CN104409587B - A kind of InGaN base blue-green light LED epitaxial structure and growing method - Google Patents
A kind of InGaN base blue-green light LED epitaxial structure and growing method Download PDFInfo
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Abstract
The invention provides epitaxial growth method and the structure thereof of a kind of InGaN base blue-green light LED, the growing method of its epitaxial structure includes step in detail below: Sapphire Substrate carries out in ammonia atmosphere the high temperature anneal, temperature is reduced to 530 580 degree, and adjust epitaxial growth atmosphere with growing low temperature InGaN nucleating layer, rise high-temperature afterwards and grow the involuntary doped layer of InGaN, N-shaped InGaN layer, In successivelyyGa1‑yN/InxGa1‑xN(y > x) multiple quantum well active layer, p AlInGaN electronic barrier layer, p-type InGaN layer and p++ type InGaN contact layer.InGaN base blue green light LED epitaxial structure provided by the present invention, owing to reducing the lattice mismatch of quantum-well materials and matrix material, can effectively reduce the piezoelectric polarization fields in active area, thus improve luminous efficiency.
Description
Technical field
The present invention relates to a kind of InGaN base blue-green light LED epitaxial structure and growing method, belong to photoelectric material
With devices field.
Background technology
GaN base high brightness blue, green, white light emitting diode (LED) owing to having that energy consumption is low, life-span length, pollution-free, anti-severe
The features such as environment capacity is strong, are widely used in multiple fields such as display and illumination.
For traditional bluish-green LED of GaN base, its active area basic structure is InGaN/GaN MQW.Although
GaN base semi-conducting material and device obtain development greatly, but still there is many Science and Technology problems and have to be solved.
Quantum confined Stark effect problem in first, InGaN/GaN SQW.Lattice paprmeter due to InGaN is more than the crystalline substance of GaN
Lattice constant, in the InGaN/GaN SQW along the growth of [0001] direction, GaN barrier layer is (the highest with InGaN potential well layer
The InGaN of In component) between there is bigger lattice mismatch, InGaN layer, by action of compressive stress, produces strong in active area
Piezoelectric polarization fields.The existence of polarized electric field can make the energy band run-off the straight of SQW, produces quantum confined Stark effect.Its knot
Fruit is that the energy gap at SQW can reduce, simultaneously the electronics eigen wave function of quantum well conduction band and the hole intrinsic ripple of valence band
Function spatially separates so that electronics is remarkably decreased at the recombination probability of active area with hole, the luminous effect of SQW
Rate reduces.It can be said that the quantum confined Stark effect caused by piezoelectric polarization electric field is to affect in InGaN/GaN base LED
The one of the main reasons of quantum efficiency.Second, efficiency rapid drawdown problem.For GaN base LED, generally close at the lowest electric current
Under degree, its external quantum efficiency just can reach peak value.Along with the continuation of electric current density increases, the external quantum efficiency of LED starts gradually
Declining and decline the most rapidly, this so-called efficiency rapid drawdown problem becomes a bottleneck of restriction GaN base great power LED development.
The lattice mismatch institute producing existence one common reason, i.e. active area potential well layer and potential barrier interlayer of problem above
The strong piezoelectric polarization fields caused.At present, GaN base is blue, green light LED epitaxial structure is typically to utilize " two-step method " to grow, due to
Lattice mismatch bigger between substrate and epitaxial material and thermal mismatching, there is unavoidable higher density position in the epitaxial layer grown
The defects such as mistake.And, for obtaining the GaN epitaxial layer of better quality, the growth temperature used is high;Expand for reducing the longitudinal direction of dislocation
Exhibition, typically requires that the u-GaN layer grown and n-GaN layer thickness reach several micron, thus causes the epitaxial growth time long.More
Seriously, owing in multiquantum well region, lattice mismatch between barrier layer GaN and potential well layer InGaN is big, cause in active area
Piezoelectric polarization fields is big, finally have impact on the luminous efficiency of LED.Many scholars propose some and solve polarized electric fields and ask in recent years
Topic method, mainly have: the heavy doping of SQW potential barrier, the nitride of growth of cubic crystallographic system, along semi-polarity or non-polar plane
Grow, utilize In content gradually variational SQW, use the SQW of In component stagger arrangement, superlattices, the quaternization of use polarization coupling
Compound, original GaN barrier layer replace with InGaN potential barrier and use p-InGaN to substitute p-type GaN etc..By these effort,
The harmful effect of device performance is decreased by polarization field, but these are the most all the improvement in GaN base LED.
