CN113488567B - Light emitting diode epitaxial wafer with composite transition layer and preparation method thereof - Google Patents

Light emitting diode epitaxial wafer with composite transition layer and preparation method thereof Download PDF

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CN113488567B
CN113488567B CN202110520704.1A CN202110520704A CN113488567B CN 113488567 B CN113488567 B CN 113488567B CN 202110520704 A CN202110520704 A CN 202110520704A CN 113488567 B CN113488567 B CN 113488567B
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sio
composite transition
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algan
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CN113488567A (en
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王群
郭炳磊
葛永晖
王江波
董彬忠
李鹏
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HC Semitek Zhejiang Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/44Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005Processes
    • H01L33/0062Processes for devices with an active region comprising only III-V compounds
    • H01L33/0066Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005Processes
    • H01L33/0062Processes for devices with an active region comprising only III-V compounds
    • H01L33/0075Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract

The invention discloses a light-emitting diode epitaxial wafer with a composite transition layer and a preparation method thereof, belonging to the field of light-emitting diode manufacturing. SiO in the composite transition layer2A sublayer laminated on the n-type GaN layer, SiO2The thermal expansion coefficient of the material of the sub-layer is small, and the influence on the multi-quantum well layer is reduced. And the light emitting quality of the multi-quantum well layer is ensured. SiO 22The orthographic projection of the sublayer on the surface of the substrate is net-shaped, SiO2The sub-layer blocks part of the dislocations. When the AlGaN sub-layers grow, dislocations generated by the growth in two directions can be annihilated mutually, defects in the AlGaN sub-layers are few, and the dislocation is effectively prevented from extending into the multiple quantum well layers while the quality of the multiple quantum well layers is ensured. The crystal quality of the multi-quantum well layer is improved, non-radiative recombination can be reduced, and the light emitting efficiency of the light emitting diode is improved.

Description

Light emitting diode epitaxial wafer with composite transition layer and preparation method thereof
Technical Field
The invention relates to the field of light emitting diode manufacturing, in particular to a light emitting diode epitaxial wafer with a composite transition layer and a preparation method thereof.
Background
A light emitting diode is a semiconductor electronic component capable of emitting light. As a novel high-efficiency, environment-friendly and green solid-state illumination light source, the solid-state illumination light source is rapidly and widely applied, such as traffic signal lamps, automobile interior and exterior lamps, urban landscape illumination, mobile phone backlight sources and the like, and the aim of improving the luminous efficiency of a chip is continuously pursued by LEDs.
The light emitting diode epitaxial wafer is a basic structure for preparing the light emitting diode, and comprises a substrate, and a GaN buffer layer, an n-type GaN layer, a multi-quantum well layer and a p-type GaN layer which are sequentially stacked on the substrate. The GaN buffer layer can relieve lattice mismatch between the n-type GaN layer and the substrate to a certain extent so as to improve the crystal quality of the obtained n-type GaN layer and the multiple quantum well layer grown on the n-type GaN layer.
However, the GaN buffer layer has a limited effect of relieving lattice mismatch, and the GaN buffer layer also accumulates more thermal stress during the growth process, the stress and defects in the GaN buffer layer extend into the multiple quantum well layer, which affects the light emitting efficiency of the multiple quantum well layer, and the light emitting efficiency of the finally obtained light emitting diode is not high.
Disclosure of Invention
The embodiment of the disclosure provides a light emitting diode epitaxial wafer with a composite transition layer and a preparation method thereof, which can improve the crystal quality of the light emitting diode epitaxial wafer so as to improve the light emitting efficiency of a light emitting diode. The technical scheme is as follows:
the embodiment of the present disclosure provides a light emitting diode epitaxial wafer with a composite transition layer, the light emitting diode epitaxial wafer comprises a substrate, and a GaN buffer layer, an n-type GaN layer, a composite transition layer, a multiple quantum well layer and a p-type GaN layer which are sequentially stacked on the substrate,
the composite transition layer comprises sequentially laminated SiO2A sublayer and an AlGaN sublayer, the SiO2The orthographic projection of the sub-layers on the surface of the substrate is in a net shape.
