CN108531989A - Adulterate gallium oxide crystal and preparation method thereof - Google Patents
Adulterate gallium oxide crystal and preparation method thereof Download PDFInfo
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- CN108531989A CN108531989A CN201710124917.6A CN201710124917A CN108531989A CN 108531989 A CN108531989 A CN 108531989A CN 201710124917 A CN201710124917 A CN 201710124917A CN 108531989 A CN108531989 A CN 108531989A
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- gallium oxide
- crystal
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- oxide crystal
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 112
- 239000013078 crystal Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010955 niobium Substances 0.000 claims abstract description 13
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000004020 conductor Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 42
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 26
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000000137 annealing Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 239000003574 free electron Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000005355 Hall effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- NVDNLVYQHRUYJA-UHFFFAOYSA-N hafnium(iv) carbide Chemical compound [Hf+]#[C-] NVDNLVYQHRUYJA-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
-
- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- 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
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
-
- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Present invention is disclosed a kind of doping gallium oxide crystal and preparation method thereof.Doping gallium oxide crystal provided by the invention is the doped formation N-type electric conductor of gallium oxide crystal, and doped chemical is niobium, and doping concentration is ranging from less than or equal to 0.8mol%.The present invention can obtain the gallium oxide crystal with high carrier concentration and high conductivity, also, by the control to doping concentration, can obtain the gallium oxide crystal of different resistivity and carrier concentration.
Description
Technical field
The present invention relates to artificial lens technical fields, more particularly to a kind of doping gallium oxide crystal and preparation method thereof.
Background technology
β-Ga2O3(gallium oxide) is a kind of direct band gap semiconductor material with wide forbidden band, and energy gap is about 4.8~4.9eV.
It has energy gap is big, saturated electron drift velocity is fast, thermal conductivity is high, disruptive field intensity is high, chemical property stablize etc. it is many excellent
Point is all transparent from deep ultraviolet (DUV) to infrared region (IR), compared with conventional transparent conductive material (TCOs), can make
The shorter new generation of semiconductor photoelectric device of standby wavelength.
Pure β-Ga2O3Crystal shows as semi-insulating or weaker N-type conduction, the raising β-Ga being currently known2O3Crystal
The main method of N-type conductive capability is to carry out the doping of 4 valence ions, main Si, Hf including the 4th main group and the 4th subgroup,
Ge, Sn, Zr, Ti etc..By taking Si as an example, the dominant mechanism reaction for improving carrier concentration is as follows
As can be seen from the above equation, the theoretical limit ability that 4 valence element dopings provide free electron is about 1:1, with doping
Concentration improves, and crystal structure difficulty increases, and conductivity improves limitation.
Invention content
The purpose of the present invention is to provide a kind of doping gallium oxide crystal and preparation method thereof, improve leading for gallium oxide crystal
Electric energy power, and obtain carrier concentration and the adjustable gallium oxide crystal of resistivity.
In order to solve the above technical problems, the present invention provides a kind of doping gallium oxide crystal, the doped formation N of gallium oxide crystal
Type electric conductor, doped chemical are niobium, and doping concentration is ranging from less than or equal to 0.8mol%.
Optionally, for the doping gallium oxide crystal, the gallium oxide crystal is the β-Ga of monoclinic system2O3Crystal.
Optionally, for the doping gallium oxide crystal, niobium doping concentration ranging from 0.0001~0.8mol%.
Optionally, for the doping gallium oxide crystal, the resistivity of the doping gallium oxide crystal is 5.5 × 10-3
~3.6 × 102Ω cm, carrier concentration is 9.55 × 1016~1.8 × 1019/cm3。
The present invention also provides a kind of preparation methods of doping gallium oxide crystal, including：
Gallium oxide powder and niobium oxide powder are provided, the proportioning of niobium oxide is less than or equal to 0.8mol%；
So that carrying out crystal growth after the gallium oxide powder and niobium oxide powder mixing, doping gallium oxide crystal is obtained.
Optionally, for the preparation method of the described doping gallium oxide crystal, the purity of the gallium oxide powder be 6N with
On, the purity of the niobium oxide powder is 4N or more.
