CN101535533A - Process for producing group iii element nitride crystal - Google Patents
Process for producing group iii element nitride crystal Download PDFInfo
- Publication number
- CN101535533A CN101535533A CNA2007800427005A CN200780042700A CN101535533A CN 101535533 A CN101535533 A CN 101535533A CN A2007800427005 A CNA2007800427005 A CN A2007800427005A CN 200780042700 A CN200780042700 A CN 200780042700A CN 101535533 A CN101535533 A CN 101535533A
- Authority
- CN
- China
- Prior art keywords
- iii nitride
- iii
- interarea
- iii group
- crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 255
- 239000013078 crystal Substances 0.000 title claims abstract description 243
- 238000000034 method Methods 0.000 title claims abstract description 91
- 239000000758 substrate Substances 0.000 claims abstract description 299
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 229910002601 GaN Inorganic materials 0.000 description 156
- 238000005520 cutting process Methods 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000000227 grinding Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 6
- 229910052594 sapphire Inorganic materials 0.000 description 5
- 239000010980 sapphire Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000003019 stabilising effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013211 curve analysis Methods 0.000 description 3
- 238000007716 flux method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005136 cathodoluminescence Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KFOYFGLMOLOHMU-BKJLMQSASA-N C1C2C3=C2[C@@H]2C3C12 Chemical compound C1C2C3=C2[C@@H]2C3C12 KFOYFGLMOLOHMU-BKJLMQSASA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021098 KOH—NaOH Inorganic materials 0.000 description 1
- 0 N=CC1*CNC1 Chemical compound N=CC1*CNC1 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012207 quantitative assay Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
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
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/02—Epitaxial-layer growth
- C30B23/025—Epitaxial-layer growth characterised by the substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/04—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their crystalline structure, e.g. polycrystalline, cubic or particular orientation of crystalline planes
- H01L29/045—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their crystalline structure, e.g. polycrystalline, cubic or particular orientation of crystalline planes by their particular orientation of crystalline planes
-
- 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
- C30B19/00—Liquid-phase epitaxial-layer growth
- C30B19/02—Liquid-phase epitaxial-layer growth using molten solvents, e.g. flux
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02387—Group 13/15 materials
- H01L21/02389—Nitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/02433—Crystal orientation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/0254—Nitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02656—Special treatments
- H01L21/02658—Pretreatments
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/20—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIIBV compounds
- H01L29/2003—Nitride compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24752—Laterally noncoextensive components
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
A process for producing a Group III element nitride crystal (20) having a main plane (20m) orienting in any specific direction other than {0001}. The process comprises: a step in which Group III element nitride crystal substrates (10p) and (10q) respectively having main planes (10pm) and (10qm) orienting in the specific direction are cut out of a Group III element nitride bulk crystal (1); a step in which these substrates (10p) and (10q) are closely arranged side by side so that the main planes (10pm) and (10qm) of these substrates (10p) and (10q) are parallel to each other and their planes facing [0001] are oriented in the same direction; and a step in which a Group III element nitride crystal (20) is grown on the main planes (10pm) and (10qm) of these substrates (10p) and (10q).
Description
Technical field
The invention relates to and make III group-III nitride crystalline method, it relates to manufacturing has except that { the III group-III nitride crystalline method of the interarea of any specified planar orientation the 0001}.
Background technology
Usually, be applicable to that the semi-conductor electronic device that comprises luminescent device and the III group-III nitride crystal in the semiconductor transducer are by following method manufacturing: according to the gaseous techniques such as hydride gas-phase epitaxy (HVPE) or metal organic chemical vapor deposition (MOCVD), perhaps by flux method for growth or other liquid technologies, make crystal on the Sapphire Substrate of interarea or have on the GaAs substrate of interarea of (111) A face and grow with (0001) face.Therefore, to have planar orientation be the { interarea of 0001} to the III group-III nitride crystal that usually obtains.
For the luminescent device on such substrate, described substrate is { the III group-III nitride crystal of the interarea of 0001} for having planar orientation, and wherein will be deposited on the described interarea as Multiple Quantum Well (MQW) structure of luminescent layer, because III group-III nitride crystalline＜0001〉polarity of orientation, make in luminescent layer, to produce spontaneous polarization, thereby cause luminous efficiency to reduce.Therefore, seeking to have except that { the III group-III nitride crystalline manufacture method of the interarea of the planar orientation the 0001}.
Reference example such as Japanese Patent spy open No.2005-162526: following method has been suggested the gallium nitride that has the surface of arbitrary face orientation as manufacturing, and does not influence the method for the planar orientation of substrate interarea.That is,, cut out a plurality of rectangular crystal pieces by GaN crystal by vapor deposition growth according to disclosed method among the patent documentation No.2005-162526.Simultaneously, silicon dioxide film is coated on the surface of Sapphire Substrate of independent preparation, and in film, forms the recess of a plurality of through substrates subsequently.So that the end face of a plurality of crystal block have the mode of identical faces orientation described a plurality of crystal block embedded in this recess thereafter.Then, carry out vapor deposition as seed, make the gallium nitride crystal growth on surface with arbitrary face orientation with described crystal block.
Summary of the invention
The problem to be solved in the present invention
Yet, for the method among the patent documentation No.2005-162526, carry out the growth of GaN crystalline owing to utilize the GaN crystal block that has embedded in the Sapphire Substrate as seed, different because of thermal expansivity between sapphire and the GaN, when at process of growth postcooling crystal, in the GaN crystal, occur breaking and being out of shape, thereby can't obtain to have excellent crystalline GaN crystal.
In addition, if make III group-III nitride crystal such as the Al that contains Al by the method among the patent documentation No.2005-162526
xGa
yIn
1-x-yN (x〉0, y 〉=0, x+y≤1) growth then because the Al precursor does not have selectivity to silicon dioxide film, makes Al
xGa
yIn
1-x-yN also grows on silicon dioxide film, therefore can't obtain to have excellent crystalline Al
xGa
yIn
1-x-yThe N crystal.
In order to address the above problem, the purpose of this invention is to provide the available manufacturing and have excellent crystalline III group-III nitride crystalline method, this III group-III nitride crystal has except that { the interarea of any specified planar orientation the 0001}.
The invention provides the III group-III nitride crystalline method of making, this III group-III nitride crystal have except that the interarea of any specified planar orientation the 0001}, this manufacturing III group-III nitride crystalline method may further comprise the steps: the step that is cut out the III group-III nitride crystalline substrates of a plurality of interareas with specified planar orientation by III group-III nitride bulk crystals; In the horizontal described substrate is arranged adjacent to each otherly, made that the interarea of described substrate is parallel to each other, and make the step that [0001] direction of described substrate is orientated in an identical manner; And the III group-III nitride crystalline step of on the described interarea of described substrate, growing.
In manufacturing III group-III nitride crystalline method of the present invention, { (wherein x is the integer more than 0 to 1-10x} with respect to being selected from, below identical), { (wherein y is the integer more than 0 to 11-2y}, below identical) and { (wherein h and k are integer except that 0 to hk-(h+k) 0}, below identical) any crystallographical equivalent planar orientation, described except that { drift angle of any specified planar orientation the 0001} can be below 5 °.In addition, with respect to being selected from { 1-100}, { 11-20}, { 1-102} and { any crystallographical equivalent planar orientation of 11-22}, the drift angle of described specified planar orientation can be below 5 °.In addition, with respect to { 1-100}, the drift angle of described specified planar orientation can be below 5 °.In addition, make in the III group-III nitride crystalline method in the present invention, described substrate can be that face below the 50nm is adjacent to each other along average roughness Ra.
In addition, make in the III group-III nitride crystalline method, III group-III nitride crystalline growth temperature can be made as more than 2000 ℃ in the present invention.In addition, III group-III nitride crystalline growth method can be made as the sublimation-grown method.
The present invention can provide to make has excellent crystalline III group-III nitride crystalline method, and this III group-III nitride crystal has except that { the interarea of any specified planar orientation the 0001}.
Description of drawings
Figure 1A is used for the embodiment that example the present invention makes III group-III nitride crystalline method for briefly to represent that substrate cuts out the schematic oblique drawing of step.
Figure 1B is used for the embodiment that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic oblique drawing of substrate alignment step.
Fig. 1 C is used for the embodiment that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic sectional view of crystal growth step.
Fig. 2 A is the expression schematic plan view, and briefly example is used to make the lower substrate (undersubstrate) of block III group-III nitride crystal growth.
Fig. 2 B is the schematic sectional view of expression IIB-IIB in Fig. 2 A, and briefly example is used to make the base substrate of block III group-III nitride crystal growth.
Fig. 3 A is used for the example that example the present invention makes III group-III nitride crystalline method for briefly to represent that substrate cuts out the schematic oblique drawing of step.
Fig. 3 B is used for the example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic oblique drawing of substrate alignment step.