Optionally, the SiO2The thickness of the sub-layer is 15-100 nm.
Optionally, the SiO2The sub-layer comprises a plurality of first strip-shaped parts parallel to each other and a plurality of second strip-shaped parts parallel to each other, each first strip-shaped part is intersected with the plurality of second strip-shaped parts, and the width of each first strip-shaped part is equal to that of each second strip-shaped part.
Optionally, the SiO2The area of the mesh corresponding to the orthographic projection of the sublayer on the surface of the substrate is 6-35 um.
Optionally, the AlGaN sublayer has a thickness of 5 to 80 nm.
Optionally, the molar doping amount of Al in the AlGaN sublayer is 1% to 6%.
The embodiment of the disclosure provides a preparation method of a light emitting diode epitaxial wafer with a composite transition layer, wherein the preparation method comprises the following steps:
providing a substrate;
growing a GaN buffer layer on the substrate;
growing an n-type GaN layer on the GaN buffer layer;
growing a composite transition layer on the n-type GaN layer, wherein the composite transition layer comprises sequentially laminated SiO2A sublayer and an AlGaN sublayer, the SiO2The orthographic projection of the sub-layer on the surface of the substrate is in a net shape;
growing a multi-quantum well layer on the composite transition layer;
and growing a p-type GaN layer on the multi-quantum well layer.
Optionally, the preparation method comprises:
the GaN buffer layer and the n-type GaN layer are grown by adopting hydride vapor phase epitaxy equipment;
and the AlGaN sublayer, the multi-quantum well layer and the p-type GaN layer are grown by adopting chemical vapor deposition equipment.
Optionally, the AlGaN sublayer grows in an atmosphere environment of nitrogen and ammonia, and the volume of the ammonia during growth of the AlGaN sublayer is 20% to 40% of the total volume of the gas in the reaction chamber.
Alternatively, the multiple quantum well layer includes InGaN well layers and GaN barrier layers alternately stacked,
the volume of ammonia gas generated during growth of the AlGaN sub-layer is 50-80% of the volume of ammonia gas generated during growth of the InGaN well layer.
The technical scheme provided by the embodiment of the disclosure has the following beneficial effects:
a composite transition layer is added between the n-type GaN layer and the multi-quantum well layer, and SiO in the composite transition layer2A sublayer laminated on the n-type GaN layer, SiO2The thermal expansion coefficient of the material of the sub-layer is small, the thermal stress accumulated in the growth process is small, the generated thermal stress is small, and the influence on the multi-quantum well layer can be reduced. And the light emitting quality of the multi-quantum well layer is ensured. SiO 22The orthographic projection of the sublayer on the surface of the substrate is net-shaped, SiO2The sub-layer may block a portion of the bitsDislocations, reducing dislocations and defects extending into the multiple quantum well layers, the AlGaN sub-layer may be in SiO2The surface of the n-type GaN layer in the mesh of the sub-layer grows and is transited to the multi-quantum well layer, and the forming quality of the multi-quantum well layer is guaranteed. And SiO2The sub-layer does not adsorb organic metal source, so that the AlGaN sub-layer grows longitudinally on the surface of the n-type GaN layer, and the AlGaN sub-layer is covered with SiO2The sub-layers grow transversely, dislocation generated by growth in two directions can be annihilated mutually, defects in the AlGaN sub-layers are few, the quality of the multi-quantum well layer is guaranteed, and dislocation is effectively prevented from extending into the multi-quantum well layer. The crystal quality of the multi-quantum well layer is improved, non-radiative recombination can be reduced, and the light emitting efficiency of the light emitting diode is improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present disclosure, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without inventive labor.
