CN100410179C - Method for preparing gallium nitride nano crystal using sol-gel method - Google Patents
Method for preparing gallium nitride nano crystal using sol-gel method Download PDFInfo
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- CN100410179C CN100410179C CNB2006100162711A CN200610016271A CN100410179C CN 100410179 C CN100410179 C CN 100410179C CN B2006100162711 A CNB2006100162711 A CN B2006100162711A CN 200610016271 A CN200610016271 A CN 200610016271A CN 100410179 C CN100410179 C CN 100410179C
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Abstract
The sol-gel process of preparing nanometer gallium nitride crystal includes the first sol-gel process to prepare gallium oxide-amorphous carbon mixture through dissolving gallium nitrate in concentrated nitric acid, dropping concentrated ammonia water to regulate pH value, heating the solution, adding citric acid, stirring for 2 hr to obtain transparent gel, and drying the gel at high temperature in a muffle; and the subsequent preparation of nanometer gallium nitride crystal inside one tubular vacuum furnace through setting the gallium oxide-amorphous carbon mixture into a ceramic tube, exhausting air and filling with nitrogen, maintaining at 850-950 deg.C for 1 hr, and introducing argon to cool. The prepared nanometer gallium nitride crystal has hexagonal structure, average particle size of 10-11 nm and homogeneous particle size, and may be used in preparing high quality one-dimensional gallium nitride material or as composite gallium nitride quantum dot material directly.
Description
(1) technical field
The present invention relates to a kind of preparation method of gallium nitride nano crystal, particularly a kind of method that adopts the Prepared by Sol Gel Method gallium nitride nano crystal.
(2) background technology
Gallium nitride as the direct wide bandgap compound semiconductor material of room temperature (energy gap is 3.4eV), with its good character such as low compressibility and high heat conductance, has widely it and uses on high temperature, high energy device, short wavelength's optics device.Since being found from the thirties in last century, be the focus of physics circle and chemical boundary broad research always.The main application of gallium nitride is at present: 1, directly as the gan quantum dot composite material; 2, adopt the gasification coagulation to prepare the raw material of bulk gan; 3, preparation high quality one dimension gan.For being directly used in as the gan quantum dot composite material, common preparation method seldom can satisfy the requirement that is directly used in the quantum dot application, for example require median size less than or little near Bohr's exciton radius (about 11nm), particle size distribution range, do not have hard aggregation to generate or the like, this and the character of gan own have very big relation.Because the uniform nano material of preparation particle diameter adopts quick nucleation, quick terminated method usually, but for gan, higher synthesis temperature, synthesis temperature and decomposition temperature comparatively near and stronger ionic linkage feature, make the preparation of desired similar II-VI family quantum dot impossible fully.Have only unit molecule nitrine gallium explosion method and organic gallium nitrogen compound thermal decomposition method at present, can produce the product that meets the quantum dot requirement, but also have a lot of problems, as output capacity is very low, the preparation method is complicated, intermediate product poor stability etc.For being used to prepare high quality one dimension gan, old little imperial group of the Chinese Academy of Sciences adopts the gallium nitride powder behind the ball milling successfully to prepare high-quality gan nanometer rod and ring rod, and contrast does not have the gallium nitride powder of ball milling as precursor, but there is not corresponding product to generate, this is owing to gan particle size behind the ball milling diminishes, surface area increases, can obtain high source vapour pressure when making gasification, this also shows the importance of small particle size gan in preparation process.
(3) summary of the invention
The objective of the invention is at the problem in the existing technology of preparing, provide a kind of simple, safe and reliable, can prepare in a large number that particle diameter is less than or equal to Bohr's exciton radius and the method for the gallium nitride nano crystal that is evenly distributed.
