CN108342775B - Tantalum-doped beta gallium oxide crystalline material and preparation method and application thereof - Google Patents

Tantalum-doped beta gallium oxide crystalline material and preparation method and application thereof Download PDF

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CN108342775B
CN108342775B CN201710061035.XA CN201710061035A CN108342775B CN 108342775 B CN108342775 B CN 108342775B CN 201710061035 A CN201710061035 A CN 201710061035A CN 108342775 B CN108342775 B CN 108342775B
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CN108342775A (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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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
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Abstract

The invention discloses a tantalum doped beta gallium oxide crystalline material, a preparation method and application thereof. The Ta is doped with beta-Ga 2 O 3 The crystalline material belongs to monoclinic system, the space group is C2/m, and the resistivity is 2.0X10 ‑4 To 1X 10 4 Omega cm range and/or carrier concentration of 5X 10 12 To 7X 10 20 /cm 3 Within the range. The preparation method comprises the following steps: ta with purity of more than 4N 2 O 5 And Ga 2 O 3 And (5) mixing and then carrying out crystal growth. The invention adopts the conventional process to prepare the beta-Ga with high conductivity and n-type conductivity 2 O 3 Crystalline materials provide a basis for their use in power electronics, optoelectronics, photocatalysts or conductive substrates.

Description

Tantalum-doped beta gallium oxide crystalline material and preparation method and application thereof
Technical Field
The invention relates to a tantalum (Ta) doped beta gallium oxide (beta-Ga) 2 O 3 ) Crystalline material and a preparation method and application thereof.
Background
β-Ga 2 O 3 Is a direct band gap wide forbidden band semiconductor material, and the forbidden band width is about 4.8-4.9eV. The preparation method has the advantages of large forbidden bandwidth, high saturated electron drift speed, high thermal conductivity, high breakdown field strength, stable chemical property and the like, is transparent from Deep Ultraviolet (DUV) to Infrared (IR) regions, and can prepare a new-generation semiconductor photoelectric device with shorter wavelength compared with the traditional transparent conductive materials (TCOs).
Pure beta-Ga 2 O 3 Crystals exhibit semi-insulating or weaker n-type conductivity, presently known to enhance beta-Ga 2 O 3 The main method of n-type conductivity of the crystal is to dope with 4-valent ions (group IV elements), mainly comprising the doping of Si, hf, ge, sn, zr, ti plasma of the fourth main group and the fourth sub-group. Taking Si as an example, the main mechanism of increasing carrier concentration reacts as follows:
from the above formula, the theoretical limiting capacity of doping IV group element to provide free electrons is about 1:1, and the degree of improvement of the conductivity is limited as the degree of crystallization difficulty of the crystal is increased with the increase of the doping concentration.
Among them, si and Sn in the group IV element are two commonly used doping elements. U.S. patent document US20070166967A1 and japanese patent document JP2015083536a disclose the doping of β -Ga with Si 2 O 3 And (3) single crystals. Although the above two documents disclose Si-doped beta-Ga 2 O 3 Single crystal resistivity of 2.0X10 -3 To 8.0X10 2 Resistivity in the range of Ω·cm can be as low as 2.0X10 -3 Ω·cm, but the lowest resistivity mentioned above is only theoretical. Is difficult to achieve in practice due to Si 4+ With Ga 3+ The radius difference is large, so as the doping concentration of Si increases, a second phase is precipitated, resulting in a decrease in crystal quality, and as in US20070166967A1 and JP2015083536A, only doped beta-Ga having a Si doping concentration of about 0.2mol% (see Applied Physics Letters,2008,92,202120) is finally produced 2 O 3 Single crystal having resistivity of 2.0X10 -2 Omega cm (see fig. 2 for details).
Journal literature (Thin Solid Films,2008,516 (17), 5763-5767) discloses the use of Sn doped beta-Ga 2 O 3 The Sn content in the obtained crystal is only in ppm level due to the strong volatility of the tin oxide, even if 2-10mol% of Sn is added in the raw material proportion, which not only brings great difficulty to control the content and uniformity thereof, but also causes pollution to preparation equipment due to the volatilization of the tin oxide.
Thus, how to prepare high-conductivity doped beta-Ga in a simple manner 2 O 3 Is an important research topic in the field.
