CN107039250B - A kind of method of the material of growing gallium nitride on a sapphire substrate, gallium nitride material and application thereof - Google Patents

A kind of method of the material of growing gallium nitride on a sapphire substrate, gallium nitride material and application thereof Download PDF

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CN107039250B
CN107039250B CN201610078061.9A CN201610078061A CN107039250B CN 107039250 B CN107039250 B CN 107039250B CN 201610078061 A CN201610078061 A CN 201610078061A CN 107039250 B CN107039250 B CN 107039250B
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gallium nitride
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CN107039250A (en
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邢志刚
林桂荣
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Zhongsheng Photoelectric Equipment (shanghai) Ltd By Share Ltd
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Abstract

The invention belongs to technical field of semiconductors,It is related to a kind of method of the material of growing gallium nitride on a sapphire substrate,Grow obtained gallium nitride material and application thereof,The present invention to reative cell during heating Sapphire Substrate by being passed through the first metallorganic,Play the desorption for promoting sapphire surface oxygen atom,And the effect in sapphire surface depositing metal atoms,Then growing gallium nitride on a sapphire substrate,Obtain the gallium nitride material of high quality,The gallium nitride material being prepared compared to conventional method,XRD (002) diffraction surfaces for the gallium nitride material that the present invention is grown and the half-peak breadth of (102) diffraction surfaces can respectively reduce 10 rads 80 rads and 30 rads 110 rads,Simultaneously,The method of the invention increases the process window of multiple steps in the technique of subsequent growth gallium nitride material,It has broad application prospects.

Description

A kind of method of the material of growing gallium nitride on a sapphire substrate, gallium nitride material and Its purposes
Technical field
The invention belongs to technical field of semiconductors, be related to a kind of method of the material of growing gallium nitride on a sapphire substrate, Grow obtained gallium nitride material and application thereof, and in particular to it is a kind of by growing gallium nitride material on a sapphire substrate most Initial stage is passed through metallo-organic compound and carries out pretreated mode to improve the crystal quality of gallium nitride material that growth obtains Method grows obtained gallium nitride material and its purposes for being used to prepare light emitting diode and laser diode.
Background technology
Gallium nitride (Gallium Nitride, GaN) is one of most important material in third generation semiconductor, at present still without Method obtains the single crystal material of bulk, and required gallium nitride material is usually all grown on other substrate materials, generally use Substrate material includes sapphire, silicon and silicon carbide etc..Since the lattice of substrate material and gallium nitride material mismatches, give birth to The long gallium nitride material obtained contains very highdensity defect, is lacked wherein most defects is line defect namely break-through dislocation It falls into.For the gallium nitride material crystal quality that epitaxial growth obtains, generally pass through gallium nitride film crystalline material diffraction surfaces X-ray The half-peak breadth of diffraction curve (XRD) characterizes.
Current growing gallium nitride material on a sapphire substrate, typically uses metal-organic chemical vapor deposition equipment (Metal-Organic Chemical Vapor Deposition, MOCVD) equipment is carried out by the two-step growth method of broad sense 's.The two-step growth method of broad sense is：1. first (T1, generally at 500-600 DEG C) is low in one layer of Grown under cryogenic Warm buffer layer, commonly used cushioning layer material are gallium nitride, are also had using AlN or AlGaN material；2. increasing temperature and in height (T2, generally at 1000-1100 DEG C) grows high-temperature ammonolysis gallium material under the conditions of temperature.
With deeply being generally included in actual mechanical process with development, the two-step growth method of broad sense for research：It is growing Before low temperature buffer layer, in H2Baking desorption is carried out under the atmosphere of flowing, and sapphire is placed under high temperature T0 and keeps the temperature a period of time, Then T1 is reduced the temperature to, keeps the temperature a period of time A1, grown buffer layer, then be increased to T2 and keep the temperature a period of time A2 and anneal Processing；Adjustment temperature to T3 and keeps the temperature a period of time A3, then growing gallium nitride is warming up to T4 and keeps the temperature a period of time A4, after Continuous growing gallium nitride, obtains gallium nitride material.
Grow obtain gallium nitride film material crystal quality in by growth course numerous process materials conditions influenced, Factor there are two wherein mostly important：(1) thickness of growth low temperature buffer layer on a sapphire substrate and buffer layer is micro- Structure is seen, wherein in the soaking time A1 of T1, the temperature T1 of grown buffer layer, pressure and source material proportion, growth rate etc. It can influence the thickness and microstructure of low temperature buffer layer；(2) temperature-rise period of T2, and the heat preservation in T2 are increased to from T1 Journey can have low temperature buffer layer important annealing effect, the microstructure of this layer of low temperature buffer layer to change, namely common name Annealing recrystallization process, heating-up time, temperature T2 from T1 to T2 and can influence low temperature buffer in the soaking time A2 etc. of T2 The microstructure of layer, and then influence the quality of final product gallium nitride film material.It can thus be optimized for these parameters, The dislocation density for reducing gallium nitride film material, improves its crystal quality.
Under the preferable growth conditions of the gallium nitride film material obtained by a large amount of Optimal Experimental, it can obtain relatively The gallium nitride of good quality, but based on above by the method for optimizing growing gallium nitride material to technological parameter, life The quality of the crystal of the long gallium nitride material obtained is strongly dependent on technique growth conditions, when these conditions have more by a small margin When fluctuation, the crystal quality of gallium nitride will appear apparent deterioration (showing as XRD half-peak breadths to become larger), similar this to technique item It is small that the strong depend-ence relationship of part is commonly referred to as process window.
Thus, it is more to temperature, the flow field of Material growth etc. when needing steadily to obtain the gallium nitride material of better quality Kind of process conditions propose harsh requirement, and then accuracy to material growing device and repeatability and source material and ring Border condition etc. is proposed almost harsh requirement.Moreover, optimizing growing gallium nitride to technological parameter using above-mentioned merely The method of material is difficult the density for the dislocation defects being further reduced in gallium nitride material, cannot still be met based on gallium nitride material Application demand, gallium nitride quality still needs to be further increased.
Thus, it is necessary to it develops a kind of with wider process window and simple and practicable improve is given birth on a sapphire substrate The method of long gallium nitride material crystal quality.
Invention content
For the above problem present in existing general technology, one of the objects of the present invention is to provide one kind with wider Process window and simple and practicable the crystal quality for improving the gallium nitride material grown on a sapphire substrate method. The crystal quality for the gallium nitride material being prepared by this method is good, the gallium nitride material that opposite conventional method is prepared, The half-peak breadth of its (002) diffraction surfaces can reduce 10 rads -80 rads, the half-peak breadth of (102) diffraction surfaces can reduce 30 rads - 110 rads, meanwhile, the method for the invention can also reduce dependence journey of the growth high-quality gallium nitride crystal to growth conditions Degree has wider GaN growth process window.
For this purpose, the present invention uses following technical scheme：
A method of growing gallium nitride material on a sapphire substrate the described method comprises the following steps：
Sapphire Substrate is placed in reative cell by S0, is heated Sapphire Substrate, is passed through to reative cell during heating First metallorganic, is pre-processed；
Growing gallium nitride, acquisition are grown on the gallium nitride material in Sapphire Substrate to S1 on a sapphire substrate.