Fig. 1 is a schematic structural diagram of an led epitaxial wafer with a composite transition layer according to an embodiment of the present disclosure;
FIG. 2 is a SiO solid provided by an embodiment of the disclosure2A top view of the sub-layer;
fig. 3 is a schematic structural diagram of another light emitting diode epitaxial wafer with a composite transition layer according to an embodiment of the present disclosure;
fig. 4 is a flowchart of a method for manufacturing an led epitaxial wafer with a composite transition layer according to an embodiment of the present disclosure;
fig. 5 is a flowchart of a method for manufacturing an led epitaxial wafer with a composite transition layer according to an embodiment of the present disclosure.
Detailed Description
To make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings.
Fig. 1 is a schematic structural diagram of a light emitting diode epitaxial wafer with a composite transition layer according to an embodiment of the present disclosure, and referring to fig. 1, the embodiment of the present disclosure provides a light emitting diode epitaxial wafer with a composite transition layer 4, where the light emitting diode epitaxial wafer includes a substrate 1, and a GaN buffer layer 2, an n-type GaN layer 3, a composite transition layer 4, a multi-quantum well layer 5, and a p-type GaN layer 6 sequentially stacked on the substrate 1.
The composite transition layer 4 comprises sequentially laminated SiO2Sublayer 41 and AlGaN sublayer 42, SiO2The orthographic projection of the sublayer 41 on the surface of the substrate 1 is in the form of a network.
A composite transition layer 4 is added between the n-type GaN layer 3 and the multiple quantum well layer 5, and SiO in the composite transition layer 42 A sublayer 41 of SiO laminated on the n-type GaN layer 32The thermal expansion coefficient of the material of the sub-layer 41 itself is small, the thermal stress that can be accumulated during the growth process is small, the generated thermal stress is small, and the influence on the multiple quantum well layer 5 can be reduced. The light emitting quality of the multiple quantum well layer 5 is ensured. SiO 22The orthographic projection of the sublayer 41 on the surface of the substrate 1 is in the form of a network, SiO2The sub-layer 41 can block a part of dislocation and reduce dislocation and defect extending to the multiple quantum well layer 5, and the AlGaN sub-layer 42 can be in SiO2The surface of the n-type GaN layer 3 in the mesh of the sub-layer 41 grows and transits to the multiple quantum well layer 5, and the forming quality of the multiple quantum well layer 5 is guaranteed. And SiO2Since the sublayer 41 does not adsorb an organic metal source, the AlGaN sublayer 42 is grown in the longitudinal direction on the surface of the n-type GaN layer 3, and the AlGaN sublayer 42 is formed so as to cover the SiO layer2The sub-layers 41 grow transversely, dislocations generated by growth in two directions can be annihilated mutually, defects in the AlGaN sub-layers 42 are few, the quality of the multiple quantum well layer 5 is guaranteed, and dislocation extension into the multiple quantum well layer 5 is effectively prevented. The crystal quality of the multiple quantum well layer 5 is improved, non-radiative recombination can be reduced, and the light emitting efficiency of the light emitting diode is improved.
Besides the influence caused by the different thicknesses of the light emitting diode, the warping also has the effect that the dislocations and the defects at different positions in the light emitting diode epitaxial wafer extend to the surface of the light emitting diode, so that the warping degree of the surface of the light emitting diode epitaxial wafer can be reduced to a certain extent due to the reduction of the dislocations and the defects.
Illustratively, the composite transition layer 4 has an overall thickness of 0.2-2 um.
When the overall thickness of the composite transition layer 4 is within the above range, dislocation and defects can be effectively blocked, the quality of the composite transition layer 4 is good, and the preparation cost of the light-emitting diode epitaxial wafer cannot be excessively increased.
Alternatively, SiO2The thickness of the sub-layer 41 is 15-100 nm.
SiO2The thickness of the sub-layer 41 is within the above range, which can effectively block dislocation and SiO2The thickness of the sublayer 41 is also reasonable, and the transition to the AlGaN sublayer 42 can be effectively realized in SiO2The AlGaN sublayer 42 grown on the sublayer 41 has fewer defects, and the quality of the finally obtained light emitting diode epitaxial wafer is also better.
