CN114823287B - Method for preparing homoepitaxial gallium oxide film on unintentionally doped substrate and molecular beam epitaxy equipment - Google Patents
Method for preparing homoepitaxial gallium oxide film on unintentionally doped substrate and molecular beam epitaxy equipment Download PDFInfo
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Abstract
The invention provides a method for preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate and a molecular beam epitaxy device, wherein the molecular beam epitaxy device comprises an MBE growth chamber, a stainless steel tray arranged in the MBE growth chamber and an unintentionally doped gallium oxide substrate fixedly arranged at the bottom end of the stainless steel tray, a laser is arranged above the stainless steel tray, and a laser spot emitted by the laser covers the whole top of the stainless steel tray. According to the invention, the laser uniformly heats the stainless steel tray in the MBE growth chamber by a laser heating method, so that the uniform heating of the unintended doped gallium oxide substrate is realized, and the unintended doped gallium oxide homoepitaxial wafer with high quality and uniform thickness is prepared.
Description
Technical Field
The invention relates to the technical field of gallium oxide film preparation, in particular to a method for preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate and molecular beam epitaxy equipment.
Background
Gallium oxide (Ga 2O3) is used as an emerging third generation wide bandgap semiconductor, and has the advantages of ultra-wide bandgap, high breakdown field strength and the like. The transparent oxide semiconductor material has excellent physical and chemical characteristics, good electrical conductivity and luminous performance, and has wide application prospect in the fields of power semiconductor devices, ultraviolet detectors, gas sensors and optoelectronic devices. Gallium oxide has a 5-crystal structure, which is respectively rhombohedral (α), monoclinic (β), defective spinel (γ), cubic (δ), and orthorhombic (ε). The stability of beta-Ga 2O3 at high temperature is becoming a research hot spot at home and abroad in recent years, and the gallium oxide mentioned below is referred to as beta-Ga 2O3.
In the epitaxial method of gallium oxide, molecular Beam Epitaxy (MBE) is one of the main means for growing high-purity and high-quality gallium oxide epitaxial films, and by utilizing ultrahigh vacuum and high-purity source materials, the concentration of unintentionally doped impurities can be effectively reduced, and the accurate regulation and control of the atomic scale growth can be realized. The gallium oxide film epitaxially grown by MBE has the advantages of good crystal quality, flat surface and controllable electron concentration, which are necessary conditions for obtaining high-performance gallium oxide-based power electronic devices and photoelectric conversion devices. Therefore, the MBE can be utilized to prepare the high-quality gallium oxide unintentionally doped homoepitaxial wafer on the unintentionally doped substrate; and a differential finger electrode (MSM) is arranged on the gallium oxide unintentionally doped homoepitaxial wafer, so that the solar blind ultraviolet detector with high performance can be prepared, and the urgent requirement of extreme occasions on the high-sensitivity solar blind ultraviolet detector can be met.
Aiming at the technical characteristics of the existing MBE, in the process of preparing the gallium oxide homoepitaxial film by using MBE equipment, the gallium oxide substrate needs to be maintained in a high-temperature state suitable for the growth of the gallium oxide film. In the prior art, the gallium oxide substrate is heated by heat radiation through a heating wire arranged behind the substrate. Due to the fact that certain space distribution exists in the arrangement of the heating wires, the heating of the substrate is uneven, the quality and thickness uniformity of the prepared epitaxial wafer are seriously affected, and even the epitaxial layer is cracked.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a method for preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate and a molecular beam epitaxy device, and aims to solve the problem that the gallium oxide epitaxial wafer prepared by the prior art is poor in quality and thickness uniformity.
The technical scheme of the invention is as follows:
A molecular beam epitaxy device for preparing homoepitaxial gallium oxide film on an unintentionally doped substrate comprises an MBE growth chamber, a stainless steel tray arranged in the MBE growth chamber, and an unintentionally doped gallium oxide substrate fixedly arranged at the bottom end of the stainless steel tray, wherein a laser is arranged above the stainless steel tray, and a laser spot emitted by the laser covers the whole top of the stainless steel tray.
The molecular beam epitaxy device is characterized in that a beam expander is arranged on the laser.
