CN108342775A - A kind of tantalum doping beta-oxidation gallium crystalline material and its preparation method and application - Google Patents

A kind of tantalum doping beta-oxidation gallium crystalline material and its preparation method and application Download PDF

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CN108342775A
CN108342775A CN201710061035.XA CN201710061035A CN108342775A CN 108342775 A CN108342775 A CN 108342775A CN 201710061035 A CN201710061035 A CN 201710061035A CN 108342775 A CN108342775 A CN 108342775A
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doping
crystalline material
crystalline
crystal
preparation
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CN108342775B (en
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夏长泰
赛青林
周威
齐红基
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Priority to EP18744070.6A priority patent/EP3572561B1/en
Priority to KR1020197025013A priority patent/KR102414621B1/en
Priority to PCT/CN2018/074058 priority patent/WO2018137673A1/en
Priority to CN201880004978.1A priority patent/CN110325671A/en
Priority to SG11202000619WA priority patent/SG11202000619WA/en
Priority to JP2019537809A priority patent/JP6956189B2/en
Publication of CN108342775A publication Critical patent/CN108342775A/en
Priority to US16/508,211 priority patent/US11098416B2/en
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • 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

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Abstract

The invention discloses a kind of tantalums to adulterate beta-oxidation gallium crystalline material and its preparation method and application.The Ta adulterates β Ga2O3Crystalline material belongs to monoclinic system, and space group C2/m, resistivity is 2.0 × 10‑4To 1 × 104Within the scope of Ω cm and/or carrier concentration is 5 × 1012To 7 × 1020/cm3In range.Preparation method includes step：By purity 4N or more Ta2O5And Ga2O3Crystal growth is carried out after mixing.High conductivity can be prepared using common process in the present invention, be in the β Ga of N-shaped conductive characteristic2O3Crystalline material provides basis for its application in power electronic devices, opto-electronic device, photochemical catalyst or conductive substrates.

Description

A kind of tantalum doping beta-oxidation gallium crystalline material and its preparation method and application
Technical field
The present invention relates to a kind of tantalum (Ta) doping beta-oxidation gallium (β-Ga2O3) crystalline material and its preparation method and application.
Background technology
β-Ga2O3It is a kind of direct band gap semiconductor material with wide forbidden band, energy gap is about 4.8-4.9eV.It has forbidden band Many advantages, such as width is big, saturated electron drift velocity is fast, thermal conductivity is high, disruptive field intensity is high, chemical property is stablized, from deep ultraviolet (DUV) all it is transparent to the infrared region (IR), compared with conventional transparent conductive material (TCOs), it is shorter wavelength can be prepared New generation of semiconductor photoelectric device.
Pure β-Ga2O3Crystal shows as semi-insulating or weaker N-shaped conduction, the raising β-Ga being currently known2O3Crystal The main method of N-shaped conductive capability is to carry out the doping of 4 valence ions (IV races element), includes mainly the 4th main group and the 4th subgroup Si, Hf, Ge, Sn, Zr, Ti plasma doping.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 IV races element doping provides free electron is about 1:1, with doping Concentration improves, and crystal structure difficulty increases, and conductivity improves limitation.
Wherein, Si and Sn is common two doped chemicals in IV races element.American documentation literature US20070166967A1 It is disclosed using Si doping β-Ga with Japanese documentation JP2015083536A2O3Monocrystalline.Although Si disclosed in above-mentioned two document Adulterate β-Ga2O3Monocrystalline resistivity is 2.0 × 10-3To 8.0 × 102Within the scope of Ω cm, resistivity can be down to 2.0 × 10-3 Ω cm, but above-mentioned lowest resistivity is only theoretic.It is extremely difficult in practice process, due to Si4+With Ga3+Radius Difference is very big, so as the doping concentration of the IV elements such as Si greatly improves, it will have Second Phase Precipitation, cause under crystal quality Drop, as US20070166967A1 and JP2015083536A has finally also only prepared Si doping concentrations in 0.2mol% or so Doping β-the Ga of (referring to Applied Physics Letters, 2008,92,202120)2O3Monocrystalline, the resistance of the doped crystal Rate is 2.0 × 10-2Ω cm or so (for details, reference can be made to specification Fig. 2).
