CN111883623B - Near ultraviolet light emitting diode epitaxial wafer and preparation method thereof - Google Patents
Near ultraviolet light emitting diode epitaxial wafer and preparation method thereof Download PDFInfo
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor 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
- H01L33/02—Semiconductor 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
- H01L33/14—Semiconductor 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 carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
- H01L33/145—Semiconductor 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 carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure with a current-blocking structure
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- H01L33/00—Semiconductor 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
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor 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
- H01L33/02—Semiconductor 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
- H01L33/04—Semiconductor 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
- H01L33/06—Semiconductor 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
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- H01L33/00—Semiconductor 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
- H01L33/02—Semiconductor 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
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
- H01L33/325—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen characterised by the doping materials
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Abstract
The disclosure provides a near ultraviolet light emitting diode epitaxial wafer and a preparation method thereof, belonging to the technical field of light emitting diodes. The component contents of Al in the AlN sublayer, the first AlInGaN sublayer and the second AlInGaN sublayer in the electron blocking layer are reduced in sequence. The ratio of the Al component content In the first AlInGaN sublayer to the Al component content In the second AlInGaN sublayer is equal to the ratio of the In component content In the first AlInGaN sublayer to the In component content In the second AlInGaN sublayer. The ratio of the doping concentration of Mg in the second AlInGaN sublayer to the doping concentration of Mg in the first AlInGaN sublayer is equal to the ratio of the composition content of Al in the first AlInGaN sublayer to the composition content of Al in the second AlInGaN sublayer. The number of holes entering the light-emitting layer is greatly increased, and the light-emitting efficiency of the light-emitting diode is improved.
Description
Technical Field
The disclosure relates to the technical field of light emitting diodes, in particular to a near ultraviolet light emitting diode epitaxial wafer and a preparation method thereof.
Background
The near ultraviolet light emitting diode is a light emitting product for photocuring, is commonly used for curing food sealing materials, medical glue and the like, and the near ultraviolet light emitting diode epitaxial wafer is used for preparing a near ultraviolet light emitting diode basic structure. The near-ultraviolet light emitting diode epitaxial wafer generally comprises a substrate and an epitaxial layer grown on the substrate, wherein the epitaxial layer comprises an N-type layer, a light emitting layer, an electron blocking layer and a P-type layer which are sequentially grown on the substrate. The electron blocking layer is usually an AlGaN electron blocking layer with high Al component content, the AlGaN electron blocking layer is usually doped with Mg, and the AlGaN electron blocking layer plays a role in blocking electrons and is used for providing partial holes.
However, the conventional AlGaN electron blocking layer with higher Al component content is doped with more Al elements, which can affect the infiltration and activation of Mg elements in the AlGaN electron blocking layer, so that the hole concentration provided by the AlGaN electron blocking layer is extremely low; and the AlGaN electron blocking layer with higher Al component content also has more non-radiative recombination centers, so that holes are subjected to non-radiative recombination in the AlGaN electron blocking layer, and finally, fewer holes which can normally enter the light emitting layer to be subjected to radiative recombination with electrons are caused, and the light emitting efficiency of the near ultraviolet light emitting diode is lower.
Disclosure of Invention
The embodiment of the disclosure provides a near ultraviolet light emitting diode epitaxial wafer and a preparation method thereof, which can improve the light emitting efficiency of a near ultraviolet light emitting diode. The technical scheme is as follows:
the embodiment of the disclosure provides a near ultraviolet light emitting diode epitaxial wafer and a preparation method thereof, the near ultraviolet light emitting diode epitaxial wafer comprises a substrate and an epitaxial layer grown on the substrate, the epitaxial layer comprises an n-type layer, a light emitting layer, an electron blocking layer and a p-type layer which are sequentially stacked on the substrate,
the electron blocking layer comprises an AlN sub-layer, a first AlInGaN sub-layer and a second AlInGaN sub-layer which are sequentially grown on the light emitting layer, the component content of Al in the AlN sub-layer, the component content of Al in the first AlInGaN sub-layer and the component content of Al in the second AlInGaN sub-layer are sequentially reduced,
the component content ratio of Al In the first AlInGaN sublayer and the component content ratio of Al In the second AlInGaN sublayer are equal to the component content ratio of In the second AlInGaN sublayer and the component content ratio of In the first AlInGaN sublayer, Mg elements are doped In the first AlInGaN sublayer and the second AlInGaN sublayer, and the doping concentration ratio of Mg In the second AlInGaN sublayer and the doping concentration ratio of Mg In the first AlInGaN sublayer is equal to the component content ratio of Al In the first AlInGaN sublayer and the component content ratio of Al In the second AlInGaN sublayer.
Optionally, the composition content of Al in the first AlInGaN sublayer is x1The In component content of the first AlInGaN sublayer is y1The doping concentration of Mg in the first AlInGaN sublayer is z1，0.3<x1≤0.6，0<y1≤0.1，2×1019cm-3<z1≤5×1019cm-3。
Optionally, in the first AlInGaN sublayer, x1:y1In the range of 10:1 to 60: 1.
Optionally, the composition content of Al in the second AlInGaN sublayer is x2The In component content of the second AlInGaN sublayer is y2The doping concentration of Mg in the second AlInGaN sublayer is z2，0.1<x2≤0.3，0<y2≤0.2，5×1019cm-3<z2≤2×1020cm-3。
Optionally, the AlN sub-layer has a thickness of 1.5 to 3nm, and the first AlInGaN sub-layer and the second AlInGaN sub-layer both have a thickness of 100 to 150 nm.