Disclosure of Invention
The invention solves the problems of overcoming the prior IV group element doped crystalline beta-Ga 2 O 3 The conductivity improvement degree is limited, and the high-conductivity IV group element doped crystalline beta-Ga is prepared 2 O 3 Has the defects of difficult crystallization and harsh process conditions, and provides a V group element Ta doped beta-Ga 2 O 3 Crystalline material and a preparation method and application thereof. The V group element Ta is doped with beta-Ga 2 O 3 The crystalline material shows n-type conductivity, and the beta-Ga with high conductivity can be prepared by adopting a conventional process 2 O 3 Crystalline material.
Usually in the crystalline state beta-Ga 2 O 3 Medium doping valence ratio Ga 3+ The high ions can improve crystalline beta-Ga to a certain extent 2 O 3 If the valence state of the doped ions is too high, however, the charge is difficult to balance, more doping defects are extremely easy to generate, the defects consume electrons, the number of carriers capable of freely moving is obviously reduced, and the crystalline beta-Ga can not be effectively improved by doping high valence ions 2 O 3 The purpose of conductivity can also seriously affect the application properties of the material. Therefore, the prior art generally adopts the ratio Ga 3+ Doping crystalline beta-Ga with higher 1-valent group IV element 2 O 3 There has been no report of doping with a group V element because of doping of beta-Ga with a group V element 2 O 3 More doping defects can be introduced, and the application performance of the material is affected.
However, the inventors of the present invention have surprisingly found that doping crystalline β -Ga with a certain amount of 5-valent Ta ions, through scientific design and experimental verification 2 O 3 Can provide more free electrons than the common +4 valence ions, improve the carrier concentration, further facilitate the improvement of conductivity, and can regulate and control beta-Ga by controlling the content of the doped element Ta 2 O 3 Conductivity of crystalline materials, mainly lackThe trapping reaction mechanism is as follows:
from the above equation, the theoretical limiting capacity of the V group element Ta doping to provide free electrons can be 1:2, and the conductivity is improved to a significantly greater extent than the IV group element. Therefore, the crystal can be obtained by crystallization under high doping concentration by adopting a conventional process.
Further, the inventors of the present invention found that crystalline β -Ga doped with Ta 2 O 3 After annealing, oxygen vacancies in the crystal lattice can be removed, and the control range of carrier concentration can be increased, so that the basis is provided for the application of the method.
Finally, the invention solves the technical problems through the following technical scheme.
The invention provides a Ta doped beta-Ga 2 O 3 Crystalline material belonging to monoclinic system, the space group is C2/m, the Ta is doped with beta-Ga 2 O 3 The resistivity of the crystalline material is 2.0X10 -4 To 1X 10 4 Omega cm range and/or carrier concentration of 5X 10 12 To 7X 10 20 /cm 3 Within the range.
In the present invention, the term crystalline (crystalline) material refers to a solid material whose internal structure exhibits a long-range order state. The crystalline material is divided into single crystal, double crystal (twin crystal), polycrystal (powder crystal), eutectic crystal, microcrystal, nanocrystalline and the like according to the macroscopic aggregation condition and grain size in the crystallization process of the crystal. In the present invention, the form of macroscopic presence of the crystalline material is not particularly limited, and may be, for example, powder, granule, film, or the like.
In the invention, the Ta is doped with beta-Ga 2 O 3 The molecular formula of the crystalline material can be Ga 2(1-x) Ta 2x O 3 ，0.000000001<x<0.01, preferably x is 0.000001<x<0.01。
In the invention, the Ta is doped with beta-Ga 2 O 3 The crystalline material is preferably Ta-doped beta-Ga 2 O 3 Crystals, more preferably Ta-doped beta-Ga 2 O 3 And (3) single crystals.
In the invention, the Ta is doped with beta-Ga 2 O 3 The resistivity of the crystalline material is preferably 2.0X10 -3 Up to 3.6X10 2 In the range of Ω·cm, more preferably in the range of 0.004-7.9 Ω·cm.
In the invention, the Ta is doped with beta-Ga 2 O 3 The carrier concentration of the crystalline material is preferably 3.7X10 15 To 6.3X10 19 /cm 3 In the range, more preferably 3.7X10 15 To 3.0X10 19 /cm 3 Within the range.
