CN108428618A - Growing method of gallium nitride based on graphene insert layer structure - Google Patents
Growing method of gallium nitride based on graphene insert layer structure Download PDFInfo
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- CN108428618A CN108428618A CN201810218102.9A CN201810218102A CN108428618A CN 108428618 A CN108428618 A CN 108428618A CN 201810218102 A CN201810218102 A CN 201810218102A CN 108428618 A CN108428618 A CN 108428618A
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Abstract
The present invention relates to a kind of growing method of gallium nitride based on graphene insert layer structure, and this method comprises the following steps：(1) the magnetron sputtering aluminium nitride film in the Sapphire Substrate in the faces α；(2) it by the transfer techniques of graphene in metal substrate, transfers graphene on magnetron sputtering aluminium nitride film；(3) substrate for covering graphene is heat-treated；(4) pulse metal organic chemical vapor is used to deposit mocvd method epitaxial nitride aluminium as transition zone；(5) sample is put into metal organic chemical vapor deposition MOCVD extension low temperature GaN epitaxial layer successively and high temperature GaN epitaxial layer.This method can obtain the epitaxial layer of gallium nitride of high quality in processing step under the premise of few, at low cost and good process repeatability.
Description
Technical field
The invention belongs to electronic technology field, the one kind further related in technical field of microelectronic material is based on graphite
The growing method of gallium nitride of alkene insert layer structure.The present invention can growing gallium nitride, the nitridation of acquisition in graphene insert layer
Gallium can be further used for making gallium nitride electronic device.
Background technology
It is the third generation semiconductor material with wide forbidden band of representative since energy gap is big, electron mobility is high, hits using gallium nitride
The advantages such as electric field is big are worn to be widely used in the fields such as photoelectric device and electronic device.
Since there are larger lattice mismatch and thermal mismatchings between gallium nitride epitaxial materials and substrate, so hetero-epitaxy obtains
To gallium nitride easy tod produce in growth course larger stress and formed high density dislocation, these dislocations are to gallium nitride base device
The Performance And Reliability of part causes very serious influence.
The dislocation density for reducing gallium nitride material growth is always the critical issue in gallium nitride research, grows high quality nitrogen
It is the key that make high-quality gallium nitride electronic device to change gallium.
Patent document " a kind of gallium nitride film and preparation method thereof and graphene film and its systems of the Liu Zhibin in its application
Preparation Method " (application number：201710192463.6 application publication number：CN106960781A a kind of gallium nitride film is disclosed in)
With the preparation method of graphene film.The step of preparation method is first, to be buffered in the Grown gallium nitride of semiconductor
Layer, then, is formed with the graphene catalyst layer of pore structure on nitride buffer layer, then, the shape in graphene catalyst layer
At the graphene mask layer with graphene catalyst layer with identical pore structure, finally, nitridation is grown on graphene mask layer
Gallium layer.This method can be reduced effectively using the graphene mask layer with pore structure as mask epitaxial growth of gallium nitride layer
The defect that epitaxial layer of gallium nitride and graphene mask layer contact portion are formed, enables to be formed by gallium nitride film and is uniformly distributed
And there is good crystal phase structure, obtain the gallium nitride of high quality.But the shortcoming that this method still has is：First,
Since this method needs first epitaxial nitride gallium buffer layer, graphene catalyst layer and graphene are then formed on nitride buffer layer
Mask layer finally carries out GaN epitaxial growth again, and processing step is more, and cost is too high.Second, since this method needs to form tool
There are the graphene catalyst layer and mask layer of identical pore structure, is difficult to ensure in technique and forms identical graphene catalysis every time
Layer and graphene mask layer, process repeatability are poor.
Invention content
It is an object of the invention to solve the problems, such as the presence of the above-mentioned prior art, provide a kind of based on graphene insert layer
The metal organic chemical vapor deposition MOCVD growing methods of gallium nitride in the Sapphire Substrate of structure, to reduce gallium nitride life
Long dislocation improves gallium nitride quality.
To improve gallium nitride quality, concrete thought of the invention is：First, one layer of nitrogen of magnetron sputtering on a sapphire substrate
Change aluminium film, to alleviate the stress generated due to lattice mismatch between substrate and gallium nitride；Then, single-layer graphene is transferred to
It has sputtered in the Sapphire Substrate of aluminium nitride film, finally, then sample has been put into metal organic chemical vapor deposition system
In the pulsed nitriding aluminium transition zone of extension, low temperature nitride gallium epitaxial layer and high-temperature ammonolysis gallium epitaxial layer successively.
