CN114059042A

CN114059042A - Preparation design for preparing gallium oxide film by Mist method

Info

Publication number: CN114059042A
Application number: CN202111363304.0A
Authority: CN
Inventors: 李培刚; 季学强; 李龙; 陈梅艳; 严旭
Original assignee: Beijing Gachuang Technology Co ltd
Current assignee: Beijing Gachuang Technology Co ltd
Priority date: 2021-11-17
Filing date: 2021-11-17
Publication date: 2022-02-18

Abstract

The invention discloses a preparation design for preparing a gallium oxide film by a Mist method, which comprises the following steps: step 1: dissolving gallium acetylacetonate in deionized water at normal temperature, adding Ga metal ions to prepare a precursor solution, and uniformly mixing the prepared precursor solution with a hydrochloric acid solution; step 2: the sapphire substrate is sequentially subjected to ultrasonic cleaning in acetone, ethanol and deionized water for 10min, then is dried by nitrogen, and then is placed into a Mist CVD device for film growth. Has the advantages that: the preparation method has the advantages of simple preparation process, commercial substrate and wide source, and meanwhile, in the preparation process, the commercial preparation method Mist CVD is adopted to grow the large-size beta-Ga 2O3 film, the process controllability is strong, the operation is easy, the obtained film has compact surface, stable and uniform thickness, large-area preparation and good repeatability, and a reliable epitaxial growth means is provided for the gallium oxide-based device.

Description

Preparation design for preparing gallium oxide film by Mist method

Technical Field

The invention relates to the technical field of gallium oxide film preparation, in particular to a preparation design for preparing a gallium oxide film by a Mist method.

Background

Ga2O3 is a transparent direct bandgap semiconductor material, has a forbidden band width of about 4.9eV, and has excellent material properties such as low on-resistance, high dielectric constant, and good thermal stability. Due to the ultra-wide forbidden band width, the high-voltage high-power LED has remarkable advantages and great development potential in the fields of deep ultraviolet light electric devices and high-voltage high-power devices. In recent years, many researchers have produced high-quality Ga2O3 thin-film materials by different epitaxial growth methods, such as Molecular Beam Epitaxy (MBE), Metal Organic Chemical Vapor Deposition (MOCVD), laser pulse deposition (PLD), Atomic Layer Deposition (ALD), magnetron sputtering, and misty chemical vapor deposition (mit CVD). The Mist CVD technology is a novel film epitaxy technology developed based on a common chemical deposition technology, and has the characteristics of high safety, no need of vacuumizing for the growth environment of a film, flexible precursor selection and the like, so that the Mist CVD technology has great development potential in the material epitaxy direction.

At present, the existing epitaxial equipment is generally expensive and complex in process, for example, MBE equipment is high in price, the growth process is complex, the growth speed is slow, large-size commercialization is not realized, MOCVD is also expensive, the used organic source belongs to flammable and explosive dangerous goods, PLD can only produce small-size epitaxial films, and epitaxial quality prepared by other physical deposition methods is poor.

Disclosure of Invention

The invention aims to solve the problems and provide a preparation design for preparing a gallium oxide thin film by a Mist method.

The invention realizes the purpose through the following technical scheme:

a preparation design for preparing a gallium oxide film by a Mist method comprises the following steps:

step 1: dissolving gallium acetylacetonate in deionized water at normal temperature, adding Ga metal ions to prepare a precursor solution, and uniformly mixing the prepared precursor solution with a hydrochloric acid solution;

step 2: ultrasonically cleaning a sapphire substrate in acetone, ethanol and deionized water for 10min in sequence, then blow-drying the sapphire substrate by using nitrogen, and then putting the sapphire substrate into a Mist CVD device for film growth;

and step 3: and carrying out in-situ annealing at corresponding temperature on the grown film to obtain the gallium oxide film.

Further, the volume ratio of the precursor solution to the hydrochloric acid solution in the step 1 is 100: 1.

Further, in the step 2, the process parameters of the sapphire substrate processed by the Mist CVD device are as follows: normal pressure, carrier gas flow of 0.5L/min, diluent gas force of 1L/min, substrate temperature of 500-750 deg.c, and growth time of 120-60 min.

Further, the carrier gas is argon, and the diluent gas is oxygen.

Further, the specific flow of processing the sapphire substrate in the mit CVD apparatus in step 2 is as follows: firstly, place the sapphire substrate on the heating tray of reaction intracavity, the reaction chamber is evacuation earlier, then let in argon gas in to the reaction chamber through advancing the argon pipe, make argon gas be full of whole reaction chamber, add the precursor solution in the ultrasonic atomization jar next, set up the heating temperature in the reaction chamber, when the temperature reaches the settlement temperature, let in oxygen through advancing the oxygen pipe, open the atomizer in the ultrasonic atomization jar simultaneously, regard as the carrier gas with flowmeter control argon gas, oxygen is as the diluent gas, send the fog droplet in the ultrasonic atomization jar into the reaction chamber and contact with the substrate, carry out the deposit.

Further, the annealing gas in the annealing process in the step 3 is oxygen.

Furthermore, in the in-situ annealing process, on one hand, water vapor in the reaction cavity can be taken out, and on the other hand, oxygen defects in the thin film are further eliminated, so that the high-quality thin film is obtained.

