CN110444640A - A kind of multi-wavelength GaN base core-shell nanometer rod LED device structure and preparation method thereof - Google Patents
A kind of multi-wavelength GaN base core-shell nanometer rod LED device structure and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/16—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular crystal structure or orientation, e.g. polycrystalline, amorphous or porous
- H01L33/18—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular crystal structure or orientation, e.g. polycrystalline, amorphous or porous within the light emitting region
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
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Abstract
The invention discloses a kind of multi-wavelength GaN base core-shell nanometer rod LED device structures and preparation method thereof.The self-organizing Ni nano island to be formed of being annealed using high temperature ammonia prepares the GaN nanometer rods of high consistency as template, then wet etch techniques are used, repair the dry etching damage of nanorod surfaces, N-shaped GaN regrowth is carried out on resulting GaN nanometer stick array, form the six face columns with top cone, then the multiple quantum well layer being coated on each surface of GaN nanometer stick array and p-type GaN layer are stacked gradually, multi-wavelength GaN base core-shell nanometer rod LED device structure is obtained.The multiple quantum well layer on each of which surface of GaN nanometer stick array and cladding, p-type GaN layer constitute three-dimensional core-shell structure, can produce more number of photons under identical current density, improve the internal quantum efficiency of LED epitaxial structure.Method of the invention is not necessarily to patterned substrate, and process costs are low, simple and easy, is suitble to scale system, and gained core-shell nanometer rod array can be widely applied to opto-electronic device and microelectronic component.
Description
Technical field
The present invention relates to light emitting semiconductor device field more particularly to a kind of multi-wavelength GaN base core-shell nanometer rod LED components
Structure and preparation method thereof.
Background technique
In the direct band-gap semicondictor of broad stopband, GaN base semiconductor most potentiality to be exploited and development prospect, it is by feat of width
Wide band gap [ 0.64 eV (InN), 3.4eV (GaN), 6.2eV, (AlN) ] and superior performance (thermostabilization, chemical stabilization and
High thermal conductivity etc.), have become the focus and emphasis of photoelectron material in recent years and device research.GaN base white light LEDs, which have, to be used
Service life is long, small in size, photoelectric conversion efficiency is high and low advantage of generating heat, and shines in instrument and equipment illumination, airplane lighting, automobile
Bright, mobile phone, decorative lighting are used widely.
Traditional white light LEDs mainly excite yellow or multicolor phosphor using ultraviolet/purple/blue LED, thus
Obtain mixed white light；Also part research realizes mixed white light using the LED of multiple color.And single-chip white unstressed configuration
The Photoemission of powder mainly passes through the blue of cross direction profiles and the InGaN/GaN multiple quantum wells of green or passes through cascaded series
At InGaN and the multiple quantum wells of AlGaInP realize that difficulty is larger, and assorted luminous efficiency is difficult to match, and becomes
The main bugbear of Single chip white light research.For general lighting application, influence luminous efficiency problem most important two influence because
Element is strong polarization field and high indium InxGa1-xN crystalline quality is poor, this is that green polarity LED internal quantum is caused to be difficult to improve
The main reason for.Because polarization field mainly generates and is present in polar growth direction [(0002) c-axis direction], in order to overcome pole
Changing field influences, and in semi-polarity ,/extension InGaN active layer can reduce on non-polar plane/eliminates polarization field to luminous negative effect.
And become research hotspot with the GaN nanometer rods of non-polar plane and semi-polarity face.
GaN nanostructure is developed so far, and has had many scientists both at home and abroad to synthesize by different approach.For example, Kim
Et al. respectively 2004 with prepare GaN double quantum well nanometer with metal organic hydride vapour phase epitaxy (MOHVPE) within 2005
Stick array and high-brightness LED device；2006, the groups such as J. Goldberger and T. kuykendall all had by metal
The method of machine vapour phase epitaxy (MOCVD) has synthesized monocrystalline One-Dimensional GaN nanotube and nano column array；R. Calarco and L. W.