Summary of the invention
The present invention solves in current existing GaN base blue green light LED epitaxial structure due between active area InGaN and GaN relatively
The strong piezoelectric polarization fields problem that big lattice mismatch is caused, it is provided that a kind of InGaN base blue-green light LED epitaxial structure
And growing method.
A kind of InGaN base blue-green light LED epitaxial structure of the present invention is to realize by the following technical solutions
: a kind of InGaN base blue-green light LED epitaxial structure, including the low temperature InGaN nucleating layer being from bottom to top arranged in order,
The involuntary doped layer of high temperature InGaN, N-shaped InGaN layer, InyGa1-yN/InxGa1-xN (y > x) multiple quantum well layer, p-AlInGaN electricity
Sub-barrier layer, p-type InGaN layer and p++ type InGaN contact layer.
The present invention uses the GaN forming core layer and involuntary doping commonly used in the InGaN current GaN base LED structure of replacement
Layer, with InxGa1-xN/InyGa1-yN MQW is as active area, design growth InGaN base blue green light LED.This epitaxial structure can
Effectively reducing the piezoelectric polarization fields in multiquantum well region, device light emitting efficiency than co-wavelength traditional GaN base blue green light LED improves
More than 5%;And epitaxial growth temperature is relatively low, in epitaxial structure, the thickness of involuntary doped layer and n-layer is less, thus reduces
Manufacturing cost.
The growing method of InGaN base blue-green light LED epitaxial structure of the present invention is by the following technical solutions
Realize: the growing method of a kind of InGaN base blue-green light LED epitaxial structure comprises the steps:
(1) substrate annealing processes: (0001) surface sapphire substrate being annealed in hydrogen atmosphere, annealing temperature is
1060 DEG C, then cool to 580 DEG C and be passed through ammonia, substrate is carried out nitrogen treatment 6 minutes;
(2) growing low temperature InGaN nucleating layer: hydrogen atmosphere is converted into nitrogen atmosphere, opens gallium source TMGa and indium source
TMIn, under being passed through 0-200sccm hydrogen atmosphere, grows the thick low temperature InGaN nucleation of about 30nm at a temperature of 530-580 DEG C
Layer, growth pressure is 600mbar;
(3) the growth involuntary doped layer of high temperature InGaN: closing TMGa and TMIn, temperature rises to 770 DEG C, pressure is down to
150mbar, is again turned on TMGa and TMIn, the involuntary doping InGaN layer of growth 0.2-1.5 micron;
(4) growing n-type InGaN layer: keep the growth temperature in previous step and pressure constant, is passed through silane, growth thickness
The N-shaped InGaN layer of the Si doping that degree is 0.3-2.5 micron, carrier concentration magnitude is 1018cm-3, growth closes silicon after terminating
Alkane;
(5) growth InyGa1-yN/InxGa1-xN(y > x) multiple quantum well layer: close TMGa, open TEGa, grow successively
InxGa1-xN barrier layer and InyGa1-yN potential well layer, wherein y > x, barrier layer thickness is 10-15nm, and growth temperature is 770 DEG C, trap
Layer thickness is 2-5nm, and growth temperature is 690-740 DEG C, and growth pressure is maintained at 400mbar, and SQW number is 2-20;
(6) growth p-AlInGaN electronic barrier layer: keep the growth temperature in previous step constant, open aluminum source TMAl
With magnesium source-two cyclopentadienyl magnesium, being adjusted by reative cell pressure to 150mbar, to grow p-type AlInGaN electronic barrier layer, its thickness is
20-30nm, with atomic number percentages Al component as 10-30%, In component is 5-8%, and hole concentration magnitude is 1017cm-3;
(7) growth p-type InGaN layer: close TMAl, keeps the growth temperature in previous step and reative cell pressure constant,
Growth thickness is 100nm, and hole concentration magnitude is 1017cm-3P-type InGaN layer;
(8) growth p++ type InGaN contact layer: the flow of two cyclopentadienyl magnesium is increased 40-60sccm, keeps in previous step
Growth temperature and pressure are constant, and growth thickness is the p++-InGaN layer of 20nm;
(9) cooling the temperature to 750 DEG C, anneal under pure nitrogen gas atmosphere, annealing time is 15 minutes, is then down to
Room temperature, terminates growth.
