CN1723302A - A substrate for epitaxy and a method of preparing the same - Google Patents
A substrate for epitaxy and a method of preparing the same Download PDFInfo
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- CN1723302A CN1723302A CNA200380105624XA CN200380105624A CN1723302A CN 1723302 A CN1723302 A CN 1723302A CN A200380105624X A CNA200380105624X A CN A200380105624XA CN 200380105624 A CN200380105624 A CN 200380105624A CN 1723302 A CN1723302 A CN 1723302A
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- 239000000758 substrate Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims description 66
- 238000000407 epitaxy Methods 0.000 title abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 73
- 150000004767 nitrides Chemical class 0.000 claims abstract description 66
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 22
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 22
- 238000001451 molecular beam epitaxy Methods 0.000 claims abstract description 13
- 238000000927 vapour-phase epitaxy Methods 0.000 claims abstract description 7
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims abstract 6
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 claims abstract 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 109
- 229910052733 gallium Inorganic materials 0.000 claims description 109
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 58
- 238000001556 precipitation Methods 0.000 claims description 49
- 238000005516 engineering process Methods 0.000 claims description 39
- 229910052782 aluminium Inorganic materials 0.000 claims description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 35
- 238000002425 crystallisation Methods 0.000 claims description 34
- 239000004411 aluminium Substances 0.000 claims description 31
- 229910021529 ammonia Inorganic materials 0.000 claims description 29
- 230000008025 crystallization Effects 0.000 claims description 28
- 230000005622 photoelectricity Effects 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 24
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 239000012808 vapor phase Substances 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
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- 238000004140 cleaning Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910002704 AlGaN Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011089 carbon dioxide Nutrition 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
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- 239000011261 inert gas Substances 0.000 claims description 2
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- 238000013517 stratification Methods 0.000 claims 1
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 81
- 229910002601 GaN Inorganic materials 0.000 description 37
- 239000002994 raw material Substances 0.000 description 29
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 15
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- 238000006243 chemical reaction Methods 0.000 description 9
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- -1 aminoacyl imines Chemical class 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
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- 150000002259 gallium compounds Chemical class 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 4
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- 229910045601 alloy Inorganic materials 0.000 description 3
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- 230000001105 regulatory effect Effects 0.000 description 3
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- 229910052717 sulfur Inorganic materials 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 206010020880 Hypertrophy Diseases 0.000 description 1
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 239000005864 Sulphur Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000001657 homoepitaxy Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
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Images
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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/005—Epitaxial layer growth
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Recrystallisation Techniques (AREA)
Abstract
The template type substrate is used for opto-electric or electrical devices and comprises A) a layer of bulk mono-crystal nitride containing at least one element of alkali metals (Group I, IUPAC 1989) and B) a layer of nitride grown by means of vapor phase epitaxy growth wherein the layer A) and the layer B) are combined at non N-polar face of the layer A) and N-polar face of the layer B). Therefore, the template type substrate has a good dislocation density and a good value of FWHM of the X-ray rocking curve from (0002) plane less than 80, so that the resulting template type substrate is very useful for the epitaxy substrate from gaseous phase such as MOCVD, MBE and HVPE, resulting in possibility of making good opto-electric devices such as Laser Diode and large-output LED and good electric devices such as MOSFET.
Description
Technical field
The present invention relates to a kind of template type substrate that is used for photoelectric device such as LED and LD or electric device such as MOSFET.
Background technology
The substrate that is used for vapour phase epitaxy at present generally includes sapphire, SiC, GaAs and Si, and the gained epitaxial film that is grown on the substrate still has disadvantageous 10
9/ cm
2High dislocation density.Therefore, in substrate, it can be reduced to 10 with dislocation desity with ELOG type structure applications in existing proposition
6/ cm
2, but this density is still too high, so that can not guarantee many electronics and photoelectric device, and especially high-power semiconductor laser is carried out correct function.In addition, another problem that also exists is because the ELOG structure causes the front face area of gained substrate to reduce.Therefore, we have proposed to obtain other technology that monocrystalline contains gallium or aluminiferous nitride, for example, and polish patent application No.P-347918, wherein having proposed a kind ofly by containing the method that recrystallization the ammonia solution obtains the bulk-shaped monocrystal nitride from overcritical, is representative with the gan.Use and aforementionedly overcritically contain the bulk-shaped monocrystal gan that ammonia solution obtains and be characterised in that low-dislocation-density is (in the example of block GaN: 10
4/ cm
2).Yet it obtains under low growth velocity, in fact, and than much lower times of the growth velocity of using method of vapor-phase growing.
The present inventor further finds from its most advanced and sophisticated research, if contain crystallization makes the ammonia solution bulk mono-crystalline gallium-containing or the substrate surface of aln precipitation is implemented this vapor phase growth technology utilizing from overcritical, the main surface that keeps all substrates simultaneously is for Ga-completely extremely is used to make the further epitaxy technique of photoelectricity or electric device in the surface, can obviously reduce the dislocation desity of gas-phase epitaxial layer and do not need the ELOG structure.This is different from ELOG type substrate fully.
Summary of the invention
Therefore, the object of the invention provides template type substrate and reaches the method for preparing template type substrate based on novel bulk-shaped monocrystal nitride.
According to first aspect present invention, be provided for the template type substrate of photoelectricity or electric device, it comprises A) contain at least a alkali metal (I family, IUPAC 1989) the bulk-shaped monocrystal nitride layer, and B) nitride layer by vapor phase epitaxial growth, its middle level A) with a layer B) be combined in a layer A) a non-N polar surface (polar face) and a layer B) N polar surface place.In this manual, the non-polar plane of the nitride meaning is the polar surface of any other element except nitrogen in nitride.In containing the example of gallium nitride, non-N polar surface is often referred to the gallium polar surface, and in the example of aluminiferous nitride, is often referred to the aluminium polar surface.
According to the present invention, if substrate can use the overcritical method preparation that contains ammonia solution, we can obtain being grown in Al so
xGa
1-xThe Ga of the single crystalline substrate of N (wherein 0≤x≤1) or the gas-phase epitaxial layer of the excellence on the Al-polar surface, and gained comprises a layer A) with a layer B) template type substrate make by vapor phase epitaxial growth aspect photoelectricity or the electric device very useful.
In the present invention, bulk-shaped monocrystal nitride layer A) comprise and contain gallium or aln precipitation and aluminiferous nitride and with general formula Al
xGa
1-xN represents, wherein 0≤x≤1.Generally with layer A) be provided as AlN or GaN single crystalline substrate, it can be by WO02/101120 and the described supercritical ammine dissolution method preparation of WO02/101124.Therefore, in this manual, the supercritical ammine dissolution method refers to the technology defined in this paper and WO02/101120 and WO02/101124.
In the present invention, the nitride layer B by vapor phase epitaxial growth) with general formula Al
xGa
1-x-yIn
yN represents, wherein 0≤x≤1,0≤y＜1,0≤x+y≤1.By MOCVD (metal organic chemical vapor deposition), HVPE (hydride gas-phase epitaxy) or MBE (molecular beam epitaxy) method, can be with layer B) preparation has a layer A) substrate on, though described method is known and not in this explanation, those skilled in the art can be easy to the known vapour phase epitaxy method of this class is applied to the present invention.In the present invention, layer B) generally include GaN, AlGaN, InGaN and AlGaInN compound semiconductor layer.