Periodical literature (Thin Solid Films, 2008,516 (17), 5763-5767) is disclosed adulterates β-using Sn Ga2O3Monocrystalline, but since the oxide volatility of tin is very strong, even if having added the Sn of 2-10mol% in usual raw material proportioning, obtained The content of Sn is also only ppm magnitudes in the crystal obtained, this not only brings great difficulty to controlling its content and its uniformity, And the volatilization of the oxide of tin can also cause the pollution to Preparation equipment.
Therefore, the doping β-Ga of high conductivity how are prepared in a simple manner2O3At the important research of this field Project.
Invention content
Problem solved by the invention is to overcome existing IV races element doping crystalline state β-Ga2O3Conductivity improves degree It is limited, the IV races element doping crystalline state β-Ga of high conductivity are prepared2O3Difficult, process conditions harshness that there are crystal structures Defect, provide a kind of V group element Ta doping β-Ga2O3Crystalline material and its preparation method and application.The V races member of the present invention Plain Ta doping β-Ga2O3Crystalline material shows N-shaped conductive characteristic, and the β-of high conductivity can be prepared using common process Ga2O3Crystalline material.
Usually in crystalline state β-Ga2O3Middle doping valence state ratio Ga3+High ion can improve crystalline state β-Ga to a certain extent2O3's Conductivity, if however Doped ions valence state is excessively high, charge is difficult to balance, and easily generates more doping defect, and defect can consume Electronics, enabling free-moving carrier quantity is substantially reduced, and cannot effectively be reached and be improved by adulterating high valence ion Crystalline state β-Ga2O3The purpose of conductivity can also seriously affect the application performance of material.Therefore, generally use ratio in the prior art Ga3+The IV races member of high 1 valence usually adulterates crystalline state β-Ga2O3, the report adulterated using V group element is there is no, because being mixed with V group element Miscellaneous β-Ga2O3More doping defect can be introduced, the application performance of material is influenced, is also still unable to get strong theoretical branch at present It holds, and is also faced with extreme difficulty in specific experiment.
However, the present inventor by scientific design and experimental verification, is surprised to find using a certain amount of 5 valence Ta Ion doping crystalline state β-Ga2O3More free electrons are provided than common+4 valence ions, improve carrier concentration, Jin Erli It is controlled in the raising of conductivity, and by the content of doped chemical Ta, controllable β-Ga2O3The electric conductivity of crystalline material, mainly Defect qualitative mechanism it is as follows：
As can be seen from the above equation, the theoretical limit ability that V group element Ta doping provides free electron can be 1:2, conductivity Raising degree is significantly greater than IV races element.Therefore, it can be crystallized under high doping concentration using common process and obtain crystal.
Further, the inventors found that the crystalline state β-Ga adulterated to Ta2O3After annealing, the oxygen in lattice can be removed Vacancy makes the crystalline state β-Ga after doping2O3Band gap is wider, and foundation is provided for its application.
The final present invention solves above-mentioned technical problem by the following technical programs.
The present invention provides a kind of Ta doping β-Ga2O3Crystalline material belongs to monoclinic system, space group C2/m, the Ta Adulterate β-Ga2O3The resistivity of crystalline material is 2.0 × 10-4To 1 × 104Within the scope of Ω cm and/or carrier concentration 5 × 1012To 7 × 1020/cm3In range.
In the present invention, term crystalline state (crystalline) material refers to solid matter and accounts for leading existing forms and internal structure The material of long-range order state, including solid crystal and the prevailing liquid crystal of solid matter etc. is presented.Wherein, crystalline material By during its crystal structure macroscopical aggregation situation and size of microcrystal divide, including monocrystalline, twin crystal (twin), polycrystalline (powder It is brilliant), eutectic, crystallite and nanocrystalline etc..In the present invention, macroscopical existence form of crystalline material is not particularly limited, example Such as can be powder, particle, film.
In the present invention, the Ta doping β-Ga2O3The molecular formula of crystalline material can be Ga2(1-x)Ta2xO3, 0.000000001< x<0.01, preferably x is 0.000001<x<0.01.
In the present invention, the Ta doping β-Ga2O3Crystalline material is preferably Ta doping β-Ga2O3Crystal is more preferably Ta Adulterate β-Ga2O3Monocrystalline.
