CN103337568B - Strained super lattice tunnel junction ultraviolet LED epitaxial structure and preparation method thereof - Google Patents
Strained super lattice tunnel junction ultraviolet LED epitaxial structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of strained super lattice tunnel junction ultraviolet LED epitaxial structure and preparation method thereof, epitaxial structure is from top to bottom: epitaxial growth substrate, AlN resilient coating, N-shaped AlGaN layer, multi layer quantum well, electronic barrier layer, strained super lattice, N-shaped degeneracy doped with Al GaN layer, N-shaped Si doped with Al GaN layer; Strained super lattice comprises p-type AlGaN layer and Al
yga
1-yn/Al
xga
1-xn.The entirety under the effect of polarized electric field of being with of AlGaN moves to low-yield direction, p-AlGaN/SSL/n*-AlGaN tunnel junction is formed after superlattice structure contacts with heavily doped N-shaped AlGaN again, electronics in p-type AlGaN valence band is under the effect of external electric field, be tunneling to N-shaped AlGaN side by tunnel effect, form hole at p-type AlGaN.Skin-material becomes n-AlGaN from p-type AlGaN, avoids the problem of p-type ohmic contact.
Description
[technical field]
The invention belongs to semiconductor diode technical field, be specifically related to a kind of strained super lattice tunnel junction structure that utilizes and strengthen ultraviolet LED epitaxial structure of p-type nitride material performance and preparation method thereof.
[background technology]
Ultraviolet light-emitting diode (lightemittingdiode, hereinafter referred to as LED), because of advantages such as its wavelength is short, photon energy is high, homogenizers, there is important application in the field such as illumination and HIGH-DENSITY OPTICAL STORAGE of physical sterilization, high color rendering index (CRI).At present, large quantifier elimination achieves important breakthrough at technical elements such as crystal mass, high Al contents and short wavelength's structural designs, the deep ultraviolet LED component of below 300 nanometers is prepared in success, realizes the power stage of milliwatt level, and obtain remarkable progress in reliability.
But the AlGaN material of high Al contents can reduce carrier concentration and carrier mobility.Along with the increase of Al component, the acceptor activation of Mg atom can linearly increase, and make p-type dopant activation very low, under room temperature, hole concentration is very low, and therefore, the preparation of p-type ohmic contact becomes very difficult.Good ohmic contact decides electrical pumping efficiency, thus directly affects the overall performance of semiconductor device.
At present, in order to improve the carrier concentration of p-type layer, reduce p-type ohmic contact resistance, the technology adopted mainly utilizes the p-type layer of superlattice structure, then on p-type AlGaN, regrowth one deck p-type GaN cap, as ohmic contact layer, and to be realized by annealing conditions optimization.But these methods can only optimize p-type ohmic contact within the specific limits, its resistivity is the several order of magnitude larger than N-shaped ohmic contact resistance rate still, and thick p-type GaN cap can produce the absorption loss of photon.
A kind of low resistance GaN/InGaN/GaN tunnel junction structure, by equal for N-shaped GaN and p-type GaN degeneracy doping, regrowth one deck N-shaped GaN on p-type GaN, and the highfield utilizing interfacial polarization electric charge to produce makes the GaNpn above quantum well tie the condition meeting tunnel diode, the electronics of such p-type GaN valence band just enters into the conduction band of N-shaped GaN by tunneling effect, thus leaves a large amount of hole in p-type GaN valence band.And the contact electrode of upper surface is the N-shaped GaN surface be directly made on p-type GaN, namely positive and negative contact electrode all realizes under N-shaped GaN structure, this not only avoids p-type ohmic contact, realizes the target of low-resistance rate, and the performance maintaining device is complete.But this method is still and make use of heavy doping to realize degeneracy, thus obtains tunnel junctions, but the difficulty of p-type nitride doping still exists.