Tu et al. successively synthesizes GaN nano wire with molecular beam epitaxy (MBE)；Deb etc. uses silica as template, MOVPE legal system
The GaN nanometer rods of standby vertical alignment out.These above-mentioned methods are exactly so-called " from the bottom to top " method, these methods are needed from original
Son or molecule rank start to grow, and then arrive molecular cluster, then arrive nanostructure.Although many people study and obtain it is certain at
Fruit, but these methods in the size, length and crystallographic direction of GaN nano-pillar all be difficult control and be difficult to success, " by down toward
On " method encounters challenge in terms of large scale preparation GaN nano-pillar.Different from the method for these above-mentioned growths, another kind is " by upper
Under " method to obtain GaN nanostructure be another selection, the present invention, which only introduces, one such uses inductively coupled plasma
Etching (ICP) method prepares GaN nano-pillar.About the specific method of inductively coupled plasma etching (ICP) GaN, have
Many reports, for example, Shul et al. Cl2/H2/ Ar mixed gas etching GaN film obtain its etch rate be about 0.5 μm/
min；The discoveries such as Smith Cl2/ Ar is 980nm/min as the flank speed of etching gas；Shul group finds Cl again2/N2/
In Ar mixed gas, etch rate is with N2The increase of partial pressure and reduce；Kim et al. also studied in Cl2/BCl3Plasma is carved
Lose the relevant issues of GaN.Need to obtain size before ICP, the uniform nano particle of topographic profile does exposure mask, although as electronics
Beam photoetching and photoetching technique etc. can be on preparing nano-form, but high expense also prevents it in large scale preparation
Application.
In the present invention, the annealing of high temperature ammonia is used to form the Ni nano island of self-organizing as template, the annealing of high temperature ammonia
It can control size and the density etc. of Ni nano island, time, temperature and the original that the size on the island Ni and distribution are annealed with high temperature ammonia
Beginning Ni film thickness etc. is related；Cost is relatively low for this method, is also easier to the size and length of control nanometer rods, can be applied to big
Scale prepares nanometer rods, and the Ni nano island exposure mask that the present invention is obtained with this method prepares the GaN nano-pillar of high consistency.By
Stablize in GaN material chemical property, so generalling use dry etching.Compared with wet etching, dry etching has each to different
Property and line width the advantages of controlling, but since plasma has higher-energy, can be brought to the material surface that is etched larger
Damage, leads to the decline of device performance, this becomes problem anxious to be resolved in dry etching.This invention address that ICP etching system
Standby GaN nanometer rods, and establish the method for repairing nano-pillar etching injury.The skill combined using dry etching and wet etching
Art route obtains the GaN nanometer rods of high quality as template, epitaxial growth nucleocapsid InGaN/GaN Quantum Well LED structure, by
It is epitaxially formed InGaN/GaN Quantum Well core-shell structure in GaN nanometer rods, multi-wave length illuminating is realized, by adjusting the ruler of nanometer rods
Very little and height and In component, obtain Single chip white light LED, this is to realize a kind of photoemissive possible way of monolithic unstressed configuration whitewash
Diameter.
Summary of the invention
The purpose of the present invention is to provide a kind of multi-wavelength GaN base core-shell nanometer rod LED device structure and preparation method thereof,
To solve the above technical problems.
To achieve the above object the invention adopts the following technical scheme:
A kind of multi-wavelength GaN base core-shell nanometer rod LED device structure, including Ni layers of deposition and high temperature ammonia anneal to form Ni nanometers
Island；It further include the consistent GaN nano-pillar of height being prepared using Ni nano island exposure mask, and repair nanometer rods table using wet etching
The dry etching damage in face carries out N-shaped GaN regrowth on resulting GaN nanometer stick array, and being formed has top hexagonal pyramid
Six face columns, then stack gradually the multiple quantum well layer for being coated on GaN nanometer stick array and p-type GaN layer.
As a further solution of the present invention: described Ni layers with a thickness of 15nm~35nm, high temperature ammonia anneals to form Ni
Nano island, the size of the Ni nano island are 300nm~500nm.
As a further solution of the present invention: forming receiving for steep side walls using being dry-etched in GaN base structural membrane
Rice stick, the dry etching are ion beam etching, inductively coupled plasma etching or reactive ion etching.
As a further solution of the present invention: the GaN nanometer stick array height be 4 μm~7 μm, diameter be 200nm~
The Ni nano island of 350nm, the nanometer rods top are removed using nitric acid.
As a further solution of the present invention: the dry etching damage of GaN nanorod surfaces, institute are repaired using KOH solution
After stating KOH solution reparation, leakage current can be caused by leaving chemical contamination in GaN nanorod surfaces, remove surface chemistry using chloroazotic acid
Pollution.
