CN109097834A - Porous network structure GaN single crystal film, preparation method and application - Google Patents
Porous network structure GaN single crystal film, preparation method and application Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 35
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 22
- 150000004820 halides Chemical class 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 12
- 239000010980 sapphire Substances 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 109
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 14
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001195 gallium oxide Inorganic materials 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002601 GaN Inorganic materials 0.000 description 77
- 229960002050 hydrofluoric acid Drugs 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000001534 heteroepitaxy Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000000927 vapour-phase epitaxy Methods 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010041662 Splinter Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003471 anti-radiation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- -1 silicon nitrides Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- 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
- 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
- C30B25/18—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
-
- 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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
-
- 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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a kind of method for preparing porous network structure GaN single crystal film, step includes: gallium oxide film of the growth thickness range at 0.1-2 microns on a sapphire substrate；It is nitrogenized under ammonia atmosphere, forms the GaN/Ga of porous web trellis distribution2O3Laminated film；Hydrofluoric acid corrosion, obtains the GaN single crystal film of porous structure.Porous network structure GaN single crystal film made from this method and its application on the substrate material as GaN thick film.High quality porous network structure GaN single crystal film can be obtained in the present invention.The crystal quality that can also improve porous network structure GaN single crystal film is further nitrogenized again.The halide gas phase epitaxial growth that thick film GaN is carried out on above-mentioned porous network structure GaN single crystal film, can obtain the GaN thick-film material of low stress high quality.
Description
Technical field
The present invention relates to a kind of porous network structure GaN single crystal films, the method and application of preparation, belong to semiconductor
Field of material technology.
Background technique
III-V nitride material (also known as GaN base material) based on GaN and InGaN, AlGaN alloy material is close
In the past few years valued novel semiconductor material again in the world.GaN base material is direct band gap semiconductor material with wide forbidden band, is had
The direct band gap of continuous variable between 1.9-6.2eV, excellent physics, chemical stability, high saturated electron drift velocity are high
The superior functions such as disruptive field intensity and high heat conductance, in short wavelength's semiconductor photoelectronic device and high frequency, high pressure, high temperature microelectronics device
Part preparation etc. has important application, purple, ultraviolet band luminescent device, sensitive detection parts such as blue for manufacture, high temperature,
High frequency, High-Field high power device, feds, anti-radiation device, piezoelectric device etc..
The fusing point of GaN single crystal is up to 2300 DEG C, and for decomposition point at 900 DEG C or so, growth needs extreme physical environment, and
Large scale GaN single crystal can not be obtained with the method that conventional crystal is grown.So most of GaN film is all in foreign substrate
What extension obtained.Mainly use heteroepitaxy method in sapphire, SiC or Si etc. applied to the GaN of semiconductor technology at present
It is prepared on substrate.In hetero-epitaxy, since there are biggish lattice mismatches and thermal expansion system between GaN material and foreign substrate
Mismatch is counted, stress is had in obtained GaN epitaxial layer and is generated in 108-109/cm2The dislocation density of magnitude, these defects drop
The low quality of epitaxial layer, limits the parameters such as thermal conductivity, the electron saturation velocities of GaN material, and leverage device can
By property, yield rate, and huge stress will cause GaN thick film and foreign substrate splinter, thus can not apply.
GaN substrate growth mainly has vapor phase method and liquid phase method.Liquid phase method include high pressure nitrogen solwution method, sodium flux growth metrhod and
Ammonia heat method etc.；Vapor phase method has vapor transportation method and halide vapor phase epitaxy etc..Obtain high-quality GaN self-supported substrate simultaneously at present
It is that halide vapor phase epitaxy high-speed is aided with using the methods of horizontal extension, suspension extension by the main method for realizing volume production
Epitaxy technology grows thick film, finally removes former substrate, to obtain the lower Free-standing GaN substrate material of dislocation density.So far
Until the present, using various technical matters and it is aided with the Free-standing GaN substrate that halide gas phase epitaxial growth obtains, dislocation density is low
In 106cm-2, area has reached 2 inches.But the demand of practical application it is not able to satisfy still far.Wherein GaN horizontal extension
The method for improving quality mainly forms specific slot or network etc. in substrate surface, such as can refer to patent: " lateral out
Prolong technology growth high-quality gallium nitride film ", patent No. ZL021113084.1.
Gallium oxide (Eg=4.8-4.9eV) is used as novel ultra-wide bandgap semiconductor, has high conductivity, high breakdown field strength etc.
