CN116154059A - Gallium nitride light-emitting diode epitaxial structure, LED and preparation method thereof - Google Patents

Gallium nitride light-emitting diode epitaxial structure, LED and preparation method thereof Download PDF

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CN116154059A
CN116154059A CN202310351870.2A CN202310351870A CN116154059A CN 116154059 A CN116154059 A CN 116154059A CN 202310351870 A CN202310351870 A CN 202310351870A CN 116154059 A CN116154059 A CN 116154059A
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layer
polarity
gan
mgn
thickness
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郑文杰
程龙
高虹
刘春杨
胡加辉
金从龙
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Jiangxi Zhao Chi Semiconductor Co Ltd
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Jiangxi Zhao Chi Semiconductor Co Ltd
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    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
    • H—ELECTRICITY
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    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • 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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    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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Abstract

The invention relates to the technical field of semiconductors, and particularly discloses a gallium nitride light-emitting diode epitaxial structure, an LED and a preparation method thereof, wherein the gallium nitride light-emitting diode epitaxial structure comprises a substrate, a buffer layer, an N-type layer, a multiple quantum well layer and a P-type layer which are sequentially arranged, a potential barrier allocation layer is arranged between the multiple quantum well layer and the P-type layer, and the potential barrier allocation layer comprises Al which is sequentially deposited along the epitaxial direction a N layer, al b In x Ga 1‑b‑x N layer, in 1‑c Al c N layer and N polarity Al d GaN/N polarity MgN superlattice layer. The barrier allocation layer is matched by a plurality of material layers, so that electron overflow is reduced, hole injection is effectively increased and accelerated, the conductivity and the hole injection rate of the P-type layer are enhanced, and the luminous efficiency is effectively improved.

Description

Gallium nitride light-emitting diode epitaxial structure, LED and preparation method thereof
Technical Field
The present invention relates to the field of semiconductor technologies, and in particular, to a gallium nitride light emitting diode epitaxial structure, an LED, and a method for manufacturing the same.
Background
The semiconductor light-emitting diode has the advantages of small volume, firmness, durability, strong light-emitting band controllability, high light efficiency, low heat loss, small light attenuation, energy conservation, environmental protection and the like, has wide application in fields of full-color display, backlight sources, signal lamps, photoelectric computer interconnection, short-distance communication and the like, and gradually becomes a hot spot for research in the current electronic and electric field. The gallium nitride material has a series of advantages of wide band gap, high electron mobility, high thermal conductivity, high stability and the like, so that the gallium nitride material has wide application and huge market prospect in a high-brightness blue light-emitting diode. The field of illumination puts higher and higher requirements on LEDs, and how to improve the luminous efficiency and brightness of GaN-based LEDs and reduce the production cost is a focus of attention in the LED industry.
At present, due to the inherent polarization effect of GaN-based materials, the generated Stark effect can lead to energy band bending in the multi-quantum well, and the superposition of wave functions is reduced, so that the effective recombination efficiency of holes and electrons is reduced, on the other hand, the existing electron blocking layer can block the overflow of electrons in the quantum well, but simultaneously, the injection efficiency of holes from the P-type GaN layer is also reduced, and the luminous efficiency is further reduced.
Disclosure of Invention
The invention aims at providing a gallium nitride light-emitting diode epitaxial structure, an LED and a preparation method thereof, aiming at the prior art, the barrier allocation layer of the invention is prepared by Al a N layer, al b In x Ga 1-b-x N layer, in 1-c Al c N layer and N polarity Al d The GaN/N polar MgN superlattice layers are matched together, so that electron overflow is reduced, hole injection is effectively increased and accelerated, conductivity and hole injection rate of the P-type layer are enhanced, and luminous efficiency is effectively improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
first, as one of the objects of the present invention, the present invention provides a gallium nitride light emitting diode epitaxial structure comprisingThe substrate comprises a substrate, a buffer layer, an N-type layer, a multiple quantum well layer and a P-type layer, wherein a potential barrier allocation layer is arranged between the multiple quantum well layer and the P-type layer, and comprises Al which is sequentially deposited along the epitaxial direction a N layer, al b In x Ga 1-b-x N layer, in 1- c Al c N layer and N polarity Al d GaN/N polarity MgN superlattice layer.
In some embodiments, 0 < d < c < b < a < 1,0 < x < 1-c < 1 in the barrier alignment layer.
In some embodiments, the Al a N layer, the Al b In x Ga 1-b-x N layer and In 1-c Al c In the N layers, the content of Al components in each layer is respectively reduced along the epitaxial direction, and the N polarity Al d In the GaN/N polar MgN superlattice layer, the content of the Al component increases gradually along the epitaxial direction.
In some embodiments, the Al a N layer, the Al b In x Ga 1-b-x N layer, the In 1-c Al c N layer and the N polarity Al d In the GaN/N polarity MgN superlattice layer, the content decreasing amplitude i of Al components among layers is more than 0.01 and less than or equal to 0.1;
the Al is a N layer, the Al b In x Ga 1-b-x N layer and In 1-c Al c In the N layers, the decreasing amplitude j of the content of the Al component in each layer is more than 0 and less than or equal to 0.01, and the N polarity Al d In the GaN/N polarity MgN superlattice layer, the increment range k of the Al component content is more than 0 and less than or equal to 0.01.
In some embodiments, the Al a N layer, the Al b In x Ga 1-b-x N layer and In 1-c Al c The thickness of the N layers is gradually decreased, and the Al a The thickness of the N layer is 4 nm-5 nm, and the Al layer is b In x Ga 1-b-x The thickness of the N layer is 3 nm-4 nm, and the In 1- c Al c The thickness of the N layer is 2 nm-3 nm, and the N polarity Al d The thickness of the GaN/N polar MgN superlattice layer is 2 nm-5 nm.