Realizing the object of the invention key problem in technology is：Using magnetron sputtering aln nucleation layer, graphene insert layer and pulse
The mode of the pulsed nitriding aluminium transition zone of metal organic-matter chemical gas-phase depositing extension, the magnetic control first in α surface sapphire substrates
Aluminium nitride film is sputtered, graphene insert layer is then shifted, finally passes through metal organic chemical vapor deposition MOCVD epitaxy again
Pulsed nitriding aluminium and low temperature nitride gallium epitaxial layer and high-temperature ammonolysis gallium epitaxial layer；By adjusting each outer layer growth condition, mainly
Including growth conditions such as chamber pressure, temperature and metal source fluxs, lattice structure is optimized, reduces the production of dislocation
It is raw, improve the quality of gallium nitride.
The specific steps of the present invention include as follows：
The magnetron sputtering aluminium nitride film in the Sapphire Substrate in the faces α, graphite is shifted on magnetron sputtering aluminium nitride film
Alkene, using metal organic-matter chemical vapor deposition method, the pulsed nitriding aluminium of extension, low temperature nitride gallium and high temperature successively on graphene
The specific steps of gallium nitride, this method include as follows：
(1) magnetron sputtering aluminium nitride：
The Sapphire Substrate in the faces α is placed in magnetic control sputtering system by (1a), and chamber pressure 1Pa is passed through nitrogen and argon
Gas 5min, the Sapphire Substrate in the faces α that obtain that treated；
The method that (1b) uses magnetron sputtering, using the aluminium of 99.999% purity as target, the sapphire in the faces α after treatment
Magnetron sputtering aluminium nitride on substrate obtains magnetron sputtering aluminium nitride substrate；
(2) graphene is shifted：
(2a) uses CVD method, grows graphene on the metallic substrate；
The metal substrate for growing graphene is placed in 12 in the mixed solution of 1mol/L iron chloride and 2mol/L hydrochloric acid by (2b)
Hour removal metal substrate, obtains the graphene of removal metal substrate；
The graphene for removing metal substrate is transferred on magnetron sputtering aluminium nitride substrate by (2c), obtains covering graphene
Substrate；
(3) substrate is heat-treated：
The substrate for covering graphene is placed in metal organic chemical vapor deposition reative cell by (3a), is led into reative cell
Enter hydrogen and ammonia 4min, the substrate to covering graphene is handled, and obtains the substrate of the covering graphene after gas treatment；
After reaction chamber temperature is raised to 620 DEG C by (3b), then hot place is carried out to the substrate of the covering graphene after gas treatment
Reason, the substrate after being heat-treated；
(4) pulsed nitriding aluminium is grown：
Chamber pressure is adjusted to 40Torr, temperature is raised to 1060 DEG C, is passed through hydrogen, ammonia and silicon source, wherein hydrogen stream
Amount is 800-1000sccm, and ammonia flow 2000-3000sccm, silicon source flow is 6-20 μm of ol/L, is had using pulse metal
Machine object CVD method, the pulsed nitriding aluminium of grown on substrates after heat treatment, obtains pulsed nitriding aluminum substrate；
(5) growing low temperature gallium nitride：
It keeps chamber pressure constant, reduces the temperature to 900 DEG C, be passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metallorganic
Vapour deposition is learned, the growing low temperature gallium nitride on pulsed nitriding aluminum substrate obtains low temperature nitride gallium substrate；
(6) high-temperature ammonolysis gallium is grown：
(6a) keeps chamber pressure constant, and temperature is raised to 950 DEG C, is passed through hydrogen, ammonia and gallium source, wherein hydrogen stream
Amount is 800-1000sccm, and ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, organic using metal
Object CVD method, in low temperature nitride gallium grown on substrates high-temperature ammonolysis gallium；
Reaction chamber temperature is cooled to room temperature taking-up sample by (6b), obtains the gallium nitride based on graphene insert layer structure.
Compared with prior art, the present invention has the following advantages：
First, due to sputtering the aluminium nitride film of 10~100nm in the α surface sapphire substrates of the present invention after treatment, obtain
It to sputtering aluminium nitride substrate, is grown again on sputtering aluminium nitride substrate, overcomes the prior art and need first epitaxial nitride gallium
Processing step caused by buffer layer is more, the too high problem of cost so that the advantage that the present invention has processing step few, at low cost.