The invention also provides a Ta doped beta-Ga 2 O 3 Preparation method of crystalline material, which can be used for preparing Ta with purity of more than 4N according to the conventional method in the field 2 O 5 And Ga 2 O 3 After mixing, crystal growth is carried out, wherein Ta is 2 O 5 And Ga 2 O 3 Preferably, the mixing is carried out in a molar ratio of (0.000000001-0.01): (0.09-0.999999999), more preferably in a molar ratio of (0.000001-0.01): (0.09-0.999999).
In the present invention, the term purity refers to Ta in a sample 2 O 5 Or Ga 2 O 3 Mass fraction of the material. Purity of 4N represents Ta 2 O 5 Or Ga 2 O 3 The mass content of (2) is 99.99%. When Ta 2 O 5 Or Ga 2 O 3 When the purity of the raw material is lower than the required purity, the conductivity of the final crystalline material is affected by excessive impurities.
In the invention, the Ta 2 O 5 And Ga 2 O 3 The purity of (C) is preferably 5N or more, namely Ta in the sample 2 O 5 Or Ga 2 O 3 The mass content of (3) is 99.999%. The Ta is doped with beta-Ga 2 O 3 The crystalline material is Ta doped beta-Ga 2 O 3 Ga used in the preparation of single crystals 2 O 3 The purity of (C) is preferably 6N or more, namely Ga in the sample 2 O 3 The mass content is 99.9999%.
In the invention, the Ta is doped with beta-Ga 2 O 3 The crystalline material may be subsequently further annealed to remove oxygen vacancies in the crystal lattice and increase the control range of carrier concentration. The temperature and time of the annealing may be conventional in the art, e.g., 1000 ℃ to 1200 ℃ for 3 to 10 hours.
In the invention, ta is doped with beta-Ga 2 O 3 The crystalline material may contain an impurity element which is inevitably contained in the raw material during the refining process and an impurity element which is inevitably mixed in the process, and the content of the impurity element is preferably 10ppm or less with respect to the entire constituent components.
In the invention, ta doped beta-Ga is prepared 2 O 3 The crystal growth method and growth conditions employed for the crystalline material are not particularly limited and may be those conventional in the art. The Ta is doped with beta-Ga 2 O 3 The crystalline material is Ta doped beta-Ga 2 O 3 When a single crystal is grown, a melt method conventionally used in the art is generally adopted, seed crystals are generally introduced into the melt in the melt growth method, nucleation of the single crystal is controlled, then phase transition is carried out on a phase interface between the seed crystals and the melt, and the continuous growth of the crystal is promoted, wherein the method generally comprises a pulling method, a kyropoulos method, a crucible descent method, an optical floating zone method, a flame melting method and the like, and the optical floating zone method is a simple and efficient method.
Wherein, an optical floating zone method is adopted to prepare Ta doped beta-Ga 2 O 3 The steps of single crystal generally include mixing, rod making, sintering, and crystal growth.
Wherein the mixing may be performed by mixing means conventionally used in the art, such as wet mixing. The kind and amount of the solvent used in the wet mixing are not particularly limited as long as Ta is allowed 2 O 5 And Ga 2 O 3 It is well mixed and then easily removed, typically using a volatile solvent such as ethanol. Ta is to 2 O 5 And Ga 2 O 3 Dispersing and mixing in volatile solvent, and completely volatilizing the solvent by baking. To make Ta 2 O 5 And Ga 2 O 3 The mixing is more uniform, and the wet mixing can also be adoptedMixing is performed using a wet ball milling process for a period of time that may be conventional in the art, for example, 12-24 hours.
Wherein, the press bar can be operated in a conventional manner in the art, and the press bar is generally performed by using an isostatic press. Those skilled in the art know Ta 2 O 5 And Ga 2 O 3 The mixture of (2) can be easily pressed in powder form and can be uniformly pressed, so that if the mixture before pressing has caking phenomenon, the mixture can be ground into powder by grinding, such as ball milling.
In one embodiment of the invention, ta having a purity of 4N or more 2 O 5 And 6N Ga 2 O 3 Mixing (0.09-0.999999) according to the molar ratio (0.000001-0.01), adding proper amount of absolute ethyl alcohol, performing wet ball milling for 12-24h to ensure Ta 2 O 5 And Ga 2 O 3 Fully and uniformly mixing, baking the obtained mixture at 80-100 ℃ for 3-6 hours to fully volatilize ethanol, and grinding the dried mixture into powder for pressing bars.