The molecular beam epitaxy device, wherein the laser emitted by the laser has a wavelength of 500-1500nm.
A method for preparing homoepitaxial gallium oxide thin films on unintentionally doped substrates based on molecular beam epitaxy equipment, comprising the steps of:
a molecular pump is started in advance to vacuumize the MBE growth chamber;
fixing an unintended doped gallium oxide substrate at the bottom end of a stainless steel tray, and enabling the growth surface of the unintended doped gallium oxide substrate to face downwards;
stopping a molecular pump, filling nitrogen into a rapid sample injection cavity, and then, placing the stainless steel tray fixed with the unintended doped gallium oxide substrate into the rapid sample injection cavity;
Setting the evaporation temperature of the Ga metal evaporation source, and controlling the rapid flow intensity of the Ga metal evaporation source when the Ga metal evaporation source reaches the preset evaporation temperature;
Starting a molecular pump, vacuumizing the rapid sample injection cavity, and when the vacuum degree of the rapid sample injection cavity is lower than 10 - 8 mbar, transferring the stainless steel tray fixed with the unintended doped gallium oxide substrate into the MBE growth chamber, and opening the laser to heat the stainless steel tray;
slowly opening an oxygen plasma source pipeline angle valve, and setting the oxygen flow to be 0.1-0.5sccm on a digital flowmeter;
after the laser heats the stainless steel tray to a preset film growth temperature, an oxygen source is started, oxygen plasma is lightened, the oxygen pressure is waited to be stable, a baffle of the Ga metal evaporation source is controlled to be set in an automatic mode, and homoepitaxial gallium oxide film growth is carried out;
When the growth thickness of the homoepitaxial gallium oxide film reaches 50-500 nanometers, the growth is completed, and a baffle of the Ga metal evaporation source is automatically closed to keep oxygen source supply; when the temperature of the stainless steel tray is lower than 200 ℃, cutting off an oxygen source, and closing the laser to finish the preparation of the homoepitaxial gallium oxide film.
The method for preparing the homoepitaxial gallium oxide film on the unintentionally doped substrate comprises the step of starting a molecular pump in advance to vacuumize an MBE growth chamber, wherein the MBE growth chamber is vacuumized to be lower than 2 multiplied by 10 -9 mbar.
The method for preparing the homoepitaxial gallium oxide film on the unintentionally doped substrate comprises the steps of setting the preset evaporation temperature of a Ga metal evaporation source to be 1000-1200 ℃ and heating the Ga metal evaporation source to be 2-10 ℃/min.
The method for preparing the homoepitaxial gallium oxide film on the unintentionally doped substrate, wherein the rapid flow intensity of the Ga metal evaporation source is 1 multiplied by 10 -8-9×10-7 mbar.
The method for preparing the homoepitaxial gallium oxide film on the unintentionally doped substrate comprises the step that the laser heats the stainless steel tray to a preset film growth temperature, wherein the preset film growth temperature is 600-1000 ℃, and the heating rate is 5-15 ℃/min.
The method for preparing the homoepitaxial gallium oxide film on the unintentionally doped substrate comprises the step of growing the homoepitaxial gallium oxide film at a growth speed of 10-100 nanometers/hour.
The method for preparing the homoepitaxial gallium oxide film on the unintentionally doped substrate comprises the steps of conveying the prepared homoepitaxial gallium oxide film from an MBE growth chamber to a rapid sample injection cavity after the homoepitaxial gallium oxide film is prepared, and sampling at normal pressure after vacuum breaking.
The beneficial effects are that: the invention provides a method for preparing homoepitaxial gallium oxide film on an unintentionally doped substrate and a molecular beam epitaxy device, and a laser is arranged above the stainless steel tray, and a laser spot emitted by the laser covers the whole top of the stainless steel tray. According to the invention, the laser uniformly heats the stainless steel tray in the MBE growth chamber by a laser heating method, so that the uniform heating of the unintended doped gallium oxide substrate is realized, and the unintended doped gallium oxide homoepitaxial wafer with high quality and uniform thickness is prepared.
Drawings
Fig. 1 is a schematic diagram of a molecular beam epitaxy apparatus for preparing homoepitaxial gallium oxide films on an unintentionally doped substrate according to the present invention.