The present invention plays rush by being passed through the first metallorganic to reative cell during heating Sapphire Substrate It is subsequent low to influence into the desorption of sapphire surface oxygen atom, and in the effect of sapphire surface depositing metal atoms The microstructure for the low temperature buffer layer that the growth course of warm buffer layer and growth obtain, and then influence growth high-temperature ammonolysis gallium material Process, the dislocation defect in the gallium nitride material reduced improves the nitrogen grown on a sapphire substrate Change the crystal quality of gallium material, the gallium nitride material that the present invention is prepared compares the gallium nitride that existing general technology is prepared Crystal quality is more preferable, the half-peak of XRD (002) diffraction surfaces and (102) diffraction surfaces of the gallium nitride material of Grown on Sapphire Substrates Width substantially reduces compared to the gallium nitride material that existing general technology is prepared, and the half-peak breadth of (002) diffraction surfaces can reduce 10 - 80 rads of rad, the half-peak breadth of (102) diffraction surfaces can reduce 30 rads -110 rads, for raw in plain film Sapphire Substrate Long gallium nitride material, (002) diffraction surfaces half-peak breadth reduce up to 20 rads -80 rads, and the reduction of (102) diffraction surfaces half-peak breadth can Up to 50 rads -110 rads；For the gallium nitride material grown on graphical sapphire substrate, (002) diffraction surfaces half-peak breadth reduces Up to 10 rads -70 rads, (102) diffraction surfaces half-peak breadth reduces up to 30 rads -90 rads.
Moreover, the method for the invention can grow nitridation on a sapphire substrate with the S1 carried out after expansion step S0 The soaking time of the process window of each step during gallium, buffer layer thickness and annealing can match in wider range Change to conjunction property without causing gallium nitride material crystal quality to decline, the ranging from 10nm-50nm of buffer layer thickness, annealing Ranging from -15 minutes 0 minute of soaking time, " conformability " refers to：Either at buffer layer thickness or annealing The soaking time of reason, is not independent from each other, but interactional, illustrates：The present invention can be in buffer layer thickness When down to 10nm, the gallium nitride material of high-crystal quality is still obtained, but the realization of this purpose needs to adjust suitable annealing Soaking time and other factor.Again for example, the item that the present invention can be 0 minute in the soaking time of annealing Still obtain the gallium nitride material of high-crystal quality under part, but the realization of this purpose need to adjust suitable buffer layer thickness and its His factor.
Although being pointed out that the soaking time of buffer layer thickness of the present invention and annealing has bigger The realization of process window adjusts with needing conformability, but those skilled in the art it is to be understood that be still relative to existing general technology There is significant high-lighting progress, because in existing general technology, in the crystal for the gallium nitride material for keeping growing It is not achieved under the premise of quality does not decline, if even if adjusting the thickness of the soaking time buffer layer of annealing of the present invention The range of 10nm-50nm, moreover, being not achieved 0 minute -15 of the present invention if even if adjusting buffer layer thickness soaking time The range of minute.
It is further preferred that the present invention buffer layer thickness change within the scope of 20nm-40nm, and conformability adjust it When his factor, crystal quality will not decline, and if buffer layer thickness can be led in 20nm-40nm variations in existing general technology Crystal quality is caused to be decreased obviously.The soaking time of the annealing of the present invention changes within the scope of -6 minutes 2 minutes, and conformability When ground adjusts other factors, crystal quality will not decline, and if the soaking time of annealing is at 2 points in existing general technology When clock changes within the scope of -6 minutes, crystal quality can be decreased obviously.
The pretreatment of S0 plays the desorption for promoting sapphire surface oxygen atom in the method for the invention, and blue precious The effect of stone surface depositing metal atoms, the mechanism of action are specific as follows：
By being passed through the first metallorganic to reative cell during heating Sapphire Substrate, in Sapphire Substrate table Face decomposites free metallic atom, and free metallic atom has both sides to act on：
The effect of first aspect is to promote the desorption of sapphire surface oxygen atom.Free metallic atom is reacted as surface Catalyst promotes one layer of oxygen atom of Sapphire Substrate most surface to be detached from substrate, and the atom of one layer of Sapphire Substrate most surface is made to be Al, the microstructure for the low temperature buffer layer that growth course and growth to influence low temperature buffer layer obtain, and then influence growth The process of high-temperature ammonolysis gallium, the dislocation defect in the gallium nitride material reduced improve the matter of gallium nitride material crystal Amount.Compared in existing general technology by H2Sapphire Substrate is heated in atmosphere makes one layer of oxygen original on Sapphire Substrate most surface layer Son is detached from, and the method for the invention is passed through the first metallorganic during heat Sapphire Substrate, can generate heat with And the synergistic effect of catalysis, this in the process can be in H2It is carried out under atmosphere, it can not also be in H2It is carried out under atmosphere, it can be opposite The desorption of one layer of oxygen atom on Sapphire Substrate most surface layer is realized in the existing lower temperature of general technology and shorter time, Traditional baking desorption generally wants 1050 DEG C or more, and the present invention can be passed through metallo-organic compound reality when temperature is down to 800 DEG C The desorption of the oxygen atom on existing Sapphire Substrate most surface layer.
The effect of second aspect is in sapphire surface depositing metal atoms.Free metallic atom is heavy in sapphire surface The metallic atom of one atomic layer of product, the classification and ingredient of the atom specifically deposited and the metal-organic type being passed through Related, the deposition of the metallic atom of this single atomic layer can largely improve the low temperature of growth on a sapphire substrate and delay The microstructure of layer is rushed, to further greatly improve the quality of the gallium nitride material of growth on it.To low temperature buffer layer The influence of microstructure, main show increase the lateral dimension of microcosmic crystal grain in low temperature buffer layer and make microcosmic crystalline substance The orientation of grain is more consistent.
The process of heating Sapphire Substrate of the present invention includes temperature rise period, holding stage and temperature-fall period.
Preferably, the temperature of the holding stage be 800 DEG C -1200 DEG C, may be, for example, 800 DEG C, 850 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, 1150 DEG C or 1200 DEG C etc., preferably 900 DEG C -1100 DEG C, further preferably 1000 DEG C.
Preferably, the time of the holding stage be -30 minutes 30 seconds, may be, for example, 30 seconds, 40 seconds, 60 seconds, 2 minutes, 4 Minute, 5 minutes, 7 minutes, 10 minutes, 13 minutes, 16 minutes, 20 minutes, 22 minutes, 25 minutes, 28 minutes or 30 minutes etc., Preferably -10 minutes 5 minutes.
The ingredient of Sapphire Substrate of the present invention is monocrystalline Al2O3, including plain film Sapphire Substrate and graphic sapphire Substrate (Patterned Sapphire Substrate, PSS).
About the first metallorganic start be passed through opportunity, can heating Sapphire Substrate whole process it is a certain Time point starts to be passed through, which can be in the temperature rise period, can also be in holding stage, can also be in temperature-fall period.
End about the first metallorganic is passed through opportunity, can also be in certain of the whole process of heating Sapphire Substrate One time point terminated to be passed through, and ensured the time point for terminating to be passed through after the time point for starting to be passed through.Terminate the time being passed through Point can be in the temperature rise period, can also be in holding stage, can also be in temperature-fall period.