Technical scheme of the present invention:
A kind of method with the Prepared by Sol Gel Method gallium nitride nano crystal is characterized in that the preparation method carries out in two steps:
The first step is for adopting Prepared by Sol Gel Method gallium oxide/agraphitic carbon mixture, and operation steps is: 1) the gallium nitrate solid is dissolved into weight percent concentration and is in 62% the concentrated nitric acid, the ammoniacal liquor that drips saturation concentration is in solution, and making its pH value is 7.5-8.2; When 2) solution being heated to 80 ℃, slowly add the citric acid solid powder in solution, present transparent thickly up to solution, continue to stir again 2 hours, stop heating then, become clear gel behind the naturally cooling; 3) clear gel is placed retort furnace, descended dry 15-45 minute for 400 ℃, obtain canescence multilayer sprills and be gallium oxide/agraphitic carbon mixture in temperature;
Second step: utilize the high-temperature tubular vacuum oven to prepare gallium nitride nano crystal, operation steps is: in the aluminum oxide porcelain boat of the cleaning of 1) gallium oxide/agraphitic carbon mix powder being packed into, powder is evenly spread out in porcelain boat bottom, then porcelain boat is pushed in the horizontal vitrified pipe of vacuum oven and be positioned at the high-temperature zone, middle part; 2) be connected with tubular type vacuum oven ferrule and with vacuum unit, the air in the vent pipe charges into ammonia then, and makes ammonia flow continually and steadily at 80ml/min; 3) setting tubular type vacuum oven temperature is 850～950 ℃, and vitrified pipe is warming up to design temperature, and temperature rise rate is 8 ℃/min, and insulation is 1 hour after temperature reaches set(ting)value, closes ammonia air-flow and furnace power then; 4) in the tubular type vacuum oven, feed argon gas and make argon flow amount continually and steadily at 100ml/min, treat that vitrified pipe naturally cools to room temperature after, take out aluminium oxide boat, the product that makes is the gallium nitride nano crystal of yellow powder powder.
Advantage of the present invention is: the gallium nitride nano crystal that utilizes this method to make is six side's phase structures, and median size is 10-11 nanometer and particle diameter stable and uniform, can be used for preparing high quality one dimension gan or directly is used as the gan quantum dot composite material; Preparation method's principle provided by the invention is simple, operation is easily gone, output capacity is high, is suitable for producing in batches.
(4) embodiment
Embodiment 1: a kind of method with the Prepared by Sol Gel Method gallium nitride nano crystal, two steps carried out: the first step is for adopting Prepared by Sol Gel Method gallium oxide/agraphitic carbon mixture, operation steps is: 1) 6g gallium nitrate solid is dissolved into weight percent concentration and is in 62% the 10ml concentrated nitric acid, the ammoniacal liquor that drips saturation concentration makes its pH value be 7.5-8.2 in solution; When 2) solution being heated to 80 ℃, slowly add the citric acid solid powder in solution, present transparent thick (addition of citric acid solid powder is about 30g), continue again to stir 2 hours up to solution, stop heating then, become clear gel behind the naturally cooling; 3) clear gel is placed retort furnace, descended dry 40 minutes, obtain canescence multilayer sprills and be gallium oxide/agraphitic carbon mixture 400 ℃ of temperature; Second step: utilize the high-temperature tubular vacuum oven to prepare gallium nitride nano crystal, operation steps is: in the aluminum oxide porcelain boat of the cleaning of 1) 1g gallium oxide/agraphitic carbon mix powder being packed into, powder is evenly spread out in porcelain boat bottom, then porcelain boat is pushed in the horizontal vitrified pipe of vacuum oven and be positioned at the high-temperature zone, middle part; 2) be connected with tubular type vacuum oven ferrule and with vacuum unit, the air in the vent pipe charges into ammonia then, and makes ammonia flow continually and steadily at 80ml/min; 3) setting tubular type vacuum oven temperature is 850 ℃, and vitrified pipe is warming up to design temperature, and temperature rise rate is 8 ℃/min, and insulation is 1 hour after temperature reaches set(ting)value, closes ammonia air-flow and furnace power then; 4) in the tubular type vacuum oven, feed argon gas and make argon flow amount continually and steadily at 100ml/min, treat that vitrified pipe naturally cools to room temperature after, take out aluminium oxide boat, the product that makes is the gallium nitride nano crystal of yellow powder powder.
