CN109003888A - Epitaxial growth GaN nano-pillar and preparation method in silicon/graphene compound substrate - Google Patents
Epitaxial growth GaN nano-pillar and preparation method in silicon/graphene compound substrate Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 109
- 239000002061 nanopillar Substances 0.000 title claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
- -1 graphene compound Chemical class 0.000 title claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 34
- 239000010703 silicon Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000001451 molecular beam epitaxy Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000004065 semiconductor Substances 0.000 claims abstract description 5
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 claims abstract description 4
- PYTMYKVIJXPNBD-UHFFFAOYSA-N clomiphene citrate Chemical compound [H+].[H+].[H+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.C1=CC(OCCN(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C(Cl)C1=CC=CC=C1 PYTMYKVIJXPNBD-UHFFFAOYSA-N 0.000 claims description 13
- 238000000407 epitaxy Methods 0.000 claims description 12
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- 238000004519 manufacturing process Methods 0.000 abstract description 3
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- 238000010586 diagram Methods 0.000 description 5
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052594 sapphire Inorganic materials 0.000 description 4
- 239000010980 sapphire Substances 0.000 description 4
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
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- 239000002131 composite material Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02373—Group 14 semiconducting materials
- H01L21/02376—Carbon, e.g. diamond-like carbon
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Abstract
The invention belongs to the technical fields of semiconductor, disclose epitaxial growth GaN nano-pillar and preparation method in silicon/graphene compound substrate.Method are as follows: (1) Si substrate cleans；(2) graphene layer is prepared on a si substrate；(3) use molecular beam epitaxy on the graphene of Si substrate in 900~1100 DEG C of high growth temperature GaN nano-pillars；(4) molecular beam epitaxy is used, the GaN nano-pillar of step (3) is continued to grow under 650~800 DEG C of low temperature.Epitaxial growth GaN nano-pillar in silicon/graphene compound substrate successively includes Si substrate, graphene layer, GaN nano-pillar from bottom to up.GaN nano-pillar uniform diameter of the invention, order are high, have low-defect-density and high-crystal quality, can be improved the carrier radiation recombination efficiency of device, the luminous efficiency and photolysis water hydrogen efficiency of nitride device.Preparation method of the invention is simple, with short production cycle.
Description
Technical field
The present invention relates to GaN nano-pillars, in particular to GaN nano-pillar and its system are grown in Si/ graphene compound substrate
Preparation Method.
Background technique
GaN and III- group-III nitride is since forbidden bandwidth is big, physicochemical properties are stable, thermal conductivity is high and electronics saturation speed
The advantages that high is spent, light emitting diode (LED), laser and opto-electronic device etc. are widely used in.With other broad stopbands half
Conductor material is compared, GaN material in addition to having the above advantages, the GaN material of nanoscale quantum effect, interfacial effect,
Bulk effect, dimensional effect etc. also show more novel characteristics.
GaN nano material is because " dimensional effect " produces a series of novel characteristic, so that it is in basic physics and newly
There is huge prospect in terms of type technical application, it has also become the hot spot of current research.And GaN nanometers of rod structures are even more to receive in preparation
More excellent performance is shown on rice range luminescent device such as LED, laser diode LD.
Currently, GaN base device is mainly based upon epitaxial growth and preparation in Sapphire Substrate, however sapphire is due to thermal conductivity
Rate is low, causes the heat generated using sapphire as the high-power GaN device of substrate that can not be released effectively, heat is caused constantly to be accumulated
Increase temperature, accelerate GaN base luminescent device, there are device performances it is poor, the service life is short the disadvantages of.In contrast, the thermal conductivity of Si
Higher than sapphire, the heat that the high-power GaN base semiconductor devices prepared on a si substrate generates at work is effectively released
It puts.
The GaN nano-pillar that growth diameter is uniform on a si substrate, upright, order is high is to prepare high-performance GaN base photoelectricity
Device first proposes condition.But since the lattice mismatch between Si and GaN is big；Meanwhile the distribution of early growth period GaN nano-pillar is not
Uniformly, the difference that Ga and N atom is distributed in growth course, causing the GaN nano-pillar of growth to have, height, path length are uneven, have
Situations such as sequence is poor.
