CN103741220A - Method for growing high-quality gallium nitride (GaN) crystals by using graphene or graphene oxide - Google Patents
Method for growing high-quality gallium nitride (GaN) crystals by using graphene or graphene oxide Download PDFInfo
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- CN103741220A CN103741220A CN201410024654.8A CN201410024654A CN103741220A CN 103741220 A CN103741220 A CN 103741220A CN 201410024654 A CN201410024654 A CN 201410024654A CN 103741220 A CN103741220 A CN 103741220A
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Abstract
The invention relates to a method for growing high-quality gallium nitride (GaN) crystals by using graphene or graphene oxide. The method comprises the following steps: (1) preparing a graphene nanosheet dispersion solution with the concentration of 0.005-0.1mg/ml or a graphene oxide nanosheet dispersion solution with the concentration of 0.001-0.02mg/ml; (2) coating a substrate, which is used for preparing the GaN crystals, directly with the prepared graphene nanosheet dispersion solution or graphene oxide nanosheet dispersion solution, and drying for later use, wherein the drying method comprises the step of drying for 1-8 hours in a vacuum drying oven at the temperature of 80-200 DEG C; (3) putting the prepared substrate in a hydride vapor-phase epitaxy system, and carrying out epitaxial growth on the GaN crystals. According to the method, the dislocation density of GaN monocrystals is reduced, the quality of the GaN crystals is obviously improved, the GaN substrate with a special structure, prepared by complicated and expensive processes, is not required to be adopted, the process is simple, the cost is low, and the growth temperature is low, so that the method is applicable to mass production.
Description
Technical field
The present invention relates to a kind of growth method of utilizing Graphene or stannic oxide/graphene nano sheet two-dimensional material to obtain high-quality gallium nitride crystal, be intended to improve epitaxially grown GaN crystal mass, belong to gallium nitride crystal growth technical field.
Background technology
In recent years, Graphene and graphene oxide were more and more subject to people's attention with its distinctive excellent properties.Scientist both domestic and external is making great efforts its application in different field of developing.
The third generation semiconductor material that the gan (GaN) of take is representative, there is broad stopband width, the features such as high-breakdown-voltage, high electron mobility, stable chemical nature, are suitable for making radioprotective, high frequency, high-power and superintegrated electron device and indigo plant, green glow and ultraviolet photoelectron device.At aspects such as semiconductor light-emitting-diode (LED), laser diode (LD), ultraviolet detector and high energy high-frequency electron devices, have broad application prospects.Because gallium nitride single crystal growth is very difficult, cost is high, and owing to lacking gan body piece monocrystalline, therefore gallium nitride material is to be all often grown in foreign substrate as sapphire, silicon carbide and silicon etc. at present again.In foreign substrate, growing crystal needs the On The Nucleation between material substrate and epitaxial film; In addition, owing to there being the difference of lattice parameter and other physical propertiess between differing materials, cause lattice mismatch and thermal mismatching between substrate material and gallium nitride single crystal larger, in the GaN of extension single crystal growth process, can produce larger stress and higher dislocation desity, had a strong impact on the performance of gallium-nitride-based devices, the dislocation desity that therefore reduces gallium nitride single crystal is to prepare the prerequisite of high-quality GaN base device.
At present, the method that reduces the dislocation desity of hetero epitaxy GaN monocrystalline has following several: room assists partition method (Void-assisted separation) [referring to Y.Oshima, et al, phys.stat.sol. (a), 194 (2002) 554-558], epitaxial lateral overgrowth outgrowth method (ELOG) is [referring to H.H.Huang, et al, J.Cryst.Growth311 (2009) 3029 – 3032] and preparation nanostructure the methods such as substrate [referring to C.L.Chao, Appl.Phys.Lett.95 (2009) 051905].The quality that adopts these methods to grow GaN monocrystalline is all improved to some extent, and corresponding dislocation desity also has reducing to a certain degree, but these methods mostly need complicated photoetching process or growth technique.