It is highly preferred that being passed through the first metallorganic when holding stage starts, and terminate to lead at the end of holding stage Enter the first metallorganic.
Of the present invention in temperature rise period, holding stage and temperature-fall period is the period, is illustrated with the temperature rise period： Temperature rise period is a period, and temperature gradually rises within the time period, described " to start to be passed through first in the temperature rise period Metallorganic " refers to that each time point within the temperature rise period can start being passed through for the first metallorganic.It is described " terminating to be passed through the first metallorganic in the temperature rise period " refers to, each time point within the temperature rise period can terminate One metallorganic is passed through, while include an Implicit Conditions being the time point for terminating to be passed through at the time point for starting to be passed through Later.
It is illustrated again with holding stage：Holding stage is also a period, and within the time period, temperature is constant , " the starting to be passed through the first metallorganic in holding stage " refers to, can at each time point of holding stage Start being passed through for the first metallorganic." the terminating to be passed through the first metallorganic in holding stage " refers to, in heat preservation rank Each time point of section can terminate being passed through for the first metallorganic, while also be to terminate to lead to comprising an Implicit Conditions The time point entered is after the time point for starting to be passed through.
Preferably, " being passed through the first metallorganic to reative cell during heating " of the present invention, it is described to be passed through It carries out as follows：With the carrier gas of very little flow, the gold that the first metallorganic liquid in the bottle of source is evaporated Belong to organic compound steam to be carried out into reative cell.
Carrier gas of the present invention be hydrogen, nitrogen, helium, neon, argon gas, Krypton or xenon in any one or at least The mixed gas of two kinds of mixed gas, preferably hydrogen, nitrogen or hydrogen and nitrogen.The carrier gas is passed through after reative cell, It is merged into purge gas of the present invention.
Preferably, the first metallorganic, which is the metal containing any one or at least two elements in aluminium, gallium or indium, has In machine compound, preferably trimethyl aluminium, trimethyl gallium, triethyl-gallium or trimethyl indium any one or at least two it is mixed Object is closed, the mixture is typical but non-limiting examples have：The mixture of trimethyl aluminium and trimethyl gallium, trimethyl aluminium and three second The mixture of the mixture of base gallium, trimethyl gallium and trimethyl indium, trimethyl aluminium, trimethyl gallium and triethyl-gallium mixture, The mixture etc. of trimethyl aluminium, triethyl-gallium and trimethyl indium.
Preferably, the type and the type for the first metallorganic being passed through of free metallic atom of the present invention have It closes, when the first metallorganic being passed through is single kind, the free metallic atom of generation is also correspondingly single kind Metallic atom, such as when the first metallorganic being passed through is trimethyl gallium, the free metallic atom of generation is that gallium is former Son；When the first metallorganic being passed through is at least two mixture, the free metallic atom of generation is correspondingly logical The combination of metallic atom in both metallo-organic compounds entered, such as when the first metallorganic being passed through is trimethyl When the mixture of aluminium, triethyl-gallium and trimethyl indium, the metallic atom of generation is the combination of aluminium atom, gallium atom and phosphide atom.
Preferably, the kind of the type and the first metallorganic being passed through of the metallic atom of sapphire surface deposition of the present invention Class is related, and the type of the metallic atom of surface deposition is identical as the free metallic atom type of generation.For example, when logical When the first metallorganic entered is trimethyl gallium, the free metallic atom of generation is gallium atom, and the metal of surface deposition is former Son is also gallium atom.
Preferably, the growing gallium nitride on a sapphire substrate specifically includes：S1-1 is cooled to the first temperature in step S0 When spending, it is passed through the second metallorganic and nitrogen source gas, on substrate grown buffer layer；
S1-2 stoppings are passed through the second metallorganic, are still connected with nitrogen source gas, Sapphire Substrate is warming up to second temperature And keep the temperature, buffer layer is made annealing treatment；
S1-3 adjusts temperature to third temperature, then passes to third metallorganic, keeps the temperature, growing gallium nitride；
S1-4 is warming up to the 4th temperature, heat preservation, continued growth gallium nitride, obtains gallium nitride material, and stopping is passed through third gold Belong to organic matter；
Wherein, from during third temperature is warming up to the 4th temperature, being passed through for third metallorganic, Huo Zheting are kept Only third metallorganic is passed through and restores third metallorganic when being warming up to four temperature and is passed through.
Preferably, nitrogen source gas is ammonia (NH3), hydrazine (N2H4) or phenylhydrazine (N2H3(C6H5)) in any one or extremely Few two kinds of mixture, further preferably ammonia.
Preferably, first temperature is 500 DEG C -600 DEG C, may be, for example, 520 DEG C, 550 DEG C, 580 DEG C or 600 DEG C etc.. The thickness of the buffer layer is preferably 10nm-50nm, may be, for example, 10nm, 13nm, 15nm, 20nm, 22nm, 25nm, 30nm, 33nm, 36nm, 40nm, 45nm or 48nm etc..By being passed through the first metal to reative cell during heating Sapphire Substrate Organic matter is to be pre-processed, during subsequent growth gallium nitride can be made, the range bigger of the thickness of grown buffer layer, from The 20-35nm of existing general technology even narrower ranges make it be increased under conditions of cooperation adjusts other factors 10nm-50nm reduces the severe of operation, improves the operability in industrial production.
Preferably, the second temperature be 900 DEG C -1100 DEG C, such as 900 DEG C, 920 DEG C, 950 DEG C, 970 DEG C, 1000 DEG C, 1060 DEG C or 1100 DEG C etc..
Preferably, the time kept the temperature described in S1-2 is -15 minutes 0 minute, be may be, for example, 0 minute, 0.5 minute, 1 point Clock, 2 minutes, 3 minutes, 5 minutes, 7 minutes, 8 minutes, 10 minutes, 12 minutes or 14 minutes etc., preferably -8 minutes 1 minute；This Invention it is described from the first temperature be warming up to second temperature temperature-rise period and second temperature insulating process occur it is annealed Journey, the soaking time can be 0 minute, it is intended that can be without the heat preservation of second temperature.The present invention passes through in heating sapphire It is passed through the first metallorganic to reative cell during substrate, is pre-processed so that this soaking time range has been expanded to 0 Minutes -15 minutes, -6 minutes 4 minutes in relatively existing general technology, process window expanded.It is pointed out that this hair Realization in -6 minutes 4 minutes of the soaking time of bright annealing -15 minutes 0 minute or existing general technology all be and other Parameter parameter such as buffer layer thickness is closely related what cooperation was realized.
Preferably, the third temperature be 900 DEG C -1100 DEG C, may be, for example, 900 DEG C, 930 DEG C, 950 DEG C, 1000 DEG C, 1020 DEG C, 1050 DEG C or 1100 DEG C etc., preferably 950 DEG C -1050 DEG C.
Preferably, the time kept the temperature described in S1-3 is -90 minutes 5 minutes, be may be, for example, 5 minutes, 10 minutes, 15 points Clock, 20 minutes, 30 minutes, 33 minutes, 35 minutes, 40 minutes, 50 minutes, 60 minutes, 65 minutes, 70 minutes, 80 minutes or 90 Minute etc., preferably 10-30 minutes, further preferably 20 minutes.