Under a kind of material is in strain system, and when producing elastic strain, can change to some extent by band.Wherein, normal strain component causes moving integrally of conduction band and valence band, and amount of movement is respectively: Δ E
c=a
c(ε
xx+ ε
yy+ ε
zz), Δ E
v=a
v(ε
xx+ ε
yy+ ε
zz), wherein a
c, a
vbe respectively semi-conducting material conduction band limit and valence-band edge hydrostatic pressure deformation potential, ε is the strain that the normal pressure of all directions produces.
When lattice mismatch is larger (7% ~ 9%), as long as the thickness of each layer of crystal is enough thin, the stress that lattice mismatch is formed just can be adjusted by the elastic strain of each layer, so just can grow the strained super lattice (StrainedSuperlattice is called for short SSL) without misfit dislocation.The defect state density utilizing superlattice structure can reduce dislocation to bring, improves efficient carrier concentration; In addition, the stress field produced by the strain controlling superlattice can make at the bottom of the conduction band of semi-conducting material quantitatively and top of valence band moves integrally, and this has very important meaning for realizing non-degenerate tunnel junctions.
[summary of the invention]
Technical problem to be solved by this invention is to provide a kind of tunnel junction ultraviolet LED epitaxial structure and preparation method, to improve the hole of p-type AlGaN layer, solves ohmic contact bottleneck problem.
To achieve these goals, the present invention adopts following technical scheme:
A kind of strained super lattice tunnel junction ultraviolet LED epitaxial structure, comprise epitaxial growth substrate, and grow AlN resilient coating, N-shaped AlGaN layer, periodic multilayer quantum well, electronic barrier layer, strained super lattice, N-shaped degeneracy doped with Al GaN layer, N-shaped Si doped with Al GaN cap in epitaxial growth substrate successively; Wherein, described strained super lattice comprises the single or multiple lift Al of p-type AlGaN layer and continued growth thereon
yga
1-yn/Al
xga
1-xn, wherein, y>x>0.65.
As the preferred embodiments of the present invention, the material of described multi layer quantum well is Al
0.65ga
0.35n/Al
0.7ga
0.3n, alternating growth.
As the preferred embodiments of the present invention, the material of described electronic barrier layer is Al
0.8ga
0.2n/Al
0.77ga
0.23n.
As the preferred embodiments of the present invention, described single or multiple lift Al
yga
1-yn/Al
xga
1-xn is that Mg and Si mixes altogether, and the doping form of mixing altogether is δ distribution.
As the preferred embodiments of the present invention, Al in described superlattice
xga
1-xin N, Al component is not absorbed with the photon ensuring active layer and send higher than the Al component in quantum-well materials.
As the preferred embodiments of the present invention, the doping content of described N-shaped degeneracy doped with Al GaN layer is greater than 1 × 10
19cm
-3, can be with as degenerate state, be beneficial to the formation of then wearing knot.
As the preferred embodiments of the present invention, the doping content of described N-shaped Si doped with Al GaN cap is greater than 1 × 10
18cm
-3, as the anode ohmic contact layer of making devices.
Prepare a preparation method for strained super lattice tunnel junction ultraviolet LED epitaxial structure, comprise the following steps:
(1) in epitaxial growth substrate, prepare AlN resilient coating, the thickness of AlN resilient coating is 10nm ~ 500nm;
(2) in the epitaxial growth substrate having grown AlN resilient coating, Si Doped n-type Al is grown
0.77ga
0.23n layer;
(3) at N-shaped Al
0.77ga
0.23alternating growth multi layer quantum well on N layer; Multi-layer quantum trap material is Al
0.65ga
0.35n/Al
0.7ga
0.3n;
(4) on the most top layer of multi layer quantum well, grow multilayer electronic barrier layer, electronic blocking layer material is Al
0.8ga
0.2n/Al
0.77ga
0.23n;
(5) on electronic barrier layer, p-type Al is grown
0.77ga
0.23n and Al
0.77ga
0.23n/AlN strained super lattice (SSL);
(6) at Al
0.77ga
0.23n/AlN strained super lattice (SSL) upper growth skim highly doped n-type Al
0.77ga
0.23n, then at highly doped n-type Al
0.77ga
0.23the upper regrowth one deck of N comparatively lightly doped n-type Al
0.77ga
0.23n.
