CN115491747B - A method for hexagonal boron nitride single crystal - Google Patents

A method for hexagonal boron nitride single crystal Download PDF

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CN115491747B
CN115491747B CN202211194854.9A CN202211194854A CN115491747B CN 115491747 B CN115491747 B CN 115491747B CN 202211194854 A CN202211194854 A CN 202211194854A CN 115491747 B CN115491747 B CN 115491747B
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boron nitride
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CN115491747A (en
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胡章贵
郭小娟
陈建丽
徐永宽
熊杰
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Tianjin University of Technology
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    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B9/00Single-crystal growth from melt solutions using molten solvents
    • C30B9/04Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12Salt solvents, e.g. flux growth
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    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/40AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403AIII-nitrides

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Abstract

本发明涉及一种六方氮化硼单晶的方法,以金属Ni和氧化锂(Li2O)作为助溶剂,氮气和硼(B)或氮化硼(BN)作为源材料,通过助溶剂法生长大尺寸高质量的h‑BN单晶,在一定化料温度下恒温一定时间,使溶剂达到饱和状态并使B或BN充分溶解在熔剂中,再升温至生长温度且在氮气或氮氩混合气中恒温一定时间,以一定的降温速率降温,实现自发形核与生长。Ni和Li2O作为助溶剂,Li+与N极易结合,增加了N在熔剂中的溶解度,B与N在熔剂中结合。采用Ni‑Li+助熔剂体系,在高温常压下通过控制熔剂比例、氮氩气比例、浸泡时间、冷却速率等参数,生长不同尺寸及高质量的h‑BN单晶。

The invention relates to a method for producing hexagonal boron nitride single crystal, using metal Ni and lithium oxide (Li 2 O) as cosolvents, nitrogen and boron (B) or boron nitride (BN) as source materials, through a cosolvent method. Grow large-sized and high-quality h-BN single crystals. Keep the solvent at a certain temperature for a certain period of time to allow the solvent to reach a saturated state and fully dissolve B or BN in the solvent. Then, heat it up to the growth temperature and mix it with nitrogen or nitrogen and argon. Keep the temperature in the air for a certain period of time and cool it at a certain cooling rate to achieve spontaneous nucleation and growth. Ni and Li 2 O serve as co-solvents. Li + combines easily with N, which increases the solubility of N in the flux. B and N combine in the flux. Using Ni‑Li + flux system, h‑BN single crystals of different sizes and high quality are grown under high temperature and normal pressure by controlling parameters such as flux ratio, nitrogen and argon gas ratio, soaking time, and cooling rate.

Description

Method for preparing hexagonal boron nitride monocrystal
Technical Field
The invention relates to the technical field of ultra-wide band gap semiconductor single crystal growth, in particular to Ni-Li + A method for preparing hexagonal boron nitride monocrystal by using cosolvent.
Background
Hexagonal boron nitride (h-BN) is a novel wide bandgap semiconductor, is similar to a graphene structure, has a bandgap reaching more than 6.0eV, and has a large bandgap, high mechanical strength, good thermal stability, high thermal conductivity, low dielectric constant, high breakdown field strength and other excellent physical and chemical properties. The method is widely applied to the fields of deep ultraviolet light emitting devices, laser devices and deep ultraviolet detectors, and can be used for preparing high-temperature and high-frequency electronic power devices. The light-emitting material can also form a full-band light-emitting material with a mature wide-band semiconductor, and is a wide-band semiconductor material with higher exploration value.