In a preferred embodiment of the invention, layer B) can constitute the first layer B1 by two-layer at least) can have a layer A by MOCVD or MBE preparation) substrate on, second layer B2) can utilize as shown in Figure 7 HVPE preparation at the first layer B1) on.
The template of this gained can be basically be made of the whole Ga-polar surface zone in a side of substrate, that is, surpass 95%, preferably surpass 99% Ga-polar surface.With by ELOG method preparation, compare owing to some N polar surface zone has on similar face less than the HVPE GaN substrate in 90%Ga polar surface zone, obtain having about the superior quality of the FWHM of dislocation desity and X ray rocking curve and the substrate of whole Ga polar surface at this.
According to second aspect present invention, template type substrate can comprise bulk-shaped monocrystal nitride layer A), its preparation overcritically contains crystalline nitride layer B in the ammonia solution having by what containing at least a alkali metal) crystal seed on.At this, shown in Fig. 8 A, template type substrate may further include the nitride layer C that contains gallium or aluminium that utilizes vapor phase epitaxial growth), wherein contain at least a alkali metal (I family, IUPAC 1989) bulk-shaped monocrystal nitride layer A) preparation in non-N polar surface, as Ga polar surface or Al polar surface and crystal seed layer B) N polar surface such as layer A1) with a layer A2) on both, and layer C) be combined in a layer A1) a non-N polar surface and a layer C) N polar surface place.Therefore, the nitride layer C that contains gallium or aluminium) can utilize MOCVD, HVPE or MBE the preparation at layer A1) substrate on.In a preferred embodiment, layer C) can constitute the first layer C1 by two-layer at least) be to utilize MOCVD or MBE preparation at layer A1) substrate on, second layer C2) can utilize HVPE preparation shown in Fig. 8 B at the first layer C1) on.According to the present invention, the first layer C1) can protect substrate A) surface is not used to a layer C2) the HVPE process disturbance and also can avoid basic metal from substrate A) be diffused into a layer C2).Layer C1) preferably prepare being lower than under the formation temperature of its monocrystalline.
According to the present invention, can obtain having 10
6/ cm
2Or lower dislocation desity and from the FWHM value of (002) planar X ray rocking curve template type substrate less than 80 rads (arcsec).
In the molten technology of supercritical ammine, we have found fast 4 times or more of the growth of growth fraction C axle of A axle, and the C axle growth of the A axle growth fraction in the supercritical ammine dissolution method in identical supercritical ammine dissolution method significantly reduced dislocation desity.Therefore, according to new aspect of the present invention, we can obtain template type substrate as shown in Figure 9, its middle level A) is substrate with a pair of C planar surface and 1 English inch or larger diameter, it is that the initial substrates that is made by the growth of the A direction of principal axis of the bulk-shaped monocrystal nitride in containing the supercritical ammine solution of at least a alkali metal is prepared, shown in dotted line.Surprised is that this initial substrates has 10
4/ cm
2Or lower dislocation desity.
Template type substrate according to the present invention is characterised in that even is containing gallium or aluminum nitride layer B) or C) and the layer B1) and B2) or C1) and alkali metal concn C2) less than crystal of nitride in by the supercritical ammine solution that contains at least a alkali metal prepared the layer A) in alkali metal concn.Because alkali-metal content is by at form layers B) or C) and a layer B1) and B2) or C1) and C2) during the technology from layer A) diffusion institute caused.At this, layer B), C B1)) or C1) can utilize MOCVD or MBE to prepare and preferred thickness is 0.1-3 μ m.
Under the situation of template type substrate, utilize the layer C of method of vapor-phase growing gained according to the present invention) also with as a layer B) qualification shown in general formula Al
xGa
1-x-yIn
yN represents, wherein 0≤x≤1,0≤y＜1,0≤x+y≤1.Therefore, in a preferred embodiment of the invention, layer B) or C) can be the combination of AlGaN and GaN bilayer.Be lower than the first layer B1 of the AlGaN of monocrystalline temperature in formation temperature) or situation C1) under, will improve the second layer B2 of GaN) or C2) crystalline quality.
Under situation according to template type substrate of the present invention, because vapor phase epitaxial growth, layer B) or C) be contain silicon (Si) or oxygen (O) as the nitride that contains gallium or aluminium of giving the body hotchpotch contain magnesium (Mg) or zinc (Zn) as the nitride that contains gallium or aluminium of acceptor doped thing.Concentration of dopant is preferably 10
17/ cm
3-10
21/ cm
3
According to a third aspect of the invention we, provide the technology of preparation template type substrate, it may further comprise the steps:
(a) by containing nitride that ammonia solution crystallization on crystal seed contains gallium or aluminium and prepare the bulk-shaped monocrystal nitride layer A of having that contains at least a alkali metal (I family, IUPAC 1989)) as the thickness of substrate from overcritical; (b) by at layer A) Al or the vapor phase epitaxial growth on the Ga-polar surface form nitride layer B) be combined in a layer A to obtain comprising) and Al or a Ga-polar surface and a layer B) the layer A at N polar surface place) with a layer B) substrate.
In a preferred embodiment of the present invention, may need another step (c): face polishing layer B) to be obtaining being used for the substrate of vapour phase epitaxy, thereby obtains being further used for epitaxially grown excellent surface characteristic.The gained template type substrate can be under not hydrogenous atmosphere, and experience comprises a layer A under about 600-1050 ℃ temperature) and the anneal of substrate B), thereby produce the material that has than more crystalline quality before the annealing.This annealing steps preferably carries out in the inert gas atmosphere that is added with 10-30 volume % oxygen, and this annealing steps can one step or multiple step implement until reaching required impurity (as hydrogen and/or ammonia or by the formed ion of the impurity that during crystallization and/or annealing process, forms) content.
In addition, need to utilize sometimes in the overcritical environment that contains ammonia solvent, water or carbonic acid gas or experience gaseous hydrogen, nitrogen or ammonia effect cleaning, from the bulk-shaped monocrystal nitride, remove impurity.In this example, preferably by means of the using ultrasound ripple or be exposed to and implement this cleaning step in the electron beam.
Description of drawings
The present invention is described in the accompanying drawings:
Fig. 1 is the figure that shows that temperature changes in time in the autoclave, p=constant wherein, and be illustrated in the relation between the temperature change and dissolving and crystallization processes in the situation of the present invention;
Fig. 2 is the figure that shows that pressure changes in time in the autoclave, and wherein T=constant, and explanation is relation between pressure change and dissolving and the crystallization processes in situation of the present invention;
Fig. 3 is autoclave and the vertical cross-section diagram that is used for implementing stove group of the present invention;
Fig. 4 is the skeleton view that is used for obtaining the equipment of bulk-shaped monocrystal gan;
Fig. 5 is presented at the supercritical ammine that comprises ammonification potassium (to have mineralizer: NH
3=0.07) GaN solubleness in and the relation between the pressure, wherein T=400 ℃ and T=500 ℃; At last,
Fig. 6 illustrates the figure that temperature changes in time in the autoclave for the present embodiment;
Fig. 7 is the schematic section according to first embodiment of template type substrate of the present invention;
Fig. 8 A, 8B are the schematic sections according to second embodiment of template type substrate of the present invention;
Fig. 9 is the orthographic plan that the technology of A direction of principal axis growth crystal seed constructed in accordance is shown.