Advantage all has high transparency in visible light and UV light region.β-Ga2O3(100) dissociation face in high temperature NH3The nitrogen of atmosphere
Will do it resurfacing phenomenon under change effect, resurfacing generates the surface to match with GaN lattice, can be used as buffer layer into
Row subsequently epitaxial growing GaN thick film.This homo-substrate epitaxial growth can significantly reduce stress and dislocation density in thick film, mention
High GaN material quality.
The present invention gives utilization gallium oxide thin film silicon nitrides to form porous network structure GaN single crystal film, and passes through hydrogen fluorine
Acid corrosion and the method and technique for further increasing its crystal quality are nitrogenized again.
Summary of the invention
The purpose of the present invention is forming porous network structure GaN single crystal film using gallium oxide thin film silicon nitride, and pass through hydrogen
Fluoric acid corrosion further increases its crystal quality.
The technical scheme adopted by the invention is as follows:
A method of porous network structure GaN single crystal film being prepared, step includes:
(1) it at 0.1-2 microns and is evenly distributed with halide gas phase epitaxial growth thickness range on a sapphire substrate
Ga2O3Film refers to Ga wherein being evenly distributed2O3The thickness uniformity is 90% or more；
(2) to Ga in ammonia atmosphere2O3Film is partly or entirely nitrogenized, and the GaN/Ga of distributed in grid is formed2O3
Laminated film or GaN single crystal film；
(3) with hydrofluoric acid by GaN/Ga2O3Ga in laminated film2O3Or remaining oxygen removal in GaN single crystal film, it obtains
To the GaN single crystal film of porous structure.
Preferably, the GaN single crystal film after corroding hydrofluoric acid in step (3) further nitrogenizes.
Preferably, in step (2), by Ga made from step (1)2O3Film is placed in high temperature process furnances, in ammonia atmosphere
Lower nitridation 1-5h, obtains porous web trellis distribution GaN/Ga by 900-1100 DEG C of temperature range2O3Compound structure film or GaN single crystal
Film, ammonia flow: 100-5000sccm.
Preferably, the GaN single crystal film after corroding hydrofluoric acid in step (3) is placed in high temperature process furnances in ammonia gas
Nitrogenize 0.5-2h under atmosphere, 1000-1100 DEG C of temperature range, ammonia flow: 200-1000sccm.
Preferably, in step (1), substrate is placed in halide gas phase epitaxial growth system, in low-temperature space, metal Ga with
HCl or Cl2Reaction generates GaCl as gallium source, and temperature is 800-900 DEG C；In high growth temperature area, O2As oxygen source, GaCl and O2
Mixing reacts, and obtains Ga2O3Film-substrate, high-temperature region temperature are 800-1050 DEG C, and pressure is 1 atmospheric pressure, O2/ Ga is defeated
Inbound traffics ratio is 1.5-15.
Preferably, hydrofluoric acid concentration is higher than 30% in step (3), etching time 1-24h.
Porous network structure GaN single crystal film and porous network structure GaN single crystal film obtained exists in aforementioned manners
As the application on the substrate material of GaN thick film.
The step of application, is: using halide gas phase epitaxial growth GaN thick film on GaN single crystal film, is then down to
Room temperature, natural separation between GaN thick film and substrate obtain Free-standing GaN thick film.
Nitridation time and ammonia flow are controlled, Ga may be implemented2O3Film portion nitridation forms the distribution of porous web trellis
GaN/Ga2O3Laminated film, but even Ga2O3All nitridation forms holey GaN single crystal film to film, until sapphire circle
All it is GaN at face, at this time still with the presence of part oxygen in film, still can be corroded with further progress hydrofluoric acid to go deoxygenation.
The present invention uses halide gas phase epitaxial growth gallium oxide film in the foreign substrates such as sapphire, and in ammonia atmosphere
In to gallium oxide film carry out nitridation form porous network structure GaN single crystal film, using hydrofluoric acid (HF) corrode method pair
Film after nitridation is corroded, and removes the gallium oxide in film, it is thin that high quality porous network structure GaN single crystal can be obtained
Film.The halide gas phase epitaxial growth that thick film GaN is carried out on above-mentioned porous network structure GaN single crystal film, can obtain low
The GaN thick-film material of stress high quality.Using HF etching away gallium oxide, can to avoid in subsequent epitaxial GaN thick film oxygen expand
It is dissipated in GaN thick film, forms various oxygen related defects, lead to higher unintentional dosed carrier concentration, reduce GaN thick film
Crystal quality；Remove gallium oxide simultaneously, is also beneficial to reduce stress and defect in monocrystalline GaN film.It further nitrogenizes again also
Atomic arrangement in GaN can be made to finely tune, further decrease defect and stress, so that it is mono- to improve porous network structure GaN
The crystal quality of brilliant film, the crystal quality of the GaN thick film of extension can also further increase on this basis.It is formed in this patent
Porous network structure GaN single crystal film, be placed on extension in halide gas phase epitaxial reaction chamber, be similar to carry out horizontal extension
(specific embodiment can refer to patent: " horizontal extension technology growth high-quality gallium nitride film ", the patent No. for growth
ZL021113084.1), high quality low dislocation density GaN thick film can be obtained.GaN thick film alleged by the present invention refers to that thickness is micro- 10
Meter or more GaN film.