At present, a method for preparing hexagonal boron nitride (h-BN), such as a chemical vapor deposition method or a physical vapor deposition method, has a plurality of influencing factors (such as a substrate, temperature, pressure, atmosphere and the like), a growth mechanism is not clear, and h-BN with larger size is difficult to grow. The fluxing agent method is that after solute is completely dissolved in metal flux at high temperature, the temperature is reduced at extremely low speedThe method has the advantages that the size of the method is controlled by the cooling rate, and the method takes a long time and is not thick. In 2007 Japanese National Institute for Materials Science, high purity cubic boron nitride (cBN) and hBN single crystals were synthesized as a Ba-BN solution at high temperature and high pressure for 20 to 40 hours. Because the high-temperature high-pressure method has harsh growth conditions and the growth size is difficult to further expand, the method is converted into a high-temperature normal-pressure method for preparing the h-BN monocrystal. Tetsuya Yamada et al, 2019, melted Li in BN crucible at normal pressure by controlling the flux and heating temperature 2 CO 3 The grown h-BN crystal has a novel polyhedral structure, the size is more than 3 microns, and a research thought is provided for subsequent experimental exploration. The existing metal fluxing agent system for growing h-BN under normal pressure comprises the following components: nickel tungsten, cobalt chromium, nickel chromium, copper chromium, iron chromium, pure iron, stainless steel alloys, etc., with growth dimensions on the order of microns to centimeters and thicknesses on the order of microns only.
In general, the h-BN single crystal material is still in the basic research stage of material preparation, and application research is just started, and mainly focused on the research of single crystal films. The preparation of h-BN single crystal materials with large size and high quality becomes a great difficulty.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing hexagonal boron nitride monocrystal, which can be used for preparing Ni-Li monocrystal + High-quality and large-size h-BN monocrystal is prepared in a fluxing agent system.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method of hexagonal boron nitride single crystal comprising the steps of:
step one, fusing agent Ni-Li 2 Placing a mixture of an O system, a source material and carbon powder in a crucible, and adding the source material B or BN; placing the crucible containing the mixture in a heater with a furnace chamber, sealing the furnace chamber, and purifying the atmosphere in the furnace chamber;
step two, argon is filled into the furnace chamber, and when the furnace chamber is heated to 1400-1600 ℃ of melting temperature, the furnace chamber is kept at constant temperature for 5-13 hours, so that the metal is fully melted and the source material is dissolved to form a solution;
step three, after the solution reaches saturation, heating from the melting temperature to the growing temperature of 1500-1650 ℃;
step four, after the solution is stabilized for 0.5 to 2 hours, starting a vacuum pump to pump the pressure in the furnace chamber to 1 multiplied by 10 -4 Filling high-purity nitrogen or nitrogen-argon mixed gas into the furnace chamber under Pa, keeping the growth temperature constant for 5-24h, dissolving nitrogen into the flux, and cooling to the lowest temperature which can be detected by a temperature detector in the furnace chamber at a cooling rate of 10-300 ℃/h;
and fifthly, naturally cooling to room temperature, and taking out the product from the crucible after deflating.
Further, in the first step, the fluxing agent Ni-Li 2 In the O system, ni accounts for 90 to 97 percent of the total mass of the system and Li is calculated by mass ratio 2 O accounts for 3-10% of the total mass of the system.
Further, in the first step, the crucible is baked in an oven at 105 ℃ for 120 minutes before use.
Further, in the first step, after the furnace chamber is sealed, a vacuum pump connected with the furnace chamber is started to pump the pressure in the furnace chamber to 1 multiplied by 10 -4 Under Pa, high-purity argon is filled into the furnace chamber until the pressure is 50000Pa-150000Pa; starting the vacuum pump to pump the pressure in the furnace chamber to 1×10 -4 Pa or less; repeating the above operation for 2-3 times, purifying the atmosphere in the furnace chamber, washing off the residual background gas in the furnace chamber, and reducing the content of carbon and oxygen impurities.
Further, in the second step, 101.325KPa of high purity argon gas is filled into the furnace chamber. The high purity argon is filled to prevent the generation of aluminum nitride under inert gas.
Further, in the second step, the heating rate is 233-300 ℃/h when the material is heated to the melting temperature.
Further, in the third step, the heating rate when heating to the growth temperature is 200 ℃/h.
Further, in the fourth step, the partial pressure ratio of the nitrogen-argon mixed gas is 50% -99% of nitrogen and 1% -50% of argon.
The invention uses metal Ni and lithium oxide (Li 2 O) as a cosolvent, nitrogen and boron (B) or Boron Nitride (BN) as source materials, by means of a cosolventThe method grows a large-size high-quality h-BN monocrystal, the temperature is kept for a certain time at a certain material temperature, so that the solvent reaches a saturated state, B or BN is fully dissolved in the flux, the temperature is raised to the growth temperature, the temperature is kept for a certain time at a constant temperature in nitrogen or nitrogen-argon mixed gas, and the temperature is lowered at a certain cooling rate, so that spontaneous nucleation and growth are realized.
