CN111501102A - HVPE-based self-supporting gallium nitride single crystal and preparation method thereof - Google Patents
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- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 117
- 239000013078 crystal Substances 0.000 title claims abstract description 81
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 10
- 239000010980 sapphire Substances 0.000 claims description 10
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- -1 ScAlMgO4 Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000006911 nucleation Effects 0.000 abstract description 8
- 238000010899 nucleation Methods 0.000 abstract description 8
- 239000010408 film Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 6
- 238000005121 nitriding Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001534 heteroepitaxy Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001657 homoepitaxy Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
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- 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
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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
- C30B25/025—Continuous growth
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- 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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- 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
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
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Abstract
The invention provides a method for preparing self-supporting gallium nitride single crystal based on HVPE, which comprises the following steps: (1) providing a substrate, and cleaning the surface of the substrate in situ; (2) growing GaN crystal nuclei on the surface of the substrate at a low temperature, forming NH4Cl solid by HCl and NH3 at the same time, and covering the substrate by competing with the GaN crystal nuclei; (3) raising the temperature to over 1000 ℃ for annealing treatment, and improving the quality of the GaN crystal nucleus; (4) growing a GaN layer on the GaN crystal nucleus in a two-dimensional manner at a high temperature; (5) continuously growing a GaN single crystal on the GaN layer at a high temperature; and cooling, and stripping the GaN single crystal from the substrate to form the self-supporting crystal. The invention provides high-quality nucleation points for the growth of the self-supporting dimensional gallium nitride through HVPE, and simultaneously reduces the warpage and eliminates cracks when the temperature is reduced after the growth is finished because the stress is released by the gaps, thereby improving the yield of the growth of the self-supporting dimensional gallium nitride.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a self-supporting gallium nitride single crystal and a preparation method thereof.
Background
GaN is a typical representative of third-generation wide bandgap semiconductors, has been widely used in semiconductor illumination, microwave power devices, power electronic devices, and the like, and shows great application prospects. The most ideal substrate for gallium nitride growth is naturally gallium nitride single crystal material, and such homoepitaxy (i.e. the epitaxial layer and the substrate are the same material) can greatly improve the crystal quality of the epitaxial film, reduce the dislocation density, prolong the service life of the device, improve the luminous efficiency and improve the working current density of the device. However, the gallium nitride single crystal growth is difficult and expensive, and large-scale homoepitaxial growth is not possible at present. Therefore, at present, heteroepitaxy is still adopted in the preparation of gallium nitride single crystals, such as silicon substrates, sapphire substrates, silicon carbide substrates and the like.
Currently, substantially all commercial GaN substrates (wafers, substrates) are fabricated by HVPE. But their size is still typically limited to 2 inches, with larger sizes such as 4 inches being limited by the radius of curvature. In HVPE, however, due to heteroepitaxy, the stress caused by the lattice constant and the thermal expansion coefficient causes gallium nitride to crack when grown thick or when cooled.
The existing solution is to grow several microns of GaN thin film on the sapphire surface by using MOCVD and carry out interface treatment to form various masks, on one hand, the initial defect during growth is reduced and a stress yielding type substrate is formed, so that the critical thickness of GaN growth is as large as possible, such as several hundred microns or even several millimeters; another aspect is to create a weak interface that can cause self-peeling of GaN and sapphire or other substrates due to shear stress induced by the difference in the number of thermal expansions at the cool down. The essence of the method is that the transition layer is inserted into the interface of the foreign substrate, so as to achieve the purpose of reducing dislocation and stress during growth, and the grown gallium nitride is easy to strip off sapphire when being cooled.
However, such methods have disadvantages: 1. high cost, requiring expensive equipment and indicator processes such as photolithography or MOCVD; 2. additional equipment and processes are required, so that the process control performance is poor and the yield is reduced; 3. the effect of absorbing the stress is not very significant. The current commercial gan self-supporting substrates are on the order of 4 inches at the most, and are far from reaching the size of foreign substrates such as silicon, sapphire, silicon carbide, e.g., 8 inches or more.
Disclosure of Invention
The invention aims at the problems and the defects of the prior art, makes research and improvement and provides a method for preparing self-supporting gallium nitride single crystal based on HVPE. All steps proposed by the invention are based on HVPE process and are completed in the same HVPE reactor.
In order to achieve the above object, the present invention provides a method for preparing a self-supporting gallium nitride single crystal based on HVPE, comprising the steps of:
(1) providing a substrate, and cleaning the surface of the substrate in situ.