In the present invention, the Ta doping β-Ga2O3The resistivity of crystalline material preferably 2.0 × 10-3To 3.6 × 102Ω· Within the scope of cm, more preferably within the scope of 0.004-7.9 Ω cm.
In the present invention, the Ta doping β-Ga2O3The carrier concentration of crystalline material is preferably 3.7 × 1015To 6.3 × 1019/cm3In range, more preferably 3.7 × 1015To 3.0 × 1019/cm3In range.
The present invention also provides a kind of Ta doping β-Ga2O3The preparation method of crystalline material, the preparation method can be according to these Field it is conventional by purity 4N or more Ta2O5And Ga2O3Crystal growth is carried out after mixing, wherein the Ta2O5And Ga2O3 Preferably according to molar ratio (0.000000001-0.01):(0.09-0.999999999) is mixed, more preferably according to mole Than (0.000001-0.01):(0.09-0.999999) is mixed.
In the present invention, term purity refers to Ta in sample2O5Or Ga2O3Shared mass fraction.Purity is that 4N indicates Ta2O5Or Ga2O3Mass content be 99.99%.Work as Ta2O5Or Ga2O3Material purity less than when requiring purity, can because of the excessive shadow of impurity Ring the electric conductivity of final crystalline material.
In the present invention, the Ta2O5And Ga2O3Purity be preferably 5N or more, i.e. Ta in sample2O5Or Ga2O3Quality Content is 99.999%.The Ta doping β-Ga2O3Crystalline material is that Ta adulterates β-Ga2O3When monocrystalline, used in preparation process Ga2O3Purity be preferably 6N or more, i.e. Ga in sample2O3Mass content be 99.9999%.
In the present invention, the Ta doping β-Ga2O3The operation that crystalline material subsequently can also further anneal, to remove Lacking oxygen in lattice increases the control range of carrier concentration.The temperature and time of the annealing can be that this field is conventional, example Such as 1000 DEG C -1200 DEG C 3-10h that anneal.
In the present invention, Ta adulterates β-Ga2O3Crystalline material containing raw material include inevitably in subtractive process it is miscellaneous Inevitably mixed impurity element on prime element and technique, relative to whole constituents, above-mentioned impurity element contains Amount is preferably in 10ppm or less.
In the present invention, Ta doping β-Ga are prepared2O3It is special that the growing method and growth conditions that crystalline material uses are not made It limits, can be the growing method and growth conditions of this field routine.The Ta doping β-Ga2O3Crystalline material is adulterated for Ta β-Ga2O3When monocrystalline, generally use melt method for growing monocrystalline commonly used in the art, melt growth method is typically in the melt Seed crystal is introduced, then control monocrystalline nucleation carries out phase transformation on the boundary of seed crystal and melt, crystal is promoted constantly to grow up, and one As include czochralski method, kyropoulos, Bridgman-Stockbarger method, floating zone method, flame melt method etc., floating zone method is a kind of is simple and efficient Method uses floating zone method in of the invention.
Wherein, Ta doping β-Ga are prepared using floating zone method2O3The step of monocrystalline generally comprise mixing, stick processed, sintering and Crystal growth.
Wherein, hybrid mode commonly used in the art, such as wet-mixing can be used in the mixing.The wet-mixing When the solvent type that uses and dosage be not particularly limited, as long as Ta can be made2O5And Ga2O3It is uniformly mixed and is subsequently easy It removes, generally uses volatile solvent such as ethyl alcohol.By Ta2O5And Ga2O3Pass through baking after disperseing mixing in volatile solvent Mode can make solvent volatilize completely.To make Ta2O5And Ga2O3Evenly, wet ball grinding also can be used in the wet-mixing for mixing Technique is mixed, and the time of the wet ball grinding can be this field routine, such as 12-24h.
Wherein, the mode of operation of this field routine can be used in the pressure bar, and pressure bar is generally carried out using isostatic pressing machine.Ability Field technique personnel know Ta2O5And Ga2O3Mixture can be easy to suppress in powdered, and compacting can be made uniform, if therefore suppressing There are caking phenomenons for preceding mixture, can be by lapping mode, such as ball milling method, shape of being clayed into power.