Ni and Li 2 O is used as a cosolvent, the capacity of dissolving B or BN of Ni is larger than that of other transition metals, and Li 2 O increases the N-dissolving capacity of the flux and has a certain BN-dissolving capacity, and B and N are combined in the flux. At present, cr which is taken as a main cosolvent for dissolving N reacts with B to generate chromium-boron compound, and Li is explored + Instead of Cr-dissolved N, it is of exploratory value that the flux system can grow large-size h-BN single crystals with fewer defects, thermal strains and impurities.
The prepared h-BN has the characteristic of high anisotropy of optical properties, and has larger performance advantages in the aspects of ultraviolet light emission, detection devices and the like.
The invention is firstly in Ni-Li + The high-quality large-size h-BN single crystal is prepared in the system, a new research thought and a new method for exploring and preparing the h-BN single crystal are provided, and Ni-Li is adopted + The flux system grows to a maximum size of 500 micrometers at 1366cm under the conditions of high temperature and normal pressure by controlling parameters such as flux proportion, nitrogen-argon proportion, soaking time, cooling rate and the like -1 The half height width of the Raman is 7.78cm -1 High quality h-BN single crystals.
In addition, the method does not need ultrahigh pressure and is carried out under normal pressure, the source materials are easy to obtain, the manufacturing cost is low, and the operation is safe and simple.
Drawings
FIG. 1 is example 1Ni-Li 2 Optical microscopy images of h-BN single crystals grown by O fluxing agent;
FIG. 2 is example 1Ni-Li 2 O fluxing agent grows a Raman spectrum of the h-BN monocrystal;
FIG. 3 is example 1Ni-Li 2 h-BN monocrystal stuck on the surface of the O system;
FIG. 4 is an optical microscope photograph of comparative example 1;
FIG. 5 is an optical microscope photograph of comparative example 2;
FIG. 6 is a photograph of the inside of a crucible of comparative example 3.
Detailed Description
The following examples are provided to further illustrate the claimed invention. However, examples and comparative examples are provided for the purpose of illustrating embodiments of the present invention and do not exceed the scope of the inventive subject matter, which is not limited by the examples. Unless specifically indicated otherwise, materials and reagents used in the present invention are available from commercial products in the art.
Example 1
The corundum crucible is put into a baking oven at 105 ℃ to bake for 120 minutes and then dried.
Adding fluxing agent Ni-Li into corundum crucible 2 A mixture of O system, BN and carbon powder. Ni-Li 2 In the O system, ni accounts for 90 percent, li 2 O accounts for 10 percent, and the cosolvent Ni-Li 2 The mass ratio of the O system to the source material BN is 20:1, and the carbon powder accounts for 1.8% of the mass of the mixture. Placing corundum crucible containing the above mixture into heater, sealing the furnace chamber of the heater, starting vacuum pump, and pumping the pressure in the furnace chamber to 1×10 -4 Under Pa, high-purity argon is filled into the furnace chamber to 100000Pa, and a vacuum pump is started to pump the pressure in the furnace chamber to 1 multiplied by 10 -4 Below Pa, this operation is repeated 3 times, the atmosphere in the furnace is purged, and the residual background gas in the furnace chamber is washed off.
And filling high-purity argon with the pressure of 101.325KPa into the furnace chamber. And starting a heating system to heat the corundum crucible in the furnace chamber, wherein the heating rate is 260 ℃/h, and the melting temperature reaches 1500 ℃. After the fluxing agent melts, it is maintained at a constant temperature for 10 hours to allow the metal to sufficiently melt and dissolve the source material to form a solution.
After the solution reaches saturation, the temperature is increased from the melting temperature of 1500 ℃ to the growing temperature of 1600 ℃ with the heating rate of 200 ℃/h.