Second, since the graphene layer for removing metal substrate is transferred on the substrate of sputtering aluminium nitride by the present invention, obtain
The substrate for covering graphene is grown on the substrate of covering graphene, overcomes the prior art and need to form with phase again
With the graphene catalyst layer and mask layer of pore structure, be difficult to ensure in technique formed every time identical graphene catalyst layer and
Graphene mask layer, the problem of process repeatability difference so that the present invention has the advantages of good process repeatability.
Description of the drawings
Fig. 1 is the flow chart of the present invention；
Fig. 2 is the cross-sectional view of the present invention.
Specific implementation mode
1 embodiment is described further technical solutions and effects of the present invention below in conjunction with the accompanying drawings.
With reference to attached drawing 1, the realization step of the present invention is further described.
Step 1. magnetron sputtering aluminium nitride.
The Sapphire Substrate in the faces α is placed in magnetic control sputtering system, chamber pressure 1Pa is passed through nitrogen and argon gas
5min handles the Sapphire Substrate in the faces α, the Sapphire Substrate in the faces α that obtain that treated.The nitrogen flow is
20-100sccm, argon flow amount 40-200sccm.Using the method for rf magnetron sputtering, using the aluminium of 99.999% purity as target
Material, sputters aluminium nitride in α surface sapphire substrates after treatment, the good sputtering aluminium nitride of crystalline quality can alleviate substrate with
Due to the stress that lattice mismatch generates between gallium nitride, sputtering aluminium nitride substrate is obtained.The thickness of the sputtering aluminium nitride is
10-100nm。
Step 2. shifts graphene.
Using CVD method, graphene is grown on the metallic substrate.The thickness of the graphene is 0.34-
3.4nm.The metal substrate for growing graphene is placed in 12 hours in the mixed solution of 1mol/L iron chloride and 2mol/L hydrochloric acid and is gone
Except metal substrate, the graphene of removal metal substrate is obtained.The graphene for removing metal substrate is transferred to sputtering aluminium nitride
On substrate, since there is graphene good thermal conduction characteristic subsequent growth temperature to be made to depend on the temperature of Sapphire Substrate,
Obtain the substrate of covering graphene.
Step 3. is heat-treated substrate.
The substrate for covering graphene is placed in metal organic chemical vapor deposition reative cell, hydrogen is passed through into reative cell
Gas and ammonia 4min, the substrate to covering graphene are handled, and hydrogen allows the substrate of covering graphene to be in ammonia as carrier gas
Among compression ring border, the substrate of the covering graphene after gas treatment is obtained.The hydrogen flowing quantity is 800sccm, ammonia flow
For 3000sccm.After reaction chamber temperature is raised to 620 DEG C, then to treated covering graphene substrate be heat-treated, go
The impurity and chemical bond for removing the substrate surface of covering graphene, the substrate surface to covering graphene optimize, and obtain heat
Treated substrate.The time of the heat treatment is 15-30min.
Step 4. grows pulsed nitriding aluminium.
Chamber pressure is adjusted to 40Torr, temperature is raised to 1060 DEG C, is passed through hydrogen, ammonia and silicon source, wherein hydrogen stream
Amount is 800-1000sccm, and ammonia flow 2000-3000sccm, silicon source flow is 6-20 μm of ol/L, is had using pulse metal
Machine object CVD method, the pulsed nitriding aluminium of grown on substrates after heat treatment, obtains pulsed nitriding aluminum substrate.Pulse nitrogen
Change aluminium as transition zone, to promote the crystalline quality of material.The pulse metal organic-matter chemical gas-phase depositing refer to
One pulse period T1+T2It is interior, in T1Ammonia is passed through in time, in T2Ammonia is not passed through in time；The T1Time is set as
12s, T2Time is set as 6s, and the number that the pulse period repeats is 80-200 times, and the thickness of pulsed nitriding aluminium is 10-40nm.
Step 5. growing low temperature gallium nitride.
It keeps chamber pressure constant, reduces the temperature to 900 DEG C, be passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metallorganic
Vapour deposition, the growing low temperature gallium nitride on pulsed nitriding aluminum substrate, to avoid graphene because being decomposed by high temperature,
Obtain low temperature nitride gallium substrate.The low temperature nitride gallium thickness is 20-500nm.