In described step (2), (3), (4), (6), (7) and (8), TMIn, TMGa and NH3Respectively as In, Ga and N
Source.
In described step (4), the adulterant of described Si doping is silane.
In described step (5), described TMIn, TEGa and NH3Source respectively as In, Ga and N.
In described step (6), described Al source is TMAl, and the adulterant of described p-type doping is two cyclopentadienyl magnesium.
In described step (7) and (8), the adulterant of described p-type doping is two cyclopentadienyl magnesium.
InGaN base blue green light LED epitaxial structure of the present invention and growing method, compared with prior art have the advantage that
Owing to III-nitride magnitude relationship of lattice paprmeter in c face is: InN > GaN > AlN, so
In employed in InGaN base LED active areayGa1-yN / InxGa1-xN(y > x) MQW than tradition GaN base LED active
InGaN/GaN MQW that district is used, the lattice mismatch of its barrier layer and potential well interlayer reduces, thus advantageously reduces
Piezoelectric polarization fields.Therefore, InGaN base blue green light LED epitaxial structure of the present invention is significantly reduced compared to traditional GaN base LED
The piezoelectric polarization fields of active area, thus realize the raising of LED epitaxial structure luminescent properties.Additionally, it is bluish-green relative to tradition GaN base
Light LED, in InGaN base blue green light LED of the present invention, the growth temperature of each main epitaxial layer reduces, the involuntary doped layer of InGaN and n
The thickness of type InGaN layer decreases, thus can shorten growth time, reduces cost;And InGaN base blue green light of the present invention
The growing method of LED epitaxial structure is mutually compatible with traditional GaN base LED growth technology, it is not necessary to big technology upgrading and
Scrap build, beneficially large-scale production and application.
Accompanying drawing explanation
Fig. 1 is InGaN base blue green light LED epitaxial structure schematic diagram.
Fig. 2 is InGaN base blue green light LED multi-quantum pit structure schematic diagram.
1-(0001) surface sapphire substrate, 2-low temperature InGaN nucleating layer, the involuntary doped layer of 3-high temperature InGaN, 4-N-shaped
InGaN layer, 5-InyGa1-yN/InxGa1-xN (y > x) multiple quantum well layer, 51-InxGa1-xN barrier layer, 52-InyGa1-yN
Potential well layer, 6-p-AlInGaN electronic barrier layer, 7-p-type InGaN layer, 8-p++ type InGaN contact layer.
Detailed description of the invention
A kind of InGaN base blue-green light LED epitaxial structure, becomes including the low temperature InGaN being from bottom to top arranged in order
Stratum nucleare 2, the involuntary doped layer of high temperature InGaN 3, N-shaped InGaN layer 4, InyGa1-yN/InxGa1-xN(y > x) multiple quantum well layer 5, p-
AlInGaN electronic barrier layer 6, p-type InGaN layer 7 and p++ type InGaN contact layer 8.
The low temperature InGaN nucleating layer 2 being positioned at the bottom in described epitaxial structure is grown in (0001) surface sapphire substrate 1
On.