Preferably, the 4th temperature be 1000 DEG C -1200 DEG C, may be, for example, 1000 DEG C, 1020 DEG C, 1050 DEG C, 1100 DEG C or 1150 DEG C etc., preferably 1050 DEG C -1150 DEG C, the time kept the temperature described in S1-4 is -60 minutes 20 minutes, preferably 40 Minute.
The thickness for the gallium nitride material that the present invention obtains is 3 μm -6 μm, may be, for example, 3 μm, 4 μm, 4.5 μm, 5 μm or 6 μm Refer to the overall thickness of step S1-3 and the gallium nitride of step S1-4 growths Deng the thickness of, the gallium nitride material.
It should be noted that including the thickness of the step S1-1 buffer layers grown in the thickness measured when actually measuring Degree, the thickness of buffer layer is with respect to being very thin for the thickness of gallium nitride.
What " the gallium nitride material crystal quality for improving Grown on Sapphire Substrates " of the present invention referred to mainly improves The quality for the gallium nitride that step S1-4 is grown, and the gallium nitride that step S1-3 is grown is as transition zone.
Preferably, second metallorganic be trimethyl aluminium, trimethyl gallium or triethyl-gallium in any one or At least two mixture, the mixture is typical but non-limiting examples have：The mixture of trimethyl aluminium and trimethyl gallium, three The mixture of aluminium methyl and triethyl-gallium, trimethyl aluminium, trimethyl gallium and triethyl-gallium mixture.
Preferably, the third metallorganic is trimethyl gallium and/or triethyl-gallium.
" trimethyl gallium and/or triethyl-gallium " of the present invention refers to：It can be trimethyl gallium, can also be triethyl-gallium, It can also be the mixture of trimethyl gallium and triethyl-gallium.
Preferably, reative cell is connected with purge gas during S0 and S1, to maintain reative cell flow field, this is because conduct The inadequate reative cell of the gas flow of source material itself is established needed for flow field.
Purge gas of the present invention be hydrogen, nitrogen, helium, neon, argon gas, Krypton or xenon in any one or The mixed gas of at least two mixed gas, preferably hydrogen, nitrogen or hydrogen and nitrogen.
In the method for the invention, the intake of the first metallorganic is critically important factor, can influence growth and obtain Gallium nitride material crystal quality quality.Intake can bring the first of reative cell by controlling carrier gas of the present invention The flow of metallorganic, the source bottle temperature of the first metallorganic and source bottle pressure these factor collective effects.First gold medal The intake for belonging to organic matter is related with the size of reative cell, and typical but non-limiting example is as follows：For graphite support disk diameter For the MOCVD reative cells of 540mm, the flow for bringing the trimethyl gallium of reative cell by carrier gas is 300 standard milliliters/minute (sccm), the temperature of trimethyl gallium fluid supply bottle is 5 DEG C, and source bottle pressure is 1300mbar.
The intake of first metallorganic of the present invention should be adjusted according to the size of reative cell, with above-mentioned example Illustrated as concrete example, if the cross-sectional area of reative cell become reative cell cross-sectional area in above-mentioned example N (N be more than 0.1 and less than 10 positive number) times, then correspondingly adjust by the carrier gas bring into reative cell the first metallorganic flow, The source bottle temperature of first metallorganic and the first metallorganic of source bottle pressure these factor collective effects control it is logical Enter N times that amount is intake in above-mentioned example.
As the optimal technical scheme of the method for the invention, a kind of side of the material of growing gallium nitride on a sapphire substrate Method the described method comprises the following steps：
Sapphire Substrate is placed in metal organic chemical vapour phase deposition reaction chamber by S0, in H2Gas as purge gas Under the conditions of atmosphere, trimethyl gallium is passed through when holding stage starts, and stopping is passed through trimethyl gallium at the end of holding stage, it is described The temperature of holding stage is 1000 DEG C, and the time of the holding stage is 8 minutes；
S1-1 is passed through trimethyl gallium and NH when step S0 is cooled to 500-600 DEG C3, 20nm-40nm is grown on substrate Buffer layer；
S1-2 stoppings are passed through trimethyl gallium, are still connected with NH3, Sapphire Substrate is warming up to 1100 DEG C of second temperature and is kept the temperature It -8 minutes 1 minute, anneals to buffer layer；
S1-3 reduces the temperature to 1000 DEG C of third temperature, is passed through trimethyl gallium, keeps the temperature 20 minutes, growing gallium nitride；
S1-4 is increased to 1100 DEG C of the 4th temperature, keeps the temperature 40 minutes, continued growth gallium nitride, obtains 3 μm of -6 μ m thick Gallium nitride material, stopping are passed through trimethyl gallium；
Wherein, from during 1000 DEG C of third temperature is warming up to 1100 DEG C of the 4th temperature, being passed through for trimethyl gallium is kept.
The second object of the present invention is to provide a kind of gallium nitride material that method as described in relation to the first aspect is prepared, institute The crystal quality for stating gallium nitride material is very high, XRD (002) diffraction for the gallium nitride material that plain film Grown on Sapphire Substrates obtains The half-peak breadth of face and (102) diffraction surfaces is respectively 130 rads -190 rads and 190 rads -250 rads；Graphic sapphire serves as a contrast XRD (002) diffraction surfaces of the gallium nitride material grown on bottom and the half-peak breadth of (102) diffraction surfaces be respectively 160 rads- 220 rads and 140 rads -200 rads.
XRD (002) diffraction surfaces of gallium nitride material of the present invention and the numerical value of the half-peak breadth of (102) diffraction surfaces are smaller, Illustrate that the crystal quality of the gallium nitride material is better.
XRD (002) diffraction for the gallium nitride material in plain film Grown on Sapphire Substrates that the method for the invention obtains The half-peak breadth in face be 130 rads -190 rads, may be, for example, 130 rads, 135 rads, 138 rads, 140 rads, 145 rads, 150 rads, 155 rads, 160 rads, 165 rads, 170 rads, 172 rads, 175 rads, 180 rads or 190 rads etc..
XRD (102) diffraction for the gallium nitride material in plain film Grown on Sapphire Substrates that the method for the invention obtains The half-peak breadth in face be 190 rads -250 rads, may be, for example, 190 rads, 195 rads, 200 rads, 202 rads, 205 rads, 210 rads, 215 rads, 220 rads, 225 rads, 228 rads, 230 rads, 235 rads, 245 rads or 250 rads etc..
The XRD (002) for the gallium nitride material grown on graphical sapphire substrate that the method for the invention obtains spreads out The half-peak breadth for penetrating face is 160 rads -220 rads, may be, for example, 160 rads, 165 rads, 170 rads, 172 rads, 175 jiaos Second, 180 rads, 185 rads, 190 rads, 193 rads, 195 rads, 200 rads, 205 rads, 210 rads, 215 rads or 220 rads etc..
