CN102746025B - Preparation method of low-cost GaN epitaxial film - Google Patents
Preparation method of low-cost GaN epitaxial film Download PDFInfo
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- CN102746025B CN102746025B CN201210214199.9A CN201210214199A CN102746025B CN 102746025 B CN102746025 B CN 102746025B CN 201210214199 A CN201210214199 A CN 201210214199A CN 102746025 B CN102746025 B CN 102746025B
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Abstract
The invention discloses a preparation method of a low-cost GaN epitaxial film and belongs to the technical field of photoelectric film material preparation. The preparation method comprises the following steps of 1, preparing an anhydrous gallium source precursor solution by dissolving gallium acetylacetonate powder in mixed solvents of acetic acid and propionic acid with heating and stirring, wherein a Ga ion concentration is in a range of 0.1 to 0.4mol/L, adding methanol into the mixed solution, wherein the volume of methanol is 1/2 of the total volume of the mixed solvents, carrying out low pressure distillation to remove impurity water, then stopping the low pressure distillation and the heating but stirring, and adding ethanolamine into the mixed solution without impurity water to obtain the anhydrous gallium source precursor solution having a concentration of 0.1 to 0.3mol/L, 2, carrying out precursor solution coating by carrying out spin coating of the anhydrous gallium source precursor solution obtained by the step 1 on a substrate, and 3, carrying out heat treatment by heating and then cooling to a room temperature to obtain the low-cost GaN epitaxial film. The preparation method needs simple equipment, has simple preparation processes which comprise preparing the anhydrous gallium source precursor solution, coating the anhydrous gallium source precursor solution on the substrate and carrying out sintering, and has a low cost and good repeatability.
Description
Technical field
The invention belongs to optoelectronic thin film material preparing technical field, be specifically related to a kind of growth method of GaN epitaxial film, can be used for making the semiconductor photoelectric device of GaN.
Background technology
GaN is the third generation semiconductor material with wide forbidden band after semiconductor material continue first and second of take that Si, GaAs be representative in generation.GaN belongs to direct band-gap semicondictor material, there is the characteristics such as energy gap is large, thermal conductivity is high, specific inductivity is low, electronic drift saturating speed height, the electron device that is suitable for making high frequency, high temperature, high-power, radioprotective and high density of integration, can be used for preparing the new devices such as metal-semiconductor field effect transistor (MESFET), High Electron Mobility Transistor (HEMT) as GaN.Utilize its broad stopband feature can also make luminescent device and the light-detecting device of blue light, green glow, UV-light, as GaN, can be used for preparing the devices such as ultraviolet detector, blue laser.Meanwhile, GaN is the main flow material of preparation indigo plant at present, green glow and white light emitting diode (LED), and is applied to gradually the fields such as flash ranging control, optical storage, demonstration, illumination.
The method of preparing at present GaN thin-film material has metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), polymkeric substance assistant depositing (PAD) and collosol and gel (Sol-Gel) method etc.The crystalline quality of MOCVD technology is high, and deposition process is lower to the susceptibility of temperature variation, reproducible, it is the mainstream technology of growing GaN film in LED industry, but this technical equipment is expensive, that metal organic source material mostly is is inflammable, explosive, have hypertoxic material, and the parameter that necessary for growth is controlled is more; MBE technology can accurately be controlled thickness, structure and the composition of film, but in this technology, film growth rate is extremely slow, and equipment cost is higher, is unsuitable for industrialization and produces, and be limited by lower growth temperature and lack effective nitrogenous source; PAD and Sol-Gel technology are simple without vacuum apparatus and technique, and cost is low, but the repeatability of above-mentioned two technology is poor.
Summary of the invention
Technical problem to be solved by this invention is that a kind of preparation method of the low-cost GaN epitaxial film without vacuum apparatus is provided.
The technical scheme that the present invention solve the technical problem employing is that the preparation method of low-cost GaN epitaxial film, is characterized in that, comprises the steps:
(1) anhydrous gallium source precursor liquid preparation: in the mixed solvent of acetic acid and propionic acid, Ga ionic concn is 0.1-0.4mol/l by methyl ethyl diketone gallium powder dissolution, heating in dissolution process, stirring; Then adding volume is the methyl alcohol of mixed solvent cumulative volume 1/2nd, and carries out low-pressure distillation and remove water impurity; Then stop low-pressure distillation and heating, only stir; Finally add thanomin, form anhydrous precursor aqueous solution, concentration is 0.1-0.3mol/l;
(2) precursor liquid applies: step (1) gained precursor aqueous solution is spin-coated on substrate;
(3) thermal treatment: after heating, cooling is until room temperature can obtain GaN film.