Wherein the sintering may be performed at a sintering temperature and time conventional in the art to remove Ta 2 O 5 And Ga 2 O 3 Moisture in the mixture and Ta 2 O 5 And Ga 2 O 3 Solid phase reaction occurs to form a polycrystalline material. The sintering temperature is preferably 1400-1600 ℃, and the sintering time is preferably 10-20h. The sintering is typically carried out in a muffle furnace.
Wherein, the atmosphere for crystal growth is preferably an inert atmosphere or an oxidizing atmosphere to ensure the stable valence state of the Ta ion. The inert atmosphere may be an inert atmosphere conventional in the art, such as a nitrogen atmosphere or an argon atmosphere; the oxidizing atmosphere may be an oxidizing atmosphere conventional in the art, such as an oxygen atmosphere or an air atmosphere.
Wherein, an optical floating zone method is adopted to prepare Ta doped beta-Ga 2 O 3 Single crystals, typically of beta-Ga 2 O 3 The crystal is used as seed crystal, the seed crystal is melted by heating, and then sintered Ta 2 O 5 And Ga 2 O 3 The polycrystalline material rod contacts with the seed crystal, the rotating speed and the rotating direction of the material rod and the seed crystal are adjusted, the seed crystal is inoculated, the crystal growth is carried out, and then the temperature is reduced and the melting area is separated, thus obtaining the Ta doped beta-Ga 2 O 3 And (3) single crystals. The growth rate of the crystals is preferably 4.5 to 6mm/h, and the rotation rate is preferably 8 to 12rpm. The cooling is usually natural cooling, and is usually cooling to room temperature. Ta doped beta-Ga prepared by optical floating zone method 2 O 3 The single crystal is typically carried out in a float zone furnace.
In one embodiment of the invention, ta-doped beta-Ga is grown by floating zone method 2 O 3 The single crystal is carried out according to the following steps: ta after sintering 2 O 5 And Ga 2 O 3 The polycrystal material rod is put into a floating zone furnace as a feeding rod,<010>directional beta-Ga 2 O 3 The crystal is used as seed crystal, the seed crystal is melted firstly by heating, then the seed crystal is contacted with a feeding rod, the rotating speed and the rotating direction of the feeding rod and the seed crystal are regulated, the seed crystal is inoculated, the growth of the crystal is started, the growth speed of the crystal is 4.5-6mm/h, the rotating speed is 8-12rpm, the growth atmosphere is air atmosphere, after the crystal is grown, the melting zone is pulled off, the temperature is slowly reduced to the room temperature, and the crystal is taken out.
The invention also provides the Ta doped beta-Ga prepared by the preparation method 2 O 3 Crystalline material.
The invention also provides the Ta doped beta-Ga 2 O 3 The crystalline material is used in power electronic device, photoelectronic device, photocatalyst or conducting substrate.
Wherein the optoelectronic device comprises a transparent electrode, a solar panel, a light emitting device, a light detector, a sensor and the like; the conductive substrate comprises a substrate material as GaN, ga 2 O 3 Self substrate material, etc.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
(1) The invention adopts a 5-valence Ta ionSub-doped crystalline beta-Ga 2 O 3 The limiting capacity for providing free electrons is 1:2, which is obviously higher than the capacity (1:1) for providing free electrons by +4 valence ion doping, so that more free electrons can be provided under the same doping concentration, the carrier concentration is more favorable, and the conductivity is improved.
(2) The invention adopts 5-valence Ta ion doped crystalline beta-Ga 2 O 3 beta-Ga can be regulated and controlled by controlling the content of doped element Ta 2 O 3 Conductivity of crystalline materials. Ta-doped beta-Ga of the invention 2 O 3 The resistivity of the crystalline material can be 2.0X10 -4 To 1X 10 4 Control is realized within the omega cm range, and the carrier concentration can be 5 multiplied by 10 12 To 7X 10 20 /cm 3 Control is realized in the range.
(3) Ta-doped beta-Ga of the invention 2 O 3 Crystalline materials can be prepared by methods conventional in the art without expensive raw materials and harsh processes.
(4) The invention discloses a Ta doped crystalline beta-Ga 2 O 3 After annealing, oxygen vacancies in the crystal lattice can be removed, and the control range of carrier concentration is increased, so that the basis is provided for the application of the method.
