CN107628637A - A kind of method for preparing III oxide and nitride nano post - Google Patents
A kind of method for preparing III oxide and nitride nano post Download PDFInfo
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- CN107628637A CN107628637A CN201710691388.8A CN201710691388A CN107628637A CN 107628637 A CN107628637 A CN 107628637A CN 201710691388 A CN201710691388 A CN 201710691388A CN 107628637 A CN107628637 A CN 107628637A
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Abstract
One kind, with Hydrothermal Growth III oxide and nitride nano post oldered array, comprises the following steps that on substrate：By III nitrate or chloride (such as Ga (NO3)3·nH2O) it is dissolved in deionized water and obtains certain X3+The solution of concentration；Alkaline matter or surface reactive material are added, regulation pH value is between 6.5 9；Substrate and solution are put into the autoclave with polytetrafluoroethyllining lining；By autoclave at a temperature of 85 150 DEG C heating water bath, the reaction time is if necessary between 2 10h.After the completion of question response, substrate is taken out, drying is washed with deionized；Substrate is placed in high temperature process furnances under air or oxygen atmosphere and annealed certain time (1 10h), 800 1000 DEG C of temperature range；Through said process, the III oxidate nano post oldered array with certain draw ratio and Density Distribution can be obtained by controlling process conditions, i.e., on substrate；III X is Ga, In or Al；Substrate includes sapphire or silicon substrate.
Description
Technical field
Gallium oxide nano-pillar oldered array is prepared using hydro-thermal method the present invention relates to a kind of, and nitrogenizes and forms gallium nitride nanometer
The method and technique of post oldered array.
Background technology
III-V nitride material (also known as GaN base material) based on GaN and InGaN, AlGaN alloy material is near
In the past few years valued novel semiconductor material again in the world.GaN base material is direct band gap semiconductor material with wide forbidden band, is had
The direct band gap of continuous variable between 1.9-6.2eV, excellent physics, chemical stability, high saturated electron drift velocity are high
The superior function such as disruptive field intensity and high heat conductance, in short wavelength's semiconductor photoelectronic device and high frequency, high pressure, high temperature microelectronics device
Part prepare etc. there is important application, for manufacture such as indigo plant, purple, ultraviolet band luminescent device, sensitive detection parts, high temperature,
High frequency, High-Field high power device, feds, radioresistance device, piezoelectric device etc..
The growth of GaN base material has a variety of methods, as gas phase epitaxy of metal organic compound (MOCVD), HTHP synthesize
Body GaN single crystal, molecular beam epitaxy (MBE), sublimed method and hydride gas-phase epitaxy (HVPE) etc..Due to GaN base material in itself
The limitation of physical property, the growth of GaN body monocrystalline has very big difficulty, not yet practical.Hydride gas-phase epitaxy is due to tool
There are high growth rate and horizontal-longitudinal extension ratio, available for isoepitaxial growth Free-standing GaN substrate, cause and widely pay attention to
And research.The outstanding advantages of this method are that GaN growth speed is very high, general up to tens Dao thousands of micro- ms/h.And in epitaxial layer
Dislocation density low 1-2 order of magnitude compared with other method, the dislocation densities of general direct HVPE epitaxial layers is up to 108cm-2Left and right.
Further research can preferably reduce the dislocation density in epitaxial layer.Using hydride gas-phase epitaxy (HVPE) method blue precious
Direct high-speed growth GaN thick-film materials on stone lining bottom, then separated except foreign substrate, obtain GaN substrate material.So far
Untill, using various technical matters and it is aided with the Free-standing GaN substrate that HVPE grows to obtain, dislocation density is less than 106cm-2, face
Product has reached 2 inches.But can not still far meet the needs of practical application.