Fig. 2 is a graph of transmittance of an unintentionally doped and Ta doped gallium oxide substrate.
Fig. 3 is a graph of the transmittance of an unintentionally doped and Fe doped gallium oxide substrate.
Fig. 4 is a flow chart of a method of preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate.
Detailed Description
The invention provides a method for preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate and a molecular beam epitaxy device, and the invention is further described in detail below for making the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Since it is necessary to maintain the gallium oxide substrate in a high temperature state suitable for the growth of the gallium oxide thin film during the preparation of the gallium oxide homoepitaxial thin film using the molecular beam epitaxy apparatus. The heating mode of the gallium oxide substrate in the existing molecular beam epitaxy equipment can lead to uneven heating of the substrate, thereby seriously affecting the quality and thickness uniformity of the epitaxial wafer and even leading to cracking of the epitaxial wafer.
Based on this, the present invention provides a molecular beam epitaxy apparatus for preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate, as shown in fig. 1, which includes an MBE growth chamber 10, a stainless steel tray 20 disposed in the MBE growth chamber 10, and an unintentionally doped gallium oxide substrate 30 fixedly disposed at the bottom end of the stainless steel tray 20, wherein a laser 40 is disposed above the stainless steel tray 20, and a laser spot emitted from the laser 40 covers the entire top of the stainless steel tray 20.
In particular, according to literature reports, since an unintentionally doped gallium oxide substrate is extremely susceptible to n-type impurity ions during single crystal growth, there are two cases of transmittance in the infrared band: (1) If the n-type impurity ion pollution of the growth environment is less, the transmittance of the substrate in the infrared band is high, see FIG. 2 (data from SCI paper: tuning Electrical Conductivity of β -Ga 2O3 SINGLE CRYSTALS by Ta dopping); (2) If the n-type impurity ions in the Growth environment are more contaminated, the transmittance of the substrate in the infrared band decreases rapidly, as shown in FIG. 3 (data from SCI paper: growth AND PHYSICAL characterization of HIGH RESISTIVITY FE: beta-Ga 2O3 crystals). That is, since the absorption of the infrared laser by the unintentionally doped gallium oxide substrate is not controllable, during the process of heating the unintentionally doped gallium oxide substrate by using the laser of the common infrared band, the laser cannot directly irradiate on the unintentionally doped gallium oxide substrate, but uniformly irradiates on the stainless steel tray, and the stainless steel tray uniformly heated by the laser transfers heat to the unintentionally doped gallium oxide substrate, so that the uniform heating of the unintentionally doped gallium oxide substrate in the MBE growth chamber is realized.
According to the molecular beam epitaxy equipment for preparing the homogeneous epitaxial gallium oxide film on the unintentionally doped substrate, as the laser light spot emitted by the laser 40 covers the whole top of the stainless steel tray 20, the stainless steel tray in the MBE growth chamber can be uniformly heated in a laser heating mode, so that the unintentionally doped gallium oxide substrate is uniformly heated, and the high-quality and uniform-thickness gallium oxide unintentionally doped gallium oxide homogeneous epitaxial wafer is prepared and used for preparing a high-sensitivity solar blind ultraviolet detector.
In some embodiments, two or more lasers may also be provided above the stainless steel tray. As an example, as shown in fig. 1, 2 lasers may be disposed below the stainless steel tray, or 3, 4, 5, 6, etc. lasers may be disposed; it is necessary to ensure that the plurality of lasers can uniformly cover the upper side of the stainless steel tray, so that the stainless steel tray is uniformly heated.
In some embodiments, a beam expander is disposed on the laser. In this embodiment, the beam expander is disposed on the laser, so that the laser spot size of the laser can be adjusted, and the laser spot of the laser can cover the top of the whole stainless steel tray.
In some embodiments, the laser emits laser light having a wavelength of 500-1500nm. Preferably, the laser emits laser light with a wavelength of 800-1200nm. By way of example, the laser emits laser wavelengths of 800nm, 900nm, 1000nm, 1200nm, etc.
The molecular beam epitaxy device is characterized in that a beam expander is arranged on the laser.
The molecular beam epitaxy device, wherein the laser emitted by the laser has a wavelength of 500-1500nm.
