CN105006427A - Method for growing high-quality gallium nitride epitaxial structure by using low-temperature transition layer - Google Patents
Method for growing high-quality gallium nitride epitaxial structure by using low-temperature transition layer Download PDFInfo
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- CN105006427A CN105006427A CN201510470018.2A CN201510470018A CN105006427A CN 105006427 A CN105006427 A CN 105006427A CN 201510470018 A CN201510470018 A CN 201510470018A CN 105006427 A CN105006427 A CN 105006427A
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- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000007704 transition Effects 0.000 title abstract 3
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 10
- 150000004767 nitrides Chemical class 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000002161 passivation Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 28
- 239000012792 core layer Substances 0.000 claims description 23
- 238000000407 epitaxy Methods 0.000 claims description 15
- 229910052594 sapphire Inorganic materials 0.000 claims description 9
- 239000010980 sapphire Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910017083 AlN Inorganic materials 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910003465 moissanite Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract 3
- 238000010899 nucleation Methods 0.000 abstract 3
- 238000003780 insertion Methods 0.000 abstract 1
- 230000037431 insertion Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 230000007547 defect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/0254—Nitrides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02455—Group 13/15 materials
- H01L21/02458—Nitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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- H01L21/2056—
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
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- Semiconductor Lasers (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a method for growing a high-quality gallium nitride epitaxial structure by using a low-temperature transition layer, and relates to the technical field of semiconductors. The method comprises the following steps: (1) performing heat treatment on a substrate at high temperature by using the MOCVD technology, and then lowering the temperature; (2) growing a low-temperature nitride nucleation layer on the substrate; (3) performing annealing to crystallize the nucleation layer; (4) raising the temperature, and growing a layer of gallium nitride on the nucleation layer after annealing; (5) stopping feeding a gallium source, stopping growing gallium nitride, and lowering the temperature; (6) continuing to feed the gallium source to grow gallium nitride, and raising the temperature; and (7) sequentially growing an insertion layer, a channel layer, a cap layer and a passivation layer on the gallium nitride layer to obtain a complete epitaxial structure. By using the low-temperature transition layer, the dislocation density of the gallium nitride epitaxial layer is reduced effectively, the quality of gallium nitride crystals is improved, and the service life and efficiency of gallium nitride based devices are improved.
Description
Technical field
The present invention relates to technical field of semiconductors, particularly relate to a kind of method utilizing low temperature buffer layer growing high-quality epitaxy of gallium nitride structure.
Background technology
As the Typical Representative of third generation semiconductor, gallium nitride material is owing to having wide energy gap, the features such as high velocity of electrons, gallium-nitride-based devices is widely used in radio communication, radar isoelectronic series system at microwave, millimeter wave frequency band, photoelectron and microelectronic development prospect very wide.
At present, obtaining the main method of gallium nitride epitaxial materials is by substrate Epitaxial growth, and substrate comprises gallium nitride, sapphire, carborundum, aluminium nitride and silicon-based substrate etc.But owing to there is larger lattice mismatch and thermal expansion mismatch between gallium nitride material and substrate, (as being 16% with sapphire mismatch, being 3.4% with carborundum mismatch, is 17% with silica-based mismatch), make the gallium nitride epitaxial materials grown introduce a large amount of dislocations and defect, defect concentration is up to 10
8~ 10
10cm
-2, and then have impact on useful life and the service efficiency of gallium-nitride-based devices.
The method of traditional growing gallium nitride epitaxial material is, first at Grown one deck nitride forming core layer, and continuous high temperature growing gallium nitride epitaxial material on the forming core layer then after annealing crystallization.Because the nitride forming core layer of low-temperature epitaxy exists a large amount of dislocations and defect, nucleus is second-rate, on this basis during high growth temperature gallium nitride epitaxial materials, the dislocation of not mate with thermal expansion and causing is not mated and defect continues to extend due to lattice, the dislocation of gallium nitride epitaxial materials and defect are still a lot, and epitaxial material crystal mass is still very poor.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method utilizing low temperature buffer layer growing high-quality epitaxy of gallium nitride structure, it is by the process of growing gallium nitride, insert growth one deck low temperature buffer layer, the crystal mass of further lifting gallium nitride, improves efficiency and the useful life of device.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method utilizing low temperature buffer layer growing high-quality epitaxy of gallium nitride structure, and the method comprises the following steps:
1) MOCVD technology is adopted, after substrate at high temperature heat treatment, cooling;
2) at Grown one deck low-temperature nitride forming core layer;
3) anneal, realize the crystallization of forming core layer;
4) raised temperature, forming core layer after annealing grows one deck gallium nitride;
5) stop passing into gallium source, stop growing gallium nitride, cooling;
6) continue to pass into gallium source growing gallium nitride, and raised temperature;
7) insert layer is grown successively on that gallium nitride layer, channel layer, cap and passivation layer, the epitaxial structure obtained.