Fig. 3 C is used for the example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic sectional view of crystal growth step.
Fig. 4 is a sectional view, represents that briefly the present invention makes the crystal growth step in another example of III group-III nitride crystalline method.
Fig. 5 A is used for another example that example the present invention makes III group-III nitride crystalline method for briefly to represent that substrate cuts out the schematic oblique drawing of step.
Fig. 5 B is used for another example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic oblique drawing of substrate alignment step.
Fig. 5 C is used for another example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic sectional view of crystal growth step.
Fig. 6 A is the schematic oblique drawing that briefly expression cuts out the step of substrate, is used for another example that example the present invention makes III group-III nitride crystalline method.
Fig. 6 B is used for another example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic oblique drawing of substrate alignment step.
Fig. 6 C is used for another example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic sectional view of crystal growth step.
Fig. 7 A is used for another example that example the present invention makes III group-III nitride crystalline method for briefly to represent that substrate cuts out the schematic oblique drawing of step.
Fig. 7 B is used for another example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic oblique drawing of substrate alignment step.
Fig. 7 C is used for another example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic oblique drawing of crystal growth step.
Fig. 8 A is used for another example that example the present invention makes III group-III nitride crystalline method for briefly to represent that substrate cuts out the schematic oblique drawing of step.
Fig. 8 B is used for another example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic oblique drawing of substrate alignment step.
Fig. 8 C is used for another example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic sectional view of crystal growth step.
Fig. 9 A is used for another example that example the present invention makes III group-III nitride crystalline method for briefly to represent that substrate cuts out the schematic oblique drawing of step.
Fig. 9 B is used for another example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic oblique drawing of substrate alignment step.
Fig. 9 C is used for another example that example the present invention makes III group-III nitride crystalline method for briefly representing the schematic sectional view of crystal growth step.
Figure 10 is schematic oblique drawing, briefly represents { the object lesson of 1-10x} (x is the integer more than 0) face in the hexagon III group-III nitride crystalline structure cell.
Figure 11 is schematic oblique drawing, briefly represents { the object lesson of 11-2y} (y is the integer more than 0) face in the hexagon III group-III nitride crystalline structure cell.
Figure 12 is schematic oblique drawing, briefly represents { the object lesson of hk-(h+k) 0} (h and k are the integer except that 0) face in the hexagon III group-III nitride crystalline structure cell.
Description of symbols
1:III group-III nitride bulk crystals
10p, 10q:III group-III nitride crystalline substrates
10pm, 10qm, 20m: interarea
10pt, 10qt: adjacent surface
20:III group-III nitride crystal
20f: facet (facet)
20s: the zone directly over the substrate
20t: the upper area of substrate adjacency
20v: recess
21:III group-III nitride wafer
90: lower substrate
91: mask
91w: window
Embodiment
In crystallography,, use such as (hkl) and the symbol (hkil) (Miller symbol) in order to represent the planar orientation of crystal face.In the crystal of the hexagonal system such as III group-III nitride crystal, the planar orientation of crystal face is represented by (hkil).Herein, h, k, i and l are the integer that is known as Miller indices, wherein have relational expression i=-(h+k).The face of planar orientation (hkil) is called (hkil) face.Be called [hkil] direction with the vertical direction of (hkil) face (normal direction of (hkil) face).Simultaneously, the planar orientation that " { hkil} " ordinary representation comprises (hkil) with and each crystallographical equivalent orientation, "＜hkil〉" then the ordinary representation direction that comprises [hkik] with and each crystallographical equivalent direction.
With reference to figure 1, the embodiment that the present invention makes III group-III nitride crystalline method has except that { any specified planar orientation { h the 0001} for making
0k
0i
0l
0The method of III group-III nitride crystal 20 of interarea 20m, and may further comprise the steps.Shown in Figure 1A, first step is that III group-III nitride bulk crystals l is cut out a plurality of { h that have
0k
0i
0l
0Interarea 10pm, the III group-III nitride crystalline substrates 10p of 10qm, 10q (below, it also will be called " substrate cuts out step ").Shown in Figure 1B, second step is in the horizontal with substrate 10p, 10q arranges adjacent to each otherly, make described a plurality of III group-III nitride crystalline substrates 10p, the interarea 10pm of 10q, 10qm is parallel to each other, and makes substrate 10p, [0001] direction of 10q is orientated (below, it also will be called " substrate arrangement step ") in an identical manner.Shown in Fig. 1 C, third step is at described a plurality of III group-III nitride crystalline substrates 10p, the interarea 10pm of 10q, the last growth of 10qm III group-III nitride crystal 20 (below, it also will be called " crystal growth step ").
In the first step (substrate cuts out step) of present embodiment, from III group-III nitride bulk crystals 1, cut out a plurality of { h that have
0k
0i
0l
0Interarea 10pm, the III group-III nitride crystalline substrates 10p of 10qm, 10q.
The III group-III nitride bulk crystals 1 that utilizes in this first step is not particularly limited; Crystal by the common method manufacturing just can meet the demands, this common method promptly is by HVPE, MOCVD or other vapor phase deposition techniques, perhaps by flux method for growth or other liquid technologies, make crystal in the Sapphire Substrate that for example has (0001) interarea or have on the GaAs substrate of interarea of (111) A face and grow.Therefore, although III group-III nitride bulk crystals is not particularly limited, it has { 0001} interarea usually.Here, from reducing dislocation desity and improving crystalline viewpoint, preferably III group-III nitride bulk crystals 1 is by growing as disclosed facet (facet) growing technology among the Japanese laid-open patent No.2001-102307, this facet growth technology is characterised in that on the surface of crystal growth (crystal growth face) and forms facet, and carries out crystal growth need not to fill under the situation of facet.
Equally, has { h for from III group-III nitride bulk crystals 1, cutting out
0k
0i
0l
0A plurality of III group-III nitride crystalline substrates 10p of interarea 10pm, 10qm, the method for 10q are not particularly limited; Shown in Figure 1A, III group-III nitride bulk crystals 1 can be cut out edge＜hkil〉direction have a plurality of of the predetermined vertical spacing (planar orientation of these faces for hkil}, and they be also referred to as the hkil} face, and below identical).
Shown in Figure 1B, in second step (substrate arrangement step) of present embodiment, in the horizontal with described a plurality of III group-III nitride crystalline substrates 10p that cut out, 10q arranges adjacent to each otherly, make substrate 10p, the interarea 10pm of 10q, 10qm is parallel to each other, and make substrate 10p, [0001] direction of 10q is orientated in an identical manner.In this case, though the III group-III nitride crystalline substrates 10p of two adjacency in described a plurality of III group-III nitride crystalline substrates, by the mark of the label among Figure 1B, the III group-III nitride crystalline substrates of other adjacency also has identical situation to 10q.
Arrange described a plurality of III group-III nitride crystalline substrates 10p in the horizontal, 10q, make substrate 10p, the interarea 10pm of 10q, 10qm is parallel to each other, it is because be, if the angle that is formed by the interarea and their crystallographic axis of substrate is inhomogeneous along the interarea of substrate, the III group-III nitride crystalline chemical constitution of then on the interarea of substrate, growing along with the face of substrate main surface parallel also with inhomogeneous.Substrate 10p, the interarea 10pm of 10q, 10qm is parallel to each other just enough; They do not need in the same plane mutually.Yet, the III group-III nitride crystalline substrates 10p of two adjacency, the interarea 10pm of 10q, the difference of altitude Δ T between the 10qm is preferably below the 0.1mm, more preferably below the 0.01mm.
In addition, from by making described a plurality of III group-III nitride crystalline substrates 10p, the identical viewpoint that designs more uniform crystal growth of the crystalline orientation of 10q is seen, so that substrate 10p, the mode lateral arrangement substrate 10p that [0001] direction of 10q is orientated in the same manner, 10q.Simultaneously, with described a plurality of III group-III nitride crystalline substrates 10p, 10q arranges that adjacent to each otherly because if there is the gap between substrate, the crystalline crystallinity of then growing will suffer damage on this gap.
With reference to Figure 1A and 1B:, from III group-III nitride bulk crystals 1, obtained { the h that has of lateral arrangement as follows by first step (substrate cuts out step) and second step (substrate arrangement step)
0k
0i
0l
0Interarea 10pm, a plurality of III group-III nitride crystalline substrates 10p of 10qm, 10q, described mode makes described a plurality of III group-III nitride crystalline substrates 10p, the interarea 10pm of 10q, and 10qm is parallel to each other, and make substrate 10p, [0001] direction of 10q is orientated in an identical manner.
