CN101381892B - Method for preparing gallium nitride crystal by solid-state displacement reaction - Google Patents
Method for preparing gallium nitride crystal by solid-state displacement reaction Download PDFInfo
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- CN101381892B CN101381892B CN2008100462791A CN200810046279A CN101381892B CN 101381892 B CN101381892 B CN 101381892B CN 2008100462791 A CN2008100462791 A CN 2008100462791A CN 200810046279 A CN200810046279 A CN 200810046279A CN 101381892 B CN101381892 B CN 101381892B
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Abstract
The invention discloses a method for preparing a gallium nitride crystal by utilizing the solid-state displacement reaction. The method mainly comprises the following steps: (1) reaction precursors of gallic acid lithium and boron nitride are mixed and pre-pressed into a block, or pre-pressed into sheets respectively, and the sheets are alternately piled into a block; (2) a block reactant which are obtained by the pre-pressing after mixing or alternate piling is put in a high-pressure synthesis block; (3) the assembled high-pressure synthesis block is placed in a synthesis cavity of a large presser for the solid-state displacement reaction, the synthesis temperature is not less than 850 DEG C, the pressure is not less than 1.0GPa, and the synthesis time is not less than 1.0 minute; and (4) after the displacement reaction, the reactant is subjected to cooling and pressure relief, and the synthesis product is taken out and soaked in acid liquor to dissolve and remove LiBO2, and the gallium nitride crystal is obtained. The method has the advantages of low raw material cost, low requirement on production specification, convenient operation, high growth rate of crystal, short synthesistime, easy popularization, mass production and the like.
Description
Technical field
The present invention relates to a kind of gallium nitride preparation method, particularly relate to a kind of method of utilizing solid-state displacement reaction to prepare gallium nitride.
Technical background
Gan (GaN) is a kind of wide bandgap compound semiconductor material, and its room temperature forbidden band is wide to be 3.4ev, has good chemistry and thermostability, is considered to make the ideal material of indigo plant, green photodiode (LED) and laser diode (LD).Such light source has a wide range of applications in all many-sides such as optical information storage, light demonstration, optical illumination and is worth and huge economic interests.
Because GaN can decompose in the time of 900 ℃ under the normal pressure, therefore, traditional growing method (as: crystal pulling method) can't be applied to the preparation of gallium nitride.Prepare in the main method at the GaN of prior art, comparatively successful method has high-pressure solution growth method (Porowski, S.J.Cryst.Growth 1996,166, and 583.), flux method (Wang, B.et al.J.Cryst.Growth, 2006,287,376.) and the hot growth method (Hashimoto of ammonia, T.et al.Nat.Mater.2007,6,568.), these methods all require to finish under higher ammonia or nitrogen pressure, though can both prepare the high quality GaN material, because crystal growth rate is low, the cycle is long, production cost is higher, is difficult for popularizing the gan large-scale industrial production.The preparation method of gallium nitride is except these methods, and document has also been reported following certain methods:
Hydride vapour phase epitaxy method (Kelly, M.K.et al.Jpn J.Appl.Phys.1999,38, L217-L219.), this method is to flow through HCl on gallium, forms GaCl
3Steam, and on substrate with NH
3React formation of deposits GaN film.This method will rely on the substrate material of lattice match, and equipment cost height, method program are complicated, and technical difficulty is bigger, is unfavorable for producing in batches.
Pressurized melt growth method (Utsumi, W.et al.Nat.Mater.2003,2,735.), this method are that under extreme conditions (pressure is 6GPa, 2200 ℃ of temperature) melts the back recrystallize to original material GaN polycrystalline.Since the cost height, the energy consumption height, the growth conditions harshness, technical difficulty is big, and this method is not suitable for scale operation equally.
Traditional solid-state displacement reaction method (Gillan, G.E.; Kaner, B.R.Chem.Mater.1996,8,333.), this method is based on the violent thermopositive reaction of (as: elevated temperature) generation under certain condition of two kinds of solid precursors, and one of resultant of reaction is prepared material.Up to now, the reactant that being used to of being reported prepares gan is halogenide and the basic metal or the alkaline-earth metal (WO2008/054522A2) of gallium.This method is carried out under normal pressure, because reaction process is violent and uncontrollable, in the reaction times very short (usually less than 1 second), the resultant of reaction crystallization is generally all bad, and granular size is usually less than 1 μ m.Many restrictions make this method should not be applied to suitability for industrialized production.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of prior art, a kind of new method for preparing gallium nitride is provided, the existing crystal growth rate of gallium nitride preparation method with the solution prior art is low, growth conditions requires harsh, the production cost height, the energy consumption height is difficult for problems such as large-scale industrial production.