Summary of the invention
In order to overcome the disadvantages mentioned above and deficiency of the prior art, the purpose of the present invention is to provide silicon/graphene composite linings
Epitaxial growth GaN nano-pillar and preparation method thereof on bottom.The present invention is compound on a si substrate by graphene, reduce Si and GaN it
Between lattice mismatch, promote the growth of the GaN nano-pillar of low-defect-density, high-crystal quality, and point of high temperature and low temperature
Section processing, further promotes the GaN nanocolumn growth that order is good, diameter is uniform.In addition, graphene has extraordinary heat
The thermal coefficient of conductive performance, pure flawless single-layer graphene is up to 5300W/mK, is thermal coefficient highest so far
Carbon material.Also, graphene has the characteristics such as excellent optics, electricity, mechanics, and composite graphite alkene is as life on a si substrate
Long substrate carries out the growth of GaN nano-pillar, facilitates the application prospect for further expanding GaN nano-pillar.
The purpose of the present invention is achieved through the following technical solutions:
Epitaxial growth GaN nano-pillar in silicon/graphene compound substrate successively includes that (i.e. silicon serves as a contrast Si substrate from bottom to up
Bottom), graphene layer, GaN nano-pillar.
Si substrate and graphene layer composition silicon/graphene compound substrate (i.e. Si/ graphene compound substrate).GaN nano-pillar
Uniform diameter is orderly distributed on graphene layer.
The Si substrate is using (111) face as the substrate of epitaxial surface；(0001) face of GaN is parallel to (111) face of Si.
Graphene number of plies is single layer or multilayer.
The diameter of GaN nano-pillar is 40-50nm.
The GaN nano-pillar is obtained by high growth temperature and low-temperature epitaxy；Molecular beam epitaxy is specifically used, successively
It is prepared by high growth temperature and low-temperature epitaxy；The temperature of high growth temperature is 900~1100 DEG C, and the temperature of low-temperature epitaxy is
650~800 DEG C.
The preparation method of epitaxial growth GaN nano-pillar in silicon/graphene compound substrate, comprising the following steps:
(1) selection of Si substrate and its crystal orientation: using Si substrate, and using (111) face as epitaxial surface, crystalline epitaxial orientation is closed
System are as follows: (0001) face of GaN is parallel to (111) face of Si；
(2) Si substrate cleans；
(3) it prepares Si/ graphene compound substrate: preparing graphene layer on a si substrate；
(4) molecular beam epitaxy, the high growth temperature GaN on the graphene layer of Si substrate high growth temperature GaN nano-pillar: are used
Nano-pillar, the temperature of high growth temperature are 900~1100 DEG C；
(5) low-temperature epitaxy GaN nano-pillar: molecular beam epitaxy is used, the GaN nano-pillar that step (4) is obtained is in low temperature
Under continue to grow, the temperature of low temperature is 650-800 DEG C.
It is 2-8sccm that the condition of step (4) high temperature growth GaN nano-pillar, which is N partial pressure, Ga line amount be (2~8) ×
10-8Torr, radio-frequency power are 50~300W, and growth time is 1.5~3 hours；
It is 2~8sccm that the condition of low-temperature epitaxy, which is N partial pressure, in step (5), and Ga line amount is (2~8) × 10-8Torr is penetrated
Frequency power is 50~300W, and growth time is 1.5~3 hours.
The cleaning of substrate described in step (2), specifically:
The HF for being 1:10 with volume ratio and deionized water mixed liquor carry out standard ultrasound to substrate and clean 1-2 minutes, then
With deionized water repeated flushing 1-2 minutes, finally dried up with high-purity drying nitrogen.
Si/ graphene compound substrate described in step (3) by vapour deposition process grow on a si substrate graphene layer or
Graphene layer is transferred on Si substrate by person；
Grow the specific preparation step of graphene layer on a si substrate by vapour deposition process are as follows: serve as a contrast the Si through over cleaning
Bottom is placed in chemical vapor depsotition equipment (CVD), carries out the growth of graphene, and using methane as carbon source, hydrogen is carrier gas, raw
Long temperature is 600~1000 DEG C, forms Si/ graphene compound substrate.The graphene number of plies of growth is single layer or multilayer.Methane
Flow be 0.4~15sccm, the volume flow of hydrogen is 10-30cm3/ min, the time of growth are 10~25min.
Specific preparation graphene layer being transferred on Si substrate are as follows: graphene is grown on copper foil, in ferric chloride solution
Middle immersion removes copper foil, obtains graphene layer；The graphene layer of acquisition is transferred on Si substrate, it is compound to form Si/ graphene
Substrate.