Step 6. grows high-temperature ammonolysis gallium.
It keeps chamber pressure constant, temperature is raised to 950 DEG C, is passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metallorganic
Learn vapour deposition, in low temperature nitride gallium grown on substrates high-temperature ammonolysis gallium so that gallium nitride under suitable growth temperature into
Row growth.The gallium nitride thickness is 600-2000nm.Reaction chamber temperature is cooled to room temperature taking-up sample, obtains being based on stone
The gallium nitride of black alkene insert layer structure.
With reference to Fig. 2, the surface layer structure that cuts open of the obtained gallium nitride based on graphene insert layer structure of the invention is made into one
The description of step.
The gallium nitride based on graphene insert layer structure that the present invention obtains to cut open surface layer structure from bottom to top be the faces α successively
Sapphire Substrate, magnetron sputtering aln layer, graphene layer, pulsed nitriding aluminium transition zone, low temperature nitride gallium layer and high-temperature ammonolysis
Gallium layer.
Below by graphene insert layer and pulsed nitriding aluminium transition layer structure growing gallium nitride, graphene insert
Enter growing gallium nitride and the growing gallium nitride three in graphene insert layer structure on layer and direct method aluminium nitride transition layer structure
A embodiment, the present invention will be further described.
Embodiment 1：The growing gallium nitride in graphene insert layer and pulsed nitriding aluminium transition layer structure.
Step 1 magnetron sputtering aluminium nitride.
The Sapphire Substrate in the faces α is placed in magnetic control sputtering system, chamber pressure 1Pa is passed through nitrogen and argon gas
5min handles the Sapphire Substrate in the faces α, the Sapphire Substrate in the faces α that obtain that treated.The nitrogen flow is
20-100sccm, argon flow amount 40-200sccm.Using the method for rf magnetron sputtering, using the aluminium of 99.999% purity as target
Material, sputters aluminium nitride in α surface sapphire substrates after treatment, the good sputtering aluminium nitride of crystalline quality can alleviate substrate with
Due to the stress that lattice mismatch generates between gallium nitride, sputtering aluminium nitride substrate is obtained.The thickness of the sputtering aluminium nitride is
10-100nm。
Step 2 shifts graphene.
Using CVD method, graphene is grown on the metallic substrate.The thickness of the graphene is 0.34-
3.4nm.The metal substrate for growing graphene is placed in 12 hours in the mixed solution of 1mol/L iron chloride and 2mol/L hydrochloric acid and is gone
Except metal substrate, the graphene of removal metal substrate is obtained.The graphene for removing metal substrate is transferred to sputtering aluminium nitride
On substrate, since there is graphene good thermal conduction characteristic subsequent growth temperature to be made to depend on the temperature of Sapphire Substrate,
Obtain the substrate of covering graphene.
Step 3 is heat-treated substrate.
The substrate for covering graphene is placed in metal organic chemical vapor deposition reative cell, hydrogen is passed through into reative cell
Gas and ammonia 4min, the substrate to covering graphene are handled, and hydrogen allows the substrate of covering graphene to be in ammonia as carrier gas
Among compression ring border, the substrate of the covering graphene after gas treatment is obtained.The hydrogen flowing quantity is 800sccm, ammonia flow
For 3000sccm.After reaction chamber temperature is raised to 620 DEG C, then to treated covering graphene substrate be heat-treated, go
The impurity and chemical bond for removing the substrate surface of covering graphene, the substrate surface to covering graphene optimize, and obtain heat
Treated substrate.The time of the heat treatment is 15-30min.
Step 4 grows pulsed nitriding aluminium.
Chamber pressure is adjusted to 40Torr, temperature is raised to 1060 DEG C, is passed through hydrogen, ammonia and silicon source, wherein hydrogen stream
Amount is 800-1000sccm, and ammonia flow 2000-3000sccm, silicon source flow is 6-20 μm of ol/L, is had using pulse metal
Machine object CVD method, the pulsed nitriding aluminium of grown on substrates after heat treatment, obtains pulsed nitriding aluminum substrate.Pulse nitrogen
Change aluminium as transition zone, to promote the crystalline quality of material.The pulse metal organic-matter chemical gas-phase depositing refer to
One pulse period T1+T2It is interior, in T1Ammonia is passed through in time, in T2Ammonia is not passed through in time；The T1Time is set as
12s, T2Time is set as 6s, and the number that the pulse period repeats is 80-200 times, and the thickness of pulsed nitriding aluminium is 10-40nm.