Preferably, the substrate in described step 1) is gallium nitride, sapphire, SiC, Si, AlN, SiO
2, diamond, any one in Graphene.
Preferably, the MOCVD technology adopted in described step 1) utilizes ammonia as nitrogenous source, and nitrogen or hydrogen are as carrier gas, and trimethyl gallium or triethyl-gallium, trimethyl aluminium, trimethyl indium are respectively as gallium source, aluminium source and indium source, and silane is as silicon source.
Preferably, described step 2) in the temperature of growing nitride forming core layer be room temperature 20 DEG C ~ 1000 DEG C, forming core layer thickness is 0 ~ 100nm.
Preferably, in described step 3), annealing temperature is 600 DEG C ~ 1200 DEG C, and annealing time is 0 ~ 1000s.
Preferably, the growth temperature described step 4) forming core layer after annealing growing one deck gallium nitride is 800 DEG C ~ 1300 DEG C, and thickness is 0 ~ 1 μm;
Preferably, in described step 5), rate of temperature fall is 0 ~ 1000 DEG C/s, and temperature is 20 DEG C ~ 1000 DEG C.
The beneficial effect that produces of technique scheme is adopted to be: the present invention is on sapphire or carborundum or the foreign substrate such as silica-based, low-temperature epitaxy one deck nitride forming core layer, subsequently after to the annealing crystallization of forming core layer, the gallium nitride of high growth temperature layer, stop subsequently passing into gallium source and lowering the temperature, form low temperature buffer layer, i.e. " dead level ", then raised temperature continued growth gallium nitride epitaxial materials; The existence of " dead level ", releases stress, blocks a part of dislocation and continues to extend, reduce the dislocation density of gallium nitride epitaxial materials, improve the crystal mass of gallium nitride epitaxial materials.The present invention can utilize low temperature " dead level " effectively to reduce epitaxial layer of gallium nitride dislocation density, improves gallium nitride quality, and then improves useful life and the efficiency of gallium-nitride-based devices, and the present invention simultaneously has wider growth technique window.
Accompanying drawing explanation
Fig. 1 is flow chart of the present invention;
Fig. 2 is the temperature curve of traditional Grown on Sapphire Substrates epitaxy of gallium nitride;
Fig. 3 is the temperature curve of the present invention's growing gallium nitride extension on a sapphire substrate;
Fig. 4 is (102) X ray double crystal diffraction curve of the gallium nitride sample of this example, and abscissa is ω scanning direction angle (arc s), and ordinate is relative intensity.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
As shown in Figure 1, the invention provides a kind of method utilizing low temperature buffer layer growing high-quality epitaxy of gallium nitride structure, for Sapphire Substrate, comprise the following steps:
1) adopt MOCVD technology, by Sapphire Substrate heat treatment in MOCVD reative cell: in a hydrogen atmosphere, temperature maintains 800 DEG C ~ 1300 DEG C, continues 300 s to 2000s; Then lower the temperature, MOCVD technology wherein utilizes ammonia as nitrogenous source, and nitrogen or hydrogen are as carrier gas, and trimethyl gallium or triethyl-gallium, trimethyl aluminium, trimethyl indium are respectively as gallium source, aluminium source and indium source, and silane is as silicon source.
2) at Grown one deck low-temperature nitride forming core layer: wherein the growth temperature of forming core layer is 20 DEG C ~ 1000 DEG C, and chamber pressure is 50 ~ 500mbar, V/III about 300 ~ 3000, forming core layer thickness is, 0 ~ 100nm.
3) anneal, realize the crystallization of forming core layer: reaction chamber temperature is elevated to annealing temperature: 600 DEG C ~ 1200 DEG C, annealing time is 0 ~ 1000s, make nitride forming core layer remain a small amount of nucleus after annealing.
4) raised temperature forming core layer after annealing grows one deck gallium nitride: wherein growth temperature is at 800 DEG C ~ 1300 DEG C, chamber pressure is 100 mbar ~ 1000 mbar, V/III about 300 ~ 400.