The growing method of a kind of InGaN base blue-green light LED epitaxial structure comprises the steps:
(1) substrate annealing processes: (0001) surface sapphire substrate being annealed in hydrogen atmosphere, annealing temperature is
1060 DEG C, then cool to 580 DEG C and be passed through ammonia, substrate is carried out nitrogen treatment 6 minutes;
(2) growing low temperature InGaN nucleating layer: hydrogen atmosphere is converted into nitrogen atmosphere, opens gallium source TMGa and indium source
TMIn, be passed through 0-200sccm(may select 0,50sccm, 100sccm, 150sccm, 200sccm) under hydrogen atmosphere, at 530-
The thick InGaN nucleation of about 30nm is grown at a temperature of 580 DEG C (optional 530 DEG C, 540 DEG C, 550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C)
Layer, growth pressure is 600mbar;
(3) the growth involuntary doped layer of high temperature InGaN: closing TMGa and TMIn, temperature rises to 770 DEG C, pressure is down to
150mbar, is again turned on TMGa and TMIn, growth 0.2-1.5 micron (optional 0.2 micron, 0.4 micron, 0.6 micron, 0.8
Micron, 1.0 microns, 1.2 microns, 1.4 microns, 1.5 microns) involuntary doping InGaN layer;
(4) growing n-type InGaN layer: keep the growth temperature in previous step and pressure constant, is passed through silane, growth thickness
Degree for 0.3-2.5 micron (optional 0.3 micron, 0.5 micron, 0.7 micron, 0.9 micron, 1.1 microns, 1.3 microns, 1.5 micro-
Rice, 1.7 microns, 1.9 microns, 2.1 microns, 2.3 microns, 2.5 microns) Si doping N-shaped InGaN layer, carrier concentration amount
Level is 1018cm-3, growth closes silane after terminating;
(5) growth InyGa1-yN/InxGa1-xN(y > x) multiple quantum well layer: close TMGa, open TEGa, grow successively
InxGa1-xN barrier layer 51 and InyGa1-yN potential well layer 52, wherein y > x, barrier layer thickness is 10-15nm, and growth temperature is 770
DEG C, well layer thickness is 2-5nm, and growth temperature is 690-740 DEG C, and growth pressure is maintained at 400mbar, and SQW number is 2-20
Individual (optional 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20);
(6) growth p-AlInGaN electronic barrier layer: keep the growth temperature in previous step constant, open aluminum source TMAl
With magnesium source-two cyclopentadienyl magnesium, being adjusted by reative cell pressure to 150mbar, to grow p-type AlInGaN electronic barrier layer, its thickness is
20-30nm, may select 30%, 25%, 20%, 15%, 10% with atomic number percentages Al component for 10-30%(), In component is about
5-8%(may select 5%, 6%, 7%, 8%), hole concentration magnitude is 1017cm-3;
(7) growth p-type InGaN layer: close TMAl, keeps the growth temperature in previous step and reative cell pressure constant,
Growth thickness is 100nm, and hole concentration magnitude is 1017cm-3P-type InGaN layer;
(8) growth p++ type InGaN contact layer: by two cyclopentadienyl magnesium flow increase 40-60sccm(may select 40sccm,
45sccm, 50sccm, 55sccm, 60sccm), keep the growth temperature in previous step and pressure constant, growth thickness is
The p++-InGaN layer of 20nm;
(9) cooling the temperature to 750 DEG C, anneal under pure nitrogen gas atmosphere, annealing time is 15 minutes, is then down to
Room temperature, terminates growth.
The growing method of 1 one kinds of InGaN base blue-green light LED epitaxial structures of embodiment, comprises the steps:
(1) substrate annealing processes: (0001) surface sapphire substrate being annealed in hydrogen atmosphere, annealing temperature is
1060 DEG C, then cool to 580 DEG C and be passed through ammonia, substrate is carried out nitrogen treatment 6 minutes;
(2) growing low temperature InGaN nucleating layer: hydrogen atmosphere is converted into nitrogen atmosphere, opens gallium source TMGa and indium source
TMIn, under being passed through 50sccm hydrogen atmosphere, grows the thick InGaN nucleating layer of 30nm at a temperature of 580 DEG C, and growth pressure is
600mbar;
(3) the growth involuntary doped layer of high temperature InGaN: closing TMGa and TMIn, temperature rises to 770 DEG C, pressure is down to
150mbar, is again turned on TMGa and TMIn, grows the involuntary doping InGaN layer of 1 micron;
(4) growing n-type InGaN layer: keep the growth temperature in previous step and pressure constant, is passed through silane, growth thickness
The N-shaped InGaN layer of the Si doping that degree is 1.5um, carrier concentration reaches 7 × 1018cm-3, growth closes silane after terminating;
(5) growth InyGa1-yN/InxGa1-xN multiple quantum well layer: close TMGa, open TEGa, grow In successivelyxGa1-xN
Barrier layer and InyGa1-yN potential well layer, wherein y > x, barrier layer thickness is 12nm, and growth temperature is 770 DEG C, and well layer thickness is
3nm, growth temperature is 690 DEG C, and growth pressure is maintained at 400mbar, and SQW number is 6;
(6) growth p-AlInGaN electronic barrier layer: keep the growth temperature in previous step constant, open aluminum source TMAl
With magnesium source-two cyclopentadienyl magnesium, being adjusted by reative cell pressure to 150mbar, to grow p-type AlInGaN electronic barrier layer, its thickness is
25nm, with atom number percentages Al component for 17%, In component is 5%, and hole concentration magnitude is 1017cm-3;
(7) growth p-type InGaN layer: close TMAl, keeps the growth temperature in previous step and reative cell pressure constant,
Growth thickness is 100nm, and hole concentration magnitude is 1017cm-3P-type InGaN layer;
(8) growth p++ type InGaN contact layer: the flow of two cyclopentadienyl magnesium is increased 50sccm, keeps the growth in previous step
Temperature and pressure are constant, and growth thickness is the p++-InGaN layer of 20nm;
(9) cooling the temperature to 750 DEG C, anneal under pure nitrogen gas atmosphere, annealing time is 15 minutes, is then down to room
Temperature, terminates growth.