In some embodiments, the N-polar Al d GaNThe growth atmosphere of the N-polarity MgN superlattice layer is N 2 。
In some embodiments, the N-polar Al d The GaN/N polarity MgN superlattice layer comprises N polarity Al which grows periodically and alternately d The GaN sub-layer and the N polarity MgN sub-layer have 3-5 growth periods.
In some embodiments, the In 1-c Al c The growth pressure of the N layer is higher than that of the Al b In x Ga 1-b-x Growth pressure of the N layer.
Next, as another object of the present invention, the present invention provides a method for preparing an epitaxial structure of a gallium nitride light emitting diode, comprising:
providing a substrate;
sequentially epitaxially growing a buffer layer, an N-type layer, a multiple quantum well layer, a potential barrier allocation layer and a P-type layer on the substrate;
the potential barrier allocation layer comprises Al which is deposited along the epitaxial direction in turn a N layer, al b In x Ga 1-b-x N layer, in 1-c Al c N layer and N polarity Al d GaN/N polarity MgN superlattice layer.
Furthermore, as another object of the present invention, the present invention provides an LED comprising the above gallium nitride light emitting diode epitaxial structure.
The invention has the beneficial effects that:
in the invention, a potential barrier allocation layer composed of a plurality of material layers is introduced between a multiple quantum well layer and a P-type layer, wherein, the potential barrier allocation layer is formed by Al a The N layer forms a higher barrier energy level to block the migration of electrons, ensure that the barrier allocation layer has better crystal quality and ensure that a stress field generated by the adaptive stress among the lattices is smaller, thereby improving the effective injection of holes; next, al b In x Ga 1-b-x N layer and In 1-c Al c The N layer is introduced with an In component, so that the barrier height is reduced, the N layer is matched with an AlaN layer with a higher barrier height, the electron overflow is reduced, the leakage channel is reduced, the energy required by hole injection is reduced, and the hole injection is increased; combining N polarity Al d GaN/N polarity MgN super-lattice layer utilizing N polarityThe polarization field and the external field have the same direction, the polarization field and the external field jointly accelerate the injection of holes into the well layer, the carrier injection efficiency is further improved, the luminous efficiency of the quantum well layer is increased, and meanwhile, the N-polarity Al d The N-polarity MgN sub-layer in the GaN/N-polarity MgN superlattice layer generates high-concentration three-dimensional hole gas due to polarization doping effect, so that the conductivity and hole injection rate of the P-type layer are effectively enhanced, and the barrier allocation layer passes through Al a N layer, al b In x Ga 1-b-x N layer, in 1-c Al c N layer and N polarity Al d The GaN/N polar MgN superlattice layers are matched together, so that electron overflow is reduced, hole injection is effectively increased and accelerated, conductivity and hole injection rate of the P-type layer are enhanced, and luminous efficiency is effectively improved.
Drawings
Fig. 1 is a schematic structural diagram of an epitaxial structure of a gan led according to the present invention.
Fig. 2 is a flow chart of a method for fabricating an epitaxial structure of a gan light emitting diode according to the present invention.
FIG. 3 is a flow chart of a method for preparing a barrier alignment layer according to the present invention.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and advantages of the present invention more apparent.
Referring to FIG. 1, the invention discloses an epitaxial structure of a GaN light emitting diode, which comprises a substrate 1, a buffer layer 2, an N-type layer 3, a multiple quantum well layer 4 and a P-type layer 6 which are sequentially arranged, wherein a potential barrier allocation layer 5 is arranged between the multiple quantum well layer 4 and the P-type layer 6, and the potential barrier allocation layer 5 comprises Al which is sequentially deposited along the epitaxial direction a N layer 51, al b In x Ga 1-b-x N layer 52, in 1-c Al c N layer 53 and N polarity Al d A GaN/N polar MgN superlattice layer 54.
In the invention, a barrier allocation layer 5 composed of a plurality of material layers is introduced between a multiple quantum well layer 4 and a P-type layer 6, wherein, the barrier allocation layer is formed by Al a N layer 51 forms a higher barrier energy level, blocks electron migration, and ensures barrier modulationThe matching layer 5 has better crystal quality, ensures that the stress field generated by the adaptive stress among the lattices is smaller, and can improve the effective injection of holes; next, al b In x Ga 1-b-x N layer 52 and In 1-c Al c The N layer 53 introduces In component, reduces the barrier height, and has higher barrier height with Al a The N layers 51 are matched, so that electron overflow is reduced, a leakage channel is reduced, energy required by hole injection is reduced, and hole injection is increased; combining N polarity Al d The GaN/N-polarity MgN superlattice layer 54 utilizes the N-polarity characteristic, the polarization electric field and the external electric field have the same direction, the polarization field and the external electric field jointly accelerate the injection of holes into the well layer, the carrier injection efficiency is further improved, the luminous efficiency of the quantum well layer is increased, and meanwhile, the N-polarity Al d The N-polar MgN sub-layer in the GaN/N-polar MgN superlattice layer 54 generates high-concentration three-dimensional hole gas due to polarization doping effect, so that the conductivity and hole injection rate of the P-type layer 6 are effectively enhanced, and the barrier allocation layer 5 passes through Al a N layer 51, al b In x Ga 1-b-x N layer 52, in 1-c Al c N layer 53 and N polarity Al d The GaN/N polar MgN superlattice layer 54 is matched with multiple material layers, so that electron overflow is reduced, hole injection is effectively increased and accelerated, and the conductivity and hole injection rate of the P-type layer 6 are enhanced, and the luminous efficiency is effectively improved.