In a certain embodiment of the present invention, Ta of the purity in 4N or more2O5With 6N Ga2O3According to molar ratio (0.000001- 0.01):After (0.09-0.999999) mixing, wet ball grinding, Ball-milling Time 12- are carried out by the way that appropriate absolute ethyl alcohol is added For 24 hours, so that Ta2O5And Ga2O3It mixes well, gained mixture is toasted into 3-6h at 80-100 DEG C later, ethyl alcohol is made to wave completely Hair, then by the mixture ball milling after drying at powdered, in case pressure bar is used.
Wherein, the sintering can be carried out according to the sintering temperature of this field routine and time, to remove Ta2O5And Ga2O3 Moisture in mixture, and make Ta2O5And Ga2O3Solid phase reaction occurs, forms polycrystal material.The temperature of the sintering is preferably 1400-1600 DEG C, the time of the sintering is preferably 10-20h.The sintering carries out generally in Muffle furnace.
Wherein, the atmosphere of the crystal growth is preferably inert atmosphere or oxidizing atmosphere, to ensure the valence state of Ta ions Stablize.The inert atmosphere can be the inert atmosphere of this field routine, such as nitrogen atmosphere or argon gas atmosphere；The oxidizing atmosphere can For the oxidizing atmosphere of this field routine, such as oxygen atmosphere or air atmosphere.
Wherein, Ta doping β-Ga are prepared using floating zone method2O3Monocrystalline, usually by β-Ga2O3Crystal as seed crystal, Heating makes seed crystal melt, then with sintered Ta2O5And Ga2O3Polycrystalline charge bar contacts seed crystal, then adjusts turn of charge bar and seed crystal Speed and direction of rotation, inoculation carry out crystal growth, and cooling separation melting zone is to get Ta doping β-Ga later2O3Monocrystalline.The crystal The speed of growth be preferably 4.5-6mm/h, the rotating speed is preferably 8-12rpm.The usually Temperature fall that cools down, one As to be cooled to room temperature.The floating zone method prepares Ta doping β-Ga2O3Monocrystalline generally carries out in the stove of floating region.
In a certain embodiment of the present invention, float-zone method grows Ta doping β-Ga2O3Monocrystalline carries out in accordance with the following steps：It will burn Ta after knot2O5And Ga2O3Polycrystalline charge bar, which is fitted into the stove of floating region, is used as loading rod,<010>β-the Ga in direction2O3Crystal is as seed Crystalline substance, heating first make seed crystal melt, and then contact loading rod, adjust rotating speed and the direction of rotation of charge bar and seed crystal, and inoculation starts brilliant Body is grown, and the speed of growth of crystal is 4.5-6mm/h, and rotating speed 8-12rpm, growth atmosphere is air atmosphere, and crystal growth is complete Bi Hou pulls melting zone, is slowly dropped to room temperature, takes out crystal.
The present invention also provides Ta made from above-mentioned preparation method to adulterate β-Ga2O3Crystalline material.
The present invention also provides Ta doping β-Ga2O3Crystalline material is urged in power electronic devices, opto-electronic device, light Application in agent or conductive substrates.
Wherein, the opto-electronic device includes transparent electrode, solar panel, luminescent device, optical detector, sensor Deng；The conductive substrates include substrate material, the Ga as GaN2O3The substrate material etc. of itself.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that：
(1) present invention uses 5 valence Ta ion doping crystalline state β-Ga2O3The limit capacity for providing free electron is 1:2, hence it is evident that Higher than the ability (1 that+4 valence ion dopings provide free electron:1), therefore under identical doping concentration can provide it is more from By electronics, it is more advantageous to raising carrier concentration, improves conductivity.
(2) present invention uses 5 valence Ta ion doping crystalline state β-Ga2O3It is controlled by the content of doped chemical Ta, controllable β- Ga2O3The electric conductivity of crystalline material.The Ta doping β-Ga of the present invention2O3Crystalline material resistivity can be 2.0 × 10-4To 1 × 104 Control is realized within the scope of Ω cm, carrier concentration can be 5 × 1012To 7 × 1020/cm3Control is realized in range
(3) Ta of the invention doping β-Ga2O3Crystalline material can be prepared using this field conventional method, without high Expensive raw material and harsh technique.
