CN115233309B - Gallium nitride substrate, gallium nitride single crystal layer, and method for producing same - Google Patents
Gallium nitride substrate, gallium nitride single crystal layer, and method for producing same Download PDFInfo
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- CN115233309B CN115233309B CN202210640644.1A CN202210640644A CN115233309B CN 115233309 B CN115233309 B CN 115233309B CN 202210640644 A CN202210640644 A CN 202210640644A CN 115233309 B CN115233309 B CN 115233309B
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- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 141
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000000758 substrate Substances 0.000 title claims abstract description 47
- 239000013078 crystal Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 claims abstract description 14
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 63
- 230000007547 defect Effects 0.000 abstract description 5
- 239000002344 surface layer Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000001534 heteroepitaxy Methods 0.000 description 1
- 238000001657 homoepitaxy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
- C30B29/406—Gallium nitride
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/04—Pattern deposit, e.g. by using masks
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/183—Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/20—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIIBV compounds
- H01L29/2003—Nitride compounds
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Abstract
The invention discloses a gallium nitride substrate, a gallium nitride single crystal layer and a manufacturing method thereof, comprising the following steps: the method comprises the following steps: providing a heterogeneous substrate; forming a seed crystal on a substrate by using MOCVD technology; forming a gallium nitride film layer on the seed crystal by using an MOCVD technology; a layer of low-temperature gallium nitride is grown on the gallium nitride film layer by using an MOCVD technology; forming a patterned mask layer on the low-temperature gallium nitride, taking the mask layer as a mask, and etching on the mask to form a hole array formed by a plurality of hole grooves on the surface of the mask; and carrying out high-temperature treatment on the composite substrate formed by the gallium nitride film layer, the low-temperature gallium nitride and the mask layer, so that the low-temperature gallium nitride forms an uneven surface. The invention has the advantages that the high temperature during the growth of the HVPE method firstly damages the low temperature gallium nitride layer, and then the subsequent growth is carried out; because the surface layer is uneven gallium nitride, the gallium nitride can collide and merge in the growth process, thereby reducing dislocation defects and improving the quality of the gallium nitride epitaxial film.
Description
Technical Field
The invention relates to a gallium nitride single crystal material growth technology, in particular to a gallium nitride substrate, a gallium nitride single crystal layer and a manufacturing method thereof, which can reduce HVPE epitaxial film defects and improve epitaxial film quality.
Background
The wide bandgap semiconductor materials such as gallium nitride, silicon carbide and diamond are called third generation semiconductors, and have the excellent properties of larger breakdown voltage, smaller dielectric constant, higher saturated electron drift rate, better heat conduction performance, wider energy gap (Eg is more than or equal to 2.3 eV) and the like. The GaN has the characteristics of more stable chemical property, high temperature resistance and corrosion resistance, and is very suitable for manufacturing high-frequency, high-power and high-density integrated electronic devices.
Due to the special nature of gallium nitride materials, it is difficult to grow single crystals using conventional single crystal growth methods. Recently, thick film growth of gallium nitride materials, which can reach several millimeters or more, has been achieved by utilizing the characteristics of high growth rate and higher crystalline quality of HVPE. Gallium nitrideEpitaxial growth of materials is currently mainly performed by using heterogeneous substrates, such as sapphire, silicon carbide and the like, and the problems of defects such as large dislocation density and the like caused by lattice mismatch and thermal mismatch are common. The gallium nitride substrate belongs to homoepitaxy, the problems of lattice mismatch and thermal mismatch are avoided, and the HVPE technology is utilized to grow the gallium nitride epitaxial film on the gallium nitride substrate, so that the quality of the epitaxial film can be improved. For example, chinese patent publication No. CN114420532a discloses a method for improving the quality of epitaxially grown gallium nitride crystal and application thereof, comprising: under the conditions that the temperature is 1100-1200 ℃ and the pressure is 500-800 torr, and pure hydrogen and pure nitrogen are alternately input, carrying out long-time annealing and etching treatment on the aluminum nitride buffer layer with the thickness of less than or equal to 20 nm; thereafter, a gallium nitride material is deposited on the aluminum nitride buffer layer. The method can stably reduce dislocation density of gallium nitride film to approximately 1 order of magnitude, and can reach 7.3x10 7 cm -2 But the data also has room for improvement; as another example, chinese patent publication No. CN114005728A discloses a low stress high quality nitride material epitaxy method, which includes steps of s1, selecting a single crystal substrate by MOCVD equipment, and removing substrate contaminants; s2, introducing a metal organic source to grow a nucleation layer; s3, closing the metal organic source, introducing trimethylgallium, and growing a first GaN buffer layer; s4, etching the first GaN buffer layer in situ until GaN presents an island shape; s5, annealing the first GaN buffer layer to enable the GaN islands to be combined rapidly; s6, introducing trimethyl gallium to grow a second GaN buffer layer; s7, continuously growing an active layer, and after the epitaxial growth is finished, cooling to room temperature and taking out the epitaxial wafer. The method utilizes in-situ etching of GaN, and then annealing inter-island combination to realize stress release and crystal quality improvement of GaN, but specific dislocation density data are not given.