Wherein, in the barrier allocation layer 5, 0 < d < c < b < a < 1,0 < x < 1-c < 1, that is, al a N layer 51, al b In x Ga 1-b-x N layer 52, in 1-c Al c N layer 53 and N polarity Al d In the GaN/N polar MgN superlattice layer 54, the Al component content between layers is gradually decreased from layer to layer, and Al b In x Ga 1-b-x N layer 52 and In 1-c Al c The In component content In the N layer 53 increases gradually layer by layer, the decrease of the Al component content can effectively reduce the barrier height, the increase of the In component content can effectively reduce the barrier height, and In the barrier blending layer 5, al a N layer 51, al b In x Ga 1-b-x N layer 52, in 1-c Al c N layer 53 and N polarity Al d Between layers of GaN/N polar MgN superlattice layer 54The interlayer decreasing of the content of the Al component shows the trend of the interlayer decreasing of the barrier height, so that the electron overflow is reduced, the electric leakage channel is reduced, the droop effect is reduced, the energy required by hole injection is reduced, the hole injection is increased, the working voltage is reduced, and the luminous efficiency is further improved.
At Al b In x Ga 1-b-x N layer 52 and In 1-c Al c In the N layer 53, the In component content is gradually increased layer by layer, and the Al component content is gradually decreased layer by layer b In x Ga 1-b-x N layer 52 and In 1-c Al c The barrier height of the N layer 53 is gradually decreased, and at the same time, the lattice mismatch is also gradually decreased, so that the generation of defects is reduced, and the luminous efficiency is further improved.
Wherein Al is a N layer 51, al b In x Ga 1-b-x N layer 52 and In 1-c Al c In the N layer 53, the Al component content in each layer decreases along the epitaxial direction, N-polarity Al d In the GaN/N polar MgN superlattice layer 54, the Al component content increases gradually along the epitaxial direction, and the Al component content of the barrier adjustment layer 5 overall presents a sliding-ladder-like variation trend of decreasing first and then increasing slightly along the epitaxial direction, so as to increase hole injection and improve hole injection efficiency.
Wherein the Al is a An N layer 51, the Al b In x Ga 1-b-x N layer 52, the In 1-c Al c N layer 53 and the N-polarity Al d In the GaN/N polar MgN superlattice layer 54, the content decreasing amplitude i of Al components among layers is more than 0.01 and less than or equal to 0.1;
the Al is a N layer 51, al b In x Ga 1-b-x N layer 52 and In 1-c Al c In the N layer 53, the decreasing amplitude j of the Al component content in each layer is 0 < j.ltoreq.0.01, the N-polarity Al d In the GaN/N polar MgN superlattice layer, the increment range k of the Al component content is more than 0 and less than or equal to 0.01, the change of the Al component content causes the change of the barrier height, and the difference is formed between the interlayer and the change range of the Al component content in the layer by controlling the decrement range j/increment range k of the Al component content in each layer to be less than the interlayer decrement range i of the Al component content, so that the electron trap is formedA trap for slowing down electron movement and reducing a Droop effect; in addition, let N polarity Al d The Al component content in the GaN/N polar MgN superlattice layer increases progressively, so that a downhill trend is formed, the hole moving speed is increased, and the hole injection efficiency is improved.
Wherein Al is a N layer 51, al b In x Ga 1-b-x N layer 52 and In 1-c Al c The thickness of the N layer 53 decreases in sequence, and Al a The thickness of the N layer 51 is 4nm to 5nm, al b In x Ga 1-b-x The thickness of the N layer 52 is 3nm to 4nm, in 1-c Al c The thickness of the N layer 53 is 2 nm-3 nm, and N polarity Al d The thickness of the GaN/N polar MgN superlattice layer 54 is 2nm to 5nm, due to Al a N layer 51, al b In x Ga 1-b-x N layer 52 and In 1-c Al c The thickness of the N layer 53 decreases gradually, lattice mismatch decreases continuously, and stress is released indirectly, so that the interface between layers is smoother, defects are reduced, electric leakage is reduced, and luminous efficiency is further improved.
Wherein, N polarity Al d The growth atmosphere of GaN/N polar MgN superlattice layer 54 is N 2 The formation of an N-polar material layer is ensured.
Wherein, N polarity Al d The GaN/N-polar MgN superlattice layer 54 includes periodically alternating growth of N-polar Al d GaN sublayers 541 and N-polar MgN sublayers 542 are grown with 3-5 growth periods, and the growth period is 3, 4 or 5, for example, but not limited thereto, preferably 3, N-polar Al d The thickness ratio between the GaN sublayer 541 and the N-polar MgN sublayer 542 is 1:1.
Wherein In 1-c Al c The growth pressure of the N layer 53 is higher than Al b In x Ga 1-b-x Growth pressure of the N layer 52, thereby effectively preventing Al b In x Ga 1-b-x In composition In N layer 52 In growth of In 1-c Al c Diffusion occurs In the process of the N layer 53, so that the incorporation efficiency of In components is further increased, and In is improved 1-c Al c The crystal quality of the N layer further improves the photoelectric performance of the epitaxial structure.
The invention discloses a preparation method of an epitaxial structure of a gallium nitride light-emitting diode, which comprises the following steps:
s10, providing a substrate 1:
wherein the substrate 1 may be a Si substrate, sapphire, siC substrate or SiO 2 Taking a sapphire substrate as an example, placing the sapphire substrate 1 in an MOCVD reaction chamber, and adopting H at the temperature of 1000-1150 DEG C 2 、NH 3 The sapphire substrate is treated at a high temperature for 14 to 15 minutes so as to prevent oxidation or surface contamination of the surface of the sapphire substrate 1.