In some embodiments, there is also provided a method for preparing a homoepitaxial gallium oxide thin film on an unintentionally doped substrate based on a molecular beam epitaxy apparatus, as shown in fig. 4, comprising the steps of:
s10, starting a molecular pump in advance to vacuumize the MBE growth chamber;
S20, fixing an unintended doped gallium oxide substrate at the bottom end of a stainless steel tray, wherein the growth surface of the unintended doped gallium oxide substrate faces downwards;
S30, stopping the molecular pump, filling nitrogen into the rapid sample injection cavity to break vacuum, and then placing the stainless steel tray fixed with the unintended doped gallium oxide substrate into the rapid sample injection cavity;
S40, setting the evaporation temperature of the Ga metal evaporation source, and controlling the rapid flow intensity of the Ga metal evaporation source when the Ga metal evaporation source reaches the preset evaporation temperature;
S50, starting a molecular pump, vacuumizing the rapid sample injection cavity, and when the vacuum degree of the rapid sample injection cavity is lower than 10 -8 mbar, transferring the stainless steel tray fixed with the unintended doped gallium oxide substrate into the MBE growth chamber, and opening the laser to heat the stainless steel tray;
s60, slowly opening an oxygen plasma source pipeline angle valve, and setting the oxygen flow to be 0.1-0.5sccm on a digital flowmeter;
s70, after the laser heats the stainless steel tray to a preset film growth temperature, starting an oxygen source, igniting oxygen plasma, waiting for stable oxygen pressure, setting baffle control of a Ga metal evaporation source to be in an automatic mode, and carrying out homoepitaxial gallium oxide film growth;
S80, when the growth thickness of the homoepitaxial gallium oxide film reaches 50-500 nanometers, the growth is completed, a baffle of the Ga metal evaporation source is automatically closed, and oxygen source supply is kept; when the temperature of the stainless steel tray is lower than 200 ℃, cutting off an oxygen source, and closing the laser to finish the preparation of the homoepitaxial gallium oxide film.
In this embodiment, the heating temperature of the stainless steel tray can be adjusted by controlling the power of the laser, thereby adjusting the heating temperature of the unintentionally doped gallium oxide substrate; the growth speed of the homoepitaxial gallium oxide film can be controlled by adjusting the beam intensity of the Ga metal evaporation source and the flow of oxygen. In the process of preparing the homoepitaxial gallium oxide film on the unintentionally doped substrate, the stainless steel tray is uniformly heated under the irradiation of laser, so that the uniform heating of the unintentionally doped gallium oxide substrate is realized. Meanwhile, the temperature of the substrate of the unintended doped gallium oxide is measured in real time through a temperature sensor and fed back to a laser, so that the laser output power is adjusted, and the temperature of the substrate of the unintended doped gallium oxide is maintained in a temperature range suitable for epitaxial growth of gallium oxide.
In some embodiments, the MBE growth chamber is evacuated to less than 2X 10 -9 mbar during the step of pre-activating the molecular pump to evacuate the MBE growth chamber.
In some embodiments, the predetermined evaporation temperature of the Ga metal evaporation source is 1000-1200 ℃, and the heating rate is 2-10 ℃/min.
In some embodiments, the Ga metal evaporation source has a fast flow strength of 1 x 10 -8-9×10-7 mbar, but is not limited thereto.
In some embodiments, the laser heats the stainless steel tray to a predetermined film growth temperature, the predetermined film growth temperature being 600-1000 ℃ and the heating rate being 5-15 ℃/min.
In some embodiments, the homoepitaxial gallium oxide film has a growth rate of 10-100 nanometers per hour.
In some embodiments, after the homoepitaxial gallium oxide film is prepared, the prepared homoepitaxial gallium oxide film is transferred from the MBE growth chamber to the rapid sample injection chamber, and the vacuum is broken and then the normal pressure sampling is performed.