The GaN nano-pillar height that step (4) obtains is 50~150nm, diameter is 40~50nm.
The GaN nano-pillar height that step (5) obtains is 350~500nm, and diameter is 40~50nm.
Epitaxial growth GaN nano-pillar is obtained by the above method in silicon/graphene compound substrate.
In silicon/graphene compound substrate epitaxial growth GaN nano-pillar be used to prepare semiconductor laser, light emitting diode or
Solar battery.
Application of the epitaxial growth GaN nano-pillar in photolysis water hydrogen in silicon/graphene compound substrate.
The principle of the present invention is as follows:
The temperature section processing that the present invention obtains high order by high temperature and low temperature keeps diameter uniform, both improves height
The inhomogeneities of temperature growth nano-pillar, and improve the column of low-temperature epitaxy nano-pillar to mixed and disorderly situation.When growth temperature is lower, receive
The direction of growth of meter Zhu is unordered, but the diameter homogeneity of nano-pillar is high, when nanocolumn growth temperature is higher, nanometer column diameter
Homogeneity is poor.As a result, the present invention in Si/ graphene compound substrate first in high growth temperature under the conditions of carry out nano-pillar just
Phase growth, makes to form the preferable GaN nano-pillar of order；Then growth temperature is reduced, low temperature is raw in high order nano-pillar
The uniform nano-pillar of long diameter.Finally obtain the GaN nano-pillar that order is good, diameter is uniform.
Compared with prior art, the present invention has the following advantages and beneficial effects:
1, the present invention is compound on a si substrate by graphene, reduces the lattice mismatch between Si and GaN, promotes low defect
The growth of density, the GaN nano-pillar of high-crystal quality, and high order and low temperature are obtained by high temperature and keep diameter uniform
Temperature section processing, had not only improved the inhomogeneities of high growth temperature nano-pillar, but also improved the column of low-temperature epitaxy nano-pillar to mixed and disorderly
Situation；
2, the present invention carries out the growth of GaN nano-pillar using Si/ graphene compound substrate, due to Si substrate and graphene
With thermal conductivity height, growth and manufacturing process are mature, are conducive to development low cost, high-performance GaN high power device；
3, GaN of the invention nanometer rod structure is deformation relaxation, and low-defect-density, crystal quality is high, therefore prepare
The carrier radiation recombination efficiency of GaN nanometers of base for post photoelectric material devices is high, can increase substantially nitride device such as semiconductor
The photoelectric conversion efficiency of laser, light-emitting diode luminous efficiency and solar battery, and improve photolysis water hydrogen efficiency；
4, the growth technique that the present invention uses does not use catalyst, does not also need the system for carrying out carrying out substrate in pattern
Make, the present invention has simple and easy, repeatability height, with short production cycle.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of epitaxial growth GaN nano-pillar in silicon of the invention/graphene compound substrate, wherein 11-
GaN nano-pillar, 12-Si/ graphene compound substrate, 13- graphene layer, 14-Si substrate；
Fig. 2 is epitaxial growth GaN nano-pillar scanning electron microscope diagram in silicon/graphene compound substrate of embodiment 1；
Fig. 3 is that the high-resolution transmitted electron of epitaxial growth GaN nano-pillar in silicon/graphene compound substrate of embodiment 1 is aobvious
Micro mirror photo.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are not
It is limited to this.
In silicon of the invention/graphene compound substrate epitaxial growth GaN nano-pillar structural schematic diagram as shown in Figure 1, from
Under it is supreme successively include Si substrate 14, graphene layer 13, GaN nano-pillar 11.
Si substrate 14 and graphene layer 13 form silicon/graphene compound substrate 12 (i.e. Si/ graphene compound substrate).
The Si substrate is using (111) face as the substrate of epitaxial surface；(0001) face of GaN is parallel to (111) face of Si.Stone
The black alkene number of plies is single layer or multilayer.The diameter of GaN nano-pillar is 40-50nm.
