CN109860058B - Preparation method of gallium oxide/copper gallium oxygen heterojunction - Google Patents
Preparation method of gallium oxide/copper gallium oxygen heterojunction Download PDFInfo
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- CN109860058B CN109860058B CN201811555045.XA CN201811555045A CN109860058B CN 109860058 B CN109860058 B CN 109860058B CN 201811555045 A CN201811555045 A CN 201811555045A CN 109860058 B CN109860058 B CN 109860058B
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Abstract
The invention belongs to the technical field of semiconductor material preparation, and provides a preparation method of a gallium oxide/copper gallium oxide heterojunction. The method comprises the steps of pretreating gallium oxide materials, pre-depositing or placing a copper source on the surface of a gallium oxide single crystal or a gallium oxide film, then placing the gallium oxide with the copper source in a high-temperature tube, and then carrying out heat treatment for a certain time under a certain condition, so that copper atoms can be controllably diffused into the gallium oxide to form corresponding copper-gallium-oxide alloy, and further forming a gallium oxide/copper-gallium-oxygen heterojunction with good interface characteristics with the gallium oxide without copper diffusion. The invention has the outstanding advantages that the high-quality copper gallium oxide material can be prepared, the required equipment and the process are simple, and the controllability is high; can form gallium oxide/copper gallium oxygen heterojunction with ideal interface to obtain ideal junction characteristic; the copper diffusion technology provided by the invention can be used for integrated manufacturing of various devices, and further, a novel copper gallium oxygen-based device which cannot be prepared by the traditional growth technology is developed.
Description
Technical Field
The invention belongs to the technical field of semiconductor material preparation, and particularly provides a preparation method of a gallium oxide/copper gallium oxide heterojunction.
Background
The wide-band gap semiconductor gallium oxide material has the outstanding advantages of large band gap, high breakdown field strength, corrosion resistance, radiation resistance and the like, and has important application in the aspects of manufacturing high-efficiency ultraviolet detectors, gas sensors, friendly biosensors, high-frequency, high-power, radiation-resistant and other electronic devices. The copper gallium oxide has excellent material characteristics and wide application prospect. At present, few researches on the preparation of gallium oxide/copper gallium oxide structures are carried out. The commonly used preparation method of the copper-gallium-oxygen material is mainly chemical synthesis or physical vapor deposition, such as sol-gel method, laser pulse deposition or magnetron sputtering. The copper gallium oxide material prepared by the method is mostly in an amorphous state or a polycrystalline state, and the crystal quality is not high, so that the material and the interface characteristics of a gallium oxide/copper gallium oxide structure are not good, and a good heterojunction characteristic cannot be formed. This greatly limits the applications of gallium oxide/copper gallium oxide heterojunctions in probing devices, power devices, optoelectronic devices, and sensing devices.
Disclosure of Invention
The invention aims to provide a method for preparing a gallium oxide/copper gallium oxide heterojunction by using a copper diffusion alloy method, aiming at the problem of lack of effective preparation of a high-quality copper gallium oxide thin film with good process compatibility. The method comprises the steps of pretreating gallium oxide materials, pre-depositing a proper amount of copper source by a proper method or placing the copper source on the surface of a gallium oxide single crystal or a gallium oxide film, then placing the gallium oxide with the copper source in a proper form in a high-temperature tube, and then carrying out heat treatment for a certain time under a certain condition, so that copper atoms can be controllably diffused into the gallium oxide to form corresponding copper-gallium oxygen alloy, and further forming a gallium oxide/copper-gallium-oxygen heterojunction with good interface characteristics with the gallium oxide without copper diffusion.