Disclosure of Invention
The invention aims to solve the technical problem that dislocation density cannot be fundamentally improved in the existing gallium nitride epitaxial film growing process, and provides a gallium nitride substrate, a gallium nitride single crystal layer and a manufacturing method thereof.
The technical scheme of the invention is as follows: a method of manufacturing a gallium nitride substrate, comprising the steps of:
providing a heterogeneous substrate;
forming a seed crystal on a substrate by using MOCVD technology;
forming a gallium nitride film layer on the seed crystal by using an MOCVD technology;
a layer of low-temperature gallium nitride is grown on the gallium nitride film layer by using an MOCVD technology;
forming a patterned mask layer on the low-temperature gallium nitride, taking the mask layer as a mask, and etching on the mask to form a hole array formed by a plurality of hole grooves on the surface of the mask, wherein the density of the hole grooves is greater than or equal to 10 7 /cm 2 The diameter is 1 μm-20 μm;
and carrying out high-temperature treatment on the composite substrate formed by the gallium nitride film layer, the low-temperature gallium nitride and the mask layer, so that the low-temperature gallium nitride layer forms an uneven morphology.
In the above scheme, the material of the heterogeneous substrate is sapphire, silicon carbide or silicon.
The seed crystal forming process in the scheme comprises the following steps: a layer of low-temperature gallium nitride 101 is grown on a substrate 100, the process temperature is 500-550 ℃, the thickness is 200-300 angstroms, high-temperature treatment is carried out on the low-temperature gallium nitride 101, the gallium nitride layer 101 can be decomposed to form island-shaped gallium nitride, the high-temperature treatment is continued, the gallium nitride layer can be continuously decomposed, a small part of island-shaped gallium nitride 101b is remained and called a seed crystal, the process temperature of the high-temperature treatment is 1000-1200 ℃, and the chamber pressure is 400-600 torr.
The forming process of the gallium nitride film layer in the scheme comprises the following steps: 3D-2D growth is carried out by utilizing seed crystals, a gallium nitride film 102,3D layer with the thickness of 2000-4000 angstroms is formed, the process temperature is 800-1100 ℃, and the chamber pressure is 200-600 torr; the thickness of the 2D layer is 0.5-1 μm, the process temperature is 800-1100 ℃, and the chamber pressure is 100-400 torr.
In the above scheme, the process of regrowing a layer of low-temperature gallium nitride on the gallium nitride film layer includes: and growing low-temperature gallium nitride 103 on the gallium nitride film 102, wherein the thickness of the low-temperature gallium nitride is 200-800A, the process temperature is 1000-1200 ℃, and the chamber pressure is 400-600 torr.
In the scheme, the process temperature of the high-temperature treatment of the composite substrate is 800-1200 ℃, the chamber pressure is 650-900 torr, the time is 5-30 min, and carrier gas H2 is introduced: n2=1: 1.
the gallium nitride substrate is manufactured by the manufacturing method of the gallium nitride substrate.
In the method for producing a gallium nitride single crystal layer, the gallium nitride substrate is grown by HVPE method, and the gallium nitride single crystal layer is obtained by automatic peeling at the end of the growth, wherein the HVPE growth rate is 100 μm/h, and the growth time is 10h.