In the third step (crystal growth step) of present embodiment, at described a plurality of III group-III nitride crystalline substrates 10p, the interarea 10pm of 10q, the last growth of 10qm III group-III nitride crystal 20.In this case, III group-III nitride crystal 20 is grown to epitaxy.Since described a plurality of III group-III nitride crystalline substrates 10p, the interarea 10pm of 10q, and 10qm has { h
0k
0i
0l
0Planar orientation, at described interarea 10pm, the interarea 20m of the last epitaxially grown III group-III nitride crystal 20 of 10qm has and described a plurality of III group-III nitride crystalline substrates 10p, the interarea 10pm of 10q, the planar orientation { h that 10qm is identical
0k
0i
0l
0.In addition, because at described a plurality of III group-III nitride crystalline substrates 10p, the interarea 10pm of 10q, the last growth of 10qm III group-III nitride crystal 20, substrate 10p, the coefficient of thermal expansion differences between the III group-III nitride crystal 20 of 10q and growth is very little, therefore the cooling period after crystal growth, in the crystal of having grown, unlikely occur breaking and being out of shape, thereby obtain having excellent crystalline III group-III nitride crystal.From these viewpoints, preferred described a plurality of III group-III nitride crystalline substrates 10p, 10q has identical chemical constitution with the III group-III nitride crystal 20 of having grown.Make it possible to preparation and have { h
0k
0i
0l
0Interarea 20m and excellent crystalline III group-III nitride crystal 20.
In the manufacturing III of present embodiment group-III nitride crystalline method, above-mentioned { h
0k
0i
0l
0Be preferably and be selected from { 1-10x} (wherein x is the integer more than 0), { 11-2y} (wherein y is the integer more than 0) and { any crystallographical equivalent planar orientation of hk-(h+k) 0} (wherein h and k are the integer except that 0).In therefore restricted III group-III nitride crystal, have { 1-10x}, { 11-2y} or { face of arbitrary planar orientation is a stabilising surface among hk-(h+k) 0}, therefore, has excellent crystalline III group-III nitride crystal having stably to grow on the interarea of this planar orientation.
In addition, if { h
0k
0i
0l
0Not to be selected from { 1-10x}, { 11-2y} and { any crystallographical equivalent planar orientation of hk-(h+k) 0}, then { h
0k
0i
0l
0Can be below 5 ° with respect to any one drift angle in these planar orientations.With respect to being selected from { 1-10x}, { 11-2y} and { any crystallographical equivalent planar orientation of hk-(h+k) 0}, the drift angle be the planar orientation below 5 ° make it possible to with { 1-10x}, { 11-2y} or { identical mode growing crystal in hk-(h+k) the 0} situation therefore has excellent crystalline III group-III nitride crystal having can stably grow on the interarea of this planar orientation.Herein, " drift angle " refers to the angle that formed by any given planar orientation and any other planar orientation, and measures according to X-ray diffraction method.
Purpose has as a reference been described { 1-10x} face (x is the integer more than 0), { 11-2y} face (y is the integer more than 0) and { hk-(h+k) 0} face (h and k are the integer except that 0) in the hexagon III group-III nitride crystalline structure cell in Figure 10～12 herein.Herein, arrow a
1, a
2, a
3With c be the crystallographic axis of hexagon III group-III nitride crystalline structure cell.
In III group-III nitride crystal, have and be selected from { 1-10x}, { 11-2y} and { face of any crystallographical equivalent planar orientation of hk-(h+k) 0} is a stabilising surface.In the growth of III group-III nitride crystalline, the high crystal growth rate that provides by vapor deposition, especially HVPE technology is characterised in that the crystal growth on the c direction of principal axis (that is [0001] direction) is rapid.Therefore, in the III group-III nitride crystal of the growth of the gaseous techniques by such as HVPE, (1-101) face, (1-102) face, (11-21) face and (11-22) face prove more stable.On the other hand because utilize the speed of crystal growth of liquid-phase growth method low, in III group-III nitride crystal by the liquid technology growth, (1-103) face and (11-23) face prove more stable.
Make in the III group-III nitride crystalline method preferably above-mentioned { h in present embodiment
0k
0i
0l
0For being selected from { 1-100}, { 11-20}, { 1-102} and { any crystallographical equivalent planar orientation of 11-22}.Herein, because planar orientation is { 1-100}, { 11-20}, { 1-102} or { the III group-III nitride crystal face of 11-22} is stabilising surface, therefore has excellent crystalline III group-III nitride crystal having can stably grow on the interarea of this planar orientation.
In addition, { h
0k
0i
0l
0Can not to be selected from { 1-100}, { 11-20}, { 1-102} and { any crystallographical equivalent planar orientation of 11-22}, but have drift angle below 5 ° with respect in these planar orientations any one.With respect to being selected from { 1-100}, { 11-20}, { 1-102} and { any crystallographical equivalent planar orientation of 11-22}, the planar orientation of drift angle below 5 ° make it possible to with { 1-100}, { 11-20}, { 1-102} and { therefore identical mode growing crystal in the 11-22} situation has excellent crystalline III group-III nitride crystal having can stably grow on the interarea of this planar orientation.
Make in the III group-III nitride crystalline method also preferred { h in present embodiment
0k
0i
0l
0Be { 1-100}.In III group-III nitride crystal, { 1-100} is stabilising surface and is cleavage surface simultaneously; Therefore, can stably grow and have excellent crystalline III group-III nitride crystal, and by along { the III group-III nitride crystal of the described growth of 1-100} face cleavage can easily be made and has that { interarea of 1-100} planar orientation also has excellent crystalline III group-III nitride crystalline substrates.
In addition, { h
0k
0i
0l
0Can not be 1-100}, but have drift angle below 5 ° with respect to this planar orientation.With respect to { 1-100}, the drift angle makes it possible to below 5 ° with { therefore identical mode growing crystal in the situation of 1-100} has excellent crystalline III group-III nitride crystal having can stably grow on the interarea of this planar orientation.
In addition, make in the III group-III nitride crystalline method in present embodiment, described a plurality of III group-III nitride crystalline substrates 10p, 10q adjacent to each other along face 10pt, the average roughness Ra of 10qt (be called " adjacent surface 10pt; 10qt " here, and following identical) is preferably below the 50nm, more preferably below the 5nm.If adjacent surface 10pt, the average roughness Ra of 10qt surpasses 50nm, adjacent surface 10pt in III group-III nitride crystal 20 then, and the crystallinity of 10qt and near upper area 20t (it will be called " the upper area 20t of substrate adjacency ") thereof will suffer damage.Here, " surface average roughness Ra " refers to the arithmetic average roughness Ra that defines in JIS B0601, specifically, it is meant from roughness curve chooses a datum length along its average line, and the distance from the average line to the roughness curve (absolute value of deviation) of this selected part summed up, and average the value of trying to achieve with datum length.The average roughness Ra on surface can utilize atomic force microscope (AFM) etc. to measure.
Then, make in the III group-III nitride crystalline method in present embodiment, in order to make described a plurality of III group-III nitride crystalline substrates 10p, the adjacent surface 10pt of 10q, the average roughness Ra of 10qt is below the 50nm, first step (substrate cuts out step) afterwards with second step (substrate arrangement step) before, preferably include becoming adjacent surface 10pt, described a plurality of III group-III nitride crystalline substrates 10p of 10qt, the step that the side of 10q is ground and/or polished (below be also referred to as grind and/or polishing step).
In addition, make in the III group-III nitride crystalline method in present embodiment, the crystalline viewpoint of III group-III nitride crystalline of having grown from further raising, first step (substrate cuts out step) afterwards with second step (substrate arrangement step) before, preferably include described a plurality of III group-III nitride crystalline substrates 10p, { h of 10q
0k
0i
0l
0Interarea 10pm, the step that 10qm (it is the surface of III group-III nitride crystal growth) grinds and/or polishes (grinding and/or polishing step).{ h by this grinding and/or polishing step generation
0k
0i
0l
0Interarea 10pm, the surfaceness of 10qm is preferably below the 50nm; Roughness is 5nm more preferably.
Make in the III group-III nitride crystalline method in present embodiment, another favourable condition is that the growth temperature of III group-III nitride crystal 20 is more than 2000 ℃.This is because for the III group-III nitride crystal of growing under the temperature more than 2000 ℃, all be that crystallinity is uniform on the whole surface of crystal growth.Here, " crystallinity is even " is illustrated in by { h
0k
0i
0l
0To distribute in the face of full width at half maximum (FWHM) at the peak that produces of the X-ray diffraction rocking curve analysis of face be narrow, and distribution is narrow in the face of the dislocation desity by cathodoluminescence Spectroscopy (CL) or the quantitative assay of etch-pit density (EPD) method of masurement.
Make in the III group-III nitride crystalline method in present embodiment, another favourable condition is that to make the growth method of III group-III nitride crystal 20 be the sublimation-grown method.This be because, by subliming method, make III group-III nitride crystal under the temperature more than 2000 ℃, grow, Sheng Chang III group-III nitride crystal all is uniform in the whole lip-deep crystallinity of crystal growth thus.
