CN105990479A - GaN-based light emitting diode epitaxial structure and manufacturing method thereof - Google Patents
GaN-based light emitting diode epitaxial structure and manufacturing method thereof Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000004888 barrier function Effects 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 229910002601 GaN Inorganic materials 0.000 claims description 84
- 230000012010 growth Effects 0.000 claims description 52
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 12
- 239000012159 carrier gas Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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Abstract
The invention provides a GaN-based light emitting diode epitaxial structure. The structure comprises a substrate. The substrate is successively provided with a stress control layer, a silicon-doping n-type GaN layer, a stress buffer layer, a multi-quantum well active layer, an interval layer, an electron blocking layer, a p-type GaN layer and a p-type ohmic contact layer. The structure is characterized in that a multi-quantum well active area includes a quantum well and quantum barriers with different silicon doping concentrations; and a silicon doping concentration of the quantum barrier which is close to one side of the p-type GaN layer is lower than a silicon doping concentration of the quantum barrier which is close to one side of the n-type GaN layer. In the invention, through doping the silicon with different concentrations in the quantum barriers, the light emitting diode epitaxial structure is manufactured; transportation of carriers in the multi-quantum well can be effectively improved so that distribution of the carriers is uniform; radiation composite efficiency is increased; and simultaneously a work voltage of a device is reduced and external quantum efficiency is increased.
Description
Technical field
The invention belongs to semi-conductor photoelectronic field, particularly relate to a kind of gallium nitride based light emitting diode epitaxial structure and preparation method thereof.
Background technology
LED (Light Emitting Diode, light emitting diode) is the semiconductor device of a kind of solid-state that can convert electrical energy into visible ray, and it directly can be converted into luminous energy electric energy.LED is widely used as a kind of new lighting source material.White light LEDs is as a kind of new type light source, fast-developing because having the advantages such as response speed is fast, shock resistance good, life-span length, energy-conserving and environment-protective.It is widely used in the field such as beautification of landscape and indoor and outdoor lighting at present.
The growth of epitaxial structure is the key technology of LED chip, and MQW is the most important part of epitaxial layer.Existing epitaxial material is mainly GaN base material, and it has stronger spontaneous polarization effect and piezoelectric polarization effect, there is the strongest polarized electric field in InGaN/GaN multi-quantum well active region structure.In GaN quantum is built, polarized electric field causes tilting by band, forms triangular form barrier structure.This triangular barrier hinders transporting of carrier, causes LED operation voltage to raise.For the barrier height that reduces during quantum is built thus reduce device operating voltages, the quantum in the multi-quantum well active region of tradition LED structure is built and is used the doping of uniform silicon more.It addition, the hole effective mass of GaN base material is very big, in material, the mobility in hole is the lowest, thus when GaN base LED operation, hole, after p-type GaN layer injects MQW, is mainly distributed in the SQW of p-type side, and Carrier Profile is the most uneven.Along with operating current increases, in last SQW, carrier concentration height can cause the series of problems such as electronics leakage, auger recombination aggravation, causes radiation recombination efficiency decline, luminous efficiency to decline.
Summary of the invention
For above-mentioned the deficiencies in the prior art, it is an object of the present invention to provide a kind of gallium nitride based light emitting diode epitaxial structure.This epitaxial structure can effectively improve transporting of carrier in MQW, makes Carrier Profile be more uniformly distributed, and improves radiation recombination efficiency, reduces device operating voltages simultaneously, improves external quantum efficiency.
To achieve these goals, the present invention is by the following technical solutions: a kind of gallium nitride based light emitting diode epitaxial structure, including substrate, it is sequentially provided with from bottom to up on this substrate: stress control layer, the n-type GaN layer of silicon doping, stress-buffer layer, multi-quantum well active region, wall, electronic barrier layer, p-type GaN layer, and p-type ohmic contact layer, described multi-quantum well active region includes that the quantum of SQW and different doping concentration is built, and the doping concentration near p-type GaN layer side quantum base is less than the doping concentration built near n-type GaN layer side quantum.
