CN1364728A - Process for preparing nitride ultromicro powder and nitride crystal wunder hydrothermal condition - Google Patents
Process for preparing nitride ultromicro powder and nitride crystal wunder hydrothermal condition Download PDFInfo
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Abstract
The present invention relates to the field of nano material and crystal growth technology. The present ivnention features that crystal and superfine powder of boron nitride, gallium nitride, aluminium nitride and indium nitride are prepared through dissolving boron, gallium, aluminium and indium in deionized water, adding metal nitride or ammonia while stirring; adding P, Zn and other reductant; heating at 100-800 deg.c for 10-120 hr and by means of reaction coupling. The present inventino has the advantages of no need of large and expensive instrument and equipment, no need of oxygen-free and water-free condition and capability of obtaining large crystal. The process is low in nitride preparing cost and suitable for large-scale production.
Description
(I) technical field
The invention relates to a new method for preparing nitride superfine powder and bulk crystal under the conditions of low temperature and low pressure by using a hydrothermal reaction method, belonging to the technical field of nanometer materials and crystal growth.
(II) background of the invention
The hexagonal boron nitride nanometer micro powder has attracted people's attention due to the high heat conductivity, good chemical stability, excellent lubricating property and sintering property. After the hexagonal boron nitride nano micro powder is added into the lubricating oil, the hexagonal boron nitride nano micro powder tends to be deposited at the defect position of the friction surface firstly, so that the defect repairing effect is achieved, and the lubricating effect can be obviously improved; as a heating container material, the hexagonal boron nitride nanometer micro powder can greatly reduce the sintering temperature (the maximum cooling amplitude can reach 1800 ℃), and simultaneously can obviously improve the density and the toughness of the container. The existing main method for preparing the hexagonal boron nitride micro powder is to react urea with borax at a high temperature, the method is poor in uniformity and high in required reaction temperature (700-1000 ℃), the particle size uniformity of the obtained powder is difficult to guarantee, and only a hexagonal phase can be obtained.
Cubic boron nitride (cBN) has second order thermal conductivity but better stability than diamond, and is the best heat dissipation material; its hardness is slightly lower than that of diamond, but it does not react with Fe group element, so greatly elongating service life of tool and increasing machining precision. The wide application of the cubic boron nitride tool has decisive effects of greatly improving the integral level of the machining industry and improving the product grade.
The large-size high-purity cubic boron nitride polycrystal can be used as a high-energy ray window or a high-efficiency radiating fin and has very important application prospect. The ceramic cutting tool and the protective coating made of the cubic boron nitride nanometer micro powder have the characteristics of low sintering temperature, high density and integrity, wear resistance and corrosion resistance. The binder originally necessary for manufacturing cutters and drills by micron cubic boron nitride can be completely discarded, and cubic boron nitride nanometer micro powder is directly sintered into a superhard ceramic body with compact structure and stable chemical property. Because of the important practical value of cubic boron nitride, the synthesis method of cubic boron nitride has been systematically explored for many years. For a long time, cubic boron nitride has been considered as a stable phase of BN at high temperature and high pressure, and can only be synthesized by a high-temperature and high-pressure method with high consumption and low output. Therefore, at present, the cubic BN is obtained by high-temperature high-pressure phase change (1500-2000 ℃, 1.5-4.0 GPa). The method has the advantages of expensive required equipment, inaccurate condition monitoring, poor repeatability and high price; in addition, the non-uniform distribution of pressure, temperature, etc. makes the uniformity of the product undesirable, and it is almost impossible to obtain a product having a uniform particle size and a size ranging from submicron to nanometer.
In view of the above situation, the applicant of the present invention has developed a synthesis method of cubic boron nitride by organic solvent liquid phase chemical reaction, which is described in "synthesis of cubic boron nitride under low temperature and low pressure" by heubang, treigrah et al, "materials chemistry" 2001, 13(8), 245-. However, this method requires the use of a large amount of toxic chemical raw materials, i.e., benzene, and the price of boron source and nitrogen source is also high, which complicates the operation process and causes great environmental pollution.
Aluminum nitride (AlN) has a wide band gap (6.2eV), so that the AlN has a wide application prospect in the field of ultraviolet electronic devices, has good chemical stability and high thermal conductivity, and has important application in the aspects of high-temperature electronic devices, substrate materials, heat sinks and field effect transistors. GaN is a semiconductor material with a wide direct band gap (3.39eV), and blue-violet semiconductor optoelectronic devices fabricated by epitaxial growth methods have now formed a market in the billions of dollars, and this market volume is expanding rapidly. In addition, gallium nitride plays a significant role in the development of high-temperature and high-speed semiconductor devices. Aluminum nitride and gallium nitride alloys and gallium nitride and indium nitride alloys have the advantages that other materials cannot match in the aspect of preparing blue-green light, blue-violet light and ultraviolet optoelectronic devices, so that the aluminum nitride and gallium nitride alloys attract the wide attention of people in the political, scientific and industrial fields and influence the fields including materials, semiconductor technology, communication, information industry and the like.