The invention is further illustrated by the following examples:
example 1
A method for preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate based on a molecular beam epitaxy device, wherein the molecular beam epitaxy device comprises an MBE growth chamber, a stainless steel tray arranged in the MBE growth chamber and an unintentionally doped gallium oxide substrate arranged on the stainless steel tray, the growth of the unintentionally doped gallium oxide substrate faces downwards, 1 laser is arranged below the stainless steel tray, and a laser spot emitted by the laser covers the whole top of the stainless steel tray; the method comprises the following steps:
Confirming that the water, electricity and gas of MBE equipment are normally supplied, and starting a molecular pump in advance to vacuumize an MBE growth chamber until the vacuum degree is lower than 2 multiplied by 10 -9 mbar;
Fixing the cleaned 2-inch unintended doped gallium oxide substrate at the bottom end of a stainless steel tray, wherein the growth surface of the unintended doped gallium oxide substrate faces downwards;
stopping a molecular pump, filling nitrogen into a rapid sample injection cavity, and then, placing the stainless steel tray fixed with the unintended doped gallium oxide substrate into the rapid sample injection cavity;
Setting the evaporation temperature of the Ga metal evaporation source to be 1100 ℃, heating up and cooling down at a speed of 6 ℃/min, measuring the beam intensity of the Ga metal evaporation source by using a beam gauge when the Ga metal evaporation source reaches the preset evaporation temperature of 1100 ℃, and adjusting the temperature of the evaporation source according to the stable beam gauge reading to ensure that the beam intensity is maintained at 5 multiplied by 10 -7 mbar until the most suitable evaporation temperature is found;
starting a molecular pump, vacuumizing the rapid sample injection cavity, when the vacuum degree of the rapid sample injection cavity is lower than 10 - 8 mbar, transferring the stainless steel tray fixed with the unintended doped gallium oxide substrate into the MBE growth chamber, opening the laser to heat the stainless steel tray to 800 ℃, setting the heating rate to 10 ℃/min, simultaneously measuring the substrate temperature in real time through a temperature sensor, feeding back to the laser, and further adjusting the laser output power, so that the substrate temperature is maintained in a temperature range suitable for epitaxial growth;
Slowly opening an oxygen plasma source pipeline angle valve, and setting the oxygen flow to be 0.3sccm on a digital flowmeter;
when the laser heats the stainless steel tray to a preset film growth temperature of 800 ℃, an oxygen source is started, oxygen plasma is lightened, the oxygen pressure is kept stable, a baffle of the Ga metal evaporation source is controlled to be set in an automatic mode, the growth speed is controlled to be 50 nanometers/hour, and homoepitaxial gallium oxide film growth is carried out;
When the growth thickness of the homoepitaxial gallium oxide film reaches 200 nanometers, the growth is completed, and a baffle of the Ga metal evaporation source is automatically closed to keep oxygen source supply; when the temperature of the stainless steel tray is lower than 200 ℃, cutting off an oxygen source, and closing the laser;
and (3) conveying the prepared sample to a rapid sample injection cavity, breaking vacuum, and sampling at normal pressure to finish the preparation of the homoepitaxial high-quality unintended doped gallium oxide film on the unintended doped gallium oxide substrate.
Example 2
A method for preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate based on a molecular beam epitaxy device, wherein the molecular beam epitaxy device comprises an MBE growth chamber, a stainless steel tray arranged in the MBE growth chamber and an unintentionally doped gallium oxide substrate arranged on the stainless steel tray, the growth of the unintentionally doped gallium oxide substrate faces downwards, 1 laser is arranged below the stainless steel tray, and a laser spot emitted by the laser covers the whole top of the stainless steel tray; the method comprises the following steps:
Confirming that the water, electricity and gas of MBE equipment are normally supplied, and starting a molecular pump in advance to vacuumize an MBE growth chamber until the vacuum degree is lower than 2 multiplied by 10 -9 mbar;
Fixing the cleaned 2-inch unintended doped gallium oxide substrate at the bottom end of a stainless steel tray, wherein the growth surface of the unintended doped gallium oxide substrate faces downwards;
stopping a molecular pump, filling nitrogen into a rapid sample injection cavity, and then, placing the stainless steel tray fixed with the unintended doped gallium oxide substrate into the rapid sample injection cavity;
Setting the evaporation temperature of the Ga metal evaporation source to be 1000 ℃, heating up and cooling down at a rate of 2 ℃/min, measuring the beam intensity of the Ga metal evaporation source by using a beam gauge when the Ga metal evaporation source reaches the preset evaporation temperature of 1000 ℃, and adjusting the temperature of the evaporation source according to the stable beam gauge reading to ensure that the beam intensity is maintained at 1 multiplied by 10 -8 mbar until the most suitable evaporation temperature is found;