Preferably, described multi-quantum well active region includes the narrow band gap In in m cyclexGa1-xN SQW and doping concentration are 0 ~ 2 × 1018cm-3In the range of broad-band gap InaAlbGa1-a-bN quantum is built, and wherein, 2≤m≤20, m is integer, 0≤x < 1,0≤a < 1,0≤b < 1.
Preferably, described stress control layer is one or more layers AlxGa1-xN shell, wherein, 0≤x≤1.
Preferably, described stress-buffer layer is InxGa1-xN shell or InxGa1-xN/GaN superlattices, wherein, 0≤x≤1.
Preferably, described wall is InxAlyGa1-x-yN, wherein, 0≤x < 1,0≤y < 1.
Preferably, described InxAlyGa1-x-yN wall is Mg doping, wherein, 0≤x < 1,0≤y < 1.
For above-mentioned the deficiencies in the prior art, it is a further object to provide the preparation method of a kind of gallium nitride based light emitting diode epitaxial structure.The epitaxial structure prepared by the method can effectively improve transporting of carrier in MQW, makes Carrier Profile be more uniformly distributed, and improves radiation recombination efficiency, reduces device operating voltages simultaneously, improves external quantum efficiency.
To achieve these goals, the present invention is by the following technical solutions: the preparation method of a kind of gallium nitride based light emitting diode epitaxial structure, the method includes: at substrate Epitaxial growth stress control layer；N-type GaN layer in the doping of stress control layer Epitaxial growth silicon；At n-type GaN layer Epitaxial growth stress-buffer layer；In stress-buffer layer Epitaxial growth multi-quantum well active region；At multi-quantum well active region epitaxial growth wall；At wall Epitaxial growth electronic barrier layer；In electronic barrier layer Epitaxial growth p-type GaN layer；At p-type GaN layer Epitaxial growth ohmic contact layer；Described multi-quantum well active region includes that the quantum of SQW and different doping concentration is built, and the doping concentration near p-type GaN layer side quantum base is less than the doping concentration built near n-type GaN layer side quantum.
Preferably, described multi-quantum well active region includes the narrow band gap In in m cyclexGa1-xN SQW and doping concentration are 0 ~ 2 × 1018cm-3In the range of broad-band gap InaAlbGa1-a-bN quantum is built, and wherein, 2≤m≤20, m is integer, 0≤x < 1,0≤a < 1,0≤b < 1.
Preferably, described wall is InxAlyGa1-x-yN, wherein, 0≤x < 1,0≤y < 1.
Preferably, described InxAlyGa1-x-yN wall is Mg doping, wherein, 0≤x < 1,0≤y < 1.
The invention has the beneficial effects as follows: the present invention prepares light emitting diode epitaxial structure by the silicon of the variable concentrations that adulterates in building at quantum, can effectively improve transporting of carrier in MQW, Carrier Profile is made to be more uniformly distributed, improve radiation recombination efficiency, reduce device operating voltages simultaneously, improve external quantum efficiency.
Accompanying drawing explanation
A kind of extension of gallium nitride-based LED structural representation that Fig. 1 provides for the present invention；
A kind of extension of gallium nitride-based LED structure preparation flow schematic diagram that Fig. 2 provides for the present invention；
Fig. 3 is the spatial distribution schematic diagram that in the embodiment of the present invention one, quantum builds doping.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment one
As shown in Figure 1, a kind of extension of gallium nitride-based LED structure that the present invention provides, this structure is followed successively by silicon substrate 1, stress control layer 2 from top to bottom, n-type GaN layer 3, stress-buffer layer 4, multi-quantum well active region 5, wall 6, electronic barrier layer 7, p-type GaN layer 8, ohmic contact layer 9, wherein multi-quantum well active region 5 includes that the InGaN SQW 5a of low energy gap and the GaN quantum of broad stopband build 5b.