The invention has the beneficial effects that:

the preparation method has the advantages of simple preparation process, commercial substrate and wide source, and meanwhile, in the preparation process, the commercial preparation method Mist CVD is adopted to grow the large-size beta-Ga 2O3 film, the process controllability is strong, the operation is easy, the obtained film has compact surface, stable and uniform thickness, large-area preparation and good repeatability, and a reliable epitaxial growth means is provided for the gallium oxide-based device.

Drawings

FIG. 1 is a block diagram of a Mist CVD apparatus used in the design of the Mist method for preparing a gallium oxide thin film according to the present invention;

FIG. 2 is an XRD diagram of a gallium oxide film prepared by the design of the Mist method for preparing the gallium oxide film according to the present invention;

FIG. 3 is a microscopic surface view of the surface of the gallium oxide film prepared by the Mist method of the present invention.

The reference numerals are explained below:

1. a flow meter; 2. an oxygen inlet pipe; 3. an argon inlet pipe; 4. an ultrasonic atomization tank; 5. a tail gas treatment pipe; 6. heating the tray; 7. a mixing chamber; 8. a reaction chamber.

Detailed Description

A preparation design for preparing gallium oxide film by Mist method comprises the following steps

Step 1: weighing gallium acetylacetonate with the purity of more than 99.99 percent as a precursor raw material according to a stoichiometric ratio, dissolving the raw material in deionized water at room temperature, preparing a precursor solution with Ga metal ions of 0.03mol/L, adding a hydrochloric acid solution with the concentration of 30 percent into the precursor solution, wherein the volume ratio of the precursor solution to the hydrochloric acid solution is 100: 1;

step 2: ultrasonically cleaning a sapphire substrate 3 in acetone, ethanol and deionized water for 10min in sequence, blow-drying the sapphire substrate by using nitrogen, and then putting the sapphire substrate into a Mist CVD device for film growth;

and step 3: after the sapphire substrate is placed in the Mist CVD device, the sapphire substrate is placed on a heating tray 6 in a reaction chamber 8, the reaction chamber 8 is firstly vacuumized, then argon is introduced into the reaction cavity 8 through the argon inlet pipe 3, so that the whole reaction cavity 8 is filled with argon, the flow rate of the argon is 0.5/min, then adding the precursor solution into the ultrasonic atomization tank 4, setting the heating temperature in the reaction cavity 8 at 700 ℃, when the temperature reaches the set temperature, oxygen is introduced through the oxygen inlet pipe 2, the oxygen flow is 1L/min, meanwhile, starting an atomizer in the ultrasonic atomization tank 4, controlling the ultrasonic atomization frequency to be 1.7MHZ, controlling argon to be used as a current-carrying gas and oxygen to be used as a diluent gas by using a flowmeter 1, sending fog drops in the ultrasonic atomization tank 4 into a reaction cavity 8 and contacting with a substrate for deposition, and obtaining a film with the thickness of 260nm after deposition for 60 min;

and 4, step 4: after deposition, the ultrasonic atomization tank 4 is closed, and in-situ annealing is carried out for 30min, so that the high-quality gallium oxide film can be prepared.

In this embodiment, as can be seen from fig. 2, the quality of the gallium oxide film prepared by the method of the present invention is high.

In this embodiment, as can be seen from fig. 3, the surface roughness of the gallium oxide thin film prepared by the method of the present invention is very small, about 1 mm.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. A preparation design for preparing a gallium oxide film by a Mist method is characterized in that: it comprises the following steps:

2. The design of claim 1, wherein the design of Mist process for preparing gallium oxide thin film comprises: the volume ratio of the precursor solution to the hydrochloric acid solution in the step 1 is 100: 1.

3. The design of claim 1, wherein the design of Mist process for preparing gallium oxide thin film comprises: the process parameters of the sapphire substrate processed by the Mist CVD device in the step 2 are as follows: normal pressure, carrier gas flow of 0.5L/min, diluent gas force of 1L/min, substrate temperature of 500-750 deg.c, and growth time of 120-60 min.

4. The design of claim 3, wherein the design of Mist process for preparing gallium oxide thin film comprises: the carrier gas is argon, and the diluent gas is oxygen.

5. The design of claim 1, wherein the design of Mist process for preparing gallium oxide thin film comprises: the specific process of processing the sapphire substrate in the Mist CVD device in the step 2 is as follows: firstly, a sapphire substrate is placed on a heating tray (6) in a reaction cavity (8), the reaction cavity (8) is firstly vacuumized, then argon is introduced into the reaction cavity (8) through an argon inlet pipe (3), the whole reaction cavity (8) is filled with the argon, then a precursor solution is added into an ultrasonic atomization tank (4), the heating temperature in the reaction cavity (8) is set, when the temperature reaches a set temperature, oxygen is introduced through an oxygen inlet pipe (2), meanwhile, an atomizer in the ultrasonic atomization tank (4) is started, a flow meter (1) is used for controlling the argon to serve as a current-carrying gas, the oxygen serves as a diluent gas, fog drops in the ultrasonic atomization tank (4) are fed into the reaction cavity (8) and are contacted with the substrate, and deposition is carried out.

6. The design of claim 1, wherein the design of Mist process for preparing gallium oxide thin film comprises: the annealing gas in the annealing process in the step 3 is oxygen.