As a further solution of the present invention: carrying out N-shaped GaN regrowth on the GaN nanometer stick array, formed to have and be received
(1-100) non-polar plane of meter ruler cun and (1-101) semi-polarity face.
As a further solution of the present invention: the multiple quantum well layer is InGaN/GaN multiple quantum well layer, InGaN well layer
With a thickness of 4nm~6nm, GaN barrier layer thickness is 10nm~15nm, and the period is 5~15, and the multiple quantum well layer has nano-scale
(1-100) non-polar plane and (1-101) semi-polarity face.
As a further solution of the present invention: the p-type GaN layer is the GaN layer of Mg doping, with a thickness of 50nm~100nm.
A kind of preparation method of multi-wavelength GaN base core-shell nanometer rod LED device structure, includes the following steps:
S1, Ni layers are deposited on substrate；
S2, high temperature ammonia anneal to form Ni nano island；
S3, using be dry-etched in GaN base structural membrane formed GaN nanometer stick array；
S4, the Ni nano island that GaN nanometer rods top is removed using nitration acid heat；
S5, the dry etching damage that GaN nanorod surfaces are repaired using KOH solution；
S6, the chemical contamination that surface is removed using chloroazotic acid；
S7, the GaN regrowth that Si doping is carried out on the GaN nanometer stick array, being formed has (1-100) of nano-scale non-
Polar surface and (1-101) semi-polarity face；
S8, the GaN nanometer rods cladding growth InGaN/GaN multiple quantum wells in the step S7
S9, p-type GaN layer is formed on the step S8 multiple quantum well layer.
As a further solution of the present invention: in the step S1, sample being cleaned by ultrasonic in acetone, alcohol, deionized water
After drying, one layer of 15nm~35nm thickness Ni metallic film is then plated on the surface thereof with physical vapor deposition (PVD)；
In the step S2, the Ni nano island forming method are as follows: Ni/GaN/ sapphire samples are put into 800 DEG C~900 DEG C of height
It in warm furnace and is passed through ammonia and carries out annealing 10min~12min, ammonia flow is 700~900ml/min, is used as template to be formed
Ni nanometer island structure, annealing be passed through nitrogen rapidly after a certain period of time with exclude the ammonia in furnace and serve as protection gas effect,
Finally, taking out sample after sample is cooling；
In the step S3, method that the dry etching forms GaN nanometer stick array are as follows: use chlorine and boron chloride as
Etching gas, flow remain 40~50sccm, 5~8sccm respectively, and intracavitary pressure, ICP power and radio frequency RF power are distinguished
It is set as 7.50 × 10-9Pa, 300W and 100W；
In the step S4, the method for the Ni nano island on nitration acid heat removal GaN nanometer rods top are as follows: temperature: 80~100
℃；Time: 5~10 min；
In the step S5, the method for KOH solution reparation GaN nanometer rods are as follows: corrode in the KOH solution that concentration is 1~1.5M and repair
Multiple, temperature is 80~10 DEG C, and the time is 10~30min；
In the step S6, the method for the chemical contamination on chloroazotic acid removal surface are as follows: be put into 10~20 min in chloroazotic acid, then going
It is cleaned by ultrasonic drying in ionized water；
In the step S7, institute's N-shaped GaN nanometer rods regrowth method are as follows: using TMGa as gallium source, SiH4For silicon source, NH3For nitrogen
Source, H2For carrier gas, growth temperature is 850 DEG C~1000 DEG C, and pressure 400mbar, V/III than being 800~1000, growth 10
~20min；Si doping concentration is about 4~6 × 1018cm-3；
In the step S8, the growing method of the multiple quantum well layer are as follows: GaN barrier layer growth temperature is 860 DEG C, InGaN well layer
Growth temperature is 750~800 DEG C, and reaction cavity pressure is controlled in 400mbar, barrier layer growth time 350~400s, TEGa flow
For 280 SCCM, well layer growth time 100~120s, TMIn flow set is 1000 SCCM, and TEGa flow is 280 SCCM,
NH3Remain at 17 slm；
In the step S9, the growing method of the p-type GaN layer are as follows: with a thickness of 50nm~100nm, Mg doping concentration is about 1
~2 × 1020 cm-3。
Compared with prior art, the invention has the following advantages that
The present invention anneals to form Ni nano island using high temperature ammonia, using the consistent GaN nano-pillar of etching method preparation height, then
The dry etching damage of nanorod surfaces is repaired using wet etching, finally passes through diauxic growth, and the smooth nucleocapsid of side wall is made
Nanometer stick array.Size and the density etc. that this preparation method can anneal to control Ni nano island by high temperature ammonia, the island Ni
Time, temperature and the original Ni film thickness that size is annealed with distribution with high temperature ammonia etc. is related；Cost is relatively low for this method, also more
It is easy to control the size and length of nano-pillar, can be applied to large scale preparation nano-pillar.