Step 5 growing low temperature gallium nitride.
It keeps chamber pressure constant, reduces the temperature to 900 DEG C, be passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metallorganic
Vapour deposition, the growing low temperature gallium nitride on pulsed nitriding aluminum substrate, to avoid graphene because being decomposed by high temperature,
Obtain low temperature nitride gallium substrate.The low temperature nitride gallium thickness is 20-500nm.
Step 6 grows high-temperature ammonolysis gallium.
It keeps chamber pressure constant, temperature is raised to 950 DEG C, is passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metallorganic
Learn vapour deposition, in low temperature nitride gallium grown on substrates high-temperature ammonolysis gallium so that gallium nitride under suitable growth temperature into
Row growth.The gallium nitride thickness is 600-2000nm.Reaction chamber temperature is cooled to room temperature taking-up sample, obtains being based on stone
The gallium nitride of black alkene insert layer structure and pulsed nitriding aluminium transition layer structure.
Embodiment 2：The growing gallium nitride in graphene insert layer and direct method aluminium nitride transition layer structure.
Step a. magnetron sputtering aluminium nitride.
The Sapphire Substrate in the faces α is placed in magnetic control sputtering system, chamber pressure 1Pa is passed through nitrogen and argon gas
5min handles the Sapphire Substrate in the faces α, the Sapphire Substrate in the faces α that obtain that treated.The nitrogen flow is
20-100sccm, argon flow amount 40-200sccm.Using the method for rf magnetron sputtering, using the aluminium of 99.999% purity as target
Material, sputters aluminium nitride in α surface sapphire substrates after treatment, the good sputtering aluminium nitride of crystalline quality can alleviate substrate with
Due to the stress that lattice mismatch generates between gallium nitride, sputtering aluminium nitride substrate is obtained.The thickness of the sputtering aluminium nitride is
10-100nm。
Step b. shifts graphene.
Using CVD method, graphene is grown on the metallic substrate.The thickness of the graphene is 0.34-
3.4nm.The metal substrate for growing graphene is placed in 12 hours in the mixed solution of 1mol/L iron chloride and 2mol/L hydrochloric acid and is gone
Except metal substrate, the graphene of removal metal substrate is obtained.The graphene for removing metal substrate is transferred to sputtering aluminium nitride
On substrate, since there is graphene good thermal conduction characteristic subsequent growth temperature to be made to depend on the temperature of Sapphire Substrate,
Obtain the substrate of covering graphene.
Step c. is heat-treated substrate.
The substrate for covering graphene is placed in metal organic chemical vapor deposition reative cell, hydrogen is passed through into reative cell
Gas and ammonia 4min, the substrate to covering graphene are handled, and hydrogen allows the substrate of covering graphene to be in ammonia as carrier gas
Among compression ring border, the substrate of the covering graphene after gas treatment is obtained.The hydrogen flowing quantity is 800sccm, ammonia flow
For 3000sccm.After reaction chamber temperature is raised to 620 DEG C, then to treated covering graphene substrate be heat-treated, go
The impurity and chemical bond for removing the substrate surface of covering graphene, the substrate surface to covering graphene optimize, and obtain heat
Treated substrate.The time of the heat treatment is 15-30min.
Step d. grows direct method aluminium nitride.
Chamber pressure is adjusted to 40Torr, temperature is raised to 1060 DEG C, is passed through hydrogen, ammonia and silicon source, has using metal
Machine object CVD method, grown on substrates aluminium nitride after heat treatment.Aluminium nitride is as transition zone, to promote material
Crystalline quality obtains aluminium nitride substrate.The thickness of the aluminium nitride is 10-40nm.
Step e. growing low temperature gallium nitride.
It keeps chamber pressure constant, reduces the temperature to 900 DEG C, be passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metallorganic
Vapour deposition, the growing low temperature gallium nitride on pulsed nitriding aluminum substrate, to avoid graphene because being decomposed by high temperature,
Obtain low temperature nitride gallium substrate.The low temperature nitride gallium thickness is 20-500nm.
Step f. grows high-temperature ammonolysis gallium.