Embodiment
The preparation 1 of III group-III nitride bulk crystals
With reference to Fig. 2, make the GaN bulk crystals by the following method, as make the III group-III nitride bulk crystals that uses in the III group-III nitride crystalline method in the present invention.
At first, making thickness by sputtering deposit is the SiO of 100nm
2Layer as mask layer 91 as lower substrate 90 and interarea, diameter with (111) A face be that 50mm, thickness are to form on the GaAs substrate of 0.8mm.Thereafter, as shown in Figure 2A and 2B, by photoetching be etched in the mask that to form diameter D be the window 91w of 2 μ m, described window 91w arranges with the spacing P of 4 μ m and forms hexagonal tight pattern.In this case, by window 91w GaAs substrate 90 is exposed.
By HVPE make as the GaN bulk crystals of III group-III nitride bulk crystals on the GaAs substrate 90 that be formed with mask 91 with a plurality of window 91ws grow thereafter.Specifically, make thickness under 500 ℃ by HVPE is that the GaN cryosphere of 80nm is grown on the GaAs substrate, be to grow on this layer in the GaN middle layer of 60 μ m making thickness under 950 ℃ subsequently, making thickness afterwards under 1050 ℃ is that the GaN bulk crystals of 5mm is grown on the middle layer.
Thereafter, removing the GaAs substrate by the etch process that adopts chloroazotic acid from the GaN bulk crystals, is that 50mm and thickness are that the GaN bulk crystals of 3mm is as III group-III nitride bulk crystals to obtain diameter.
At first, with reference to figure 3A, to two interareas (0001) face of GaN bulk crystals (III group-III nitride bulk crystals 1) and (000-1) face grind and polish so that the average roughness Ra of these two interareas is 5nm.Here, surface average roughness Ra is measured with AFM.
Thereafter, with reference to figure 3A, along with＜1-100 the average roughness Ra of vertical a plurality of two interarea of cutting of direction all have been the above-mentioned GaN bulk crystals (III group-III nitride bulk crystals 1) of 5nm, have to cut out 1-100} interarea and width S be 3mm, length L be 20～50mm and thickness T be 1mm a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, 10q).Subsequently, not grinding and unpolished four sides of each GaN crystalline substrates of cutting out are ground and polished, so that the average roughness Ra of these four faces is 5nm.Thus, { average roughness Ra of 1-100} interarea is a plurality of GaN crystalline substrates of 5nm in acquisition.In these GaN crystalline substrates, the planar orientation that has interarea is with { the GaN crystalline substrates that 1-100} is not quite identical is still in all situations, with respect to { 1-100}, the drift angle of the planar orientation of this GaN crystalline substrates interarea is below 5 °.Here, the drift angle is measured by X-ray diffraction method.
Thereafter, with reference to figure 3B, in the horizontal these GaN crystalline substrates are arranged adjacent to each otherly, make described a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, (1-100) interarea 10pm 10q), 10qm is parallel to each other, and makes that (III group-III nitride crystalline substrates 10p, [0001] direction 10q) is orientated the GaN crystalline substrates in an identical manner.In this case, further with reference to figure 3C, (average roughness Ra of 10qt is 5nm to described a plurality of GaN crystalline substrates for III group-III nitride crystalline substrates 10p, adjacent surface 10pt 10q).
Thereafter, refer again to Fig. 3 C, in the atmosphere of the gaseous mixture of 10 volume % hydrogenchloride and 90 volume % nitrogen, under 800 ℃, to described a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, (1-100) interarea 10pm 10q) that is arranged, 10qm handled 2 hours, then by HVPE and under 1050 ℃ crystal growth temperature, make GaN crystal (III group-III nitride crystal 2 0) at interarea 10pm with the deposition rate of 20 μ m/hr, the last growth of 10qm 50 hours.
That obtained in addition in the upper area 20t of substrate adjacency also no abnormal Grown GaN crystal (III group-III nitride crystal 2 0) have (1-100) interarea 20m.The crystallinity of GaN crystal (III group-III nitride crystal 2 0) is estimated by the X-ray diffraction rocking curve analysis of (1-100) face.For this GaN crystal, the regional 20s directly over the substrate (meaning is at described a plurality of III group-III nitride crystalline substrates 10p, the regional 20s directly over the 10q, below identical) demonstrate at the tip not splitted diffraction peak, full width at half maximum (FWHM) is 100 arcseconds simultaneously.In the upper area 20t of substrate adjacency, demonstrate in most advanced and sophisticated splitted diffraction peak, full width at half maximum (FWHM) is 300 arcseconds simultaneously.
In addition, by the threading dislocation density of cathodoluminescence Spectroscopy (hereinafter referred to as " CL ") mensuration GaN crystalline (1-100) interarea 20m, the density among the regional 20s of result directly over substrate is 1 * 10
7Cm
-2, the density in the upper area 20t of substrate adjacency is 3 * 10
7Cm
-2In addition, by the carrier concentration in the Hall effect method of masurement mensuration GaN crystal, the result is 5 * 10
18Cm
-3Major impurity in the GaN crystal that detects according to SIMS (second ion mass spectroscopy, below identical) is oxygen (O) atom and silicon (Si) atom.The results are shown in the table 1.
Be to be understood that, in embodiment 1, the planar orientation of the interarea of described a plurality of GaN crystalline substrates (face that it is grown thereon for the GaN crystal) is (1-100), even but several or more interareas be (1100) (itself and (1-100) crystallographical equivalent), still can obtain identical result.
Embodiment 2
Refer again to Fig. 3 A: except that to two interareas of GaN bulk crystals (III group-III nitride bulk crystals 1) promptly (0001) face and (000-1) face grind and polish so that the average roughness Ra of these two interareas is the 50nm, with with embodiment 1 in identical method cut out a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, 10q), and not grinding and unpolished four sides to each GaN crystalline substrates are ground and are polished, so that the average roughness Ra of these four faces is 5nm.In described a plurality of GaN crystalline substrates, the planar orientation that has interarea is with { the GaN crystalline substrates that 1-100} is not quite identical is still in all situations, with respect to { 1-100}, the planar orientation drift angle of the interarea of this GaN crystalline substrates is below 5 °.
Thereafter, with reference to figure 3B, with embodiment 1 in identical mode arrange described a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, 10q).In this case, further with reference to figure 4, the adjacent surface 10pt of described a plurality of GaN crystalline substrates, the average roughness Ra of 10qt is 50nm.
Thereafter, again with reference to figure 4: with embodiment 1 in identical described a plurality of GaN crystalline substrates (the III group-III nitride crystalline substrates 10p of mode to being arranged, (1-100) interarea 10pm 10q), 10qm handles, thereafter with embodiment 1 under the identical condition, at interarea 10pm, the last growing GaN crystal of 10qm (III group-III nitride crystal 2 0).
The GaN crystal that is obtained (III group-III nitride crystal 2 0) has (1-100) interarea 20m, is formed with the recess 20v that is made of a plurality of facet 20f in this interarea 20m in the upper area 20t of substrate adjacency.In addition, in the X-ray diffraction rocking curve of (1-100) face of GaN crystal (III group-III nitride crystal 2 0) was analyzed, the regional 20s directly over the substrate demonstrated at the tip not splitted diffraction peak, and full width at half maximum (FWHM) is 100 arcseconds simultaneously.In the upper area 20t of substrate adjacency, demonstrate in most advanced and sophisticated splitted diffraction peak simultaneously, full width at half maximum (FWHM) is 800 arcseconds simultaneously.
In addition, be 1 * 10 among the regional 20s of threading dislocation density directly over substrate of GaN crystalline (1-100) interarea 20m
7Cm
-2, in the upper area 20t of substrate adjacency, be 8 * 10
7Cm
-2In addition, the carrier concentration in the GaN crystal is 5 * 10
18Cm
-3, and major impurity is Sauerstoffatom and Siliciumatom.The results are shown in the table 1.
Be to be understood that, in embodiment 2, the planar orientation of the interarea of described a plurality of GaN crystalline substrates (face that it is grown thereon for the GaN crystal) is (1-100), even if but several or more interarea is (1100) (its with (1-100) crystallographical equivalent), still can obtain identical result.
Embodiment 3
At first, with reference to figure 5A, to two interareas (0001) face of GaN bulk crystals (III group-III nitride bulk crystals 1) and (000-1) face grind and polish so that the average roughness Ra of these two interareas is 5nm.