Illustratively, SiO2The sub-layer 41 includes a plurality of first strip portions 411 and a plurality of second strip portions 412, wherein the first strip portions 411 are parallel to each other, each of the first strip portions 411 intersects with the plurality of second strip portions 412, and a width of each of the first strip portions 411 is equal to a width of each of the second strip portions 412.
SiO2The width of the first stripe portion 411 in the sub-layer 41 is equal to the width of the second stripe portion 412, so that a more regular mesh structure can be formed, the quality of the AlGaN sub-layer 42 grown on the first stripe portion 411 and the second stripe portion 412 is better, and the quality of the composite transition layer 4 itself can be improved to improve the crystal quality of the multiple quantum well layer 5.
Alternatively, the first bar portions 411 and the second bar portions 412 may be perpendicular to each other, and a distance between two adjacent first bar portions 411 is the same as a distance between two adjacent second bar portions 412.
SiO2In the sub-layer 41, the first stripe portions 411 and the second stripe portions 412 are perpendicular to each other, and the distances between two adjacent first stripe portions 411 and second stripe portions 412 are equal, so that a very regular mesh can be constructedThe shape ensures that the AlGaN sublayers 42 can grow well and uniformly in the meshes, and improves the quality of the finally obtained composite transition layer 4 so as to improve the crystal quality of the multiple quantum well layer 5.
It is noted that in other implementations provided by the present disclosure, SiO2An included angle between the first strip portions 411 and the second strip portions 412 in the sub-layer 41 may be an acute angle, or a distance between two adjacent first strip portions 411 is different from a distance between two adjacent second strip portions 412, which is not limited in this disclosure.
Alternatively, SiO2The area of the mesh corresponding to the orthographic projection of the sublayer 41 on the surface of the substrate 1 is 6-35 um.
SiO2When the area of the mesh corresponding to the orthographic projection of the sublayer 41 on the surface of the substrate 1 is within the above range, the AlGaN sublayer 42 can be effectively grown in the mesh, the stratum of the AlGaN sublayer 42 does not have more defects, the crystal quality of the AlGaN sublayer 42 can be improved, and the AlGaN sublayer 42 can cover the SiO layer2Dislocation formed by growth of the AlGaN material behind the sublayer 41 is annihilated well, and the crystal quality of the AlGaN sublayer 42 is effectively improved. The improvement of the crystal quality of the AlGaN sublayer 42 can effectively improve the crystal quality of the multiple quantum well layer 5 grown on the AlGaN sublayer 42, the dislocation and the defect in the multiple quantum well layer 5 are reduced, the non-radiative recombination is reduced, the probability of the normal light emission of carriers is improved, and the light emission efficiency is improved.
Illustratively, the AlGaN sublayers 42 are 5-80nm thick.
When the thickness of the AlGaN sublayer 42 is within the above range, the quality of the AlGaN sublayer 42 is good, and the quality of the AlGaN sublayer 42 is improved, which can ensure that the quality of the multiple quantum well layer 5 grown on the AlGaN sublayer 42 is good.
Optionally, the molar doping amount of Al in the AlGaN sublayer 42 is 1% to 6%.
When the molar doping amount of Al in the AlGaN sublayer 42 is within the above range, the AlGaN sublayer 42 can form good lattice matching with the gallium nitride material, thereby reducing defects caused by lattice mismatch between the AlGaN sublayer 42 and the gallium nitride material, and ensuring the crystal quality of the finally obtained composite transition layer 4 and the multiple quantum well layer 5.
In the implementation manner provided by the present disclosure, in the growth direction of the AlGaN sub-layer 42, the molar doping amount of Al in the AlGaN sub-layer 42 may be uniformly doped, or may be gradually increased or decreased, which is not limited by the present disclosure.