Although aluminum nitride, gallium nitride, indium nitride materials and devices have extremely important practical values, the currently prepared optoelectronic devices are all grown on sapphire and silicon carbide with large lattice mismatch through heteroepitaxy, so that a large number of defects appear in a nitride epitaxial layer, and the performance of the devices is seriously influenced. Therefore, the nitride single crystal substrate material is obtained, the homoepitaxial growth of the short-wavelength semiconductor photoelectronic device is realized, the photoelectric efficiency and the stability of the device are greatly improved, and the nitride single crystal substrate material becomes a dream of research and development personnel in the fields of material science, semiconductor devices and information technology. The realization of the dream brings inestimable economic benefits, and brings great changes to the fields of information technology, material science and the like, thereby generating profound social influences.
Up to now, the methods for synthesizing AlN and GaN mainly include: the metal is reacted with nitrogen or ammonia gas under high temperature and high pressure conditions (for example, gallium metal is reacted with ammonia under high temperature and high pressure, gallium metal is reacted with nitrogen under approximately ten thousand atmospheric pressure, etc.), a metal halide is reacted with an alkali metal nitride under solvothermal conditions, and the like. These methods either have high corrosivity, impose strict requirements on equipment, or require high temperature and pressure conditions, and use extremely expensive large precision equipment. On the one hand, they require too severe conditions and on the other hand, it is difficult to obtain a material with complete crystallization and uniform particle size and to obtain large crystals. When the nitride material is grown by the hydrothermal synthesis method, the granularity and uniformity of the material can be well controlled, and nitride crystals with complete crystals and controllable components can be grown.
Disclosure of the invention
Theinvention provides a technical scheme for preparing boron nitride, gallium nitride, indium nitride and aluminum nitride by using an aqueous solution chemical reaction method aiming at the problems in the prior art so as to realize low-cost mass production of the nitride micro powder and the crystal material.
The preparation method of the nitride micro powder comprises the following steps of: (1) dissolving a boron source, a gallium source, an indium source or an aluminum source in water, rapidly stirring while dissolving, and continuously stirring for 20-120 minutes to obtain a solution or suspension with the content of 0.01-20 mol/L. (2) The boron source solution or suspension obtained above is added with constant stirring to a stoichiometric ratio of finely divided nitrogen source powder or soluble nitrogen source solution. (3) Stirring is continued and stoichiometric proportions of one or more of phosphorus, zinc, iron, aluminum, silicon, sulfur, carbon, etc., or of the lower-valent compounds composed thereof, are added as reducing agents. (4) And continuously stirring for 0.5-2 hours, then filling into a closed reaction container, heating to 100-800 ℃ with the filling rate of 20-95%, and reacting for 2-240 hours under the condition of continuous oscillation or stirring. (5) And after the reaction is finished, performing suction filtration on the product, washing the product with deionized water at the temperature of 20-100 ℃, performing suction filtration for multiple times, or performing suction filtration after treatment with an alkaline or acidic solution until the filtrate is neutral. (6) Heating the obtained powder in vacuum at 40-80 ℃ and drying to obtain the boron nitride, gallium nitride, indium nitride or aluminum nitride superfine powder with the granularity of 5-500 nanometers and uniform particles. The method for producing a nitride crystal of the present invention includes all the steps described above, and is characterized in that: (7) adding small nitride crystal grains as seed crystal into the reaction system, and growing nitride crystal material by controlling the temperature gradient distribution and reactant concentration.
The sources of boron, aluminum, gallium and indium used in step (1) are halides, borides, borates, hydroxides, oxides, metallorganics and the like thereof, respectively, and are required to have moderate stability.
The water used in steps (1) and (2) is distilled deionized water or ion-exchanged high-purity water, and before use, high-purity nitrogen gas is preferably bubbled into the water to remove oxygen dissolved in the water.
The nitrogen source used in step (2) is a nitride, an azide, ammonia, an ammonia halide, and an organic amine. They may be water-soluble or may be solid powders of relatively small particle size, in which the nitrogen atoms are required to readily participate in the reaction.