Embodiment
The present invention is based on ammonobase crystal growth and can obtain the nitride that the monocrystalline of selective deposition on seed surface contains gallium or aluminium by producing chemistry transmission in the ammonia solvent in overcritical the containing of containing one or more mineralizers that influence its ammonobase characteristic.
This technology is characterised in that it can obtain having the bulk-shaped monocrystal template type substrate of high structural quality layer, wherein contain ammonia solution and alkalimetal ion, and on the nitride layer that contains gallium or aluminium that obtains by method of vapor-phase growing, deposit the nitride layer that contains gallium or aluminium because generation is overcritical in autoclave.With material dissolution in autoclave, then than the material dissolution that will contain gallium in described supercritical solvent under higher temperature and/or the lower pressure, the nitride that will contain gallium or aluminium from described solution selective crystallization at seed surface.
The purpose of first embodiment is during second technology-crystallization, carries out selective crystallization at seed surface.Therefore, second embodiment of the invention is paid close attention to the crystallization processes of the nitride of bulk mono-crystalline gallium-containing or aluminium, it is characterized in that it can obtain having the bulk-shaped monocrystal template type substrate of high structural quality layer, wherein on the nitride layer that contains gallium or aluminium that obtains by method of vapor-phase growing, the nitride layer that contains gallium or aluminium that deposition has high structural quality, and described technology is included in dissolves overcritical containing in ammonia solution and the alkalimetal ion, generation has the supercritical solution of the negative temperature coefficient of gan solubleness, and at least in the autoclave zone of placing crystal seed, produce the oversaturated zone of the relative crystal seed of this supercritical solution, and by suitable increase temperature and/or reduce pressure and regulate concentration so that guarantee not take place spontaneous crystallization, and finish on the seed surface of element nitride crystal in being placed on autoclave that contains gallium or aluminium independent selective growth.
Though second embodiment produces simultaneously two zones in autoclave: dissolve area and crystallizing field, suggestion is controlled supersaturation with respect to the supercritical solution of crystal seed by regulating solvent temperature and Tc.And, if the temperature of crystal region is set in 300-600 ℃,, and the temperature head between dissolve area in the autoclave and the crystallizing field kept below 150 ℃ with easy controlled temperature, be preferably below 100 ℃.Can regulate supercritical solution supersaturation by in autoclave, placing one or more baffle plates, to isolate dissolve area (having lesser temps) and crystallizing field (having comparatively high temps) and to control convection rate between the described zone with respect to crystal seed.In addition, if in autoclave, produce two zones: dissolve area and crystallizing field with proper temperature difference, can utilize the raw material that contains gallium or aluminium to regulate supercritical solution supersaturation with respect to crystal seed, this raw material is introduced the GaN of crystallized form, and its total surface area surpasses the total surface area of this crystal seed.
In the first embodiment, introduce alkalimetal ion, especially do not contain XVII family element (halogen) with the form of basic metal and/or alkali metal compound and/or its mixture.This alkalimetal ion can comprise and is selected from Li
+, Na
+And K
+One or more types.Be 1 with basic metal and amide thereof and trinitride to the mol ratio of ammonia preferably: 200-1: 2 form is used them.The raw material that is dissolved in the supercritical solution is to contain the nitride of gallium or aluminium or the precursor of gallium, and it can form the gallium compound that dissolves in the supercritical solvent.
Though the technology described in the present invention is based on the reaction in the ammonobase environment of cleaning, if other element of chlorine or XVII family does not have negative impact to the environment that described reaction takes place, then also can use raw material by the GaN form that HVPE method or other chemical processes obtain.
Raw material can be overcritical contain in the ammonia solvent experience reversible dissolution process contain gallium or aln precipitation.Its also can with merge at the overcritical gallium that contains in the ammonia solvent experience irreversible reaction.
Use with the form of gan and to contain gallium or aln precipitation helps controlling whole crystallisation process.The preferred crystal seed that uses monocrystalline GaN, yet below also can use: by the GaN of HVPE method or scorification acquisition, by the crystal seed that high pressure method obtains, this crystal seed has A (1120), M (1 100) or R (1 102) surface that the bulk-shaped monocrystal that obtains from the supercritical ammine dissolution method cuts out.For the crystallization purpose, also can use to have N polar C (0001) surface.
In the present invention, common parallel the carrying out of dissolving and crystallisation process, and its while spatial separation in autoclave.In other words, in alkali metal containing ionic autoclave, obtain the overcritical ammonia solvent that contains.This dissolution with solvents contains the raw material of gallium or aluminium, and under the condition of temperature higher than the dissolution process of raw material and/or lower pressure, contains the crystallization of gallium or aln precipitation from supercritical solution on seed surface.
In the first embodiment, recommend with shift supercritical solution to have higher temperature and/or more the separate processes at low pressure place replenish the dissolution process that contains gallium or aluminum-containing raw material.At this, form two zones in the autoclave at least, and the raw material that will contain gallium or aluminium is configured in cryogenic dissolving zone, and crystal seed is configured in the pyritous crystal region with differing temps.Should set the feasible chemistry transmission of guaranteeing through supercritical solution of the temperature difference between dissolving zone and the crystal region, it mainly takes place by convection process.The temperature difference between dissolving zone and the crystal region surpasses 1 ℃, is preferably 5-150 ℃, most preferably is lower than 100 ℃.
Preferably, the nitride of gained of the present invention has general formula Al
xGa
1-x-yIn
yN, wherein 0≤x≤1,0≤y＜1,0≤x+y≤1.Supercritical solvent limits as follows: it comprises NH
3And/or its derivative and alkalimetal ion form or the mineralizer of sodium or potassium ion form at least.Mainly by containing gallium or aln precipitation or its precursor is formed, described precursor is selected from raw material: trinitride, imide, aminoacyl imines (amido-imides), acid amides (amides), hydride, the metallic compound that contains gallium or aluminium and alloy and gallium etc.Can further find the definition of precursor in this article.
In the present invention, crystal seed contains the crystallizing layer of the element (IUPAC 1989) that contains gallium or aln precipitation or other XIII family at least.The surface dislocation density of preferred this layer is lower than 10
6/ cm
2
In the present invention, this crystallization that contains gallium or aln precipitation can occur under 100 ℃-800 ℃ the temperature, and preferred 300 ℃-600 ℃, most preferably 400 ℃-550 ℃.During containing gallium or aln precipitation crystallization, pressure can be 10-1000MPa, is preferably 100-550MPa, most preferably is 150-300MPa.
The concentration of regulating the alkalimetal ion in the supercritical solvent is to guarantee raw material and the appropriate solubility matter that contains gallium or aln precipitation, and alkalimetal ion is controlled at 1 to the mol ratio of other materials in supercritical solvent: 200-1: 2 scope, be preferably 1: 100-1: 5, most preferably be 1: 20-1: 8.
In the present invention, obtain the growth that monocrystalline contains gallium or aln precipitation by containing one or more mineralizers that influence its ammonobase characteristic.Therefore, this is the ammonobase crystallization technique, and term used in this invention should be according to understanding to give a definition:
XIII family element nitride refers to the XIII family element of independent or any combination, the i.e. nitride of aluminium, gallium and indium.Containing gallium nitride is most preferred nitride.
Contain the nitride that gallium or aln precipitation refer to gallium (or aluminium) and any other XIII family element (according to IUPAC, 1989).It include but not limited to binary compound-GaN (or AlN), and ternary compound-AlGaN, InGaN or quaternary compound AlInGaN are in any case preferably comprise the gallium of the main part that all is higher than the hotchpotch contents level.Can in its structure, improve characteristic for the composition of other element of gallium (or aluminium) until its non-contravention ammonobase crystallization technique.(described general formula only attempts to provide the composition of nitride.It does not plan to point out its relative quantity.)