The multiple quantum well layer on each of which surface of GaN nanometer stick array of the present invention and cladding, p-type GaN layer constitute three-dimensional
Core-shell structure, large specific surface area compare thin-film material, can produce more number of photons under identical current density, improve
The internal quantum efficiency of the LED epitaxial structure.This core-shell structure can change the direction of propagation of photon simultaneously, increase photon
The probability of outgoing greatly improves external quantum efficiency to make more photon escapes into air.
Core-shell structure of GaN base nanometer rods of the present invention has (1-101) semi-polarity face and/(1-100) of nano-scale
Non-polar plane can effectively contain Stark effect, reduce polarized electric field, promote electron-hole recombination probability, improve outside LED
Prolong the internal quantum efficiency of structure.
The present invention repairs the dry etching damage of GaN nanorod surfaces using KOH solution, effectively improves nanometer rods quality,
To the non-radiative recombination center of rare source region, the internal quantum efficiency of LED epitaxial structure is improved.
InGaN/GaN multiple quantum well layer of the present invention is as luminous active area, (1-101) semi-polarity face and (1-
100) non-polar plane, these different faces have different In contents and trap thick, simultaneously because the diffusion of In atomic ratio Ga atom
Length is longer and nanometer rods are higher, has different In contents and trap thick in nanometer rods side wall different location, can be directly realized by
Multi-wave length illuminating.
The method of the present invention is not necessarily to patterned substrate, low in cost, simple and easy, is suitble to scale system, preparation gained core
Shell nanometer stick array can be widely applied to opto-electronic device and microelectronic component.
Detailed description of the invention
Fig. 1 is preparation flow figure of the present invention.
Fig. 2 (a) is the electron scanning micrograph of Ni nano island；It (b) is GaN base core-shell nanometer rod LED device structure
Cross sectional scanning electron microscope photo；(c) aobvious for the cross sectional scanning electron of single GaN base core-shell nanometer rod LED device structure
Micro mirror photo.
Specific embodiment
The present invention is further elaborated in the following with reference to the drawings and specific embodiments.The multi-wavelength GaN as shown in Fig. 1
The preparation flow figure of base core-shell nanometer rod LED device structure, Fig. 2 (a) are the electron scanning micrograph of Ni nano island；(b)
For the cross sectional scanning electron microscope photo of GaN base core-shell nanometer rod LED device structure；It (c) is single GaN base core-shell nanometer rod
The cross sectional scanning electron microscope photo of LED device structure.A kind of multi-wavelength GaN base core-shell nanometer rod LED component of the invention
The preparation method of structure the following steps are included:
1) primary sample is about 20 μm of thickness of the GaN film that HVPE is grown in (0001) Sapphire Substrate, by sample third
In ketone, alcohol, deionized water after ultrasonic cleaning drying；Then one layer of 25nm is plated on the surface thereof with physical vapor deposition (PVD)
Thick Ni metallic film；
2) then Ni/GaN/ sapphire samples are put into 850 DEG C of high temperature furnace and are passed through ammonia and carry out hot ammonia annealing 12min,
Ammonia flow is 800ml/min, and the size of Ni nano island is 350nm；
3) nanometer rods are prepared by ICP etching technics: puts it into the island inductively coupled plasma etching apparatus Zhong Yi Ni as mould
Plate performs etching.In etching process, use chlorine and boron chloride as etching gas, flow remain respectively 48sccm,
6sccm, intracavitary pressure, ICP power and radio frequency RF power are set to 7.5 × 10-9 Pa, 300W and 100W；
4) sample after etching is put into the Ni nano island that 5min in the nitric acid that concentration is 100 °C removes GaN nanometer rods top；
5) sample after etching is put into Corrosion Repair in the KOH solution that concentration is 1M, and temperature is 90 DEG C, time 20min；
6) sample is put into the chemical contamination that 15 min in chloroazotic acid remove surface, drying is then cleaned by ultrasonic in deionized water；
7) MOCVD is used to carry out the GaN nanometer rods regrowth of Si doping: using TMGa as gallium source, SiH4For silicon source, NH3For nitrogen source,
H2 For carrier gas, growth temperature is 860 DEG C, and pressure 400mbar, V/III, than being 895, grows 15min；Being formed has nanometer ruler
Very little (1-100) non-polar plane and/(1-101) semi-polarity face；Si doping concentration is about 5 × 1018 cm-3。
8) MOCVD is used to carry out multiple quantum well layer as InGaN/GaN multiple quantum well layer: InGaN well layer growth conditions, temperature
It is 730 DEG C；Pressure is 400 mbar；TEGa flow is 280 SCCM；TMI flow n is 800 SCCM；NH3Flow is 17000
SCCM；Time is 110s；10 layers of growth.Barrier layer growth conditions: growth temperature is 820 DEG C；Pressure is 400 mbar；TEGa flow
For 280SCCM；NH317000 SCCM of flow；Time is 390s.