Embodiment 1
(1) selection of Si substrate and its crystal orientation: general commercial Si substrate is used, using (111) face as epitaxial surface, outside crystal
Prolong orientation relationship are as follows: (0001) face of GaN is parallel to (111) face of Si, i.e. it is raw to facilitate extension by GaN (0001) //Si (111)
Long high-quality GaN nano-pillar；
(2) Si substrate surface polishes: Si substrate surface being polished with diamond mud, cooperates optical microphotograph sem observation
Substrate surface is processed by shot blasting after not having scratch, then using the method for chemically mechanical polishing；
(3) Si substrate cleans: it is clear that the HF for being 1:10 with volume ratio with deionized water mixed liquor carries out standard ultrasound to substrate
It washes 1 minute, then uses deionized water repeated flushing 1 minute, finally dried up with high-purity drying nitrogen；
(4) it is big that grown on copper foil 3 layers of graphene the preparation of Si/ graphene compound substrate: are cut into 1 × 1cm
It is small, removal copper foil is impregnated in ferric chloride solution, obtains graphene layer；The graphene layer of acquisition is transferred on Si substrate, shape
At Si/ graphene compound substrate, cleaning drying；
(5) Si/ graphene compound substrate is placed in the growth room of molecular beam epitaxial growth system, using molecular beam epitaxy
Growing method, the high growth temperature GaN nano-pillar on the graphene layer of Si substrate, the condition of high growth temperature are that underlayer temperature is 1000
DEG C, N partial pressure is 6sccm, and Ga line amount is 6 × 10-8Torr, radio-frequency power 100W, growth time are 2 hours, obtain height
The high order GaN nano-pillar that about 80nm, diameter are about 40nm；
(6) underlayer temperature is down to 800 DEG C, continues the growth of GaN nano-pillar using molecular beam epitaxy accretion method,
N partial pressure is 6sccm, and Ga line amount is 6 × 10-8Torr, radio-frequency power 100W are grown 2 hours, are finally obtained height and are about
300nm, diameter are about the GaN nano-pillar that 40nm high is orderly, diameter is uniform.
Fig. 1 is the nano-pillar schematic diagram of this example.Fig. 2 is epitaxial growth in silicon/graphene compound substrate of embodiment 1
GaN nano-pillar scanning electron microscope diagram, from Fig. 2 it is observed that the uniformity of nano-pillar is higher, and diameter is uniform, does not have
Occur the inhomogenous nano-pillar of infundibulate, pyramid equal diameter.Show that present invention GaN nano-pillar obtained has with height
Sequence and the uniform feature of diameter.Fig. 3 is the high score of epitaxial growth GaN nano-pillar in silicon/graphene compound substrate of embodiment 1
It distinguishes transmission electron microscope photo, can be observed that lattice arrangement is neat, show the nano-pillar crystal matter grown using the present invention
Amount is high.
Embodiment 2
(1) selection of Si substrate and its crystal orientation: general commercial Si substrate is used, using (111) face as epitaxial surface, outside crystal
Prolong orientation relationship are as follows: (0001) face of GaN is parallel to (111) face of Si, i.e. it is raw to facilitate extension by GaN (0001) //Si (111)
Long high-quality GaN nano-pillar；
(2) Si substrate surface polishes: Si substrate surface being polished with diamond mud, cooperates optical microphotograph sem observation
Substrate surface is processed by shot blasting after not having scratch, then using the method for chemically mechanical polishing.
(3) Si substrate cleans: it is clear that the HF for being 1:10 with volume ratio with deionized water mixed liquor carries out standard ultrasound to substrate
It washes 1 minute, then uses deionized water repeated flushing 1 minute, finally dried up with high-purity drying nitrogen.
(4) preparation of Si/ graphene compound substrate: Si substrate is placed in chemical vapor depsotition equipment (CVD), carries out stone
The growth of black alkene grows the graphene layer that the number of plies is 5 layers, forms Si/ graphene compound substrate.
(5) the Si/ graphene compound substrate for growing the graphene that is of five storeys is transmitted to the growth of molecular beam epitaxial growth system
Room first sets underlayer temperature as 900 DEG C, carries out the growth of GaN at high temperature using molecular beam epitaxy, and N partial pressure is 6sccm, Ga
Line amount is 6 × 10-8Torr, radio-frequency power 100W, growth time are 3 hours, obtain height about 100nm, diameter and are about
The high order GaN nano-pillar of 45nm.
(6) underlayer temperature is down to 700 DEG C, continues the growth of GaN nano-pillar using molecular beam epitaxy.N is divided
6sccm, Ga line amount are 6 × 10-8Torr, radio-frequency power 100W are grown 2 hours, and finally obtaining height is 350nm, diameter
For the GaN nano-pillar that 45nm high is orderly, diameter is uniform.