The XRD (102) for the gallium nitride material grown on graphical sapphire substrate that the method for the invention obtains spreads out The half-peak breadth for penetrating face is 140 rads -200 rads, may be, for example, 140 rads, 145 rads, 148 rads, 150 rads, 155 jiaos Second, 160 rads, 165 rads, 170 rads, 175 rads, 180 rads, 182 rads, 185 rads, 195 rads or 200 rads Deng.
The third object of the present invention is to provide a kind of purposes of gallium nitride material as described above, the gallium nitride material It is used to prepare light emitting diode (Light-Emitting Diode, LED) and laser diode (Laser Diode, LD), preferably For gallium nitride material using the present invention, as substrate, growth material prepares light emitting diode or laser diode on it.By It is very high in the gallium nitride material crystal quality that the method for the invention is prepared, so being grown in gallium nitride material of the present invention The performance of device such as LED and LD on material also can be promoted effectively, such as anti-electric creepage performance and antistatic property obtain obviously Improve.
In the present invention, the technology of growth material is existing general technology on gallium nitride material, and those skilled in the art can root Prepared according to method disclosed in existing general technology, the material being grown in gallium nitride material substrate for example may include but It is not limited only to the combination of following any one or at least two materials, typical but non-limiting single layer can be：Gallium nitride material Material, mixes the gallium nitride material (GaN of Si:Si), the gallium nitride material (GaN of Mg is mixed:Mg), AlGaN material mixes the AlGaN materials of Si Expect (AlGaN:Si), the AlGaN material (AlGaN of Mg is mixed:Mg), InGaN materials mix the InGaN materials (InGaN of Si:Si), mix InGaN materials (the InGaN of Mg:Mg), AlGaInN materials mix the AlGaInN materials (AlGaInN of Si:Si), mix Mg's AlGaInN materials (AlGaInN:Mg) etc..The combination refers to that multilayer material is grown in successively in gallium nitride material substrate, described Multilayer can be several layers of, tens of layers or hundreds of layers, and each layer of material category can be the same or different, typical but unrestricted The combination of property can be：The combination that gallium nitride material and the gallium nitride material alternating growth for mixing Si are formed, mixes the gallium nitride material of Si The combination that material is formed with InGaN material alternating growths, the gallium nitride material for mixing Mg are formed with the AlGaN material alternating growth for mixing Mg Combination, above-mentioned single layer and combination enumerating and known in this field and unrequited, all only composition of LED or LD structures Part.
Compared with the prior art, the present invention has the advantages that：
(1) present invention by initial stage of growing gallium nitride material on a sapphire substrate be passed through the first metallorganic into Row pretreatment, plays the desorption for promoting sapphire surface oxygen atom, and in the effect of sapphire surface depositing metal atoms, Other than it can promote the desorption of Sapphire Substrate one layer of oxygen atom of most surface by catalytic action, it is often more important that Ke Yiji The earth improves the microstructure of the low temperature buffer layer of growth on substrate, to further greatly improve the nitridation of growth on it The crystal quality of gallium material can steadily obtain the gallium nitride film crystalline material of high-crystal quality；
(2) process window during the method for the invention makes subsequent growth gallium nitride material increases very much, after The thickness of the low temperature buffer layer of continuous growth increases to 10nm-50nm, annealing time by existing by the 20nm-35nm of existing general technology Have general technology -6 minutes 4 minutes increase to -15 minutes 0 minute, improve the operability in industrial production, make production item The severe of part reduces, and the gallium nitride material of high quality can be steadily grown, for plain film Grown on Sapphire Substrates The half-peak breadth of gallium nitride material, XRD (002) diffraction surfaces and (102) diffraction surfaces respectively can be down to 130 rads and 190 rads；It is right In the gallium nitride material grown on graphical sapphire substrate, the half-peak breadth point of XRD (002) diffraction surfaces and (102) diffraction surfaces It can not be down to 160 rads and 140 rads；
(3) performance of the LED and LD that are grown on gallium nitride material of the present invention such as tracking-resistant and antistatic Property has obtained very big promotion.
Description of the drawings
Fig. 1 (a) and Fig. 1 (b) is that the gallium nitride film material that the specific embodiment of the invention 1 obtains spreads out through X-ray respectively Penetrate the rocking curve of (002) diffraction surfaces and (102) diffraction surfaces of measurement；
Fig. 2 (a) and Fig. 2 (b) is that the gallium nitride film material that the specific embodiment of the invention 9 obtains spreads out through X-ray respectively Penetrate the rocking curve of (002) diffraction surfaces and (102) diffraction surfaces of measurement；
Fig. 3 (a) and Fig. 3 (b) is the gallium nitride film material that the specific embodiment of the invention 1 and comparative example 2 obtain respectively (002) diffraction surfaces through X-ray diffraction measurement and (102) diffraction surfaces rocking curve comparison diagram；
Fig. 4 (a) and Fig. 4 (b) is the gallium nitride film material that the specific embodiment of the invention 9 and comparative example 6 obtain respectively The rocking curve comparison diagram of (002) diffraction surfaces and (102) diffraction surfaces through X-ray diffraction measurement.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
(1) metal-organic chemical vapor deposition equipment (MOCVD) will be placed in as the plain film sapphire sheet of substrate used in growth Reative cell in graphite pallet on, in H2The temperature of graphite pallet is increased to 1000 DEG C under the atmospheric condition of flowing； Under conditions of 1000 DEG C, it is passed through trimethyl gallium (TMGa) into reative cell, and keep the temperature 5 minutes, completes to the pre- of sapphire surface Processing；
Typically, for the MOCVD reative cells that graphite support disk diameter is 540mm, the trimethyl of reative cell is brought by carrier gas The flow of gallium is 300 standard milliliters/minute (sccm), and the temperature of corresponding trimethyl gallium fluid supply bottle is 5 DEG C here, source bottle Pressure is 1300mbar.
(2) stop being passed through trimethyl gallium to reative cell, and graphite temperature of tray is reduced to 550 DEG C, then by anti- Room is answered to be passed through trimethyl gallium and ammonia (NH3), grow the nitride buffer layer of 30nm thickness in sapphire substrate surface；
(3) stop being passed through trimethyl gallium to reative cell, terminate growing gallium nitride buffer layer, still keep NH3The atmosphere of flowing Graphite temperature of tray is increased to 1000 DEG C, and keeps the temperature 4 minutes by condition, completes the annealing to gallium nitride low temperature buffer layer；
(4) start to be passed through trimethyl gallium to reative cell immediately, start growing gallium nitride, growth course under the conditions of 1000 DEG C It maintains 20 minutes；
(5) growth temperature is gradually increased to 1100 DEG C with 5 minutes, gallium nitride material is kept in this temperature-rise period Growth, subsequent growing gallium nitride at a temperature of 1100 DEG C；
(6) when the thickness of the gallium nitride film grown reaches 5 μm, stop being passed through trimethyl gallium to reative cell, terminate Growth, in NH3Under the atmosphere of flowing, the temperature of graphite pallet is reduced to room temperature, you can obtain growing on a sapphire substrate Gallium nitride film material.
The gallium nitride film material that growth obtains measures its crystal quality by X-ray diffraction, typical (002) diffraction The numerical value of face half-peak breadth is 150 ± 5 rads, and the numerical value of (102) diffraction surfaces half-peak breadth is 210 ± 5 rads.
