CN109132997A - (In) the GaN nano-pillar and the preparation method and application thereof being grown on Ti substrate - Google Patents
(In) the GaN nano-pillar and the preparation method and application thereof being grown on Ti substrate Download PDFInfo
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Abstract
The invention discloses (In) GaN nano-pillars being grown on Ti substrate and the preparation method and application thereof, including the AlN buffer layer being grown on Ti substrate, (In) GaN nano-pillar for being grown on AlN buffer layer.The Ti substrate that the present invention uses is cheap, advantageously reduces device cost;Secondly, the Ti substrate conduction performance that the present invention uses is good, device technology can be simplified without preparing Ohm contact electrode directly as the electrode of device.The preparation method of (In) GaN nano-pillar on Ti substrate disclosed by the invention, it is simple with growth technique, the low advantage of preparation cost, and (In) GaN nano-pillar crystal quality prepared by the present invention is good, forbidden bandwidth is adjustable, large specific surface area is, it can be achieved that visible light responds, suitable for photoelectrolysis aquatic products hydrogen.
Description
Technical field
The present invention relates to (In) GaN nano-pillar field, in particular to (In) the GaN nano-pillar being grown on Ti substrate and
Preparation method and application.
Background technique
Hydrogen Energy has many advantages, such as that energy density is high, recyclable and environmentally protective, in science and techniques of defence, space flight and aviation, work
It is largely used in industry production.As a kind of ideal energy carrier, hydrogen can generate power (such as Hydrogen fuel wheel by burning
Machine, hydrogen vehicle engine etc.), each class of electronic devices and electric drive vehicle can also be driven by modes such as hydrogen fuel cells.Photoelectricity
Chemical (Photoelectrochemical, PEC) solution aquatic products hydrogen can solar energy effectively be converted and be stored as it is clean, can
Regenerated Hydrogen Energy has important research significance.
In the past few decades, researcher is directed generally to explore the semiconductor material that can be realized efficient PEC Xie Shui
Material.Wherein, (In) GaN material band gap is adjustable, it can be achieved that photoelectrolysis aquatic products hydrogen in visible spectrum, causes researcher
Extensive concern.In addition, showing some unique performances when (In) GaN material narrows down to the nano-pillar of nano-scale:
(1) (In) GaN nano-pillar has high specific surface area, and high specific surface area makes strain in nano-pillar side wall by effective relaxation,
It can significantly reduce defect concentration, and then reduce the probability of carrier non-radiative recombination;(2) nanometer rod structure reduces photoproduction current-carrying
Son arrive semiconductor/electrolyte interface migration distance, reduce the probability of recombination of photo-generated carrier, be more advantageous to light induced electron,
Hole respectively attends liberation of hydrogen, oxygen evolution reaction;(3) specific surface area of nano-pillar superelevation can enhance light absorption, improve to sunlight
Utilization, and increase semiconductor/electrolyte interfacial reaction area.In conclusion (In) GaN nano-pillar is in photoelectrolysis water
Producing hydrogen field has unique advantage, is ideal photoelectrolysis water material.
Currently, (In) GaN nano-pillar is mainly based upon sapphire, single crystal Si substrate.And they often there is resistivity
Larger (1014 Ω cm of sapphire, adulterate the Ω of Si~10 cm), it is at high cost the problems such as.The biggish sapphire of resistivity, monocrystalline
Substrate material of the Si as (In) GaN nanometers of base for post optoelectronic poles needs to be deposited more metal layers and prepares ohm when preparing electrode
Electrode is contacted, the complexity of device technology is increased.Therefore one kind substrate material that is cheap, conducting electricity very well is found to answer
It is great to (In) GaN nano-pillar photoelectrolysis aquatic products hydrogen application value for growing (In) GaN nano-pillar.
Summary of the invention
In order to overcome the disadvantages mentioned above and deficiency of the prior art, the present invention uses the Ti that one kind is at low cost, conducts electricity very well
Metal substrate.Metal Ti substrate conducts electricity very well, can directly as the electrode of device, without preparing Ohm contact electrode,
Simplify device technology.Again, metal Ti substrate price is relatively low, advantageously reduces device cost.
The purpose of the present invention is to provide a kind of (In) GaN nano-pillars and preparation method thereof being grown on Ti substrate.
(In) the nanometer rod structure for being reduced in size to nanometer range formation of GaN epitaxial layer is deformation relaxation, brilliant almost without defect
Weight is high.
Another object of the present invention is to provide the photoelectrolysis aquatic products of above-mentioned (In) GaN nano-pillar being grown on Ti substrate
Hydrogen application.