For ease of understanding, FIG. 2 is provided herein, and FIG. 2 is a SiO solid provided by an embodiment of the disclosure2Top view of the sub-layer, see fig. 2, SiO2The sub-layer comprises a first strip portion 411 and a second strip portion 412 intersecting.
Fig. 3 is a schematic structural diagram of another light emitting diode epitaxial wafer with a composite transition layer 4 according to an embodiment of the present disclosure, and as can be seen from fig. 3, in another implementation manner provided by the present disclosure, the light emitting diode epitaxial wafer with the composite transition layer 4 may include a substrate 1, and a GaN buffer layer 2, an n-type GaN layer 3, a composite transition layer 4, a multi-quantum well layer 5, an electron blocking layer 7, a p-type GaN layer 6, and a p-type contact layer 8 grown on the substrate 1.
It should be noted that the composite transition layer 4 shown in fig. 3 has the same structure as the composite transition layer 4 shown in fig. 1, and the description thereof is omitted here.
Alternatively, the substrate 1 may be a sapphire substrate 1. Easy to manufacture and obtain.
Illustratively, the thickness of the GaN buffer layer 2 is 1-2 um. The lattice mismatch can be effectively alleviated.
In other implementations provided by the present disclosure, the buffer layer 2 may also be one of aluminum nitride, aluminum gallium nitride, or aluminum indium gallium nitride. The present disclosure is not so limited.
Alternatively, the doping element of the n-type GaN layer 3 may be Si or Ge, and the doping concentration of the Si element or Ge element may be 1 × 1019~5×1019cm-3. The overall quality of the n-type GaN layer 3 is good.
Alternatively, the thickness of the n-type GaN layer 3 is 0.5-1.5 um. The quality of the n-type GaN layer 3 itself is good.
Illustratively, the MQW layer 5 includes a plurality of InGaN well layers 51 and GaN barrier layers 52 alternately stacked, the thickness of the InGaN well layers 51 may be 2-3 nm, and the thickness of the GaN barrier layers 52 may be 8-20 nm.
Illustratively, the overall thickness of the MQW layer 5 may be 50 to 130nm, and the In molar content may be 15 to 30%.
Alternatively, the thickness of the p-type GaN layer 6 may be 100-200 nm.
Illustratively, the p-type contact layer 8 may have a thickness of 10 to 50 nm.
In the epitaxial wafer structure shown in fig. 3, compared with the epitaxial wafer structure shown in fig. 1, the buffer layer 2 is added between the multiple quantum well layer 5 and the p-type GaN layer 6, and the p-type contact layer 8 is also grown on the p-type GaN layer 6. The obtained epitaxial wafer has better quality and luminous efficiency.
Fig. 4 is a flowchart of a method for manufacturing a light emitting diode epitaxial wafer with a composite transition layer according to an embodiment of the present disclosure, and as shown in fig. 4, the method for manufacturing a light emitting diode epitaxial wafer with a composite transition layer includes:
s101: a substrate is provided.
S102: a GaN buffer layer is grown on the substrate.
S103: and growing an n-type GaN layer on the GaN buffer layer.
S104: growing a composite transition layer on the n-type GaN layer, wherein the composite transition layer comprises sequentially laminated SiO2Sub-layer and AlGaN sub-layer, SiO2The sub-layers are network-shaped in an orthographic projection of the surface of the substrate.
S105: and growing the multi-quantum well layer on the composite transition layer.
S106: and growing a p-type GaN layer on the multi-quantum well layer.
Illustratively, in step S104, SiO2The sub-layer may be grown by evaporation. SiO 22The quality of the sub-layer is better.
Optionally, growing SiO on the n-type GaN layer2A sublayer, comprising: depositing a layer of SiO on the n-type GaN layer2A film; using photolithographic processes on SiO2Forming a plurality of meshes on the film to form SiO2And a sublayer. By adopting the method, SiO with better quality can be obtained2And a sublayer.