The technical scheme of the invention is as follows:
a preparation method of a gallium oxide/copper gallium oxygen heterojunction comprises the following steps:
step 1, placing the gallium oxide material into a corrosive liquid for 5min-5h to corrode the gallium oxide material to obtain an ideal surface;
step 2, placing the gallium oxide material in a quartz boat or a quartz tube, and keeping the temperature at 700-1100 ℃ and the pressure at 1 multiplied by 10-4Pa～1×105Pa, heat treating for 1min to 120min in reducing gas or inert gas atmosphere; taking out after the temperature is reduced to the room temperature;
step 3, pre-depositing a copper source layer on the gallium oxide material or directly covering the copper source layer on the gallium oxide material, wherein the thickness of the copper source layer is 10 nm-10 mu m;
step 4, placing the gallium oxide material treated in the step 1 into a quartz boat or a quartz tube, and keeping the temperature at 700-1300 ℃ and the pressure at 1 multiplied by 10-3Pa～1×106Pa, heat treatment for 1min to 50min under the atmosphere of reducing gas, air, water vapor or nitrogen; taking out after the temperature is reduced to the room temperature;
and 5, subsequent treatment of copper, gallium and oxygen: cleaning residues on the surface of the copper gallium oxide by using a cleaning solution for the first time, and cleaning the generated residues by using deionized water for the second time; adding copper and galliumDrying the oxygen material, and properly storing to obtain the copper gallium oxide film; the copper gallium oxide film comprises CuGa2O4Or CuGaO2Alloys, and copper doping.
The gallium oxide material is single crystal, polycrystal and epitaxial film prepared on the substrate.
The copper source is copper simple substance or copper oxide.
The invention has the beneficial effects that: the invention has the outstanding advantages that the high-quality copper gallium oxide material can be prepared, the required equipment and the process are simple, and the controllability is high; can form gallium oxide/copper gallium oxygen heterojunction with ideal interface to obtain ideal junction characteristic; the copper diffusion technology provided by the invention can be used for integrated manufacturing of various devices, and further, a novel copper gallium oxygen-based device which cannot be prepared by the traditional growth technology is developed.
Drawings
FIG. 1 is a schematic structural diagram of a gallium oxide single crystal with a pre-deposited layer of elemental copper.
Fig. 2 is a schematic structural view of a gallium oxide/copper gallium oxide heterojunction formed on the basis of a gallium oxide single crystal.
FIG. 3 is an X-ray diffraction pattern of a gallium oxide/copper gallium oxide heterojunction.
Fig. 4 is a schematic structural diagram of a gallium oxide film with a pre-deposited layer of elemental copper.
Fig. 5 is a schematic structural view of a gallium oxide/copper gallium oxide heterojunction formed on the basis of a gallium oxide thin film.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
The embodiment provides a preparation method of a gallium oxide/copper gallium oxide heterojunction, which comprises the following process steps:
step 1: the thickness of the selected gallium oxide single crystal is 600 μm, and the surface is 5mm square; the selected copper source is high-purity metal copper; placing the gallium oxide single crystal in an acid corrosion solution for treatment for 5 hours;
step 2: placing gallium oxide material in quartz boat or quartz tube in air atmosphere, setting temperature at 900 deg.C, controlling pressure at 0.1Pa, and heat treating for 60 min; taking out after the temperature is reduced to the room temperature;
and step 3: pre-depositing a copper layer with the thickness of 1 mu m on the gallium oxide single crystal after the acid treatment by adopting a thermal evaporation method, as shown in figure 1;
and 4, step 4: putting the sample prepared in the step 3 into a single-temperature-zone tubular furnace for heat treatment; the treatment temperature is 1200 ℃, the treatment time is 50min, and the treatment is carried out in the air atmosphere;
and 5: taking out the sample after the temperature is reduced to the room temperature;
step 6: cleaning residues on the surface of the sample by using dilute hydrochloric acid;
and 7: performing secondary cleaning on the residue generated in the step 6 by using deionized water;
and 8: the gallium oxide material was blow dried to form the gallium oxide/copper gallium oxide heterojunction shown in figure 2.
It was examined that a gallium oxide/copper gallium oxide heterojunction has been formed in this example. FIG. 3 shows the X-ray diffraction spectrum of the gallium oxide/copper gallium oxide heterojunction. The copper gallium oxide material prepared by the technology has single orientation, high crystal quality and good structural characteristics of a heterojunction.