Optionally, the epitaxial layer further includes a current spreading layer disposed between the n-type layer and the light emitting layer, and the current spreading layer includes a plurality of AlGaN sublayers and GaN sublayers alternately stacked.
Optionally, in the growth direction of the epitaxial layer, the thickness of each AlGaN sublayer is sequentially reduced, and the content of the Al component in each AlGaN sublayer is sequentially increased.
Optionally, the thickness of the current spreading layer is 1-2 nm.
The embodiment of the disclosure provides a method for preparing a near ultraviolet light emitting diode epitaxial wafer, which comprises the following steps:
providing a substrate;
growing an n-type layer on the substrate;
growing a light emitting layer on the n-type layer;
growing an electron blocking layer on the light emitting layer, wherein the electron blocking layer comprises an AlN sub-layer, a first AlInGaN sub-layer and a second AlInGaN sub-layer which are sequentially grown on the light emitting layer, the Al component content In the AlN sub-layer, the Al component content In the first AlInGaN sub-layer and the Al component content In the second AlInGaN sub-layer are sequentially reduced, the ratio of the Al component content In the first AlInGaN sub-layer to the Al component content In the second AlInGaN sub-layer is equal to the ratio of the In component content In the second AlInGaN sub-layer to the In component content In the first AlInGaN sub-layer,
the first AlInGaN sublayer and the second AlInGaN sublayer are doped with Mg, and the ratio of the doping concentration of Mg in the second AlInGaN sublayer to the doping concentration of Mg in the first AlInGaN sublayer is equal to the ratio of the composition content of Al in the first AlInGaN sublayer to the composition content of Al in the second AlInGaN sublayer;
and growing a p-type layer on the electron blocking layer.
Optionally, the growth temperature of the first AlInGaN sublayer is 950-1000 ℃, the first AlInGaN sublayer grows in a mixed gas environment of nitrogen and ammonia, the growth temperature of the second AlInGaN sublayer is 850-900 ℃, and the second AlInGaN sublayer grows in a mixed gas environment of nitrogen, ammonia and hydrogen.
The beneficial effects brought by the technical scheme provided by the embodiment of the disclosure include:
the epitaxial layer of the near ultraviolet light emitting diode epitaxial wafer comprises an n-type layer, a light emitting layer, an electron blocking layer and a p-type layer which are sequentially grown on a substrate. And the electron blocking layer comprises an AlN sublayer, a first AlInGaN sublayer and a second AlInGaN sublayer which sequentially grow on the light emitting layer, the Al component content in the AlN sublayer, the Al component content in the first AlInGaN sublayer and the Al component content in the second AlInGaN sublayer are sequentially reduced, the AlN sublayer with a higher barrier can block electrons from jumping over the AlN sublayer to move into the first AlInGaN sublayer and the second AlInGaN sublayer, and similarly, the first AlInGaN sublayer and the second AlInGaN sublayer with a lower barrier can not excessively block the inflow of holes which are the same as the carriers with the electrons to the light emitting layer. And the ratio of the Al component content In the first AlInGaN sublayer to the Al component content In the second AlInGaN sublayer is equal to the ratio of the In component content In the second AlInGaN sublayer to the In component content In the first AlInGaN sublayer, so that the barrier of the first AlInGaN sublayer and the barrier of the second AlInGaN sublayer can be kept to be stably reduced. Mg elements are doped In the first AlInGaN sublayer and the second AlInGaN sublayer, the activation energy of Mg can be reduced by the In elements In the first AlInGaN sublayer and the second AlInGaN sublayer, the number of holes In the first AlInGaN sublayer and the second AlInGaN sublayer can be increased by the activation of Mg, and the number of holes entering the light emitting layer is increased. And the ratio of the doping concentration of Mg in the second AlInGaN sublayer to the doping concentration of Mg in the first AlInGaN sublayer is equal to the ratio of the composition content of Al in the first AlInGaN sublayer to the composition content of Al in the second AlInGaN sublayer. The second AlInGaN sublayer can be used as a main hole source, so that the number of holes entering the light-emitting layer is greatly increased, 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 are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present disclosure, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a near ultraviolet light emitting diode epitaxial wafer according to an embodiment of the present disclosure;
fig. 2 is a schematic structural diagram of another near ultraviolet light emitting diode epitaxial wafer provided in an embodiment of the present disclosure;
fig. 3 is a flowchart of a method for manufacturing a near ultraviolet light emitting diode epitaxial wafer according to an embodiment of the present disclosure;
fig. 4 is a flowchart of another method for manufacturing an epitaxial wafer of a near-ultraviolet light emitting diode according to an embodiment of the present disclosure.
Detailed Description
To make the objects, technical solutions and advantages of the present disclosure 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 near ultraviolet light emitting diode epitaxial wafer according to an embodiment of the present disclosure. Referring to fig. 1, the embodiment of the present disclosure provides a near ultraviolet light emitting diode epitaxial wafer, which includes a substrate 1 and an epitaxial layer 2 grown on the substrate 1, wherein the epitaxial layer 2 includes an n-type layer 21, a light emitting layer 22, an electron blocking layer 23, and a p-type layer 24, which are sequentially stacked on the substrate 1.
The electron blocking layer 23 includes an AlN sublayer 231, a first AlInGaN sublayer 232, and a second AlInGaN sublayer 233, which are sequentially grown on the light emitting layer 22, and the Al composition content in the AlN sublayer 231, the Al composition content in the first AlInGaN sublayer 232, and the Al composition content in the second AlInGaN sublayer 233 are sequentially decreased.