Bulk mono-crystalline gallium-containing or aln precipitation refer to for containing the single crystalline substrate of gallium or aln precipitation form, can obtain opto-electronic device thereon, as: utilize the MOCVD method or utilize epitaxial growth method such as photodiode of HVPE method (LED) or laser diode (LD).
C-, A-or M-plane refer to C-, A-, the M-planar surface of six sides' XIII family element nitride crystal.
The precursor that contains gallium or aln precipitation is to comprise the material or the mixture of gallium (aluminium) at least, its element that also can comprise basic metal, XIII family is (according to IUPAC, 1989), nitrogen and/or hydrogen, and gallium, its alloy or metallic compound, hydride, acid amides, imide, aminoacyl imines and trinitride, it can form gallium compound in following defined overcritical containing in the ammonia solvent.
The raw material that contains gallium or aluminium is nitride or its precursor that contains gallium or aluminium.The form of raw material can be: the GaN (AlN) that obtains by any means, for example, melting method, HNP method, HVPE method, or by the overcritical polycrystal GaN (AlN) that chemical reaction caused obtains from gallium (aluminium) original position that contains in the ammonia solvent.
The overcritical ammonia solvent that contains is the supercritical solvent of being made up of the ammonia that is used for dissolving the raw material that contains gallium or aluminium at least, and it contains the alkalimetal ion of one or more types.This is overcritical to contain derivative and/or its mixture, the especially hydrazine that ammonia solvent also can contain ammonia.
Mineralizer is to transmit the alkalimetal ion of one or more types to the overcritical ammonia solvent that contains, and supports to contain gallium or aln precipitation dissolved substances.
The material that contains the oxygen-free species that the ammonobase characteristic that causes supercritical solution weakens is selected from:
A) A
mB
nCompound, wherein A refers to H
+And/or metal, be preferably basic metal, NH
4 +, Si, S, P, wherein B refers to halogen, S, P, and n and m refer to corresponding be not less than 1 stoichiometric coefficient and/or
B) species as:
-S
4N
4，S
2N
2，SN，S
4N
2，S
11N
2，P
3N
5，P
4N
6，PN，
-pN
2 -，PN
3 4-，PN
4 7-，PN
-，PN
2-，
-PNCl
2，P(NH)
2NH
2，P
4S
10，NP(SNH
4)
2，NPSNH
4SH，NP(SH)
2，PNS，
Sulphur or silicon species that implantation contains the crystal lattice of gallium nitride are used as to body; Magnesium, zinc or cadmium are acceptors; Hotchpotch in crystalline gan lattice such as manganese or chromium provide it to have magnetic; And phosphorus atom is isoelectronic with respect to nitrogen-atoms, thus its make energy gap than pure contain in the gallium nitride narrow.Described species cause that not only the ammonobase characteristic of supercritical solvent weakens, but also change light, electricity and the magnetic property that contains gallium nitride.
The dissolving that contains gallium material is to form the gallium compound that dissolves in supercritical solvent, for example reversible or irreversible process of gallium title complex by raw material.The gallium title complex is a chemical complex, and the gallium atom that wherein is in the center is by NH
3 -Type dentate or derivatives thereof is as NH
2 -, NH2
-Surround.Similarly definition is applied to the dissolving of aluminum-containing raw material.
The overcritical ammonia solution that contains refers to dissolve the solution that contains gallium or aluminum-containing raw material gained in the ammonia solvent in overcritical containing.
Solubleness: our experience is pointed out can reach balance at the solid that contains gallium or aln precipitation and between the supercritical solution under high enough temp and the pressure.Therefore, the solubleness that contains gallium or aln precipitation can be defined in the equilibrium concentration of solvable gallium (aluminium) compound of gained in the above-mentioned dissolution process that contains gallium or aln precipitation.In this process, equilibrium concentration, that is solubleness can be controlled by the composition, temperature and/or the pressure that change solvent.
The negative temperature coefficient of solubleness (negative TCR) refers to that the solubleness of each compound is the monotone decreasing function of temperature if all other parameters keep constant.Similarly, the thrust coefficient of solubleness (positive PCS) refers to that if all other parameters keep constant, solubleness is the monotone increasing function of pressure.In our research, now be shown in the overcritical solubleness that contains gallium or aln precipitation that contains in the ammonia solvent and under at least 300 ℃-550 ℃ temperature range and 100-550MPa pressure, have negative temperature coefficient and thrust coefficient.This means that according to Fig. 1 dissolving raw material in autoclave is after 400 ℃ of temperature keep 8 days down, (that is, behind the dissolving step), by improving the temperature to 500 ℃ in the autoclave, keep the constant pressure of 200MPa can finish the recrystallize (crystallisation step) of gan simultaneously.On the other hand, as shown in Figure 2, dissolved under pressure in autoclave after 350MPa down keeps 2 days (that is, behind the dissolving step), keeps 500 ℃ steady temperature to finish the recrystallize of gan (crystallisation step) by reducing pressure to 200MPa simultaneously.
Supersaturation: if contain solvable gallium (aluminium) compound concentrations in the ammonia solvent and be higher than the solubleness that contains gallium or aln precipitation under specific physical and chemical condition, so for can be defined as poor between actual concentrations and the solubleness in the overcritical supersaturation that contains ammonia solution that contains gallium or aln precipitation under this condition overcritical.When dissolving contains gallium or aln precipitation in closed system, for example can obtain hypersaturated state by improving temperature or reducing pressure.
To contain the chemistry transmission that contains gallium or aln precipitation in the ammonia solution be to comprise containing gallium or aluminum-containing raw material dissolves, transmit soluble gallium compound by supercritical solution and contain gallium or aln precipitation crystalline successive processes from the supersaturation supercritical solution in supercritical solution overcritical.Usually, chemical transmission can be caused by the difference of the temperature head between dissolved raw material and the crystallized product, pressure difference, concentration difference or other chemistry or physics.Because the technology according to the present invention causes and can obtain bulk mono-crystalline gallium-containing or aln precipitation owing to the chemistry transmission under the condition of the temperature difference, but need keep than dissolving the higher temperature in zone at crystal region.According to the present invention, chemistry transmission is preferably caused by convection current.
As mentioned above, crystal seed is for obtaining required bulk gallium-containing or the aln precipitation monocrystalline is extremely important in technology according to the present invention.In view of the quality of the crystal seed vital fact of crystalline quality for bulk gallium-containing that is obtained by technology according to the present invention or aln precipitation monocrystalline, the selected crystal seed of technology should have high as far as possible quality.Also can use various structures or wafer with modified surface.The structure on the surface with many appropriate intervals each other that for example is configured on the main substrate and is easy to the side direction hypertrophy of crystallization nitride can be used as crystal seed.And, can use the crystal seed that has the homoepitaxy surface, presents n type electroconductibility (for example, Si mixes).This crystal seed can use vapor phase growth to contain gallium nitride crystalline technology and make, as HVPE or MOCVD also or MBE.10
16To 10
21/ cm
2Doping Si guarantees n type electroconductibility during the growth technique of level.And, can use compound crystal seed and this crystal seed can directly be deposited on the main substrate or on-layer made by the GaN of doping Si by the buffer layer that for example AlN makes.In addition, for special following purposes, bulk-shaped monocrystal can be grown on the homogeneous phase crystal seed by technology according to the present invention, this crystal seed has the qualification orientation with respect to the crystal lattice of six side's zink sulphide types of specific XIII family element nitride, as C-plane, A-plane or the M-plane of each nitride.