Fig. 2 is Fig. 1 one extension of gallium nitride-based LED structure preparation flow schematic diagram, concrete preparation method is as follows: use Metalorganic Chemical Vapor Deposition (MOCVD) to carry out epitaxial growth, at silicon (111) substrate 1 Epitaxial growth stress control layer 2, including AlN-Al0.5Ga0.5N-Al0.2Ga0.8The three-decker of N.During growth, substrate is placed in reative cell, and reaction chamber temperature is set in 800 DEG C ~ 1200 DEG C, and in reative cell, be passed through trimethyl aluminium (TMAl), ammonia (NH3), at H2Under conditions of carrier gas, the AlN layer of growth a layer thickness 300nm, then pass to trimethyl gallium (TMGa), and keep being passed through trimethyl aluminium and ammonia, the Al of growth 400nm0.5Ga0.5N shell.Then by regulating the flow of trimethyl aluminium, the Al component of epitaxial layer, the Al of growth 400nm are changed0.2Ga0.8N shell.In stress control layer 2 Epitaxial growth n-type GaN layer 3, including GaN layer and one layer of n-type GaN layer thick for 3mm of involuntary doping thick for one layer of 500nm；N-shaped GaN is with silane (SiH4) as adulterant, doping content is 8 × 1018cm-3, growth temperature is at 900 DEG C ~ 1100 DEG C.At n-type GaN layer 3 Epitaxial growth stress-buffer layer 4, it is temperature to be reduced to 750 DEG C ~ 900 DEG C, with N2As carrier gas, and it is continually fed into TMGa, NH3, the intermittent trimethyl indium (TMIn) that is passed through, the total logarithm of alternating growth is the InGaN/GaN(1nm/2nm of 30 couples) superlattices, wherein the In component in InGaN is 1%, and stress-buffer layer 4 uses silicon to adulterate, and its concentration is 1 × 1018cm-3.Stress-buffer layer 4 grows multi-quantum well active region 5, it is included in 750 DEG C ~ 900 DEG C alternating growths 9 and the InGaN SQW 5a of low energy gap and the GaN quantum of broad stopband are built 5b, the thickness at SQW/base is respectively 3nm/12nm, wherein, quantum is built and is divided into three groups, and first three quantum is built and mixed silicon concentration in (5b_1,5b_2,5b_3) is 4 × 1017cm-3, middle three quantum are built and mixed silicon concentration in (5b_4,5b_5,5b_6) is 2 × 1017cm-3, last three quantum are built and mixed silicon concentration in (5b_7,5b_8,5b_9) is 1 × 1017 cm-3, its quantum builds the spatial distribution schematic diagram of doping as shown in Figure 3.On MQW 5, grow one layer of 5nm plain GaN wall 6 at 750 DEG C ~ 950 DEG C.Wall 6 grows electronic barrier layer 7, including being passed through TMAl, TMGa, NH3, with N2As carrier gas, using two cyclopentadienyls magnesium (Cp2Mg) as adulterant, it is grown to the Al of thickness 20nm at 750 DEG C ~ 1000 DEG C0.2Ga0.8N shell, wherein Mg doping content is 1.5 × 1019 cm-3.On electronic barrier layer 7, it is passed through TMGa, NH at 750 DEG C ~ 1000 DEG C3, with H2As carrier gas, growth thickness is 100nm, doping content is 3 × 1019cm-3P-type GaN layer 8.In p-type GaN layer 8, at 750 DEG C ~ 1000 DEG C, increase the Cp being passed through reative cell2Mg and TMGa ratio, with H2As carrier gas, growth thickness 20nm, doping content is 2 × 1020cm-3Ohmic contact layer 9.
