CN114038954A - Epitaxial structure of light emitting diode and manufacturing method thereof - Google Patents

Epitaxial structure of light emitting diode and manufacturing method thereof Download PDF

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CN114038954A
CN114038954A CN202111140799.0A CN202111140799A CN114038954A CN 114038954 A CN114038954 A CN 114038954A CN 202111140799 A CN202111140799 A CN 202111140799A CN 114038954 A CN114038954 A CN 114038954A
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carbon
doped
nitride layer
layer
light emitting
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高默然
郑锦坚
王曼
毕京锋
范伟宏
李森林
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Xiamen Silan Advanced Compound Semiconductor Co Ltd
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Xiamen Silan Advanced Compound Semiconductor Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01L33/005—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01L33/26—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

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Abstract

Disclosed are an epitaxial structure of a light emitting diode and a method for manufacturing the same, the epitaxial structure of the light emitting diode includes: a substrate; the epitaxial layer is positioned on the substrate and comprises a first semiconductor layer, a light emitting layer, an electron blocking layer and a second semiconductor layer which are sequentially stacked on the substrate, the first semiconductor layer is provided with a first doping type, the second semiconductor layer is provided with a second doping type, and the polarities of the first doping type and the second doping type are opposite; the carbon-doped nitride layer comprises a first carbon-doped nitride layer located on the secondThe carbon doping concentration of the first carbon-doped nitride layer between a semiconductor layer and the light-emitting layer is 1E18cm‑3～1E19cm‑3. The epitaxial structure of the light emitting diode and the manufacturing method thereof can improve the antistatic capability of the light emitting diode.

Description

Epitaxial structure of light emitting diode and manufacturing method thereof
Technical Field
The invention belongs to the technical field of semiconductor devices, and particularly relates to an epitaxial structure of a light emitting diode and a manufacturing method thereof.
Background
Nitride semiconductor light emitting diodes have the advantages of wide adjustable wavelength range, high light emitting efficiency, energy saving, environmental protection, long service life, small size, strong designability and the like, have gradually replaced incandescent lamps and halogen lamps, become light sources for common household illumination, and are widely applied to new scenes, such as various fields of display screens, car lamps, plant illumination, medical treatment, curing, sterilization and disinfection and the like.
However, the nitride semiconductor inevitably brings defects due to lattice mismatch by growing the epitaxial structure of the light emitting diode on sapphire by using heteroepitaxy, and the threading dislocation causes an increase in leakage current and a decrease in light emitting efficiency of the nitride semiconductor light emitting diode, and may cause a short lifetime of the nitride semiconductor laser element.
Disclosure of Invention
The invention aims to provide an epitaxial structure of a light-emitting diode and a manufacturing method thereof, which can avoid the increase of the leakage current of the light-emitting diode so as to improve the antistatic capability of the light-emitting diode.
The invention provides an epitaxial structure of a light emitting diode, which comprises: a substrate; an epitaxial layer on the substrate, the epitaxial layer including a first semiconductor layer, a light emitting layer, an electron blocking layer and a second semiconductor layer stacked in sequence on the substrate, the first semiconductor layer having a first doping type, the second semiconductor layerThe semiconductor has a second doping type, and the polarity of the first doping type is opposite to that of the second doping type; a carbon-doped nitride layer in the epitaxial layer; the carbon-doped nitride layer comprises a carbon-doped first nitride layer, the carbon-doped first nitride layer is positioned between the first semiconductor layer and the light-emitting layer, and the carbon-doped first nitride layer has a carbon doping concentration of 1E18cm-3～1E19cm-3。
Preferably, the carbon-doped nitride layer further comprises a carbon-doped second nitride layer, the carbon-doped second nitride layer being located between the light emitting layer and the electron blocking layer.
Preferably, the carbon doping concentration of the carbon-doped second nitride layer is 1E18cm-3～1E19cm-3。
Preferably, the thickness of the carbon-doped second nitride layer is 1-100 nm.
Preferably, the thickness of the carbon-doped first nitride layer is 1-1000 nm.
Preferably, the carbon concentration in the carbon-doped nitride layer varies in a gradient along a thickness direction of the nitride layer.