After the solution is stabilized for 1 hour, a vacuum pump is started to pump the pressure in the furnace to 1 multiplied by 10 -4 Filling high-purity nitrogen into furnace chamber under Pa, keeping constant temperature at 1600 deg.C for 18 hr to ensure that nitrogen is dissolved into flux, and cooling at 95.5 deg.C/hrThe temperature is reduced to 700 ℃, and 700 ℃ is the lowest temperature which can be detected by a temperature detector in the furnace chamber.
And after the lowest temperature measurement is reached, the power supply is turned off, and the growth is finished.
And (5) taking out the product from the corundum crucible after naturally cooling to room temperature and deflating.
Example 2
The corundum crucible is put into a baking oven at 105 ℃ to bake for 120 minutes and then dried.
Adding fluxing agent Ni-Li into corundum crucible 2 A mixture of O system, B and carbon powder. Ni-Li 2 In the O system, ni accounts for 97 percent, li 2 O accounts for 3%, and cosolvent Ni-Li 2 The mass ratio of the O system to the source material B is 20:1, and the carbon powder accounts for 1.8% of the mass of the mixture. Placing corundum crucible containing the above mixture into heater, sealing the furnace chamber of the heater, starting vacuum pump, and pumping the pressure in the furnace chamber to 1×10 -4 Under Pa, high-purity argon is filled into the furnace chamber to 50000Pa, and a vacuum pump is started to pump the pressure in the furnace chamber to 1 multiplied by 10 -4 Below Pa, this operation is repeated 2 times, the atmosphere in the furnace is purged, and the residual background gas in the furnace chamber is washed off.
And filling high-purity argon with the pressure of 101.325KPa into the furnace chamber. And starting a heating system to heat the corundum crucible in the furnace chamber, wherein the heating rate is 233 ℃/h, and the melting temperature is 1450 ℃. After the fluxing agent melts, it is held at constant temperature for 13 hours to allow the metal to sufficiently melt and dissolve the source material to form a solution.
After the solution reaches saturation, the temperature is increased from the melting temperature of 1450 ℃ to the growing temperature of 1550 ℃ at the heating rate of 200 ℃/h.
After the solution is stabilized for 0.5 hour, a vacuum pump is started to pump the pressure in the furnace to 1 multiplied by 10 -4 And filling nitrogen-argon mixed gas with the partial pressure ratio of 70% and 30% into the furnace chamber under Pa, keeping the constant temperature at 1550 ℃ for 24 hours at the growth temperature, ensuring that the nitrogen is dissolved into the flux, and then reducing the temperature to 700 ℃ at the cooling rate of 200 ℃/h, wherein the temperature is the lowest temperature which can be detected by a temperature measuring instrument in the furnace chamber.
And after the lowest temperature measurement is reached, the power supply is turned off, and the growth is finished.
And (5) taking out the product from the corundum crucible after naturally cooling to room temperature and deflating.
Example 3
The corundum crucible is put into a baking oven at 105 ℃ to bake for 120 minutes and then dried.
Adding fluxing agent Ni-Li into corundum crucible 2 A mixture of O system, B and carbon powder. Ni-Li 2 In O system, ni accounts for 95 percent, li 2 O accounts for 5 percent, and the cosolvent Ni-Li 2 The mass ratio of the O system to the source material B is 20:1, and the carbon powder accounts for 1.8% of the mass of the mixture. Placing corundum crucible containing the above mixture into heater, sealing the furnace chamber of the heater, starting vacuum pump, and pumping the pressure in the furnace chamber to 1×10 -4 Under Pa, high-purity argon is filled into the furnace chamber to 150000Pa, and a vacuum pump is started to pump the pressure in the furnace chamber to 1 multiplied by 10 -4 Below Pa, this operation is repeated 2 times, the atmosphere in the furnace is purged, and the residual background gas in the furnace chamber is washed off.
And filling high-purity argon with the pressure of 101.325KPa into the furnace chamber. And starting a heating system to heat the corundum crucible in the furnace chamber, wherein the heating rate is 300 ℃/h, and the melting temperature is 1550 ℃. After the fluxing agent melts, it is held at constant temperature for 5 hours to allow the metal to fully melt and dissolve the source material to form a solution.
After the solution reaches saturation, the temperature is increased from 1550 ℃ of the melting temperature to 1650 ℃ of the growing temperature, and the heating rate is 200 ℃/h.
