CN109860058A - A kind of preparation method of gallium oxide/copper gallium oxygen hetero-junctions - Google Patents
A kind of preparation method of gallium oxide/copper gallium oxygen hetero-junctions Download PDFInfo
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- CN109860058A CN109860058A CN201811555045.XA CN201811555045A CN109860058A CN 109860058 A CN109860058 A CN 109860058A CN 201811555045 A CN201811555045 A CN 201811555045A CN 109860058 A CN109860058 A CN 109860058A
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- copper
- gallium
- gallium oxide
- oxygen
- junctions
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- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 62
- 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 60
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000001301 oxygen Substances 0.000 title claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003708 ampul Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 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
- 239000007788 liquid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 10
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 229910000979 O alloy Inorganic materials 0.000 abstract description 2
- 150000001879 copper Chemical class 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 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
- 238000003475 lamination Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention belongs to technical field of semiconductor material preparation, provide a kind of preparation method of gallium oxide/copper gallium oxygen hetero-junctions.This method is after gallium oxide material is pre-processed, by copper source pre-deposition or it is placed on the surface of gallium oxide single crystal or film, then this gallium oxide with copper source is placed in high temperature pipe, it is then heat-treated certain time under certain conditions, enable copper atom is controllable to be diffused into gallium oxide, corresponding copper gallium oxygen alloy is formed, and then forms the good gallium oxide/copper gallium oxygen hetero-junctions of interfacial characteristics with the gallium oxide that copper diffusion does not occur.Present invention advantage outstanding is the copper gallium oxygen material that can prepare high quality, and required equipment and technical process are simple, and controllability is high；The ideal gallium oxide in interface/copper gallium oxygen hetero-junctions can be formed, ideal junction characteristic is obtained；Multiple types device Integrated manufacture can be carried out using the mentioned copper diffusion technique of the present invention, and then develops the copper gallium oxygroup new device that conventional growing technique can not be prepared.
Description
Technical field
The invention belongs to technical field of semiconductor material preparation, a kind of gallium oxide/copper gallium oxygen hetero-junctions is specifically provided
Preparation method.
Background technique
Wide bandgap semiconductor gallium oxide material because its forbidden bandwidth is big, disruptive field intensity is high, corrosion-resistant and Flouride-resistani acid phesphatase etc. it is prominent
Advantage, in production high efficiency ultraviolet detector, gas sensor, friendly biosensor and high frequency, high power, anti-spoke
There is important application in terms of penetrating equal electronic devices.Copper gallium oxygen has excellent material property and wide application prospect.It closes at present
It is few in gallium oxide/copper gallium oxide structure preparation research.The common preparation method of copper gallium oxygen material is with chemical synthesis or physics
Based on vapor deposition, such as sol-gal process, pulsed laser deposition or magnetron sputtering.The copper gallium oxygen prepared using the above method
Material is mostly amorphous state or polycrystalline state, and crystal quality is not high, causes gallium oxide/copper gallium oxide structure material and interface special
Property is bad, can't form good heterojunction characteristics.This significantly limits gallium oxide/copper gallium oxygen hetero-junctions in detector
Application in terms of part, power device, photoelectric device and senser element.
Summary of the invention
It is an object of the present invention to for the high-quality copper gallium oxygen film that above-mentioned shortage is effective, processing compatibility is good
Preparation problem, propose a kind of method of copper diffusion alloy to prepare gallium oxide/copper gallium oxygen hetero-junctions method.This method is handle
After gallium oxide material is pre-processed, suitable copper source pre-deposition or is placed on gallium oxide single crystal or thin in a suitable approach
On the surface of film, then this gallium oxide with copper source is placed in a suitable form in high temperature pipe, then certain
Under the conditions of be heat-treated certain time, enable copper atom is controllable to be diffused into gallium oxide, form corresponding copper gallium oxygen alloy, into
And the good gallium oxide/copper gallium oxygen hetero-junctions of interfacial characteristics is formed with the gallium oxide that copper diffusion does not occur.