In step (1), the volume ratio of acetic acid and propionic acid mixing solutions is 1:1-2:1;
Described substrate is c-Al
2o
3or (111) Si monocrystal chip.
Further, in described step (1), in dissolution process, carry out 40-65 ℃ of oil bath heating, magnetic agitation simultaneously; Stop low-pressure distillation and the rear magnetic agitation 15-20 hour of oil bath heating.
In described step (2), spin coating speed is 1500-3500rpm, and the time is 30-60s.
Described step (3) is: the substrate of surface attachment liquid film described in step (2) is placed in to tube furnace, first pass into excessive nitrogen with excluding air, then close nitrogen and start heating, first the speed with 1-3 ℃/min is warming up to 120 ℃ from room temperature, while being warming up to 750-800 ℃ with the speed of 15-20 ℃/min afterwards, pass into ammonia, gas flow is controlled as 20-60mL/min, continue to be warming up to 850-1000 ℃, and be incubated 60-120min, after insulation finishes, stop passing into ammonia, and naturally lower the temperature until room temperature can obtain GaN film.
The present invention also comprises step (4): repeating step (2) and step (3), until obtain the multilayer film of the default number of plies.
The invention has the beneficial effects as follows:
(1) required equipment is simple, and preparation technology is simple, only prepared anhydrous organosilane precursor solution need be coated on to substrate sintering, and cost is low, reproducible.
(2) adopt Organogallium salt as gallium source, adopt ammonia as nitrogenous source, raw material is simple, utilization ratio is high, and cost is low, environmentally safe.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction θ-2 θ scintigram of the GaN film of the embodiment of the present invention one preparation.
Fig. 2 is the AFM two and three dimensions figure of the GaN film of the embodiment of the present invention one preparation.
Fig. 3 is the GaN film of the embodiment of the present invention one preparation and the Φ scintigram of sapphire single-crystal substrate.
Fig. 4 is the X-ray diffraction θ-2 θ scintigram of the GaN film of the embodiment of the present invention two preparations.
Fig. 5 is the X-ray diffraction θ-2 θ scintigram of the GaN film of the embodiment of the present invention three preparations.
Embodiment
The present invention includes following step:
(1) anhydrous gallium source precursor liquid preparation: methyl ethyl diketone gallium powder dissolution, in the mixed solvent (Ga ionic concn is 0.1-0.4mol/l) of acetic acid and propionic acid, is carried out to 40-65 ℃ of oil bath heating, magnetic agitation simultaneously in dissolution process; After 10min, adding volume is the methyl alcohol of mixed solvent cumulative volume 1/2nd, and carries out low-pressure distillation and remove water impurity; After 20min, stop low-pressure distillation and oil bath heating, only magnetic agitation 15-20 hour; Finally add thanomin, form anhydrous precursor aqueous solution, concentration is 0.1-0.3mol/l.
(2) precursor liquid applies: precursor aqueous solution in step (1) is dropped on substrate, adopt whirler to be evenly coated on substrate.
(3) thermal treatment: the substrate of surface attachment liquid film described in step (2) is placed in to tube furnace, first pass into excessive nitrogen with excluding air, then close nitrogen and start heating, first the speed with 1-3 ℃/min is warming up to 120 ℃ from room temperature, while being warming up to 750-800 ℃ with the speed of 15-20 ℃/min afterwards, pass into ammonia, gas flow is controlled as 20-60mL/min, continue to be warming up to 850-1000 ℃, and be incubated 60-120min, after insulation finishes, stop passing into ammonia, and naturally lower the temperature until room temperature can obtain GaN film.
In step (1), the volume ratio of acetic acid and propionic acid mixing solutions is 1:1-2:1, and such ratio can guarantee solubleness and the wetting property of solvent.
In step (2), spin coating speed is 1500-3500rpm, and the time is 30-60s, and spin coating speed and time can effectively be controlled film thickness.
In step (2), substrate is c-Al
2o
3or (111) Si monocrystal chip.
In step (3), the GaN film obtaining is individual layer, if will prepare multilayer film, in (3), repeating step (2) (3) on GaN film, can obtain bilayer film, and repeating step (2) (3) can obtain multilayer film repeatedly.
Be below embodiment more specifically.
Embodiment mono-
This routine preparation method consists of following steps successively:
(1) anhydrous gallium source precursor liquid preparation: 0.734g methyl ethyl diketone gallium powder is dissolved in the mixed solvent of 5mL acetic acid and 5mL propionic acid, carries out 60 ℃ of oil bath heating, magnetic agitation in dissolution process simultaneously; After 10min, add 5mL methyl alcohol, and carry out low-pressure distillation and remove water impurity; After 20min, stop low-pressure distillation and oil bath heating, only magnetic agitation is 20 hours; Finally add thanomin with stabilizing solution and increase its viscosity, the Concentration of precursor solution of preparation is 0.2mol/l.