Above-mentioned technical problem to be solved by this invention can realize by the method for utilizing solid-state displacement reaction to prepare gallium nitride of taking following technical scheme.
The method of utilizing solid-state displacement reaction to prepare gallium nitride provided by the invention may further comprise the steps:
(1) reaction precursor body lithium gallium oxide and boron nitride are mixed back presuppression adult piece, are stacked alternately the adult piece after perhaps it being pre-pressed into the piece sheet respectively;
(2) the body piece that is prefabricated into or the body deblocking reaction thing that is stacked alternately being placed into height is pressed in the piece;
(3) height that will assemble is pressed into piece and places the press synthetic cavity to carry out solid-state replacement synthesis, and synthesis temperature is not less than 850 ℃, and pressure is not less than 1.0GPa, and synthesising reacting time is no less than 1.0 minutes;
(4) synthetic product was taken out in the cooling pressure release after replacement synthesis finished, and used the acid soak synthetic product, and LiBO is removed in dissolving
2, promptly obtain gallium nitride.
In technique scheme, solid-state replacement synthesis condition is preferentially taked, and temperature is controlled at 850-1800 ℃, and pressure-controlling is at 1.0-6.0GPa, and the time was controlled at 1-120 minute, preferably was controlled at 20-30 minute.
In technique scheme, described acid solution is can dissolve to remove LiBO
2Acid, generally select commercial acid for use, a kind of greater than in 10% hydrochloric acid, sulfuric acid and the nitric acid of optional mass concentration rule of thumb, preferably selects for use mass concentration to be not less than 20% hydrochloric acid.The concentration of acid is relevant with the replacement(metathesis)reaction time, and the high replacement(metathesis)reaction time of the concentration of acid is short, and the low replacement(metathesis)reaction time of the concentration of acid is long.
In technique scheme, described presoma lithium gallium oxide and boron nitride can be the lithium gallium oxide and the boron nitride of allotropic substance, and lithium gallium oxide is preferentially selected the lithium gallium oxide of four directions phase or six side's phases for use, and boron nitride is preferentially selected the boron nitride of cube phase or six side's phases for use.The form of presoma lithium gallium oxide and boron nitride can be powder, particle or block.
In technique scheme, described height is pressed into constituting of piece, and prefabricated body piece or the body piece that is stacked alternately are put into the carbon tube of agalmatolite assembly block, and the upper/lower terminal of carbon tube is assembled graphite flake, molybdenum sheet and conducting steel ring successively.Described synthesis press is preferentially selected the big cavity press of cubic apparatus for use.
In technique scheme, synthetic product is removed LiBO through the pickling dissolving
2After, can insert again and carry out ultrasonic cleaning in the ultrasonic cleaning equipment, higher-quality gallium nitride is easy to get.
The present invention prepares the method for gallium nitride, the solid-state displacement reaction process of in the High Temperature High Pressure synthesis device, carrying out, and its chemical equation is: LiGaO
2+ BN → LiBO
2+ GaN, reaction process is boron atom of a gallium atomic substitutions, based on the displacement behavior of same main group element boron (B) and gallium (Ga), reaction product LiBO
2Can be at subsequently acid cleaning process by eccysis, therefore the ratio of lithium gallium oxide and boron nitride can not influence the generation of gan building-up reactions, and lithium gallium oxide and boron nitride can be arbitrary ratio, certainly, when both ratio during, can improve the productive rate of gan near ideal proportioning (1:1).
(chemical equation is: LiGaO to the present invention is based on the controlled solid-state displacement reaction of lithium gallium oxide and boron nitride
2+ BN → LiBO
2+ GaN) preparation gallium nitride, original material need not gas or liquid (as N
2Or NH
3) participate in, can in short preparation time (the reaction shortest time only is 1 minute), grow well-crystallized's gallium nitride.The crystal of preparation is through scanning electron microscopic observation, and the well-crystallized is hexagonal prism, and crystal size is 20-100 μ m; Through the EDAX constituent content analysis, the Ga:N ratio is near 1:1.The present invention can (minimum synthesis condition only be: 850 ℃ of temperature under lower temperature, pressure condition, pressure 1.1GPa) carries out the gallium nitride preparation, preparation condition is lower than synthesis condition (1400 ℃ of the temperature that now are used for diamond and cubic boron nitride suitability for industrialized production, pressure 5.5GPa), therefore can carry out scale operation nowadays being widely used on the big cavity press of diamond and cubic boron nitride suitability for industrialized production, manufacturing enterprises such as existing diamond and cubic boron nitride need not carry out scrap build, the gan product of just can changing the line of production smoothly.The method of utilizing solid-state displacement reaction to prepare gallium nitride provided by the invention, it is cheap to have material cost, and production specifications require low, easy to operate, the crystal growth rate height, generated time is short, is easy to advantages such as popularization and large-scale production.