Technical solution of the present invention:
A kind of preparation method of gallium oxide/copper gallium oxygen hetero-junctions, steps are as follows:
Gallium oxide material is put into 5min-5h in corrosive liquid by step 1., obtains ideal surfaced with corrosion oxidation gallium material；
Gallium oxide material is placed in quartz boat or quartz ampoule by step 2., is 700 DEG C~1100 DEG C, pressure 1 in temperature
×10-4Pa~1 × 105Pa, atmosphere are to be heat-treated 1min~120min in reducibility gas or inert gas；Temperature drops to room
It is taken out after temperature；
Step 3. pre-deposition copper source layer or copper source layer on gallium oxide material directly overlay on gallium oxide material, copper source layer
With a thickness of 10nm~10 μm；
Treated that gallium oxide material is placed in quartz boat or quartz ampoule by step 1 for step 4., temperature be 700 DEG C~
1300 DEG C, pressure be 1 × 10-3Pa~1 × 106Pa, atmosphere are heat treatment under reducibility gas, air, vapor or nitrogen
1min~50min；Temperature is taken out after dropping to room temperature；
The subsequent processing of step 5. copper gallium oxygen: it is once cleaned, then is used with residue of the cleaning solution to copper gallium oxygen surface
Deionized water carries out secondary cleaning to the residue of generation；Copper gallium oxygen material is dried up, is properly saved, as copper gallium oxygen film；
The copper gallium oxygen film includes CuGa2O4Or CuGaO2Alloy and Copper-cladding Aluminum Bar.
The gallium oxide material is monocrystalline, the epitaxial film of polycrystalline and preparation on substrate.
The copper source is the oxide of copper simple substance or copper.
Beneficial effects of the present invention: present invention advantage outstanding is the copper gallium oxygen material that can prepare high quality, institute
Need equipment and technical process simple, controllability is high；The ideal gallium oxide in interface/copper gallium oxygen hetero-junctions can be formed, is obtained ideal
Junction characteristic；Multiple types device Integrated manufacture can be carried out using the mentioned copper diffusion technique of the present invention, and then develops traditional life
The copper gallium oxygroup new device that long technology can not be prepared.
Detailed description of the invention
Fig. 1 is the structural schematic diagram with the gallium oxide single crystal of copper simple substance preliminary sedimentation lamination.
Fig. 2 is the gallium oxide/copper gallium oxygen hetero-junctions structural schematic diagram formed based on gallium oxide single crystal.
Fig. 3 is gallium oxide/copper gallium oxygen hetero-junctions X-ray diffraction spectrogram.
Fig. 4 is the structural schematic diagram with the gallium oxide film of copper simple substance preliminary sedimentation lamination.
Fig. 5 is the gallium oxide/copper gallium oxygen hetero-junctions structural schematic diagram formed based on gallium oxide film.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
Embodiment 1
The preparation method for present embodiments providing a kind of gallium oxide/copper gallium oxygen hetero-junctions, comprises the following steps that:
Step 1: selected gallium oxide single crystal is with a thickness of 600 μm, surface 5mm square；Selected copper source is High-Purity Metallic Copper；By oxygen
Change algan single crystal, which is placed in acid corrosion liquid, handles 5h；
Step 2: gallium oxide material is placed in the quartz boat in air atmosphere or quartz ampoule, by temperature be set as 900 DEG C,
Pressure control is heat-treated 60min in 0.1Pa；Temperature is taken out after dropping to room temperature；
Step 3: using thermal evaporation method, the copper of one layer of 1 μ m-thick of pre-deposition on above-mentioned acid treated gallium oxide single crystal
Layer, as shown in Figure 1；
Step 4: by sample ready in step 3, being put into single temperature zone tube furnace and be heat-treated；Treatment temperature is
1200 DEG C, the processing time is 50min, in air atmosphere；
Step 5: after temperature drops to room temperature, taking out sample；
Step 6: once being cleaned using residue of the dilute hydrochloric acid to sample surfaces；
Step 7: carrying out secondary cleaning using residue of the deionized water to the generation in step 6；
Step 8: gallium oxide material being dried up, gallium oxide as shown in Figure 2/copper gallium oxygen hetero-junctions is formed.
It is detected and has formd gallium oxide/copper gallium oxygen hetero-junctions in the present embodiment.Fig. 3 show gallium oxide/copper gallium oxygen
The X-ray diffraction spectrum profiling results of hetero-junctions show.Using technology of the present invention, the copper gallium oxygen material prepared has single
Orientation, crystal quality is higher, and the architectural characteristic of hetero-junctions is good.