(2) precursor liquid applies: adopt spin coating method that precursor liquid described in step (1) is evenly coated on sapphire single-crystal substrate, spin coating speed is 1500rpm, and the time is 40s.
(3) thermal treatment: the sapphire single-crystal substrate of surface attachment liquid film described in step (2) is placed in to tube furnace and heat-treats, first pass into excessive nitrogen with excluding air, then close nitrogen and start heating, first the speed with 2 ℃/min is warming up to 120 ℃ from room temperature, while being warming up to 850 ℃ with the speed of 20 ℃/min afterwards, pass into ammonia, gas flow is controlled as 30mL/min, continue to be warming up to 950 ℃, insulation 60min, after finishing, insulation stops passing into ammonia, and naturally lower the temperature until room temperature can obtain GaN film.
Fig. 1 is the X-ray diffraction θ-2 θ scintigram (in figure, ordinate zou is diffracted intensity, and unit is cps, and X-coordinate is 2 θ diffraction angle, and unit is deg) of the GaN film of the present embodiment one preparation.At 34.3 °, there is very sharp-pointed diffraction peak, i.e. a GaN(0002 in it), and without other assorted peaks, show that GaN film is pure c-axis oriented epitaxial growth.
Fig. 2 is that (in figure, ordinate zou is diffracted intensity for the GaN film of the present embodiment one preparation and the Φ scintigram of sapphire substrate, unit is cps, X-coordinate is Φ diffraction angle, unit is deg), in collection of illustrative plates, 3 diffraction peaks of sapphire single-crystal substrate are separated by 120 °, 6 diffraction peaks of GaN film are all separated by 60 °, and the interior orientation of face that prepared film has possessed is described.And differ 30 ° between GaN film and the diffraction peak of sapphire substrate, and illustrating when GaN film is grown on sapphire substrate and in face, rotated 30 °, in face, epitaxial relationship is
Fig. 3 is the AFM two and three dimensions figure of the GaN film of the present embodiment one preparation, as seen from the figure: film sample surfacing, densification, flawless.
Embodiment bis-
This routine preparation method consists of following steps successively:
(1) anhydrous gallium source precursor liquid preparation: 0.294g methyl ethyl diketone gallium powder is dissolved in the mixed solvent of 3mL acetic acid and 2mL propionic acid, carries out 60 ℃ of oil bath heating, magnetic agitation in dissolution process simultaneously; After 10min, add 2.5mL methyl alcohol, and carry out low-pressure distillation and remove water impurity; After 20min, stop low-pressure distillation and oil bath heating, only magnetic agitation is 15 hours; Finally add thanomin with stabilizing solution and increase its viscosity, the Concentration of precursor solution of preparation is 0.2mol/l.
(2) precursor liquid applies: adopt spin coating method that precursor liquid described in step (1) is evenly coated on sapphire single-crystal substrate, spin coating speed is 2500rpm, and the time is 40s.
(3) thermal treatment: the sapphire single-crystal substrate of surface attachment liquid film described in step (2) is placed in to tube furnace and heat-treats, first pass into excessive nitrogen with excluding air, then close nitrogen and start heating, first the speed with 2 ℃/min is warming up to 120 ℃ from room temperature
While being warming up to 800 ℃ with the speed of 15 ℃/min afterwards, pass into ammonia, gas flow is controlled as 30mL/min, continues to be warming up to 900 ℃, and insulation 120min stops passing into ammonia after insulation finishes, and naturally lowers the temperature until room temperature can obtain GaN film.
Fig. 4 is the X-ray diffraction θ-2 θ scintigram (in figure, ordinate zou is diffracted intensity, and unit is cps, and X-coordinate is 2 θ diffraction angle, and unit is deg) of the GaN film of the present embodiment two preparations.At 34.2 °, there is very sharp-pointed diffraction peak, i.e. a GaN(0002 in it), and without other assorted peaks, show that GaN film is pure c-axis oriented epitaxial growth.
Embodiment tri-
This routine preparation method consists of following steps successively:
(1) anhydrous gallium source precursor liquid preparation: 0.734g methyl ethyl diketone gallium powder is dissolved in the mixed solvent of 5mL acetic acid and 5mL propionic acid, carries out 65 ℃ of oil bath heating, magnetic agitation in dissolution process simultaneously; After 10min, add 5mL methyl alcohol, and carry out low-pressure distillation and remove water impurity; After 20min, stop low-pressure distillation and oil bath heating, only magnetic agitation is 20 hours; Finally add thanomin with stabilizing solution and increase its viscosity, the Concentration of precursor solution of preparation is 0.2mol/l.