S20, sequentially epitaxially growing a buffer layer 2, an N-type layer 3, a multiple quantum well layer 4, a potential barrier allocation layer 5 and a P-type layer 6 on a substrate 1;
the barrier alignment layer 5 comprises Al deposited sequentially in the epitaxial direction a N layer 51, al b In x Ga 1-b-x N layer 52, in 1-c Al c N layer 53 and N polarity Al d A GaN/N polar MgN superlattice layer 54.
The specific steps of step S20 are as follows:
s21, growing a buffer layer 2 on the substrate 1:
the buffer layer 2 is an AlN/GaN buffer layer, a high-temperature AlN two-dimensional nucleation layer is deposited on the substrate 1 by PVD sputtering, then the substrate is transferred into an MOCVD reaction chamber to deposit the GaN buffer layer 2, and the thickness of the buffer layer is 10 nm-30 nm.
S22, growing an N-type layer 3 on the buffer layer 2:
the N-type layer 3 is an N-type GaN layer, the growth temperature is 1000-1150 ℃, the thickness is 2-3 um, and the doping concentration of Si is 1.5X10 18 cm -3 。
S23, growing a multi-quantum well layer 4 on the N-type layer 3:
the multi-quantum well layer 4 comprises InGaN quantum well layers and GaN quantum barrier layers which are grown periodically and alternately, wherein the thickness of the InGaN quantum well layers is 1 nm-4 nm, the growth temperature is 780-825 ℃, the growth pressure is 200-250 torr, and the period is 8-10. The thickness of the GaN quantum barrier layer is 10 nm-15 nm, the growth temperature is 780-820 ℃, and the growth pressure is 200-250 torr.
S24, growing a barrier blending layer 5 on the multiple quantum well layer 4:
sequentially depositing Al on the multiple quantum well layer 4 a N layer 51, al b In x Ga 1-b-x N layer 52, in 1-c Al c N layer 53 and N polarity Al d The GaN/N polar MgN superlattice layer 54 has a growth temperature of 750-1010 ℃ and a growth pressure of 100-600 torr;
wherein Al is a The thickness of the N layer 51 is 4nm to 5nm, al b In x Ga 1-b-x The thickness of the N layer 52 is 3nm to 4nm, in 1-c Al c The thickness of the N layer 53 is 2 nm-3 nm, and N polarity Al d The thickness of the GaN/N polar MgN superlattice layer 54 is 2 nm-5 nm;
wherein Al is a N layer 51, al b In x Ga 1-b-x N layer 52 and In 1-c Al c The growth atmosphere of the N layer 53 is H 2 N polarity Al d The growth atmosphere of GaN/N polar MgN superlattice layer 54 is N 2 ；
In growth process, control In 1-c Al c The growth pressure of the N layer 53 is higher than Al b In x Ga 1-b-x The growth pressure of N layer 52;
and controlling the feed-in amount of the Al source so that the Al component content between the layers in the barrier blending layer 5 is gradually decreased by a magnitude smaller than or equal to 0.1, and Al a N layer 51, al b In x Ga 1-b-x N layer 52 and In 1-c Al c In the N layer 53, the Al component content in each layer decreases in the epitaxial direction by an amount of 0.01 or less, N-polar Al d The Al composition content in the GaN/N polar MgN superlattice layer 54 increases in the epitaxial direction by an amount of less than or equal to 0.01.
S25, growing a P-type layer 6 on the barrier blending layer 5:
the P-type layer 6 comprises a P-type GaN layer and a P-type contact layer, the thickness of the P-type GaN layer is 15 nm-30 nm, the growth temperature is 900-1000 ℃, and the pressure of a reaction chamber is 200-300 torr; the P-type contact layer is a GaN layer with the thickness of 1 nm-6 nm and the doping concentration of Mg of 1.0X10 19 cm -3 ~3.0×10 20 cm -3 The growth temperature is 800-950 ℃.
The invention discloses an LED, which comprises the gallium nitride light-emitting diode epitaxial structure.
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
example 1
Referring to fig. 1, the embodiment discloses an epitaxial structure of a gallium nitride light emitting diode, which comprises a substrate 1, a buffer layer 2, an N-type layer 3, a multiple quantum well layer 4 and a P-type layer 6 which are sequentially arranged, wherein a potential barrier allocation layer 5 is arranged between the multiple quantum well layer 4 and the P-type layer 6, and the potential barrier allocation layer 5 comprises Al which is sequentially deposited along the epitaxial direction a N layer 51, al b In x Ga 1-b-x N layer 52, in 1-c Al c N layer 53 and N polarity Al d A GaN/N polar MgN superlattice layer 54.
In the barrier blending layer 5, d is more than 0 and less than c is more than less than b and less than a is less than 1, x is more than 0 and less than 1-c is less than 1, the content decreasing amplitude i of Al components among the layers is 0.1, in the embodiment, a is decreased from 0.7 to 0.69, and x is 0.2.
Wherein Al is a N layer 51, al b In x Ga 1-b-x N layer 52 and In 1-c Al c In the N layer 53, the Al component content in each layer decreases in the epitaxial direction by 0.01 for decreasing the amplitude j, N-polarity Al d In the GaN/N polar MgN superlattice layer 54, the Al component content is increased in the epitaxial direction by an increment k of 0.01.
Wherein Al is a The thickness of the N layer 51 is 5nm, al b In x Ga 1-b-x N layer 52 has a thickness of 4nm, in 1-c Al c N layer 53 has a thickness of 3nm and N polarity Al d The thickness of the GaN/N polar MgN superlattice layer 54 is 5nm.