(4) crystalline state β-Ga of the present invention to Ta doping2O3After annealing, the Lacking oxygen in lattice can be removed, it is dense to increase carrier The control range of degree provides foundation for its application.
Description of the drawings
Fig. 1 is that embodiment 1-4Ta adulterates β-Ga2O3The Ta of native transistors2O5Doping concentration and carrier concentration and resistivity Between relational graph.
Fig. 2 is that the Ta after embodiment 1-3 annealing adulterates β-Ga2O3The Ta of crystal2O5Between doping concentration and carrier concentration Relational graph.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient Product specification selects.
In following embodiments, raw materials used and reagent is all commercially available.
Embodiment 1
A kind of Ta doping β-Ga2O3Monocrystalline, molecular formula Ga2(1-x)Ta2xO3(x=0.0001%), belong to monoclinic system, it is empty Between group be C2/m, by being made following preparation method, the specific steps are：
(1) dispensing：According to molar ratio 0.999999:0.000001 weigh purity 6N or more Ga2O3With purity 4N with On Ta2O5Raw material；
(2) batch mixing：The raw material weighed is put into clean polytetrafluoroethylene (PTFE) ball grinder, is put into high-purity corundum ball, Enter appropriate absolute ethyl alcohol, after sealing, is put into ball mill, batch mixing 12h；
(3) it dries：By ball grinder as in baking oven, 6h is toasted at 80 DEG C, ethyl alcohol is made to volatilize completely, is then placed again into Ball mill ball milling 10 minutes clays into power the block stock after drying shape；
(4) pressure bar：Mixed powder after drying is put into organic mold, charge bar is pressed into using isostatic pressing machine；
(5) it is sintered：The charge bar suppressed is put into Muffle furnace, 10h is sintered at 1500 DEG C, removes the water in raw material Point, and make Ta2O5With Ga2O3Solid phase reaction occurs for raw material, forms polycrystal material；
(6) crystal growth：The polycrystalline charge bar sintered is fitted into the stove of floating region and is used as loading rod, and will<010>Direction β-Ga2O3Crystal is placed on is used as seed crystal below；Heating first makes seed crystal melt, and then contacts charge bar above, reaches and starts after stablizing The growth of crystal；Rate of crystalline growth is 5mm/h, and rotating speed 10rpm, growth atmosphere is air atmosphere；After crystal growth, The decline for stopping loading rod making melting zone be gradually disengaged, is slowly dropped to naturally using about 1h by the natural decline of lower faceted crystal Room temperature takes out crystal；For gained native transistors completely without cracking, color is uniform；
(7) it anneals：Gained native transistors are annealed 3h at 1000 DEG C.
Embodiment 2
A kind of Ta doping β-Ga2O3Monocrystalline, molecular formula Ga2(1-x)Ta2xO3(x=0.005%), belong to monoclinic system, it is empty Between group be C2/m, preparation process and condition with embodiment 1, only Ta in step (1)2O5Doping concentration it is different, Ga2O3And Ta2O5Molar ratio be 0.99995:0.00005.
Embodiment 3
A kind of Ta doping β-Ga2O3Monocrystalline, molecular formula Ga2(1-x)Ta2xO3(x=0.1%), belong to monoclinic system, space Group is C2/m, preparation process and condition with embodiment 1, only Ta in step (1)2O5Doping concentration it is different, Ga2O3And Ta2O5Molar ratio be 0.999:0.001, and annealing operation is not carried out.
Embodiment 4
A kind of Ta doping β-Ga2O3Monocrystalline, molecular formula Ga2(1-x)Ta2xO3(x=1%), belong to monoclinic system, space group For C2/m, preparation process and condition are with embodiment 1, only Ta in step (1)2O5Doping concentration it is different, Ga2O3 And Ta2O5Molar ratio be 0.99:0.01, and annealing operation is not carried out.