Because GaN can only be grown in foreign substrate such as on sapphire, silicon substrate, lattice mismatch and thermal mismatching cause GaN
There is big stress inside film, it is difficult to improve to cause GaN base device performance.In addition, huge stress can cause GaN thick films and
Foreign substrate splinter, thus can not apply.Therefore the stress in GaN thick films is reduced or eliminated, is effective performance GaN materials
Expect the important solution method of potential.Various nanometer structure inserted layers are first prepared before HVPE thick film epitaxial growths, can be used for dropping
Stress in low HVPE-GaN thick films.But existing III-group nitride nano-structure such as GaN nano-pillars oldered array etc., one
As be high using the growth of the low pressure method such as gas phase process such as MOCVD, MBE, complex process, cost of material.
The present invention gives prepare III oxidate nano post array, frequent pressure using simple, low cost hydro-thermal method
Nitridation obtains nitride nano post array.Particularly for extension again, hydride gas-phase epitaxy (HVPE) growth GaN is reduced
The method and technique of stress and acquisition self-supporting GaN substrate in thin-film material.
The content of the invention
The present invention seeks to：The present invention proposes the Hydrothermal Growth III oxidate nano post using simple low cost
Oldered array, it is nitrogenized by ammonia atmosphere to obtain the method for group III-nitride nano-pillar oldered array.Especially growth can
For extension again, hydride gas-phase epitaxy (HVPE) growth GaN film material is reduced.Existing group III-nitride nano junction
Structure such as GaN nano-pillars oldered array etc., usually grown using low pressure methods such as gas phase process such as MOCVD, MBE, complex process,
Cost of material is high.
The technical scheme is that：One kind uses Hydrothermal Growth III oxide and nitrogen on substrate (sapphire or silicon)
Compound nano-pillar oldered array, it is characterized in that comprising the following steps that：By III nitrate or chloride (such as Ga (NO3)3·
nH2O) it is dissolved in deionized water and obtains certain X3+The solution of concentration；Alkaline matter or surface reactive material are added, adjusts pH value
Between 6.5-9；Substrate and solution are put into the autoclave with polytetrafluoroethyllining lining；By autoclave at 85-150 DEG C
At a temperature of heating water bath, the reaction time is if necessary between 2-10h.After the completion of question response, substrate is taken out, is washed with deionized water
Wash drying；Substrate is placed in high temperature process furnances under air or oxygen atmosphere and annealed certain time (1-10h), temperature range 800-
1000℃；Through said process, it can obtain that there is certain draw ratio and Density Distribution by controlling process conditions, i.e., on substrate
III oxidate nano post oldered array；III X is Ga, In or Al.Substrate includes sapphire or silicon substrate.Nano-pillar
Length is typically in 100-1000nm.
Adjust above-mentioned technological parameter such as temperature, time and ammonia flow etc., obtain nitride cladding oxidation during partial nitridation
Thing is XN@X2O3The nano-pillar oldered array of core shell structure；Above-mentioned technological parameter such as temperature, time and ammonia flow etc. are adjusted, entirely
Portion obtains nitride XN nano-pillar oldered arrays when nitrogenizing.
Nano-pillar draw ratio and density are relevant with the pH value of X ion concentrations and solution, nano-pillar draw ratio (general 1-10)
It is directly proportional to X ion concentrations with the density of growth, it is also relevant with the pH value of solution.
It is oxide coated that nitride is formed to oxidate nano post progress partial nitridation or all nitridation in ammonia atmosphere
That is XN@X2O3Or nitride XN nano-pillar oldered arrays；III X is Ga, In or Al；Nitridation III oxidate nano post has
The method that sequence array forms nitride nano post oldered array, III oxidate nano post array prepared by hydro-thermal method is placed in
In high temperature process furnances, annealed certain time under ammonia atmosphere, specified temp, the nitride nano partly or entirely nitrogenized
Post oldered array.Adjusting process parameter such as temperature, time and ammonia flow etc., it is oxide coated that nitride is obtained during partial nitridation
That is XN@X2O3The nano-pillar oldered array of core shell structure；Adjusting process parameter such as temperature, time and ammonia flow etc., can whole nitrogen
Nitride XN nano-pillar oldered arrays are obtained during change；Ammonia flow：100-5000sccm, temperature：500-1500 DEG C, nitridation annealing
Time：0.5-5h.X=Ga, In or Al；During X=Ga, nitriding temperature is 800-1100 DEG C；During X=In, nitriding temperature is generally
500-750℃；During X=Al, nitriding temperature is 900-1500 DEG C.Control ammonia atmosphere flow, temperature and time, it is possible to control
It is that oxide is nitrided into nitride, or partial nitridation completely, it is nitride to form outer layer, and inside is still the nucleocapsid of oxide
Structure.The control of nitriding process condition will not typically change original oxidate nano post.