Embodiment 2
In addition to step (1), other preparation conditions and method are same as Example 1.
The present embodiment (1) step is specific as follows：
It will be placed on the graphite pallet in the reative cell of MOCVD as the plain film sapphire sheet of substrate used in growth, in N2 The temperature of graphite pallet is increased to 800 DEG C under the atmospheric condition of flowing；Under conditions of 800 DEG C, three are passed through into reative cell Methyl gallium (TMGa), and 10 minutes are kept the temperature, complete the pretreatment to sapphire surface；
The gallium nitride film material that growth obtains measures its crystal quality by X-ray diffraction, (002) diffraction surfaces half-peak Wide numerical value is 150 ± 5 rads, and the numerical value of (102) diffraction surfaces half-peak breadth is 210 ± 5 rads.
Embodiment 3
In addition to step (1), other preparation conditions and method are same as Example 1.
The present embodiment (1) step is specific as follows：
It will be placed on the graphite pallet in the reative cell of MOCVD as the plain film sapphire sheet of substrate used in growth, in H2 The temperature of graphite pallet is increased to 1200 DEG C under the atmospheric condition of flowing；Under conditions of 1200 DEG C, it is passed through into reative cell Trimethyl gallium (TMGa), and 2 minutes are kept the temperature, complete the pretreatment to sapphire surface；
The gallium nitride film material that growth obtains measures its crystal quality by X-ray diffraction, (002) diffraction surfaces half-peak Wide numerical value is 150 ± 5 rads, and the numerical value of (102) diffraction surfaces half-peak breadth is 210 ± 5 rads.
Embodiment 4
In addition to the soaking time of step (1) became 15 minutes from 5 minutes, other preparation methods and condition and 1 phase of embodiment Together.
The gallium nitride film material that the present embodiment growth obtains measures its crystal quality by X-ray diffraction, and (002) spreads out The numerical value for penetrating face half-peak breadth is 150 ± 5 rads, and the numerical value of (102) diffraction surfaces half-peak breadth is 210 ± 5 rads.
By embodiment 1 and embodiment 4 it is found that being passed through metallorganic during heating plain film Sapphire Substrate, The process window of the soaking time of step (1) is prodigious, and soaking time is and to control it under conditions of 5 minutes and 15 minutes The gallium nitride material of high quality can be prepared in the condition of his step.
Embodiment 5
In addition to the thickness of nitride buffer layer in step (2) is 20nm, other preparation conditions and method and 1 phase of embodiment Together.
The gallium nitride film material obtained is grown, the exemplary value of (002) diffraction surfaces half-peak breadth also can reach 150 ± 5 jiaos Second, the exemplary value of (102) diffraction surfaces half-peak breadth also can reach 210 ± 5 rads.
Embodiment 6
In addition to the thickness of nitride buffer layer in step (2) is 40nm, other preparation conditions and method and 1 phase of embodiment Together.
The gallium nitride film material obtained is grown, the exemplary value of (002) diffraction surfaces half-peak breadth also can reach 150 ± 5 jiaos Second, the exemplary value of (102) diffraction surfaces half-peak breadth also can reach 210 ± 5 rads.
Embodiment 7
In addition to keeping the temperature 2 minutes after being increased to 1000 DEG C in step (3), other preparation conditions and method are same as Example 1.
The gallium nitride film material obtained is grown, the exemplary value of (002) diffraction surfaces half-peak breadth also can reach 150 ± 5 jiaos Second, the exemplary value of (102) diffraction surfaces half-peak breadth also can reach 210 ± 5 rads.
Embodiment 8
In addition to keeping the temperature 6 minutes after being increased to 1000 DEG C in step (3), other preparation conditions and method are same as Example 1.
The gallium nitride film material obtained is grown, the exemplary value of (002) diffraction surfaces half-peak breadth also can reach 150 ± 5 jiaos Second, the exemplary value of (102) diffraction surfaces half-peak breadth also can reach 210 ± 5 rads.
It can be seen that using method of the present invention by embodiment 1-8, during two-step method growing gallium nitride, The good gallium nitride film material of crystal quality is still can get in larger process window, low temperature can substantially be expanded by embodying the present invention The process window of the growth of buffer layer and the annealing process that heats up.
Embodiment 9
In addition to the substrate used in the step (1) is graphical sapphire substrate, other preparation conditions and method and embodiment 1 It is identical.
The gallium nitride film material obtained is grown, the exemplary value of (002) diffraction surfaces half-peak breadth can reach 180 ± 5 rads, (102) exemplary value of diffraction surfaces half-peak breadth can reach 160 ± 5 rads.
Embodiment 10
Except in step (1) to reative cell simultaneously be passed through metal organic source trimethyl gallium (TMGa) and trimethyl aluminium (TMAl) Outside, other preparation conditions and method are same as Example 1.
The gallium nitride film material obtained is grown, the exemplary value of (002) diffraction surfaces half-peak breadth also can reach 150 ± 5 jiaos Second, the exemplary value of (102) diffraction surfaces half-peak breadth also can reach 210 ± 5 rads.
Embodiment 11
Except in step (2) when low temperature growth buffer layer, while the metal organic source being passed through to reative cell is trimethyl gallium (TMGa) and trimethyl aluminium (TMAl) outside, other preparation conditions and method are same as Example 1.
The gallium nitride film material obtained is grown, the exemplary value of (002) diffraction surfaces half-peak breadth also can reach 150 ± 5 jiaos Second, the exemplary value of (102) diffraction surfaces half-peak breadth also can reach 210 ± 5 rads.
Comparative example 1
In addition to step (1), other preparation methods and condition are same as Example 1.
Step (1) in this comparative example is as follows：
(1) it will be placed on the graphite pallet in the reative cell of MOCVD as the plain film sapphire sheet of substrate used in growth, H2The temperature of graphite pallet is increased to 1000 DEG C under the atmospheric condition of flowing, and is kept for 5 minutes.
It heats up in the type of the Sapphire Substrate used in this comparative example, MOCVD boards equipment, experimentation and when cooling The conditions such as rate keep same as Example 1.
The gallium nitride film material that acquisition is grown in this comparative example measures its crystal quality by X-ray diffraction, (002) The numerical value of diffraction surfaces half-peak breadth is 240 ± 5 rads, and the numerical value of (102) diffraction surfaces half-peak breadth is 330 ± 5 rads.
It is compared the XRD it is found that the gallium nitride film material that comparative example 1 obtains by comparative example 1 and embodiment 1 (002) diffraction surfaces half-peak breadth is 240 ± 5 rads, XRD (002) the diffraction surfaces half-peak for the gallium nitride film material that embodiment 1 obtains Width is 150 ± 5 rads；XRD (102) the diffraction surfaces half-peak breadth for the gallium nitride film material that comparative example 1 obtains is 330 ± 5 rads, XRD (102) the diffraction surfaces half-peak breadth for the gallium nitride film material that embodiment 1 obtains is 210 ± 5 rads.It can be obtained by comparison Go out to be passed through metallorganic trimethyl gallium during heating plain film Sapphire Substrate and pre-processed, can improve in plain film The crystal quality for the gallium nitride film material that Grown on Sapphire Substrates obtains.