The thickness of the thick film of the gallium nitride layer in the scheme is 500 mu m-10 mm.
The gallium nitride single crystal layer is manufactured by the manufacturing method of the gallium nitride single crystal layer.
The invention has the advantages that the high temperature during the growth by using the HVPE method firstly damages the low temperature gallium nitride layer, and then the subsequent growth is carried out; because the surface layer is uneven gallium nitride, the gallium nitride can collide and merge in the growth process, thereby reducing dislocation defects and improving the quality of the gallium nitride epitaxial film. The dislocation density of the gallium nitride film is at a relatively low level, and the gallium nitride film has good practical value.
Drawings
Fig. 1 is a flow chart of a gallium nitride substrate manufacturing method of the present invention;
FIG. 2 is a schematic view of the substrate of FIG. 1;
FIG. 3 is a schematic diagram of low temperature gallium nitride 101 during seed formation;
FIG. 4 is a schematic illustration of the formation of island-like gallium nitride by decomposition of a gallium nitride layer after high temperature treatment of gallium nitride during seed formation;
FIG. 5 is a schematic illustration of the seed crystal of FIG. 1 after formation;
FIG. 6 is a schematic view of 3D-2D growth of the seed crystal of FIG. 1;
fig. 7 is a schematic diagram showing growth of low temperature gallium nitride 103 on top of gallium nitride film 102 of fig. 1;
FIG. 8 is a schematic illustration of the mask layer of FIG. 1 after formation;
FIG. 9 is a schematic diagram of the long pre-high temperature process of FIG. 1;
FIG. 10 is a schematic diagram of gallium nitride layer thick film growth using HVPE;
FIG. 11 is a rocking curve of the (002) plane of the sample obtained in example 1 and example 2 of the present invention;
FIG. 12 is a rocking curve of the (102) plane of the sample obtained in example 1 and example 2 of the present invention;
in the figure, 100, a substrate, 101, low-temperature gallium nitride, 101a, island-shaped gallium nitride, 101b, a seed crystal, 102, a gallium nitride thin film, 103, low-temperature gallium nitride, 103a, an uneven surface, 104, an array of holes, 105, a thick gallium nitride layer film, 105a and a dislocation annihilation region.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. Based on the embodiments of the present invention, all other embodiments of the invention are within the scope of the present invention for those of ordinary skill in the art without making any inventive effort.
Example 1, a method of manufacturing a gallium nitride substrate, comprising the steps of:
as shown in fig. 2, a substrate 100 is provided, and the material of the substrate 100 may be sapphire (Al 2 O 3 ) Silicon carbide (SiC) and the like, and a material with small lattice mismatch degree with the epitaxial layer, similar expansion coefficient with the epitaxial layer and chemical stability matched with the epitaxial layer can be selected as a substrate of heteroepitaxy.