Present invention has the advantages that：The present invention gives it is a kind of simple, that low cost obtains group III-nitride nano-pillar is orderly
The methods and techniques of array.
Brief description of the drawings
Fig. 1 is the technology of the present invention implementation route schematic diagram.
Fig. 2 is schematic diagram of the embodiment of the present invention, gallium oxide nano-pillar prepared by hydro-thermal method.(a), (b), (c), (d) difference
Four different magnification ratios are corresponded to.
Embodiment
The inventive method and technique mainly include two parts：Hydro-thermal method prepares III (mainly gallium or indium) oxide and received
Rice post oldered array；Oxidate nano post array nitrogenizes to form nitride nano post array, sees Fig. 1.
By III nitrate or chloride etc. such as Ga (NO3)3·nH2O, which is dissolved in deionized water, obtains certain X3+It is dense
The solution of degree；Alkaline matter or surface reactive material are added, regulation pH value is between 6.5-9.Substrate and solution are put into tool
Have in the autoclave of polytetrafluoroethyllining lining, packing ratio 80%.By autoclave heating water bath (85-150 at a certain temperature
DEG C), the reaction time is if necessary between 2-10h.After the completion of question response, substrate is taken out, drying is washed with deionized.Will lining
Bottom is placed in high temperature process furnances and annealed certain time (1-10h) under air or oxygen atmosphere, 800-1000 DEG C of temperature range.It is oxygen-containing
Ambiance annealing is advantageous to improve the quality of oxide.Through said process, by controlling process conditions, i.e., can obtain on substrate
III oxidate nano post oldered array with certain draw ratio and Density Distribution.
The method that III oxidate nano post oldered array forms nitride nano post oldered array is nitrogenized, by hydro-thermal method
The III oxidate nano post array of preparation is placed in high temperature process furnances, a timing of being annealed under ammonia atmosphere, specified temp
Between, the nitride nano post oldered array that can partly or entirely be nitrogenized.Adjusting process parameter such as temperature, time and ammonia
Flow etc., XN@X are obtained during partial nitridation2O3The nano-pillar oldered array of core shell structure；Adjusting process parameter such as temperature, time and
Ammonia flow etc., all obtain XN nano-pillar oldered arrays during nitridation.Ammonia flow：100-5000sccm, temperature：500-1500
DEG C, nitrogenize annealing time：0.5-5h.X=Ga, In or Al.During X=Ga, nitriding temperature is generally 800-1100 DEG C；During X=In,
Nitriding temperature is generally 500-750 DEG C；During X=Al, nitriding temperature is generally 900-1500 DEG C.
The technology of the present invention embodiment：
1st, the cleaning and processing of substrate (sapphire or silicon chip).
2nd, the solution of certain group-III element concentration and pH value is configured.Such as：In the present embodiment, by Ga (NO3)3NH2O dissolves
Cause Ga in deionized water3+Concentration is that 0.01-0.05mol/L is gallium source, is continuously added hexa powder by solution
PH is adjusted to 6.7.
