CN115196645A - Preparation method of boron arsenide powder - Google Patents
Preparation method of boron arsenide powder Download PDFInfo
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- CN115196645A CN115196645A CN202211001821.8A CN202211001821A CN115196645A CN 115196645 A CN115196645 A CN 115196645A CN 202211001821 A CN202211001821 A CN 202211001821A CN 115196645 A CN115196645 A CN 115196645A
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- C01B35/00—Boron; Compounds thereof
- C01B35/02—Boron; Borides
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- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The invention discloses a preparation method of boron arsenide powder, and relates to the field of preparation of boron arsenide powder. The method comprises the following steps: cleaning the crucible, and drying the crucible for later use after ultrasonic treatment; uniformly mixing alkaline earth metal EA, boron arsenate and a molten salt medium, and placing the mixture into a crucible; according to the reaction formula BAsO 4 +4EA = BAs +4EA (O) for reduction of boron arsenate BAsO 4 Putting the crucible into a reaction furnace, introducing argon protective gas, heating to 700-900 ℃, and preserving heat for 1-5h; and (3) soaking the sample obtained in the step two in concentrated hydrochloric acid at room temperature, heating in a water bath, preserving heat, washing to be neutral by using deionized water, and performing ball milling and drying to obtain boron arsenide powder. The method does not need high-pressure or complex equipment, can provide boron arsenide in a short time in a simple and economic manner, and overcomes the defects of the prior art; can be used for preparing boron arsenide target material and preparing boron arsenide single crystal film material by physical vapor phase method; the difficulty of preparing the boron arsenide single crystal material is reduced.
Description
Technical Field
The invention relates to the field of preparation of boron arsenide powder, in particular to a preparation method of boron arsenide powder.
Background
A semiconductor material is an electronic material having a conductivity between that of a conductor and an insulator, which can be used to fabricate semiconductor devices and integrated circuits, such as boron, diamond, germanium, silicon, gray tin, antimony, selenium, tellurium, etc., or SiC, which is a composite material.
At present, the modern technology of human civilization is based on the semiconductor material represented by silicon, which cannot be separated from solar cells to chips, but silicon is also determined to be the most ideal semiconductor material for heat conduction and other reasons.
A cubic boron arsenide material breaks through these two limitations, providing both high mobility for electrons and holes, and excellent electrical conductivity, as well as extremely high thermal conductivity characteristics. Of course, cubic boron arsenide has so far been produced and tested only in small quantities in the laboratory and is not homogeneous.
Boron arsenide is a group III-V semiconductor compound whose crystalline material has an ultra-high thermal conductivity, higher than all common metals and semiconductors, three times that of silicon carbide, next to diamond. Compared with the diamond which is expensive, cannot be produced in batch and has harsh application conditions, the boron arsenide has good thermal conductivity, good compatibility with silicon materials and feasibility of batch production. Is expected to become a semiconductor cooling and heat dissipation material of the next generation, and provides an optimal scheme for solving the technical bottleneck of heat dissipation of semiconductor devices and photoelectric devices. Cubic boron arsenide is made from boron and arsenic, and has some unique advantages over silicon, being more efficient in heat transfer than silicon, and having a higher thermal conductivity than the second copper of the metal, the first name being silver, and having a thermal conductivity of 414, but is expensive and therefore not commonly used. Specifically, the thermal conductivity of copper is 384, that of silicon is 148, and that of cubic boron arsenide can reach 1200, which is approximately 10 times that of silicon! Therefore, cubic boron arsenide is likely to be the most desirable semiconductor fabrication material in the future. In 2018, the semiconductor material cubic boron arsenide (c-BA) experiment proves that the material has ultrahigh room temperature thermal conductivity coefficient (kappa)>1300 W m −1 K −1 ) The introduction of (1). Meanwhile, theoretical prediction shows that the carrier mobility of c-BA is high, and the electron mobility is 1400 cm 2 V −1 s −1 Hole mobility of 2100 cm 2 V −1 s −1 (ii) a Especially under a small stress of 1%, the hole mobility can be as high as 3000 cm 2 V −1 s −1 (ii) a Meanwhile, the material has high thermal conductivity and carrier mobility, so that c-BA can become a star material in the field of electronics and optoelectronics at a time.
Boron arsenide has high preparation cost and the reaction raw materials or intermediate products have high toxicity. At present, the boron arsenide is generally synthesized by adopting a gas-solid synthesis technology, namely, the boron arsenide is synthesized by taking a simple substance B and simple substance arsenic as raw materials under the conditions of high temperature, vacuum and the like. Because B has a high melting point of 2300 ℃; as has high vapor pressure, and the saturated vapor pressure at 800 ℃ reaches more than 30 atmospheric pressure; BAs are easily decomposed into by-products at high temperatures, making the preparation of BAs crystals rather difficult. It is reported that a sample having a maximum size of only 10mm of BAs crystal is prepared at present abroad. However, boron arsenide powder is difficult to commercialize on an industrial scale so far due to the lack of a relatively simple and economical preparation method, and thus its use is limited.