Wherein, N polarity Al d The growth atmosphere of GaN/N polar MgN superlattice layer 54 is N 2 。
Wherein, N polarity Al d The GaN/N-polar MgN superlattice layer 54 includes periodically alternating growth of N-polar Al d The GaN sub-layer and the N polarity MgN sub-layer have 3 growth periods.
Wherein In 1-c Al c The growth pressure of the N layer 53 is higher than Al b In x Ga 1-b-x Growth pressure of N layer 52.
Referring to fig. 2 and 3, the method for preparing the epitaxial structure includes:
s100, providing a sapphire substrate 1;
s200, growing a buffer layer on the substrate 1:
the buffer layer 2 is an AlN/GaN buffer layer, a high-temperature AlN two-dimensional nucleation layer is deposited on the substrate 1 by PVD sputtering, then the substrate is transferred into an MOCVD reaction chamber to deposit a GaN buffer layer, and the thickness of the buffer layer 2 is 15nm.
S300, growing an N-type layer 3 on the buffer layer 2:
the N-type layer 3 is an N-type GaN layer with a growth temperature of 1000 ℃, a thickness of 2.5um and a Si doping concentration of 1.5X10 18 cm -3 。
S400, growing a multi-quantum well layer 4 on the N-type layer 3:
the multi-quantum well layer 4 comprises InGaN quantum well layers and GaN quantum barrier layers which are alternately grown periodically, wherein the thickness of the InGaN quantum well layers is 2.3nm, the growth temperature is 825 ℃, the growth pressure is 200torr, and the period is 8. The thickness of the GaN quantum barrier layer is 12nm, the growth temperature is 7820 ℃, and the growth pressure is 200torr.
Referring to fig. 3, s500. Growing a barrier alignment layer 5 on the multiple quantum well layer 4:
s510, depositing Al on the multiple quantum well layer 4 a N layer 51, growth temperature 950 ℃, growth pressure 200torr, thickness 5nm, growth atmosphere H 2 ；
S520 at Al a Deposition of Al on N layer 51 b In x Ga 1-b-x N layer 52, growth temperature 900 ℃, growth pressure 200torr, thickness 4nm, growth atmosphere H 2 ；
S530, at Al b In x Ga 1-b-x Deposition of In on N layer 52 1-c Al c N layer 53, growth temperature 850 ℃, growth pressure 250torr, thickness 3nm, growth atmosphere H 2 ；
S540 at In 1-c Al c Deposition of N-polarity Al on N layer 53 d GaN/N polar MgN superlattice layer 54, growth temperature of 850 ℃, growth pressure of 250torr, thickness of 5nm, and growth atmosphere of N 2 ；
In the growth process, the input amount of an Al source is controlled so as to adjust potential barriersIn layer 5, the Al component content between the layers decreases layer by layer in an amplitude of 0.1, al a N layer 51, al b In x Ga 1-b-x N layer 52 and In 1-c Al c In the N layer 53, the Al component content in each layer decreases in the epitaxial direction by 0.01, N-polarity Al d The Al composition content in the GaN/N polar MgN superlattice layer 54 increases in the epitaxial direction by an amount of 0.01.
S600, growing a P-type layer 6 on the barrier blending layer 5:
the P-type layer 6 comprises a P-type GaN layer and a P-type contact layer, the thickness of the P-type GaN layer is 15nm, the growth temperature is 900 ℃, and the pressure of a reaction chamber is 200torr; the P-type contact layer is a GaN layer with the thickness of 2nm and the doping concentration of Mg of 3.0X10 20 cm -3 The growth temperature was 900 ℃.
Example 2
The embodiment discloses an epitaxial structure of a gallium nitride light-emitting diode, which comprises a substrate, a buffer layer, an N-type layer, a multiple quantum well layer and a P-type layer which are sequentially arranged, wherein a potential barrier allocation layer is arranged between the multiple quantum well layer and the P-type layer, and comprises Al which is sequentially deposited along the epitaxial direction a N layer, al b In x Ga 1-b-x N layer, in 1-c Al c N layer and N polarity Al d GaN/N polarity MgN superlattice layer.
Wherein, in the barrier blending layer, d is more than 0 and less than c is more than less than b and less than a is less than 1,0 is more than x is less than 1-c is less than 1, the content decreasing amplitude i of Al components among the layers is 0.05, in the embodiment, a is decreased from 0.7 to 0.69, and x is 0.2.
Wherein Al is a N layer, al b In x Ga 1-b-x N layer and In 1-c Al c In the N layer, the content of Al component in each layer is respectively decreased along the epitaxial direction, the decreasing amplitude j is 0.01, and the polarity of N Al d In the GaN/N polarity MgN superlattice layer, the content of the Al component increases gradually along the epitaxial direction, and the increasing amplitude k is 0.01.
Wherein Al is a The thickness of the N layer is 4nm, al b In x Ga 1-b-x The thickness of the N layer is 3nm, in 1-c Al c The thickness of the N layer is 2nm, and N polarity Al d Thickness of GaN/N polar MgN superlattice layerIs 2nm.
Wherein, N polarity Al d The growth atmosphere of the GaN/N polar MgN superlattice layer is N 2 。
Wherein, N polarity Al d The GaN/N polarity MgN superlattice layer comprises N polarity Al which grows periodically and alternately d The GaN sub-layer and the N polarity MgN sub-layer have 3 growth periods.
Wherein In 1-c Al c The growth pressure of the N layer is higher than that of Al b In x Ga 1-b-x Growth pressure of the N layer.
The preparation method of the epitaxial structure comprises the following steps:
s100, providing a sapphire substrate;
s200, growing a buffer layer on the substrate:
the buffer layer is an AlN/GaN buffer layer, a high-temperature AlN two-dimensional nucleation layer is deposited on the substrate by PVD sputtering, then the substrate is transferred into an MOCVD reaction chamber to deposit the GaN buffer layer, and the thickness of the buffer layer is 15nm.