(2) Growing GaN crystal nuclei on the surface of the substrate at a low temperature, forming NH4Cl solid by HCl and NH3 at the same time, and covering the substrate by competing with the GaN crystal nuclei;
(3) raising the temperature to over 1000 ℃ for annealing treatment, and improving the quality of the GaN crystal nucleus;
(4) growing a GaN layer on the GaN crystal nucleus in a two-dimensional manner at a high temperature;
(5) continuously growing a GaN single crystal on the GaN layer at a high temperature;
(6) and cooling, and stripping the GaN single crystal from the substrate to form the self-supporting crystal.
As a preferred arrangement of the present invention, the substrate includes, but is not limited to, sapphire substrate, Si C, GaAs, ScAlMgO4, ZnO, Si substrate, and the like.
As a preferable configuration of the present invention, the step (1) is performed at a high temperature of 1000 to 1100 ℃, and comprises cleaning the surface of the substrate using a mixed gas of H2 and N2.
As a preferred arrangement of the present invention, if the substrate is sapphire, it is also necessary to nitride the surface of the substrate with NH 3.
In the preferred configuration of the present invention, the partial pressure of NH3 is 0.05-0.5, and the nitriding time is 0.2-5 min.
As a preferable setting of the invention, the low temperature range of the step (2) is 300-500 ℃, the coverage rate of the GaN crystal nucleus is lower than 70%, and the thickness of the GaN crystal nucleus is 50-2000 nm.
As a preferable setting of the invention, the GaN layer in the step (4) is subjected to two-dimensional growth at a high temperature of 800-1100 ℃, the V/III is less than 20, the growth rate is less than 50um/hr, and the thickness is 1-20 um.
As a preferable setting of the invention, the GaN layer in the step (4) is subjected to two-dimensional growth at a high temperature of 800-1100 ℃, the V/III is less than 5, the growth rate is less than 20um/hr, and the thickness is 5-10 um.
As a preferred arrangement of the present invention, the step (5) further comprises a method for maintaining the growth and morphology of the GaN single crystal thick film, wherein the method comprises the following steps:
①, continuously increasing the temperature, wherein the increase range is that the temperature of the GaN monocrystal thick film increases by 1-10 ℃ every time the GaN monocrystal thick film increases by 1 mm;
② NH3 is continuously increased, and the increase amplitude is 5% -50% of the increase of NH3 (or corresponding V/III) when the GaN monocrystal thick film grows for each 1 mm.
The invention also provides a HVPE-based self-supporting gallium nitride single crystal prepared by the preparation method according to any one of claims 1 to 6.
The invention has the following beneficial effects: 1) the GaN crystal nucleus is nucleated in a low-temperature range and is heated for annealing treatment, so that the quality is high, and dislocation is low; 2) low technological temperature during nucleation of GaN crystal nucleus and NH generated synchronously with the GaN crystal nucleus4The Cl solid will not sublime, so that part of the substrate surface will be coated with solid NH4Cl is covered, so that the nucleation density is greatly reduced, and the crystal quality is effectively improved; 3) NH after temperature rise4Cl decomposes and sublimates, at the moment, only GaN crystal nuclei exist on the surface of the substrate, GaN does not grow or rarely grows on the substrate under a high-temperature environment, but selectively grows on the GaN crystal nuclei, and gaps are formed between the substrate and gallium nitride crystals, so that the stress effect is effectively reduced; 4) when the temperature is reduced, the gallium nitride and the substrate can be more easily peeled off due to the stress caused by the different thermal expansion coefficients of the substrate and the gallium nitride crystal due to the gap between the substrate and the crystal. Compared with the prior art, the method has the advantages of low cost, high yield and obvious stress absorption.
Drawings
FIG. 1 is a schematic structural diagram of step (1) in the embodiment of the present invention.
FIG. 2 is a schematic structural diagram of step (2) in the embodiment of the present invention.
FIG. 3 is a schematic structural diagram of step (3) in the embodiment of the present invention.
FIG. 4 is a schematic structural diagram of step (4) in the embodiment of the present invention.
FIG. 5 is a schematic structural diagram of step (5) in the embodiment of the present invention.
FIG. 6 is a schematic structural diagram of step (6) in the embodiment of the present invention.