The seed crystal forming process comprises the following steps: as shown in fig. 3, a layer of low-temperature gallium nitride 101 is grown on a substrate 100 by using an MOCVD technique, wherein the process temperature is 500-550 ℃, specifically 500 ℃, 540 ℃ or 550 ℃, and the thickness is 200 a-300 a, specifically 200 a or 300 a; as shown in fig. 4 and 5, the low-temperature gallium nitride 101 is subjected to high-temperature treatment, the gallium nitride layer 101 is decomposed to form island-shaped gallium nitride 101a, the high-temperature treatment is continued, the gallium nitride layer is decomposed, and a small part of island-shaped gallium nitride 101b is remained and called a seed crystal, the process temperature is 1000-1200 ℃, the process temperature can be 1000 ℃ or 1200 ℃, the chamber pressure can be 400 torr-600 torr, and the process temperature can be 400torr or 600 torr;
as shown in fig. 6, 3D and 2D growth is performed by using seed crystal to form a gallium nitride film 102,3D layer with a thickness of 2000 a-4000 a, specifically 2000 a or 4000 a, the process temperature is 800 ℃ to 1100 ℃, specifically 800 ℃ or 1100 ℃, the chamber pressure is 200 torr to 600torr, specifically 200 torr or 600torr, the 2D layer thickness is 0.5 μm to 1 μm, specifically 0.5 μm or 1 μm, the process temperature is 800 ℃ to 1100 ℃, specifically 800 ℃ or 1100 ℃, and the chamber pressure is 100 torr to 400torr, specifically 100 torr or 400torr. The above may be referred to as a first buffer layer;
as shown in fig. 7, a low temperature gallium nitride 103 is grown on the gallium nitride film 102, where the thickness of the low temperature gallium nitride is 200 a-800 a, specifically 200 a or 800 a, the process temperature is 1000 ℃ to 1200 ℃, specifically 1000 ℃ or 1200 ℃, and the chamber pressure is 400 torr-600 torr, specifically 400torr or 600 torr; the low temperature gallium nitride may be referred to as a second buffer layer;
as shown in fig. 8, a patterned mask layer is formed on the low-temperature gallium film, and etching is performed on the mask layer by taking the mask layer as a mask, so that a hole array 104 formed by a plurality of hole grooves is formed on the surface of the mask layer;
as shown in fig. 9, before growing the thick gallium nitride film, the composite substrate is first subjected to high temperature treatment by using a Hydride Vapor Phase Epitaxy (HVPE) method, wherein the composite substrate is formed by a gallium nitride thin film layer, low temperature gallium nitride and a mask layer, so that the low temperature gallium nitride forms an uneven surface 103a, the high temperature treatment is performed at a process temperature of 800-1200 ℃, specifically 800-1200 ℃, the chamber pressure is 650-900 torr, specifically 650-900 torr, and the time is 5-30 min, specifically 5 min or 30min, and carrier gas H2 is introduced: n2=1: 1.
as shown in fig. 10, the growth of the thick film 105 of the gallium nitride layer is performed by Hydride Vapor Phase Epitaxy (HVPE), wherein the thick film of gallium nitride is 500 μm or 10mm, and partial dislocation generated in the growth process collides with the merging 105a, so that dislocation defects are reduced, and the quality of the epitaxial film of gallium nitride is improved. The final sample obtained is labeled sample a.
The density and diameter of the cells are such that the product is affected, for example, the greater the cell density, the greater the diameter, the easier it is to peel, but at the same time it is easy to peel, the wafer quality is affected, thus rational parameters are designed, the cell density is greater than or equal to 10 7 /cm 2 Such as 10 7 /cm 2 、11 7 /cm 2 And so on, the diameter of the pore groove is 1 μm to 20 μm, such as 1 μm, 5 μm, 10 μm or 20 μm.
The sample a obtained in example 1 was subjected to an X-ray diffraction test, and rocking curves of 002 crystal face and 102 crystal face were obtained as shown in fig. 11 and 12, the former having a half-width representing the number of threading dislocations to some extent, and the latter representing edge dislocations. XRD test is used to obtain gallium nitride thick film with 002 face half-width of 34.0 arc sec and 102 face half-width of 38.3 arc sec, and the dislocation density of 9.6X10 sample can be estimated from the half-width 6 CM -2 The dislocation density of the gallium nitride film grown by the method is proved to be at a relatively low level.
Claims (9)
1. A method for manufacturing a gallium nitride substrate is characterized in that: the method comprises the following steps:
providing a heterogeneous substrate;
forming a seed crystal on a substrate by using MOCVD technology, wherein the forming process of the seed crystal comprises the following steps: growing a layer of low-temperature gallium nitride 101 on a substrate 100, wherein the process temperature is 500-550 ℃, the thickness is 200A-300A, carrying out high-temperature treatment on the low-temperature gallium nitride 101, decomposing the gallium nitride layer 101 to form island-shaped gallium nitride, continuing the high-temperature treatment, continuously decomposing the gallium nitride layer, and leaving a small part of island-shaped gallium nitride 101b called seed crystal, wherein the process temperature of the high-temperature treatment is 1000-1200 ℃ and the chamber pressure is 400-600 torr;
forming a gallium nitride film layer on the seed crystal by using an MOCVD technology;
a layer of low-temperature gallium nitride is grown on the gallium nitride film layer by using an MOCVD technology;
forming a patterned mask layer on the low-temperature gallium nitride, taking the mask layer as a mask, and etching on the mask to form a hole array formed by a plurality of hole grooves on the surface of the maskRows of holes and grooves with a density of 10 or more 7 /cm 2 The diameter is 1 μm-20 μm;
and carrying out high-temperature treatment on the composite substrate formed by the gallium nitride film layer, the low-temperature gallium nitride and the mask layer, so that the low-temperature gallium nitride forms an uneven surface.