Embodiment 5
A kind of Ta doping β-Ga2O3Monocrystalline, molecular formula Ga2(1-x)Ta2xO3(x=0.0001%), belong to monoclinic system, it is empty Between group be C2/m, by being made following preparation method, the specific steps are：
(1) dispensing：According to molar ratio 0.999999:0.000001 weigh purity 6N or more Ga2O3With purity 4N with On Ta2O5Raw material；
(2) batch mixing：The raw material weighed is put into clean polytetrafluoroethylene (PTFE) ball grinder, is put into high-purity corundum ball, Enter appropriate absolute ethyl alcohol, after sealing, be put into ball mill, batch mixing is for 24 hours；
(3) it dries：By ball grinder as in baking oven, 3h is toasted at 100 DEG C, ethyl alcohol is made to volatilize completely, is then put again Enter ball mill ball milling 10 minutes the block stock after drying is clayed into power shape；
(4) pressure bar：Mixed powder after drying is put into organic mold, charge bar is pressed into using isostatic pressing machine；
(5) it is sintered：The charge bar suppressed is put into Muffle furnace, 20h is sintered at 1400 DEG C, removes the water in raw material Point, and make Ta2O5With Ga2O3Solid phase reaction occurs for raw material, forms polycrystal material；
(6) crystal growth：The polycrystalline charge bar sintered is fitted into the stove of floating region and is used as loading rod, and will<010>Direction β-Ga2O3Crystal is placed on is used as seed crystal below；Heating first makes seed crystal melt, and then contacts charge bar above, reaches and starts after stablizing The growth of crystal；Rate of crystalline growth is 4.5mm/h, and rotating speed 12rpm, growth atmosphere is air atmosphere；Crystal growth finishes Afterwards, the decline for stopping loading rod, makes melting zone be gradually disengaged by the natural decline of lower faceted crystal, is slowly dropped naturally using about 1h To room temperature, crystal is taken out；For gained native transistors completely without cracking, color is uniform；
(7) it anneals：Gained native transistors are annealed 4h at 1200 DEG C.
Embodiment 6
A kind of Ta doping β-Ga2O3Monocrystalline, molecular formula Ga2(1-x)Ta2xO3(x=0.0001%), belong to monoclinic system, it is empty Between group be C2/m, by being made following preparation method, the specific steps are：
(1) dispensing：According to molar ratio 0.999999:0.000001 weigh purity 6N or more Ga2O3With purity 4N with On Ta2O5Raw material；
(2) batch mixing：The raw material weighed is put into clean polytetrafluoroethylene (PTFE) ball grinder, is put into high-purity corundum ball, Enter appropriate absolute ethyl alcohol, after sealing, is put into ball mill, batch mixing 18h；
(3) it dries：By ball grinder as in baking oven, 5h is toasted at 90 DEG C, ethyl alcohol is made to volatilize completely, is then placed again into Ball mill ball milling 10 minutes clays into power the block stock after drying shape；
(4) pressure bar：Mixed powder after drying is put into organic mold, charge bar is pressed into using isostatic pressing machine；
(5) it is sintered：The charge bar suppressed is put into Muffle furnace, 10h is sintered at 1600 DEG C, removes the water in raw material Point, and make Ta2O5With Ga2O3Solid phase reaction occurs for raw material, forms polycrystal material；
(6) crystal growth：The polycrystalline charge bar sintered is fitted into the stove of floating region and is used as loading rod, and will<010>Direction β-Ga2O3Crystal is placed on is used as seed crystal below；Heating first makes seed crystal melt, and then contacts charge bar above, reaches and starts after stablizing The growth of crystal；Rate of crystalline growth is 6mm/h, and rotating speed 8rpm, growth atmosphere is air atmosphere；After crystal growth, The decline for stopping loading rod making melting zone be gradually disengaged, is slowly dropped to naturally using about 1h by the natural decline of lower faceted crystal Room temperature takes out crystal；For gained native transistors completely without cracking, color is uniform；
(7) it anneals：Gained native transistors are annealed 10h at 1000 DEG C.
Reference examples
A kind of pure β-Ga2O3Monocrystalline, preparation process and condition do not carry out Ta only with embodiment 12O5Doping.