Wherein,
100-a substrate;
101-GaN crystal nucleus;
102-solid NH4Cl；
103-GaN layer;
104-GaN single crystal thick film.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
The self-supporting GaN single crystal based on HVPE provided by the invention has the core that the stress action between the foreign substrate and the GaN single crystal thick film is reduced, and the GaN single crystal is warped and cracked in the preparation process due to the stress action. In the invention, under low temperature environment, GaN crystal nucleus and NH4Cl solid is synchronously covered on the surface of the nitrided substrate, and then the temperature is raised to cause NH4The Cl solid is sublimated, the nucleation density is effectively reduced, meanwhile, the dislocation of the GaN layer nucleated on the Cl solid is low, and the dislocation is further reduced through the two-dimensional lateral growth of the GaN; on the other hand, because of the presence of a large number of voids at the interface, a yielding substrate is formed, absorbing stress during growth, and low dislocations and stress absorption can effectively reduce warpage. And finally, the gaps of the substrate interface are more favorable for stripping when the temperature is reduced after the growth is finished.
Example 1
According to fig. 1 to 5, the invention provides a self-supporting gallium nitride single crystal based on HVPE, and the preparation method of the self-supporting gallium nitride single crystal based on HVPE comprises the following steps:
(1) providing a substrate, and cleaning and nitriding the surface of the substrate.
(2) Growing GaN crystal nuclei on the surface of the substrate at a low temperature, forming NH4Cl solid by HCl and NH3 at the same time, and covering the substrate by competing with the GaN crystal nuclei;
(3) raising the temperature to over 1000 ℃ for annealing treatment, and improving the quality of the GaN crystal nucleus;
(4) growing a GaN layer on the GaN crystal nucleus in a two-dimensional manner at a high temperature;
(5) continuously growing a GaN single crystal on the GaN layer at a high temperature;
(6) and cooling and stripping, and stripping the GaN single crystal from the substrate to form the self-supporting crystal.
As a preferable aspect of the present invention, the substrate is a sapphire substrate.
As a preferable scheme of the invention, the step (1) is carried out at a high temperature of 1000-1100 ℃, and comprises the steps of cleaning the surface of the substrate by using a mixed gas of H2 and N2 and nitriding the surface of the substrate by using NH 3.
As a preferable setting of the embodiment of the invention, the partial pressure of NH3 is 0.05-0.5, and the nitriding treatment time is 0.2-5 min.
In the invention, in a low-temperature environment, the GaN crystal nucleus and NH are subjected to step (2)4Cl solid is synchronously covered on the surface of the nitrided substrate, and then the temperature is raised to cause NH4The Cl solid is sublimated, a gap is formed between the substrate and the gallium nitride crystal, the stress action and the nucleation density are effectively reduced, and the dislocation of the GaN layer on which the nucleation is carried out is lower.
As a preferable setting of the embodiment of the invention, the low temperature range of the step (2) is 300-370 ℃, V/III is set as 100, the GaN crystal nucleus coverage rate is 42%, and the growth thickness is 50-60 nm.
As a preferable setting of the embodiment of the invention, the GaN layer in the step (4) is subjected to two-dimensional growth at a high temperature of 800-1100 ℃, the V/III is set to be 5, the growth speed is 10um/hr, and the thickness is 4-7 um.
As a preferred configuration of the embodiment of the present invention, step (5) may further include a method for maintaining the growth and morphology of the GaN single crystal thick film:
①, continuously increasing the temperature, wherein the increase range is that the temperature of the GaN monocrystal thick film increases by 1-10 ℃ every time the GaN monocrystal thick film increases by 1 mm;
② NH3 is continuously increased, and the increase amplitude is 5% -50% of the increase of NH3 (or corresponding V/III) when the GaN monocrystal thick film grows for each 1 mm.
Example 2
The HVPE-based free-standing gallium nitride single crystal provided in this example was substantially the same as the method provided in example 1, except that: the low temperature range of the step (2) is 370-440 ℃, the V/III is 200, the GaN crystal nucleus coverage rate is 56%, and the growth thickness is 60-80 nm.
As a preferable setting of the embodiment of the invention, the GaN layer in the step (4) is subjected to two-dimensional growth at a high temperature of 800-1100 ℃, the V/III is set to be 10, the growth speed is 20um/hr, and the thickness is 8-10 um.
In addition, the technical features disclosed in embodiment 1 are also applicable to this embodiment, and other technical features already disclosed in embodiment 1 are not described repeatedly herein.
Example 3
The HVPE-based free-standing gallium nitride single crystal provided in this example was substantially the same as the method provided in example 1, except that: the low temperature range of the step (2) is 440-500 ℃, the V/III is 200, the GaN crystal nucleus coverage rate is 65%, and the growth thickness is 70-100 nm.