It keeps chamber pressure constant, temperature is raised to 950 DEG C, is passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metallorganic
Learn vapour deposition, in low temperature nitride gallium grown on substrates high-temperature ammonolysis gallium so that gallium nitride under suitable growth temperature into
Row growth.The gallium nitride thickness is 600-2000nm.Reaction chamber temperature is cooled to room temperature taking-up sample, obtains being based on stone
The gallium nitride of black alkene insert layer structure and direct method aluminium nitride transition layer structure.
Embodiment 3：The growing gallium nitride in graphene insert layer structure.
Step I magnetron sputtering aluminium nitride.
The Sapphire Substrate in the faces α is placed in magnetic control sputtering system, chamber pressure 1Pa is passed through nitrogen and argon gas
5min handles the Sapphire Substrate in the faces α, the Sapphire Substrate in the faces α that obtain that treated.The nitrogen flow is
20-100sccm, argon flow amount 40-200sccm.Using the method for rf magnetron sputtering, using the aluminium of 99.999% purity as target
Material, sputters aluminium nitride in α surface sapphire substrates after treatment, the good sputtering aluminium nitride of crystalline quality can alleviate substrate with
Due to the stress that lattice mismatch generates between gallium nitride, sputtering aluminium nitride substrate is obtained.The thickness of the sputtering aluminium nitride is
10-100nm。
Step II shifts graphene.
Using CVD method, graphene is grown on the metallic substrate.The thickness of the graphene is 0.34-
3.4nm.The metal substrate for growing graphene is placed in 12 hours in the mixed solution of 1mol/L iron chloride and 2mol/L hydrochloric acid and is gone
Except metal substrate, the graphene of removal metal substrate is obtained.The graphene for removing metal substrate is transferred to sputtering aluminium nitride
On substrate, since there is graphene good thermal conduction characteristic subsequent growth temperature to be made to depend on the temperature of Sapphire Substrate,
Obtain the substrate of covering graphene.
Step III, is heat-treated substrate.
The substrate for covering graphene is placed in metal organic chemical vapor deposition reative cell, hydrogen is passed through into reative cell
Gas and ammonia 4min, the substrate to covering graphene are handled, and hydrogen allows the substrate of covering graphene to be in ammonia as carrier gas
Among compression ring border, the substrate of the covering graphene after gas treatment is obtained.The hydrogen flowing quantity is 800sccm, ammonia flow
For 3000sccm.After reaction chamber temperature is raised to 620 DEG C, then to treated covering graphene substrate be heat-treated, go
The impurity and chemical bond for removing the substrate surface of covering graphene, the substrate surface to covering graphene optimize, and obtain heat
Treated substrate.The time of the heat treatment is 15-30min.
Step IV, growing low temperature gallium nitride.
It keeps chamber pressure constant, reduces the temperature to 900 DEG C, be passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metallorganic
Vapour deposition, the growing low temperature gallium nitride on pulsed nitriding aluminum substrate, to avoid graphene because being decomposed by high temperature,
Obtain low temperature nitride gallium substrate.The low temperature nitride gallium thickness is 20-500nm.
Step V, grows high-temperature ammonolysis gallium.
It keeps chamber pressure constant, temperature is raised to 950 DEG C, is passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metallorganic
Learn vapour deposition, in low temperature nitride gallium grown on substrates high-temperature ammonolysis gallium so that gallium nitride under suitable growth temperature into
Row growth.The gallium nitride thickness is 600-2000nm.Reaction chamber temperature is cooled to room temperature taking-up sample, obtains being based on stone
Black alkene insert layer structure and the gallium nitride without aluminium nitride transition layer structure.