CN 114105157A discloses a double-temperature-zone tube-sealing synthesis technology of a boron arsenide powder material, which specifically comprises the following steps: accurately weighing boron powder with the purity of 99.999% and arsenic granules with the purity of 99.999%, and then filling the boron powder and the arsenic granules into a quartz tube, wherein the charging amount of each tube is 50 to 100g, and the molar ratio of boron to arsenic is 1: (1.5 to 1.9), the length of a quartz tube is 750 to 1100mm, a high-temperature end and a low-temperature end are arranged at two ends of the tube, boron is arranged at the high-temperature end, and arsenic is arranged at the low-temperature end; vacuumizing the quartz tube until the air pressure in the quartz tube is 0.01 torr, and sealing the quartz tube; heating the quartz tube in a double-tube synthetic furnace, heating the high-temperature end to 800-890 ℃, heating the low-temperature end to 500-615 ℃, preserving the heat for 2~6 days, purifying and ball-milling a product to obtain cubic boron arsenide powder with the purity of more than 99.995%.
As described in the prior art, the processes used to date for the preparation of boron arsenide require expensive, toxic and aggressive reagents, complex technical implementation, high labor intensity and time consumption. There is therefore a great need for a simple, convenient and low-cost method for preparing boron arsenide.
Disclosure of Invention
The invention provides a preparation method of boron arsenide powder, aiming at solving the problems that the preparation cost of the boron arsenide powder material is high, the method is complex, and large-scale preparation is difficult.
The invention is realized by the following technical scheme: a preparation method of boron arsenide powder comprises the following steps:
1. cleaning the crucible, and drying the crucible for later use after ultrasonic treatment; uniformly mixing alkaline earth metal EA, boron arsenate and a molten salt medium, and placing the mixture into a crucible;
2. according to reaction formula (1):
BAsO 4 +4EA=BAs+4EA(O) （1）
reaction formula (1) for reducing boron arsenate BAsO 4 Putting the crucible into a reaction furnace, introducing argon protective gas, heating to 700 to 900 ℃, and keeping the temperature for 1 to 5h;
3. and (3) soaking the sample obtained in the step two in concentrated hydrochloric acid at room temperature, heating in a water bath, preserving heat, washing to be neutral by using deionized water, and performing ball milling and drying to obtain boron arsenide powder.
The preparation method of the boron arsenide powder provided by the invention is carried out by simply heating a mixture containing at least one alkaline earth metal, boron arsenate, at least one alkali metal chloride molten salt and the like, reducing the boron arsenate BAsO4 according to the reaction formula (1) to synthesize the boron arsenide powder, does not need high-pressure or complex equipment, and can provide the boron arsenide in a simple and economic manner in a short time, thereby overcoming the defects of the prior art.
Further, in the first step, the alkaline earth metal EA is one or two of magnesium and calcium.
Further, in the first step, 1~5 parts of alkaline earth metal powder, 1 part of boron arsenate and 1~5 parts of a molten salt medium are weighed according to parts by mass of alkaline earth metal EA, boron arsenate and the molten salt medium.
Further, in the step one, the crucible is a corrosion-resistant boron nitride crucible.
Further, in the first step, the molten salt medium is at least one of lithium chloride, sodium chloride and potassium chloride.
Further, the temperature rise rate in the second step is 2~8 ℃/min.
And further, in the third step, soaking in concentrated hydrochloric acid at room temperature for 30 to 120min, heating in a water bath to 60 ℃, preserving heat for 30 to 120min, and then washing with deionized water to be neutral.
Further, the ball mill adopted in the ball milling in the third step is an argon protective planetary agate ball mill, and the proportion of large, medium and small balls in the ball milling is 1:1:1, wherein the diameter of the big ball is 8mm, the diameter of the middle ball is 5.2mm, and the diameter of the small ball is 3.8mm; the ball material ratio is 2.8; the revolution of the ball mill is 200r/min, and the ball milling time is 2 to 5 hours.
Compared with the prior art, the invention has the following beneficial effects: according to the preparation method of the boron arsenide powder, the boron arsenide powder synthesized by the method can be used for preparing a boron arsenide target material and can be further used for preparing a boron arsenide single crystal thin film material by a physical vapor phase method; can also be used for preparing boron arsenide single crystal material by a chemical vapor method; the difficulty of preparing the boron arsenide single crystal material is reduced.
Drawings
FIG. 1 is an XRD spectrum of boron arsenide.
Detailed Description
The present invention is further illustrated by the following specific examples.