Effect example 1
By the Ta doping β-Ga obtained by embodiment 1-62O3Pure β-the Ga of monocrystalline and reference examples2O3Monocrystalline (including primary crystal Crystal after body and annealing) it is cut into 5mm × 5mm × 0.3mm samples respectively, after making indium electrode on quadrangle, imitated using Hall Tester is answered to be tested.Test result show embodiment 1-6 doped crystals conduction type be N-shaped, wherein embodiment 1-4 and The carrier concentration and resistivity measurement result of reference examples sample are as shown in table 1 below：
The carrier concentration and resistivity of table 1 embodiment 1-4 and reference examples
By upper table data it is found that pure β-Ga2O3After native transistors annealing, almost insulate.And compared to pure β-Ga2O3 Native transistors, with Ta doping β-Ga2O3Carrier concentration is significantly increased after monocrystalline, and conductivity is obviously improved, wherein carrier concentration Increasing degree is at least 103More than, resistivity reduces at least 500 times, shows that Ta ions are successfully doped into β-Ga2O3In lattice. The resistivity and carrier concentration of embodiment 5 and 6 samples are substantially suitable with embodiment 1.
Further, it is the relationship of Ta doping concentrations and carrier concentration and resistivity in research native transistors, the present invention paints Tas of the embodiment 1-4 without annealing specimen is made2O5The curve of doping concentration-carrier concentration-resistivity, for details, reference can be made to attached Fig. 1.In addition, for Ta after research annealing2O5The relationship of doping concentration and carrier concentration, the present invention depict embodiment 1-3 annealing The Ta of sample afterwards2O5Doping concentration-carrier concentration curve, for details, reference can be made to attached drawings 2.
It will be noted from fig. 1 that Ta2O5Doping concentration and carrier concentration and Ta2O5Doping concentration and resistivity it Between it is substantially in a linear relationship.Within the scope of the doping concentration of the present invention, sample is with Ta before annealing2O5The increase of doping concentration carries It flows sub- concentration to linearly increase substantially, resistivity linearly declines substantially.From figure 2 it can be seen that carrier after sample annealing Concentration decline, and anneal after sample Ta2O5It is also substantially in a linear relationship between doping concentration and carrier concentration.
It should be noted that above-mentioned Ta doping β-Ga2O3The carrier concentration and resistivity of monocrystalline are specific experiment of the present invention It obtains, due to the influence of material purity, preparation process and test condition etc. in practice, the load of actually measured doped crystal can be made There are gaps with theoretical value for fluid concentrations and resistivity, or in the presence of the case where can not detecting.Therefore, above-described embodiment is only It is for example, those skilled in the art can deduce Ta according to Ta doping concentrations combination general knowledge known in this field disclosed by the invention Adulterate β-Ga2O3The carrier concentration of crystalline material substantially can be 5 × 1012To 7 × 1020/cm3Control, electricity are realized in range Resistance rate can be 2.0 × 10-4To 1 × 104Control is realized within the scope of Ω cm.It is specific to calculate that process is as follows：
β-the Ga obtained according to present invention experiment2O3The maximum value that Ta is mixed in monocrystalline is 1at%,
And 1mol β-Ga2O3Volume be 184.44/5.94cm3=31cm3；
Then 1mol mixes the β-Ga of Ta 1at%2O3In the number of atom containing Ta be：1 × 2 × 1% × 6.023 × 1023=1.2 ×1022；
Therefore, the β-Ga of Ta 1at% are mixed2O3The theoretical value of carrier concentration is=2 × 1.2 × 1022/ 31=7.7 × 1020/cm3。
Furthermore the limiting value of used Hall effects low-resistance module testing resistivity is 105, experiments indicate that 6N is pure β-Ga2O3Exceed test limits after crystal annealing, illustrates its resistivity>105, therefore use in the pure β-Ga of 6N2O3Mixing Ta completely can be with By resistivity control to 1 × 104, this numerical value is the 1/1266 of embodiment 1, and the carrier concentration in embodiment is multiplied by 1/ 1266 can obtain 3 × 1012/cm3, so Ta doping β-Ga2O3The resistivity of crystalline material realizes 5 × 1012/cm3It is also feasible. The doping concentration of Ta corresponding with the carrier concentration is then 10-7At%.
Therefore, Ta adulterates β-Ga2O3The Ta dopings of crystalline material can in 0.0000001mol% to 1mol% ranges, Resistivity can be 2.0 × 10-4To 1 × 104Control is realized within the scope of Ω cm, carrier concentration can be 5 × 1012To 7 × 1020/ cm3Control is realized in range.