Embodiment two
Epitaxial growth GaN stress control layer on a sapphire substrate.During growth, substrate is placed in reative cell, and reaction chamber temperature is set in 450 DEG C ~ 700 DEG C, it is preferable that temperature, at 500 DEG C ~ 600 DEG C, is passed through TMGa, NH in reative cell3, at H2Under conditions of carrier gas, the GaN layer of growth a layer thickness 10 ~ 50nm, it is preferable that thickness is 20 ~ 40nm.In GaN stress control layer Epitaxial growth n-type GaN layer, thickness is 3mm, with silane (SiH4) as adulterant, doping content is 2 × 1019cm-3.At n-type GaN layer Epitaxial growth stress-buffer layer, this stress-buffer layer is the InGaN/GaN(2nm/5nm that total logarithm is 20 couples of alternating growth) superlattices, wherein the In component in InGaN is 10%.Growing multi-quantum well active region on stress-buffer layer, this multi-quantum well active region is to build the InGaN SQW of low energy gap and the GaN quantum of broad stopband at 750 DEG C ~ 900 DEG C alternating growths 15.From N-shaped GaN side toward direction, p-type GaN side, the doping concentration in quantum base is by 2 × 1018cm-3Gradually linear decrease is to 0, and last quantum undopes in building.At the InGaN wall of Mg doping thick for one layer of 50nm of multi-quantum well active region Epitaxial growth, wherein In component is about 0.5%.InGaN wall grows 8 to AlGaN/InGaN(3nm/3nm) electronic barrier layer, wherein Al component is more than or equal to 10%, and less than or equal to 30%, In component is more than or equal to 1%, and less than or equal to 10%, Mg doping content is more than or equal to 5 × 1018 cm-3, and less than or equal to 2 × 1020 cm-3.Growing doping content on electronic barrier layer is 6 × 1019cm-3, thickness is the p-type GaN layer of 200nm.Growth thickness 5nm in p-type GaN layer, doping content is 3 × 1020cm-3Ohmic contact layer.
Embodiment three
At silicon (111) substrate Epitaxial growth stress control layer, including AlN-Al0.5Ga0.5N-Al0.2Ga0.8The three-decker of N, during growth, is placed in substrate reative cell, and reaction chamber temperature is set in 800 DEG C ~ 1200 DEG C, and be passed through trimethyl aluminium (TMAl), ammonia (NH in reative cell3), at H2Under conditions of carrier gas, the AlN layer of growth a layer thickness 300nm, then pass to trimethyl gallium (TMGa), and keep being passed through trimethyl aluminium and ammonia, the Al of growth 300nm0.5Ga0.5N shell.Then by regulating the flow of trimethyl aluminium, the Al component of epitaxial layer, the Al of growth 200nm are changed0.2Ga0.8N shell.In stress control layer Epitaxial growth n-type GaN layer, including GaN layer and one layer of n-type GaN layer thick for 3mm of involuntary doping thick for one layer of 1um；N-shaped GaN is with silane (SiH4) as adulterant, doping content is 1.2 × 1018cm-3, growth temperature is at 900 DEG C ~ 1100 DEG C.At n-type GaN layer Epitaxial growth stress-buffer layer, it is temperature to be reduced to 750 DEG C ~ 900 DEG C, with N2As carrier gas, and it is continually fed into triethyl-gallium (TEGa), NH3, the intermittent trimethyl indium (TMIn) that is passed through, the total logarithm of alternating growth is the InGaN/GaN(1nm/2nm of 20 couples) superlattices, wherein the In component in InGaN is 5%, and stress-buffer layer uses silicon doping, and its concentration is 8 × 1017cm-3.Stress-buffer layer grows multi-quantum well active region, it is included in 750 DEG C ~ 900 DEG C alternating growths 6 the InGaN SQW of low energy gap and the GaN quantum of broad stopband are built, the thickness at SQW/base is respectively 3nm/5nm, wherein, in addition to last quantum is built, the silicon during other quantum are built adulterates from 4 × 1017cm-3Gradual change is decremented to 5 × 1016cm-3.In multi-quantum well active region, at the GaN wall of one layer of 5nm of 750 DEG C ~ 950 DEG C growths, GaN wall Mg doping content is 5 × 1017cm-3.GaN wall grows electronic barrier layer, including being passed through TMAl, TMGa, NH3, with N2As carrier gas, using two cyclopentadienyls magnesium (Cp2Mg) as adulterant, it is grown to the Al of thickness 50nm at 750 DEG C ~ 1000 DEG C0.07Ga0.93N shell, wherein Mg doping content is 3 × 1019 cm-3.On electronic barrier layer, it is passed through TMGa, NH at 750 DEG C ~ 1000 DEG C3, with H2As carrier gas, growth thickness is 50nm, doping content is 1.5 × 1019cm-3P-type GaN layer.In p-type GaN layer, at 750 DEG C ~ 1000 DEG C, increase the Cp being passed through reative cell2Mg and TMGa ratio, with H2As carrier gas, growth thickness 20nm, doping content is 2 × 1020cm-3Ohmic contact layer.