The growing method of 2 one kinds of InGaN base blue-green light LED epitaxial structures of embodiment, comprises the steps:
(1) substrate annealing processes: (0001) surface sapphire substrate being annealed in hydrogen atmosphere, annealing temperature is
1060 DEG C, then cool to 580 DEG C and be passed through ammonia, substrate is carried out nitrogen treatment 6 minutes;
(2) growing low temperature InGaN nucleating layer: hydrogen atmosphere is converted into nitrogen atmosphere, opens gallium source TMGa and indium source
TMIn, under being passed through 50sccm hydrogen atmosphere, grows the thick low temperature InGaN nucleating layer of 30nm, growth pressure at a temperature of 580 DEG C
For 600mbar.
(3) the growth involuntary doped layer of high temperature InGaN: closing TMGa and TMIn, temperature rises to 770 DEG C, pressure is down to
150mbar, is again turned on TMGa and TMIn, grows the involuntary doping InGaN layer of 1 micron;
(4) growing n-type InGaN layer: keep the growth temperature in previous step and pressure constant, is passed through silane, growth thickness
Degree is the N-shaped InGaN layer of 1.5um, and carrier concentration reaches 7 × 1018cm-3, growth closes silane after terminating;
(5) growth InyGa1-yN/InxGa1-xN multiple quantum well layer: close TMGa, open TEGa, grow In successivelyxGa1-xN
Barrier layer and InyGa1-yN potential well layer, wherein y > x, barrier layer thickness is 12nm, and growth temperature is 770 DEG C, and well layer thickness is
3nm, growth temperature is 740 DEG C, and growth pressure is maintained at 400mbar, and SQW number is 6;
(6) growth p-AlInGaN electronic barrier layer: keep the growth temperature in previous step constant, open aluminum source TMAl
With magnesium source-two cyclopentadienyl magnesium, being adjusted by reative cell pressure to 150mbar, to grow p-type AlInGaN electronic barrier layer, its thickness is
25nm, with atomic number percentages Al component for 17%, In component is 5%, and hole concentration magnitude is 1017cm-3;
(7) growth p-type InGaN layer: close TMAl, keeps the growth temperature in previous step and reative cell pressure constant,
Growth thickness is 100nm, and hole concentration magnitude is 1017cm-3P-type InGaN layer;
(8) growth p++ type InGaN contact layer: the flow of two cyclopentadienyl magnesium is increased 50sccm, keeps the growth in previous step
Temperature and pressure are constant, and growth thickness is the p++-InGaN layer of 20nm;
(9) cooling the temperature to 750 DEG C, anneal under pure nitrogen gas atmosphere, annealing time is 15 minutes, is then down to room
Temperature, terminates growth.
In component is controlled, wherein by the intake in aggregate balancing source, growth temperature, pressure and the hydrogen flowing quantity being passed through
Low temperature InGaN nucleating layer 2, the involuntary doped layer of high temperature InGaN 3, N-shaped InGaN layer 4, p-type AlInGaN layer 6, p-type InGaN layer 7
With In atom number all controls between 5-8% than content in p++ type InGaN layer 8.