Embodiment 2
Gallium oxide/copper gallium oxygen hetero-junctions preparation method is present embodiments provided, is comprised the following steps that:
Step 1: selected gallium oxide material is, using MOCVD method prepare on a sapphire substrate with a thickness of 1 μm, table
The gallium oxide film of face 10mm square；Selected copper source is High-Purity Metallic Copper；Gallium oxide single crystal is placed in acid corrosion liquid and is handled
5min；
Step 2: gallium oxide material is placed in the quartz boat in atmosphere of hydrogen or quartz ampoule, by temperature be set as 850 DEG C,
Pressure control is heat-treated 30min in 100Pa；Temperature is taken out after dropping to room temperature；
Step 3: using thermal evaporation method, the layers of copper of one layer of 100nm thickness of pre-deposition, such as Fig. 4 on above-mentioned gallium oxide film
It is shown；
Step 4: by step 3, treated that sample is put into quartz ampoule, and controlling vacuum degree in quartz ampoule is 1 × 10-3Pa, and
By quartzy duct occlusion；
Step 5: the closed quartz tube that step 4 is placed is put into single temperature zone tube furnace and is heat-treated；Processing temperature
Degree is 900 DEG C, and the processing time is 50min；
Step 6: after temperature drops to room temperature, taking out sample；
Step 7: once being cleaned using residue of the dilute hydrochloric acid to gallium oxide material surface；
Step 8: carrying out secondary cleaning using residue of the deionized water to the generation in step 7；
Step 9: sample being dried up, gallium oxide as shown in Figure 5/copper gallium oxygen hetero-junctions is formed.
It is detected and has formd copper gallium oxygen material in the present embodiment.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (3)
1. a kind of gallium oxide/copper gallium oxygen hetero-junctions preparation method, which is characterized in that steps are as follows:
Gallium oxide material is put into 5min-5h in corrosive liquid by step 1., obtains ideal surfaced with corrosion oxidation gallium material；
Gallium oxide material is placed in quartz boat or quartz ampoule by step 2., temperature is 700 DEG C~1100 DEG C, pressure is 1 × 10- 4Pa~1 × 105Pa, atmosphere are to be heat-treated 1min~120min in reducibility gas or inert gas；Temperature takes after dropping to room temperature
Out；
Step 3. pre-deposition copper source layer or copper source layer on gallium oxide material directly overlay on gallium oxide material, the thickness of copper source layer
Degree is 10nm~10 μm；
Treated that gallium oxide material is placed in quartz boat or quartz ampoule by step 1 for step 4., is 700 DEG C~1300 in temperature
DEG C, pressure be 1 × 10-3Pa~1 × 106Pa, atmosphere be reducibility gas, air, vapor or nitrogen under, heat treatment 1min~
50min；Temperature is taken out after dropping to room temperature；
The subsequent processing of step 5. copper gallium oxygen: once being cleaned with residue of the cleaning solution to copper gallium oxygen surface, then spend from
Sub- water carries out secondary cleaning to the residue of generation；Copper gallium oxygen material is dried up, is properly saved, as copper gallium oxygen film；It is described
Copper gallium oxygen film include CuGa2O4Or CuGaO2Alloy and Copper-cladding Aluminum Bar.
2. the preparation method of copper gallium oxygen film according to claim 1, which is characterized in that the gallium oxide material is single
The epitaxial film of brilliant, polycrystalline and preparation on substrate.
3. the preparation method of copper gallium oxygen film according to claim 1 or 2, which is characterized in that the copper source is copper list
The oxide of matter or copper.
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| CN201811555045.XA CN109860058B (en) | 2018-12-19 | 2018-12-19 | Preparation method of gallium oxide/copper gallium oxygen heterojunction |
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| CN109860058B CN109860058B (en) | 2021-04-20 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111129122A (en) * | 2019-12-13 | 2020-05-08 | 中国科学技术大学 | Gallium oxide based heterojunction semiconductor structure and device thereof |
| WO2020124413A1 (en) * | 2018-12-19 | 2020-06-25 | 大连理工大学 | Method for preparing gallium oxide/copper-gallium oxide heterojunction |
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 |
-
2018
- 2018-12-19 CN CN201811555045.XA patent/CN109860058B/en not_active Expired - Fee Related
Patent 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020124413A1 (en) * | 2018-12-19 | 2020-06-25 | 大连理工大学 | Method for preparing gallium oxide/copper-gallium oxide heterojunction |
| CN111129122A (en) * | 2019-12-13 | 2020-05-08 | 中国科学技术大学 | Gallium oxide based heterojunction semiconductor structure and device thereof |
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