Compared with prior art, the present invention has following beneficial effect: the strain field that the present invention utilizes superlattice structure to produce is to affect band structure.In Superlattice band structure, AlGaN can be with under the effect of polarized electric field, and entirety moves to low-yield direction.After superlattice structure contacts with heavily doped N-shaped AlGaN again, form p-AlGaN/SSL/n*-AlGaN tunnel junction, the electronics in p-type AlGaN valence band, under the effect of external electric field, is tunneling to N-shaped AlGaN side by tunnel effect, hole, i.e. holoe carrier is formed at p-type AlGaN.Meanwhile, skin-material becomes n-AlGaN from p-type AlGaN, avoids the problem of p-type ohmic contact, by the anode of N-shaped contact electrode as LED component, significantly reduces resistivity, improves current expansion performance, thus the performance of enhance device.
[accompanying drawing explanation]
Fig. 1 is the ultraviolet LED epitaxial structure schematic diagram that the present invention contains ssl tunneling knot.
Fig. 2 is the structural representation of electronic barrier layer.
Fig. 3 is Al
yga
1-yn/Al
xga
1-xn strained super lattice structural representation.
Fig. 4 be formed tunnel junction can be with schematic diagram.
Wherein, 1-epitaxial growth substrate, 2-AlN resilient coating, 3-n type Si doped with Al GaN layer, 4-periodic multilayer quantum well, 5-multi-layered thickness grading structure electronic barrier layer, 6-p type AlGaN layer, Al
yga
1-yn/Al
xga
1-xn superlattice, 601-tunnel junction, 7-n type degeneracy Si doped with Al GaN layer, 8-n type Si doped with Al GaN layer, 51-Al
0.8ga
0.2n, 52-Al
0.77ga
0.23n, 61-Al
yga
1-yn, 62-Al
xga
1-xn.
[embodiment]
The invention provides a kind of manufacture method of tunnel junction enhanced ultraviolet LED epitaxial structure, the strain field utilizing superlattice to produce makes AlGaN material in SSL structure that entirety can be with to move to low-yield direction, form p-AlGaN/SSL/n*-AlGaN tunnel junction with N-shaped AlGaN, holoe carrier is provided.At least comprise the following steps:
MOCVD (Metal-organicChemicalVaporDepositiong, MOCVD) or PAMBE system is adopted to carry out epitaxial growth:
1) in epitaxial substrate 1, prepare AlN resilient coating 2, thickness is 10nm ~ 500nm;
2) on the substrate 1 having grown AlN resilient coating 2, Si Doped n-type Al is grown
0.77ga
0.23n layer;
3) alternating growth 5 multiple quantum well layers 4 in N-shaped AlGaN layer 3; Multiple Quantum Well layer material is Al
0.65ga
0.35n/Al
0.7ga
0.3n;
4) on most top layer quantum well layer, multilayer electronic barrier layer 5 is grown, electronic barrier layer 5 gradient thickness.Material is Al
0.8ga
0.2n/Al
0.77ga
0.23n.
5) on electronic barrier layer, p-type Al is grown
0.77ga
0.23n and Al
0.77ga
0.23n/AlNSSL;
6) at Al
0.77ga
0.23n/AlNSSL upper growth skim highly doped n-type Al
0.77ga
0.23n, then at highly doped n-type Al
0.77ga
0.23the upper regrowth one deck of N comparatively lightly doped n-type Al
0.77ga
0.23n.