Detailed description of the invention
Fig. 1 is the surface topography SEM figure in the embodiment of the present invention 1 after gallium oxide thin film silicon nitride, and porous structure is GaN single crystal
Film.
Fig. 2 is to be corroded using hydrofluoric acid to the film formed after gallium oxide nitridation in the embodiment of the present invention 1, is obtained
The section SEM of porous network structure GaN single crystal film schemes.
Specific embodiment
Embodiment 1
This prepares the method for porous network structure GaN single crystal film, and step includes:
(1) Sapphire Substrate is cleaned and handled, is evenly distributed on a sapphire substrate with halide gas phase epitaxial growth
Ga2O3Film；In low-temperature space, metal Ga and HCl or Cl2Reaction generates GaCl as gallium source, and temperature is 850 DEG C；In high growth temperature
Area, O2As oxygen source, GaCl and O2Mixing reacts, and obtains Ga2O3Film, high-temperature region temperature are 950 DEG C, and pressure is 1 big
Air pressure, O2/ Ga input flow rate ratio is 3.Adjust growth time, the gallium oxide film of available different-thickness.Control Ga2O3It is thin
The growth thickness of film is at 1 micron.
(2) sample of step 1 is taken out at room temperature and is placed in high-temperature tubular quartz furnace, nitrogenizes 2h under ammonia atmosphere,
1000 DEG C of temperature range；Obtain distributed in grid GaN/Ga2O3Compound structure film, surface topography is as shown in Figure 1, from figure
It can be seen that the surface of otherwise smooth forms porous reticular structure, this is because nitridation causes gallium oxide to decompose and forms GaN
Caused by；Ammonia flow: 3000sccm；
(3) 2 sample of above-mentioned steps is placed in 46% concentration hydrofluoric acid and impregnates 12h, the GaN for obtaining porous structure is mono-
Brilliant film, as shown in Fig. 2, can be seen from the chart that bore dia becomes larger, pore surface structure is more apparent；Partial hole is intended to GaN
Hexagonal structure；Platform becomes smaller between hole, this is because caused by the gallium oxide that part does not nitrogenize is corroded.
Embodiment 2
This prepares the method for porous network structure GaN single crystal film, and step includes:
(1) Sapphire Substrate is cleaned and handled, is evenly distributed on a sapphire substrate with halide gas phase epitaxial growth
Ga2O3Film；In low-temperature space, metal Ga and HCl or Cl2Reaction generates GaCl as gallium source, and temperature is 800 DEG C；In high growth temperature
Area, O2As oxygen source, GaCl and O2Mixing reacts, and obtains Ga2O3Film, high-temperature region temperature are 800 DEG C, and pressure is 1 big
Air pressure, O2/ Ga input flow rate ratio is 1.5.Adjust growth time, the gallium oxide film of available different-thickness.Control Ga2O3
The growth thickness of film is at 0.1 micron.
(2) sample of step 1 is taken out at room temperature and is placed in high-temperature tubular quartz furnace, nitrogenizes 1h under ammonia atmosphere,
900 DEG C of temperature range；Obtain distributed in grid GaN/Ga2O3Compound structure film；Ammonia flow: 100sccm；
(3) corrosion 1h is carried out to sample with 53% concentration hydrofluoric acid, obtains the GaN single crystal film of porous structure；
(4) the GaN single crystal film of porous structure is placed in high temperature process furnances and nitrogenizes 0.5-2h again under ammonia atmosphere,
900-1100 DEG C of temperature range, ammonia flow: 100-5000sccm.
Embodiment 3
This prepares the method for porous network structure GaN single crystal film, and step includes:
(1) Sapphire Substrate is cleaned and handled, is evenly distributed on a sapphire substrate with halide gas phase epitaxial growth
Ga2O3Film；In low-temperature space, metal Ga and HCl or Cl2Reaction generates GaCl as gallium source, and temperature is 900 DEG C；In high growth temperature
Area, O2As oxygen source, GaCl and O2Mixing reacts, and obtains Ga2O3Film, high-temperature region temperature are 1050 DEG C, and pressure is 1
Atmospheric pressure, O2/ Ga input flow rate ratio is 15.Adjust growth time, the gallium oxide film of available different-thickness.Control Ga2O3
The growth thickness of film is at 2 microns.