Starting a molecular pump, vacuumizing the rapid sample injection cavity, when the vacuum degree of the rapid sample injection cavity is lower than 10 - 8 mbar, transferring the stainless steel tray fixed with the unintended doped gallium oxide substrate into the MBE growth chamber, opening the laser to heat the stainless steel tray to 600 ℃, setting the heating rate to 5 ℃/min, simultaneously measuring the substrate temperature in real time through a temperature sensor, feeding back to the laser, and further adjusting the laser output power, so that the substrate temperature is maintained in a temperature range suitable for epitaxial growth;
slowly opening an oxygen plasma source pipeline angle valve, and setting the oxygen flow to be 0.1-0.5sccm on a digital flowmeter;
When the laser heats the stainless steel tray to a preset film growth temperature of 600 ℃, an oxygen source is started, oxygen plasma is lightened, the oxygen pressure is kept stable, a baffle of the Ga metal evaporation source is controlled to be in an automatic mode, the growth speed is controlled to be 10 nanometers/hour, and homoepitaxial gallium oxide film growth is carried out;
When the growth thickness of the homoepitaxial gallium oxide film reaches 200 nanometers, the growth is completed, and a baffle of the Ga metal evaporation source is automatically closed to keep oxygen source supply; when the temperature of the stainless steel tray is lower than 200 ℃, cutting off an oxygen source, and closing the laser;
and (3) conveying the prepared sample to a rapid sample injection cavity, breaking vacuum, and sampling at normal pressure to finish the preparation of the homoepitaxial high-quality unintended doped gallium oxide film on the unintended doped gallium oxide substrate.
Example 3
A method for preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate based on a molecular beam epitaxy device, wherein the molecular beam epitaxy device comprises an MBE growth chamber, a stainless steel tray arranged in the MBE growth chamber and an unintentionally doped gallium oxide substrate arranged on the stainless steel tray, the growth of the unintentionally doped gallium oxide substrate faces downwards, 1 laser is arranged below the stainless steel tray, and a laser spot emitted by the laser covers the whole top of the stainless steel tray; the method comprises the following steps:
Confirming that the water, electricity and gas of MBE equipment are normally supplied, and starting a molecular pump in advance to vacuumize an MBE growth chamber until the vacuum degree is lower than 2 multiplied by 10 -9 mbar;
Fixing the cleaned 2-inch unintended doped gallium oxide substrate at the bottom end of a stainless steel tray, wherein the growth surface of the unintended doped gallium oxide substrate faces downwards;
stopping a molecular pump, filling nitrogen into a rapid sample injection cavity, and then, placing the stainless steel tray fixed with the unintended doped gallium oxide substrate into the rapid sample injection cavity;
Setting the evaporation temperature of the Ga metal evaporation source as 1200 ℃, heating up and cooling down at a speed of 10 ℃/min, measuring the beam intensity of the Ga metal evaporation source by using a beam gauge when the Ga metal evaporation source reaches the preset evaporation temperature of 1200 ℃, and adjusting the temperature of the evaporation source according to the stable beam gauge reading to ensure that the beam intensity is maintained at 9 multiplied by 10 -7 mbar until the most suitable evaporation temperature is found;
Starting a molecular pump, vacuumizing the rapid sample injection cavity, when the vacuum degree of the rapid sample injection cavity is lower than 10 - 8 mbar, transferring the stainless steel tray fixed with the unintended doped gallium oxide substrate into the MBE growth chamber, opening the laser to heat the stainless steel tray to 1000 ℃, setting the heating rate to 15 ℃/min, simultaneously measuring the substrate temperature in real time through a temperature sensor, feeding back to the laser, and further adjusting the laser output power, so that the substrate temperature is maintained in a temperature range suitable for epitaxial growth;
Slowly opening an oxygen plasma source pipeline angle valve, and setting the oxygen flow to be 0.5sccm on a digital flowmeter;
When the laser heats the stainless steel tray to a preset film growth temperature of 1000 ℃, an oxygen source is started, oxygen plasma is lightened, the oxygen pressure is kept stable, a baffle of the Ga metal evaporation source is controlled to be set in an automatic mode, the growth speed is controlled to be 100 nanometers/hour, and homoepitaxial gallium oxide film growth is carried out;
When the growth thickness of the homoepitaxial gallium oxide film reaches 200 nanometers, the growth is completed, and a baffle of the Ga metal evaporation source is automatically closed to keep oxygen source supply; when the temperature of the stainless steel tray is lower than 200 ℃, cutting off an oxygen source, and closing the laser;
and (3) conveying the prepared sample to a rapid sample injection cavity, breaking vacuum, and sampling at normal pressure to finish the preparation of the homoepitaxial high-quality unintended doped gallium oxide film on the unintended doped gallium oxide substrate.