Preferably, the carbon concentration in the carbon-doped nitride layer changes according to a gradual gradient, or the carbon concentration in the carbon-doped nitride layer changes according to a transition gradient; wherein, in the gradual gradient change, the carbon concentration is a numerical value which is continuously changed in sequence; in the transition type gradient change, the change value of the carbon concentration is a fixed value.
Preferably, the carbon concentration in the carbon-doped nitride layer is constant along the thickness direction of the nitride layer.
Preferably, the carbon-doped nitride layer is at least one of nitride, ternary mixed crystal nitride, quaternary mixed crystal nitride, superlattice structure and shallow quantum well structure.
Preferably, the carbon-doped nitride layer is at least one of GaN, AlN, InN, AlGaN, AlInN, InGaN, AlInGaN, GaN/InN superlattice, GaN/AlN superlattice, InN/GaN superlattice, GaN/AlGaN superlattice, GaN/AlInN superlattice, GaN/InGaN superlattice, GaN/AlInN superlattice, InGaN/AlGaN superlattice, InGaN/AlInN superlattice, AlGaN/AlInN superlattice, AlInGaN/AlInGaN superlattice, InGaN/GaN shallow quantum wells, InGaN/AlGaN shallow quantum wells, and InGaN/AlInGaN shallow quantum wells.
According to another aspect of the present invention, there is provided a method for manufacturing an epitaxial structure of a light emitting diode, including: forming an epitaxial layer on a substrate, wherein the epitaxial layer comprises a first semiconductor layer, a light emitting layer, an electron blocking layer and a second semiconductor layer which are sequentially stacked on the substrate, the first semiconductor layer is provided with a first doping type, the second semiconductor layer is provided with a second doping type, and the polarities of the first doping type and the second doping type are opposite; epitaxially growing a carbon-doped nitride layer in the epitaxial layer; wherein the carbon-doped nitride layer comprises a first carbon-doped nitride layer, the first carbon-doped nitride layer is positioned between the first semiconductor layer and the light-emitting layer, and the carbon-doped first nitride layer has a carbon doping concentration of 1E18cm-3～1E19cm-3。
Preferably, the carbon-doped nitride layer further comprises a carbon-doped second nitride layer, the carbon-doped second nitride layer being located between the light emitting layer and the electron blocking layer.
Preferably, the carbon doping concentration of the carbon-doped second nitride layer is 1E 18-1E 19cm-3。
Preferably, the thickness of the carbon-doped second nitride layer is 1-100 nm.
Preferably, the thickness of the carbon-doped first nitride layer is 1-1000 nm.
Preferably, a nitrogen source gas is introduced during the epitaxial growth of the carbon-doped nitride layer, and the nitrogen source gas includes at least one of hydrogen, ammonia, and nitrogen.
Preferably, the growth temperature of the carbon-doped first nitride layer is 600-800 ℃; the growth pressure is less than 250 Torr; the volume fraction of ammonia in the introduced nitrogen source gas is less than 65 percent.
Preferably, the growth temperature of the carbon-doped second nitride layer is 600-800 ℃; the growth pressure is less than 250 Torr; the volume fraction of ammonia in the introduced nitrogen source gas is less than 65%, and the volume fraction of hydrogen in the introduced nitrogen source gas is more than 45%.
Preferably, the carbon concentration in the carbon-doped nitride layer varies in a gradient along a thickness direction of the nitride layer.
Preferably, the carbon concentration in the carbon-doped nitride layer changes according to a gradual gradient, or the carbon concentration in the carbon-doped nitride layer changes according to a transition gradient; wherein, in the gradual gradient change, the carbon concentration is a numerical value which is continuously changed in sequence; in the transition type gradient change, the change value of the carbon concentration is a fixed value.
Preferably, the carbon concentration in the carbon-doped nitride layer is constant along the thickness direction of the nitride layer.
Preferably, the carbon-doped nitride layer is at least one of nitride, ternary mixed crystal nitride, quaternary mixed crystal nitride, superlattice structure and shallow quantum well structure.