A preparation method of boron arsenide powder comprises the following steps:
1. cleaning the crucible, and drying the crucible for later use after ultrasonic treatment; uniformly mixing alkaline earth metal EA, boron arsenate and a molten salt medium, and placing the mixture into a crucible;
2. according to reaction formula (1):
BAsO 4 +4EA=BAs+4EA(O) （1）
reaction formula (1) for reducing boron arsenate BAsO 4 Putting the crucible into a reaction furnace, introducing argon protective gas, heating to 700 to 900 ℃, and keeping the temperature for 1 to 5h;
3. and (3) soaking the sample obtained in the step two in concentrated hydrochloric acid at room temperature, heating in a water bath, preserving heat, washing to be neutral by using deionized water, and performing ball milling and drying to obtain boron arsenide powder.
In step one of the following examples: the alkaline earth metal EA is one or two of magnesium and calcium; weighing 1~5 parts of alkaline earth metal powder, 1 part of boron arsenate and 1~5 parts of a molten salt medium according to parts by mass; the crucible is a corrosion-resistant boron nitride crucible; the molten salt medium is at least one of lithium chloride, sodium chloride and potassium chloride. The temperature rise rate in the second step is 2~8 ℃/min. Step three, soaking the mixture in concentrated hydrochloric acid at room temperature for 30 to 120min, heating the mixture in a water bath to 60 ℃, preserving the heat for 30 to 120min, and then washing the mixture to be neutral by deionized water; in the ball milling process, the adopted ball mill is an argon protective planetary agate ball mill, and the proportion of large, medium and small ball milling balls is 1:1:1, wherein the diameter of a large ball is 8mm, the diameter of a middle ball is 5.2mm, and the diameter of a small ball is 3.8mm; the ball material ratio is 2.8; the revolution of the ball mill is 200r/min, and the ball milling time is 2 to 5 hours.
Example one
A preparation method of boron arsenide powder comprises the following steps:
1. cleaning the crucible, and drying the BN crucible for later use after ultrasonic treatment; the alkaline earth metal EA in the embodiment is magnesium powder, the magnesium powder, boron arsenate and a molten salt medium are used as raw materials, the molten salt medium is single-salt NaCl, and the mass ratio of the magnesium powder to the boron arsenate to the sodium chloride is 1; uniformly mixing, and placing into a BN crucible;
2. the crucible was placed in a reaction furnace according to the following reaction formula:
4Mg+BAsO 4 =4MgO+BAs (Overall reaction) (1)
B 2 O 3 +3MgO=Mg 3 B 2 O 6 (Side reaction) (2)
the above reaction formula is used for reducing boron arsenate BAsO 4 Introducing argon protective gas into the reaction furnace, heating to 850 ℃, and preserving heat for 1h;
3. and (3) soaking the sample obtained in the second step in concentrated hydrochloric acid at room temperature, stirring in a water bath at 60 ℃ for 2 h, then performing vacuum filtration, washing with deionized water to be neutral, and putting into an oven for drying to obtain boron arsenide powder BAs.
Example two
A preparation method of boron arsenide powder comprises the following steps:
1. cleaning the crucible, and drying the BN crucible for later use after ultrasonic treatment; the alkaline earth metal EA in the embodiment is magnesium powder, the magnesium powder, boron arsenate and a molten salt medium are used as raw materials, the molten salt medium is double salt n (NaCl) =1:1, and the mass ratio of the magnesium powder to the boron arsenate to the double salt is 1; uniformly mixing, and placing into a BN crucible;
2. the crucible was placed in a reaction furnace according to the following reaction formula:
4Mg+BAsO 4 =4MgO+BAs (Overall reaction) (1)
B 2 O 3 +3MgO=Mg 3 B 2 O 6 (Side reaction) (2)
the above reaction formula is used for reducing boron arsenate BAsO 4 Introducing argon protective gas into the reaction furnace, heating to 850 ℃, and preserving heat for 5 hours;
3. and (3) soaking the sample obtained in the second step in concentrated hydrochloric acid at room temperature, stirring in a water bath at 60 ℃ for 2 h, then performing vacuum filtration, washing with deionized water to be neutral, and putting into an oven for drying to obtain boron arsenide powder BAs.
EXAMPLE III
A preparation method of boron arsenide powder comprises the following steps:
1. cleaning the crucible, and drying the BN crucible for later use after ultrasonic treatment; the alkaline earth metal EA in the embodiment is magnesium powder, the magnesium powder, boron arsenate and a molten salt medium are used as raw materials, the molten salt medium is a three-salt n (NaCl): n (KCl) = 5, and the mass ratio of the fixed magnesium powder to the boron arsenate to the three-salt is 1; uniformly mixing, and placing into a BN crucible;
2. the crucible was placed in a reaction furnace according to the following reaction formula:
4Mg+BAsO 4 =4MgO+BAs (Overall reaction) (1)
B 2 O 3 +3MgO=Mg 3 B 2 O 6 (Side reaction) (2)
the above reaction formula is used for reducing boron arsenate BAsO 4 Introducing argon protective gas into the reaction furnace, heating to 850 ℃, and preserving heat for 10 hours;
3. and (3) soaking the sample obtained in the second step in concentrated hydrochloric acid at room temperature, stirring in a water bath at 60 ℃ for 2 h, then performing vacuum filtration, washing with deionized water to be neutral, and putting into an oven for drying to obtain boron arsenide powder BAs.