Illustratively, SiO2Of filmsThe deposition temperature is 200-600 ℃. Can ensure the SiO finally obtained2The quality of the sub-layer is better.
Illustratively, the growth temperature of the AlGaN sublayer is 1000-1200 ℃, and the growth pressure of the AlGaN sublayer is 100-400 torr. The AlGaN sub-layer with better quality can be obtained, so that the quality of the subsequently obtained multi-quantum well layer is better.
Optionally, the AlGaN sub-layer grows in an atmosphere environment of nitrogen and ammonia, and the volume of the ammonia during the growth of the AlGaN sub-layer is 20% to 40% of the total volume of the gas in the reaction chamber.
The AlGaN sublayer grows in the atmosphere environment of nitrogen and ammonia, and the volume of the ammonia during the growth of the AlGaN sublayer is 20-40% of the total volume of the gas in the reaction cavity, so that the pre-reaction generated during the growth of the AlGaN material can be effectively controlled, and the crystal quality of the finally obtained AlGaN sublayer is improved.
It should be noted that, when the AlGaN sublayer grows, the gas in the reaction chamber includes ammonia and nitrogen, and therefore the total volume of the gas in the reaction chamber is the total volume of the ammonia and the nitrogen in the reaction chamber.
Illustratively, the multiple quantum well layer includes InGaN well layers and GaN barrier layers alternately stacked. The volume of ammonia gas in the growth of the AlGaN sublayer is 50 to 80% of the volume of ammonia gas in the growth of the InGaN well layer.
The volume of ammonia gas generated during the growth of the AlGaN sublayer is 50-80% of that of ammonia gas generated during the growth of the InGaN well layer, so that the matching between the AlGaN sublayer and gallium nitride materials in the multi-quantum well layer can be effectively controlled, and the quality of the finally obtained AlGaN sublayer and the multi-quantum well layer is ensured to be good.
Alternatively, a method of making, comprising: the GaN buffer layer and the n-type GaN layer are grown by adopting hydride vapor phase epitaxy equipment; and the AlGaN sublayer, the multi-quantum well layer and the p-type GaN layer are grown by adopting chemical vapor deposition equipment.
In the implementation mode provided by the disclosure, the GaN buffer layer and the n-type GaN layer are grown by hydride vapor phase epitaxy equipment, so that the crystal quality of the GaN buffer layer and the n-type GaN layer can be improved, the forming rate of the GaN buffer layer and the n-type GaN layer is improved, the preparation time required by the light emitting diode epitaxial wafer is reduced, and the preparation rate of the light emitting diode is improved. The AlGaN sub-layer and the epitaxial structure behind the AlGaN sub-layer grow in a chemical vapor deposition mode, so that the quality of the AlGaN sub-layer and the epitaxial structure behind the AlGaN sub-layer can be guaranteed, and the AlGaN sub-layer can play a good transition role.
In the hydride vapor phase epitaxy apparatus, liquid metal gallium (Ga) reacts with Hydrogen Chloride (HCI) at a gallium boat to generate gallium chloride (GaCI), and the GaCl is transported to the substrate surface by a carrier gas (H2/N2) and reacts with ammonia (NH3) to generate a GaN crystal.
The light emitting diode epitaxial wafer structure with the composite transition layer after the step S106 is performed can be seen in fig. 1.
The specific technical effect of the method shown in fig. 4 can refer to the technical effect of the light emitting diode epitaxial wafer structure with the composite transition layer shown in fig. 1, and therefore, the detailed description thereof is omitted here.
Fig. 5 is a flowchart of a method for manufacturing a light emitting diode epitaxial wafer with a composite transition layer according to an embodiment of the present disclosure, and as shown in fig. 5, the method for manufacturing a light emitting diode epitaxial wafer with a composite transition layer includes:
s201: a substrate is provided.
Wherein the substrate may be a sapphire substrate. Easy to realize and manufacture.
Optionally, step S201 may further include: and under the hydrogen atmosphere, the time for treating the surface of the substrate is 6-10 min.