After the solution is stabilized for 2 hours, a vacuum pump is started to pump the pressure in the furnace to 1 multiplied by 10 -4 And filling nitrogen-argon mixed gas with the partial pressure ratio of 50% of nitrogen and 50% of argon into the furnace chamber below Pa, keeping the constant temperature at the growth temperature of 1650 ℃ for 5 hours, ensuring that the nitrogen is dissolved into the flux, and then reducing the temperature to 700 ℃ at the cooling rate of 300 ℃/h, wherein the temperature is the lowest temperature which can be detected by a temperature measuring instrument in the furnace chamber.
And after the lowest temperature measurement is reached, the power supply is turned off, and the growth is finished.
And (5) taking out the product from the corundum crucible after naturally cooling to room temperature and deflating.
Comparative example 1
The only difference from example 1 is that: adding a mixture of BN and carbon powder into a corundum crucible, wherein the carbon powder accounts for 1.8% of the mass of the mixture.
Comparative example 2
The only difference from example 1 is that: adding a mixture of fluxing agent Ni, BN and carbon powder into a corundum crucible, wherein the mass ratio of the cosolvent Ni to the source material BN is 20:1, and the carbon powder accounts for 1.8% of the mass of the mixture.
Comparative example 3
The only difference from example 1 is that: adding fluxing agent Li into corundum crucible 2 O, BN and carbon powder, fluxing agent Li 2 The mass ratio of O to the source material BN is 20:1, and the carbon powder accounts for 1.8% of the mass of the mixture.
FIG. 1 is a drawing of example 1Ni-Li 2 An optical microscopic image of an O flux grown h-BN single crystal, a size exceeding 200 μm, FIG. 2 is a view of example 1Ni-Li 2 Raman spectrum of the grown h-BN single crystal with O fluxing agent at Raman peak position 1366cm -1 Is provided with a half width of 7.78 and 7.78cm -1 Is not shown in the figure). FIG. 3 is example 1Ni-Li 2 h-BN monocrystal adhered to O system surface.
The surface of the product of comparative example 1 was observed, and as shown in FIG. 4, the optical microscope showed no significant change in BN sheet and no formation of h-BN crystals. Comparative example 2 the sample surface, as shown in fig. 5 by optical microscopy, showed no h-BN crystals were generated on the metal surface. Comparative example 3 As shown in FIG. 6, the crucible had partially undissolved BN therein, and no formation of h-BN crystals was observed, and as a result, ni-Li 2 The O system can grow h-BN monocrystal with large size and high quality.

Claims (7)

1.一种六方氮化硼单晶的方法,其特征在于,包括以下步骤:1. A method for producing hexagonal boron nitride single crystal, characterized in that it includes the following steps: 步骤一,将助熔剂Ni-Li2O体系、源材料、碳粉的混合物置于坩埚中,将上述含有所述源材料B或BN;将含有混合物的坩埚放置于带有炉腔的加热器中,炉腔密封后净化炉腔内的气氛;Step 1: Place the mixture of flux Ni-Li 2 O system, source material, and carbon powder in a crucible, and place the source material B or BN as mentioned above; place the crucible containing the mixture in a heater with a furnace cavity In the process, the atmosphere in the furnace cavity is purified after the furnace cavity is sealed; 所述助熔剂Ni-Li2O体系中,以质量比百分比计,Ni占体系总质量的90%-97%、Li2O占体系总质量的3%-10%;In the flux Ni-Li 2 O system, in terms of mass ratio percentage, Ni accounts for 90%-97% of the total mass of the system, and Li 2 O accounts for 3%-10% of the total mass of the system; 步骤二,向炉腔内充入氩气,并进行加热达到化料温度1400-1600℃时,恒温保持5-13小时,使金属充分熔融并溶解源材料形成溶液;Step 2: Fill the furnace cavity with argon gas and heat it to reach the