The purpose of the present invention is achieved through the following technical solutions.
(In) the GaN nano-pillar being grown on Ti substrate, including Ti substrate 1, the AlN buffer layer being grown on Ti substrate 1
2, (In) the GaN nano-pillar 3 being grown on AlN buffer layer 2.
Preferably, the Ti substrate is general T i metal.
Preferably, the AlN buffer layer with a thickness of 5~50nm, it is raw when the thickness of AlN buffer layer reaches 5~50nm
The stress of long (In) GaN nano-pillar is released.In addition, (In) GaN nano-pillar makes strain receive due to biggish specific surface area
Rice column side wall is conducive to (In) GaN nano-pillar that high quality is grown in Ti metal substrate by effective relaxation.
Preferably, described (In) the GaN nano-pillar includes GaN, InGaN, InN nano-pillar and InGaN/GaN, InN/
InGaN core/shell structure nano-pillar.
Preferably, the height of described (In) the GaN nano-pillar is 60~2000nm, and diameter is 15~500nm.
The preparation method of above-described (In) GaN nano-pillar being grown on Ti substrate, comprising the following steps:
(1) selection of substrate: Ti substrate is used;
(2) substrate surface polishes: Ti substrate surface being polished with diamond mud, cooperates optical microphotograph sem observation Ti
Substrate surface is processed by shot blasting after not having scratch, then using the method for chemically mechanical polishing;
(3) substrate cleans: the Ti substrate after step (2) polishing being cleaned by ultrasonic, to remove remained on surface organic matter, finally
It is dried up with high-purity drying nitrogen;
(4) substrate annealing is handled: Ti substrate obtained by step (3) being put into reaction chamber, is served as a contrast at 900~1100 DEG C to Ti
Bottom is made annealing treatment, to obtain smooth surface;
(5) preparation of AlN buffer layer: Ti underlayer temperature obtained by rate-determining steps (4) is 450~550 DEG C, revolving speed 5-10r/
Min, deposition thickness are the metal Al film of 5~50nm, are then nitrogenized using Nitrogen plasma source to metal Al film, etc.
Source power is 200~450W, and nitrogen flow is 1~5sccm, and AlN buffer layer is obtained on Ti substrate, is conducive to carry out
The growth of subsequent (In) GaN nano-pillar;
(6) growth of (In) GaN nano-pillar: using molecular beam epitaxial growth technique, and control underlayer temperature is 450~1000
DEG C, substrate revolving speed is 5-10r/min, and Ga line flow is 1.0 × 10-8~1.5 × 10-7Torr, In line flow be 1.0 ×
10-8~5 × 10-7Torr, nitrogen flow are 1~5sccm, plasma source power 200-450W, are obtained in step (5)
(In) GaN nano-pillar is grown on AlN buffer layer.
Preferably, step (3) ultrasonic cleaning be Al substrate acetone, ethyl alcohol, water is cleaned by ultrasonic to 2 respectively~
5min。
Preferably, the time of step (4) described annealing is 0.5~1 hour.
Preferably, the time of step (5) described nitridation is 10~30 minutes.
Application of above-described (In) the GaN nano-pillar being grown on Ti substrate in photoelectrolysis aquatic products hydrogen.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) present invention uses general T i metal as substrate, serves as a contrast relative to other substrate materials, such as sapphire, single crystalline Si
Bottom, cheaper can reduce device manufacturing cost.
(2) substrate material of the Ti metal as growth (In) GaN nano-pillar, can be directly as the electrode of device.In this way, nothing
Multiple layer metal need to be deposited and prepare Ohm contact electrode, simplify device preparation technology.
(3) at normal temperature, one layer easily generated of surface of metal titanium very thin fine and close oxide film, can resist strong acid
The even effect of chloroazotic acid, shows excellent chemical stability.Accordingly, with respect to other metal substrate materials, Ti metal is more suitable
For growing (In) GaN nano-pillar as substrate material applied to photoelectrolysis aquatic products hydrogen.
(4) present invention uses Ti metal as substrate, first deposits one layer of metal aluminium film, then carries out nitrogen treatment, shape
At AlN buffer layer, be conducive to forming core and the growth of subsequent (In) GaN nano-pillar.Also, when AlN buffer layer thickness reaches 5~
50nm, (In) GaN nano-pillar are in relaxed state.In addition, (In) GaN nano-pillar makes strain exist due to biggish specific surface area
Nano-pillar side wall is conducive to (In) GaN nano-pillar that high quality is grown in Ti metal substrate by effective relaxation.