S300, growing an N-type layer on the buffer layer:
the N-type layer is an N-type GaN layer with a growth temperature of 1000deg.C, a thickness of 2.5um, and a Si doping concentration of 1.5X10 18 cm -3 。
S400, growing a multi-quantum well layer on the N-type layer:
the multi-quantum well layer comprises InGaN quantum well layers and GaN quantum barrier layers which are alternately grown periodically, wherein the thickness of the InGaN quantum well layers is 2.3nm, the growth temperature is 825 ℃, the growth pressure is 200torr, and the period is 8. The thickness of the GaN quantum barrier layer is 12nm, the growth temperature is 7820 ℃, and the growth pressure is 200torr.
S500, growing a barrier blending layer on the multiple quantum well layer:
s510, depositing Al on the multiple quantum well layer a N layer with growth temperature of 950 deg.c, growth pressure of 200torr, thickness of 4nm and growth atmosphere of H 2 ；
S520 at Al a Deposition of Al on N layer b In x Ga 1-b-x N layer with growth temperature of 900 deg.c, growth pressure of 200torr, thickness of 3nm and growth atmosphere of H 2 ；
S530, at Al b In x Ga 1-b-x Deposition of In on N layer 1-c Al c N layer with growth temperature of 850 deg.c, growth pressure of 250torr, thickness of 2nm and growth atmosphere of H 2 ；
S540 at In 1-c Al c Deposition of N-polar Al on N layer d GaN/N polar MgN superlattice layer with growth temperature of 850 ℃, growth pressure of 250torr, thickness of 2nm and growth atmosphere of N 2 ；
In the growth process, the feeding amount of an Al source is controlled so that the content of Al components among layers in the barrier allocation layer is gradually decreased by 0.1, and the Al a N layer, al b In x Ga 1-b-x N layer and In 1-c Al c In the N layers, the content of Al components in each layer is reduced in the epitaxial direction by 0.01, and the polarity of Al is N d In the GaN/N polar MgN superlattice layer, the Al component content increases gradually along the epitaxial direction in the amplitude of 0.01.
S600, growing a P-type layer on the barrier blending layer:
the P-type layer comprises a P-type GaN layer and a P-type contact layer, the thickness of the P-type GaN layer is 15nm, the growth temperature is 900 ℃, and the pressure of a reaction chamber is 200torr; the P-type contact layer is a GaN layer with the thickness of 2nm and the doping concentration of Mg of 3.0X10 20 cm -3 The growth temperature was 900 ℃.
Example 3
The embodiment discloses an epitaxial structure of a gallium nitride light-emitting diode, which comprises a substrate, a buffer layer, an N-type layer, a multiple quantum well layer and a P-type layer which are sequentially arranged, wherein a potential barrier allocation layer is arranged between the multiple quantum well layer and the P-type layer, and comprises Al which is sequentially deposited along the epitaxial direction a N layer, al b In x Ga 1-b-x N layer, in 1-c Al c N layer and N polarity Al d GaN/N polarity MgN superlattice layer.
In the barrier alignment layer, d=c=b=a=0.7, and x is 0.2.
Wherein Al is a The thickness of the N layer is 5nm, al b In x Ga 1-b-x The thickness of the N layer is 4nm, in 1-c Al c The thickness of the N layer is 3nm, and N polarity Al d GaN/N polarity MThe thickness of the gN superlattice layer was 5nm.
Wherein, N polarity Al d The growth atmosphere of the GaN/N polar MgN superlattice layer is N 2 。
Wherein, N polarity Al d The GaN/N polarity MgN superlattice layer comprises N polarity Al which grows periodically and alternately d The GaN sub-layer and the N polarity MgN sub-layer have 3 growth periods.
Wherein In 1-c Al c The growth pressure of the N layer is higher than that of Al b In x Ga 1-b-x Growth pressure of the N layer.
The preparation method of the epitaxial structure comprises the following steps:
s100, providing a sapphire substrate;
s200, growing a buffer layer on the substrate:
the buffer layer is an AlN/GaN buffer layer, a high-temperature AlN two-dimensional nucleation layer is deposited on the substrate by PVD sputtering, then the substrate is transferred into an MOCVD reaction chamber to deposit the GaN buffer layer, and the thickness of the buffer layer is 15nm.
S300, growing an N-type layer on the buffer layer:
the N-type layer is an N-type GaN layer with a growth temperature of 1000deg.C, a thickness of 2.5um, and a Si doping concentration of 1.5X10 18 cm -3 。
S400, growing a multi-quantum well layer on the N-type layer:
the multi-quantum well layer comprises InGaN quantum well layers and GaN quantum barrier layers which are alternately grown periodically, wherein the thickness of the InGaN quantum well layers is 2.3nm, the growth temperature is 825 ℃, the growth pressure is 200torr, and the period is 8. The thickness of the GaN quantum barrier layer is 12nm, the growth temperature is 7820 ℃, and the growth pressure is 200torr.