The above; it is only the detailed description of the invention in the present invention; but protection scope of the present invention is not limited thereto, any being familiar with the people of this technology in the technical scope that disclosed herein, the conversion that can readily occur in or replace all should be contained within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (10)
1. a gallium nitride based light emitting diode epitaxial structure, including substrate, it is sequentially provided with from bottom to up on this substrate: stress control layer, the n-type GaN layer of silicon doping, stress-buffer layer, multi-quantum well active region, wall, electronic barrier layer, p-type GaN layer, and p-type ohmic contact layer, it is characterised in that, described multi-quantum well active region includes that the quantum of SQW and different doping concentration is built, and the doping concentration near p-type GaN layer side quantum base is less than the doping concentration built near n-type GaN layer side quantum.
A kind of gallium nitride based light emitting diode epitaxial structure the most according to claim 1, it is characterised in that described multi-quantum well active region includes the narrow band gap In in m cyclexGa1-xN SQW and doping concentration are 0 ~ 2 × 1018cm-3In the range of broad-band gap InaAlbGa1-a-bN quantum is built, and wherein, 2≤m≤20, m is integer, 0≤x < 1,0≤a < 1,0≤b < 1.
A kind of gallium nitride based light emitting diode epitaxial structure the most according to claim 1, it is characterised in that described stress control layer is one or more layers AlxGa1-xN shell, wherein, 0≤x≤1.
A kind of gallium nitride based light emitting diode epitaxial structure the most according to claim 1, it is characterised in that described stress-buffer layer is InxGa1-xN shell or InxGa1-xN/GaN superlattices, wherein, 0≤x≤1.
A kind of gallium nitride based light emitting diode epitaxial structure the most according to claim 1, it is characterised in that described wall is InxAlyGa1-x-yN, wherein, 0≤x < 1,0≤y < 1.
A kind of gallium nitride based light emitting diode epitaxial structure the most according to claim 5, it is characterised in that described InxAlyGa1-x-yN wall is Mg doping, wherein, 0≤x < 1,0≤y < 1.
7. a preparation method for gallium nitride based light emitting diode epitaxial structure, the method includes:
At substrate Epitaxial growth stress control layer；
N-type GaN layer in the doping of stress control layer Epitaxial growth silicon；
At n-type GaN layer Epitaxial growth stress-buffer layer；
In stress-buffer layer Epitaxial growth multi-quantum well active region；
At multi-quantum well active region epitaxial growth wall；
At wall Epitaxial growth electronic barrier layer；
In electronic barrier layer Epitaxial growth p-type GaN layer；
At p-type GaN layer Epitaxial growth p-type ohmic contact layer；
It is characterized in that, described multi-quantum well active region includes that the quantum of SQW and different doping concentration is built, and the doping concentration near p-type GaN layer side quantum base is less than the doping concentration built near n-type GaN layer side quantum.
The preparation method of a kind of gallium nitride based light emitting diode epitaxial structure the most according to claim 7, it is characterised in that described multi-quantum well active region includes the narrow band gap In in m cyclexGa1-xN SQW and doping concentration are 0 ~ 2 × 1018cm-3In the range of broad-band gap InaAlbGa1-a-bN quantum is built, and wherein, 2≤m≤20, m is integer, 0≤x < 1,0≤a < 1,0≤b < 1.
The preparation method of a kind of gallium nitride based light emitting diode epitaxial structure the most according to claim 7, it is characterised in that described wall is InxAlyGa1-x-yN, wherein, 0≤x < 1,0≤y < 1.
The preparation method of a kind of gallium nitride based light emitting diode epitaxial structure the most according to claim 9, it is characterised in that described InxAlyGa1-x-yN wall is Mg doping, wherein, 0≤x < 1,0≤y < 1.
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2015
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