(5) (In) GaN nano-pillar that the present invention is prepared, crystal quality is high, and dislocation density is low.On the one hand, AlN is buffered
The use of layer, reduces the lattice mismatch between Ti substrate and (In) GaN, can efficiently reduce the formation of dislocation, be conducive to
The growth of high quality (In) GaN nano-pillar;On the other hand, (In) GaN nanometers of rod structures are deformation relaxations, almost without lacking
It falls into, crystal quality is high.(In) the GaN nano-pillar for the high-crystal quality being finally prepared, it is non-radiative to significantly reduce carrier
Compound probability can increase substantially (In) GaN nano-pillar in photoelectrolysis aquatic products hydrogen using upper photoelectric conversion efficiency.
(6) for (In) GaN nano-pillar by adjusting In component, band gap is adjustable in 0.67-3.4eV range, it can be achieved that can
Photoelectrolysis aquatic products hydrogen in light-exposed spectral region improves the utilization rate to sunlight.
(7) (In) the GaN nano-pillar on Ti substrate is grown in when being applied to photoelectrolysis aquatic products hydrogen, (In) GaN nano-pillar
Nanometer rod structure reduce photo-generated carrier to semiconductor/electrolyte interface migration distance, reduce photo-generated carrier
The probability of recombination is more advantageous to light induced electron, hole is gone to participate in liberation of hydrogen, oxygen evolution reaction respectively.
(8) specific surface area of (In) GaN nano-pillar superelevation can enhance light absorption, improve the utilization to sunlight, and
Semiconductor/electrolyte interfacial reaction area is increased, is conducive to improve the energy conversion efficiency that solar energy is converted into Hydrogen Energy.
Detailed description of the invention
Fig. 1 is the schematic cross-section that embodiment 1 is grown in the InGaN nano-pillar on Ti substrate.
Fig. 2 is the SEM top view that embodiment 1 is grown in InGaN nano-pillar on Ti substrate.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1
It is grown in the preparation method of the InGaN nano-pillar on Ti substrate, comprising the following steps:
(1) selection of substrate: using general T i metal as substrate.
(2) substrate surface polishes: Ti substrate surface being polished with diamond mud, cooperation optical microphotograph sem observation lining
Bottom surface is processed by shot blasting after not having scratch, then using the method for chemically mechanical polishing.
(3) substrate cleans: Ti substrate acetone, ethyl alcohol, deionized water are subjected to ultrasonic cleaning 3 minutes to substrate respectively,
Finally dried up with high-purity drying nitrogen.
(4) substrate annealing is handled: being placed the substrate into reaction chamber, it is small to carry out annealing 0.5 to Ti substrate at 900 DEG C
When.
(5) formation of AlN buffer layer: at 500 DEG C, substrate revolving speed is 10r/min for underlayer temperature control, and deposition thickness is
Then the metal Al film of 30nm nitrogenizes metallic film using Nitrogen plasma source, plasma source power 350W,
Nitrogen flow is 2sccm, and nitridation time is 20 minutes, obtains AlN film.
(6) preparation of high quality InGaN nano-pillar: using molecular beam epitaxial growth technique, and underlayer temperature is 550 DEG C, lining
Bottom revolving speed is 10r/min, and In line flow is 8 × 10-8Torr, Ga line flow are 2.8 × 10-8Torr, nitrogen flow are
2.5sccm, plasma source power 400W, growth obtains InGaN nano-pillar on the AlN buffer layer that step (5) obtains.
As shown in Figure 1, the present embodiment is grown in the schematic cross-section of the InGaN nano-pillar on Ti substrate, including Ti substrate
1, the AlN buffer layer 2 being grown on Ti substrate 1, the InGaN nano-pillar 3 being grown on AlN buffer layer 2.
As shown in Fig. 2, the present embodiment is grown in the scanning electron microscope top view of InGaN nano-pillar on Ti substrate.