Drawings
FIG. 1 shows examples 1 to 4 Ta-doped beta-Ga 2 O 3 Ta of primary crystal 2 O 5 A plot of doping concentration versus carrier concentration and resistivity.
FIG. 2 shows Ta-doped beta-Ga after annealing according to examples 1-3 2 O 3 Ta of crystal 2 O 5 A plot of doping concentration versus carrier concentration.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the examples described below, the starting materials and reagents used are all commercially available.
Example 1
Ta doped beta-Ga 2 O 3 Single crystal of formula Ga 2(1-x) Ta 2x O 3 (x=0.0001%) belonging to monoclinic system, the space group is C2/m, which is prepared by the following preparation method, the specific steps are:
(1) And (3) batching: ga with the purity of more than 6N is weighed according to the mol ratio of 0.999999:0.000001 2 O 3 And Ta having a purity of 4N or more 2 O 5 Raw materials;
(2) Mixing: placing the weighed raw materials into a clean polytetrafluoroethylene ball milling tank, placing high-purity corundum balls into the tank, pouring a proper amount of absolute ethyl alcohol into the tank, sealing the tank, placing the tank into a ball mill, and mixing the materials for 12 hours;
(3) And (3) drying: placing the ball milling tank into a baking oven, baking at 80 ℃ for 6 hours to volatilize ethanol completely, then placing the ball milling tank into a ball mill again for ball milling for 10 minutes, and grinding the dried block-shaped raw materials into powder;
(4) Pressing a rod: placing the dried mixed powder into an organic die, and pressing into a material rod by using an isostatic pressing machine;
(5) Sintering: placing the pressed material rod into a muffle furnace, sintering at 1500 ℃ for 10h, removing water in the raw materials, and enabling Ta 2 O 5 With Ga 2 O 3 The raw materials undergo solid phase reaction to form polycrystal materials;
(6) Crystal growth: loading the sintered polycrystalline material rod into a floating zone furnace as a loading rod, and loading<010>Directional beta-Ga 2 O 3 The crystal is placed below as seed crystal; heating to melt seed crystal, contacting the seed crystal with the upper material rod to stabilize and then starting crystal growth; the crystal growth speed is 5mm/h, the rotating speed is 10rpm, and the growth atmosphere is air atmosphere; stopping descending of the feeding rod after the crystal grows, gradually separating a melting zone through natural descending of the lower crystal, naturally and slowly cooling to room temperature for about 1 hour, and taking out the crystal; the obtained primary crystal is complete and has no cracking and uniform color;
(7) Annealing: the resulting as-grown crystals were annealed at 1000℃for 3h.
Example 2
Ta doped beta-Ga 2 O 3 Single crystal of formula Ga 2(1-x) Ta 2x O 3 (x=0.005%) belonging to monoclinic system and having a space group of C2/m, the preparation procedure and conditions were the same as in example 1 except for Ta in step (1) 2 O 5 Is different in doping concentration of Ga 2 O 3 And Ta 2 O 5 The molar ratio of (2) is 0.99995:0.00005.
Example 3
Ta doped beta-Ga 2 O 3 Single crystal of formula Ga 2(1-x) Ta 2x O 3 (x=0.1%) belonging to monoclinic system and having a space group of C2/m, the preparation procedure and conditions were the same as in example 1 except for Ta in step (1) 2 O 5 Is different in doping concentration of Ga 2 O 3 And Ta 2 O 5 Is 0.999:0.001, and no annealing operation is performed.
Example 4
Ta doped beta-Ga 2 O 3 Single crystal of formula Ga 2(1-x) Ta 2x O 3 (x=1%) belonging to monoclinic system and having a space group of C2/m, the preparation procedure and conditions were the same as in example 1 except for Ta in step (1) 2 O 5 Is different in doping concentration of Ga 2 O 3 And Ta 2 O 5 Is 0.99:0.01 and no annealing operation is performed.