The ratio of the Al composition In the first AlInGaN sublayer 232 to the Al composition In the second AlInGaN sublayer 233 is equal to the ratio of the In composition In the second AlInGaN sublayer 233 to the In composition In the first AlInGaN sublayer 232. The first AlInGaN sublayer 232 and the second AlInGaN sublayer 233 are doped with Mg, and the ratio of the doping concentration of Mg in the second AlInGaN sublayer 233 to the doping concentration of Mg in the first AlInGaN sublayer 232 is equal to the ratio of the composition content of Al in the first AlInGaN sublayer 232 to the composition content of Al in the second AlInGaN sublayer 233.
The epitaxial layer 2 of the near ultraviolet light emitting diode epitaxial wafer comprises an n-type layer 21, a light emitting layer 22, an electron blocking layer 23 and a p-type layer 24 which are sequentially grown on a substrate 1. And the electron blocking layer 23 includes an AlN sublayer 231, a first AlInGaN sublayer 232, and a second AlInGaN sublayer 233, which are sequentially grown on the light emitting layer 22, and the Al composition content in the AlN sublayer 231, the Al composition content in the first AlInGaN sublayer 232, and the Al composition content in the second AlInGaN sublayer 233 are sequentially decreased, so that the AlN sublayer 231 with a higher barrier can block electrons from jumping over the AlN sublayer 231 to migrate into the first AlInGaN sublayer 232 and the second AlInGaN sublayer 233, and similarly, the first AlInGaN sublayer 232 and the second AlInGaN sublayer 233 with a lower barrier can not excessively block the inflow of holes, which are carriers together with electrons, into the light emitting layer 22. And the ratio of the Al component content In the first AlInGaN sublayer 232 to the Al component content In the second AlInGaN sublayer 233 is equal to the ratio of the In component content In the second AlInGaN sublayer 233 to the In component content In the first AlInGaN sublayer 232, so that the barrier potential of the first AlInGaN sublayer 232 and the second AlInGaN sublayer 233 can be kept stably lowered. The first AlInGaN sublayer 232 and the second AlInGaN sublayer 233 are doped with Mg, the In element In the first AlInGaN sublayer 232 and the second AlInGaN sublayer 233 can reduce the activation energy of Mg, the activation of Mg can increase the number of holes In the first AlInGaN sublayer 232 and the second AlInGaN sublayer 233, and the number of holes entering the light emitting layer 22 is increased. The ratio of the doping concentration of Mg in the second AlInGaN sublayer 233 to the doping concentration of Mg in the first AlInGaN sublayer 232 is equal to the ratio of the composition of Al in the first AlInGaN sublayer 232 to the composition of Al in the second AlInGaN sublayer 233. The second AlInGaN sublayer 233 can serve as a main hole source, which greatly increases the number of holes entering the light-emitting layer 22, thereby improving the light-emitting efficiency of the light-emitting diode.
In the implementation manner provided by the present disclosure, the distribution of Al, In, and Mg elements In the first AlInGaN sublayer 232 and the second AlInGaN sublayer 233 is more reasonable, and the obtained growth quality of the first AlInGaN sublayer 232 and the second AlInGaN sublayer 233 is also better.
Illustratively, the composition content of Al in the first AlInGaN sublayer 232 is x1The In component content of the first AlInGaN sublayer 232 is y1The doping concentration of Mg in the first AlInGaN sublayer 232 is z1，0.3<x1≤0.6，0<y1≤0.1，2×1019cm-3<z1≤5×1019cm-3。
0.3<x1≤0.6，0<y1≤0.1，2×1019cm-3<z1≤5×1019cm-3While the growth quality of the first AlInGaN sublayer 232 is stable, Mg in the first AlInGaN sublayer 232 can also be activated, so that the first AlInGaN sublayer 232 can provide a certain number of holes to enter the light emitting layer 22, and the light emitting efficiency of the near-ultraviolet light emitting diode is improved.
Optionally, x in the first AlInGaN sublayer 2321:y1Can be in the range of 10:1 to 60: 1. At the moment, the whole luminous efficiency of the near ultraviolet light emitting diode is higher.
Illustratively, In one implementation manner provided by the present disclosure, the ratio of the Al composition content In the first AlInGaN sub-layer 232 to the Al composition content In the second AlInGaN sub-layer 233 may be 2:1, and the ratio of the In composition content In the first AlInGaN sub-layer 232 to the In composition content In the second AlInGaN sub-layer 233 may also be 1: 2. The near ultraviolet light emitting diode has high luminous efficiency.
Alternatively, the Al composition content in the second AlInGaN sublayer 233 may be x2The In composition content of the second AlInGaN sublayer 233 may be y2The doping concentration of Mg in the second AlInGaN sublayer 233 may be z2，0.1<x2≤0.3，0<y2≤0.2，5×1019cm-3<z2≤2×1020cm-3。
0.1<x2≤0.3，0<y2≤0.2，5×1019cm-3<z2≤2×1020cm-3In the meantime, the second AlInGaN sublayer 233 has sufficient active Mg elements, so that the second AlInGaN sublayer 233 can provide sufficient holes, and the light emitting efficiency of the light emitting diode is effectively improved.
Exemplarily, in the second AlInGaN sublayer 233, x2:y2Can also be in the range of 10: 1-60: 1. At the moment, the whole luminous efficiency of the near ultraviolet light emitting diode is higher.
Alternatively, x2:y2Can be reacted with x1:y1Equal, y2:z2May also be reacted with y1:z1Are equal. The growth and preparation of the epitaxial layer 2 are facilitated, and the growth quality of the first AlInGaN sublayer 232 and the second AlInGaN sublayer 233 can be ensured.
