CN109860058B - A kind of preparation method of gallium oxide/copper gallium oxygen heterojunction - Google Patents
A kind of 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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- gallium oxide
- copper
- gallium
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- oxide material
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- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 98
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000001301 oxygen Substances 0.000 title claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 4
- 239000010453 quartz Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000979 O alloy Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
本发明属于半导体材料制备技术领域，提供一种氧化镓/铜镓氧异质结的制备方法。该方法是把氧化镓材料进行预处理后，将铜源预沉积或者放置在氧化镓单晶或薄膜的表面上，然后将这种带有铜源的氧化镓放置在高温管内，而后在一定的条件下热处理一定时间，使得铜原子能可控的扩散到氧化镓中，形成相应的铜镓氧合金，进而与未发生铜扩散的氧化镓形成界面特性好的氧化镓/铜镓氧异质结。本发明突出的优势是能够制备出高质量的铜镓氧材料，其所需设备和工艺过程简单，可控性高；可以形成界面理想的氧化镓/铜镓氧异质结，获得理想的结特性；利用本发明所提铜扩散技术可以进行多种类器件集成制造，进而研制出传统生长技术无法制备出的铜镓氧基新型器件。
The invention belongs to the technical field of semiconductor material preparation, and provides a preparation method of a gallium oxide/copper gallium oxygen heterojunction. The method is that after the gallium oxide material is pretreated, the copper source is pre-deposited or placed on the surface of the gallium oxide single crystal or film, and then the gallium oxide with the copper source is placed in a high temperature tube, and then placed in a certain temperature. Under the condition of heat treatment for a certain time, the copper atoms can controllably diffuse into the gallium oxide to form the corresponding copper gallium oxide alloy, and then form a gallium oxide/copper gallium oxygen heterojunction with good interface properties with the gallium oxide without copper diffusion. The outstanding advantage of the present invention is that high-quality copper gallium oxide material can be prepared, the required equipment and process are simple, and the controllability is high; an ideal gallium oxide/copper gallium oxide heterojunction can be formed, and an ideal junction can be obtained. Characteristics; the copper diffusion technology proposed in the present invention can be used for integrated manufacturing of various types of devices, and then new copper gallium oxide devices that cannot be prepared by traditional growth technologies can be 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)
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| US20200312659A1 (en) * | 2018-12-19 | 2020-10-01 | Dalian University Of Technology | Method for the preparation of gallium oxide/copper gallium oxide heterojunction |
| CN111129122B (en) * | 2019-12-13 | 2022-05-06 | 合肥中科微电子创新中心有限公司 | Heterojunction semiconductor structures based on gallium oxide and their devices |
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 doped gallium oxide film and doped gallium oxide film |
| 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 doped gallium oxide film and doped gallium oxide film |
| 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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