Comparative example 2
In addition to the retention time became 15 minutes from 5 minutes in step (1), other preparation methods and condition and 1 phase of comparative example Together.
The gallium nitride film material that the growth of this comparative example obtains measures its crystal quality by X-ray diffraction, and (002) spreads out The numerical value for penetrating face half-peak breadth is 210 ± 5 rads, and the numerical value of (102) diffraction surfaces half-peak breadth is 300 ± 5 rads.
By comparative example 2 it is found that the soaking time of step (1) was extended to 15 minutes from 5 minutes compared with comparative example 1, The crystal quality for the gallium nitride film material that can be improved.
It is organic compared with embodiment 4 it is found that during heating plain film Sapphire Substrate it to be passed through metal by comparative example 2 Object trimethyl gallium is pre-processed, and the crystal of the gallium nitride film material obtained in plain film Grown on Sapphire Substrates can be improved Quality.
Comparative example 3
In addition to the thickness of nitride buffer layer in step (2) is 20nm, other preparation conditions and method and 2 phase of comparative example Together.
The gallium nitride film material that growth obtains measures its crystal quality by X-ray diffraction, (002) diffraction surfaces half-peak Wide numerical value is 250 ± 5 rads, and the numerical value of (102) diffraction surfaces half-peak breadth is 330 ± 5 rads.
Comparative example 4
In addition to the thickness of nitride buffer layer in step (2) is 40nm, other preparation conditions and method and 2 phase of comparative example Together.
The gallium nitride film material that growth obtains measures its crystal quality by X-ray diffraction, (002) diffraction surfaces half-peak Wide numerical value is 240 ± 5 rads, and the numerical value of (102) diffraction surfaces half-peak breadth is 350 ± 5 rads.
By comparative example 3-4 as can be seen that the two-step growth method using existing general technology grows nitrogen compared with comparative example 2 When changing gallium, process window is small, harsh to the thickness requirement of nitride buffer layer, the gallium nitride film that thickness change can cause The quality of material declines.
Comparative example 5
In addition to keeping the temperature 2 minutes after being increased to 1000 DEG C in step (3), other preparation conditions and method are identical as comparative example 2.
The gallium nitride film material that growth obtains measures its crystal quality by X-ray diffraction, (002) diffraction surfaces half-peak Wide numerical value is 250 ± 5 rads, and the numerical value of (102) diffraction surfaces half-peak breadth is 350 ± 5 rads.
By comparative example 5 as can be seen that the two-step growth method using existing general technology grows nitridation compared with comparative example 2 When gallium, process window is small, requires harsh to being increased to the soaking time after required temperature in step (3), time change can cause The quality of obtained gallium nitride film material declines.
Comparative example 6
In addition to the substrate used in the step (1) is graphical sapphire substrate, other preparation conditions and method and comparative example 2 It is identical.
The gallium nitride film material that growth obtains measures its crystal quality by X-ray diffraction, (002) diffraction surfaces half-peak Wide numerical value is 230 ± 5 rads, and the numerical value of (102) diffraction surfaces half-peak breadth is 230 ± 5 rads.
It is compared the nitridation it is found that for being grown on graphical sapphire substrate by comparative example 6 and embodiment 9 Gallium thin-film material, during heating pattern Sapphire Substrate being passed through metallorganic trimethyl gallium is pre-processed, can To improve the crystal quality of the gallium nitride film material grown on graphical sapphire substrate.
The present invention is can be seen that by growing nitridation on a sapphire substrate by embodiment 1-11 and comparative example 1-6 The initial stage of gallium material is passed through metallorganic, realizes the pretreatment of sapphire surface, greatly improves the nitrogen of growth on it The quality for changing gallium thin-film material crystal, can steadily obtain the gallium nitride film material of high-crystal quality, be served as a contrast in plain film sapphire XRD (002) diffraction surfaces of the gallium nitride film material grown on bottom and the half-peak breadth of (102) diffraction surfaces be respectively 130 rads- 190 rads and 190 rads -250 rads；XRD (002) diffraction of the gallium nitride film material grown on graphical sapphire substrate The half-peak breadth of face and (102) diffraction surfaces is respectively 160 rads -220 rads and 140 rads -200 rads, and of the present invention Method can increase the process window of each step during subsequent two-step growth method, and can be than existing general technology bigger The gallium nitride film material of high quality is steadily grown under the conditions of process window.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.

Claims (29)

1. a kind of method of the material of growing gallium nitride on a sapphire substrate, which is characterized in that the described method comprises the following steps：
Sapphire Substrate is placed in reative cell by S0, heats Sapphire Substrate, first is passed through to reative cell during heating Metallorganic is pre-processed；
Growing gallium nitride, acquisition are grown on the gallium nitride material in Sapphire Substrate to S1 on a sapphire substrate；
The growing gallium nitride on a sapphire substrate specifically includes：S1-1 is passed through when step S0 is cooled to the first temperature Two metallorganics and nitrogen source gas, on substrate grown buffer layer；
S1-2 stoppings are passed through the second metallorganic, are still connected with nitrogen source gas, Sapphire Substrate is warming up to second temperature and is protected Temperature makes annealing treatment buffer layer；
S1-3 adjusts temperature to third temperature, then passes to third metallorganic, keeps the temperature, growing gallium nitride；
S1-4 is warming up to the 4th temperature, heat preservation, continued growth gallium nitride, obtains gallium nitride material, stopping, which is passed through third metal, to be had Machine object；
Wherein, from during third temperature is warming up to the 4th temperature, keeping being passed through for third metallorganic, or stop the Three metallorganics are passed through and restore being passed through for third metallorganic when being warming up to four temperature；
It is not passed through nitrogen source gas in the S0 steps.
2. according to the method described in claim 1, it is characterized in that, the process of the heating Sapphire Substrate includes heating rank Section, holding stage and temperature-fall period.
3. according to the method described in claim 2, it is characterized in that, the temperature of the holding stage be 800 DEG C -1200 DEG C, institute The time for stating holding stage is -30 minutes 30 seconds.
4. according to the method described in claim 1, it is characterized in that, starting the first metal during heating Sapphire Substrate Organic matter is passed through, and terminates being passed through for the first metallorganic during heating Sapphire Substrate.
5. according to the method described in claim 2, it is characterized in that, to be passed through the first metal when the holding stage starts organic Object, and end is passed through the first metallorganic at the end of holding stage.
6. according to the method described in claim 1, it is characterized in that, first metallorganic is containing in aluminium, gallium or indium The metallo-organic compound of any one or at least two elements.
7. according to the method described in claim 1, it is characterized in that, first temperature is 500 DEG C -600 DEG C.
8. according to the method described in claim 1, it is characterized in that, the thickness of the buffer layer is 10nm-50nm.
9. according to the method described in claim 1, it is characterized in that, the second temperature is 900 DEG C -1100 DEG C.
10. according to the method described in claim 1, it is characterized in that, the time kept the temperature described in S1-2 is -15 minutes 0 minute.
11. according to the method described in claim 10, it is characterized in that, the time kept the temperature described in S1-2 is -8 minutes 1 minute.
12. according to the method described in claim 1, it is characterized in that, the third temperature is 900 DEG C -1100 DEG C.