The selection range of the reducing agent used in the step (3) comprises the following steps: simple substances such as carbon, phosphorus, zinc, iron, aluminum, silicon, sulfur and the like or low-valence simple compounds composed of the simple substances are required to be combined with oxygen atoms in the reaction process to form compounds with higher stability, such as oxysalts.
When the seed crystal used in step (7) is the same substance as the nitride to be prepared, for example, a gallium nitride seed crystal is added to a reaction system for preparing gallium nitride, and a large nitride crystal can be obtained by controlling the distribution of temperature and concentration; and when they are different species, the seed crystal has a structure-inducing effect on the generated nitride, that is, the generated nitride has the same crystal structure as the seed crystal. For example, when aluminum nitride crystal grains having a cubic structure areadded to a reaction system for synthesizing boron nitride, near-phase cubic boron nitride can be obtained.
In the preparation method, the higher the concentration of the reaction raw materials and the higher the stirring speed, the smaller the granularity of the obtained nitride is, and the better the uniformity is; in addition, the reducing agent should be added in stoichiometric proportion, and not be excessive, otherwise more by-products are generated, and the yield and purity of the nitride are affected.
The method is characterized in that: the process for preparing the nitride ultra-fine powder and the crystal is carried out in aqueous solution, and low-pressure or normal-pressure (one atmosphere) reaction conditions are used, so that extreme conditions such as high temperature and high pressure are avoided. The method is easy to realize low-cost mass production, and water is used as a solvent in the preparation process, so that the environment is not polluted. In addition, the characteristics of the aqueous solution reaction enable the prepared nitride superfine powder to have high uniformity and integrity, and the aqueous solution environment is very favorable for the mass transfer of inorganic ions, so that a large nitride crystal material can be easily grown. The invention carries out systematic research on key influencing factors of the preparation process, such as concentration, molar ratio, reaction temperature, pressure and the like.
The method has the following excellent effects: 1. the cost is low. When the nitride is synthesized by the hydrothermal method, the used raw materials are common chemical reagents or chemical raw materials, special protective atmosphere is not needed, the operation procedure is simple, the yield is improved, and the cost is reduced. 2. Various parameters (temperature, pressure, concentration and the like) in the reaction process are easy to monitor and control, so that the reaction mechanism can be easily researched, the most critical influencing factors can be found, and the process conditions can be stabilized as soon as possible. 3. The environmental pollution is less. Compared with other methods, the method of the invention takes water as a medium, and can basically eliminate pollution and be beneficial to environmental protection by recycling water. 4. The uniformity of the reaction system is good. Because water is a good pressure and mass transfer medium, the temperature, the pressure and the reactant concentration in the system are uniform and consistent in the reaction process. The characteristic can not only ensure the consistency of the product, but also prepare submicron or even nanoscale powder materials with uniform and controllable granularity. 5. Hydrothermal conditions are favorable for growing large crystals of inorganic substances. By artificially producing the distribution of temperature or concentration, the crystal can be continuously grown by the transportation of water, thereby obtaining a large nitride crystal.
The nitride ultra-fine powder and the nitride crystal prepared by the method can be widely applied to the manufacture of precision machining tools and high-stability and high-hardness drill bits, the manufacture of superhard corrosion-resistant protective coatings, substrate materials of blue-violet light and ultraviolet light semiconductor optoelectronic devices, high-stability and high-temperature-resistant heating containers, high-thermal-conductivity insulating materials, grinding and cutting tools, high-performance nano lubricating liquid, military special window materials, high-power electronic device packaging materials and the like.
The method of the present invention is further described with reference to the following description and specific examples.
(IV) description of the drawings
FIG. 1 is an X-ray diffraction pattern of the fine boron nitride powder prepared in example 1, wherein peaks marked with dots belong to hexagonal boron nitride and the remaining peaks correspond to orthorhombic boron nitride.
FIG. 2 is an infrared spectrum of the fine boron nitride powder prepared in example 1, which is 1080cm in length-1Corresponding to orthorhombic boron nitride and located at 1630cm-1And 988cm-1The infrared absorption peak of (a) is hexagonal boron nitride.
FIG. 3 is an X-ray diffraction pattern of the fine gallium nitride powder prepared in example 7.
Fig. 4 is an infrared spectrum of the gallium nitride fine powder prepared in example 7, and an absorption peak on the spectrum can be assigned to gallium nitride crystal grains.