Example 5
Ta doped beta-Ga 2 O 3 Single crystal of formula Ga 2(1-x) Ta 2x O 3 (x=0.0001%) belonging to monoclinic system, the space group is C2/m, which is prepared by the following preparation method, the specific steps are:
(1) And (3) batching: ga with the purity of more than 6N is weighed according to the mol ratio of 0.999999:0.000001 2 O 3 And Ta having a purity of 4N or more 2 O 5 Raw materials;
(2) Mixing: placing the weighed raw materials into a clean polytetrafluoroethylene ball milling tank, placing high-purity corundum balls into the tank, pouring a proper amount of absolute ethyl alcohol into the tank, sealing the tank, placing the tank into a ball mill, and mixing the materials for 24 hours;
(3) And (3) drying: placing the ball milling tank into a baking oven, baking at 100 ℃ for 3 hours to volatilize ethanol completely, then placing the ball milling tank into a ball mill again for ball milling for 10 minutes, and grinding the dried block-shaped raw materials into powder;
(4) Pressing a rod: placing the dried mixed powder into an organic die, and pressing into a material rod by using an isostatic pressing machine;
(5) Sintering: placing the pressed material rod into a muffle furnace, sintering at 1400 ℃ for 20h, removing water in the raw materials, and enabling Ta 2 O 5 With Ga 2 O 3 The raw materials undergo solid phase reaction to form polycrystal materials;
(6) Crystal growth: loading the sintered polycrystalline material rod into a floating zone furnace as a loading rod, and loading<010>Directional beta-Ga 2 O 3 The crystal is placed below as seed crystal; heating to melt seed crystal, contacting the seed crystal with the upper material rod to stabilize and then starting crystal growth; the crystal growth speed is 4.5mm/h, the rotating speed is 12rpm, and the growth atmosphere is air atmosphere; stopping descending of the feeding rod after the crystal grows, gradually separating a melting zone through natural descending of the lower crystal, naturally and slowly cooling to room temperature for about 1 hour, and taking out the crystal; the obtained primary crystal is complete and has no cracking and uniform color;
(7) Annealing: the resulting as-grown crystals were annealed at 1200 ℃ for 4h.
Example 6
Ta doped beta-Ga 2 O 3 Single crystal of formula Ga 2(1-x) Ta 2x O 3 (x=0.0001%) belonging to monoclinic system, the space group is C2/m, which is prepared by the following preparation method, the specific steps are:
(1) And (3) batching: ga with the purity of more than 6N is weighed according to the mol ratio of 0.999999:0.000001 2 O 3 And Ta having a purity of 4N or more 2 O 5 Raw materials;
(2) Mixing: placing the weighed raw materials into a clean polytetrafluoroethylene ball milling tank, placing high-purity corundum balls into the tank, pouring a proper amount of absolute ethyl alcohol into the tank, sealing the tank, placing the tank into a ball mill, and mixing the materials for 18 hours;
(3) And (3) drying: placing the ball milling tank into a baking oven, baking at 90 ℃ for 5 hours to volatilize ethanol completely, then placing the ball milling tank into a ball mill again for ball milling for 10 minutes, and grinding the dried block-shaped raw materials into powder;
(4) Pressing a rod: placing the dried mixed powder into an organic die, and pressing into a material rod by using an isostatic pressing machine;
(5) Sintering: placing the pressed material rod into a muffle furnace, sintering at 1600 ℃ for 10 hours, removing water in the raw materials, and enabling Ta 2 O 5 With Ga 2 O 3 The raw materials undergo solid phase reaction to form polycrystal materials;
(6) Crystal growth: loading the sintered polycrystalline material rod into a floating zone furnace as a loading rod, and loading<010>Directional beta-Ga 2 O 3 The crystal is placed below as seed crystal; heating to melt seed crystal, contacting the seed crystal with the upper material rod to stabilize and then starting crystal growth; the crystal growth speed is 6mm/h, the rotating speed is 8rpm, and the growth atmosphere is air atmosphere; stopping descending of the feeding rod after the crystal grows, gradually separating a melting zone through natural descending of the lower crystal, naturally and slowly cooling to room temperature for about 1 hour, and taking out the crystal; the obtained primary crystal is complete and has no cracking and uniform color;
(7) Annealing: the resulting primary crystals were annealed at 1000℃for 10h.
Comparative example
Pure beta-Ga 2 O 3 Single crystals, the preparation steps and conditions were the same as in example 1, except that Ta was not used 2 O 5 Doping.