Thereafter, refer again to Fig. 5 A: along with＜11-20 the average roughness Ra of vertical a plurality of two interarea of cutting of direction have been the above-mentioned GaN bulk crystals of 5nm (III group-III nitride bulk crystals 1), have to cut out 11-20} interarea and width S be 3mm, length L be 20～50mm and thickness T be 1mm a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, 10q).Subsequently, not grinding and unpolished four sides of each GaN crystalline substrates of cutting out are ground and polished, so that the average roughness Ra of these four faces is 5nm.{ average roughness Ra of 11-20} interarea is a plurality of GaN crystalline substrates of 5nm in acquisition thus.In these GaN crystalline substrates, the planar orientation that has interarea is with { the GaN crystalline substrates that 11-20} is not quite identical is still in all situations, with respect to { 11-20}, the drift angle of the planar orientation of the interarea of this GaN crystalline substrates is below 5 °.
Thereafter, with reference to figure 5B, in the horizontal these GaN crystalline substrates are arranged adjacent to each otherly, make described a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, (11-20) interarea 10pm 10q), 10qm is parallel to each other, and makes [0001] direction of GaN crystalline substrates be orientated in an identical manner.In this case, further with reference to figure 5C, the adjacent surface 10pt of described a plurality of GaN crystalline substrates, the average roughness Ra of 10qt is 5nm.
Thereafter, again with reference to figure 5C: with embodiment 1 in identical described a plurality of GaN crystalline substrates (the III group-III nitride crystalline substrates 10p of mode to being arranged, (11-20) interarea 10pm 10q), 10qm handles, thereafter with embodiment 1 under the identical condition, at interarea 10pm, the last growing GaN crystal of 10qm (III group-III nitride crystal 2 0).
The GaN crystal that is obtained (III group-III nitride crystal 2 0) has (11-20) interarea 20m, is formed with the recess 20v that is limited by a plurality of facet 20f in this interarea 20m in the upper area 20t of substrate adjacency.In addition, in the X-ray diffraction rocking curve of (11-20) face of GaN crystal (III group-III nitride crystal 2 0) was analyzed, the regional 20s directly over the substrate demonstrated at the tip not splitted diffraction peak, and full width at half maximum (FWHM) is 250 arcseconds simultaneously.In the upper area 20t of substrate adjacency, demonstrate in most advanced and sophisticated splitted diffraction peak, full width at half maximum (FWHM) is 620 arcseconds simultaneously.
In addition, be 1 * 10 among the regional 20s of threading dislocation density directly over substrate of GaN crystalline (11-20) interarea 20m
7Cm
-2, in the upper area 20t of substrate adjacency, be 8 * 10
7Cm
-2In addition, the carrier concentration in the GaN crystal is 5 * 10
18Cm
-3, and major impurity is Sauerstoffatom and Siliciumatom.The results are shown in the table 1.
Be to be understood that, in embodiment 3, the planar orientation of described a plurality of GaN crystalline substrates interareas (face that it is grown thereon for the GaN crystal) is (11-20), even if but several or more a plurality of interarea is that (1-120) (with (11-20) crystallographical equivalent) still can obtain identical result.
Embodiment 4
At first, with reference to figure 6A, to two interareas (0001) face of GaN bulk crystals (III group-III nitride bulk crystals 1) and (000-1) face grind so that the average roughness Ra of these two interareas is 50nm.
Thereafter, refer again to Fig. 6 A: along with＜1-102 the average roughness Ra of vertical a plurality of two interarea of cutting of direction have been the above-mentioned GaN bulk crystals of 50nm (III group-III nitride bulk crystals 1), have to cut out 1-102} interarea and width S be 5mm, length L be 20～50mm and thickness T be 1mm a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, 10q).Subsequently, six sides of each GaN crystalline substrates of cutting out are ground and polished, so that the average roughness Ra on surface is 5nm.{ average roughness Ra of 1-102} interarea is a plurality of GaN crystalline substrates of 5nm in acquisition thus.In these GaN crystalline substrates, the planar orientation that has interarea is with { the GaN crystalline substrates that 1-102} is not quite identical is still in all situations, with respect to { 1-102}, the drift angle of the planar orientation of the interarea of this GaN crystalline substrates is below 5 °.
Thereafter, with reference to figure 6B, in the horizontal these GaN crystalline substrates are arranged adjacent to each otherly, make described a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, (1-102) interarea 10pm 10q), 10qm is parallel to each other, and makes [0001] direction of GaN crystalline substrates be orientated in an identical manner.In this case, further with reference to figure 6C, the adjacent surface 10pt of described a plurality of GaN crystalline substrates, the average roughness Ra of 10qt is 5nm.
Thereafter, again with reference to figure 6C: with embodiment 1 in identical described a plurality of GaN crystalline substrates (the III group-III nitride crystalline substrates 10p of mode to being arranged, (1-102) interarea 10pm 10q), 10qm handles, thereafter with embodiment 1 under the identical condition, at interarea 10pm, the last growing GaN crystal of 10qm (III group-III nitride crystal 2 0).
That obtained in addition in the upper area 20t of substrate adjacency also no abnormal Grown GaN crystal have (1-102) interarea 20m.In the X-ray diffraction rocking curve of (1-102) face of GaN crystal (III group-III nitride crystal 2 0) was analyzed, the regional 20s directly over the substrate demonstrated at the tip not splitted diffraction peak, and full width at half maximum (FWHM) is 120 arcseconds simultaneously.In the upper area 20t of substrate adjacency, demonstrate in most advanced and sophisticated splitted diffraction peak simultaneously, full width at half maximum (FWHM) is 480 arcseconds.
In addition, be 1 * 10 among the regional 20s of threading dislocation density directly over substrate of GaN crystalline (1-102) interarea 20m
7Cm
-2, in the upper area 20t of substrate adjacency, be 6 * 10
7Cm
-2In addition, the carrier concentration in the GaN crystal is 5 * 10
18Cm
-3, and major impurity is Sauerstoffatom and Siliciumatom.The results are shown in the table 1.
Be to be understood that, in embodiment 4, the planar orientation of the interarea of described a plurality of GaN crystalline substrates (face that it is grown thereon for the GaN crystal) is (1-102), even if but several or more a plurality of interarea is (1102) (with (1-102) crystallographical equivalent), still can obtain identical result.
Embodiment 5
At first, with reference to figure 7A, to two interareas (0001) face of GaN bulk crystals (III group-III nitride bulk crystals 1) and (000-1) face grind so that the average roughness Ra of these two interareas is 50nm.
Thereafter, refer again to Fig. 7 A: along with＜11-22 the average roughness Ra of vertical a plurality of two interarea of cutting of direction have been the above-mentioned GaN bulk crystals of 50nm (III group-III nitride bulk crystals 1), have to cut out 11-22} interarea and width S be 5mm, length L be 20～50mm and thickness T be 1mm a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, 10q).Subsequently, six sides of each GaN crystalline substrates of cutting out are ground and polished, so that the average roughness Ra of these six faces is 5nm.{ average roughness Ra of 11-22} interarea is a plurality of GaN crystalline substrates of 5nm in acquisition thus.In these GaN crystalline substrates, the planar orientation that has interarea is with { the GaN crystalline substrates that 11-22} is not quite identical is still in all situations, with respect to { 11-22}, the drift angle of the planar orientation of the interarea of this GaN crystalline substrates is below 5 °.
Thereafter, with reference to figure 7B, in the horizontal these GaN crystalline substrates are arranged adjacent to each otherly, make described a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, (11-22) interarea 10pm 10q), 10qm is parallel to each other, and makes [0001] direction of GaN crystalline substrates be orientated in an identical manner.In this case, the adjacent surface 10pt of described a plurality of GaN crystalline substrates, the average roughness Ra of 10qt is 5nm.
Thereafter, with reference to figure 7C: with embodiment 1 in identical described a plurality of GaN crystalline substrates (the III group-III nitride crystalline substrates 10p of mode to being arranged, (11-22) interarea 10pm 10q), 10qm handles, thereafter with embodiment 1 under the identical condition, at interarea 10pm, the last growing GaN crystal of 10qm (III group-III nitride crystal 2 0).
That obtained in addition in the upper area 20t of substrate adjacency also no abnormal Grown GaN crystal have (11-22) interarea 20m.In the X-ray diffraction rocking curve of (11-22) face of GaN crystal (III group-III nitride crystal 2 0) was analyzed, the regional 20s directly over the substrate demonstrated at the tip not splitted diffraction peak, and full width at half maximum (FWHM) is 90 arcseconds simultaneously.In the upper area 20t of substrate adjacency, demonstrate in most advanced and sophisticated splitted diffraction peak, full width at half maximum (FWHM) is 380 arcseconds simultaneously.
In addition, be 1 * 10 among the regional 20s of threading dislocation density directly over substrate of GaN crystalline (11-22) interarea 20m
7Cm
-2, in the upper area 20t of substrate adjacency, be 4 * 10
7Cm
-2In addition, the carrier concentration in the GaN crystal is 5 * 10
18Cm
-3, and major impurity is Sauerstoffatom and Siliciumatom.The results are shown in the table 1.