(V) detailed description example 1 preparation of boron nitride nanopowder
The raw material for hydrothermally synthesizing boron nitride is H3BO3White phosphorus, NaN3Their stepwise reaction in water occurs as follows: (a) (b) (c)
taken together (d)
(in the reaction scheme, the symbol with "+" indicates a highly reactive atom)
The specific method comprises the following steps: 100ml of water are initially introduced into a 250ml triangular flask, followed by 3.1g of boric acid (H)3BO3) Dissolving the mixture into water, stirring while dissolving, and stirring for 10-30 minutes to obtain a solution with the concentration of 0.5 mol/L. While stirring was continued, 9.8g of sodium bunanide was added to the boric acid solution obtained above, and after stirring was continued for 20 minutes, 1.6g of phosphorus was added. Stirring for 1.5 hr, transferring the mixed solution to reactor, adding water to fill 70%, sealing, removing residual air with high-purity nitrogen gas, heating to 300 deg.C, and maintaining for 2 hr. After the reaction is finished, the product is washed by deionized water and filtered for many times until the filtrate is neutral. The powder thus obtained is dried by heating in vacuum at 60 ℃ to obtain boron nitride with a particle size of nanometerAnd (3) ultra-fine powder.
FIG. 1 shows an X-ray diffraction pattern of the boron nitride nanopowder of this example, wherein the peaks marked with dots belong to hexagonal boron nitride and the remaining peaks correspond to orthorhombic boron nitride. It can be seen that the sample contains both hexagonal and orthorhombic phases, and the broadening of the diffraction peaks indicates that the resulting sample has a very small particle size. FIG. 2 is an infrared spectrum of the boron nitride nanopowder obtained in this example, wherein the spectrum is 1080cm-1Corresponding to orthorhombic boron nitride and located at 1630cm-1And 988cm-1The infrared absorption peak of (a) is hexagonal boron nitride. EXAMPLE 2 preparation of boron nitride nanopowder
120ml of water are initially introduced into a 250ml triangular flask, followed by 3.7g of boric acid (H)3BO3) Dissolving the mixture into water, stirring while dissolving, and continuously stirringfor 10-30 minutes to obtain a solution with the concentration of 0.5 mol/L. 2.7g of ammonium chloride (NH) are added with continuous stirring4Cl) was added to the boric acid solution obtained previously. Then stirring for 30 minutes, adding 1.6g of phosphorus, continuing stirring for 2 hours, transferring the uniformly stirred mixed solution into a reaction kettle, adding water to enable the filling rate to reach 75%, sealing the kettle, and heating the reaction kettle to 400 ℃ and preserving the heat for 10 hours. After the reaction is finished, the product is filtered by suction, washed by deionized water and filtered for many times until the filtrate is neutral. The obtained powder is heated in vacuum at 60 ℃ and dried to obtain the boron nitride micro powder with the nano-scale particle size. EXAMPLE 3 preparation of boron nitride nanopowder III
100ml of water was put into a 250ml triangular flask, and 9.8g of sodium nitride was dissolved in the water with stirring, and 3.5g of boron trioxide was added to the solution obtained above with continuous stirring. Adding 1.6g of phosphorus, continuing stirring for 2 hours, transferring the uniformly stirred mixed solution into a reaction kettle, adding water to ensure that the filling rate reaches 60 percent, sealing the kettle, and heating the reaction kettle to 350 ℃ for 10 hours. After the reaction is completed, the product is filtered by suction with deionized water for many times until the filtrate is neutral. The powder thus obtained is dried by heating in vacuum to obtain boron nitride nanopowder. Example 4 preparation of boron nitride nanopowder
150ml of water was put into a 250ml triangular flask, and then 27g of ammonium hydrogen phosphate was dissolved in the water with stirring, and 3.5g of boron trioxide was added to the solution obtained above with continuous stirring. And then stirring for 10-30 minutes, adding 5g of metal zinc powder, continuously stirring for 0.5-2 hours, transferring the uniformly stirred mixed solution into a reaction kettle, adding water to enable the filling rate to reach 75%, sealing the kettle, heating the reaction kettle to 450 ℃, and keeping the temperature for 16 hours. The product was suction filtered with deionized water until the filtrate was neutral. The obtained powder is heated in vacuum at 50-60 ℃ and dried to obtain boron nitride nano micro powder with the granularity of dozens of nanometers. EXAMPLE 5 preparation of boron nitride nanopowder
120ml of water are initially introduced into a 250ml triangular flask, followed by 9.8g of sodium nitride (NaN)3) Dissolving in water under stirring, and adding 6g sodium borate (Na) under stirring3BO3) Added to the solution obtained previously. Stirring for 25 min, adding 0.8g of active carbon fine powder, stirring for 1.5 hr, transferring the mixed solution to reactor, adding water to fill 70%, sealing, heating to 500 deg.C, and maintaining for 20 hr. Thus, a fine boron nitride powder having a uniform particle size can be obtained. EXAMPLE 6 preparation of boron nitride crystalline Material
As described in example 1, except that: boric acid (H)3BO3) After the sodium nitride and the phosphorus are stirred uniformly, 0.6 g of boron nitride microcrystal is added into the reaction system as seed crystal. After the air remained in the reactor is removed by high-purity nitrogen, the reactor is heated to 300 ℃ and is kept warm for 20 hours, and then the temperature is slowly reduced by controlling the temperature reduction speed by a program temperature controller. After the reaction is finished, the product is washed by deionized water and filtered for many times until the filtrate is neutral. This can give boron nitride single crystals having a particle size of from micrometer to millimeter.