Effect example 1
Ta-doped beta-Ga as obtained in examples 1-6 2 O 3 Single crystal and pure beta-Ga of comparative example 2 O 3 Single crystals (including as-grown crystals and annealed crystals) were cut into 5mm×5mm×0.3mm samples, and after indium electrodes were fabricated at four corners, they were tested using a hall effect tester. The test results show that the conductivity type of the doped crystals of examples 1-6 is n-type, with the carrier concentration and resistivity test results for the samples of examples 1-4 and the control example shown in table 1 below:
TABLE 1 Carrier concentration and resistivity for examples 1-4 and comparative example
As can be seen from the above table data, pure beta-Ga 2 O 3 After the primary crystal is annealed, it is nearly insulating. Compared with pure beta-Ga 2 O 3 Primary crystal, beta-Ga doped with Ta 2 O 3 The carrier concentration is greatly increased after single crystal, the conductivity is obviously improved, wherein the carrier concentration increase range is at least 10 3 The resistivity was reduced by at least 500 times above, indicating that the Ta ion has been successfully doped into beta-Ga 2 O 3 In the crystal lattice. The resistivity and carrier concentration of the samples of examples 5 and 6 were substantially equivalent to example 1.
Further, to investigate the relationship between Ta doping concentration in the primary crystal and carrier concentration and resistivity, the present invention plots Ta for the unannealed samples of examples 1-4 2 O 5 The curve of doping concentration-carrier concentration-resistivity can be seen in particular in fig. 1. In addition, to investigate the post-annealing Ta 2 O 5 The relationship between doping concentration and carrier concentration is plotted for Ta of the annealed samples of examples 1-3 2 O 5 The doping concentration-carrier concentration curve can be seen in fig. 2.
As can be seen from FIG. 1, ta 2 O 5 Doping concentration and carrier concentration, and Ta 2 O 5 The doping concentration and resistivity are substantially linear. Within the doping concentration range of the invention, the sample before annealing follows Ta 2 O 5 The doping concentration increases, the carrier concentration increases substantially linearly, and the resistivity decreases substantially linearly. As can be seen from fig. 2, the carrier concentration of the sample after annealing decreases, and Ta of the sample after annealing 2 O 5 The doping concentration and the carrier concentration are also substantially linear.
The Ta-doped beta-Ga 2 O 3 The carrier concentration and the resistivity of the single crystal are obtained by the specific experiments of the invention, and the influence of the purity of raw materials, the preparation process, the testing conditions and the like in practice canThe actual measured carrier concentration and resistivity of the doped crystal are separated from the theoretical value, or the actual measured carrier concentration and resistivity of the doped crystal cannot be detected. Accordingly, the above examples are merely illustrative, and one skilled in the art can infer Ta doped beta-Ga based on the Ta doping concentration disclosed in the present invention in combination with the common general knowledge in the art 2 O 3 The carrier concentration of the crystalline material may be substantially 5×10 12 To 7X 10 20 /cm 3 Control is realized in a range of 2.0X10 resistivity -4 To 1X 10 4 Control is realized within the omega cm range. The specific calculation process is as follows:
beta-Ga obtained according to the experiments of the invention 2 O 3 The maximum value of Ta doped in the single crystal is 1at%,
and 1mol of beta-Ga 2 O 3 Is 184.44/5.94cm in volume 3 ＝31cm 3 ；
1mol of beta-Ga doped with Ta 1at% 2 O 3 The number of Ta atoms contained in the composition is as follows: 1X 2X 1%. Times. 6.023X 10 23 ＝1.2×10 22 ；
Thus, ta 1at% doped beta-Ga 2 O 3 Theoretical value of carrier concentration is=2×1.2×10 22 /31＝7.7×10 20 /cm 3 。
Furthermore, the limit value of the test resistivity of the Hall effect low resistance module is 10 5 The experiment of the invention shows that 6N pure beta-Ga 2 O 3 Exceeding the test limit after annealing the crystal, indicating the resistivity>10 5 Therefore, the method adopts 6N pure beta-Ga 2 O 3 Ta doped can control resistivity to 1X 10 completely 4 This value is 1/1266 of example 1, and multiplying the carrier concentration in example by 1/1266 gives 3×10 12 /cm 3 Thus Ta is doped with beta-Ga 2 O 3 Carrier concentration of crystalline material is 5×10 12 /cm 3 Also possible. The doping concentration of Ta corresponding to the carrier concentration is 10 -7 at％。
Thus, ta is doped with beta-Ga 2 O 3 The Ta doping amount of the crystalline material can be in the range of 0.0000001mol% to 1mol%, and the resistivity can be 2.0X10 -4 To 1X 10 4 Control is realized within the omega cm range, and the carrier concentration can be 5 multiplied by 10 12 To 7X 10 20 /cm 3 Control is realized in the range.