Preferably, the carbon-doped nitride layer is at least one of GaN, AlN, InN, AlGaN, AlInN, InGaN, AlInGaN, GaN/InN superlattice, GaN/AlN superlattice, InN/GaN superlattice, GaN/AlGaN superlattice, GaN/AlInN superlattice, GaN/InGaN superlattice, GaN/AlInN superlattice, InGaN/AlGaN superlattice, InGaN/AlInN superlattice, AlGaN/AlInN superlattice, AlInGaN/AlInGaN superlattice, InGaN/GaN shallow quantum wells, InGaN/AlGaN shallow quantum wells, and InGaN/AlInGaN shallow quantum wells.
According to the epitaxial structure of the light emitting diode and the manufacturing method thereof, the carbon-doped nitride layer is formed in the epitaxial layer, so that the antistatic capability of the light emitting diode and the light emitting efficiency of the light emitting diode can be improved.
Further, a first nitride layer doped with carbon is formed between the first semiconductor layer of the epitaxial layer and the light emitting layer, the first nitride layer doped with carbonThe carbon doping concentration of the nitride layer is 1E18cm-3～1E19cm-3The carbon doped first nitride layer of the invention has high carbon doping concentration, and can be segregated (concentrated) near the threading dislocation to play a role of compensating an acceptor, thereby leading to a nitride compensation mechanism, preventing leakage current and improving the antistatic capability of the light-emitting diode.
Furthermore, a carbon-doped second nitride layer is formed between the light-emitting layer and the electron blocking layer of the epitaxial layer, so that the distribution of electron holes of the light-emitting layer in the light-emitting layer can be regulated and controlled, the injection efficiency of the holes is obviously enhanced, and the repetition probability of the hole and electron wave functions is improved; the electron confinement effect of the luminescent layer is enhanced, and the recombination efficiency of electron holes is enhanced, so that the luminous efficiency of the light-emitting diode is improved.
According to the manufacturing method of the epitaxial structure of the light emitting diode, the nitride layer with a certain carbon doping concentration is formed in at least one mode of growing temperature of 600-800 ℃, doping aluminum or other metals, growing pressure lower than 250Torr, volume fraction of ammonia in nitrogen source gas lower than 65%, and volume fraction of hydrogen in the nitrogen source gas higher than 45%. The carbon doping concentration can be controlled, so that resistance increase caused by overhigh carbon doping concentration and a compensation mechanism that the nitride cannot be started caused by overlow carbon doping concentration are avoided, and the light emitting efficiency and the reliability of the light emitting diode are further prevented from being influenced.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent from the following description of the embodiments of the present invention with reference to the accompanying drawings, in which:
fig. 1 shows a cross-sectional view of an epitaxial structure of a light emitting diode provided in accordance with a first embodiment of the present invention;
fig. 2 shows a cross-sectional view of an epitaxial structure of a light emitting diode provided in accordance with a second embodiment of the present invention;
fig. 3 illustrates a cross-sectional view of an epitaxial structure of a light emitting diode provided in accordance with a third embodiment of the present invention.
Detailed Description
Various embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Like elements in the various figures are denoted by the same or similar reference numerals. For purposes of clarity, the various features in the drawings are not necessarily drawn to scale.
The present invention may be embodied in various forms, some examples of which are described below.
The first embodiment:
fig. 1 illustrates a cross-sectional view of an epitaxial structure of a light emitting diode provided according to a first embodiment of the present invention. Referring to fig. 1, an epitaxial structure 100 of a light emitting diode is illustrated by taking an epitaxial structure of a nitride light emitting diode as an example. The epitaxial structure 100 of the light emitting diode includes a substrate 110, an epitaxial layer 120, and a carbon-doped nitride layer 130 in the epitaxial layer 120.
In the present embodiment, the substrate 110 includes, but is not limited to, one of a mirror or micro/nano patterned sapphire substrate, and in the preferred embodiment, the substrate 110 is micro patterned sapphire. In other alternative embodiments, the substrate 110 may also be gallium oxide, zinc oxide, lithium gallate, lithium aluminate.
The epitaxial layer 120 includes a first semiconductor layer 121, a light emitting layer 122, an electron blocking layer 123, and a second semiconductor layer 124, which are sequentially stacked on the substrate 100. The first semiconductor layer 121 is a gallium nitride material layer of a first doping type, and the second semiconductor layer 124 is a gallium nitride material layer of a second doping type, where polarities of the first doping type and the second doping type are opposite. For example, the first doping type is N-type doping, and the second doping type is P-type doping; or the first doping type is P-type doping, and the second doping type is N-type doping.