Comparative example 1
A method for preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate based on a molecular beam epitaxy device, wherein the molecular beam epitaxy device comprises an MBE growth chamber, a stainless steel tray arranged in the MBE growth chamber, and an unintentionally doped gallium oxide substrate arranged on the stainless steel tray, and a heating wire is arranged above the stainless steel tray; the method comprises the following steps:
Confirming that the water, electricity and gas of MBE equipment are normally supplied, and starting a molecular pump in advance to vacuumize an MBE growth chamber until the vacuum degree is lower than 2 multiplied by 10 -9 mbar;
Fixing the cleaned 2-inch unintended doped gallium oxide substrate at the bottom end of a stainless steel tray, wherein the growth surface of the unintended doped gallium oxide substrate faces downwards;
stopping a molecular pump, filling nitrogen into a rapid sample injection cavity, and then, placing the stainless steel tray fixed with the unintended doped gallium oxide substrate into the rapid sample injection cavity;
Setting the evaporation temperature of the Ga metal evaporation source to be 1100 ℃, heating up and cooling down at a speed of 6 ℃/min, measuring the beam intensity of the Ga metal evaporation source by using a beam gauge when the Ga metal evaporation source reaches the preset evaporation temperature of 1100 ℃, and adjusting the temperature of the evaporation source according to the stable beam gauge reading to ensure that the beam intensity is maintained at 5 multiplied by 10 -7 mbar until the most suitable evaporation temperature is found;
Starting a molecular pump, vacuumizing the rapid sample injection cavity, when the vacuum degree of the rapid sample injection cavity is lower than 10 - 8 mbar, transferring the stainless steel tray fixed with the unintended doped gallium oxide substrate into the MBE growth chamber, heating the stainless steel tray to 800 ℃ through a heating wire, setting the heating rate of 10 ℃/min, simultaneously measuring the substrate temperature in real time through a temperature sensor, feeding back to a laser, and further adjusting the laser output power, so that the substrate temperature is maintained in a temperature range suitable for epitaxial growth;
Slowly opening an oxygen plasma source pipeline angle valve, and setting the oxygen flow to be 0.3sccm on a digital flowmeter;
when the laser heats the stainless steel tray to a preset film growth temperature of 800 ℃, an oxygen source is started, oxygen plasma is lightened, the oxygen pressure is kept stable, a baffle of the Ga metal evaporation source is controlled to be set in an automatic mode, the growth speed is controlled to be 50 nanometers/hour, and homoepitaxial gallium oxide film growth is carried out;
when the growth thickness of the homoepitaxial gallium oxide film reaches 200 nanometers, the growth is completed, and a baffle of the Ga metal evaporation source is automatically closed to keep oxygen source supply; when the temperature of the stainless steel tray is lower than 200 ℃, cutting off an oxygen source, and turning off a power supply of the heating wire;
and (3) conveying the prepared sample to a rapid sample injection cavity, breaking vacuum, and sampling at normal pressure to finish the preparation of the homoepitaxial high-quality unintended doped gallium oxide film on the unintended doped gallium oxide substrate.