When preparing tunnel junction, corresponding material, dopant and doping content can be selected according to the characteristic of required tunnel junction.If when tunnel junction material selects AlGaN/AlNSSL and N-shaped AlGaN to prepare, with the doping form of Mg and Si be the mixing altogether of δ distribution, Si element respectively as the dopant of AlGaN/AlNSSL and N-shaped AlGaN, p-type AlGaN district thickness is relatively thin.
Above-mentioned 2nd) in step, N-shaped Al
0.77ga
0.23the Al component proportion of N carries out suitable selection according to quantum well center material but must be higher than Al component in quantum hydrazine, to guarantee that the photon that active layer sends is not absorbed.
Above-mentioned 3rd) in step, the reflective center material Al of multiple quantum well layer
0.65ga
0.35the Al component proportion of N is determined by required wavelength.If select Al
0.65ga
0.35n is as quantum well radiation center material, and luminous centre wavelength is 248nm.
Above-mentioned 5th) Al in step
0.77ga
0.23the N/AlN superlattice number of plies and thickness are all that the Al component of foundation p-type AlGaN changes, and the number of plies of AlGaN/AlN superlattice changes between 1-10 layer.The thickness of every layer all changes between 0.5-2nm.
Below in conjunction with the drawings and specific embodiments, structure of the present invention and preparation method are further described.At concrete device layout with in manufacturing, the needs that the ultraviolet LED structure that the present invention proposes will be implemented according to application and manufacturing process, modify its part-structure and material and accommodation.
Embodiment describes the preparation process of strained super lattice tunnel junction enhanced ultraviolet LED of the present invention in detail, and is specifically described relevant parameter.
(1) select sapphire as epitaxial growth substrate, first prepare AlN resilient coating 2 in Sapphire Substrate 1 along on [0001] direction, thickness is 10nm-500nm.
(2) growing n-type Si doped with Al GaN layer 3, periodic multilayer quantum well 4 successively on the AlN resilient coating 2 of low temperature, the electronic barrier layer 5 of multilayer gradual change.
(3) grown the rear continued growth p-type AlGaN of electronic barrier layer 5, and the doping form of Mg and Si is the single or multiple lift Al mixed altogether of δ distribution
yga
1-yn/Al
xga
1-xn strained super lattice 6.Its structure is shown in Fig. 3.Al in superlattice
xga
1-xin N, Al component is higher than the Al component in quantum-well materials.The Al component magnitude relationship of the bi-material of superlattice is y>x>0.65.Al in superlattice
xga
1-xn and Al
yga
1-ythe thickness of N is all between 0.5nm-2nm.Al
yga
1-yn/Al
xga
1-xthe number of plies of N strained super lattice is between 1-20.
(4) at Al
yga
1-yn/Al
xga
1-xthe AlGaN layer 7 that on N strained super lattice 6, the heavily doped N-shaped Si of regrowth one deck adulterates, doping content is greater than 1 × 10
19cm
-3, can be with as degenerate state, be beneficial to the formation of then wearing knot.Its thickness is between 1nm-500nm
(5) in the N-shaped AlGaN layer 7 of degeneracy doping, regrowth one deck is compared with the Si Doped n-type AlGaN layer of low doping concentration, and doping content is greater than 1 × 10
18cm
-3, as the anode ohmic contact layer of making devices.
Electronic barrier layer is multilayer Al GaN structure as shown in Figure 2.Barrier width is grading structure.The number of plies of electronic barrier layer is 1-10 layer, and thickness is 2nm-10nm.According to different needs, electronic blocking layer thickness can be fixed, and also can be gradual change.