Fixing the boron nitride seed crystal in a lower temperature area, and growing larger crystal by controlling the gradient of the furnace temperature and enabling the reaction system to form convection. Example 7 preparation of gallium nitride nanopowder
The main raw material for hydrothermally synthesizing gallium nitride is H3GaO3(Ga(OH)3) White phosphorus, NaN3Their stepwise reaction in water occurs as follows: (a) (b)
taken together (c) (d)
(in the reaction scheme, the symbol with "+" indicates a highly reactive atom)
The specific operation steps are as follows: firstly weighing 5.0g of gallium oxide, adding into a triangular flask, adding 20ml of hydrochloric acid with the concentration of 1.18mol/L into the flask, heating and stirring to dissolve the gallium oxide, cooling to room temperature, continuing stirring, adding a sodium hydroxide solution into the flask to make the solution alkalescent, obtaining white gallium hydroxide precipitate, filtering the product, and washing with deionized water for multiple times; 100ml of water was put into a triangular flask having a capacity of 250ml, the obtained gallium hydroxide was added to the water, and after stirring for 25 minutes, 7.0g of sodium nitride was added to the triangular flask. And then stirring for 30 minutes, adding 1.6g of phosphorus, continuously stirring for 0.5-2 hours, transferring the uniformly stirred mixed solution into a reaction kettle, addingwater to ensure that the filling rate reaches 70%, removing air in the kettle by using high-purity nitrogen, sealing the kettle, heating the reaction kettle to 300 ℃, and keeping the temperature for 24 hours. After the reaction is finished, the product is filtered by suction, washed by deionized water and filtered for many times until the filtrate is neutral. The powder thus obtained is heated in vacuum at 60 ℃ and dried to obtain gallium nitride nanopowder with uniform particle size.
Fig. 3 is an X-ray diffraction spectrum of the gallium nitride fine powder prepared in this example, and fig. 4 is an infrared spectrum of the gallium nitride fine powder, and an absorption peak on the spectrum can be attributed to gallium nitride crystal grains. EXAMPLE 8 preparation of gallium nitride nanopowder
Firstly, 300ml of water, 4.0g of gallium oxide, 6.3g of sodium nitride and 3.0g of phosphorus are added into a reaction kettle with the capacity of 500ml, and the kettle is sealed. The reaction kettle is heated to 300 ℃ and is kept warm for 24 hours, and the pressure in the reaction kettle is 4 MPa. After the reaction is finished, the product is filtered by suction, washed by hot sodium hydroxide solution for 15 minutes, filtered again, washed by deionized water and filtered for many times until the filtrate is neutral. The powder thus obtained is heated in vacuum at 60 ℃ and dried to obtain gallium nitride nanopowder with uniform particles. EXAMPLE 9 preparation of gallium nitride nanopowder
Firstly weighing 4.5g of gallium oxide, adding into a triangular flask, adding 20ml of 1.18mol/l hydrochloric acid into the flask, heating and stirring to dissolve the gallium oxide, cooling to room temperature, continuously stirring, adding a sodium hydroxide solution into the flask to make the solution alkalescent, obtaining white gallium hydroxide precipitate, filtering the product, and washing with deionized water for multiple times; 100ml of water was put into a 250ml triangular flask, the obtained gallium hydroxide was added to the water, and after stirring for 25 minutes, 5.2g of ammonium chloride was added to the triangular flask. Then stirring for 20 minutes, then adding 1.5g of phosphorus, continuing stirring for 2 hours, transferring the uniformly stirred mixed solution into a reaction kettle, adding water to ensure that the filling rate reaches 70%, sealing the kettle, and heating the reaction kettle to 300 ℃ and preserving heat for 24 hours. After the reaction is finished, the product is filtered by suction, washed by hot sodium hydroxide solution, washed by deionized water and filtered by suction for multiple times until the filtrate is neutral. The powder thus obtained is heated in vacuum at 60 ℃ and dried to obtain gallium nitride nanopowder with uniform particle size. EXAMPLE 10 preparation of gallium nitride nanopowder
120ml of water are initially introduced into a 250ml triangular flask, followed by 9.8g of sodium nitride (NaN)3) Dissolving in water under stirring, and adding 6g sodium gallate (Na) under stirring3GaO3) Added to the solution obtained previously. Then stirring for 10-30 minutes, adding 0.8g of active carbon fine powder, continuously stirring for 0.5-2 hours, transferring the uniformly stirred mixed solution into a reaction kettle, and then stirringAdding water to make the filling rate reach 70%, sealing the kettle, heating the kettle to 550 ℃, and preserving the heat for 20 hours. After the reaction is finished, the product is filtered by suction, washed by deionized water and filtered for many times until the filtrate is neutral. The powder thus obtained is dried by heating at 70 ℃ in vacuum to obtain gallium nitride micropowder with uniform particle size. EXAMPLE 11 preparation of gallium nitride nanopowder