Optionally, for the preparation method of the doping gallium oxide crystal, the gallium oxide powder and niobium oxide powder
The proportioning of middle niobium oxide is 0.0001~0.8mol%.
Optionally, for the preparation method of the doping gallium oxide crystal, the gallium oxide powder and niobium oxide powder
It is uniformly mixed in organic solvent.
Optionally, for the preparation method of the doping gallium oxide crystal so that the gallium oxide powder and niobium oxide
Powder is uniformly mixed in organic solvent as batch mixing 12h-24h in the ball mill in a sealed meter environment.
Optionally, for the preparation method of the doping gallium oxide crystal, carrying out crystal growth includes：
Drying removal organic solvent is carried out to mixed powder；
Mixed powder is pressed into charge bar；
It is sintered so that solid phase reaction, formation polycrystal material occur for gallium oxide and niobium oxide；
Seed crystal is provided, is grown using the polycrystal material, doping gallium oxide crystal is obtained.
Optionally, for the preparation method of the doping gallium oxide crystal, the drying is to be dried at 80 DEG C~100 DEG C
Roasting 3h~6h.
Optionally, described to be sintered in Muffle furnace 1400 DEG C for the preparation method of the doping gallium oxide crystal
~1600 DEG C of sintering 10h-20h.
Optionally, for the preparation method of the doping gallium oxide crystal, the seed crystal is gallium oxide crystal.
Optionally, for the preparation method of the doping gallium oxide crystal, the speed of the growth is 2~6mm/h, is turned
Speed is 5~15rpm.
Doping gallium oxide crystal provided by the invention and preparation method thereof is that the doped formation N-type of gallium oxide crystal is conductive
Body, doped chemical are niobium, can provide more free electrons, and doping concentration is ranging from less than or equal to 0.8mol%.The present invention
The gallium oxide crystal with high carrier concentration and high conductivity can be obtained, also, by the control to doping concentration, it can
Obtain the gallium oxide crystal of different resistivity and carrier concentration.
Description of the drawings
Fig. 1 is the flow chart of the preparation method of doping gallium oxide crystal in one embodiment of the invention；
Fig. 2 be different niobium doping concentrations under, carrier, resistivity change schematic diagram.
Specific implementation mode
The doping gallium oxide crystal and preparation method thereof of the present invention is described in more detail below in conjunction with schematic diagram,
Which show the preferred embodiment of the present invention, it should be appreciated that and those skilled in the art can change invention described herein,
And still realize the advantageous effects of the present invention.Therefore, following description should be understood as the extensive of those skilled in the art
Know, and is not intended as limitation of the present invention.
The present invention is more specifically described by way of example with reference to attached drawing in the following passage.It is wanted according to following explanation and right
Ask book, advantages and features of the invention that will become apparent from.It should be noted that attached drawing is all made of very simplified form and uses non-
Accurately ratio, only for the purpose of facilitating and clarifying the purpose of the embodiments of the invention.
Main idea is that providing a kind of doping gallium oxide crystal, the doped formation N-type of gallium oxide crystal is conductive
Body, doped chemical are niobium, and doping concentration is ranging from less than or equal to 0.8mol%.The present invention can be obtained with high current-carrying as a result,
The gallium oxide crystal of sub- concentration and high conductivity, also, by the control to doping concentration, different resistivity and load can be obtained
Flow the gallium oxide crystal of sub- concentration.
The key reaction mechanism of the present invention is as follows：
For formula 2 as it can be seen that relative to IV races element compared with formula 1 in the prior art, Nb (niobium) element dopings of+5 valences can be with
More free electrons are provided than+4 valence elements, it is possible thereby to achieve the effect that the present invention.
Heretofore described gallium oxide crystal is the β-Ga of monoclinic system2O3Crystal, space group C2/m.The niobium doping
Concentration range may further be 0.0001~0.8mol%.The resistivity of the doping gallium oxide crystal is 5.5 × 10-3~
3.6×102Ω cm, carrier concentration is 9.55 × 1016~1.8 × 1019/cm3.Such as Fig. 1, part niobium doping concentration is shown
Under, the variation of carrier, resistivity.