Be to be understood that, in embodiment 5, the planar orientation of the interarea of described a plurality of GaN crystalline substrates (face that it is grown thereon for the GaN crystal) is (11-22), even if but several or more a plurality of interarea is (2112) (with (11-22) crystallographical equivalent), still can obtain identical result.
Embodiment 6
At first, with reference to figure 8A, to two interareas (0001) face of GaN bulk crystals (III group-III nitride bulk crystals 1) and (000-1) face grind and polish so that the average roughness Ra of these two interareas is 5nm.
Thereafter, refer again to Fig. 8 A: along with＜12-30 the average roughness Ra of vertical a plurality of two interarea of cutting of direction have been the above-mentioned GaN bulk crystals of 5nm (III group-III nitride bulk crystals 1), have to cut out 12-30} interarea and width S be 3mm, length L be 20～50mm and thickness T be 1mm a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, 10q).Subsequently, not grinding and unpolished four sides of each GaN crystalline substrates of cutting out are ground and polished, so that the average roughness Ra of these four faces is 5nm.{ average roughness Ra of 12-30} interarea is a plurality of GaN crystalline substrates of 5nm in acquisition thus.In these GaN crystalline substrates, the planar orientation that has interarea is with { the GaN crystalline substrates that 12-30} is not quite identical is still in all situations, with respect to { 12-30}, the drift angle of the planar orientation of the interarea of this GaN crystalline substrates is below 5 °.
Thereafter, with reference to figure 8B, in the horizontal these GaN crystalline substrates are arranged adjacent to each otherly, make described a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, (12-30) interarea 10pm 10q), 10qm is parallel to each other, and makes [0001] direction of GaN crystalline substrates be orientated in an identical manner.In this case, further with reference to figure 8C, the adjacent surface 10pt of described a plurality of GaN crystalline substrates, the average roughness Ra of 10qt is 5nm.
Thereafter, refer again to Fig. 8 C: with embodiment 1 in identical described a plurality of GaN crystalline substrates (the III group-III nitride crystalline substrates 10p of mode to being arranged, (12-30) interarea 10pm 10q), 10qm handles, thereafter with embodiment 1 under the identical condition, at interarea 10pm, the last growing GaN crystal of 10qm (III group-III nitride crystal 2 0).
The GaN crystal that is obtained (III group-III nitride crystal 2 0) has (12-30) interarea 20m, is formed with the recess 20v that is made of a plurality of facet 20f in this interarea 20m in the upper area 20t of substrate adjacency.In addition, in the X-ray diffraction rocking curve of (12-30) face of GaN crystal (III group-III nitride crystal 2 0) was analyzed, the regional 20s directly over the substrate demonstrated at the tip not splitted diffraction peak, and full width at half maximum (FWHM) is 280 arcseconds simultaneously.Simultaneously, in the upper area 20t of substrate adjacency, demonstrate in most advanced and sophisticated splitted diffraction peak, full width at half maximum (FWHM) is 660 arcseconds.
In addition, be 1 * 10 among the regional 20s of threading dislocation density directly over substrate of GaN crystalline (12-30) interarea 20m
7Cm
-2, in the upper area 20t of substrate adjacency, be 7 * 10
7Cm
-2In addition, the carrier concentration in the GaN crystal is 4 * 10
18Cm
-3, and major impurity is Sauerstoffatom and Siliciumatom.The results are shown in the table 1.
Be to be understood that, in embodiment 6, the planar orientation of the interarea of described a plurality of GaN crystalline substrates (face that it is grown thereon for the GaN crystal) is (12-30), even if but several or more a plurality of interarea is (3210) (with (12-30) crystallographical equivalent), still can obtain identical result.
Embodiment 7
At first, with reference to figure 9A, to two interareas (0001) face of GaN bulk crystals (III group-III nitride bulk crystals 1) and (000-1) face grind and polish so that the average roughness Ra of these two interareas is 5nm.
Thereafter, refer again to Fig. 9 A: along with＜23-50 the average roughness Ra of vertical a plurality of two interarea of cutting of direction have been the above-mentioned GaN bulk crystals of 5nm (III group-III nitride bulk crystals 1), have to cut out 23-50} interarea and width S be 3mm, length L be 20～50mm and thickness T be 1mm a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, 10q).Subsequently, not grinding and unpolished four sides of each GaN crystalline substrates of cutting out are ground and polished, so that the average roughness Ra of these four faces is 5nm.{ average roughness Ra of 23-50} interarea is a plurality of GaN crystalline substrates of 5nm in acquisition thus.In these GaN crystalline substrates, the planar orientation that has interarea is with { the GaN crystalline substrates that 23-50} is not quite identical is still in all situations, with respect to { 23-50}, the drift angle of the planar orientation of the interarea of this GaN crystalline substrates is below 5 °.
Thereafter, with reference to figure 9B, in the horizontal these GaN crystalline substrates are arranged adjacent to each otherly, make described a plurality of GaN crystalline substrates (III group-III nitride crystalline substrates 10p, (23-50) interarea 10pm 10q), 10qm is parallel to each other, and makes [0001] direction of GaN crystalline substrates be orientated in an identical manner.In this case, the adjacent surface 10pt of described a plurality of GaN crystalline substrates, the average roughness Ra of 10qt is 5nm.
With reference to figure 9C: then by flux method for growth, (III group-III nitride crystalline substrates 10p, (23-50) interarea 10pm 10q) is on the 10qm for the described a plurality of GaN crystalline substrates that GaN crystal (III group-III nitride crystal 2 0) are deposited on arranged.Specifically, make Ga-Na melt (mixture of Ga and Na fusing) at (23-50) of described a plurality of GaN crystalline substrates interarea 10pm, the last contact of 10qm, and under the condition of the crystal growth temperature of 870 ℃ and 4MPa (40 normal atmosphere) and crystal growth pressure (nitrogen pressure), deposition rate with 5 μ m/hr makes GaN crystal (III group-III nitride crystal 2 0) in (23-50) of GaN crystalline substrates interarea 10pm, the last growth of 10qm 100 hours.
That obtained in addition in the upper area 20t of substrate adjacency also no abnormal Grown GaN crystal have (23-50) interarea 20m.In the X-ray diffraction rocking curve of (23-50) face of GaN crystal (III group-III nitride crystal 2 0) was analyzed, the regional 20s directly over the substrate demonstrated at the tip not splitted diffraction peak, and full width at half maximum (FWHM) is 230 arcseconds simultaneously.Simultaneously, in the upper area 20t of substrate adjacency, demonstrate in most advanced and sophisticated splitted diffraction peak, full width at half maximum (FWHM) is 490 arcseconds.
In addition, be 1 * 10 among the regional 20s of threading dislocation density directly over substrate of GaN crystalline (23-50) interarea 20m
7Cm
-2, in the upper area 20t of substrate adjacency, be 4 * 10
7Cm
-2In addition, the carrier concentration in the GaN crystal is 3 * 10
18Cm
-3, and major impurity is Sauerstoffatom and Siliciumatom.The results are shown in the table 1.
Be to be understood that, in embodiment 7, the interarea 10pm of described a plurality of GaN crystalline substrates, the planar orientation of 10qm (face that it is grown thereon for the GaN crystal) is (23-50), even if but several or more a plurality of interarea is (5230) (with (23-50) crystallographical equivalent), still can obtain identical result.
Table 1
As obvious, has { h by table 1
0k
0i
0l
0The III group-III nitride crystal of interarea is to obtain by the III group-III nitride crystal manufacture method that may further comprise the steps: cut out by III group-III nitride bulk crystals and a plurality ofly have except that { any given side orientation { h the 0001}
0k
0i
0l
0The III group-III nitride crystalline substrates of interarea; In the horizontal described a plurality of III group-III nitride crystalline substrates are arranged adjacent to each otherly, make that the interarea of described a plurality of III group-III nitride crystalline substrates is parallel to each other, and make [0001] direction of substrate be orientated in an identical manner; And the III group-III nitride crystal of on the interarea of described a plurality of III group-III nitride crystalline substrates, growing.
Herein shown in embodiment 1～7, described { h
0k
0i
0l
0Be, with respect to being selected from { 1-10x} (wherein x is the integer more than 0), { 11-2y} (wherein y is the integer more than 0) and { any crystallographical equivalent planar orientation of hk-(h+k) 0} (wherein h and k are the integer except that 0), the drift angle is below 5 °, can obtain to have { h thus
0k
0i
0l
0Interarea and excellent crystalline III group-III nitride crystal.Especially, shown in embodiment 1, by making { h
0k
0i
0l
0For { 1-100} can obtain to have excellent especially crystalline III group-III nitride crystal.
In addition, shown in embodiment 1 and 2, from making the viewpoint of III group-III nitride crystalchecked growth, described a plurality of III group-III nitride crystalline substrates are preferably below the 50nm in abutting connection with the average roughness Ra of the face on institute edge, more preferably below the 5nm.