13. according to the method for claim 12, which is characterized in that the third temperature is 950 DEG C -1050 DEG C.
14. according to the method described in claim 1, it is characterized in that, the time kept the temperature described in S1-3 is -90 minutes 5 minutes.
15. according to the method for claim 14, which is characterized in that the time kept the temperature described in S1-3 be 10 minutes -30 points Clock.
16. according to the method for claim 15, which is characterized in that the time kept the temperature described in S1-3 is 20 minutes.
17. according to the method described in claim 1, it is characterized in that, the 4th temperature is 1000 DEG C -1200 DEG C.
18. according to the method for claim 17, which is characterized in that the 4th temperature is 1050 DEG C -1150 DEG C.
19. according to the method described in claim 1, it is characterized in that, the time kept the temperature described in S1-4 be 20 minutes -60 points Clock.
20. according to the method for claim 19, which is characterized in that the time kept the temperature described in S1-4 is 40 minutes.
21. according to the method described in claim 1, it is characterized in that, the thickness of the gallium nitride material is 3 μm -6 μm.
22. according to the method described in claim 1, it is characterized in that, second metallorganic is trimethyl aluminium, trimethyl In gallium or triethyl-gallium any one or at least two mixture.
23. according to the method described in claim 1, it is characterized in that, the third metallorganic is trimethyl gallium and/or three Ethyl gallium.
24. according to claim 1-23 any one of them methods, which is characterized in that reative cell is logical during step S0 and S1 There is purge gas, to maintain reative cell flow field.
25. according to the method for claim 24, which is characterized in that the purge gas be hydrogen, nitrogen, helium, neon, In argon gas, Krypton or xenon any one or at least two mixed gas.
26. according to the method for claim 25, which is characterized in that the purge gas is hydrogen, nitrogen or hydrogen and nitrogen The mixed gas of gas.
27. according to claim 1-23 any one of them methods, which is characterized in that the described method comprises the following steps：
Sapphire Substrate is placed in metal organic chemical vapour phase deposition reaction chamber by S0, in H2Atmosphere item as purge gas Under part, trimethyl gallium is passed through when holding stage starts, and stopping is passed through trimethyl gallium, the heat preservation at the end of holding stage The temperature in stage is 1000 DEG C, and the time of the holding stage is 8 minutes；
S1-1 is passed through trimethyl gallium and ammonia, grows on substrate when step S0 is cooled to 500 DEG C -600 DEG C of the first temperature The buffer layer of 20nm-40nm thickness；
S1-2 stoppings are passed through trimethyl gallium, are still connected with ammonia, and Sapphire Substrate is warming up to 1100 DEG C of second temperature and keeps the temperature 1 point Clock -8 minutes completes the annealing to buffer layer；
S1-3 reduces the temperature to 1000 DEG C of third temperature, is passed through trimethyl gallium, keeps the temperature 20 minutes, growing gallium nitride；
S1-4 is increased to 1100 DEG C of the 4th temperature, keeps the temperature 40 minutes, continued growth gallium nitride obtains the nitridation of 3 μm of -6 μ m thick Gallium material, stopping are passed through trimethyl gallium.
28. a kind of gallium nitride being grown in Sapphire Substrate being prepared using any one of claim 1-23 the methods Material, which is characterized in that XRD (002) diffraction surfaces and (102) diffraction of the gallium nitride material grown on a sapphire substrate The half-peak breadth in face is respectively 130 rads -190 rads and 190 rads -250 rads；The nitridation grown on graphical sapphire substrate XRD (002) diffraction surfaces of gallium material and the half-peak breadth of (102) diffraction surfaces are respectively 160 rads -220 rads and 140 rad -200 Rad.
29. a kind of purposes of gallium nitride material as claimed in claim 28, which is characterized in that using the gallium nitride material as Substrate on it growth material and prepare Light-emitting diode LED or laser diode LD.
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Publication number Priority date Publication date Assignee Title
CN108807609B (en) * 2018-05-03 2020-07-14 五邑大学 Preparation method of metal nanoparticle modified patterned substrate L ED
CN108878273A (en) * 2018-06-27 2018-11-23 潍坊华光光电子有限公司 A kind of solid-state expansion zinc method of GaAs base epitaxial wafer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1618116A (en) * 2000-08-18 2005-05-18 昭和电工株式会社 Method of fabricating group-III nitride semiconductor crystal, method of fabricating gallium nitride-based compound semiconductor, gallium nitride-based compound semiconductor, gallium nitride-based c
CN1639393A (en) * 2002-02-15 2005-07-13 昭和电工株式会社 Group III nitride semiconductor crystal, production method thereof and group III nitride semiconductor epitaxial wafer
CN101180420A (en) * 2005-04-04 2008-05-14 东北技术使者株式会社 Method for growth of GaN single crystal, method for preparation of GaN substrate, process for producing GaN-based element, and GaN-based element
CN101663413A (en) * 2007-02-22 2010-03-03 摩赛科结晶公司 Group-iii metal nitride and preparation thereof
CN102925968A (en) * 2012-10-17 2013-02-13 中国电子科技集团公司第五十五研究所 Strain control method of nitride single crystal thin film
CN104347761A (en) * 2013-08-06 2015-02-11 甘志银 Crystal quality-controllable GaN thin film epitaxial growth method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6563144B2 (en) * 1999-09-01 2003-05-13 The Regents Of The University Of California Process for growing epitaxial gallium nitride and composite wafers
JP4396816B2 (en) * 2003-10-17 2010-01-13 日立電線株式会社 Group III nitride semiconductor substrate and manufacturing method thereof
US20060175681A1 (en) * 2005-02-08 2006-08-10 Jing Li Method to grow III-nitride materials using no buffer layer
US7491626B2 (en) * 2005-06-20 2009-02-17 Sensor Electronic Technology, Inc. Layer growth using metal film and/or islands
KR101762177B1 (en) * 2010-12-17 2017-07-27 삼성전자 주식회사 Semiconductor device and method of manufacturing the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1618116A (en) * 2000-08-18 2005-05-18 昭和电工株式会社 Method of fabricating group-III nitride semiconductor crystal, method of fabricating gallium nitride-based compound semiconductor, gallium nitride-based compound semiconductor, gallium nitride-based c
CN1639393A (en) * 2002-02-15 2005-07-13 昭和电工株式会社 Group III nitride semiconductor crystal, production method thereof and group III nitride semiconductor epitaxial wafer
CN101180420A (en) * 2005-04-04 2008-05-14 东北技术使者株式会社 Method for growth of GaN single crystal, method for preparation of GaN substrate, process for producing GaN-based element, and GaN-based element
CN101663413A (en) * 2007-02-22 2010-03-03 摩赛科结晶公司 Group-iii metal nitride and preparation thereof
CN102925968A (en) * 2012-10-17 2013-02-13 中国电子科技集团公司第五十五研究所 Strain control method of nitride single crystal thin film
CN104347761A (en) * 2013-08-06 2015-02-11 甘志银 Crystal quality-controllable GaN thin film epitaxial growth method

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Denomination of invention: A method for growing gallium nitride materials on sapphire substrates, gallium nitride materials and their applications

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