For example, the AlN sub-layer 231 may have a thickness of 1.5 to 3nm, and both the first AlInGaN sub-layer 232 and the second AlInGaN sub-layer 233 may have a thickness of 100 to 150 nm.
The AlN sublayer 231 can be 1.5-3 nm thick, the first AlInGaN sublayer 232 and the second AlInGaN sublayer 233 can both be 100-150 nm thick, and the AlN sublayer 231 blocking electrons is thin, so that electrons can be blocked, and holes cannot be excessively blocked, and the holes can conveniently enter the light-emitting layer 22 for radiation and light emission. The first AlInGaN sublayer 232 and the second AlInGaN sublayer 233 have a larger thickness as a whole, and a larger number of holes can be accumulated in the first AlInGaN sublayer 232 and the second AlInGaN sublayer 233, and the holes can enter the light emitting layer 22 more evenly to be recombined with electrons to emit light.
Fig. 2 is a schematic structural diagram of another near ultraviolet light emitting diode epitaxial wafer according to an embodiment of the present disclosure, and as can be seen from fig. 2, in another implementation manner provided by the present disclosure, the near ultraviolet light emitting diode epitaxial wafer may include a substrate 1 and an epitaxial layer 2 grown on the substrate 1, and the epitaxial layer 2 may further include a buffer layer 25, an n-type layer 21, a current spreading layer 26, a light emitting layer 22, an electron blocking layer 23, a p-type layer 24, and a p-type contact layer 27, which are sequentially stacked on the substrate 1.
It should be noted that the structure of the electron blocking layer 23 shown in fig. 2 is the same as the structure of the electron blocking layer 23 shown in fig. 1, and details thereof are not repeated here.
Alternatively, the substrate 1 may be a sapphire substrate 1. Easy to manufacture and obtain.
Illustratively, the buffer layer 25 may include an AlN buffer layer 251, a GaN low-temperature three-dimensional nucleation layer 252, and an undoped GaN layer 253, which are sequentially stacked on the substrate 1. The quality of the n-type layer 21 and the light-emitting layer 22 grown on the buffer layer 25 can be ensured, and the overall quality of the epitaxial layer 2 can be finally ensured.
Alternatively, the AlN buffer layer 251 may have a thickness of 10 to 50 nm. The lattice mismatch between the n-type layer 21 and the substrate 1 can be reduced, and the growth quality of the epitaxial layer 2 is ensured.
Illustratively, the thickness of the GaN low-temperature three-dimensional nucleation layer 252 may be 0.5 to 1 μm. Ensuring the quality of the epitaxial layer 2 grown subsequently.
Alternatively, the thickness of the undoped GaN layer 253 can be 1.5-5 μm. The quality of the near ultraviolet light emitting diode epitaxial wafer obtained at the moment is better.
Alternatively, the current spreading layer 26 may include a plurality of AlGaN sublayers 261 and GaN sublayers 262 alternately stacked.
The current spreading layer 26 includes a plurality of AlGaN sublayers 261 and GaN sublayers 262 alternately stacked, which can play roles of effectively blocking electrons and spreading current, slow down the speed of electrons entering the light-emitting layer 22, and reduce the pressure of the electron blocking layer 23 behind the light-emitting layer 22 for blocking electrons, so that holes with a slow moving speed can enter the light-emitting layer 22 more to effectively emit light, thereby further preventing electrons from overflowing the light-emitting layer 22.
Alternatively, GaN sublayer 262 of current spreading layer 26 may be doped with Si element.
The GaN sublayer 262 is doped with Si element so that the GaN sublayer 262 can also serve as an electron source to ensure that sufficient electrons can enter the light-emitting layer 22 for recombination.
Illustratively, in the current spreading layer 26, the thickness of each AlGaN sublayer 261 decreases in turn, and the content of the Al component content in each AlGaN sublayer 261 increases in turn, in the growth direction of the epitaxial layer 2.
The thickness of each AlGaN sublayer 261 is reduced in sequence, the content of Al in each AlGaN sublayer 261 increases in sequence, the barrier of the current expansion layer 26 for blocking electrons gradually rises along the electron moving direction, but the region with the high barrier is reduced in sequence, so that enough electrons can be ensured to enter the current expansion layer 26 and be accumulated in the current expansion layer 26, the electrons can gradually cross the AlGaN sublayer 261 to enter the light emitting layer 22, and the light emission of the near ultraviolet light emitting diode is more uniform.
Alternatively, the current spreading layer 26 may have a thickness of 1 to 2 nm.
The thickness of the current spreading layer 26 is 1-2 nm, the current spreading layer 26 can effectively spread current, the overall cost of the current spreading layer 26 is not too high, and meanwhile, the current spreading layer can be matched with the electron blocking layer 23 behind the light emitting layer 22, so that the overall light emitting efficiency of the near ultraviolet light emitting diode is high.
Optionally, the number of the AlGaN sublayer 261 and the GaN sublayer 262 in the current spreading layer 26 may be 4 to 10. The obtained near ultraviolet light emitting diode epitaxial layer 2 has good quality,
Optionally, the composition content of Al in the AlGaN sublayer 261 may be in a range of 0.1 to 0.5. The effect of blocking the electron spreading current is better.
Illustratively, the n-type layer 21 may be an n-type GaN layer. Is convenient for preparation and acquisition.
Alternatively, the doping element of the n-type GaN layer may be Si, and the doping concentration of the Si element may be 1 × 1018～1×1019cm-3. The overall quality of the n-type GaN layer is better.
Illustratively, the thickness of the n-type layer 21 may be 1.5 to 5 μm. The obtained n-type GaN layer has good overall quality.