material temperature of 1400-1600°C. Keep the temperature constant for 5-13 hours to fully melt the metal and dissolve the source material to form a solution; 步骤三,待溶液达到饱和后,从化料温度升温至生长温度1500-1650℃;Step 3: After the solution reaches saturation, raise the temperature from the chemical material temperature to the growth temperature of 1500-1650°C; 步骤四,待溶液稳定0.5-2时后,开启真空泵,将炉腔内压强抽至1×10-4Pa以下,向炉腔内充入高纯氮气或氮氩混合气,在生长温度恒温5-24h,使氮气溶入熔剂中,再以10-300℃/h的降温速率降温至炉腔内测温仪能检测到的最低温度;Step 4: After the solution is stable for 0.5-2 hours, turn on the vacuum pump, pump the pressure in the furnace cavity to below 1×10 -4 Pa, fill the furnace cavity with high-purity nitrogen or a nitrogen-argon mixture, and maintain the growth temperature at a constant temperature of 5 -24h, let the nitrogen gas dissolve into the flux, and then cool it down to the lowest temperature that can be detected by the thermometer in the furnace cavity at a cooling rate of 10-300℃/h; 步骤五,自然冷却至室温,放气后从坩埚中取出产品。Step 5: Cool to room temperature naturally, deflate and take out the product from the crucible. 2.根据权利要求1所述的六方氮化硼单晶的方法,其特征在于:步骤一中,坩埚在使用前,先在105℃烘箱烘烤120分钟。2. The method of hexagonal boron nitride single crystal according to claim 1, characterized in that in step one, the crucible is baked in an oven at 105°C for 120 minutes before use. 3.根据权利要求1或2所述的六方氮化硼单晶的方法,其特征在于:步骤一中,炉腔密封后,开启与炉腔相连接的真空泵,将炉腔内压强抽至1×10-4Pa以下,再向炉腔内充入高纯氩气至压强为50000Pa-150000Pa;再开起真空泵,将炉腔内压强抽至1×10-4Pa以下;上述操作重复2-3次,净化炉腔内气氛,洗去炉腔内残余背景气体。3. The method for hexagonal boron nitride single crystal according to claim 1 or 2, characterized in that: in step one, after the furnace cavity is sealed, the vacuum pump connected to the furnace cavity is turned on to pump the pressure in the furnace cavity to 1 ×10 -4 Pa below, then fill the furnace cavity with high-purity argon gas until the pressure is 50000Pa-150000Pa; then turn on the vacuum pump to pump the pressure in the furnace cavity to below 1×10 -4 Pa; repeat the above operations 2- 3 times to purify the atmosphere in the furnace cavity and wash away the residual background gas in the furnace cavity. 4.根据权利要求3所述的六方氮化硼单晶的方法,其特征在于:步骤二中,向炉腔内充入101.325KPa的高纯氩气。4. The method of hexagonal boron nitride single crystal according to claim 3, characterized in that: in step two, high-purity argon gas of 101.325KPa is filled into the furnace cavity. 5.根据权利要求4所述的六方氮化硼单晶的方法,其特征在于:步骤二中,加热至化料温度时的升温速率为233-300℃/h。5. The method of hexagonal boron nitride single crystal according to claim 4, characterized in that in step two, the heating rate when heating to the temperature of the chemical material is 233-300°C/h. 6.根据权利要求5所述的六方氮化硼单晶的方法,其特征在于:步骤三中,加热至生长温度时的升温速率为200℃/h。6. The method for hexagonal boron nitride single crystal according to claim 5, characterized in that in step three, the heating rate when heating to the growth temperature is 200°C/h. 7.根据权利要求6所述的六方氮化硼单晶的方法,其特征在于:步骤四中,氮氩混合气中的分压比例为氮气50%-99%,氩气1%-50%。7. The method for hexagonal boron nitride single crystal according to claim 6, characterized in that: in step four, the partial pressure ratio in the nitrogen-argon gas mixture is 50%-99% for nitrogen and 1%-50% for argon. .
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JPH1025192A (en) * 1996-07-05 1998-01-27 Kobe Steel Ltd Crystal growing method
JP2001220130A (en) * 2000-01-31 2001-08-14 National Institute For Materials Science Rare earth polyborides containing carbon and nitrogen and method for producing the same
CN109695053A (en) * 2019-02-15 2019-04-30 东南大学 A kind of preparation method of large scale hexagonal boron nitride monocrystalline

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