(2) precursor liquid applies: adopt spin coating method that precursor liquid described in step (1) is evenly coated on the tangential sapphire single-crystal substrate of c, spin coating speed is 3500rpm, and the time is 60s.
(3) thermal treatment: the sapphire single-crystal substrate of surface attachment liquid film described in step (2) is placed in to tube furnace and heat-treats, first pass into excessive nitrogen with excluding air, then close nitrogen and start heating, first the speed with 2 ℃/min is warming up to 120 ℃ from room temperature, while being warming up to 800 ℃ with the speed of 15 ℃/min afterwards, pass into ammonia, gas flow is controlled as 30mL/min, continue to be warming up to 900 ℃, insulation 60min, after finishing, insulation stops passing into ammonia, and naturally lower the temperature until room temperature can obtain GaN film.
Fig. 5 is the X-ray diffraction θ-2 θ scintigram (in figure, ordinate zou is diffracted intensity, and unit is cps, and X-coordinate is 2 θ diffraction angle, and unit is deg) of the GaN film of the present embodiment two preparations.At 34.2 °, there is very sharp-pointed diffraction peak, i.e. a GaN(0002 in it), and without other assorted peaks, show that GaN film is pure c-axis oriented epitaxial growth.With embodiment mono-and embodiment bis-relatively, GaN diffraction peak a little less than, be mainly because spin coating speed is higher in step (2), due to the film of coating is thinner.
Claims (3)
1. the preparation method of low-cost GaN epitaxial film, is characterized in that, comprises the steps:
(1) anhydrous gallium source precursor liquid preparation: in the mixed solvent of acetic acid and propionic acid, Ga ionic concn is 0.1-0.4mol/L by methyl ethyl diketone gallium powder dissolution, heating in dissolution process, stirring; Then adding volume is the methyl alcohol of mixed solvent cumulative volume 1/2nd, and carries out low-pressure distillation and remove water impurity; Then stop low-pressure distillation and heating, only stir; Finally add thanomin, form anhydrous precursor aqueous solution, concentration is 0.1-0.3mol/L;
(2) precursor liquid applies: step (1) gained precursor aqueous solution is spin-coated on substrate;
(3) thermal treatment: the substrate of surface attachment liquid film in step (2) is placed in to tube furnace, first pass into excessive nitrogen with excluding air, then close nitrogen and start heating, first the speed with 1-3 ℃/min is warming up to 120 ℃ from room temperature, while being warming up to 750-800 ℃ with the speed of 15-20 ℃/min afterwards, pass into ammonia, gas flow is controlled as 20-60mL/min, continue to be warming up to 850-1000 ℃, and be incubated 60-120min, after insulation finishes, stop passing into ammonia, and naturally lower the temperature until room temperature obtains GaN film;
The volume ratio that in step (1), acetic acid and propionic acid mix is 1:1-2:1;
Described substrate is c-Al
2o
3or (111) Si monocrystal chip.
2. the preparation method of low-cost GaN epitaxial film as claimed in claim 1, is characterized in that, in described step (2), spin coating speed is 1500-3500rpm, and the time is 30-60s.
3. the preparation method of low-cost GaN epitaxial film as claimed in claim 1, is characterized in that, also comprises step (4): repeating step (2) and step (3), until obtain the multilayer film of the default number of plies.
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| CN1800840A (en) * | 2005-01-07 | 2006-07-12 | 华东理工大学 | Gallium oxide gas sensing film doped with metal oxide and preparation method thereof |
| CN1906738A (en) * | 2004-06-28 | 2007-01-31 | 住友电气工业株式会社 | GaAs substrate cleaning method, GaAs substrate manufacturing method, epitaxial substrate manufacturing method and GaAs wafer |
| CN102005370A (en) * | 2010-10-12 | 2011-04-06 | 北京大学 | Method for preparing homoepitaxy substrate |
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| CN1906738A (en) * | 2004-06-28 | 2007-01-31 | 住友电气工业株式会社 | GaAs substrate cleaning method, GaAs substrate manufacturing method, epitaxial substrate manufacturing method and GaAs wafer |
| CN1800840A (en) * | 2005-01-07 | 2006-07-12 | 华东理工大学 | Gallium oxide gas sensing film doped with metal oxide and preparation method thereof |
| CN102005370A (en) * | 2010-10-12 | 2011-04-06 | 北京大学 | Method for preparing homoepitaxy substrate |
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