For example, the temperature of the reaction chamber may be 1000 to 1200 ℃ and the pressure of the reaction chamber may be 200to 500Torr when processing the surface of the substrate.
In one implementation provided by the present disclosure, the temperature of the reaction chamber may also be 1100 ℃ when processing the substrate, and the time period for processing the surface of the substrate may be 8 min.
Step S201 may further include: and nitriding the surface of the substrate, and paving a layer of nitrogen atoms on the surface of the substrate. Rapid growth of gallium nitride material may be facilitated.
S202: a GaN buffer layer is grown on the substrate.
Optionally, the temperature of the reaction chamber is controlled to be 450-600 ℃, the pressure of the reaction chamber is controlled to be 200-500 torr, and the GaN buffer layer grows. And obtaining the GaN buffer layer with better quality.
S203: and growing an n-type GaN layer on the GaN buffer layer.
Alternatively, the growth temperature of the n-type GaN layer may be 950 ℃ to 1200 ℃, and the growth pressure of the n-type GaN layer may be 200Torr to 500 Torr.
S204: and growing a composite transition layer on the n-type GaN layer.
The step of growing the composite transition layer in step S204 can refer to step S104 shown in fig. 3, and therefore, the description thereof is omitted here.
S205: and growing a multi-quantum well layer on the composite transition layer.
Optionally, in the multiple quantum well layer, the growth temperature of the InGaN well layer is 700-900 ℃, and the growth temperature of the GaN barrier layer is 800-950 ℃. The quality of the multiple quantum well layer grown under the condition is good, and the light emitting efficiency of the light emitting diode can be ensured.
S206: and growing an electron barrier layer on the multi-quantum well layer.
Illustratively, the material of the electron blocking layer is AlGaN, the growth temperature of the electron blocking layer is 1000-1200 ℃, and the growth pressure of the electron blocking layer is 100-400 torr. An electron blocking layer with better quality can be obtained.
S207: and growing a p-type GaN layer on the electron blocking layer.
Alternatively, the growth pressure of the p-type GaN layer may be 100Torr to 300Torr, and the growth temperature of the p-type GaN layer may be 800 ℃ to 950 ℃.
In one implementation provided by the present disclosure, the growth temperature of the p-type GaN layer may be 900 ℃, and the growth pressure of the p-type GaN layer may be 200 Torr.
S208: and growing a p-type contact layer on the p-type GaN layer.
Alternatively, the growth pressure of the p-type contact layer may be 100Torr to 300Torr, and the growth temperature of the p-type contact layer may be 850 ℃ to 1050 ℃.
In one implementation provided by the present disclosure, the growth temperature of the p-type contact layer may be 950 ℃, and the growth pressure of the p-type contact layer may be 200 Torr.
The method for manufacturing the light emitting diode epitaxial wafer with the composite transition layer shown in fig. 5 provides a more detailed method for growing the light emitting diode epitaxial wafer with the composite transition layer than the method for manufacturing the light emitting diode shown in fig. 4.
S209: and annealing the light emitting diode epitaxial wafer with the composite transition layer.
Step S209 may include: adjusting the temperature to 650-850 ℃, and annealing the light emitting diode epitaxial wafer with the composite transition layer for 5-15 minutes in a hydrogen atmosphere.
In one implementation provided by the present disclosure, the annealing temperature may be 750 ℃ and the annealing time may be 10 min.
The structure of the light emitting diode epitaxial wafer with the composite transition layer after the step S209 is performed can be seen in fig. 3.