Illustratively, the light emitting layer 22 provided by the present disclosure may include an AlGaN/InGaN/AlGaN superlattice multiple quantum well structure, and the period of the AlGaN/InGaN/AlGaN superlattice multiple quantum well structure may be 6 to 12. Such a light-emitting layer 22 is easy to prepare, and the obtained light-emitting effect is also enhanced.
Optionally, in the AlGaN/InGaN/AlGaN superlattice multi-quantum well structure, the thickness of the InGaN layer 221 may be 1 to 3nm, and the thicknesses of the AlGaN layers 222 on the two sides of the InGaN layer 221 may be 2 to 5nm and 9 to 20nm, respectively. The quality of the entire light-emitting layer 22 is good.
It should be noted that in the AlGaN/InGaN/AlGaN superlattice multi-quantum well structure, the Al content in the AlGaN layer 222 may be in a range of 0.05 to 0.2. Electrons can be properly blocked and captured in the InGaN layer 221 with a lower barrier to perform recombination light emission.
Illustratively, in the AlGaN/InGaN/AlGaN superlattice multi-quantum well structure, the ratio of the Al component content to the Ga component content in each AlGaN layer 222 is the same. Facilitating the fabrication of the light-emitting layer 22.
Illustratively, the p-type layer 24 may be a p-type GaN layer. Is convenient for preparation and acquisition.
Illustratively, the p-type layer 24 may have a thickness of 100 to 200 nm. The obtained p-type GaN layer has good overall quality.
Illustratively, the p-type contact layer 27 may be a p-type AlInGaN layer. Is convenient for preparation and acquisition.
Illustratively, the thickness of the p-type AlInGaN layer can be 100-200 nm. The obtained p-type AlInGaN layer has better overall quality.
Fig. 3 is a flowchart of a method for manufacturing a near ultraviolet light emitting diode epitaxial wafer according to an embodiment of the present disclosure, and as shown in fig. 3, the method for manufacturing a near ultraviolet light emitting diode epitaxial wafer includes:
s101: a substrate is provided.
S102: an n-type layer is grown on the substrate.
S103: a light emitting layer is grown on the n-type layer.
S104: an electron blocking layer is grown on the light emitting layer.
The electron blocking layer comprises an AlN sub-layer, a first AlInGaN sub-layer and a second AlInGaN sub-layer which sequentially grow on the light emitting layer, the Al component content In the AlN sub-layer, the Al component content In the first AlInGaN sub-layer and the Al component content In the second AlInGaN sub-layer are sequentially reduced, and the ratio of the Al component content In the first AlInGaN sub-layer to the Al component content In the second AlInGaN sub-layer is equal to the ratio of the In component content In the second AlInGaN sub-layer to the In component content In the first AlInGaN sub-layer. Mg elements are doped in the first AlInGaN sublayer and the second AlInGaN sublayer, and the ratio of the doping concentration of Mg in the second AlInGaN sublayer to the doping concentration of Mg in the first AlInGaN sublayer is equal to the ratio of the component content of Al in the first AlInGaN sublayer to the component content of Al in the second AlInGaN sublayer.
S105: a p-type layer is grown on the electron blocking layer.
The epitaxial layer of the near ultraviolet light emitting diode epitaxial wafer comprises an n-type layer, a light emitting layer, an electron blocking layer and a p-type layer which are sequentially grown on a substrate. The electron blocking layer comprises an AlN sublayer, a first AlInGaN sublayer and a second AlInGaN sublayer which sequentially grow on the light emitting layer, the Al component content in the AlN sublayer, the Al component content in the first AlInGaN sublayer and the Al component content in the second AlInGaN sublayer are sequentially reduced, the barrier potential of the AlN sublayer, the first AlInGaN sublayer and the second AlInGaN sublayer is sequentially reduced, the AlN sublayer can well block electrons, and meanwhile the first AlInGaN sublayer and the second AlInGaN sublayer cannot excessively block the inflow of holes to the light emitting layer. And the ratio of the Al component content In the first AlInGaN sublayer to the Al component content In the second AlInGaN sublayer is equal to the ratio of the In component content In the second AlInGaN sublayer to the In component content In the first AlInGaN sublayer, so that the barrier of the first AlInGaN sublayer and the barrier of the second AlInGaN sublayer can be kept to be stably reduced. Mg elements are doped In the first AlInGaN sublayer and the second AlInGaN sublayer, the activation energy of Mg can be reduced by the In elements In the first AlInGaN sublayer and the second AlInGaN sublayer, the number of holes In the first AlInGaN sublayer and the second AlInGaN sublayer can be increased by the activation of Mg, and the number of holes entering the light emitting layer is increased. And the ratio of the doping concentration of Mg in the second AlInGaN sublayer to the doping concentration of Mg in the first AlInGaN sublayer is equal to the ratio of the composition content of Al in the first AlInGaN sublayer to the composition content of Al in the second AlInGaN sublayer. The second AlInGaN sublayer can be used as a main hole source, so that the number of holes entering the light-emitting layer is greatly increased, and the light-emitting efficiency of the light-emitting diode is improved.
The structure of the near ultraviolet led epitaxial wafer after step S105 is completed can be seen in fig. 1.
Fig. 4 is a flowchart of another method for manufacturing a near ultraviolet light emitting diode epitaxial wafer according to an embodiment of the present disclosure, and as shown in fig. 4, the method for manufacturing a near ultraviolet light emitting diode epitaxial wafer includes:
s201: a substrate is provided.
Wherein the substrate may be a sapphire substrate. Easy to realize and manufacture.
S202: a buffer layer is grown on a substrate.