The preparation 2 of III group-III nitride bulk crystals
Make the AlN bulk crystals by the following method, as make the III group-III nitride bulk crystals that uses in the III group-III nitride crystalline method in the present invention.
At first, making the AlN bulk crystals be deposited on diameter as lower substrate by the sublimation-grown method is that 51mm, thickness are on the interarea of (0001) face of SiC substrate of 0.5mm.During the AlN bulk crystal growth, when making growth temperature be 1700 ℃, supply with 0.1 quality %CO
2Gas (gas that contains IV family element) is to be entrained in together with crystal with as the carbon atom of IV family doping agent, till crystal growth to thickness is 0.5mm., growth temperature maintained 1800 ℃, stop to supply with the gas of the described IV of containing family element simultaneously, and make and grow to the AlN bulk crystals that thickness is 5.5mm (comprising the thick part of above-mentioned 0.5mm that is doped with carbon atom) thereafter.On (0001) face of the AlN bulk crystals of growing, be formed with a plurality of hexagonal tapered recess that limit by a plurality of facets.
Thereafter, adopting mechanical polishing, the SiC substrate is removed from above-mentioned AlN bulk crystals, is that 50mm and thickness are the AlN bulk crystals of 3mm with the diameter that obtains as III group-III nitride bulk crystals.At this moment, will be doped with IV family doping agent (carbon) and grow to the thick described part of 0.5mm by the gas that supply contains IV family element and remove.
Embodiment 8
At first, with reference to figure 3A, to two interareas (0001) face of AlN bulk crystals (III group-III nitride bulk crystals 1) and (000-1) face grind and polish so that the average roughness Ra of two interareas is 5nm.
Thereafter, refer again to Fig. 3 A: along with＜1-100 the average roughness Ra of vertical a plurality of two interarea of cutting of direction have been the above-mentioned AlN bulk crystals of 5nm, have to cut out 1-100} interarea and width S be 3mm, length L be 20～50mm and thickness T be 1mm a plurality of AlN crystalline substrates (III group-III nitride crystalline substrates 10p, 10q).Subsequently, not grinding and unpolished four sides of each AlN crystalline substrates of cutting out are ground and polished, so that the average roughness Ra of these four faces is 5nm.{ average roughness Ra of 1-100} interarea is a plurality of AlN crystalline substrates of 5nm in acquisition thus.In these AlN crystalline substrates, the planar orientation that has interarea is with { the AlN crystalline substrates that 1-100} is not quite identical is still in all situations, with respect to { 1-100}, the drift angle of the planar orientation of the interarea of this AlN crystalline substrates is below 5 °.
Thereafter, with reference to figure 3B, in the horizontal these AlN crystalline substrates are arranged adjacent to each otherly, make described a plurality of AlN crystalline substrates (III group-III nitride crystalline substrates 10p, (1-100) interarea 10pm 10q), 10qm is parallel to each other, and makes [0001] direction of AlN crystalline substrates be orientated in an identical manner.In this case, further with reference to figure 3C, the adjacent surface 10pt of described a plurality of AlN crystalline substrates, the average roughness Ra of 10qt is 5nm.
Thereafter, refer again to Fig. 3 C, at 2200 ℃ under nitrogen environment, by the sublimation-grown method, deposition rate with 100 μ m/hr makes AlN crystal (III group-III nitride crystal 2 0) at described a plurality of AlN crystalline substrates of having arranged (III group-III nitride crystalline substrates 10p, (1-100) interarea 10pm 10q), the last deposit of 10qm 50 hours.
That obtained in addition in the upper area 20t of substrate adjacency also the AlN crystal of no abnormal growth (III group-III nitride crystal 2 0) have (1-100) interarea 20m.X-ray diffraction rocking curve analysis by (1-100) face is estimated the crystallinity of AlN crystal (III group-III nitride crystal 2 0).For this AlN crystal, the regional 20s directly over the substrate demonstrates at the tip not splitted diffraction peak, and full width at half maximum (FWHM) is 30 arcseconds simultaneously.Similarly, in the upper area 20t of substrate adjacency, also demonstrate at the tip not splitted diffraction peak, full width at half maximum (FWHM) is 50 arcseconds simultaneously.
In addition, measure the threading dislocation density of AlN crystal (1-100) interarea 20m in the following manner.That is, shown in Fig. 3 C, will have (1-100) face and cut out for the AlN wafer (III group-III nitride crystal wafer 21) in wide zone.This AlN wafer (III group-III nitride crystal wafer 21) is heated to 250 ℃, and by (mass ratio, KOH:NaOH=50:50) middle this wafer of dipping came etching (1-100) interarea in 1 hour at fusion KOH-NaOH liquified mixt.(1-100) interarea by the etched AlN wafer of observation post under opticmicroscope (III group-III nitride crystal wafer 21), corrosion pit number in 100 μ m * 100 μ m facings is counted, to calculate etch-pit density (EPD) as interarea threading dislocation density.
Among the regional 20s of threading dislocation density directly over substrate of above-mentioned AlN crystal (1-100) interarea 20m is 1 * 10
5Cm
-2, in the upper area 20t of substrate adjacency, be 2 * 10
5Cm
-2Simultaneously, the major impurity that detects in the AlN crystal according to SIMS (second ion mass spectroscopy) is Sauerstoffatom and carbon atom.The results are shown in the table 2.
Be to be understood that, in embodiment 8, the planar orientation of the interarea of described a plurality of AlN crystalline substrates (face that it is grown thereon for the AlN crystal) is (1-100), even if but several or more a plurality of interarea is (1100) (with (1-100) crystallographical equivalent), still can obtain identical result.
Embodiment 9
At first, with reference to figure 3A, to two interareas (0001) face of AlN bulk crystals and (000-1) face grind and polish so that the average roughness Ra of two interareas is 50nm.
Thereafter, refer again to Fig. 3 A: along with＜1-100 the average roughness Ra of vertical a plurality of two interarea of cutting of direction have been the above-mentioned AlN bulk crystals of 50nm, have to cut out 1-100} interarea and width S be 3mm, length L be 20～50mm and thickness T be 1mm a plurality of AlN crystalline substrates (III group-III nitride crystalline substrates 10p, 10q).Subsequently, not grinding and unpolished four sides of each AlN crystalline substrates of cutting out are ground and polished, so that the average roughness Ra of these four faces is 5nm.{ average roughness Ra of 1-100} interarea is a plurality of AlN crystalline substrates of 5nm in acquisition thus.In these AlN crystalline substrates, the planar orientation that has interarea is with { the AlN crystalline substrates that 1-100} is not quite identical is still in all situations, with respect to { 1-100}, the drift angle of the planar orientation of the interarea of this AlN crystalline substrates is below 5 °.
Thereafter, with reference to figure 3B, in the horizontal these AlN crystalline substrates are arranged adjacent to each otherly, make described a plurality of AlN crystalline substrates (III group-III nitride crystalline substrates 10p, (1-100) interarea 10pm 10q), 10qm is parallel to each other, and makes [0001] direction of AlN crystalline substrates be orientated in an identical manner.In this case, further with reference to figure 3C, the adjacent surface 10pt of described a plurality of AlN crystalline substrates, the average roughness Ra of 10qt is 50nm.
Thereafter, again with reference to figure 3C, at 2200 ℃ under nitrogen environment, by the sublimation-grown method, deposition rate with 100 μ m/hr makes AlN crystal (III group-III nitride crystal 2 0) at described a plurality of AlN crystalline substrates of having arranged (III group-III nitride crystalline substrates 10p, (1-100) interarea 10pm 10q), the last deposit of 10qm 50 hours.
That obtained in addition in the upper area 20t of substrate adjacency also the AlN crystal of no abnormal growth (III group-III nitride crystal 2 0) have (1-100) interarea 20m.In the X-ray diffraction rocking curve of AlN crystalline (1-100) face was analyzed, the regional 20s directly over the substrate demonstrated at the tip not splitted diffraction peak, and full width at half maximum (FWHM) is 100 arcseconds simultaneously.Similarly, in the upper area 20t of substrate adjacency, also demonstrate at the tip not splitted diffraction peak, full width at half maximum (FWHM) is 150 arcseconds simultaneously.In addition, be 3 * 10 among the regional 20s of threading dislocation density directly over substrate of AlN crystalline (1-100) interarea 20m
5Cm
-2, in the upper area 20t of substrate adjacency, be 4 * 10
5Cm
-2Simultaneously, the major impurity in the AlN crystal is Sauerstoffatom and carbon atom.The results are shown in the table 2.
Be to be understood that, in embodiment 9, the planar orientation of the interarea of described a plurality of AlN crystalline substrates (face that it is grown thereon for the AlN crystal) is (1-100), even if but several or more a plurality of interarea is (1100) (its with (1-100) crystallographical equivalent), still can obtain identical result.