Embodiment 2: a kind of method with the Prepared by Sol Gel Method gallium nitride nano crystal, and preparation process and embodiment 1 are identical, but the design temperature of tubular type vacuum oven is 900 ℃, the product that makes also is the gallium nitride nano crystal of yellow powder powder.
Embodiment 3: a kind of method with the Prepared by Sol Gel Method gallium nitride nano crystal, and preparation process and embodiment 1 are identical, but the design temperature of tubular type vacuum oven is 950 ℃, the product that makes also is the gallium nitride nano crystal of yellow powder powder.
Now utilize X-ray powder diffraction analyser (XRD), scanning electronic microscope (SEM), transmission electron microscope (TEM), energy dispersive X-ray energy spectrometer (EDS) and UV, visible light optical absorption spectra meter (UV-vis U4100 type) and fourier infrared absorption spectrum (FTIR), above-mentioned three prepared gallium nitride nano crystals of embodiment are carried out check and analysis.
Utilize X-ray powder diffraction analyser test shows: above-mentioned three prepared gallium nitride nano crystals of embodiment are in the scanning angle scope, all diffraction peaks that can detect can indexing to wurtzite-type six side's phase GaN, through calculating its unit cell parameters a=3.191, c=5.198, (card number: six sides that JCPDS 76-0703) the list diffraction data of GaN mutually match with standard powdery diffractometry card JCPDS for this; In the detection limit of instrument, do not have to find to have the diffraction peak of other crystalline state materials, show that product is the GaN of pure six side's phase crystalline structure; Wide peak width at half height The data Scherrer formula calculates, and the size of crystal grain is the 10-11 nanometer; Transmission and stereoscan photograph show that the product particle diameter is even relatively, and electron beam color (ED) photo shows that it has six side's phase structures and degree of crystallinity preferably; The detected result of energy dispersive X-ray energy spectrometer (EDS) shows that gallium nitrogen ratio was near 1: 1; Fourier infrared absorption spectrum (FTIR) is observed the absorption peak that only belongs to the Ga-N key, does not have the absorption peak of Ga-0 key, shows that the Ga in the product is mainly existed by the form of Ga-N key; Absorption spectrum that UV, visible light optical absorption spectra meter (UV-vis U4100 type) records and block gan intrinsic absorb (365nm, 3.4eV) the spectrum contrast, all showed tangible blue shift peak, illustrated that the gallium nitride nano crystal of present method preparation shows certain quantum size effect.
Claims (1)
1. method with the Prepared by Sol Gel Method gallium nitride nano crystal is characterized in that preparation process is as follows:
(1) adopt Prepared by Sol Gel Method gallium oxide and agraphitic carbon mixture, operation steps is: 1) the gallium nitrate solid is dissolved into weight percent concentration and is in 62% the concentrated nitric acid, the ammoniacal liquor that drips saturation concentration is in solution, and making its pH value is 7.5-8.2; When 2) solution being heated to 80 ℃, slowly add the citric acid solid powder in solution, present transparent thickly up to solution, continue to stir again 2 hours, stop heating then, become clear gel behind the naturally cooling; 3) clear gel is placed retort furnace, descended dry 15-45 minute for 400 ℃, obtain canescence multilayer sprills and be gallium oxide and agraphitic carbon mixture in temperature;
(2) utilize the high-temperature tubular vacuum oven to prepare gallium nitride nano crystal, operation steps is: in the aluminum oxide porcelain boat of the cleaning of 1) gallium oxide and agraphitic carbon mix powder being packed into, powder is evenly spread out in porcelain boat bottom, then porcelain boat is pushed in the horizontal vitrified pipe of vacuum oven and be positioned at the high-temperature zone, middle part; 2) be connected with tubular type vacuum oven ferrule and with vacuum unit, the air in the vent pipe charges into ammonia then, and makes ammonia flow continually and steadily at 80ml/min; 3) setting tubular type vacuum oven temperature is 850～950 ℃, and vitrified pipe is warming up to design temperature, and temperature rise rate is 8 ℃/min, and insulation is 1 hour after temperature reaches set(ting)value, closes ammonia air-flow and furnace power then; 4) in the tubular type vacuum oven, feed argon gas and make argon flow amount continually and steadily at 100ml/min, treat that vitrified pipe naturally cools to room temperature after, take out aluminium oxide boat, the product that makes is the gallium nitride nano crystal of yellow powder powder.