(2) sample of step 1 is taken out at room temperature and is placed in high-temperature tubular quartz furnace, nitrogenizes 5h under ammonia atmosphere,
1100 DEG C of temperature range；Obtain the GaN single crystal film of porous web trellis distribution；Ammonia flow: 5000sccm；
(3) corrosion 48h is carried out to sample with 30% concentration hydrofluoric acid, obtains the GaN single crystal film of porous structure.
Embodiment 4
The halide gas phase extension that GaN thick film is carried out on the porous network structure GaN single crystal film made from embodiment 1 is raw
It is long, obtain GaN thick film；In halide gas phase epitaxial system, low-temperature space metal Ga is reacted with HCl generates GaCl as gallium source,
Temperature is 800-900 DEG C；In high growth temperature area, ammonia is as nitrogen source, GaCl and NH3Mixing reacts, and obtains GaN thick film,
High-temperature region temperature is 950-1100 DEG C；Pressure be 1 atmospheric pressure, control growth time, make the thickness of GaN thick film 10 microns with
On.
Claims (9)
1. a kind of method for preparing porous network structure GaN single crystal film, step include:
(1) on a sapphire substrate with halide gas phase epitaxial growth thickness range at 0.1-2 microns and the Ga that is evenly distributed2O3
Film；
(2) to Ga in ammonia atmosphere2O3Film is partly or entirely nitrogenized, and the GaN/Ga of distributed in grid is formed2O3It is compound
Film or GaN single crystal film；
(3) with hydrofluoric acid by GaN/Ga2O3Ga in laminated film2O3Or remaining oxygen removal in GaN single crystal film, it obtains porous
Change the GaN single crystal film of structure.
2. the method according to claim 1 for preparing porous network structure GaN single crystal film, it is characterised in that: step (3)
It is middle hydrofluoric acid is corroded after GaN single crystal film further nitrogenize.
3. the method according to claim 1 or 2 for preparing porous network structure GaN single crystal film, it is characterised in that: step
(2) in, by Ga made from step (1)2O3Film is placed in high temperature process furnances, and 1-5h, temperature range are nitrogenized under ammonia atmosphere
900-1100 DEG C, obtain porous web trellis distribution GaN/Ga2O3Compound structure film or GaN single crystal film, ammonia flow: 100-
5000sccm。
4. the method according to claim 3 for preparing porous network structure GaN single crystal film, it is characterised in that: step (3)
It is middle hydrofluoric acid is corroded after GaN single crystal film be placed in high temperature process furnances under ammonia atmosphere and nitrogenize 0.5-2h, temperature model
1000-1100 DEG C is enclosed, ammonia flow: 200-1000sccm.
5. the method according to claim 3 for preparing porous network structure GaN single crystal film, it is characterised in that: step (1)
In, substrate is placed in halide gas phase epitaxial growth system, in low-temperature space, metal Ga and HCl or Cl2Reaction generates GaCl conduct
Gallium source, temperature are 800-900 DEG C；In high growth temperature area, O2As oxygen source, GaCl and O2Mixing reacts, and obtains Ga2O3It is thin
Film, high-temperature region temperature are 800-1050 DEG C, and pressure is 1 atmospheric pressure, O2/ Ga input flow rate ratio is 1.5-15.
6. the method according to claim 5 for preparing porous network structure GaN single crystal film, it is characterised in that: step (3)
Middle hydrofluoric acid concentration is higher than 30%, etching time 1-48h.
7. porous network structure GaN single crystal film-substrate made from the method in claim 1-6.
8. application of the porous network structure GaN single crystal film on the substrate material as GaN thick film.
9. application according to claim 8, step are: using halide on porous network structure GaN single crystal film
Vapor phase epitaxial growth GaN thick film, is then down to room temperature, and natural separation between GaN thick film and substrate obtains Free-standing GaN thick film.
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| CN113702447A (en) * | 2020-05-22 | 2021-11-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gallium oxide nano-structure device and preparation method and application thereof |
| CN114262938A (en) * | 2021-12-17 | 2022-04-01 | 南京大学 | (010) Application of surface gallium oxide single crystal in preparation of nonpolar GaN substrate |
| CN114293251A (en) * | 2021-12-20 | 2022-04-08 | 南京大学 | Method for preparing high-quality porous GaN template crystal |
| CN117457497A (en) * | 2023-12-21 | 2024-01-26 | 太原理工大学 | Porous gallium oxide/gallium nitride heterojunction and preparation method and application thereof |
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