May contain in the present invention element that the raw material that usually can obtain inevitably contains in subtractive process and
The inevitably mixed impurity in technique.Above-mentioned element and above-mentioned impurity, relative to whole constituents, preferably
10ppm is hereinafter, to ensure that the performance of gained doping gallium oxide crystal is unaffected.
The preparation of the doping gallium oxide crystal of the present invention may be used floating zone method and be grown, it is to be understood that
Those skilled in the art on the basis of disclosed by the invention, can selection other methods appropriate prepared, such as czochralski method,
Bridgman-Stockbarger method, EFG technique etc..
Referring to FIG. 1, the preparation method of the doping gallium oxide crystal of the present invention, including：
First, step S11 is executed, gallium oxide (Ga is provided2O3) powder and niobium oxide (Nb2O5) powder, the proportioning of gallium oxide
To be less than or equal to 0.8mol%, for example, it may be 0.0001~0.8mol%；Preferably, in order to reduce the shadow of impurity as far as possible
It rings, the purity of niobium oxide powder is 4N (99.99m%) or more in the raw material used, and the purity of gallium oxide powder is in 6N
More than (99.9999m%).In one embodiment, gallium oxide powder described in raw material proportioning and niobium oxide powder be in molar ratio
0.999999:0.000001 ratio weighs, and in other embodiments, remembers that the molar ratio of niobium oxide powder is x, gallium oxide powder
Molar ratio is 1-x, wherein 0 x≤0.008 ＜, such as 0.00001,0.0001,0.002,0.005,0.008 etc..
Then, step S12 is executed so that carry out crystal growth after the gallium oxide powder and niobium oxide powder mixing, obtain
Gallium oxide crystal must be adulterated.
This step S12 is specifically included：Step S121, batch mixing.The mixing of the gallium oxide powder and niobium oxide powder can be with
Using wet-mixing, the solvent and dosage that use simultaneously are not specially limited, it is only necessary to contribute to the gallium oxide powder and oxidation
Niobium powder is uniformly mixed, and is subsequently easily removed.Such as the organic solvents such as selection ethyl alcohol, methanol, isopropanol.The present invention is real
It applies and selects absolute ethyl alcohol in example, in a sealed meter environment so that the gallium oxide powder and niobium oxide powder mix in ethanol
It is even.This step S121 can be that the gallium oxide powder and niobium oxide powder are put into clean polytetrafluoroethylene (PTFE) ball grinder,
It is put into high-purity corundum ball, pours into appropriate absolute ethyl alcohol, after sealing, is put into ball mill, batch mixing 12h~for 24 hours, so it may insure
The gallium oxide powder and niobium oxide powder are uniformly mixed.
Step S122, drying.Drying removal ethyl alcohol is carried out to mixed powder；Specifically, this step can be by ball
Grinding jar is placed on inside baking oven, toasts 3h~6h at 80 DEG C~100 DEG C until ethyl alcohol volatilizees completely.According to actual conditions, if second
It lumps after alcohol volatilization, can also continue to be placed on ball mill ball milling and the block stock after drying be clayed into power in 10 minutes or so
Shape.
Step S123, pressure bar.Mixed powder is pressed into charge bar；Specifically, this step can be will be mixed
Mixed-powder is put into organic mold, and charge bar is pressed into using isostatic pressing machine.