Example 2
The embodiment provides a preparation method of a gallium oxide/copper gallium oxide heterojunction, which comprises the following process steps:
step 1: the selected gallium oxide material is a gallium oxide film which is prepared on a sapphire substrate by adopting an MOCVD method and has the thickness of 1 mu m and the surface with a square of 10 mm; the selected copper source is high-purity metal copper; placing the gallium oxide single crystal in an acid corrosion solution for treatment for 5 min;
step 2: placing gallium oxide material in quartz boat or quartz tube in hydrogen atmosphere, setting temperature at 850 deg.C and pressure at 100Pa, and heat treating for 30 min; taking out after the temperature is reduced to the room temperature;
and step 3: pre-depositing a copper layer with the thickness of 100nm on the gallium oxide film by adopting a thermal evaporation method, as shown in figure 4;
and 4, step 4: putting the sample treated in the step 3 into a quartz tube, and controlling the vacuum degree in the quartz tube to be 1 multiplied by 10-3Pa, and sealing the quartz tube;
and 5: putting the sealed quartz tube placed in the step 4 into a single-temperature-zone tube furnace for heat treatment; the treatment temperature is 900 ℃, and the treatment time is 50 min;
step 6: taking out the sample after the temperature is reduced to the room temperature;
and 7: cleaning residues on the surface of the gallium oxide material by using dilute hydrochloric acid for the first time;
and 8: performing secondary cleaning on the residue generated in the step 7 by using deionized water;
and step 9: the sample was blow dried to form the gallium oxide/copper gallium oxide heterojunction shown in figure 5.
It was examined that the copper gallium oxide material was formed in this example.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (3)
1. A preparation method of a gallium oxide/copper gallium oxide heterojunction is characterized by comprising the following steps:
step 1, placing the gallium oxide material into a corrosive liquid for 5min-5h to corrode the gallium oxide material to obtain an ideal surface;
step 2, placing the gallium oxide material in a quartz boat or a quartz tube, and keeping the temperature at 700-1100 ℃ and the pressure at 1 multiplied by 10- 4Pa～1×105Pa, heat treating for 1min to 120min in reducing gas or inert gas atmosphere; taking out after the temperature is reduced to the room temperature;
step 3, pre-depositing a copper source layer on the gallium oxide material or directly covering the copper source layer on the gallium oxide material, wherein the thickness of the copper source layer is 10 nm-10 mu m;
step 4, placing the gallium oxide material processed in the step 3 in a quartz boat or a quartz tube, and keeping the temperature at 700-1300 ℃ and the pressure at 1 multiplied by 10-3Pa～1×106Pa, heat treatment for 1min to 50min under the atmosphere of reducing gas, air, water vapor or nitrogen; taking out after the temperature is reduced to the room temperature;
and 5, subsequent treatment of copper, gallium and oxygen: cleaning residues on the surface of the copper gallium oxide by using a cleaning solution for the first time, and cleaning the generated residues by using deionized water for the second time; drying the copper gallium oxide material, and properly storing to obtain the copper gallium oxide film; the copper gallium oxide film comprises CuGa2O4Or CuGaO2Alloys, and copper doping.
2. The method of claim 1, wherein the gallium oxide material is single crystal, polycrystalline, and epitaxial thin film formed on a substrate.
3. The method of claim 1 or 2, wherein the copper source is elemental copper or copper oxide.
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| CN111129122B (en) * | 2019-12-13 | 2022-05-06 | 合肥中科微电子创新中心有限公司 | Gallium oxide based heterojunction semiconductor structure and device thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397095A (en) * | 2000-01-28 | 2003-02-12 | 科学技术振兴事业团 | Light emitting diode and semiconductor laser |
| CN103469299A (en) * | 2013-09-05 | 2013-12-25 | 大连理工大学 | Preparation method of gallium oxide-doped membrane and gallium oxide-doped membrane |
| CN106816366A (en) * | 2017-02-16 | 2017-06-09 | 大连理工大学 | A kind of tin dope N-shaped gallium oxide preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397095A (en) * | 2000-01-28 | 2003-02-12 | 科学技术振兴事业团 | Light emitting diode and semiconductor laser |
| CN103469299A (en) * | 2013-09-05 | 2013-12-25 | 大连理工大学 | Preparation method of gallium oxide-doped membrane and gallium oxide-doped membrane |
| CN106816366A (en) * | 2017-02-16 | 2017-06-09 | 大连理工大学 | A kind of tin dope N-shaped gallium oxide preparation method |
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