Example 4
Measurement of the thickness and Standard deviation of thickness of homoepitaxial gallium oxide films prepared in examples 1 to 3 and comparative example 1
After the preparation of the homoepitaxial gallium oxide film on the wafer is finished, 32 points (8 points are distributed at equal intervals in four radial directions, 45-degree angles are formed at equal intervals in the four directions and the circle center is not included) are selected in a Chinese character 'mi' shape on the wafer, and film thickness measurement is carried out: the interface between the epitaxial layer and the substrate can be clearly seen by using a Focused Ion Beam (FIB) epitaxial wafer to perform cross-section fault at the test point position, and the thickness of the homoepitaxial gallium oxide film can be accurately measured by using the SEM, and the result is shown in table 1:
TABLE 1 homoepitaxial gallium oxide film thickness measurement results
As can be seen from the results of Table 1, the thickness of the homoepitaxial gallium oxide film prepared by the method is closer to the target thickness, and the standard deviation of the thickness of the homoepitaxial gallium oxide film prepared by the method is smaller, which indicates that the homoepitaxial gallium oxide film prepared by the method has higher thickness uniformity and better quality.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (3)
1. A method for preparing homoepitaxial gallium oxide film on unintentionally doped substrate based on molecular beam epitaxy equipment is characterized in that,
The molecular beam epitaxy equipment comprises an MBE growth chamber, a stainless steel tray arranged in the MBE growth chamber and an unintended doped gallium oxide substrate fixedly arranged at the bottom end of the stainless steel tray, wherein a laser is arranged above the stainless steel tray, the laser wavelength emitted by the laser is 500-1500nm, and the laser light spot emitted by the laser covers the whole top of the stainless steel tray;
the method comprises the steps of:
a molecular pump is started in advance to vacuumize the MBE growth chamber;
fixing an unintended doped gallium oxide substrate at the bottom end of a stainless steel tray, and enabling the growth surface of the unintended doped gallium oxide substrate to face downwards;
stopping a molecular pump, filling nitrogen into a rapid sample injection cavity, and then, placing the stainless steel tray fixed with the unintended doped gallium oxide substrate into the rapid sample injection cavity;
Setting the evaporation temperature of the Ga metal evaporation source, and controlling the rapid flow intensity of the Ga metal evaporation source when the Ga metal evaporation source reaches the preset evaporation temperature;
Starting a molecular pump, vacuumizing the rapid sample injection cavity, and when the vacuum degree of the rapid sample injection cavity is lower than 10 -8 mbar, transferring the stainless steel tray fixed with the unintended doped gallium oxide substrate into the MBE growth chamber, and opening the laser to heat the stainless steel tray;
slowly opening an oxygen plasma source pipeline angle valve, and setting the oxygen flow to be 0.1-0.5sccm on a digital flowmeter;
after the laser heats the stainless steel tray to a preset film growth temperature, an oxygen source is started, oxygen plasma is lightened, the oxygen pressure is waited to be stable, a baffle of the Ga metal evaporation source is controlled to be set in an automatic mode, and homoepitaxial gallium oxide film growth is carried out;
When the growth thickness of the homoepitaxial gallium oxide film reaches 50-500 nanometers, the growth is completed, and a baffle of the Ga metal evaporation source is automatically closed to keep oxygen source supply; when the temperature of the stainless steel tray is lower than 200 ℃, cutting off an oxygen source, and closing the laser to finish the preparation of the homoepitaxial gallium oxide film;
In the step of starting a molecular pump in advance to vacuumize an MBE growth chamber, vacuumizing the MBE growth chamber to be lower than 2 multiplied by 10 -9 mbar;
The preset evaporation temperature of the Ga metal evaporation source is 1000-1200 ℃, and the heating rate is 2-10 ℃/min; the rapid flow intensity of the Ga metal evaporation source is 1 multiplied by 10 -8-9×10-7 mbar;
the laser heats the stainless steel tray to a preset film growth temperature, wherein the preset film growth temperature is 600-1000 ℃, and the heating rate is 5-15 ℃/min;
the growth rate of the homoepitaxial gallium oxide film is 10-100 nanometers/hour.
2. The method of claim 1, wherein after the homoepitaxial gallium oxide film is prepared, the prepared homoepitaxial gallium oxide film is transferred from the MBE growth chamber to the rapid sample injection chamber, and the sample is taken at normal pressure after breaking the vacuum.
3. The method of preparing a homoepitaxial gallium oxide film on an unintentionally doped substrate according to claim 1, wherein a beam expander is provided on the laser.
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