S500, growing a barrier blending layer on the multiple quantum well layer:
s510, depositing Al on the multiple quantum well layer a N layer with growth temperature of 950 deg.c, growth pressure of 200torr, thickness of 5nm and growth atmosphere of H 2 ；
S520 at Al a Deposition of Al on N layer b In x Ga 1-b-x N layer with growth temperature of 900 deg.c, growth pressure of 200torr, thickness of 4nm and growth atmosphere of H 2 ；
S530, at Al b In x Ga 1-b-x Deposition of In on N layer 1-c Al c N layer with growth temperature of 850 deg.c, growth pressure of 250torr, thickness of 3nm and growth atmosphere of H 2 ；
S540 at In 1-c Al c Deposition of N-polar Al on N layer d GaN/N polar MgN superlattice layer with growth temperature of 850 ℃, growth pressure of 250torr, thickness of 5nm and growth atmosphere of N 2 ；
S600, growing a P-type layer on the barrier blending layer:
the P-type layer comprises a P-type GaN layer and a P-type contact layer, the thickness of the P-type GaN layer is 15nm, the growth temperature is 900 ℃, and the pressure of a reaction chamber is 200torr; the P-type contact layer is a GaN layer with the thickness of 2nm and the doping concentration of Mg of 3.0X10 20 cm -3 The growth temperature was 900 ℃.
Example 4
The embodiment discloses an epitaxial structure of a gallium nitride light-emitting diode, which comprises a substrate, a buffer layer, an N-type layer, a multiple quantum well layer and a P-type layer which are sequentially arranged, wherein a potential barrier allocation layer is arranged between the multiple quantum well layer and the P-type layer, and comprises Al which is sequentially deposited along the epitaxial direction a N layer, al b In x Ga 1-b-x N layer, in 1-c Al c N layer and N polarity Al d GaN/N polarity MgN superlattice layer.
Wherein, in the barrier blending layer, d is more than 0 and less than c is more than less than b and less than a is less than 1,0 is more than x is less than 1-c is less than 1, the content decreasing amplitude i of Al components among the layers is 0.1, in the embodiment, a is decreased from 0.7 to 0.6, and x is 0.2.
Wherein Al is a N layer, al b In x Ga 1-b-x N layer and In 1-c Al c In the N layers, the content of Al components in each layer is respectively decreased along the epitaxial direction, the decreasing amplitude j is 0.1, and the polarity of N is Al d In the GaN/N polarity MgN superlattice layer, the content of the Al component increases gradually along the epitaxial direction, and the increasing amplitude k is 0.1.
Wherein Al is a The thickness of the N layer is 5nm, al b In x Ga 1-b-x The thickness of the N layer is 4nm, in 1-c Al c The thickness of the N layer is 3nm, and the polarity of NAl d The thickness of the GaN/N polar MgN superlattice layer is 5nm.
Wherein, N polarity Al d The growth atmosphere of the GaN/N polar MgN superlattice layer is N 2 。
Wherein, N polarity Al d The GaN/N polarity MgN superlattice layer comprises N polarity Al which grows periodically and alternately d The GaN sub-layer and the N polarity MgN sub-layer have 3 growth periods.
Wherein In 1-c Al c The growth pressure of the N layer is higher than that of Al b In x Ga 1-b-x Growth pressure of the N layer.
The preparation method of the epitaxial structure comprises the following steps:
s100, providing a sapphire substrate;
s200, growing a buffer layer on the substrate:
the buffer layer is an AlN/GaN buffer layer, a high-temperature AlN two-dimensional nucleation layer is deposited on the substrate by PVD sputtering, then the substrate is transferred into an MOCVD reaction chamber to deposit the GaN buffer layer, and the thickness of the buffer layer is 15nm.
S300, growing an N-type layer on the buffer layer:
the N-type layer is an N-type GaN layer with a growth temperature of 1000deg.C, a thickness of 2.5um, and a Si doping concentration of 1.5X10 18 cm -3 。
S400, growing a multi-quantum well layer on the N-type layer:
the multi-quantum well layer comprises InGaN quantum well layers and GaN quantum barrier layers which are alternately grown periodically, wherein the thickness of the InGaN quantum well layers is 2.3nm, the growth temperature is 825 ℃, the growth pressure is 200torr, and the period is 8. The thickness of the GaN quantum barrier layer is 12nm, the growth temperature is 7820 ℃, and the growth pressure is 200torr.
S500, growing a barrier blending layer on the multiple quantum well layer:
s510, depositing Al on the multiple quantum well layer a N layer with growth temperature of 950 deg.c, growth pressure of 200torr, thickness of 5nm and growth atmosphere of H 2 ；
S520 at Al a Deposition of Al on N layer b In x Ga 1-b-x N layer with growth temperature of 900 deg.c, growth pressure of 200torr, thickness of 4nm and growth atmosphere of H 2 ；
S530, at Al b In x Ga 1-b-x Deposition of In on N layer 1-c Al c N layer with growth temperature of 850 deg.c, growth pressure of 250torr, thickness of 3nm and growth atmosphere of H 2 ；
S540 at In 1-c Al c Deposition of N-polar Al on N layer d GaN/N polar MgN superlattice layer with growth temperature of 850 ℃, growth pressure of 250torr, thickness of 5nm and growth atmosphere of N 2 ；
In the growth process, the feeding amount of an Al source is controlled so that the content of Al components among layers in the barrier allocation layer is gradually decreased by 0.1, and the Al a N layer, al b In x Ga 1-b-x N layer and In 1-c Al c In the N layers, the content of Al components in each layer is reduced in the epitaxial direction by 0.01, and the polarity of Al is N d In the GaN/N polar MgN superlattice layer, the Al component content increases gradually along the epitaxial direction in the amplitude of 0.01.
S600, growing a P-type layer on the barrier blending layer:
the P-type layer comprises a P-type GaN layer and a P-type contact layer, the thickness of the P-type GaN layer is 15nm, the growth temperature is 900 ℃, and the pressure of a reaction chamber is 200torr; the P-type contact layer is a GaN layer with the thickness of 2nm and the doping concentration of Mg of 3.0X10 20 cm -3 The growth temperature was 900 ℃.
Comparative example 1
The present comparative example is different from example 1 in that the barrier formulated layer of the present comparative example does not include Al a N layer, corresponding, does not include Al in the preparation method a And (3) preparing an N layer.