2. A method of manufacturing a gallium nitride substrate according to claim 1, wherein: the heterogeneous substrate is made of sapphire, silicon carbide or silicon.
3. A method of manufacturing a gallium nitride substrate according to claim 1, wherein: the forming process of the gallium nitride film layer comprises the following steps: 3D-2D growth is carried out by utilizing seed crystal, so as to form a gallium nitride film 102,3D layer with the thickness of 2000A-4000A, the process temperature is 800-1100 ℃, and the chamber pressure is 200-600 torr; the thickness of the 2D layer is 0.5-1 μm, the process temperature is 800-1100 ℃, and the chamber pressure is 100-400 torr.
4. A method of manufacturing a gallium nitride substrate according to claim 1, wherein: the process for regrowing a layer of low-temperature gallium nitride on the gallium nitride film layer comprises the following steps: and growing low-temperature gallium nitride 103 on the gallium nitride film 102, wherein the thickness of the low-temperature gallium nitride is 200-800A, the process temperature is 1000-1200 ℃, and the chamber pressure is 400-600 torr.
5. A method of manufacturing a gallium nitride substrate according to claim 1, wherein: the high-temperature treatment process of the composite substrate is carried out at the temperature of 800-1200 ℃, the pressure of a chamber is 650-900 torr, the time is 5-30 min, and carrier gas H2 is introduced: n2=1: 1.
6. a gallium nitride substrate characterized by: manufactured by the manufacturing method of the gallium nitride substrate according to any one of claims 1 to 5.
7. A method for producing a gallium nitride single crystal layer is characterized by comprising the steps of: gallium nitride substrate according to claim 6 is subjected to gallium nitride layer thick film growth by using an HVPE method, and gallium nitride single crystal layer is obtained by automatic stripping at the end of growth, wherein the HVPE growth rate is 100 μm/h, and the growth time is 10h.
8. The method for producing a single crystal layer according to claim 7, wherein: the thickness of the thick film of the gallium nitride layer is 500 mu m-10 mm.
9. The gallium nitride single crystal layer is characterized in that: manufactured by the manufacturing method of the gallium nitride single crystal layer according to claim 7 or 8.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1828837A (en) * | 2006-01-27 | 2006-09-06 | 中国科学院上海微系统与信息技术研究所 | Growth method for gallium nitride film using multi-hole gallium nitride as substrate |
| CN107170668A (en) * | 2017-06-01 | 2017-09-15 | 镓特半导体科技（上海）有限公司 | A kind of self-standing gan preparation method |
| CN107275187A (en) * | 2017-06-26 | 2017-10-20 | 镓特半导体科技（上海）有限公司 | Self-standing gan layer and preparation method thereof, method for annealing |
| CN114005728A (en) * | 2021-09-17 | 2022-02-01 | 中国电子科技集团公司第五十五研究所 | Low-stress high-quality nitride material epitaxy method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1828837A (en) * | 2006-01-27 | 2006-09-06 | 中国科学院上海微系统与信息技术研究所 | Growth method for gallium nitride film using multi-hole gallium nitride as substrate |
| CN107170668A (en) * | 2017-06-01 | 2017-09-15 | 镓特半导体科技（上海）有限公司 | A kind of self-standing gan preparation method |
| CN107275187A (en) * | 2017-06-26 | 2017-10-20 | 镓特半导体科技（上海）有限公司 | Self-standing gan layer and preparation method thereof, method for annealing |
| CN114005728A (en) * | 2021-09-17 | 2022-02-01 | 中国电子科技集团公司第五十五研究所 | Low-stress high-quality nitride material epitaxy method |
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