150ml of water are initially introduced into a 250mltriangular flask, 8.9g of trimethylamine are subsequently dissolved in the water with stirring, and 3.5g of gallium trioxide are added to the solution obtained above with continuous stirring. And then stirring for 10-30 minutes, adding 5g of metal zinc powder, continuously stirring for 0.5-2 hours, transferring the uniformly stirred mixed solution into a reaction kettle, adding water to enable the filling rate to reach 75%, sealing the kettle, heating the reaction kettle to 470 ℃, and keeping the temperature for 15 hours. After the reaction is finished, the product is washed by deionized water and filtered for many times, and then is heated and dried in vacuum to obtain the nano gallium nitride micro powder with the nano-scale particle size. EXAMPLE 12 preparation of gallium nitride crystalline Material
All the procedures were substantially the same as in example 7, except that: gallium acid (H)3GaO3) After the sodium nitride and the white phosphorus are stirred uniformly, 0.5 g of gallium nitride microcrystal is added into the reaction system as seed crystal. After removing residual air in the kettle by using high-purity nitrogen, heating the reaction kettle to 260-300 ℃, preserving the temperature for 20 hours, and then controlling the cooling speed by using a program temperature controller to slowly cool. After the reaction is completed, the product is filtered by suction with deionized water until the filtrate is neutral. This can obtain gallium nitride single crystals with a grain size of from micrometer to millimeter.
The gallium nitride seed crystal is suspended in a lower temperature area, the temperature gradient in the reaction kettle is controlled, and the reaction system forms convection, so that larger gallium nitride crystal can be grown. EXAMPLE 13 preparation of aluminum nitride nanopowder
100ml of water were placed in a 250ml triangular flask, followed by 6.7g of aluminium trichloride (AlCl)3) Slowly adding into water, dissolving and stirring, continuously stirring for 10-30 min to obtain aluminum hydroxide precipitate, filteringWashed with distilled water and then added to the reaction kettle. Under the condition of continuous stirring, 3.3g of sodium nitride is added into a triangular flask, distilled water is added for stirring and dissolving, then stirring is carried out for 10-30 minutes, 1.6g of phosphorus is added, stirring is continued for 1.5 hours, the uniformly stirred mixed solution is transferred into a reaction kettle, water is added, the filling rate reaches 70%, the reaction kettle is sealed, and the reaction kettle is heated to 350 ℃ and is kept warm for 12 hours. After the reaction is finished, carrying out suction filtration, washing a product by using a hot sodium hydroxide solution, washing by using deionized water, and carrying out suction filtration for multiple times until the filtrate is neutral. The powder thus obtained is dried by heating in vacuum at 60 ℃ to obtain aluminum nitride nanopowder with uniform particle size. EXAMPLE 14 preparation of aluminum nitride nanopowder
The preparation method is basically the same as that of example 15, and the operation procedure is as follows: 120ml of water are introduced into a 250ml triangular flask, followed by 5g of sodium metaaluminate (NaAlO)2) Slowly adding the sodium metaaluminate solution into water, dissolving and stirring the sodium metaaluminate solution, continuously stirring the solution for 10 to 30 minutes to obtain a sodium metaaluminate solution, and then adding the sodium metaaluminate solution into a reaction kettle; adding 3.3g of sodium nitride into a triangular flask, adding distilled water, stirring for dissolving, stirring for 25 minutes, adding 5g of metal zinc powder, stirring for 1 hour, transferring the uniformly stirred mixed solution into a reaction kettle, adding water to ensure that the filling ratereaches 75 percent, sealing the kettle, heating the reaction kettle to 400 ℃, and keeping the temperature for 20 hours. After the reaction is finished, the product is washed by hot sodium hydroxide solution, and then is filtered by deionized water for multiple times until the filtrate is neutral. The obtained powder is heated in vacuum at 75 ℃ and dried to obtain the aluminum nitride micro powder with uniform particle size. EXAMPLE 15 preparation of aluminum nitride crystalline Material
The procedure was essentially the same as in example 13, except that: aluminium hydroxide (Al (OH)3Or H3AlO3After the sodium nitride and the white phosphorus are stirred uniformly, 0.5 g of aluminum nitride microcrystal is added into the reaction system as seed crystal. After the air remained in the reactor is removed by high-purity nitrogen, the reactor is heated to 300-350 ℃ and is kept warm for 20 hours, and then the temperature is slowly reduced (for example, 0.2 ℃/min) by controlling the temperature reduction speed by a program temperature controller. After the reaction is finished, the product is filtered and filtered for many times by deionized water until the filtrate is neutral. This can give aluminum nitride single crystals having a particle size of the order of micrometers to millimeters.