Embodiments of the present invention are explained above, the right embodiment is illustrated only for the purposes of explanation, not To limit the present invention, those skilled in the art can make several changes without departing from the spirit and scope of the present invention With retouching, the protection domain that the present invention is advocated should be subject to described in claims.

Claims (10)

1. a kind of Ta doping β-Ga2O3Crystalline material belongs to monoclinic system, space group C2/m, the Ta doping β-Ga2O3Crystalline state The resistivity of material is 2.0 × 10-4To 1 × 104Within the scope of Ω cm and/or carrier concentration is 5 × 1012To 7 × 1020/cm3 In range.
2. Ta doping β-Ga as described in claim 12O3Crystalline material, which is characterized in that the Ta doping β-Ga2O3Crystalline state material The molecular formula of material is Ga2(1-x)Ta2xO3, 0.000000001<x<0.01.
3. Ta doping β-Ga as claimed in claim 22O3Crystalline material, which is characterized in that 0.000001<x<0.01.
4. Ta doping β-Ga as claimed in claim 22O3Crystalline material, which is characterized in that the Ta doping β-Ga2O3Crystalline state material Material is that Ta adulterates β-Ga2O3Crystal；
And/or the Ta doping β-Ga2O3The resistivity of crystalline material is 2.0 × 10-3To 3.6 × 102Within the scope of Ω cm；
And/or the Ta doping β-Ga2O3The carrier concentration of crystalline material is 3.7 × 1015To 6.3 × 1019/cm3In range.
5. Ta doping β-Ga as claimed in claim 42O3Crystalline material, which is characterized in that the Ta doping β-Ga2O3Crystalline state material Material is that Ta adulterates β-Ga2O3Monocrystalline；
And/or the Ta doping β-Ga2O3The resistivity of crystalline material is within the scope of 0.004-7.9 Ω cm；
And/or the Ta doping β-Ga2O3The carrier concentration of crystalline material is 3.7 × 1015To 3.0 × 1019/cm3In range.
6. a kind of Ta doping β-Ga2O3The preparation method of crystalline material, the preparation method include the following steps：By purity in 4N Above Ta2O5And Ga2O3Crystal growth is carried out after mixing；
Wherein, the Ta2O5And Ga2O3The preferred 5N or more of purity；The Ta doping β-Ga2O3Crystalline material is that Ta adulterates β- Ga2O3When monocrystalline, the Ga that is used in preparation process2O3Purity is preferably in 6N or more；
Wherein, the Ta2O5And Ga2O3Preferably according to molar ratio (0.000000001-0.01):(0.09-0.999999999), More preferably according to molar ratio (0.000001-0.01):(0.09-0.999999) is mixed；
Optionally, after crystal growth, gained Ta doping β-Ga2O3Crystalline material also carries out annealing steps.
7. preparation method as claimed in claim 6, which is characterized in that the Ta doping β-Ga2O3Crystalline material is that Ta adulterates β- Ga2O3When monocrystalline, using melt method for growing monocrystalline, it is preferred to use floating zone method；
Wherein, Ta doping β-Ga are prepared using floating zone method2O3Monocrystalline includes mixing, stick processed, sintering and crystal growth step；
Optionally, the mixing uses wet-mixing, it is preferred to use wet ball grinding technique is mixed；
Optionally, the temperature of the sintering is 1400-1600 DEG C, and the time of the sintering is 10-20h；
Optionally, the atmosphere of the crystal growth is inert atmosphere or oxidizing atmosphere；
Optionally, the speed of growth of the crystal is 4.5-6mm/h, rotating speed 8-12rpm.
8. Ta doping β-Ga made from a kind of preparation method as claimed in claims 6 or 72O3Crystalline material.
9. Ta adulterates β-Ga as described in any one of claim 1-5 and 82O3Crystalline material is in power electronic devices, photoelectron device Application in part, photochemical catalyst or conductive substrates.
10. application as claimed in claim 9, which is characterized in that the opto-electronic device includes transparent electrode, solar cell Plate, luminescent device, optical detector and sensor；The conductive substrates include being used as GaN and Ga2O3The substrate material of itself.
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