Step S124, sintering.It is sintered so that solid phase reaction, formation polycrystal material occur for gallium oxide and niobium oxide；Specifically
, this step can be 1400 DEG C~1600 DEG C sintering 10h-20h in Muffle furnace.Can also so remove in charge bar may deposit
Moisture, with improve generate polycrystal material quality.For example, can be sintered at 1500 DEG C in one embodiment
10h。
Step S125, growth.Seed crystal is provided, is grown using the polycrystal material, doping gallium oxide crystal is obtained.Growth
Atmosphere is inert atmosphere or oxidizing atmosphere, to ensure the valence stability of high valence ion.Specifically, for the optics floating region taken
The polycrystal material sintered can be fitted into the stove of floating region and be used as loading rod by method, be placed below as seed crystal, example using gallium oxide crystal
It can such as select<010>Direction,<100>Direction or<001>The gallium oxide crystal in direction etc. is as seed crystal, preferably<010>
The gallium oxide crystal in direction, to be conducive to obtain the gallium oxide single crystal of better quality.Heating first makes seed crystal melt, then in contact
The loading rod in face reaches the growth for starting crystal after stablizing.The stabilization speed of growth of crystal is preferably 2~6mm/h, such as 3mm/
H, 4.5mm/h etc., rotating speed are preferably 5~15rpm, such as 8rpm, 12rpm etc., and growth atmosphere is in one embodiment of the invention
Air.After crystal growth, stop the decline of loading rod, so that melting zone is gradually disengaged by the natural decline of lower faceted crystal, then
It is slowly dropped to room temperature naturally by 1-3h, takes out crystal.Can be the speed with 5mm/h for example, in one embodiment of the invention
The growth of crystal is carried out, rotating speed 10rpm is naturally cooling to room temperature by 2h after the growth was completed.
The doping gallium oxide crystal obtained using this method, for gained crystal perfection without cracking, color is uniform.
The present invention has also carried out electrical measurement to the doping gallium oxide crystal of acquisition.For example, for the gallium oxide
Powder and niobium oxide powder in molar ratio 0.999999:The doping gallium oxide crystal obtained after 0.000001, will adulterate gallium oxide
Crystal is cut into 5mm × 5mm × 0.3mm (length, width and height) sample, on quadrangle make indium electrode after, using Hall effect tester into
Row detection, the conduction type that can measure the doping gallium oxide crystal are N-type, and carrier concentration is 2.01 × 1018/cm3, resistivity
It is 7.7 × 10-2Ω cm, further, it is contemplated that growth can generate oxygen in crystal under air atmosphere (or oxidizing atmosphere)
Vacancy, can be by sample 1000 DEG C of annealing elimination Lacking oxygen influence in 3 hours in air atmosphere, and continues to measure, and can be carried
Stream a concentration of 9.6 × 1016/cm3, resistivity is 36.63 Ω cm.
In conjunction with Fig. 2 and such as the following table 1 it is found that for other raw material proportionings, can obtain with different resistivity and current-carrying
The gallium oxide crystal of sub- concentration.Wherein doping concentration is 10-6With 10-5In the case of Fig. 2 shows be annealing after data, mix
Miscellaneous is the pure β-Ga of 0 expression2O3Crystal, as a contrast.
Table 1
By can see in Fig. 2, carrier concentration is higher after doping, and increases substantially as doping concentration and increase,
After annealing, carrier concentration still keeps higher level compared to decline before annealing.Resistivity is relatively low after doping,
And increase substantially as doping concentration and reduce, after annealing, resistivity is still compared pure compared to rising before annealing
Gallium oxide be improved significantly, and after annealing, resistivity is promoted, can it is wider regulated and controled, therefore have more
To be widely applied range.
Based on above-mentioned parameter, doping gallium oxide crystal provided by the invention can be realized in multiple fields and be applied, such as
Application in power electronic devices, opto-electronic device, conductive substrates etc..
In conclusion doping gallium oxide crystal provided by the invention, is the doped formation N-type electric conductor of gallium oxide crystal,
Doped chemical is niobium, and doping concentration is ranging from less than or equal to 0.8mol%.The present invention can obtain with high carrier concentration and
The gallium oxide crystal of high conductivity, also, by the control to doping concentration, different resistivity and carrier concentration can be obtained
Gallium oxide crystal.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
God and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (14)
1. a kind of doping gallium oxide crystal, the doped formation N-type electric conductor of gallium oxide crystal, doped chemical is niobium, doping concentration
Ranging from it is less than or equal to 0.8mol%.
2. doping gallium oxide crystal as described in claim 1, which is characterized in that the gallium oxide crystal is the β-of monoclinic system
Ga2O3Crystal.