In step S202, the buffer layer may include an AlN buffer layer, a GaN low-temperature three-dimensional nucleation layer, and an undoped GaN layer sequentially stacked on the substrate.
Optionally, the AlN buffer layer can be obtained by sputtering deposition, the sputtering temperature of the AlN buffer layer is 600-800 ℃, the sputtering power is 3000-5000W, and the sputtering pressure is 4-10 mtorr. An AlN buffer layer having a high quality can be obtained.
Optionally, the growth temperature of the GaN low-temperature three-dimensional nucleation layer can be 1000-1060 ℃, and the growth pressure is 100-500 Torr. The obtained GaN low-temperature three-dimensional nucleation layer has better quality.
Illustratively, the growth temperature of the non-doped GaN layer can be 1100-. The obtained undoped GaN layer has better quality.
S203: an n-type layer is grown on the buffer layer.
Alternatively, the n-type layer may be an n-type GaN layer. Is convenient for preparation and acquisition.
Alternatively, the growth temperature of the N-type GaN layer may be 1000 to 2100 ℃, and the growth pressure of the N-type GaN layer may be 100 to 300 Torr.
S204: and growing a current expansion layer on the n-type layer.
The current spreading layer may include a plurality of AlGaN sublayers and GaN sublayers alternately stacked. The growth temperature of the current spreading layer can be 950-1050 ℃, and the growth pressure can be 50-150 Torr.
The current expansion layer grows under the conditions of high temperature and low pressure, so that the doping element can be favorably infiltrated, and the growth quality of the current expansion layer is ensured.
Alternatively, the current spreading layer may be grown under an atmosphere of pure nitrogen. The obtained current spreading layer has better quality.
S205: and growing a light emitting layer on the current spreading layer.
Alternatively, the light emitting layer may include an AlGaN/InGaN/AlGaN superlattice multi-quantum well structure.
In an example, in the AlGaN/InGaN/AlGaN superlattice multi-quantum well structure, the growth temperature of an InGaN layer may be 720 to 830 ℃, the growth temperatures of AlGaN layers on both sides of the InGaN layer may be 750 to 850 ℃ and 850 to 950 ℃, respectively, and the growth pressure of the entire light emitting layer may be 100 to 300 Torr. The obtained luminescent layer has better quality.
S206: an electron blocking layer is grown on the light emitting layer.
The electron blocking layer comprises an AlN sub-layer, a first AlInGaN sub-layer and a second AlInGaN sub-layer which sequentially grow on the light emitting layer, the Al component content In the AlN sub-layer, the Al component content In the first AlInGaN sub-layer and the Al component content In the second AlInGaN sub-layer are sequentially reduced, and the ratio of the Al component content In the first AlInGaN sub-layer to the Al component content In the second AlInGaN sub-layer is equal to the ratio of the In component content In the second AlInGaN sub-layer to the In component content In the first AlInGaN sub-layer. Mg elements are doped in the first AlInGaN sublayer and the second AlInGaN sublayer, and the ratio of the doping concentration of Mg in the second AlInGaN sublayer to the doping concentration of Mg in the first AlInGaN sublayer is equal to the ratio of the component content of Al in the first AlInGaN sublayer to the component content of Al in the second AlInGaN sublayer.
Optionally, the growth temperature of the first AlInGaN sublayer is 950-1000 ℃, the first AlInGaN sublayer grows in a mixed gas environment of nitrogen and ammonia, the growth temperature of the second AlInGaN sublayer is 850-900 ℃, and the second AlInGaN sublayer grows in the mixed gas environment of nitrogen, ammonia and hydrogen.
The growth temperature of the first AlInGaN sublayer is 950-1000 ℃, the growth temperature of the second AlInGaN sublayer is 850-900 ℃, the growth temperature of the first AlInGaN sublayer is higher than that of the second AlInGaN sublayer, the first AlInGaN sublayer can obtain the first AlInGaN sublayer with a higher Al component relative to the second AlInGaN sublayer, the effect of blocking electrons is better, the second AlInGaN sublayer grows at a lower temperature in an environment doped with hydrogen, doping and infiltration of Mg elements in the second AlInGaN sublayer can be facilitated, the surface smoothness of the second AlInGaN sublayer can be improved by the hydrogen, and the electronic barrier layer with high surface quality can be obtained.
In other implementations provided by the present disclosure, the growth temperature of the whole electron blocking layer may also be 900-1000 ℃, and the growth pressure may be 100-300 Torr. The present disclosure is not so limited.
S207: a p-type layer is grown on the electron blocking layer.
Illustratively, the p-type layer may be a p-type GaN layer.
Alternatively, the growth pressure of the p-type GaN layer may be 200 to 600Torr, and the growth temperature of the p-type GaN layer may be 800 to 1000 ℃.
S208: a p-type contact layer is grown on the p-type layer.
Illustratively, the p-type contact layer may be a p-type AlInGaN layer.
Alternatively, the growth pressure of the p-type GaN layer may be 100 to 300Torr, and the growth temperature of the p-type GaN layer may be 700 to 950 ℃.
The structure of the near ultraviolet light emitting diode epitaxial wafer after the step S208 is performed can be seen in fig. 2, and the thickness of each layer in the epitaxial layer is described in the near ultraviolet light emitting diode epitaxial wafer shown in fig. 2, so the growth thickness of each layer in the epitaxial wafer is not described in detail in the structure shown in fig. 4.