Chinese patent literature CN102769081A discloses a kind of Graphene that utilizes as structure and the preparation method of buffer layer extension GaN, the method is by adopting graphene layer as the buffer layer between substrate and epitaxial layer of gallium nitride, between graphene layer and GaN layer, insert nitride thin layer, obtain low-stress, high-quality GaN epitaxial film.But the method operating process is complicated, and cost is high.
Summary of the invention
The present invention is directed to the existing problem of method of existing reduction GaN monocrystalline dislocation desity, a kind of method that provides utilization simple to operate, with low cost to scribble Graphene or stannic oxide/graphene nano sheet growing high-quality gallium nitride on substrate, the method utilizes hydride gas-phase epitaxy (HVPE) directly in part, to cover the Grown GaN monocrystalline of two-dimensional material.
The method of utilizing Graphene or graphene oxide growing high-quality gallium nitride of the present invention, after Graphene or graphene oxide are applied on substrate, obtain the substrate partly being covered by Graphene or graphene oxide, further on this substrate, carry out HVPE epitaxy GaN crystal; Specifically comprise the following steps:
(1) the graphene nanometer sheet dispersion liquid that compound concentration is 0.005-0.1mg/ml, or the concentration stannic oxide/graphene nano sheet dispersion liquid that is 0.001-0.02mg/ml; Graphene nanometer sheet dispersion liquid is that graphene nanometer sheet is dispersed in DMF (DMF) or N-Methyl pyrrolidone (NMP); Stannic oxide/graphene nano sheet dispersion liquid is that stannic oxide/graphene nano sheet is dispersed in ultrapure water;
The concentration of dispersion liquid should not be too large, otherwise Graphene or stannic oxide/graphene nano sheet will cover whole substrate, like this nucleation, growth and the quality that are unfavorable for GaN crystal improved.The preferred concentration of graphene nanometer sheet dispersion liquid is 0.01-0.05mg/ml.The preferred concentration of stannic oxide/graphene nano sheet dispersion liquid is 0.005-0.008mg/ml.
(2) the graphene nanometer sheet dispersion liquid preparing or stannic oxide/graphene nano sheet dispersion liquid are directly applied on the substrate for the preparation of GaN crystal, stand-by after drying, furnace drying method is 80 ℃ of-200 ℃ of dry 1-8 hour in vacuum drying oven;
Described substrate is that the substrate (2 microns-5 microns) of the gallium nitride film of growing on sapphire, silicon carbide or silicon chip by metal organic chemical vapor deposition technique (MOCVD) is thick, and the following stated " substrate " all refers to this substrate.
The distribution in Graphene or stannic oxide/graphene nano sheet dispersion liquid whole region on substrate should be tried one's best evenly, is conducive to like this raising of GaN crystal mass in subsequent step.
The temperature of selecting during oven dry will with for solvent phase adapt to, for high boiling solvent, selected temperature is higher, can do the high temperature anneal if desired.In step (2), for the preferred furnace drying method of graphene nanometer sheet dispersion liquid, be 120 ℃ of-180 ℃ of dry 2-4 hour in vacuum drying oven.For stannic oxide/graphene nano sheet dispersion liquid furnace drying method, be 40 ℃ of-120 ℃ of dry 1-8 hour in vacuum drying oven, preferred furnace drying method is 80 ℃ of-120 ℃ of dry 2-3 hour in vacuum drying oven.
(3) substrate preparing is put into hydride gas-phase epitaxy (HVPE) system and carried out GaN crystal epitaxy.
The present invention adopts in the GaN epitaxial thin-film layer of MOCVD growth and scribbles Graphene or graphene oxide two-dimensional material, obtained the substrate that part is exposed by nanometer sheet covering, subregion, the substrate partial action exposing is to provide nucleation and the growth in HVPE stage, the extension of dislocation has been blocked in capped region, thereby the dislocation desity that has reduced GaN monocrystalline, GaN crystal mass is significantly improved.The present invention is simple to operate, does not need the plant and instrument of complex and expensive, with low cost, and growth temperature low (1000 ℃-1050 ℃), is suitable for batch production.