Description of drawings:
Fig. 1 represents to utilize the solid phase replacement(metathesis)reaction of lithium gallium oxide and boron nitride to prepare the temperature and pressure condition graphic representation of gallium nitride.Square representative can be synthesized the temperature and pressure condition of GaN among the figure, the condition that the trilateral representative fails to synthesize GaN.The above zone of dotted line is considered to be fit to the temperature and pressure zone of preparation gallium nitride.
Fig. 2 is the photo figure in kind of the gallium nitride for preparing of the present invention.
Embodiment
Embodiment 1: getting mol ratio is cubic phase lithium gallium oxide and the hexagonal boron nitride pellet of 1:1, put into three-dimensional mixer, mixed about about 30 minutes, with mould batch mixing is pressed into the cylinder piece, the cylindrical blocks that suppresses is packed in the carbon tube of agalmatolite assembly block, and the upper/lower terminal of carbon tube is assembled graphite flake, molybdenum sheet and conducting steel ring successively.After assembling height is pressed into piece and places big cavity press, about about 850 ℃ in temperature, about the about 1.1GPa of pressure, through about 1 minute heat-insulation pressure keeping, synthetic material is taken out in pressure release cooling back, is about 20% salt acid soak, eccysis LiBO with mass concentration
2Deng just obtaining gallium nitride behind the impurity.
Embodiment 2: getting mol ratio is cubic phase lithium gallium oxide and the hexagonal boron nitride pellet of 1:0.9, put into three-dimensional mixer, mixed about about 45 minutes, with mould batch mixing is pressed into cylindric block of material, the cylindrical blocks that suppresses is packed in the carbon tube of agalmatolite assembly block, and the upper/lower terminal of carbon tube is assembled graphite flake, molybdenum sheet and conducting steel ring successively.After assembling height is pressed into piece and places big cavity press, about about 1600 ℃ in temperature, about the about 5.0GPa of pressure, through about 20 minutes heat-insulation pressure keeping, synthetic material is taken out in pressure release cooling back, is about 50% nitric acid dousing with mass concentration, eccysis LiBO
2Deng just obtaining gallium nitride behind the impurity.
Embodiment 3:
Getting mol ratio is six side's phase lithium gallium oxides and the hexagonal boron nitride pellet of 1:0.8, put into three-dimensional mixer, mixed about about 40 minutes, with mould batch mixing is pressed into cylindric block of material, the cylindrical blocks that suppresses is packed in the carbon tube of agalmatolite assembly block, and the upper/lower terminal of carbon tube is assembled graphite flake, molybdenum sheet and conducting steel ring successively.After assembling height is pressed into piece and places big cavity press, about about 1400 ℃ in temperature, about the about 5.5GPa of pressure, through about 25 minutes heat-insulation pressure keeping, synthetic material is taken out in pressure release cooling back, is 30% salt acid soak with mass concentration, eccysis LiBO
2Deng just obtaining gallium nitride behind the impurity.
Embodiment 4:
Getting mol ratio is cubic phase lithium gallium oxide and the cubic boron nitride powder of 1:1, put into three-dimensional mixer, mixed about about 30 minutes, with mould batch mixing is pressed into cylindric block of material, the cylindrical blocks that suppresses is packed in the carbon tube of agalmatolite assembly block, and the upper/lower terminal of carbon tube is assembled graphite flake, molybdenum sheet and conducting steel ring successively.After assembling height is pressed into piece and places big cavity press, in temperature about about 1200 ℃, about the about 4.0GPa of pressure, through about about 30 minutes heat-insulation pressure keeping, synthetic material is taken out in pressure release cooling back, with mass concentration is 35% salt acid soak, inserts after the pickling again and carries out ultrasonic cleaning, eccysis LiBO in the ultrasonic cleaning equipment
2Deng just obtaining gallium nitride behind the impurity.Ultrasonic cleaning equipment is general ultrasonic cleaning equipment.