3rd, substrate and above-mentioned solution are put into autoclave, at a certain temperature heating water bath, you can aoxidized
Gallium nano-pillar oldered array.In the present embodiment, substrate and solution are put into the autoclave with polytetrafluoroethyllining lining, filled out
It is 80% to fill than (solution accounts for the volume ratio of autoclave liner volume).Heating water bath is in 95 DEG C of reaction 5h of reaction temperature.React
Cheng Hou, substrate is taken out, drying is washed with deionized.Then substrate is placed in high temperature process furnances, in air or oxygen gas
Under atmosphere, 900 DEG C of annealing 5h.Gallium oxide nano-pillar is shown in Fig. 2.
4th, the sample in step 3 is put into high temperature process furnances and carries out the high temperature anneal.Parameter：Temperature 800-1100
DEG C, hour time 1-10；Atmosphere is ammonia or ammonia nitrogen mixed gas, flow 500-5000sccm.It is fast after the completion of annealing
Speed is passed through nitrogen to empty ammonia, and sample is taken out after room temperature is cooled to.
Those of ordinary skills in the art should understand that：The specific embodiment of the present invention is the foregoing is only, and
The limitation present invention is not used in, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc.,
It should be included within protection scope of the present invention.
Claims (2)
1. one kind uses Hydrothermal Growth III oxide and nitride nano post oldered array on substrate, it is characterized in that specifically
Step is as follows：By III nitrate or chloride (such as Ga (NO3)3·nH2O) it is dissolved in deionized water and obtains certain X3+It is dense
The solution of degree；Alkaline matter or surface reactive material are added, regulation pH value is between 6.5-9；Substrate and solution are put into tool
Have in the autoclave of polytetrafluoroethyllining lining；By autoclave at a temperature of 85-150 DEG C heating water bath, the reaction time if necessary in
Between 2-10h.After the completion of question response, substrate is taken out, drying is washed with deionized；It is hollow that substrate is placed in high temperature process furnances
Annealed under gas or oxygen atmosphere certain time (1-10h), 800-1000 DEG C of temperature range；Through said process, by controlling technique
Condition, i.e., the III oxidate nano post oldered array with certain draw ratio and Density Distribution can be obtained on substrate；III X
It is Ga, In or Al；Substrate includes sapphire or silicon substrate.
2. the method according to claim 1 for preparing III oxide and nitride nano post, it is characterized in that in ammonia gas
Partial nitridation is carried out in atmosphere to oxidate nano post or is all nitrogenized to form the oxide coated i.e. XN@X of nitride2O3Or nitridation
Thing XN nano-pillar oldered arrays；Nitrogenize the side that III oxidate nano post oldered array forms nitride nano post oldered array
Method, III oxidate nano post array prepared by hydro-thermal method is placed in high temperature process furnances, under ammonia atmosphere, specified temp
Anneal certain time, the nitride nano post oldered array partly or entirely nitrogenized；Ammonia flow：100-5000sccm,
Temperature：500-1500 DEG C, nitrogenize annealing time：0.5-5h；X=Ga, In or Al；During X=Ga, nitriding temperature 800-1100
℃；During X=In, nitriding temperature is generally 500-750 DEG C；During X=Al, nitriding temperature is 900-1500 DEG C.
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| JP2010006670A (en) * | 2008-06-30 | 2010-01-14 | National Univ Corp Shizuoka Univ | Nanowire structure and method for producing the same |
| CN106517109A (en) * | 2016-10-21 | 2017-03-22 | 南开大学 | A preparing method of gallium nitride nanorods |
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| CN101063225A (en) * | 2001-09-19 | 2007-10-31 | 住友电气工业株式会社 | Single crystal gan substrate, method of growing same and method of producing same |
| JP2010006670A (en) * | 2008-06-30 | 2010-01-14 | National Univ Corp Shizuoka Univ | Nanowire structure and method for producing the same |
| CN106517109A (en) * | 2016-10-21 | 2017-03-22 | 南开大学 | A preparing method of gallium nitride nanorods |
| CN206116446U (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | GaN nanometer post of growth on aluminic acid strontium tantalum lanthanum substrate |
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