5) stop growing gallium nitride, cooling: under NH3 atmosphere protection, and stop passing into trimethyl gallium, rate of temperature fall is 0 ~ 1000 DEG C/s, and temperature is 20 DEG C ~ 1000 DEG C, and chamber pressure is constant, as shown in Figure 3.
6) heat up, continued growth gallium nitride: pass into trimethyl gallium source, heat up, wherein growth temperature is at 800 DEG C ~ 1300 DEG C, and chamber pressure is 100 mbar ~ 1000 mbar, and V/III about 300 ~ 400.
7) grow insert layer successively at gallium nitride layer, channel layer, cap and passivation layer, obtain complete epitaxial structure.
As shown in Figure 4, (102) X-ray diffraction twin crystal curve of the gallium nitride sample of the invention process case, wherein abscissa is ω scanning direction angle (second of arc), and ordinate is relative intensity; X-ray diffraction twin crystal curve halfwidth degree is very little, about 300 second of arcs, illustrates that the gallium nitride quality that the present invention obtains is improved, and then improves useful life and the efficiency of device, and the method growing gallium nitride epitaxial structure has very wide growth technique window simultaneously.
Claims (7)
1. utilize a method for low temperature buffer layer growing high-quality epitaxy of gallium nitride structure, it is characterized in that: the method comprises the following steps:
1) MOCVD technology is adopted, after substrate at high temperature heat treatment, cooling;
2) at Grown one deck low-temperature nitride forming core layer;
3) anneal, realize the crystallization of forming core layer;
4) raised temperature, forming core layer after annealing grows one deck gallium nitride;
5) stop passing into gallium source, stop growing gallium nitride, cooling;
6) continue to pass into gallium source growing gallium nitride, and raised temperature;
7) insert layer is grown successively on that gallium nitride layer, channel layer, cap and passivation layer, the epitaxial structure obtained.
2. a kind of method utilizing low temperature buffer layer growing high-quality epitaxy of gallium nitride structure according to claim 1, is characterized in that: the substrate in described step 1) is gallium nitride, sapphire, SiC, Si, AlN, SiO
2, diamond, any one in Graphene.
3. a kind of method utilizing low temperature buffer layer growing high-quality epitaxy of gallium nitride structure according to claim 1, it is characterized in that: the MOCVD technology adopted in described step 1), utilize ammonia as nitrogenous source, nitrogen or hydrogen are as carrier gas, trimethyl gallium or triethyl-gallium, trimethyl aluminium, trimethyl indium are respectively as gallium source, aluminium source and indium source, and silane is as silicon source.
4. a kind of method utilizing low temperature buffer layer growing high-quality epitaxy of gallium nitride structure according to claim 1, is characterized in that: described step 2) in the temperature of growing nitride forming core layer be room temperature 20 DEG C ~ 1000 DEG C, forming core layer thickness is 0 ~ 100nm.
5. a kind of method utilizing low temperature buffer layer growing high-quality epitaxy of gallium nitride structure according to claim 1, is characterized in that: in described step 3), annealing temperature is 600 DEG C ~ 1200 DEG C, and annealing time is 0 ~ 1000s.
6. a kind of method utilizing low temperature buffer layer growing high-quality epitaxy of gallium nitride structure according to claim 1, it is characterized in that: the growth temperature described step 4) forming core layer after annealing growing one deck gallium nitride is 800 DEG C ~ 1300 DEG C, and thickness is 0 ~ 1 μm.
7. a kind of method utilizing low temperature buffer layer growing high-quality epitaxy of gallium nitride structure according to claim 1, is characterized in that: in described step 5), rate of temperature fall is 0 ~ 1000 DEG C/s, and temperature is 20 DEG C ~ 1000 DEG C.
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Cited By (3)
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| CN110517950A (en) * | 2019-07-29 | 2019-11-29 | 太原理工大学 | A method of preparing Zinc-Blende GaN film on a diamond substrate |
| CN111681953A (en) * | 2020-05-20 | 2020-09-18 | 中国电子科技集团公司第五十五研究所 | A growth method for improving the interface quality of gallium nitride heteroepitaxy |
| CN112687525A (en) * | 2020-12-24 | 2021-04-20 | 中国电子科技集团公司第五十五研究所 | Epitaxial method for improving quality of ultrathin gallium nitride field effect transistor |
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