Contain ammonia solution spontaneous crystallization and refer to that except on seed surface any position contains gallium or any unwanted nucleation and growth process of aln precipitation crystalline in autoclave from supersaturation is overcritical.This definition is also included within the growth on the seed surface, and wherein institute's growing crystal has the orientation that is different from this crystal seed.
Refer to occur in the crystallisation process on the seed surface that does not have spontaneous crystallization at the selective crystallization on the crystal seed, but comprise that also generation can ignore the spontaneous crystallization situation of degree.Obtain bulk-shaped monocrystal, this process is indispensable, and simultaneously, it also is one of key element of the present invention.
Temperature of reaction and pressure: in the embodiment that this specification sheets proposes, utilize empty autoclave to measure the interior temperature curve of autoclave, and need not the overcritical ammonia solution that contains.Therefore, this is not the true temperature of the process of being carried out under super critical condition.Direct measuring stress or the technological temperature and the autoclave volume of hypothesis come calculating pressure according to the physical-chemical data that contains ammonia solvent.
MOCVD method (metal organic chemical vapor deposition) refers to from the technology of vapour deposition epitaxial film, wherein under the situation of gan, uses ammonia and organo-metallic gallium compound as substrate.
HVPE method (halogenide vapour phase epitaxy) refers to from the technology of vapour deposition epitaxial film, wherein under the situation of nitride, uses metal halide and ammonia as reagent.
Autoclave refers to airtight pressurized reactor, and it has the reaction chamber of enforcement according to ammonobase technology of the present invention.
In order to finish according to technology of the present invention, the preferred equipment that uses as shown in Figures 3 and 4 describes in detail below.
Aforementioned technology and equipment allow to obtain bulk mono-crystalline gallium-containing or aln precipitation.This bulk-shaped monocrystal has low-dislocation-density (under the situation of block GaN: 10
4/ cm
2).Importantly bulk-shaped monocrystal GaN can have the diameter that surpasses 1 English inch, simultaneously, has the thickness of 3mm (preferred 5mm).Be cut to wafer with scroll saw and can obtain the thick bulk-shaped monocrystal substrate of 0.5mm.This bulk-shaped monocrystal substrate can be used as crystal seed after a while.In order to improve its n type electroconductibility, preferably during vapor phase growth, mixing to increase the concentration of n type current carrier by Si.
Contain gallium or aln precipitation if adopt, then contain gallium or aln precipitation, preferably have Al for what in supercritical ammine, obtain from the method for vapor-phase growing deposition
xGa
1-xThe form of N (0≤x≤1) or use are deposited on the bulk-shaped monocrystal Al on the GaN
xGa
1-xN (0≤x≤1).At the Al that during vapor phase growth, mixes and to obtain having n type electroconductibility by the Si that contains gallium or aln precipitation
xGa
1-x-yIn
yN (0≤x≤1,0≤y＜1,0≤x+y≤1), and have high crystalline quality and dislocation desity is lower than 10 because its crystallization in containing on gallium or the aln precipitation of obtaining, can be made with it in supercritical ammine under the condition of vapor phase growth
5/ cm
2Template type substrate.
The preferred embodiments of the invention
Allow from supercritical solution being passed to higher temperature and/or more isolating the technology of dissolving raw material the technology of low pressure according to technology according to the present invention, the crystallization that wherein contains gallium or aln precipitation occurs in surface of seed.And this technology is included in the autoclave and produces at least two steps with zone of differing temps simultaneously, and the raw material that contains gallium or aln precipitation is configured in dissolving zone and crystal seed with lesser temps and is configured in the crystal region with comparatively high temps.The temperature difference between control dissolving zone and the crystal region surpasses 1 ℃ the temperature difference to guarantee to utilize between dissolving zone and the crystal region, with the chemical transport of convection type by supercritical solution.In supercritical ammine, obtain contain gallium or aln precipitation has Al
xGa
1-xThe form of N, 0≤x＜1 wherein, and from gas phase obtain contain gallium or aln precipitation has Al
xGa
1-x-yIn
yThe form of N, 0≤x≤1,0≤y＜1,0≤x+y≤1 wherein, and can contain hotchpotch to build, receptor type or magnetic type.The ammonia that contains alkalimetal ion and/or its derivative can be used as supercritical solvent.Raw material mainly is selected from trinitride, imide, amino-imide, acid amides, hydride, metallic compound and contains gallium or the precursor of aluminium-containing alloy and gallium is formed by containing gallium or aln precipitation or its.This crystal seed contains the crystallizing layer that contains gallium or aln precipitation or other XIII family element (according to IUPAC, 1989) at least.
The crystallization that contains gallium or aln precipitation occurs under 100-800 ℃ the pressure of temperature and-10-1000MPa, controls alkalimetal ion concentration in the supercritical solvent simultaneously to guarantee raw material and to contain the suitable solubleness of gallium or aln precipitation.Alkalimetal ion is controlled in 1 to the mol ratio of other species in supercritical solvent: 200-1: in 2 the scope.
The measurement of carrying out shows that the bulk-shaped monocrystal GaN of best gained can have and is lower than 10
4/ cm
2Dislocation desity, simultaneously the half-width from (0002) planar X ray rocking curve is lower than 60 rads, it has guaranteed the suitable quality and the life-span of semiconducter device.Simultaneously, because the electroconductibility of substrate can deposit n type weld pad (pad) electrode thereon.
Suppose with basic metal or its compound, as KNH
2Introduce overcritical NH
3In, then at overcritical NH
3Middle GaN shows good solubility.Fig. 5 is illustrated under the 400-500 ℃ of temperature that the solubleness of GaN is the function of pressure in supercritical solvent, solubleness is defined as mol ratio: S
m≡ GaN
-solution: (KNH
2+ NH
3) * 100%.In the present embodiment, this solvent is the KNH of supercritical ammine
2The form of solution has mol ratio x ≡ KNH
2: NH
3Equal 0.07.
Should expect solubleness S
mBe the smooth function of temperature, pressure and mineralizer content, with equation S
m≡ S
m(T, p, x) expression.S
mInfinitesimal change and can be expressed as follows:
ΔS
m≈(S
m/T)
p，xΔT+(S
m/p)
T，xΔp+(S
m/x)
T，pΔx，
Partial derivative ( S wherein
m/ T)
P, x, ( S
m/ p)
T, x, ( S
m/ x)
T, pRegulation S
mBehavior with specific parameter change.In this manual, these derivatives are called " coefficient " (for example, ( S
m/ T)
P, xBe called " solubility temperature coefficient (TCS) ").