As a preferable setting of the embodiment of the invention, the GaN layer in the step (4) is subjected to two-dimensional growth at a high temperature of 950-1100 ℃, the V/III is set to be 20, the growth rate is 30um/hr, and the thickness is 6-10 um.
In addition, the technical features disclosed in embodiment 1 are also applicable to this embodiment, and other technical features already disclosed in embodiment 1 are not described repeatedly herein.
In summary, the present invention utilizes the formation of low density and low coverage GaN crystal nucleus at low temperature, and simultaneously forms NH4Cl solid to deposit on the substrate, so that the GaN crystal nucleus only partially covers the substrate, forms high quality small crystal as a nucleation point after temperature rise annealing, and then performs two-dimensional growth to form a void layer between the substrate and the GaN layer for absorbing the stress during growth. The present invention provides high quality nucleation sites for free-standing dimensional gallium nitride growth by HVPE while reducing warpage due to stress relaxation from the voids. And the temperature is reduced at the end of the growth to eliminate cracking (the yield of the growth of the self-supporting gallium nitride is improved.
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. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments described herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A method for preparing self-supporting gallium nitride single crystal based on HVPE is characterized by comprising the following steps:
(1) providing a substrate, and cleaning the surface of the substrate in situ.
(2) Growing GaN crystal nuclei on the surface of the substrate at a low temperature, forming NH4Cl solid by HCl and NH3 at the same time, and covering the substrate by competing with the GaN crystal nuclei;
(3) raising the temperature to over 1000 ℃ for annealing treatment, and improving the quality of the GaN crystal nucleus;
(4) growing a GaN layer on the GaN crystal nucleus in a two-dimensional manner at a high temperature;
(5) continuously growing a GaN single crystal on the GaN layer at a high temperature;
(6) and cooling, and stripping the GaN single crystal from the substrate to form the self-supporting crystal.
2. The HVPE-based self-supporting gallium nitride single crystal production method according to claim 1, wherein the substrate includes, but is not limited to, sapphire substrate, SiC, GaAs, ScAlMgO4, ZnO, Si substrate, and the like.
3. The HVPE-based self-supporting gallium nitride single crystal production method according to claim 1, wherein step (1) is carried out at a high temperature of 1000-1100 ℃, comprising cleaning the surface of the substrate using a mixture of H2 and N2.
4. The HVPE-based self-supporting gallium nitride single crystal production method according to claim 3, wherein, if the substrate is sapphire, it is further necessary to nitride the surface of the substrate with NH 3.
5. The HVPE-based method for preparing a self-supporting single crystal of gallium nitride according to claim 2, wherein the partial pressure of NH3 is 0.05 to 0.5 and the nitridation treatment time is 0.2 to 5 min.
6. The HVPE-based self-supporting gallium nitride single crystal production method according to claim 1, wherein step (2) is performed at a low temperature ranging from 300 to 500 ℃, the coverage of GaN nuclei is less than 70%, and the thickness is 50 to 200 nm.
7. The HVPE-based method for preparing a free-standing gallium nitride single crystal according to claim 1, wherein the GaN layer of step (4) is grown in two dimensions at a high temperature of 800-1100 ℃, V/III is less than 20, growth rate is less than 50um/hr, and thickness is 1-20 um.
8. The HVPE-based method for preparing a free-standing gallium nitride single crystal according to claim 7, wherein the GaN layer of step (4) is grown in two dimensions at a high temperature of 800-1100 ℃, V/III is less than 5, growth rate is less than 20um/hr, and thickness is 5-10 um.
9. The HVPE-based self-supporting gallium nitride single crystal preparation method according to claim 1, wherein step (5) further comprises maintaining the GaN single crystal thick film for continued growth and morphology by:
①, continuously increasing the temperature, wherein the increase range is that the temperature of the GaN monocrystal thick film increases by 1-10 ℃ every time the GaN monocrystal thick film increases by 1 mm;
② NH3 is continuously increased, and the increase amplitude is 5% -50% of the increase of NH3 (or corresponding V/III) when the GaN monocrystal thick film grows for each 1 mm.
10. An HVPE-based self-supporting gallium nitride single crystal, characterized in that it is prepared by the preparation method according to any one of claims 1 to 6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112575378A (en) * | 2020-12-07 | 2021-03-30 | 无锡吴越半导体有限公司 | Method for realizing one-time or multiple-time hole buried insertion layer in HPVE growth |
| CN113046712A (en) * | 2021-03-10 | 2021-06-29 | 无锡吴越半导体有限公司 | Method for manufacturing gallium nitride single crystal substrate based on magnetron sputtering aluminum nitride |
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