Table 2
As obvious, has { h by table 2
0k
0i
0l
0The III group-III nitride crystal of interarea is to obtain by the III group-III nitride crystal manufacture method that may further comprise the steps: cut out by III group-III nitride bulk crystals and a plurality ofly have except that { any given side orientation { h the 0001}
0k
0i
0l
0The III group-III nitride crystalline substrates of interarea; In the horizontal described substrate is arranged adjacent to each otherly, made that the interarea of described a plurality of III group-III nitride crystalline substrates is parallel to each other, and make [0001] direction of substrate be orientated in an identical manner; And the III group-III nitride crystal of on the interarea of described a plurality of III group-III nitride crystalline substrates, growing.
Herein, as obvious by the comparison between the embodiment 8～9 in embodiment in the table 1 1～7 and the table 2, discovery is in III group-III nitride crystalline manufacture method, by making III group-III nitride crystalline growth temperature is more than 2000 ℃, and the result significantly reduces the threading dislocation density of III group-III nitride crystalline interarea.
It is exemplary that embodiment disclosed by the invention and embodiment all should be considered in all respects, rather than restrictive.Scope of the present invention is not to limit by above-mentioned specification sheets, but limits by the scope of the application's claim, and is intended to comprise scope and all changes in this scope that are equivalent to claim of the present invention.
Industrial usability
By the III family element nitride crystal of manufacture method manufacturing of the present invention be used for comprising optical element (as Light emitting diode and laser diode) application, and be used for semi-conductor electronic device (such as rectification Device, bipolar transistor, field-effect transistor or HEMT (HEMTs)), half The conductor sensor is (such as temperature sensor, pressure sensor, radiation sensor or visible-blind area ultraviolet Detector), SAW device (SAW device), acceleration transducer, MEMS (MEMS) Parts, piezoelectric oscillator, resonator, piezoelectric actuator.
Claims (7)
1. make III group-III nitride crystalline method for one kind, described III group-III nitride crystal have except that the interarea of any specified planar orientation the 0001}, described III group-III nitride crystal manufacture method comprises:
Cut out the step of the III group-III nitride crystalline substrates of a plurality of interareas with described specified planar orientation by III group-III nitride bulk crystals;
In the horizontal described substrate is arranged adjacent to each otherly, made that the interarea of described substrate is parallel to each other, and make the step that [0001] direction of described substrate is orientated in an identical manner; And
Growth III group-III nitride crystalline step on the described interarea of described substrate.
2. manufacturing III group-III nitride crystalline method according to claim 1, wherein with respect to being selected from { 1-10x}, { 11-2y} and { any crystallographical equivalent planar orientation of hk-(h+k) 0}, the drift angle of described specified planar orientation is below 5 °, wherein x is the integer more than 0, y is the integer more than 0, and h and k are the integer except that 0.
3. manufacturing III group-III nitride crystalline method according to claim 1 is wherein with respect to being selected from { 1-100}, { 11-20}, { 1-102} and { any crystallographical equivalent planar orientation of 11-22}, the drift angle of described specified planar orientation is below 5 °.
4. manufacturing III group-III nitride crystalline method according to claim 1 is wherein with respect to { 1-100}, the drift angle of described specified planar orientation is below 5 °.
5. according to each described manufacturing III group-III nitride crystalline method in the claim 1～4, wherein said substrate is that face below the 50nm is adjacent to each other along average roughness Ra.
6. according to each described manufacturing III group-III nitride crystalline method in the claim 1～5, wherein said III group-III nitride crystalline growth temperature is more than 2000 ℃.
7. according to each described manufacturing III group-III nitride crystalline method in the claim 1～6, wherein said III group-III nitride crystalline growth method is the sublimation-grown method.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP311622/2006 | 2006-11-17 | ||
| JP2006311622 | 2006-11-17 | ||
| JP258567/2007 | 2007-10-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101535533A true CN101535533A (en) | 2009-09-16 |
Family
ID=39604350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800427005A Pending CN101535533A (en) | 2006-11-17 | 2007-11-14 | Process for producing group iii element nitride crystal |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5765367B2 (en) |
| CN (1) | CN101535533A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102959141A (en) * | 2010-08-03 | 2013-03-06 | 住友电气工业株式会社 | Group iii nitride crystal growing method |
| CN103124811A (en) * | 2010-09-27 | 2013-05-29 | 住友电气工业株式会社 | Method for growing GaN crystal and GaN crystal substrate |
| CN105483833A (en) * | 2015-11-24 | 2016-04-13 | 北京华进创威电子有限公司 | Dislocation etching method for aluminum nitride single crystal |
| CN107208312A (en) * | 2015-01-29 | 2017-09-26 | 日本碍子株式会社 | Self-supporting substrate, function element and its manufacture method |
| CN107338477A (en) * | 2016-05-02 | 2017-11-10 | 国立大学法人大阪大学 | The manufacture method and crystalline growth substrate of crystal of nitride substrate |
| CN108085745A (en) * | 2017-12-28 | 2018-05-29 | 北京华进创威电子有限公司 | A kind of aluminum nitride crystal growth is prepared with homo-substrate and expanding growing method |
| CN108166059A (en) * | 2017-12-21 | 2018-06-15 | 北京华进创威电子有限公司 | A kind of aluminium nitride substrate prepares and expanding growing method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5127983A (en) * | 1989-05-22 | 1992-07-07 | Sumitomo Electric Industries, Ltd. | Method of producing single crystal of high-pressure phase material |
| JP3350992B2 (en) * | 1993-02-05 | 2002-11-25 | 住友電気工業株式会社 | Diamond synthesis method |
| JP3968968B2 (en) * | 2000-07-10 | 2007-08-29 | 住友電気工業株式会社 | Manufacturing method of single crystal GaN substrate |
| JP4915128B2 (en) * | 2005-04-11 | 2012-04-11 | 日亜化学工業株式会社 | Nitride semiconductor wafer and method for manufacturing the same |
-
2007
- 2007-11-14 CN CNA2007800427005A patent/CN101535533A/en active Pending
-
2013
- 2013-05-07 JP JP2013097711A patent/JP5765367B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102959141A (en) * | 2010-08-03 | 2013-03-06 | 住友电气工业株式会社 | Group iii nitride crystal growing method |
| CN102959141B (en) * | 2010-08-03 | 2015-11-25 | 住友电气工业株式会社 | For growing the method for group III-nitride crystal |
| CN103124811A (en) * | 2010-09-27 | 2013-05-29 | 住友电气工业株式会社 | Method for growing GaN crystal and GaN crystal substrate |
| CN107208312A (en) * | 2015-01-29 | 2017-09-26 | 日本碍子株式会社 | Self-supporting substrate, function element and its manufacture method |
| CN107208312B (en) * | 2015-01-29 | 2019-10-01 | 日本碍子株式会社 | Self-supporting substrate, function element and its manufacturing method |
| CN105483833A (en) * | 2015-11-24 | 2016-04-13 | 北京华进创威电子有限公司 | Dislocation etching method for aluminum nitride single crystal |
| CN107338477A (en) * | 2016-05-02 | 2017-11-10 | 国立大学法人大阪大学 | The manufacture method and crystalline growth substrate of crystal of nitride substrate |
| CN107338477B (en) * | 2016-05-02 | 2021-12-07 | 国立大学法人大阪大学 | Method for producing nitride crystal substrate and substrate for crystal growth |
| CN108166059A (en) * | 2017-12-21 | 2018-06-15 | 北京华进创威电子有限公司 | A kind of aluminium nitride substrate prepares and expanding growing method |
| CN108085745A (en) * | 2017-12-28 | 2018-05-29 | 北京华进创威电子有限公司 | A kind of aluminum nitride crystal growth is prepared with homo-substrate and expanding growing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5765367B2 (en) | 2015-08-19 |
| JP2013147426A (en) | 2013-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5332168B2 (en) | Method for producing group III nitride crystal | |
| CN104250853B (en) | Group III nitride crystal | |
| US7964477B2 (en) | Method of manufacturing III nitride crystal, III nitride crystal substrate, and semiconductor device | |
| US7998847B2 (en) | III-nitride crystal manufacturing method, III-nitride crystal substrate, and III-nitride semiconductor device | |
| CN101410950B (en) | Growth method using nanostructure compliant layers and HVPE for producing high quality compound semiconductor materials | |
| JP5765367B2 (en) | GaN crystal | |
| JP6187576B2 (en) | Group III nitride crystals | |
| JP2001284314A (en) | Method of manufacturing nitride-based semiconductor layer | |
| US9064706B2 (en) | Composite of III-nitride crystal on laterally stacked substrates | |
| JP5012700B2 (en) | Group III nitride crystal bonded substrate, method of manufacturing the same, and method of manufacturing group III nitride crystal | |
| JP2022514918A (en) | Semiconductor substrate with n-doped intermediate layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20090916 |