Fig. 5 represents solubility with pressure and increases and reduce with temperature.These relations make us obtain bulk mono-crystalline gallium-containing or aln precipitation in the dissolving under the higher solubility condition and its than the crystallization under the low solubility condition by it.Negative temperature coefficient refers to exist under the condition of thermograde, will take place from dissolving zone with lesser temps to the chemistry transmission that contains gallium or aln precipitation of the crystal region with comparatively high temps.Verified other gallium compound, or even gallium also can be the source of the amine complex of gallium.For example, based on the simplest substrate,, the gallium title complex of above-mentioned specific composition can be introduced in the solvent as gallium.Then, by appropriate change condition (for example elevated temperature), can be contained the supersaturated solution of gallium or aln precipitation and crystallization relatively on crystal seed.Allow to obtain bulk mono-crystalline gallium-containing or aln precipitation in the growth on the crystal seed and especially cause generating the stoichiometric gan that obtains with the bulk single crystal layer form on the gan crystal seed according to technology according to the present invention.Because this monocrystalline derives from the alkali metal containing ionic supercritical solution, it also contains the alkali metal concn that is higher than 0.1ppm.Because preferably keep the soda ash (mainly being) of supercritical solution, on purpose halogenide do not introduced in the solvent for fear of etching apparatus.Also allow us on purpose to replace the Ga of 0.05-0.5 according to technology of the present invention with AL.Steadily change the lattice parameter that the possibility of forming causes controlling the gained nitride.And it is 10 that this bulk-shaped monocrystal GaN can receive concentration
17-10
21/ cm
3Give body type dopant thing (for example, Si, O) and/or receptor type hotchpotch (for example, Mg, Zn) and/or magnetic type hotchpotch (for example, Mn, Cr).These hotchpotchs have changed photoelectricity, electricity and the magnetic property that contains gallium or aln precipitation.About other physical properties, the bulk-shaped monocrystal gan of gained has and is lower than 10
6/ cm
2Surface dislocation density, preferably be lower than 10
5/ cm
2, most preferably be lower than 10
4/ cm
2In addition, its half-width from (0002) planar X ray rocking curve is lower than 600 rads, preferably is lower than 300 rads, most preferably is lower than 60 rads.The best bulk-shaped monocrystal gan that obtains can have and is lower than 10
4/ cm
2Surface dislocation density, simultaneously the half-width from (0002) planar X ray rocking curve is lower than 60 rads (to CuK α
1).
The equipment that is used for obtaining bulk-shaped monocrystal is shown among Fig. 3 and Fig. 4.The elementary cell of this equipment is the autoclave 1 that is used for obtaining the supercritical state solvent, and it is equipped with and is used for providing by the supercritical solution in the autoclave 1 device 2 of chemical transport.Autoclave 1 is placed in the cavity 3 of one group of two stove 4 that disposes heating unit 5 and/or refrigerating unit 6 and utilizes the closing device 7 of screw type to guarantee to be positioned at the desired location of relative stove 4.Stove 4 is installed on the bedstead 8 and with steel band 9 and firmly coats stove 4 and bedstead 8.Bedstead 8 is rotatably installed in the pedestal 10 with this group stove 4 and utilizes pin interlocking 11 with required fixed angle, allows the speed and the kenel of convection flow in the control autoclave 1.Be placed in the autoclave 1 in this group stove 4 convection flow that supercritical solution takes place, it separates dissolving zone 13 and crystal region 14 by to occupy device 2 controls of the form that surpasses 70% autoclave cross section horizontal baffle 12 in autoclave 1.Horizontal baffle 12 is placed near the centre of autoclave length.Control device 15 is set the temperature value of individual region in the autoclave 1 in stove 4, makes it to drop in the 100-800 ℃ of scope.In autoclave 1, the dissolving zone 13 consistent with the low-temperature region of furnace system 4 is arranged in the top of horizontal baffle (or baffle plate) 12 and raw material 16 joined zone 13.Raw material introducing amount is no more than 50% of the regional volume of dissolving.Should make shared volume be no more than 80% of the regional volume of dissolving the introducing amount of gallium (or aluminium) form raw material.Crystal region 14 is consistent with the high-temperature area of stove group 4 and be positioned at the below of horizontal baffle (or baffle plate) 12.Crystal seed 17 is placed in this district.The position of crystal seed 17 under the intersection point of lifting convection current streamline, a little higher than furnace bottom.Device 2 zones of living in of regulating convection flow are equipped with refrigerating unit 6.Because the temperature difference between dissolving zone 13 and the crystal region 14 can be controlled in refrigerated baffle 12 zones.Refrigerating unit 18 is positioned at the crystal region bottom level, and it allows this zone, and fast cooling and the stove cooling period crystallization processes after prevent that obviously crystalline from dissolving after technology is finished.
Thereby the bulk-shaped monocrystal gan of gained can have and is lower than 10
5/ cm
2Surface dislocation density and be lower than 60 rads (for CuK α from the half-width of (0002) planar x ray rocking curve
1).With the drift angle of the 0.05-0.2 degree of relative crystal main shaft, be cut to wafer with scroll saw after, can add them in these conditions, use the HVPE method, obtained having the GaN of the 3mm of n type electroconductibility in 100 hours by the growth velocity of keeping 30 μ m/h.
Thereby the bulk-shaped monocrystal GaN that gained is had the 5mm width became the thick wafer of 0.5mm in 25 hours with the lasting section of scroll saw.Like this, can obtain at least 4 substrates.Except high crystalline quality, these substrates also have electroconductibility, so they can be used as with the semi-conductor substrate of the photoelectric device (as laser diode) that is the basis manufacturing.
Embodiment
At 600cm with internal diameter 40mm and length 480mm
3Pack into the raw material of 53.0g gallium (6N) form of the dissolving zone 13 of autoclave 1.With pack into the seeding crystals of gallium nitride wafer (having about 1 English inch diameter and the 2.0g quality) form by A direction of principal axis in supercritical ammine method as shown in Figure 9 growth gained of the crystal region 14 of identical autoclave.(this crystal seed is by having length (L), from the wafer manufacturing of both sides, A plane and the A direction of principal axis growth (W) on every side of M planar edge).
With 12.0g, the sodium Metal 99.5 of 4N and 19.5g, the potassium metal of 4N is put into autoclave as mineralizer.Then, the ammonia (5N) of the 255.0g that packs in the autoclave, airtight and put into one group of stove 4.The temperature in dissolving zone 13 rise to 450 ℃ (Fig. 6, with 1 ℃/min), and this crystal region does not heat and its temperature is no more than 250 ℃.Like this, the overcritical ammonia solution that contains of acquisition has following mol ratio: KNH
2: NH
3=0.035; NaNH
2: NH
3=0.035.Temperature distribution in this autoclave is kept 4 days (Fig. 6), during gallium takes place the part dissolving become polycrystal GaN with undissolved gallium complete reaction.
Then, with the temperature in dissolving zone rise to 500 ℃ (with 1 ℃/min), with the temperature in polycrystalline zone slowly rise to 550 ℃ (Fig. 6, with 0.1 ℃/min), the pressure in the autoclave reaches about 280MPa simultaneously.This autoclave keeps these conditions (second step of technology) to continue 20 days (Fig. 6).The result of this technology observes partly dissolving and on the HVPE crystal gallium nitride crystal takes place in crystal region of raw material (that is, polycrystal GaN) in the dissolving zone.The crystallization on the crystal both sides of this gallium nitride crystal becomes and has the single crystalline layer form that total thickness is 2mm.
For with it as substrate, the crystal that will obtain in similar supercritical ammine method experiences following technology:
1) will be deposited on the annealing that the 5mm single crystalline layer on the HVPE-GaN crystal seed is put into stove and experienced 1-5 hour in the nitrogen atmosphere that contains a small amount of oxygen under 600 ℃-900 ℃.