The InGaN nano-pillar that the present embodiment is grown on Ti substrate is used for photoelectrolysis aquatic products hydrogen: manufactured in the present embodiment
InGaN nano-pillar In content is 45%, according toCalculation formula obtains
Prepared InGaN nano-pillar band gap is 1.84eV, and spectral absorption range is 200~670nm.Prepared wide spectrum is rung
InGaN nano-pillar is fabricated to optoelectronic pole on the Ti substrate answered, the specific steps are as follows: forming ohm it is not necessary that multiple layer metal is deposited connects
Touching directly in Ti metal back side bonded metal conducting wire, and protects entire metal back side with insulating epoxy.Later, using electricity
Chem workstation carries out optical electro-chemistry test, specific as follows: using 0.5mol/L H2SO4Solution is as electrolyte, prepared light
Electrode is used as reference electrode as anode, saturated calomel electrode (SCE), and Pt line is as cathode and 300W Xe lamp (luminous intensity
~100mW/cm2) it is used as light source, test obtains density of photocurrent-bias plot.On the Ti substrate that this technique is prepared
InGaN nanometers of base for post optoelectronic poles are in 1.0V vs.SCE bias, density of photocurrent 25mA/cm2, bias photoelectric conversion efficiency
It (ABPE) is 5.75%.
Embodiment 2
It is grown in the preparation method of the InN nano-pillar on Ti substrate, comprising the following steps:
(1) selection of substrate: using general T i metal as substrate.
(2) substrate surface polishes: Ti substrate surface being polished with diamond mud, cooperation optical microphotograph sem observation lining
Bottom surface is processed by shot blasting after not having scratch, then using the method for chemically mechanical polishing.
(3) substrate cleans: Ti substrate acetone, ethyl alcohol, deionized water respectively carrying out substrate to be cleaned by ultrasonic each 2 points
Clock is finally dried up with high-purity drying nitrogen.
(4) substrate annealing is handled: being placed the substrate into reaction chamber, it is small to carry out annealing 0.5 to Ti substrate at 900 DEG C
When.
(5) formation of AlN buffer layer: at 450 DEG C, substrate revolving speed is 5r/min for underlayer temperature control, and deposition thickness is
Then the metal aluminium film of 50nm nitrogenizes metallic film using Nitrogen plasma source, the power of plasma source is
200W, nitrogen flow 5sccm, nitridation time are 30 minutes, obtain AlN buffer layer.
(6) preparation of high quality InV nano-pillar: using molecular beam epitaxial growth technique, and underlayer temperature is 400 DEG C, substrate
Revolving speed is 10r/min, and In line flow is 5 × 10-7Torr, Ga line flow are 1.0 × 10-8Torr, nitrogen flow are
5.0sccm, plasma source power 450W, growth obtains InGaN nano-pillar on the AlN buffer layer that step (5) obtains.
Embodiment 3
It is grown in the preparation method of the GaN nano-pillar on Ti substrate, comprising the following steps:
(1) selection of substrate: using general T i metal as substrate.
(2) substrate surface polishes: Ti substrate surface being polished with diamond mud, cooperation optical microphotograph sem observation lining
Bottom surface is processed by shot blasting after not having scratch, then using the method for chemically mechanical polishing.
(3) substrate cleans: Ti substrate acetone, ethyl alcohol, deionized water respectively carrying out substrate to be cleaned by ultrasonic each 5 points
Clock is finally dried up with high-purity drying nitrogen.
(4) substrate annealing is handled: being placed the substrate into reaction chamber, it is small to carry out annealing 1 to Ti substrate at 1100 DEG C
When.
(5) formation of AlN buffer layer: at 550 DEG C, substrate revolving speed is 10r/min for underlayer temperature control, and deposition thickness is
Then the metal aluminium film of 50nm nitrogenizes metallic film using Nitrogen plasma source, the power of plasma source is
450W, nitrogen flow 1sccm, nitridation time are 10 minutes, obtain AlN buffer layer.
(6) preparation of high-quality GaN nano-pillar: using molecular beam epitaxial growth technique, and underlayer temperature is 1000 DEG C, substrate
Revolving speed is 5r/min, and In line flow is 1.0 × 10-8Torr, Ga line flow are 1.5 × 10-7Torr, nitrogen flow are
1.0sccm, plasma source power 200W, growth obtains GaN nano-pillar on the AlN buffer layer that step (5) obtains.
The GaN nano-pillar that the present embodiment is grown in Ti metal substrate is used for photoelectrolysis aquatic products hydrogen: the present embodiment preparation
InN nano-pillar band gap be 3.4eV, spectral absorption range be 200~365nm.By GaN nano-pillar on prepared Ti substrate
It is fabricated to optoelectronic pole, the specific steps are as follows: form Ohmic contact it is not necessary that multiple layer metal is deposited, be directly bonded gold in Ti metal back side
Belong to conducting wire, and protects entire metal back side with insulating epoxy.Later, optical electro-chemistry survey is carried out using electrochemical workstation
Examination, it is specific as follows: to use 0.5mol/L HBr solution as electrolyte, prepared optoelectronic pole is as anode, saturated calomel electrode
(SCE) it is used as reference electrode, Pt line is as cathode and 300W Xe lamp (luminous intensity~100mW/cm2) it is used as light source, test
Obtain density of photocurrent-bias plot.GaN nanometers of base for post optoelectronic poles are in 1.0V on the Ti substrate that this technique is prepared
When vs.SCE bias, density of photocurrent 10mA/cm2, bias photoelectric conversion efficiency (ABPE) is 2.3%.