The aluminum nitride seed crystal is suspended in a lower temperature area, the temperature gradient in the reaction kettle is controlled, and the reaction system forms convection, so that larger aluminum nitride crystals can be grown. EXAMPLE 16 preparation of indium nitride nanopowder
100ml of water are initially introduced into a 250ml triangular flask, and 11.1g of indium trichloride (InCl)3) Slowly adding the mixture into water, dissolving while stirring, adding 3.3g of sodium nitride into a triangular flask to dissolve the sodium nitride, stirring for 30 minutes, adding 1.6g ofphosphorus, continuously stirring for 2 hours, transferring the uniformly stirred mixed solution into a reaction kettle, adding water to enable the filling rate to reach 65%, sealing the kettle, and heating the reaction kettle to 300 ℃ and preserving the heat for 8 hours. After the reaction is finished, washing the product with acid liquor, and performing suction filtration with deionized water for multiple times until the filtrate is neutral. The powder thus obtained is dried by heating at 60 ℃ in vacuum to obtain indium nitride nanopowder having a uniform particle size.
Claims (6)
1. The method for preparing the nitride ultra-fine powder under the hydrothermal condition is characterized by comprising the following steps:
(1) dissolving a boron source, a gallium source, an aluminum source or an indium source in water, rapidly stirring while dissolving, and continuously stirring for a period of time to obtain a solution or suspension with the concentration of 0.01-20 mol/L;
(2) under the condition of continuous stirring, adding the grinded nitrogen source powder or soluble nitrogen source solution with stoichiometric ratio into the obtained boron source solution or suspension;
(3) continuously stirring, and adding one or more of phosphorus, zinc, iron, aluminum or carbon, silicon, sulfur and the like or low-valence compounds composed of the phosphorus, the zinc, the iron, the aluminum or the carbon, the silicon, the sulfur and the like in a stoichiometric ratio as a reducing agent;
(4) continuously stirring for a period of time, putting into a closed reaction container, heating to 100-800 ℃ at a filling rate of 20-95%, and reacting for 2-120 hours under the condition of continuous oscillation or stirring at a pressure of 1-1500 atm;
(5) after the reaction is finished, washing and filtering the product for many times by deionized water, or performing suction filtration after the product is treated by alkaline or acidic solution until the filtrate is neutral;
(6) heating the obtained powder in vacuum at 40-100 ℃, and drying to obtain the boron nitride, gallium nitride, indium nitride or aluminum nitride superfine powder with the granularity of 5-500 nanometers and uniform particles.
2. The method for preparing nitride ultra fine powder under hydrothermal conditions as set forth in claim 1, wherein the water used as the reaction medium is distilled water or high purity water.
3. The method for preparing nitride ultra fine powder under hydrothermal conditions according to claim 1, wherein the boron source, the gallium source, the indium source and the aluminum source are selected from the range comprising halide, hydroxide, oxide, boride, oxyacid and oxyacid salt.
4. The method for preparing nitride ultra fine powder under hydrothermal condition according to claim 1, wherein the nitrogen source is selected from metal nitride, azide, ammonia salt and organic amine, and is water soluble or solid powder.
5. The method for preparing nitride ultra fine powder under hydrothermal condition according to claim 1, wherein the reducing agent is selected from phosphorus, zinc, iron, aluminum or carbon, silicon, sulfur and other simple substance and low valence state simple compound composed of them.
