detector working in the waveband has the characteristic of low false alarm rate, and has important application prospects in civil fields such as high-voltage transmission line detection, meteorological early warning and fire early warning and military fields such as missile identification tracking and ship-borne communication. Gallium oxide (Ga)₂O₃) As a novel direct band gap wide band gap semiconductor material, the band gap width is 4.9eV, the corresponding absorption wavelength is 253nm, the photoelectric response characteristic is high in a deep ultraviolet region, and the direct band gap wide band gap semiconductor material has great application potential in the field of deep ultraviolet solar blind photodetectors.

However, oxygen vacancy defects are highly likely to occur in gallium oxide materials due to the lower energy of formation of oxygen vacancies in gallium oxide materials. The presence of oxygen vacancies as deep level donor impurities results in a gallium oxide material with a static dielectric constant₀The absorption in the visible light region is enhanced, and the absorption coefficient is increased. Therefore, in the practical application of gallium oxide, the oxygen vacancy directly influences the transient response, electrode contact and other characteristics of the gallium oxide-based ultraviolet detector.

Disclosure of Invention

The invention aims to provide a preparation method of a gallium oxide epitaxial material with low-density oxygen vacancy defects, which solves the problem that the oxygen vacancy defects are easy to appear in the gallium oxide material in the prior art.

The technical scheme adopted by the invention is that the preparation method of the gallium oxide epitaxial material with the low-density oxygen vacancy defect is implemented according to the following steps:

step 1, putting a metal gallium source into a quartz boat, and putting the quartz boat into a double-temperature-zone quartz tube type furnace inner temperature zone 1;

step 2: placing the cleaned and dried substrate on a substrate holder, and placing the substrate holder carrying the substrate sheet into a quartz tube type furnace inner temperature zone 2; vacuumizing the reaction cavity, wherein the pressure of the cavity is 1pa after vacuumizing;

and step 3: introducing inert gas serving as carrier gas into the quartz reaction chamber;

and 4, step 4: simultaneously heating a quartz boat loaded with a metal gallium source in a temperature zone 1 in the heat pipe furnace and a substrate in the temperature zone 2; setting the temperature rise time to enable the working temperature of the temperature zone 1 and the working temperature of the temperature zone 2 to reach the corresponding set temperatures at the same time, wherein the working temperature of the metal gallium source in the temperature zone 1 is 550-650 ℃; the working temperature of the substrate in the temperature zone 2 is 700-1050 ℃;

and 5: when the working temperature of the reaction boat in the temperature zone 1 and the working temperature of the substrate in the temperature zone 2 in the quartz tube reach set temperatures, opening an oxygen gas path to allow inert gas to carry oxygen into the quartz reaction tube; setting growth time, and depositing a gallium oxide film on the substrate;

step 6: after the growth of the gallium oxide film is finished, closing an oxygen source gas path, and keeping the temperature of the temperature zone 1 and the temperature zone 2 and the flow of the inert gas unchanged for a period of time;

and 7: and after the holding time is over, repeating the step 5 and the step 6, and then closing the gas and reducing the temperature to finish the preparation of the gallium oxide film.

The present invention is also characterized in that,

in the step 1, the metal gallium source is metal gallium particles, and the purity is 99.99-99.99999%.

In the step 2, the substrate is one of silicon, sapphire, silicon carbide, gallium nitride, gallium oxide or diamond.

And in the step 2, the distance between the metal gallium source and the substrate is set to be 5-25 cm.

In the step 3, the inert gas is one or a mixture of several of argon, nitrogen, helium and neon.

In the step 5, the purity of oxygen carried by the inert gas is 99.999% -99.99999%, the flow of the oxygen is controlled to be 5-100 sccm, and the growth time is set to be 10-300 s.

And in the step 6, keeping the temperature of the temperature zone 1 and the temperature zone 2 and the inert gas flow for a constant time of 60-600 s.

The invention has the advantages that the preparation method of the gallium oxide epitaxial material with the low-density oxygen vacancy defect adopts the double-temperature-zone high-temperature tube furnace, the equipment structure is simple, and the temperature of the metal gallium source and the temperature of the substrate can be respectively and accurately set; in the invention, by adopting the growth process of intermittently regulating oxygen at high temperature, the density of oxygen vacancy defects in the gallium oxide film can be reduced while the high-crystalline gallium oxide film can be obtained. Compared with the existing post-treatment process methods such as annealing and the like adopted for reducing the defect density of the oxygen vacancy, the invention provides the method for reducing the defect density while the gallium oxide is epitaxially grown, the process is simpler and more convenient, and the method is suitable for large-scale industrial production.

Drawings

FIG. 1 is a flow chart of the epitaxial growth process of gallium oxide thin films with low oxygen vacancy defect density in accordance with the present invention.

Detailed Description

The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

The invention relates to a preparation method of a gallium oxide epitaxial material with low-density oxygen vacancy defects, which is implemented according to the following steps, wherein the flow chart is shown in figure 1:

step 1, putting a metal gallium source into a quartz boat, wherein the metal gallium source is metal gallium particles with the purity of 99.99-99.99999 percent, and the quartz boat is put into a double-temperature-zone quartz tube type furnace inner temperature zone 1;

step 2: placing the cleaned and dried substrate on a substrate holder, and placing the substrate holder carrying the substrate sheet into a quartz tube type furnace inner temperature zone 2; vacuumizing the reaction cavity, wherein the pressure of the cavity is 1pa after vacuumizing, the substrate is one of silicon, sapphire, silicon carbide, gallium nitride, gallium oxide or diamond, and the distance between the metal gallium source and the substrate is set to be 5-25 cm;

and step 3: introducing inert gas serving as carrier gas into the quartz reaction chamber, wherein the inert gas is one or a mixture of more of argon, nitrogen, helium and neon;

and 4, step 4: simultaneously heating a quartz boat loaded with a metal gallium source in a temperature zone 1 in the heat pipe furnace and a substrate in the temperature zone 2; setting the temperature rise time to enable the working temperature of the temperature zone 1 and the working temperature of the temperature zone 2 to reach the corresponding set temperatures at the same time, wherein the working temperature of the metal gallium source in the temperature zone 1 is 550-650 ℃; the working temperature of the substrate in the temperature zone 2 is 700-1050 ℃;

and 5: when the working temperature of the reaction boat in the temperature zone 1 and the working temperature of the substrate in the temperature zone 2 in the quartz tube reach set temperatures, opening an oxygen gas path to allow inert gas to carry oxygen into the quartz reaction tube; setting growth time, depositing a gallium oxide film on a substrate, wherein the purity of oxygen carried by inert gas is 99.999% -99.99999%, the flow of the oxygen is controlled to be 5-100 sccm, and the growth time is set to be 10-300 s;

step 6: after the growth of the gallium oxide film is finished, closing an oxygen source gas path, keeping the temperature of the temperature zone 1 and the temperature zone 2 and the flow of the inert gas unchanged for a period of time, and keeping the temperature of the temperature zone 1 and the temperature zone 2 and the flow of the inert gas unchanged for 60-600 s;

and 7: and after the holding time is over, repeating the step 5 and the step 6, and then closing the gas and reducing the temperature to finish the preparation of the gallium oxide film.