Accompanying drawing explanation
Fig. 1 in the present invention is coated in graphene nanometer sheet the electron scanning micrograph on substrate.
Fig. 2 is coated in the electron scanning micrograph on substrate by stannic oxide/graphene nano sheet in the present invention.
Fig. 3 be the present invention obtain in the high resolution XRD figure that scribbles the Grown GaN crystal of graphene nanometer sheet, wherein the left side be GaN crystal along the diffraction peak of (002) face, the right is that GaN crystal is along the diffraction peak of (102) face.
Fig. 4 be the present invention obtain in the high resolution XRD figure that scribbles the Grown GaN crystal of stannic oxide/graphene nano sheet, wherein the left side be GaN crystal along the diffraction peak of (002) face, the right is that GaN crystal is along the diffraction peak of (102) face.
Embodiment
Embodiment 1
(1) dispersion liquid of compound concentration 0.05mg/ml Graphene and N-Methyl pyrrolidone.
(2) substrate is placed on spin coating instrument, dropwise by Graphene and N-Methyl pyrrolidone dispersant liquid drop on substrate, after dispersion liquid is evenly distributed on substrate, on substrate, can see the film of skim.As shown in Figure 1.
(3) substrate in step (2) being put into 120 ℃ of vacuum drying ovens is dried after 4 hours, substrate is put into HVPE system epitaxy (process of growth is the same with existing GaN crystal epitaxy process), obtain at the GaN crystal that scribbles the Grown of graphene nanometer sheet, as shown in Figure 3.
Embodiment 2
The present embodiment difference from Example 1 is: the concentration of the Graphene of preparation and N-Methyl pyrrolidone dispersion liquid is 0.01mg/ml.Substrate in step (2) in vacuum drying oven 180 ℃ dry 2 hours.
Embodiment 3
(1) dispersion liquid of compound concentration 0.1mg/ml Graphene and DMF.
(2) substrate is placed on spin coating instrument, dropwise by Graphene and dimethyl formamide dispersant liquid drop on substrate, after dispersion liquid is evenly distributed on substrate, on substrate, can see the film of skim.
(3) substrate in step (2) is put into 160 ℃ of vacuum drying ovens and be dried after 4 hours, substrate is put into the epitaxy of HVPE system, obtain at the GaN crystal that scribbles the Grown of graphene nanometer sheet.
Embodiment 4
The present embodiment difference from Example 3 is: the concentration of the Graphene of preparation and DMF dispersion liquid is 0.005mg/ml.Substrate in step (2) in vacuum drying oven 80 ℃ dry 8 hours.
Embodiment 5
(1) dispersion liquid that compound concentration 0.08mg/ml Graphene mixes with N-Methyl pyrrolidone.
(2) with spray gun, joined solution is painted on substrate.On substrate, can see the film of skim.
(3) substrate in step (2) is put into 200 ℃ of vacuum drying ovens and be dried after 1 hour, substrate is put into the epitaxy of HVPE system, obtain at the GaN crystal that scribbles the Grown of graphene nanometer sheet
Embodiment 6
The present embodiment difference from Example 5 is: the concentration of the Graphene of preparation and N-Methyl pyrrolidone dispersion liquid is 0.01mg/ml.Substrate in step (2) in vacuum drying oven 200 ℃ dry 3 hours.
Embodiment 7
(1) dispersion liquid that compound concentration 0.1mg/ml Graphene mixes with dimethyl formamide.
(2) with spray gun, joined solution is painted on substrate.On substrate, can see the film of skim.
(3) substrate in step (2) is put into 160 ℃ of vacuum drying ovens and be dried after 4 hours, substrate is put into the epitaxy of HVPE system, obtain at the GaN crystal that scribbles the Grown of graphene nanometer sheet
Embodiment 8
The present embodiment difference from Example 3 is: the concentration of the Graphene of preparation and DMF dispersion liquid is 0.008mg/ml.Substrate in step (2) in vacuum drying oven 160 ℃ dry 2 hours.