While the embodiments of the present invention have been described in detail, the foregoing embodiments are illustrative only and not intended to be limiting, as the invention may be modified or practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein.

Claims (14)

1. Ta doped beta-Ga 2 O 3 Crystalline material belonging to monoclinic system, the space group is C2/m, the Ta is doped with beta-Ga 2 O 3 The resistivity of the crystalline material is 2.0X10 -4 To 1X 10 4 Control and/or carrier concentration in the range of 5X 10 are realized in the range of omega cm 12 To 7X 10 20 /cm 3 Control is realized in the range, and the Ta is doped with beta-Ga 2 O 3 The molecular formula of the crystalline material is Ga 2(1-x) Ta 2x O 3 ，0.000000001<x<0.01。
2. Ta doped beta-Ga as claimed in claim 1 2 O 3 Crystalline material characterized by 0.000001<x<0.01。
3. Ta doped beta-Ga as claimed in claim 1 2 O 3 Crystalline material characterized in that the Ta is doped with beta-Ga 2 O 3 The crystalline material is Ta doped beta-Ga 2 O 3 A crystal;
and/or the Ta is doped with beta-Ga 2 O 3 The resistivity of the crystalline material is 2.0X10 -3 Up to 3.6X10 2 Control is realized within the omega cm range;
and/or the Ta is doped with beta-Ga 2 O 3 The carrier concentration of the crystalline material is 3.7X10 15 To 6.3X10 19 /cm 3 Control is realized in the range.
4. Ta doped beta-Ga as claimed in claim 3 2 O 3 Crystalline material characterized in that the Ta is doped with beta-Ga 2 O 3 The crystalline material is Ta doped beta-Ga 2 O 3 A single crystal;
and/or the Ta is doped with beta-Ga 2 O 3 The resistivity of the crystalline material is controlled within the range of 0.004-7.9Ω cm;
and/or the Ta is doped with beta-Ga 2 O 3 The carrier concentration of the crystalline material is 3.7X10 15 To 3.0X10 19 /cm 3 Control is realized in the range.
5. Ta doped beta-Ga 2 O 3 The preparation method of the crystalline material comprises the following steps: ta with purity of more than 4N 2 O 5 And Ga 2 O 3 Mixing the materials according to the molar ratio of (0.000000001-0.01) to (0.09-0.999999999), and then growing crystals; after the crystal growth is finished, the obtained Ta doped beta-Ga 2 O 3 The crystalline material is also subjected to an annealing step.
6. The method of preparing according to claim 5, wherein the Ta is selected from the group consisting of 2 O 5 And Ga 2 O 3 The purity of (2) is above 5N.
7. The method of claim 5, wherein the Ta is doped with beta-Ga 2 O 3 The crystalline material is Ta doped beta-Ga 2 O 3 Ga used in the preparation of single crystals 2 O 3 The purity is above 6N.
8. The method of claim 5, wherein the Ta is doped with beta-Ga 2 O 3 The crystalline material is Ta doped beta-Ga 2 O 3 When the single crystal is grown, the melt method is adopted.
9. The method of claim 8, wherein the melt-grown single crystal is grown by an optical float zone method;
wherein, an optical floating zone method is adopted to prepare Ta doped beta-Ga 2 O 3 The single crystal comprises the steps of mixing, rod making, sintering and crystal growth.
10. The method of claim 9, wherein the mixing is by wet mixing;
and/or the sintering temperature is 1400-1600 ℃, and the sintering time is 10-20h;
and/or the atmosphere for crystal growth is an inert atmosphere or an oxidizing atmosphere;
and/or the growth speed of the crystal is 4.5-6mm/h, and the rotating speed is 8-12rpm.
11. The method of claim 10, wherein the wet mixing is performed using a wet ball milling process.
12. Ta doped beta-Ga as prepared by the method of any one of claims 5 to 11 2 O 3 Crystalline material.
13. Ta doped beta-Ga as claimed in any one of claims 1-4 and 12 2 O 3 The crystalline material is used in power electronic device, photoelectronic device or conducting substrate.
14. The use of claim 13, wherein the optoelectronic device comprises a transparent electrode, a solar panel, a light emitting device, a light detector, and a sensor; the conductive substrate includes GaN and Ga 2 O 3 A substrate material of its own.
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