The GaN nano-pillar that embodiment 2 is grown is roughly the same with the GaN nano-pillar that embodiment 1 is grown, and example 2 is given birth to
The height of long GaN nano-pillar is higher, and diameter is slightly larger than the GaN nano-pillar that embodiment 1 is grown, crystal quality and implementation
1 indifference of example, repeats no more in the present embodiment.
The present invention is during epitaxial growth GaN nano-pillar on preparing silicon/graphene compound substrate, high growth temperature and low
When temperature growth GaN nano-pillar, the condition of high growth temperature GaN nano-pillar is that N partial pressure is 2-8sccm, Ga line amount be (2~8) ×
10-8Torr, radio-frequency power are 50~300W, and growth time is 1.5~3 hours；The condition of low-temperature epitaxy be N partial pressure be 2~
8sccm, Ga line amount are (2~8) × 10-8Torr, radio-frequency power are 50~300W, and growth time is 1.5~3 hours.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. epitaxial growth GaN nano-pillar in silicon/graphene compound substrate, it is characterised in that: from bottom to up successively include Si substrate,
Graphene layer, GaN nano-pillar.
2. epitaxial growth GaN nano-pillar in silicon/graphene compound substrate according to claim 1, it is characterised in that: the Si
Substrate is using (111) face as epitaxial surface；(0001) face of GaN is parallel to (111) face of Si；
The diameter of GaN nano-pillar is 40~50nm.
3. epitaxial growth GaN nano-pillar in silicon/graphene compound substrate according to claim 1, it is characterised in that: described
GaN nano-pillar is obtained by high growth temperature and low-temperature epitaxy；The temperature of high growth temperature is 900~1100 DEG C, low-temperature epitaxy
Temperature is 650~800 DEG C.
4. any one of according to claim 1~3 in the silicon/graphene compound substrate epitaxial growth GaN nano-pillar preparation side
Method, it is characterised in that: the following steps are included:
(1) Si substrate cleans；
(2) it prepares Si/ graphene compound substrate: preparing graphene layer on a si substrate；
(3) high growth temperature GaN nano-pillar: molecular beam epitaxy is used, high growth temperature GaN nanometers on the graphene layer of Si substrate
Column, the temperature of high growth temperature are 900~1100 DEG C；
(4) low-temperature epitaxy GaN nano-pillar: use molecular beam epitaxy, by the GaN nano-pillar of step (3) continue at low temperature into
Row growth, the temperature of low temperature are 650~800 DEG C.
5. according to claim 4 in silicon/graphene compound substrate epitaxial growth GaN nano-pillar preparation method, feature
It is: the selection of Si substrate and its crystal orientation: using Si substrate, using (111) face as epitaxial surface, crystalline epitaxial orientation relationship are as follows:
(0001) face of GaN is parallel to (111) face of Si.
6. according to claim 4 in silicon/graphene compound substrate epitaxial growth GaN nano-pillar preparation method, feature
Be: the condition of step (3) high temperature growth GaN nano-pillar is that N partial pressure is 2~8sccm, and Ga line amount is (2~8) × 10- 8Torr, radio-frequency power are 50~300W, and growth time is 1.5~3 hours；
It is 2~8sccm that the condition of low-temperature epitaxy, which is N partial pressure, in step (4), and Ga line amount is (2~8) × 10-8Torr, radio frequency function
Rate is 50~300W, and growth time is 1.5~3 hours.
7. according to claim 4 in silicon/graphene compound substrate epitaxial growth GaN nano-pillar preparation method, feature
Be: Si/ graphene compound substrate described in step (2) grows graphene layer by vapour deposition process on a si substrate or incites somebody to action
Graphene layer is transferred on Si substrate.
8. according to claim 4 in silicon/graphene compound substrate epitaxial growth GaN nano-pillar preparation method, feature
Be: the GaN nano-pillar height of step (3) high temperature growth is 50~150nm, diameter is 40~50nm；
The GaN nano-pillar height finally obtained in step (4) is 350~500nm, diameter 40-50nm.
9. any one of according to claim 1~3 in the silicon/graphene compound substrate epitaxial growth GaN nano-pillar application,
Be characterized in that: epitaxial growth GaN nano-pillar is used to prepare semiconductor laser, light emitting diode in silicon/graphene compound substrate
Or solar battery.
10. any one of according to claim 1~3 in the silicon/graphene compound substrate epitaxial growth GaN nano-pillar application,
It is characterized by: application of the epitaxial growth GaN nano-pillar in photolysis water hydrogen in silicon/graphene compound substrate.
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