As shown in Figure 3, the doping form of Mg and Si is used to be the multilayer Al of mixing altogether that δ distributes
yga
1-yn/Al
xga
1-xn strained super lattice structure.Wherein, Al
yga
1-yn layer is in tensile strain state, and Al
xga
1-xn layer is in compressive strain state, so at Al
yga
1-yn and Al
xga
1-xthe strain polarized electric field along [0001] and [000-1] direction is formed respectively in N layer.This electric field moves causing the conduction band of AlGaN in superlattice and valence band entirety to low-yield direction.See Fig. 4, when conduction level higher than the N-shaped AlGaN of strained super lattice opposite side of the valence-band level of p-type AlGaN, and the very thin thickness of strained superlattice layer, just define tunnel junction 601, at this moment the electronics of p district valence band just can enter into n district conduction band by this tunnel junction, and leaves hole in p district.
See Fig. 1-Fig. 4, be strained super lattice tunnel junction ultraviolet LED epitaxial structure of the present invention, comprising:
-epitaxial growth substrate 1;
-AlN resilient coating 2, is positioned in this epitaxial growth substrate 1;
-N-shaped AlGaN layer 3, is positioned on this AlN resilient coating 2;
-periodic multilayer quantum well 4, is positioned in this N-shaped AlGaN layer 3;
-electronic barrier layer 5, is positioned on this multi layer quantum well 4;
The doping form of-p-type AlGaN layer, Mg and Si is the multilayer Al of mixing altogether of δ distribution
yga
1-yn/Al
xga
1-xn strained super lattice 6, is positioned on this electronic barrier layer 5;
-N-shaped degeneracy doped with Al GaN layer 7, is positioned at this multilayer Al
yga
1-yn/Al
xga
1-xon N strained super lattice 6;
-N-shaped Si doped with Al GaN cap 8, is positioned in this N-shaped degeneracy doped with Al GaN layer 7.
The present invention in epitaxial growth substrate with AlN resilient coating for initial layers, then growing n-type AlGaN layer, multiquantum well region, electronic barrier layer, p-type AlGaN layer, Al successively in order
yga
1-yn/Al
xga
1-xn strained super lattice, N-shaped degeneracy doped with Al GaN layer, N-shaped AlGaN cap layers.The form of the doping of Mg and Si is utilized to be the multilayer Al of mixing altogether that δ distributes
yga
1-yn/Al
xga
1-xthe transformation of N strained super lattice can be with, and makes a large amount of electronics be entered N-shaped AlGaN on it by tunnel junction, thus leaves a large amount of holoe carrier in p district, provides enough hole for active area is luminous.In addition, the N-shaped AlGaN structure of upper epidermis, as device positive contact layer, solves the problem of ohmic contact, reduces device cut-in voltage, improves current expansion ability.UV LED chip prepared by the method has broken away from p-type layer doping difficulty, and ohmic contact is difficult to the difficulty of making, improves the performance of uv-LED device greatly.
Advantage of the present invention comprises:
1) utilize the form of the doping of Mg and Si to be that the stress field that produces of the multilayer Al GaN/AlNSSL structure of mixing altogether of δ distribution moves to low-yield direction to the entirety of being with realizing AlGaN in SSL, thus jointly form tunnel junction with p-type AlGaN and heavy doping to the N-shaped AlGaN of degenerate state.This method utilizes stress to realize tunnel junction structure, instead of relies on simple Mg element heavy doping to realize degenerate state.
2) a large amount of electronics pierces into conduction band into N-shaped material by tunnel junction then from the valence band of p-type material, will leave a large amount of holoe carrier like this in p-type layer.This solves the problem of p-type material Mg element doping difficulty, improve carrier concentration.
3) the N-shaped AlGaN in p-type layer surface coverage, anode ohmic contact just can directly make on N-shaped material, substantially increases ohm contact performance, reduction contact resistance, raising current expansion ability.
Claims (9)
1. a strained super lattice tunnel junction ultraviolet LED epitaxial structure, it is characterized in that: comprising: epitaxial growth substrate (1), and grow AlN resilient coating (2), N-shaped AlGaN layer, periodic multilayer quantum well (4), electronic barrier layer (5), strained super lattice (6), N-shaped degeneracy doped with Al GaN layer (7), N-shaped Si doped with Al GaN cap (8) in epitaxial growth substrate successively; Wherein, described strained super lattice (6) comprises the single or multiple lift Al of p-type AlGaN layer and continued growth thereon
yga
1-yn/Al
xga
1-xn, wherein, y>x>0.65.