Embodiment 9
(1) graphene oxide of compound concentration 0.02mg/ml and the dispersion liquid of ultrapure water.
(2) substrate is placed on spin coating instrument, dropwise by dispersant liquid drop on substrate, after dispersion liquid is evenly distributed on substrate, on substrate, can see the film of skim.As shown in Figure 2.
(3) substrate in step (2) is put into 120 ℃ of vacuum drying ovens and be dried after 5 hours, substrate is put into the epitaxy of HVPE system, obtain at the GaN crystal that scribbles the Grown of graphene oxide.As shown in Figure 4.
Embodiment 10
(1) graphene oxide of compound concentration 0.001mg/ml and the dispersion liquid of ultrapure water.
(2) substrate is placed on spin coating instrument, dropwise by dispersant liquid drop on substrate, after dispersion liquid is evenly distributed on substrate, on substrate, can see the film of skim.
(3) substrate in step (2) is put into 120 ℃ of vacuum drying ovens and be dried after 1 hour, substrate is put into the epitaxy of HVPE system, obtain at the GaN crystal that scribbles the Grown of graphene oxide.
Embodiment 11
(1) dispersion liquid that the graphene oxide of compound concentration 0.005mg/ml mixes with ultrapure water.
(2) joined dispersion liquid is painted on substrate, on substrate, can sees the film of skim.
(3) by the substrate in step (2) in vacuum drying oven 80 ℃ after dry 3 hours, substrate is put into the epitaxy of HVPE system, obtain at the GaN crystal that scribbles the Grown of graphene oxide.
Embodiment 12
(1) dispersion liquid that the graphene oxide of compound concentration 0.008mg/ml mixes with ultrapure water.
(2) joined dispersion liquid is painted on substrate, on substrate, can sees the film of skim.
(3) by the substrate in step (2) in vacuum drying oven 120 ℃ after dry 2 hours, substrate is put into the epitaxy of HVPE system, obtain at the GaN crystal that scribbles the Grown of graphene oxide.
Embodiment 13
(1) dispersion liquid that the graphene oxide of compound concentration 0.01mg/ml mixes with ultrapure water.
(2) joined dispersion liquid is painted on substrate.On substrate, can see the film of skim.
(3) by the substrate in step (2) in vacuum drying oven 40 ℃ after dry 8 hours, substrate is put into the epitaxy of HVPE system, obtain at the GaN crystal that scribbles the Grown of graphene oxide.
Embodiment 14
(1) dispersion liquid that the graphene oxide of compound concentration 0.015mg/ml mixes with ultrapure water.
(2) joined dispersion liquid is painted on substrate.On substrate, can see the film of skim.
(3) by the substrate in step (2) in vacuum drying oven 100 ℃ after dry 6 hours, substrate is put into the epitaxy of HVPE system, obtain at the GaN crystal that scribbles the Grown of graphene oxide.
Claims (6)
1. a method of utilizing Graphene or graphene oxide growing high-quality gallium nitride, is characterized in that, comprises the following steps:
(1) the graphene nanometer sheet dispersion liquid that compound concentration is 0.005-0.1mg/ml, or the concentration stannic oxide/graphene nano sheet dispersion liquid that is 0.001-0.02mg/ml; Graphene nanometer sheet dispersion liquid is that graphene nanometer sheet is dispersed in DMF or N-Methyl pyrrolidone; Stannic oxide/graphene nano sheet dispersion liquid is that stannic oxide/graphene nano sheet is dispersed in ultrapure water;
(2) the graphene nanometer sheet dispersion liquid preparing or stannic oxide/graphene nano sheet dispersion liquid are directly applied on the substrate for the preparation of GaN crystal, stand-by after drying, furnace drying method is 80 ℃ of-200 ℃ of dry 1-8 hour in vacuum drying oven;
(3) substrate preparing is put into hydride gas-phase epitaxy system and carry out GaN crystal epitaxy.