The scope of the invention is not limited to the above embodiments, and various modifications and changes may be made by those skilled in the art, and any modifications, improvements and equivalents within the spirit and principle of the invention should be included in the scope of the invention.
Claims (8)
1. A preparation method of boron arsenide powder is characterized by comprising the following steps: the method comprises the following steps:
1. cleaning the crucible, and drying the crucible for later use after ultrasonic treatment; uniformly mixing alkaline earth metal EA, boron arsenate and a molten salt medium, and placing the mixture into a crucible;
2. according to reaction formula (1):
BAsO 4 +4EA=BAs+4EA(O) （1）
reaction formula (1) for reducing boron arsenate BAsO 4 Putting the crucible into a reaction furnace, introducing argon protective gas, heating to 700-900 ℃, and preserving heat for 1-5h;
3. and (3) soaking the sample obtained in the step two in concentrated hydrochloric acid at room temperature, heating in a water bath, preserving heat, washing to be neutral by using deionized water, and performing ball milling and drying to obtain boron arsenide powder.
2. The method of claim 1, wherein the method comprises: in the first step, the alkaline earth metal EA is one or two of magnesium and calcium.
3. The method of claim 1, wherein the method comprises: in the first step, 1~5 parts of alkaline earth metal powder, 1 part of boron arsenate and 1~5 parts of a molten salt medium are weighed by mass parts of alkaline earth metal EA, boron arsenate and the molten salt medium.
4. The method of claim 1, wherein the method comprises: in the first step, the crucible is a corrosion-resistant boron nitride crucible.
5. The method of claim 1, wherein the method comprises: in the first step, the molten salt medium is at least one of lithium chloride, sodium chloride and potassium chloride.
6. The method of claim 1, wherein the method comprises: the temperature rise rate in the second step is 2~8 ℃/min.
7. The method of claim 1, wherein the method comprises: and in the third step, soaking the mixture in concentrated hydrochloric acid at room temperature for 30 to 120min, heating the mixture in a water bath to 60 ℃, preserving the heat for 30 to 120min, and then washing the mixture to be neutral by using deionized water.
8. The method of claim 1, wherein the method comprises: the ball mill adopted in the ball milling in the third step is an argon protective planetary agate ball mill, and the proportion of large, medium and small balls in the ball milling is 1:1:1, wherein the diameter of a large ball is 8mm, the diameter of a middle ball is 5.2mm, and the diameter of a small ball is 3.8mm; the ball material ratio is 2.8; the revolution of the ball mill is 200r/min, and the ball milling time is 2 to 5 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777128A (en) * | 2016-03-01 | 2016-07-20 | 郑州大学 | Method for synthesizing hafnium carbide ceramic powder at low temperature through assisting of molten salts and magnesiothermic reduction |
| CN110723740A (en) * | 2019-10-23 | 2020-01-24 | 西安交通大学 | Method for preparing high-thermal-conductivity boron phosphide by molten salt growth method |
| AU2020101794A4 (en) * | 2019-08-29 | 2020-09-17 | Guizhou University | A method for reducing nano-silica by molten-salt-mediated magnesiothermic reduction |
| CN114105157A (en) * | 2021-12-09 | 2022-03-01 | 江西科泰新材料有限公司 | Double-temperature-zone dense tube synthesis technology of boron arsenide powder material |
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- 2022-08-20 CN CN202211001821.8A patent/CN115196645A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777128A (en) * | 2016-03-01 | 2016-07-20 | 郑州大学 | Method for synthesizing hafnium carbide ceramic powder at low temperature through assisting of molten salts and magnesiothermic reduction |
| AU2020101794A4 (en) * | 2019-08-29 | 2020-09-17 | Guizhou University | A method for reducing nano-silica by molten-salt-mediated magnesiothermic reduction |
| CN110723740A (en) * | 2019-10-23 | 2020-01-24 | 西安交通大学 | Method for preparing high-thermal-conductivity boron phosphide by molten salt growth method |
| CN114105157A (en) * | 2021-12-09 | 2022-03-01 | 江西科泰新材料有限公司 | Double-temperature-zone dense tube synthesis technology of boron arsenide powder material |
Non-Patent Citations (1)
| Title |
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| "超级导热材料--从钻石到立方氮化硼晶体", 《超硬材料工程》, pages 487 * |
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