2. strained super lattice tunnel junction ultraviolet LED epitaxial structure as claimed in claim 1, is characterized in that: the material of described multi layer quantum well is Al
0.65ga
0.35n/Al
0.7ga
0.3n, alternating growth.
3. strained super lattice tunnel junction ultraviolet LED epitaxial structure as claimed in claim 1, is characterized in that: the material of described electronic barrier layer is Al
0.8ga
0.2n/Al
0.77ga
0.23n.
4. strained super lattice tunnel junction ultraviolet LED epitaxial structure as claimed in claim 1, is characterized in that: described single or multiple lift Al
yga
1-yn/Al
xga
1-xn is that Mg and Si mixes altogether, and the doping form of mixing altogether is δ distribution.
5. the strained super lattice tunnel junction ultraviolet LED epitaxial structure as described in claim 1 or 4, is characterized in that: Al in described superlattice
xga
1-xin N, Al component is not absorbed with the photon ensuring active layer and send higher than the Al component in quantum-well materials.
6. strained super lattice tunnel junction ultraviolet LED epitaxial structure as claimed in claim 1, is characterized in that: the doping content of described N-shaped degeneracy doped with Al GaN layer (7) is greater than 1 × 10
19cm
-3, can be with as degenerate state, be beneficial to the formation of then wearing knot.
7. strained super lattice tunnel junction ultraviolet LED epitaxial structure as claimed in claim 1, is characterized in that: the doping content of described N-shaped Si doped with Al GaN cap (8) is greater than 1 × 10
18cm
-3, as the anode ohmic contact layer of making devices.
8. strained super lattice tunnel junction ultraviolet LED epitaxial structure as claimed in claim 1, is characterized in that: in strained super lattice structure, Al
yga
1-yn layer is in tensile strain state, Al
xga
1-xn layer is in compressive strain state.
9., based on a preparation method for strained super lattice tunnel junction ultraviolet LED epitaxial structure according to claim 1, it is characterized in that: comprise the following steps:
(1) in epitaxial growth substrate (1) upper preparation AlN resilient coating (2), the thickness of AlN resilient coating is 10nm ~ 500nm;
(2) epitaxial growth substrate (1) the upper growth Si Doped n-type Al of AlN resilient coating (2) is being grown
0.77ga
0.23n layer;
(3) at N-shaped Al
0.77ga
0.23alternating growth multi layer quantum well (4) on N layer; Multi-layer quantum trap material is Al
0.65ga
0.35n/Al
0.7ga
0.3n;
(4) on the most top layer of multi layer quantum well, grow multilayer electronic barrier layer (5), material is Al
0.8ga
0.2n/Al
0.77ga
0.23n;
(5) on electronic barrier layer, p-type Al is grown
0.77ga
0.23n and Al
0.77ga
0.23n/AlN strained super lattice;
(6) at Al
0.77ga
0.23n/AlN strained super lattice grows skim highly doped n-type Al
0.77ga
0.23n, then at highly doped n-type Al
0.77ga
0.23the upper regrowth one deck of N comparatively lightly doped n-type Al
0.77ga
0.23n.
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| CN105870270B (en) * | 2016-06-01 | 2018-07-13 | 湘能华磊光电股份有限公司 | LED extensional superlattice growing methods |
| CN106981548A (en) * | 2017-04-01 | 2017-07-25 | 中蕊（武汉）光电科技有限公司 | A kind of deep ultraviolet LED epitaxial structure and preparation method thereof |
| US11211525B2 (en) | 2017-05-01 | 2021-12-28 | Ohio State Innovation Foundation | Tunnel junction ultraviolet light emitting diodes with enhanced light extraction efficiency |
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