9) growth of the p-type GaN layer of Mg doping is carried out using MOCVD, with a thickness of 60nm, Mg doping concentration is 1 ×
1020cm-3。
Traditional white light LEDs mainly excite yellow or multicolor phosphor using ultraviolet/purple/blue LED, thus obtain
The white light that must be mixed；Also part research realizes mixed white light using the LED of multiple color.And single-chip white unstressed configuration powder
Photoemission, mainly by cross direction profiles blue and green InGaN/GaN multiple quantum wells or by cascade composition
InGaN and the multiple quantum wells of AlGaInP realize that difficulty is larger, and assorted luminous efficiency is difficult to match, and becomes single
The main bugbear of chip white light research.The present invention provides a kind of methods for simply and easily obtaining multi-wave length illuminating, by dry
The GaN nanometer rods that method etching and the method for wet process reparation obtain high quality are template, epitaxial growth multi-wavelength nucleocapsid InGaN/GaN
Quantum Well LED structure.In addition, non-polar plane InGaN/GaN quantum well structure eliminates polarized electric field, reduce this support of quantum confinement
Gram this effect (QCSE) improves internal quantum efficiency.Meanwhile nucleocapsid GaN base nanometer rods LED structure reduces photon and sends out in inside
The probability of raw total reflection, increases light-emitting area, finally improves the luminous efficiency of device, optical property is often better than two dimension
GaN film.In addition, InGaN/GaN multiple quantum well layer is as luminous active area, (1- during isoepitaxial growth
101) semi-polarity face and (1-100) non-polar plane, these different faces have different In contents and trap thick, while In group split-phase
It is easier to migrate upwards from the bottom of non-polar plane than Ga, forms high In ingredient Quantum Well, to realize multi-wave length illuminating.
The above is present pre-ferred embodiments, for the ordinary skill in the art, according to the present invention
Introduction, in the case where not departing from the principle of the present invention and spirit, changes, modifications, replacement and change that embodiment is carried out
Type is still fallen within protection scope of the present invention.
Claims (10)
1. a kind of multi-wavelength GaN base core-shell nanometer rod LED device structure, it is characterised in that: including Ni layers of deposition and high temperature ammonia
Annealing forms Ni nano island；It further include the consistent GaN nano-pillar of height being prepared using Ni nano island exposure mask, and utilize wet process corruption
The dry etching damage of nanorod surfaces is repaired in erosion, and N-shaped GaN regrowth is carried out on resulting GaN nanometer stick array, forms tool
There are six face columns of top hexagonal pyramid, then stacks gradually the multiple quantum well layer for being coated on GaN nanometer stick array and p-type GaN layer.
2. a kind of multi-wavelength GaN base core-shell nanometer rod LED device structure according to claim 1, it is characterised in that: described
Ni layers with a thickness of 15nm~35nm, high temperature ammonia anneals to form Ni nano island, the size of the Ni nano island be 300nm~
500nm。
3. a kind of multi-wavelength GaN base core-shell nanometer rod LED device structure according to claim 1, it is characterised in that: use
The nanometer rods that steep side walls are formed in GaN base structural membrane are dry-etched in, the dry etching is ion beam etching, induction coupling
Close plasma etching or reactive ion etching.