It should be noted that, in the examples of the present disclosure, VeecoK465iorC4 orrbmcvd (metalorganic chemical vapor deposition, metal organic chemical vapor phase chemical vapor deposition) is usedDeposition) device implements a method of growing LEDs. 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 method can also comprise the steps of reducing the temperature in the MOCVD (chemical vapor deposition) process chamber after the epitaxial structure is grown, annealing the epitaxial wafer in a nitrogen atmosphere, wherein the annealing temperature range is 650-850 ℃, annealing for 5-15 minutes, and turning to room temperature to finish the epitaxial growth. The annealing can further remove the defects in the epitaxial wafer, and is beneficial to improving the luminous efficiency of the light-emitting diode.
In order to prove the effect of the embodiment of the present invention, a photoelectric test is performed on the light emitting diode chip prepared by the epitaxial wafer in the related art and the epitaxial wafer obtained in the embodiment of the present disclosure, and the light emitting effect of the light emitting diode chip prepared by the epitaxial wafer in the related art and the epitaxial wafer obtained in the embodiment of the present disclosure is compared, and the comparison result is as follows in table 1:
table 1;
the light emitting diode chip corresponding to the serial number 1 is prepared by an epitaxial wafer in the background art, and the first column in table 1 is the growth parameter of the epitaxial wafer of the light emitting diode chip corresponding to the serial number 1, the growth parameter of the light emitting diode chip and the luminous intensity of the light emitting diode chip; the led chip corresponding to serial number 2 is prepared from the epitaxial wafer provided in the present disclosure, and the second column in table 1 is the growth parameters of the epitaxial wafer of the led chip corresponding to serial number 2, the growth parameters of the led chip, and the light emission intensity. As can be seen from table 1, under the conditions of the same growth pressure, the same growth time, and the similar growth temperature, the upper limit and the lower limit of the peak wavelength of the light emitting diode chip prepared by the epitaxial wafer obtained in the present disclosure are both significantly improved, the luminous intensity of the epitaxial wafer is also significantly improved, and the light emitting diode chip prepared by the epitaxial wafer provided in the present disclosure has a better luminous effect.
It should be noted that, except for the difference in the structure of the electron blocking layer, the epitaxial wafer in the related art and the epitaxial wafer obtained in the embodiment of the present disclosure have the structure of the substrate, the n-type layer, the light emitting layer, and the p-type layer, and the substrate, the buffer layer, the n-type layer, the light emitting layer, and the p-type layer in the epitaxial wafer in the related art and the epitaxial wafer obtained in the embodiment of the present disclosure are obtained under the same conditions. Corresponding to the epitaxial wafer in table 1, the buffer layer may include an AlN buffer layer obtained by sputtering and an undoped GaN layer obtained by deposition, which are sequentially stacked, and the AlN buffer layer has a sputtering temperature of 400 to 700 ℃, a sputtering power of 3 to 5kw, a sputtering pressure of 1 to 10mTorr, and a thickness of 15 to 35 nm; the buffer layer can be an AlN buffer layer obtained by sputtering, the sputtering temperature of the AlN buffer layer is 400-700 ℃, the sputtering power is 3-5 kw, the sputtering pressure is 1-10 mTorr, and the thickness is 15-35 nm; the growth temperature of the non-doped GaN layer is 1000-1200 ℃, the growth pressure is 100-500 Torr, and the thickness is 1-3 micrometers; the n-type layer is an n-type GaN layer, the growth temperature of the n-type GaN layer is 1000-1200 ℃, the growth pressure is 100-300 Torr, and the thickness is 1-5 micrometers; the light emitting layer comprises AlGaN barrier layers and InGaN well layers which grow alternately, the growth temperatures of the AlGaN barrier layers and the InGaN well layers are 850-960 ℃ and 720-830 ℃, respectively, and the growth pressure is 100-300 Torr; the p-type layer is a p-type GaN layer, the growth temperature of the p-type GaN layer is 900-980 ℃, the growth pressure is 300-600 Torr, and the thickness is 10-30 nm.
In another implementation manner provided by the present disclosure, the Al component content, the In component content, and the Mg doping concentration In the epitaxial wafer obtained In the embodiment of the present disclosure are adjusted, and the light emitting parameters of the light emitting diode chip prepared by using the corresponding epitaxial wafer are obtained, which may specifically refer to table 2 below:
table 2;
note that the stacking method of the epitaxial wafers of the light emitting diode chips No. 1 to 3 in table 2 is the same as the stacking method of the epitaxial wafers of the light emitting diode chips No. 2 in table 1, and the growth conditions of the epitaxial wafers of the light emitting diode chips No. 1 to 3 in table 2 are the same as the growth conditions of the epitaxial wafers No. 2 in table 1.
Referring to table 2 only, it can be seen that, In the first AlInGaN sublayer and the second AlInGaN sublayer In the electron blocking layer, either the doping concentration of Mg, the composition content of Al, or the ratio between the composition contents of In satisfies the following conditions: the ratio of the Al component content In the first AlInGaN sublayer to the Al component content In the second AlInGaN sublayer is equal to the ratio of the In component content In the second AlInGaN sublayer to the In component content In the first AlInGaN sublayer; or the ratio of the doping concentration of Mg in the second AlInGaN sublayer to the doping concentration of Mg in the first AlInGaN sublayer is equal to the ratio of the component content of Al in the first AlInGaN sublayer to the component content of Al in the second AlInGaN sublayer; the maximum luminous power of the light emitting diode prepared by the epitaxial wafer can be improved. As can be seen by referring to tables 1 and 2, the ratio of the Al component content In the first AlInGaN sublayer to the Al component content In the second AlInGaN sublayer is equal to the ratio of the In component content In the second AlInGaN sublayer to the In component content In the first AlInGaN sublayer; and the ratio of the doping concentration of Mg in the second AlInGaN sublayer to the doping concentration of Mg in the first AlInGaN sublayer is equal to the ratio of the component content of Al in the first AlInGaN sublayer to the component content of Al in the second AlInGaN sublayer, so that the light emitting power of the light emitting diode can be further improved.