2) then this sample is placed on the scroll saw of making by Takatori company.In order to give the drift angle suitable with respect to the crystal main shaft, this sample is placed on the position that angle is lower than 1 degree.Then, use scroll saw that this sample is cut into 5 wafer, obtain having the sample of drift angle between the 0.05-0.2 degree thus.
3) annealing of then this sample being put into stove and under 600 ℃-900 ℃, experiencing 1-5 hour in the nitrogen atmosphere that contains a small amount of oxygen once more.(hereinafter the sample that will prepare like this is called: the GaN substrate)
4) then this GaN substrate is fixed on the worktable, puts into by the polishing machine of Logitech company manufacturing and in its both sides continuous polishing.In polishing process, use jewelling tool and silicon-dioxide or aluminum oxide slurries (have the pH value and be 3-6 or 9-11).The roughness on gained surface is lower than 10 .
5) then use HVPE or MOCVD method that GaN or AlGaN protective layer (1 to several micron thickness) are added to the GaN substrate surface, thereby obtain template type substrate.
6) alternately, have on the GaN substrate of aforementioned protective layer, or do not have on the GaN substrate of protective layer, using the HVPE method under following specified conditions, to generate the thick GaN layer of 3mm.After according to preceding method section and polishing, obtain being used for the thick template type substrate of 0.5mm of photoelectric device.
The HVPE processing condition are as follows: temperature of reaction: 1050 ℃, and reaction pressure: normal atmosphere (0.1MPa), ammonia
Dividing potential drop: 0.03MPa, GaCl
3Dividing potential drop: 100Pa, the hydrogen carrier gas.
If desired, can be by at the overcritical ammonia solvent that contains, in the environment of water or carbonic acid gas or the cleaning of the effect of experience gaseous hydrogen, nitrogen or ammonia carry out removing the step of impurity from the bulk-shaped monocrystal nitride.At this, preferably cleaning step can or be exposed to electron beam by the using ultrasound ripple and carries out.
Commercial Application
The template type substrate of gained is highly suitable for from the vapour phase epitaxy substrate, such as MOCVD, MBE and HVPE, Cause making good photoelectric device such as laser diode and big output LED and good electric device as MOSFET.
Claims (29)
1. template type substrate that is used for photoelectricity or electric device, it comprises A) contain at least a alkali metal (I family, IUPAC 1989) bulk-shaped monocrystal nitride layer and B) nitride layer by vapor phase epitaxial growth method growth, its middle level A) with a layer B) be combined in a layer A) and a non-N polar surface and a layer B) N polar surface place.
2. the template type substrate that is used for photoelectricity or electric device as claimed in claim 1, wherein said bulk-shaped monocrystal nitride layer A) comprise and contain gallium or aln precipitation and aluminiferous nitride and with general formula Al
xGa
1-xN represents, wherein 0≤x≤1.
3. the template type substrate that is used for photoelectricity or electric device as claimed in claim 1, wherein said nitride layer B by the growth of vapor phase epitaxial growth method) with general formula Al
xGa
1-x-yIn
yN represents, wherein 0≤x≤1,0≤y≤1,0≤x+y≤1.
4. the template type substrate that is used for photoelectricity or electric device as claimed in claim 1, wherein said layer B) have described layer A by MOCVD, HVPE or the preparation of MBE method) substrate on.
5. the template type substrate that is used for photoelectricity or electric device as claimed in claim 4, wherein said layer B) constitute by two-layer at least, the first layer B1) have described layer A by the preparation of MOCVD or MBE method) substrate on, and second layer B2) by the preparation of HVPE method at the first layer B1) on.
6. the template type substrate that is used for photoelectricity or electric device as claimed in claim 1, wherein bulk-shaped monocrystal nitride layer A) by contain at least a alkali metal overcritical contain crystallization nitride in the ammonia solution be prepared in have described layer B) crystal seed on.
7. the template type substrate that is used for photoelectricity or electric device as claimed in claim 1, its also comprise contain gallium or aluminum nitride layer C by vapor phase epitaxial growth method growth), wherein contain at least a alkali metal (I family, IUPAC 1989) bulk-shaped monocrystal nitride layer A) at crystal seed layer B) and non-N polar surface and the N polar surface on be produced stratification A1) with a layer A2), and layer C) be combined in a layer A1) a non-N polar surface and a layer C) N polar surface place.
8. the template type substrate that is used for photoelectricity or electric device as claimed in claim 8, wherein said gallium or the aluminum nitride layer C of containing) be prepared in described layer A1 by MOCVD, HVPE or MBE method) substrate on.
9. the template type substrate that is used for photoelectricity or electric device as claimed in claim 9, wherein said layer C) constitute by two-layer at least institute, the first layer C1) by the preparation of MOCVD or MBE method at described layer A1) substrate on, and second layer C2) by the preparation of HVPE method at the first layer C1) on.
10. the template type substrate that is used for photoelectricity or electric device as claimed in claim 1, wherein said substrate comprise muriate and have the major surfaces of being made up of the Ga polar surface substantially.
11. the template type substrate that is used for photoelectricity or electric device as claimed in claim 1, wherein said substrate has 10
6/ cm
2Or lower dislocation desity.
12. the template type substrate that is used for photoelectricity or electric device as claimed in claim 1, wherein said layer A) or layer A1) with a layer A2) have by overcritically containing the prepared bulk-shaped monocrystal nitride of crystallization nitride in the ammonia solution what contain at least a alkali metal.
13. the template type substrate that is used for photoelectricity or electric device as claimed in claim 1, the described layer A that wherein has a pair of C planar surface and 1 inch or larger diameter) prepare by growing at the overcritical A direction of principal axis that contains the bulk-shaped monocrystal nitride in the ammonia solution that contains at least a alkali metal.
14. as the template type substrate that is used for photoelectricity or electric device of claim 13, wherein said substrate has 10
4/ cm
2Or lower dislocation desity.
15. the template type substrate that is used for photoelectricity or electric device as claimed in claim 1 is wherein at described gallium or the aluminum nitride layer B of containing) or C) and a layer B1) and B2) or C1) and C2) at least a alkali-metal concentration be lower than by the overcritical prepared layer A of crystallization nitride that contains in the ammonia solution that contains at least a alkali metal) in described alkali-metal concentration.
16. the template type substrate that is used for photoelectricity or electric device as claimed in claim 2, wherein said nitride layer A) constitute by AlN or GaN.
17., wherein said layer B), C B1)) or C1) by the MOCVD preparation and have the thickness of 0.1-3 μ m as each the template type substrate that is used for photoelectricity or electric device in the claim 1,5,7 and 9.
18. as the template type substrate that is used for photoelectricity or electric device of claim 17, wherein by described layer B from the method for vapor-phase growing gained) or C) have a general formula Al
xGa
1-x-yIn
yN, wherein 0≤x≤1,0≤y≤1,0≤x+y≤1.
19., wherein said layer B) or C) be the combination of AlGaN and GaN bilayer as the template type substrate that is used for photoelectricity or electric device of claim 18.
20., wherein said layer B) or C) be to contain to contain gallium or aln precipitation as the silicon (Si) of giving the body hotchpotch or oxygen (O) as the template type substrate that is used for photoelectricity or electric device of claim 1 or 8.
21., wherein said layer B) or C) be as the template type substrate that is used for photoelectricity or electric device of claim 1 or 7 contain magnesium (Mg) as acceptor doped thing or zinc (Zn) contain gallium or aln precipitation.