4. a kind of multi-wavelength GaN base core-shell nanometer rod LED device structure according to claim 1, it is characterised in that: described
GaN nanometer stick array height is 4 μm~7 μm, and diameter is 200nm~350nm, and the Ni nano island on the nanometer rods top utilizes nitre
Acid removes.
5. a kind of multi-wavelength GaN base core-shell nanometer rod LED device structure according to claim 1, it is characterised in that: use
KOH solution is repaired the dry etching damage of GaN nanorod surfaces and is left after the KOH solution is repaired in GaN nanorod surfaces
Chemical contamination can cause leakage current, using chloroazotic acid removal surface chemistry pollution.
6. a kind of multi-wavelength GaN base core-shell nanometer rod LED device structure according to claim 1, it is characterised in that: described
N-shaped GaN regrowth is carried out on GaN nanometer stick array, forms (1-100) non-polar plane with nano-scale and (1-101) half
Polar surface.
7. a kind of multi-wavelength GaN base core-shell nanometer rod LED device structure according to claim 1, it is characterised in that: described
Multiple quantum well layer is InGaN/GaN multiple quantum well layer, InGaN well layer with a thickness of 4nm~6nm, GaN barrier layer thickness be 10nm~
15nm, period are 5~15, and the multiple quantum well layer has (1-100) non-polar plane and (1-101) semi-polarity of nano-scale
Face.
8. a kind of preparation method of multi-wavelength GaN base core-shell nanometer rod LED device structure according to claim 1, special
Sign is: the p-type GaN layer is the GaN layer of Mg doping, with a thickness of 50nm~100nm.
9. a kind of such as a kind of described in any item preparations of multi-wavelength GaN base core-shell nanometer rod LED device structure of claim 1-8
Method, characterized by the following steps:
S1, Ni layers are deposited on substrate；
S2, high temperature ammonia anneal to form Ni nano island；
S3, using be dry-etched in GaN base structural membrane formed GaN nanometer stick array；
S4, the Ni nano island that GaN nanometer rods top is removed using nitration acid heat；
S5, the dry etching damage that GaN nanorod surfaces are repaired using KOH solution；
S6, the chemical contamination that surface is removed using chloroazotic acid；
S7, the GaN regrowth that Si doping is carried out on the GaN nanometer stick array, being formed has (1-100) of nano-scale non-
Polar surface and (1-101) semi-polarity face；
S8, the GaN nanometer rods cladding growth InGaN/GaN multiple quantum wells in the step S7；
S9, p-type GaN layer is formed on the step S8 multiple quantum well layer.
10. a kind of preparation method of multi-wavelength GaN base core-shell nanometer rod LED device structure according to claim 9, special
Sign is,
It is then heavy with physical vapor after sample to be cleaned by ultrasonic to drying in acetone, alcohol, deionized water in the step S1
Product (PVD) plates one layer of 15nm~35nm thickness Ni metallic film on the surface thereof；
In the step S2, the Ni nano island forming method are as follows: Ni/GaN/ sapphire samples are put into 800 DEG C~900 DEG C of height
It in warm furnace and is passed through ammonia and carries out annealing 10min~12min, ammonia flow is 700~900ml/min, is used as template to be formed
Ni nanometer island structure, annealing be passed through nitrogen rapidly after a certain period of time with exclude the ammonia in furnace and serve as protection gas effect,
Finally, taking out sample after sample is cooling；
In the step S3, method that the dry etching forms GaN nanometer stick array are as follows: use chlorine and boron chloride as
Etching gas, flow remain 40~50sccm, 5~8sccm respectively, and intracavitary pressure, ICP power and radio frequency RF power are distinguished
It is set as 7.50 × 10-9Pa, 300W and 100W；
In the step S4, the method for the Ni nano island on nitration acid heat removal GaN nanometer rods top are as follows: temperature: 80~100
℃；Time: 5~10 min；
In the step S5, the method for KOH solution reparation GaN nanometer rods are as follows: corrode in the KOH solution that concentration is 1~1.5M and repair
Multiple, temperature is 80~10 DEG C, and the time is 10~30min；