Obviously, above-described embodiment is only for clearly demonstrating example, and not restriction to embodiment.Right
For those of ordinary skill in the field, can also make on the basis of the above description other multi-form change or
Variation.Here without also cannot all of embodiment be given exhaustive.And the obvious change thus amplified out or
Change among still in the protection domain of the invention.
Claims (2)
1. a growing method for InGaN base blue-green light LED epitaxial structure, described InGaN base blue green light light-emitting diodes
Pipe epitaxial structure includes low temperature InGaN nucleating layer (2), the involuntary doped layer of high temperature InGaN (3), the n being from bottom to top arranged in order
Type InGaN layer (4), InyGa1-yN/InxGa1-xN(y > x) multiple quantum well layer (5), p-AlInGaN electronic barrier layer (6), p-type
InGaN layer (7) and p++ type InGaN contact layer (8);Low temperature InGaN nucleating layer (2) being positioned at the bottom is grown in (0001) face
In Sapphire Substrate (1);
It is characterized in that, described method comprises the steps:
(1) substrate annealing processes: (0001) surface sapphire substrate being annealed in hydrogen atmosphere, annealing temperature is 1060
DEG C, then cool to 580 DEG C and be passed through ammonia, substrate is carried out nitrogen treatment 6 minutes;
(2) growing low temperature InGaN nucleating layer: hydrogen atmosphere is converted into nitrogen atmosphere, opens gallium source TMGa and indium source TMIn,
It is passed through under 0-200sccm hydrogen atmosphere, at a temperature of 530-580 DEG C, grows the thick low temperature InGaN nucleating layer of 30nm, growth pressure
For 600mbar;
(3) the growth involuntary doped layer of high temperature InGaN: closing TMGa and TMIn, temperature rises to 770 DEG C, pressure is down to
150mbar, is again turned on TMGa and TMIn, the involuntary doping InGaN layer of growth 0.2-1.5 micron;
(4) growing n-type InGaN layer: keeping the growth temperature in previous step and pressure constant, be passed through silane, growth thickness is
The N-shaped InGaN layer of the Si doping of 0.3-2.5 micron, carrier concentration magnitude is 1018cm-3, growth closes silane after terminating;
(5) growth InyGa1-yN/InxGa1-xN(y > x) multiple quantum well layer: close TMGa, open TEGa, grow In successivelyxGa1-xN
Barrier layer and InyGa1-yN potential well layer, wherein y > x, barrier layer thickness is 10-15nm, and growth temperature is 770 DEG C, and well layer thickness is
2-5nm, growth temperature is 690-740 DEG C, and growth pressure is maintained at 400mbar, and SQW number is 2-20;
(6) growth p-AlInGaN electronic barrier layer: keep the growth temperature in previous step constant, open aluminum source TMAl and magnesium
Source-two cyclopentadienyl magnesium, adjusts reative cell pressure to 150mbar, and to grow p-type AlInGaN electronic barrier layer, its thickness is 20-
30nm, with atomic number percentages Al component as 10-30%, In component is 5-8%, and hole concentration magnitude is 1017cm-3;
(7) growth p-type InGaN layer: close TMAl, keeps the growth temperature in previous step and reative cell pressure constant, growth
Thickness is 100nm, and hole concentration magnitude is 1017cm-3P-type InGaN layer;
(8) growth p++ type InGaN contact layer: the flow of two cyclopentadienyl magnesium is increased 40-60sccm, keeps the growth in previous step
Temperature and pressure are constant, and growth thickness is the p++-InGaN layer of 20nm;
(9) cooling the temperature to 750 DEG C, anneal under pure nitrogen gas atmosphere, annealing time is 15 minutes, is then down to room temperature,
Terminate growth.
The growing method of a kind of InGaN base blue-green light LED epitaxial structure the most according to claim 1, its feature
It is: control In component by the intake in aggregate balancing source, growth temperature, pressure and the hydrogen flowing quantity being passed through, the lowest
Temperature InGaN nucleating layer (2), the involuntary doped layer of high temperature InGaN (3), N-shaped InGaN layer (4), p-type AlInGaN layer (6), p-type
In InGaN layer (7) and p++ type InGaN layer (8), In atom number all controls between 5-8% than content.
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