Comparative example 2
The present comparative example is different from example 1 in that the barrier formulated layer of the present comparative example does not include Al b In x Ga 1-b- x N layer and In 1-c Al c N layer, corresponding, does not include Al in the preparation method b In x Ga 1-b-x N layer and In 1-c Al c And (3) preparing an N layer.
Comparative example 3
This comparative example and example 1The difference is that the barrier alignment layer of this comparative example does not include N-polar Al d GaN/N polarity MgN superlattice layer, corresponding to the preparation method, does not comprise N polarity Al d And preparing the GaN/N polar MgN superlattice layer.
Comparative example 4
The present comparative example is different from example 1 in that a barrier alignment layer is not provided between the multiple quantum well layer and the P-type layer, but an electron blocking layer is provided, which is P-AlGaN.
And testing the luminous efficiencies corresponding to the epitaxial wafers prepared in the examples 1-4 and the comparative examples 1-4, and comparing the luminous efficiencies measured in the examples 1-4 and the comparative examples 1-3 with the luminous efficiency measured in the comparative example 4 to obtain the luminous efficiency improvement rates of the examples 1-4 and the comparative examples 1-3, wherein the luminous efficiency improvement rates are positive values, which indicate that the luminous efficiency of the experimental group is higher than that of the comparative example 4, and the luminous efficiency improvement rates are negative values, which indicate that the luminous efficiency of the experimental group is lower than that of the comparative example 4.
The results were measured as follows:
Figure SMS_1
as can be seen from the experimental results, the examples 1 to 4 of the present invention have more remarkable improvement in luminous efficiency than the comparative examples 1 to 3, and are Al a N layer, al b In x Ga 1-b-x N layer, in 1-c Al c N layer and N polarity Al d The synergy exists among the multi-layer material layers of the GaN/N polar MgN superlattice layer, and the embodiment 1 is superior to the embodiment 3 and the embodiment 4, so that the arrangement of the difference between the interlayer and the Al component content variation amplitude in the layer can obviously improve the luminous efficiency.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.

Claims (10)

1. The epitaxial structure of the gallium nitride light-emitting diode comprises a substrate, a buffer layer, an N-type layer, a multiple quantum well layer and a P-type layer which are sequentially arranged, and is characterized in that a potential barrier allocation layer is arranged between the multiple quantum well layer and the P-type layer, and comprises Al which is sequentially deposited along the epitaxial direction a N layer, al b In x Ga 1-b-x N layer, in 1-c Al c N layer and N polarity Al d GaN/N polarity MgN superlattice layer.
2. The epitaxial structure of claim 1, wherein 0 < d < c < b < a < 1,0 < x < 1-c < 1 in the barrier alignment layer.
3. The gallium nitride light emitting diode epitaxial structure of claim 2, wherein the Al a N layer, the Al b In x Ga 1-b-x N layer and In 1-c Al c In the N layers, the content of Al components in each layer is respectively reduced along the epitaxial direction, and the N polarity Al d In the GaN/N polar MgN superlattice layer, the content of the Al component increases gradually along the epitaxial direction.
4. A gallium nitride light emitting diode epitaxial structure according to claim 3, wherein said Al a N layer, the Al b In x Ga 1-b-x N layer, the In 1-c Al c N layer and the N polarity Al d In the GaN/N polarity MgN superlattice layer, the content decreasing amplitude i of Al components among layers is more than 0.01 and less than or equal to 0.1;
the Al is a N layer, the Al b In x Ga 1-b-x N layer and In 1-c Al c In the N layer, the decreasing amplitude j of the Al component content in each layer is more than 0 and less than or equal to 0.01The N polarity Al d In the GaN/N polarity MgN superlattice layer, the increment range k of the Al component content is more than 0 and less than or equal to 0.01.
5. The gallium nitride light emitting diode epitaxial structure of claim 1, wherein the Al a N layer, the Al b In x Ga 1-b-x N layer and In 1-c Al c The thickness of the N layers is gradually decreased, and the Al a The thickness of the N layer is 4 nm-5 nm, and the Al layer is b In x Ga 1-b-x The thickness of the N layer is 3 nm-4 nm, and the In 1-c Al c The thickness of the N layer is 2 nm-3 nm, and the N polarity Al d The thickness of the GaN/N polar MgN superlattice layer is 2 nm-5 nm.
6. The gallium nitride light emitting diode epitaxial structure of claim 1, wherein the N-polar Al d The growth atmosphere of the GaN/N polar MgN superlattice layer is N 2 。
7. The gallium nitride light emitting diode epitaxial structure of claim 1, wherein the N-polar Al d The GaN/N polarity MgN superlattice layer comprises N polarity Al which grows periodically and alternately d The GaN sub-layer and the N polarity MgN sub-layer have 3-5 growth periods.
8. The gallium nitride light emitting diode epitaxial structure of claim 1, wherein the In 1-c Al c The growth pressure of the N layer is higher than that of the Al b In x Ga 1-b-x Growth pressure of the N layer.
9. The preparation method of the gallium nitride light-emitting diode epitaxial structure is characterized by comprising the following steps of:
providing a substrate;
sequentially epitaxially growing a buffer layer, an N-type layer, a multiple quantum well layer, a potential barrier allocation layer and a P-type layer on the substrate;
the potential barrier allocation layer comprises A which are deposited along the epitaxial directionl a N layer, al b In x Ga 1-b-x N layer, in 1-c Al c N layer and N polarity Al d GaN/N polarity MgN superlattice layer.
10. An LED comprising a gallium nitride light emitting diode epitaxial structure according to any one of claims 1 to 8.
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