In the step S6, the method for the chemical contamination on chloroazotic acid removal surface are as follows: be put into 10~20 min in chloroazotic acid, then going
It is cleaned by ultrasonic drying in ionized water；
In the step S7, institute's N-shaped GaN nanometer rods regrowth method are as follows: using TMGa as gallium source, SiH4For silicon source, NH3For nitrogen source,
H2For carrier gas, growth temperature is 850 DEG C~1000 DEG C, and pressure 400mbar, V/III than being 800~1000, growth 10~
20min；Si doping concentration is about 4~6 × 1018cm-3；
In the step S8, the growing method of the multiple quantum well layer are as follows: GaN barrier layer growth temperature is 860 DEG C, InGaN well layer
Growth temperature is 750~800 DEG C, and reaction cavity pressure is controlled in 400mbar, barrier layer growth time 350~400s, TEGa flow
For 280 SCCM, well layer growth time 100~120s, TMIn flow set is 1000 SCCM, and TEGa flow is 280 SCCM,
NH3Remain at 17 slm；
In the step S9, the growing method of the p-type GaN layer are as follows: with a thickness of 50nm~100nm, Mg doping concentration is about 1
~2 × 1020cm-3。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110993755A (en) * | 2019-12-18 | 2020-04-10 | 天津工业大学 | Electro-injection three-dimensional GaN core-shell structure Nano-LED and manufacturing method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898751A (en) * | 2009-05-27 | 2010-12-01 | 中国科学院半导体研究所 | Method for growing group III nitride nanometer material |
| US20130134440A1 (en) * | 2011-04-08 | 2013-05-30 | Zhong L. Wang | High-resolution Parallel-detection Sensor Array Using Piezo-Phototronics Effect |
| CN105932121A (en) * | 2016-05-05 | 2016-09-07 | 太原理工大学 | Three-dimensional LED epitaxial structure and preparation method thereof |
| CN107425095A (en) * | 2017-05-05 | 2017-12-01 | 江南大学 | A kind of method that the luminous InGaN/GaN quantum well structures of multiband are prepared using Ni nano-forms |
-
2019
- 2019-08-14 CN CN201910746696.5A patent/CN110444640A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898751A (en) * | 2009-05-27 | 2010-12-01 | 中国科学院半导体研究所 | Method for growing group III nitride nanometer material |
| US20130134440A1 (en) * | 2011-04-08 | 2013-05-30 | Zhong L. Wang | High-resolution Parallel-detection Sensor Array Using Piezo-Phototronics Effect |
| CN105932121A (en) * | 2016-05-05 | 2016-09-07 | 太原理工大学 | Three-dimensional LED epitaxial structure and preparation method thereof |
| CN107425095A (en) * | 2017-05-05 | 2017-12-01 | 江南大学 | A kind of method that the luminous InGaN/GaN quantum well structures of multiband are prepared using Ni nano-forms |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110993755A (en) * | 2019-12-18 | 2020-04-10 | 天津工业大学 | Electro-injection three-dimensional GaN core-shell structure Nano-LED and manufacturing method thereof |
| CN110993755B (en) * | 2019-12-18 | 2021-09-21 | 天津工业大学 | Electro-injection three-dimensional GaN core-shell structure Nano-LED and manufacturing method thereof |
| CN111293134A (en) * | 2020-02-06 | 2020-06-16 | 厦门大学 | Three-color Micro/Nano LED array without mass transfer and manufacturing method thereof |
| CN111293134B (en) * | 2020-02-06 | 2024-06-04 | 厦门大学 | Three-color Micro/Nano LED array without huge transfer and manufacturing method thereof |
| CN111724699A (en) * | 2020-06-12 | 2020-09-29 | 福州大学 | NLED pixel setting and repairing method |
| CN111724699B (en) * | 2020-06-12 | 2021-07-06 | 福州大学 | NLED pixel setting and repairing method |
| CN113044809A (en) * | 2021-03-22 | 2021-06-29 | 南京大学 | Vertical Ga2O3 nanotube ordered array and preparation method thereof |
| CN113044809B (en) * | 2021-03-22 | 2022-03-18 | 南京大学 | Vertical Ga2O3 nanotube ordered array and preparation method thereof |
| CN116936705A (en) * | 2023-07-27 | 2023-10-24 | 星钥(珠海)半导体有限公司 | RGB device and preparation method thereof |
| CN118380524A (en) * | 2024-06-20 | 2024-07-23 | 聚灿光电科技股份有限公司 | GaN-based spontaneous white light LED epitaxial film structure and preparation method thereof |
| CN118380524B (en) * | 2024-06-20 | 2024-09-13 | 聚灿光电科技股份有限公司 | GaN-based spontaneous white light LED epitaxial film structure and preparation method thereof |
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