2. the method for utilizing Graphene or graphene oxide growing high-quality gallium nitride according to claim 1, is characterized in that, in described step (1), the concentration of graphene dispersing solution is 0.01-0.05mg/ml.
3. the method for utilizing Graphene or graphene oxide growing high-quality gallium nitride according to claim 1, is characterized in that, in described step (1), the preferred concentration of stannic oxide/graphene nano sheet dispersion liquid is 0.005-0.008mg/ml.
4. the method for utilizing Graphene growing high-quality gallium nitride according to claim 1, is characterized in that, in described step (2), for the preferred furnace drying method of graphene nanometer sheet dispersion liquid, is 120 ℃ of-180 ℃ of dry 2-4 hour in vacuum drying oven.
5. the method for utilizing Graphene or graphene oxide growing high-quality gallium nitride according to claim 1, it is characterized in that, be 40 ℃ of-120 ℃ of dry 1-8 hour in vacuum drying oven for stannic oxide/graphene nano sheet dispersion liquid furnace drying method in described step (2).
6. the method for utilizing Graphene or graphene oxide growing high-quality gallium nitride according to claim 1, it is characterized in that, be 80 ℃ of-120 ℃ of dry 2-3 hour in vacuum drying oven for stannic oxide/graphene nano sheet dispersion liquid furnace drying method in described step (2).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947071A (en) * | 2015-05-14 | 2015-09-30 | 天津理工大学 | Hierarchical GaN nano-array on graphene substrate as well as preparation method and application thereof |
| CN107808819A (en) * | 2017-09-27 | 2018-03-16 | 中国科学院长春光学精密机械与物理研究所 | A kind of liquid graphene is applied to the method for GaN base material and device |
| CN109841556A (en) * | 2017-11-28 | 2019-06-04 | 桦榆国际有限公司 | Silicon wafer bearing disk method for maintaining |
| CN113832546A (en) * | 2021-09-26 | 2021-12-24 | 齐鲁工业大学 | Method for growing gallium nitride single crystal by high-temperature heat treatment assisted two-dimensional coating mask substrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2634824A2 (en) * | 2010-10-26 | 2013-09-04 | LG Siltron Inc. | Compound semiconductor device and method for manufacturing same |
| CN103378223A (en) * | 2012-04-25 | 2013-10-30 | 清华大学 | Preparation method of epitaxial structure body |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2634824A2 (en) * | 2010-10-26 | 2013-09-04 | LG Siltron Inc. | Compound semiconductor device and method for manufacturing same |
| CN103378223A (en) * | 2012-04-25 | 2013-10-30 | 清华大学 | Preparation method of epitaxial structure body |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947071A (en) * | 2015-05-14 | 2015-09-30 | 天津理工大学 | Hierarchical GaN nano-array on graphene substrate as well as preparation method and application thereof |
| CN104947071B (en) * | 2015-05-14 | 2017-11-28 | 天津理工大学 | GaN nano-arrays and preparation method and application are classified on a kind of graphene substrate |
| CN107808819A (en) * | 2017-09-27 | 2018-03-16 | 中国科学院长春光学精密机械与物理研究所 | A kind of liquid graphene is applied to the method for GaN base material and device |
| CN109841556A (en) * | 2017-11-28 | 2019-06-04 | 桦榆国际有限公司 | Silicon wafer bearing disk method for maintaining |
| CN109841556B (en) * | 2017-11-28 | 2020-11-03 | 桦榆国际有限公司 | Method for maintaining wafer bearing plate |
| CN113832546A (en) * | 2021-09-26 | 2021-12-24 | 齐鲁工业大学 | Method for growing gallium nitride single crystal by high-temperature heat treatment assisted two-dimensional coating mask substrate |
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Application publication date: 20140423 |