Embodiment 5:
Getting mol ratio is six side's phase lithium gallium oxides and the cubic boron nitride pellet of 1:1, put into three-dimensional mixer, mixed about about 40 minutes, with mould batch mixing is pressed into cylindric block of material, the cylindrical blocks that suppresses is packed in the carbon tube of agalmatolite assembly block, and the upper/lower terminal of carbon tube is assembled graphite flake, molybdenum sheet and conducting steel ring successively.After assembling height is pressed into piece and places big cavity press, in temperature about about 1400 ℃, about the about 4.0GPa of pressure, through about 5 minutes heat-insulation pressure keeping, synthetic material is taken out in pressure release cooling back, with mass concentration is that 65% sulfuric acid soaks, and inserts after the pickling again and carries out ultrasonic cleaning, eccysis LiBO in the ultrasonic cleaning equipment
2Deng just obtaining gallium nitride behind the impurity.Ultrasonic cleaning equipment is general ultrasonic cleaning equipment.
Embodiment 6:
Getting mol ratio is cubic phase lithium gallium oxide and the hexagonal boron nitride of 1:1, after elder generation is pressed into slice of cylinder with mould respectively, again their compartment of terrains is stacked into right cylinder.The cylindrical blocks that stacks is packed in the carbon tube of agalmatolite assembly block, and the upper/lower terminal of carbon tube is assembled graphite flake, molybdenum sheet and conducting steel ring successively.After assembling height is pressed into piece and places big cavity press, about about 1600 ℃ in temperature, about the about 6.0GPa of pressure, the heat-insulation pressure keeping through 60 minutes, the sample with 20% salt acid treatment after synthetic just obtains gallium nitride.
Be noted that the above embodiments just illustrate the present invention with six concrete examples, and be not limitation of the present invention.Simultaneously, those of ordinary skill in the art know, can carry out in the text the not various improvement of description to the present invention, yet these improvement can not depart from the scope that this patent is protected.
Claims (10)
1. method of utilizing solid-state displacement reaction to prepare gallium nitride is characterized in that may further comprise the steps:
(1) reaction precursor body lithium gallium oxide and boron nitride are mixed back presuppression adult piece, are stacked alternately the adult piece after perhaps it being pre-pressed into the piece sheet respectively;
(2) the body piece that is prefabricated into or the body deblocking reaction thing that is stacked alternately being placed into height is pressed in the piece;
(3) height that will assemble is pressed into piece and places the synthetic chamber of press to carry out solid-state displacement reaction, and synthesis temperature is not less than 850 ℃, and pressure is not less than 1.0GPa, and synthesising reacting time is no less than 1.0 minutes;
(4) synthetic product was taken out in the cooling pressure release after replacement(metathesis)reaction finished, and used the acid soak synthetic product, and LiBO is removed in dissolving
2, promptly obtain gallium nitride.
2. the method for utilizing solid-state displacement reaction to prepare gallium nitride according to claim 1, the temperature that it is characterized in that synthesis of gallium nitride is 850-1800 ℃, and pressure is 1.0-6.0GPa, and the time is 1-120 minute.
3. the method for utilizing solid-state displacement reaction to prepare gallium nitride according to claim 2 is characterized in that the solid-state displacement reaction time is 20-30 minute.
4. the method for utilizing solid-state displacement reaction to prepare gallium nitride according to claim 1 is characterized in that described press is the big cavity press of cubic apparatus, four sides top press or belt type press.
5. the method for utilizing solid-state displacement reaction to prepare gallium nitride according to claim 1 is characterized in that described solid-state displacement reaction is based on the displacement behavior of same main group element boron (B) and gallium (Ga).
6. the method for utilizing solid-state displacement reaction to prepare gallium nitride according to claim 1 is characterized in that described presoma lithium gallium oxide is four directions phase or six side's phase lithium gallium oxides, and described presoma boron nitride is cube phase or six side's phase boron nitrides.
7. the method for utilizing solid-state displacement reaction to prepare gallium nitride according to claim 1, the form that it is characterized in that described presoma lithium gallium oxide and boron nitride is powder, particle or block.
8. the method for utilizing solid-state displacement reaction to prepare gallium nitride according to claim 1 is characterized in that described acid solution is that mass concentration is not less than 10% hydrochloric acid, nitric acid or sulfuric acid.
9. the method for utilizing solid-state displacement reaction to prepare gallium nitride according to claim 8 is characterized in that described acid solution is that mass concentration is not less than 20% hydrochloric acid, nitric acid or sulfuric acid.
10. according to the described method of utilizing solid-state displacement reaction to prepare gallium nitride of each claim in the claim 1 to 9, it is characterized in that inserting again after the synthetic product pickling and carry out ultrasonic cleaning in the ultrasonic cleaning equipment.
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| CN1289867A (en) * | 1999-09-29 | 2001-04-04 | 中国科学院物理研究所 | Hot liquid method for growing monocrystal of gallium nitride |
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| CN1289867A (en) * | 1999-09-29 | 2001-04-04 | 中国科学院物理研究所 | Hot liquid method for growing monocrystal of gallium nitride |
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