Claims (10)
1. a kind of growing method of gallium nitride based on graphene insert layer structure, which is characterized in that in the Sapphire Substrate in the faces α
Magnetron sputtering aluminium nitride film shifts graphene on magnetron sputtering aluminium nitride film, is formed sediment using metal organic-matter chemical meteorology
Area method, the pulsed nitriding aluminium of extension, low temperature nitride gallium and high-temperature ammonolysis gallium, the specific steps of this method include successively on graphene
It is as follows：
(1) magnetron sputtering aluminium nitride：
The Sapphire Substrate in the faces α is placed in magnetic control sputtering system by (1a), and chamber pressure 1Pa is passed through nitrogen and argon gas
5min, the Sapphire Substrate in the faces α that obtain that treated；
The method that (1b) uses magnetron sputtering, using the aluminium of 99.999% purity as target, the Sapphire Substrate in the faces α after treatment
Upper magnetron sputtering aluminium nitride, obtains magnetron sputtering aluminium nitride substrate；
(2) graphene is shifted：
(2a) uses CVD method, grows graphene on the metallic substrate；
The metal substrate for growing graphene is placed in the mixed solution of 1mol/L iron chloride and 2mol/L hydrochloric acid 12 hours by (2b)
Metal substrate is removed, the graphene of removal metal substrate is obtained；
The graphene for removing metal substrate is transferred on magnetron sputtering aluminium nitride substrate by (2c), obtains the base of covering graphene
Plate；
(3) substrate is heat-treated：
The substrate for covering graphene is placed in metal organic chemical vapor deposition reative cell by (3a), and hydrogen is passed through into reative cell
Gas and ammonia 4min, the substrate to covering graphene are handled, and obtain the substrate of the covering graphene after gas treatment；
After reaction chamber temperature is raised to 620 DEG C by (3b), then the substrate of the covering graphene after gas treatment is heat-treated, is obtained
Substrate after to heat treatment；
(4) pulsed nitriding aluminium is grown：
Chamber pressure is adjusted to 40Torr, temperature is raised to 1060 DEG C, is passed through hydrogen, ammonia and silicon source, and wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, silicon source flow is 6-20 μm of ol/L, using pulse metal organic matter
CVD method, the pulsed nitriding aluminium of grown on substrates after heat treatment, obtains pulsed nitriding aluminum substrate；
(5) growing low temperature gallium nitride：
It keeps chamber pressure constant, reduces the temperature to 900 DEG C, be passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is 800-
1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metal organic-matter chemical gas
Phase sedimentation, the growing low temperature gallium nitride on pulsed nitriding aluminum substrate obtain low temperature nitride gallium substrate；
(6) high-temperature ammonolysis gallium is grown：
(6a) keeps chamber pressure constant, and temperature is raised to 950 DEG C, is passed through hydrogen, ammonia and gallium source, wherein hydrogen flowing quantity is
800-1000sccm, ammonia flow 2000-3000sccm, gallium source flux is 60-120 μm of ol/L, using metallorganic
Vapour deposition is learned, in low temperature nitride gallium grown on substrates high-temperature ammonolysis gallium；
Reaction chamber temperature is cooled to room temperature taking-up sample by (6b), obtains the gallium nitride based on graphene insert layer structure.
2. the growing method of gallium nitride according to claim 1 based on graphene insert layer structure, which is characterized in that step
Nitrogen flow described in (1a) is 20-100sccm, argon flow amount 40-200sccm.
3. the growing method of gallium nitride according to claim 1 based on graphene insert layer structure, which is characterized in that step
The thickness of magnetron sputtering aluminium nitride described in (1b) is 10-100nm.
4. the growing method of gallium nitride according to claim 1 based on graphene insert layer structure, which is characterized in that step
The thickness of graphene described in (2a) is 0.34-3.4nm.
5. the growing method of gallium nitride according to claim 1 based on graphene insert layer structure, which is characterized in that step
Hydrogen flowing quantity described in (3a) is 800sccm, ammonia flow 3000sccm.
6. the growing method of gallium nitride according to claim 1 based on graphene insert layer structure, which is characterized in that step
The time of heat treatment described in (3b) is 15-30min.
7. the growing method of gallium nitride according to claim 1 based on graphene insert layer structure, which is characterized in that step
(4) pulse metal organic-matter chemical gas-phase depositing described in refers in a pulse period T1+T2It is interior, in T1It is passed through in time
Ammonia, in T2Ammonia is not passed through in time；The T1Time is set as 12s, T2Time is set as 6s, what the pulse period repeated
Number is 80-200 times.
8. the growing method of gallium nitride according to claim 1 based on graphene insert layer structure, which is characterized in that step
(4) thickness of pulsed nitriding aluminium described in is 10-40nm.
9. the growing method of gallium nitride according to claim 1 based on graphene insert layer structure, which is characterized in that step
(5) the low temperature nitride gallium thickness described in is 20-500nm.
10. the growing method of gallium nitride according to claim 1 based on graphene insert layer structure, which is characterized in that step
Suddenly the high-temperature ammonolysis gallium thickness described in (6a) is 600-2000nm.
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