6. A method for preparing nitride crystal under hydrothermal condition, comprising all the stepsof preparing nitride ultra-fine powder as claimed in claim 1-5, characterized in that corresponding nitride particles are added to the reaction raw materials as seed crystal, and the nitride crystal is obtained under the condition of prolonging reaction time and controlling temperature and concentration distribution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021100667A CN1173879C (en) | 2002-02-07 | 2002-02-07 | Process for preparing nitride ultromicro powder and nitride crystal wunder hydrothermal condition |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329290C (en) * | 2004-09-01 | 2007-08-01 | 山东大学 | Phase selection in-situ synthesis method used for controlling boron nitride object phase |
| CN100390048C (en) * | 2003-08-07 | 2008-05-28 | 中国科学技术大学 | Water heat synthesis preparation method of wurtzite phase nano-nitride and its solid solution |
| CN102398897A (en) * | 2011-11-07 | 2012-04-04 | 北京航空航天大学 | Method for preparing two-dimensional nano boron nitride with jet flow cavitation technology |
| CN103320899A (en) * | 2013-07-01 | 2013-09-25 | 中国计量学院 | Preparation method of nanometer aluminum nitride fiber |
| CN103539088A (en) * | 2013-11-05 | 2014-01-29 | 河北工业大学 | Synthetic method of aluminium nitride nanoparticles |
| CN105347317A (en) * | 2015-12-11 | 2016-02-24 | 江苏理工学院 | New method for preparing indium nitride nano material |
| CN107326655A (en) * | 2017-07-11 | 2017-11-07 | 湖南金戈新材料有限责任公司 | A kind of method of carbon fiber surface modification |
| CN108439992A (en) * | 2018-03-13 | 2018-08-24 | 绍兴文理学院 | A kind of preparation method of dense form aluminium nitride ceramics |
| CN110125140A (en) * | 2019-04-30 | 2019-08-16 | 安徽浩悦环境科技有限责任公司 | A kind of method of heavy metal waste removing toxic substances stabilization processes |
| CN113753867A (en) * | 2021-08-31 | 2021-12-07 | 湖南邦普循环科技有限公司 | Preparation method of aluminum nitride |
| CN114667267A (en) * | 2019-12-06 | 2022-06-24 | 电化株式会社 | Boron nitride particles and method for producing same |
| CN114728789A (en) * | 2019-12-06 | 2022-07-08 | 电化株式会社 | Boron nitride particles and method for producing same |
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2002
- 2002-02-07 CN CNB021100667A patent/CN1173879C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390048C (en) * | 2003-08-07 | 2008-05-28 | 中国科学技术大学 | Water heat synthesis preparation method of wurtzite phase nano-nitride and its solid solution |
| CN1329290C (en) * | 2004-09-01 | 2007-08-01 | 山东大学 | Phase selection in-situ synthesis method used for controlling boron nitride object phase |
| CN102398897A (en) * | 2011-11-07 | 2012-04-04 | 北京航空航天大学 | Method for preparing two-dimensional nano boron nitride with jet flow cavitation technology |
| CN102398897B (en) * | 2011-11-07 | 2013-04-24 | 北京航空航天大学 | Method for preparing two-dimensional nano boron nitride with jet flow cavitation technology |
| CN103320899A (en) * | 2013-07-01 | 2013-09-25 | 中国计量学院 | Preparation method of nanometer aluminum nitride fiber |
| CN103539088A (en) * | 2013-11-05 | 2014-01-29 | 河北工业大学 | Synthetic method of aluminium nitride nanoparticles |
| CN105347317A (en) * | 2015-12-11 | 2016-02-24 | 江苏理工学院 | New method for preparing indium nitride nano material |
| CN107326655A (en) * | 2017-07-11 | 2017-11-07 | 湖南金戈新材料有限责任公司 | A kind of method of carbon fiber surface modification |
| CN108439992A (en) * | 2018-03-13 | 2018-08-24 | 绍兴文理学院 | A kind of preparation method of dense form aluminium nitride ceramics |
| CN110125140A (en) * | 2019-04-30 | 2019-08-16 | 安徽浩悦环境科技有限责任公司 | A kind of method of heavy metal waste removing toxic substances stabilization processes |
| CN114667267A (en) * | 2019-12-06 | 2022-06-24 | 电化株式会社 | Boron nitride particles and method for producing same |
| CN114728789A (en) * | 2019-12-06 | 2022-07-08 | 电化株式会社 | Boron nitride particles and method for producing same |
| CN114728789B (en) * | 2019-12-06 | 2024-04-30 | 电化株式会社 | Boron nitride particles and method for producing same |
| CN113753867A (en) * | 2021-08-31 | 2021-12-07 | 湖南邦普循环科技有限公司 | Preparation method of aluminum nitride |
| CN113753867B (en) * | 2021-08-31 | 2023-09-12 | 湖南邦普循环科技有限公司 | Preparation method of aluminum nitride |
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