22. as the template type substrate that is used for photoelectricity or electric device of claim 20 or 21, the concentration of wherein said hotchpotch is 10
17/ cm
3-10
21/ cm
3
23. one kind prepares template type substrate technology, it may further comprise the steps:
(a) by containing nitride that ammonia solution crystallization on crystal seed contains gallium or aluminium and prepare the bulk-shaped monocrystal nitride layer A of having that contains at least a alkali metal (I family, IUPAC 1989)) as the thickness of substrate from overcritical; (b) by vapor phase epitaxial growth at layer A) Al or the Ga-polar surface on form nitride layer B) be combined in a layer A to obtain comprising) and Al or a Ga-polar surface and a layer B) the layer A at N polar surface place) with a layer B) substrate.
24. the technology as the preparation template type substrate of claim 23 wherein also comprises polishing layer B) one side with the step (c) of the substrate that obtains being used for vapour phase epitaxy.
25. technology as the preparation template type substrate of claim 24, wherein also be included in not hydrogeneous, but in the oxygen containing atmosphere, under about 600-1050 ℃ temperature, make to comprise described layer A) and the step of substrate annealing B), the material of Zhi Zaoing has than better crystalline quality before annealing thus.
26., wherein in the inert gas atmosphere that is added with 10-30 volume % oxygen, carry out described annealing steps as the technology of the preparation template type substrate of claim 25.
27. technology as the preparation template type substrate of claim 26, wherein said annealing steps can one step or multiple step carry out until reaching required foreign matter content described impurity such as hydrogen and/or ammonia or by the formed ion of the impurity that during crystallization and/or annealing process, forms.
28. technology as the preparation template type substrate of claim 25, comprising utilizing in the overcritical environment that contains ammonia solvent, water or carbonic acid gas or the cleaning of experience gaseous hydrogen, nitrogen or ammonia effect, other step of from the bulk-shaped monocrystal nitride, removing impurity.
29. as the technology of the preparation template type substrate of claim 23, wherein by means of the using ultrasound ripple or be exposed to electron beam and carry out described cleaning step.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL357696A PL225423B1 (en) | 2002-12-11 | 2002-12-11 | Method of producing substrate standardized with epitaxial layer (template type substrates) from voluminal mono-crystalline nitride containing gallium with surface of high structural quality |
| PLP357709 | 2002-12-11 | ||
| PLP357696 | 2002-12-11 | ||
| PLP357707 | 2002-12-11 | ||
| PLP357708 | 2002-12-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1723302A true CN1723302A (en) | 2006-01-18 |
| CN1329561C CN1329561C (en) | 2007-08-01 |
Family
ID=32733396
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801056254A Expired - Fee Related CN100415946C (en) | 2002-12-11 | 2003-12-11 | Epitaxial substrate and manufacturing method thereof |
| CNB200380105624XA Expired - Lifetime CN1329561C (en) | 2002-12-11 | 2003-12-11 | A substrate for epitaxy and a method of preparing the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
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| CNB2003801056254A Expired - Fee Related CN100415946C (en) | 2002-12-11 | 2003-12-11 | Epitaxial substrate and manufacturing method thereof |
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| Country | Link |
|---|---|
| CN (2) | CN100415946C (en) |
| PL (1) | PL225423B1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102409400A (en) * | 2011-11-21 | 2012-04-11 | 扬州乾照光电有限公司 | Light-emitting diode (LED) epitaxial growth device |
| CN103534391A (en) * | 2011-03-18 | 2014-01-22 | 日本碍子株式会社 | Process for producing group 13 metal nitride, and seed crystal substrate for use in same |
| CN109449261A (en) * | 2018-09-10 | 2019-03-08 | 华灿光电(苏州）有限公司 | A kind of preparation method and LED epitaxial slice of LED epitaxial slice |
| CN109799251A (en) * | 2019-03-06 | 2019-05-24 | 中国电子科技集团公司第四十六研究所 | It is a kind of can macroscopic view identification chip domain distribution detection method |
| CN110808319A (en) * | 2019-11-11 | 2020-02-18 | 中国科学院半导体研究所 | Reverse polarity vertical light emitting diode and method of making the same |
| CN114420787A (en) * | 2021-12-22 | 2022-04-29 | 西安隆基乐叶光伏科技有限公司 | A kind of solar cell annealing method and annealing equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110195258A (en) * | 2019-07-10 | 2019-09-03 | 上海玺唐半导体科技有限公司 | Gallium nitride crystal growth device and its growing method |
| CN117423612B (en) * | 2023-09-19 | 2024-12-03 | 深圳大学 | Method for preparing semi-insulating gallium nitride substrate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997013891A1 (en) * | 1995-10-13 | 1997-04-17 | Centrum Badan Wysokocisnieniowych | METHOD OF MANUFACTURING EPITAXIAL LAYERS OF GaN OR Ga(A1,In)N ON SINGLE CRYSTAL GaN AND MIXED Ga(A1,In)N SUBSTRATES |
| GB2363518A (en) * | 2000-06-17 | 2001-12-19 | Sharp Kk | A method of growing a nitride layer on a GaN substrate |
| US6488767B1 (en) * | 2001-06-08 | 2002-12-03 | Advanced Technology Materials, Inc. | High surface quality GaN wafer and method of fabricating same |
-
2002
- 2002-12-11 PL PL357696A patent/PL225423B1/en unknown
-
2003
- 2003-12-11 CN CNB2003801056254A patent/CN100415946C/en not_active Expired - Fee Related
- 2003-12-11 CN CNB200380105624XA patent/CN1329561C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103534391A (en) * | 2011-03-18 | 2014-01-22 | 日本碍子株式会社 | Process for producing group 13 metal nitride, and seed crystal substrate for use in same |
| CN102409400A (en) * | 2011-11-21 | 2012-04-11 | 扬州乾照光电有限公司 | Light-emitting diode (LED) epitaxial growth device |
| CN102409400B (en) * | 2011-11-21 | 2014-03-19 | 扬州乾照光电有限公司 | Light-emitting diode (LED) epitaxial growth device |
| CN109449261A (en) * | 2018-09-10 | 2019-03-08 | 华灿光电(苏州）有限公司 | A kind of preparation method and LED epitaxial slice of LED epitaxial slice |
| CN109799251A (en) * | 2019-03-06 | 2019-05-24 | 中国电子科技集团公司第四十六研究所 | It is a kind of can macroscopic view identification chip domain distribution detection method |
| CN109799251B (en) * | 2019-03-06 | 2021-01-12 | 中国电子科技集团公司第四十六研究所 | Detection method capable of macroscopically identifying crystal domain distribution range of wafer |
| CN110808319A (en) * | 2019-11-11 | 2020-02-18 | 中国科学院半导体研究所 | Reverse polarity vertical light emitting diode and method of making the same |
| CN110808319B (en) * | 2019-11-11 | 2021-08-17 | 中国科学院半导体研究所 | Reverse polarity vertical light emitting diode and method of making the same |
| CN114420787A (en) * | 2021-12-22 | 2022-04-29 | 西安隆基乐叶光伏科技有限公司 | A kind of solar cell annealing method and annealing equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| PL357696A1 (en) | 2004-06-14 |
| CN1329561C (en) | 2007-08-01 |
| PL225423B1 (en) | 2017-04-28 |
| CN1723303A (en) | 2006-01-18 |
| CN100415946C (en) | 2008-09-03 |
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