3. doping gallium oxide crystal as claimed in claim 1 or 2, which is characterized in that niobium doping concentration ranging from 0.0001~
0.8mol%.
4. doping gallium oxide crystal as claimed in claim 1 or 2, which is characterized in that the resistance of the doping gallium oxide crystal
Rate is 5.5 × 10-3~3.6 × 102Ω cm, carrier concentration is 9.55 × 1016~1.8 × 1019/cm3。
5. a kind of preparation method of doping gallium oxide crystal as described in any one of claim 1-4, including：
Gallium oxide powder and niobium oxide powder are provided, the proportioning of niobium oxide is less than or equal to 0.8mol%；
So that carrying out crystal growth after the gallium oxide powder and niobium oxide powder mixing, doping gallium oxide crystal is obtained.
6. as claimed in claim 5 doping gallium oxide crystal preparation method, which is characterized in that the gallium oxide powder it is pure
Degree is 6N or more, and the purity of the niobium oxide powder is 4N or more.
7. the preparation method of doping gallium oxide crystal as claimed in claim 5, which is characterized in that the gallium oxide powder and oxygen
The proportioning for changing niobium oxide in niobium powder is 0.0001~0.8mol%.
8. the preparation method of doping gallium oxide crystal as claimed in claim 5, which is characterized in that the gallium oxide powder and oxygen
Change niobium powder to be uniformly mixed in organic solvent.
9. the preparation method of doping gallium oxide crystal as claimed in claim 8, which is characterized in that so that the gallium oxide powder
It is uniformly mixed in organic solvent with niobium oxide powder as batch mixing 12h-24h in the ball mill in a sealed meter environment.
10. the preparation method of doping gallium oxide crystal as claimed in claim 8, which is characterized in that carrying out crystal growth includes：
Drying removal organic solvent is carried out to mixed powder；
Mixed powder is pressed into charge bar；
It is sintered so that solid phase reaction, formation polycrystal material occur for gallium oxide and niobium oxide；
Seed crystal is provided, is grown using the polycrystal material, doping gallium oxide crystal is obtained.
11. the preparation method of doping gallium oxide crystal as claimed in claim 10, which is characterized in that the drying is at 80 DEG C
3h~6h is toasted at~100 DEG C.
12. the preparation method of doping gallium oxide crystal as claimed in claim 10, which is characterized in that described to be sintered in Muffle
1400 DEG C~1600 DEG C sintering 10h-20h in stove.
13. the preparation method of doping gallium oxide crystal as claimed in claim 10, which is characterized in that the seed crystal is gallium oxide
Crystal.
14. the preparation method of doping gallium oxide crystal as claimed in claim 5, which is characterized in that the speed of the growth is 2
~6mm/h, rotating speed are 5~15rpm.
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| CN201710124917.6A CN108531989A (en) | 2017-03-03 | 2017-03-03 | Adulterate gallium oxide crystal and preparation method thereof |
| EP18744070.6A EP3572561B1 (en) | 2017-01-25 | 2018-01-24 | Gallium oxide-doped crystalline material, preparation method and application thereof |
| KR1020197025013A KR102414621B1 (en) | 2017-01-25 | 2018-01-24 | Doped gallium oxide crystalline material and its manufacturing method and application |
| JP2019537809A JP6956189B2 (en) | 2017-01-25 | 2018-01-24 | Dope gallium oxide crystal material, its manufacturing method and use |
| SG11202000619WA SG11202000619WA (en) | 2017-01-25 | 2018-01-24 | Gallium oxide-doped crystalline material, preparation method and application thereof |
| CN201880004978.1A CN110325671A (en) | 2017-01-25 | 2018-01-24 | Adulterate gallium oxide crystalline material and its preparation method and application |
| PCT/CN2018/074058 WO2018137673A1 (en) | 2017-01-25 | 2018-01-24 | Gallium oxide-doped crystalline material, preparation method and application thereof |
| US16/508,211 US11098416B2 (en) | 2017-01-25 | 2019-07-10 | Doped gallium oxide crystalline material and preparation method and application thereof |
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