It should be noted that, in the embodiment of the present disclosure, a VeecoK 465i or C4 or RB MOCVD (Metal Organic Chemical Vapor Deposition) apparatus is adopted to implement the growth method of the light emitting diode. By using high-purity H2(Hydrogen) or high purity N2(Nitrogen) or high purity H2And high purity N2The mixed gas of (2) is used as a carrier gas, high-purity NH3As an N source, trimethyl gallium (TMGa) and triethyl gallium (TEGa) as gallium sources, trimethyl indium (TMIn) as indium sources, silane (SiH4) as an N-type dopant, trimethyl aluminum (TMAl) as an aluminum source, and magnesium dicylocene (CP)2Mg) as a P-type dopant.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. The light-emitting diode epitaxial wafer with the composite transition layer is characterized by comprising a substrate, and a GaN buffer layer, an n-type GaN layer, the composite transition layer, a multi-quantum well layer and a p-type GaN layer which are sequentially laminated on the substrate,
the composite transition layer comprises sequentially laminated SiO2A sub-layer of AlGaN, the SiO being2The orthographic projection of the sublayer on the surface of the substrate is in a net shape, and the SiO layer2The area of a mesh corresponding to the orthographic projection of the sublayer on the surface of the substrate is 6-35um, and the molar doping amount of Al in the AlGaN sublayer is 1% -6%.
2. The light emitting diode epitaxial wafer with the composite transition layer as claimed in claim 1, wherein the SiO is2The thickness of the sub-layer is 15-100 nm.
3. The light emitting diode epitaxial wafer with composite transition layer as claimed in claim 1, wherein the SiO is2The sub-layer comprises a plurality of first strip-shaped parts parallel to each other and a plurality of second strip-shaped parts parallel to each other, each first strip-shaped part is intersected with the plurality of second strip-shaped parts, and the width of each first strip-shaped part is equal to that of each second strip-shaped part.
4. The light-emitting diode epitaxial wafer with the composite transition layer is characterized in that the thickness of the AlGaN sub-layer is 5-80 nm.
5. A preparation method of a light emitting diode epitaxial wafer with a composite transition layer is characterized by comprising the following steps:
providing a substrate;
growing a GaN buffer layer on the substrate;
growing an n-type GaN layer on the GaN buffer layer;
growing a composite transition layer on the n-type GaN layer, wherein the composite transition layer comprises sequentially laminated SiO2A sublayer and an AlGaN sublayer, the SiO2The orthographic projection of the sublayer on the surface of the substrate is in a net shape, and the SiO layer2The sub-layer is on the surface of the substrateThe area of the mesh corresponding to the projection is 6-35um, and the molar doping amount of Al in the AlGaN sublayer is 1% -6%;
growing a multi-quantum well layer on the composite transition layer;
and growing a p-type GaN layer on the multi-quantum well layer.
6. The method of manufacturing according to claim 5, comprising:
the GaN buffer layer and the n-type GaN layer are grown by adopting hydride vapor phase epitaxy equipment;
and the AlGaN sublayer, the multi-quantum well layer and the p-type GaN layer are grown by adopting chemical vapor deposition equipment.
7. The preparation method according to claim 6, wherein the AlGaN sub-layer is grown in an atmosphere of nitrogen and ammonia, and the volume of the ammonia during the growth of the AlGaN sub-layer is 20% -40% of the total volume of the gas in the reaction chamber.
8. The method according to any one of claims 5 to 7, wherein the multiple quantum well layer comprises InGaN well layers and GaN barrier layers which are alternately stacked,
the volume of ammonia gas generated during growth of the AlGaN sub-layer is 50-80% of the volume of ammonia gas generated during growth of the InGaN well layer.
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KR20150076966A (en) * 2013-12-27 2015-07-07 영남대학교 산학협력단 Method of manufacturing a light-emitting element
CN109244199A (en) * 2018-09-19 2019-01-18 华灿光电(苏州)有限公司 A kind of preparation method and epitaxial wafer of the epitaxial wafer of light emitting diode
CN112687776A (en) * 2020-12-18 2021-04-20 华灿光电(苏州)有限公司 Light emitting diode epitaxial wafer and preparation method thereof
CN112687777A (en) * 2020-12-18 2021-04-20 华灿光电(苏州)有限公司 Light emitting diode epitaxial wafer and preparation method thereof

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