Although the present invention has been described with reference to the above embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A near ultraviolet light emitting diode epitaxial wafer comprises a substrate (1) and an epitaxial layer (2) grown on the substrate (1), wherein the epitaxial layer (2) comprises an n-type layer (21), a light emitting layer (22), an electron blocking layer (23) and a p-type layer (24) which are sequentially stacked on the substrate (1),
characterized in that the electron blocking layer (23) comprises an AlN sublayer (231), a first AlInGaN sublayer (232) and a second AlInGaN sublayer (233) which are grown on the light emitting layer (22) in sequence, the Al component content in the AlN sublayer (231), the Al component content in the first AlInGaN sublayer (232) and the Al component content in the second AlInGaN sublayer (233) are reduced in sequence,
a composition content ratio of Al in the first AlInGaN sub-layer (232) to the second AlInGaN sub-layer (233), is equal to the ratio of the In composition content In the second AlInGaN sub-layer (233) to the In composition content In the first AlInGaN sub-layer (232), and the ratio of the In component content In the first AlInGaN sub-layer (232) to the In component content In the second AlInGaN sub-layer (233) is 1:2, the first AlInGaN sublayer (232) and the second AlInGaN sublayer (233) are both doped with Mg, and the ratio of the doping concentration of Mg in the second AlInGaN sub-layer (233) to the doping concentration of Mg in the first AlInGaN sub-layer (232), equal to the ratio of the Al composition in the first AlInGaN sub-layer (232) to the Al composition in the second AlInGaN sub-layer (233), the ratio of the Al composition in the first AlInGaN sublayer (232) to the Al composition in the second AlInGaN sublayer (233) is 2: 1.
2. Near-uv led epitaxial wafer according to claim 1, characterized in that the composition content of Al in the first AlInGaN sublayer (232) is x1The first AlInGaN sublayer (232) having a composition content of In of y1The doping concentration of Mg in the first AlInGaN sublayer (232) is z1，0.3<x1≤0.6，0<y1≤0.1，2×1019cm-3<z1≤5×1019cm-3。
3. Near ultraviolet light emitting diode epitaxial wafer according to claim 2, characterized in that in the first AlInGaN sublayer (232), x1:y1In the range of 10:1 to 60: 1.
4. The near ultraviolet light emitting diode epitaxial wafer according to any one of claims 1 to 3, characterized in that the Al component content in the second AlInGaN sub-layer (233) is x2The composition content of In the second AlInGaN sublayer (233) is y2The doping concentration of Mg in the second AlInGaN sublayer (233) is z2，0.1<x2≤0.3，0<y2≤0.2，5×1019cm-3<z2≤2×1020cm-3。
5. The near-ultraviolet light emitting diode epitaxial wafer according to any one of claims 1 to 3, wherein the AlN sub-layer (231) has a thickness of 1.5 to 3nm, and the first AlInGaN sub-layer (232) and the second AlInGaN sub-layer (233) both have a thickness of 100 to 150 nm.
6. A near ultraviolet light emitting diode epitaxial wafer according to any one of claims 1 to 3, characterized in that the epitaxial layer (2) further comprises a current spreading layer disposed between the n-type layer (21) and the light emitting layer (22), the current spreading layer comprising a plurality of AlGaN sublayers (261) and GaN sublayers (262) which are alternately stacked.
7. The near-ultraviolet light emitting diode epitaxial wafer according to claim 6, characterized in that in the growth direction of the epitaxial layer (2), the thickness of each AlGaN sublayer (261) is sequentially reduced, and the content of the Al component content in each AlGaN sublayer (261) is sequentially increased.
8. The near ultraviolet light emitting diode epitaxial wafer as claimed in claim 6, wherein the thickness of the current spreading layer is 1 to 2 nm.
9. A preparation method of a near ultraviolet light emitting diode epitaxial wafer is characterized by comprising the following steps:
providing a substrate;
growing an n-type layer on the substrate;
growing a light emitting layer on the n-type layer;
growing an electron blocking layer on the light emitting layer, wherein the electron blocking layer comprises an AlN sub-layer, a first AlInGaN sub-layer and a second AlInGaN sub-layer which are sequentially grown on the light emitting layer, the Al component content In the AlN sub-layer, the Al component content In the first AlInGaN sub-layer and the Al component content In the second AlInGaN sub-layer are sequentially reduced, the ratio of the Al component content In the first AlInGaN sub-layer to the Al component content In the second AlInGaN sub-layer is equal to the ratio of the In component content In the second AlInGaN sub-layer to the In component content In the first AlInGaN sub-layer,
the first AlInGaN sublayer and the second AlInGaN sublayer are doped with Mg, and the ratio of the doping concentration of Mg in the second AlInGaN sublayer to the doping concentration of Mg in the first AlInGaN sublayer is equal to the ratio of the composition content of Al in the first AlInGaN sublayer to the composition content of Al in the second AlInGaN sublayer;
and growing a p-type layer on the electron blocking layer.
10. The method for preparing the near ultraviolet light emitting diode epitaxial wafer according to claim 9, wherein the growth temperature of the first AlInGaN sublayer is 950-1000 ℃, the first AlInGaN sublayer grows in a mixed gas environment of nitrogen and ammonia, the growth temperature of the second AlInGaN sublayer grows in a mixed gas environment of nitrogen, ammonia and hydrogen, and the second AlInGaN sublayer grows in a mixed gas environment of nitrogen, ammonia and hydrogen.
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