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. (In) the GaN nano-pillar being grown on Ti substrate, which is characterized in that including Ti substrate (1), be grown in Ti substrate (1)
On AlN buffer layer (2), (In) the GaN nano-pillar (3) being grown on AlN buffer layer (2).
2. (In) GaN nano-pillar according to claim 1 being grown on Ti substrate, which is characterized in that the Ti substrate
For general T i metal.
3. (In) GaN nano-pillar according to claim 1 being grown on Ti substrate, which is characterized in that the AlN buffering
Layer with a thickness of 5 ~ 50 nm.
4. (In) GaN nano-pillar according to claim 1 being grown on Ti substrate, which is characterized in that (In) GaN
Nano-pillar includes GaN, InGaN, InN nano-pillar.
5. (In) GaN nano-pillar according to claim 4 being grown on Ti substrate, which is characterized in that (In) GaN
The height of nano-pillar is 60 ~ 2000 nm, and diameter is 15 ~ 500 nm.
6. the method for preparing described in any item (In) the GaN nano-pillars being grown on Ti substrate of claim 1-5, feature exist
In, comprising the following steps:
(1) selection of substrate: Ti substrate is used;
(2) substrate surface polishes: Ti substrate surface being polished with diamond mud, cooperates optical microphotograph sem observation Ti substrate
Surface is processed by shot blasting after not having scratch, then using the method for chemically mechanical polishing;
(3) substrate cleans: the Ti substrate after step (2) polishing being cleaned by ultrasonic, to remove remained on surface organic matter, finally with height
Pure drying nitrogen drying;
(4) substrate annealing is handled: Ti substrate obtained by step (3) is put into reaction chamber, at 900 ~ 1100 oC to Ti substrate into
Row annealing, to obtain smooth surface;
(5) preparation of AlN buffer layer: Ti underlayer temperature obtained by rate-determining steps (4) is 450 ~ 550 oC, and revolving speed is 5-10 r/
Min, deposition thickness are the metal Al film of 5 ~ 50 nm, are then nitrogenized using Nitrogen plasma source to metal Al film, etc.
Source power is 200 ~ 450 W, and nitrogen flow is 1 ~ 5 sccm, and AlN buffer layer is obtained on Ti substrate;
(6) growth of (In) GaN nano-pillar: using molecular beam epitaxial growth technique, and control underlayer temperature is 450 ~ 1000 oC,
Substrate revolving speed is 5-10 r/min, and Ga line flow is 1.0 × 10-8~1.5×10-7 Torr, In line flow are 1.0 × 10-8
~5×10-7 Torr, nitrogen flow are 1 ~ 5 sccm, and plasma source power is 200-450 W, in the AlN that step (5) obtains
(In) GaN nano-pillar is grown on buffer layer.
7. preparation method according to claim 6, which is characterized in that step (3) ultrasonic cleaning is to use Al substrate
Acetone, ethyl alcohol, water are cleaned by ultrasonic 2 ~ 5 min respectively.
8. preparation method according to claim 6, which is characterized in that the time of step (4) described annealing is 0.5 ~ 1
Hour.
9. preparation method according to claim 6, which is characterized in that the time of step (5) described nitridation is 10 ~ 30 points
Clock.
10. described in any item (In) the GaN nano-pillars being grown on Ti substrate of claim 1-5 are in photoelectrolysis aquatic products hydrogen
Using.
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CN110284198A (en) * | 2019-07-22 | 2019-09-27 | 南京大学 | A kind of molecular beam epitaxy accretion method controlling GaN nano wire structure and pattern |
CN110747506A (en) * | 2019-10-22 | 2020-02-04 | 华南理工大学 | Transition metal doped InxGa1-xN nano column and preparation method and application thereof |
CN112951956A (en) * | 2021-03-12 | 2021-06-11 | 广东先导稀材股份有限公司 | GaN-based LED epitaxial wafer and preparation method thereof |
CN116377594A (en) * | 2023-04-04 | 2023-07-04 | 华南理工大学 | Passivation method based on InN nano-column on p-GaAs substrate, passivation final product composite structure and application thereof |
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