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| CN100410179C true CN100410179C (en) | 2008-08-13 |
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| CN105543968B (en) * | 2015-12-21 | 2018-06-05 | 江苏锡沂高新区科技发展有限公司 | A kind of method that low cost prepares gallium nitride |
| CN105502313B (en) * | 2015-12-24 | 2018-06-05 | 上海欣鑫化工有限公司 | A kind of method that gallium nitride nano crystal is prepared using double screw extruder |
| CN105483828B (en) * | 2015-12-24 | 2018-06-26 | 成都新柯力化工科技有限公司 | A kind of preparation method for improving gallium nitride quality |
| CN107364838B (en) * | 2017-06-19 | 2019-12-03 | 南开大学 | The preparation method of the gallium nitride nano material of iron series element doping |
Citations (5)
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|---|---|---|---|---|
| US4144116A (en) * | 1975-03-19 | 1979-03-13 | U.S. Philips Corporation | Vapor deposition of single crystal gallium nitride |
| CN1398790A (en) * | 2002-08-20 | 2003-02-26 | 浙江大学 | Rod-like polycrystal GaN and its two-step prepn process |
| CN1490243A (en) * | 2002-10-17 | 2004-04-21 | 中国科学技术大学 | Hot synthetic preparation of metastable rock salt phase nano gallium nitride in solvent |
| JP2005154193A (en) * | 2003-11-25 | 2005-06-16 | Kitagawa Ind Co Ltd | Method of manufacturing group iii nitride |
| CN1789114A (en) * | 2005-12-15 | 2006-06-21 | 太原理工大学 | High purity gallium nitride nanometer line preparation method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144116A (en) * | 1975-03-19 | 1979-03-13 | U.S. Philips Corporation | Vapor deposition of single crystal gallium nitride |
| CN1398790A (en) * | 2002-08-20 | 2003-02-26 | 浙江大学 | Rod-like polycrystal GaN and its two-step prepn process |
| CN1490243A (en) * | 2002-10-17 | 2004-04-21 | 中国科学技术大学 | Hot synthetic preparation of metastable rock salt phase nano gallium nitride in solvent |
| JP2005154193A (en) * | 2003-11-25 | 2005-06-16 | Kitagawa Ind Co Ltd | Method of manufacturing group iii nitride |
| CN1789114A (en) * | 2005-12-15 | 2006-06-21 | 太原理工大学 | High purity gallium nitride nanometer line preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 立方相β-GaN纳米晶的气相化学反应制备研究. 方鲲，高善民，邱海林，曹传宝，朱鹤孙.物理学报，第54卷第5期. 2005 |
| 立方相β-GaN纳米晶的气相化学反应制备研究. 方鲲，高善民，邱海林，曹传宝，朱鹤孙.物理学报，第54卷第5期. 2005 * |
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Assignee: Tianjin Ranyue Environmental Protection Innovative Technology Co., Ltd. Assignor: China National Academy Nanotechnology & Engineering Contract record no.: 2010120000122 Denomination of invention: Method for preparing gallium nitride nano crystal using sol-gel method Granted publication date: 20080813 License type: Exclusive License Open date: 20070411 Record date: 20100910 |
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