The light-emitting layer 122 is, for example, a Multi Quantum Well (MQW) structure layer. The MQW multi-quantum well structure includes, for example, GaN/InN/AlN, but is not limited thereto. The electron blocking layer 123 may be AlN or AlGaN, and in this embodiment, AlGaN is preferably used as the electron blocking layer.
The carbon-doped nitride layer 130 includes a carbon-doped first nitride layer 131 and a carbon-doped second nitride layer 132, wherein the carbon-doped first nitride layer 131 is located between the first semiconductor layer 121 and the light emitting layer 122; the carbon-doped second nitride layer 132 is located between the light-emitting layer 122 and the electron blocking layer 123.
In the present embodiment, the carbon doping concentration of the carbon-doped first nitride layer 131 is 1E18cm-3～1E19cm-3The carbon doping concentration of the carbon-doped second nitride layer 132 is 1E18cm-3～1E19cm-3The carbon doping concentration of the carbon-doped first nitride layer 131 and the carbon-doped second nitride layer 132 may be the same or different, and preferably, the carbon-doped first nitride layer 131 is higher than the carbon-doped second nitride layer 132. For example, the carbon-doped first nitride layer 131 preferably has a carbon doping concentration of 1.1E18cm-3The carbon doping concentration of the carbon-doped second nitride layer 132 is 1.05E18 cm-3。
Preferably, the thicknesses of the first and second carbon-doped nitride layers 131 and 132 are different, wherein the thickness of the first carbon-doped nitride layer 131 is 1 to 1000nm, and the thickness of the second carbon-doped nitride layer 132 is 1 to 100 nm. The thicker the thickness of the carbon-doped first nitride layer 131, the more favorable the segregation (concentration) of carbon atoms in the vicinity of threading dislocations. The carbon-doped second nitride layer 132 is used to control the distribution of the electron holes of the light-emitting layer 122 in the light-emitting layer 122.
The carbon concentration in the carbon-doped nitride layer 130 varies in a gradient along the thickness direction of the nitride layer 130. Specifically, the carbon concentration in the carbon-doped nitride layer 130 changes according to a gradual gradient, or the carbon concentration in the carbon-doped nitride layer 130 changes according to a transition gradient; wherein, in the gradual gradient change, the carbon concentration is a numerical value which is continuously changed in sequence; in the transition type gradient change, the change value of the carbon concentration is a fixed value. In a preferred embodiment, the carbon concentration in the carbon-doped nitride layer 130 is gradually increased or gradually decreased, so as to obtain better spreading of electrons and holes, thereby facilitating uniform distribution of electrons and holes in the quantum well.
In other embodiments, the carbon concentration in the carbon-doped nitride layer 130 is constant along the thickness direction of the nitride layer, and is a fixed value.
The carbon-doped nitride layer 130 is formed by at least one of reducing a growth temperature, doping aluminum or other metals, reducing a growth pressure, reducing a volume fraction of ammonia gas in a nitrogen source gas, and increasing a volume fraction of hydrogen gas in the nitrogen source gas. The nitrogen source gas includes at least one of hydrogen, ammonia, and nitrogen. Specifically, since the cracking of ammonia gas is not facilitated at low temperature and low pressure, the carbon doping concentration of the carbon-doped nitride layer can be increased at low temperature and low pressure.
The carbon-doped first nitride layer 131 may be formed in any one of a low-temperature + low-pressure ratio, a low-temperature + low ammonia ratio, or a low-temperature + low-pressure + low ammonia ratio. Preferably, the growth temperature of the carbon-doped first nitride layer 131 is 600-800 ℃ in a low temperature + low pressure + low ammonia gas ratio mode; the growth pressure is less than 250 Torr; the volume fraction of ammonia in the nitrogen source gas is less than 65%.
The carbon-doped second nitride layer 133 may be formed in any one of a low temperature + low pressure, a low temperature + low ammonia gas ratio, a low temperature + high hydrogen gas ratio, or a low temperature + low pressure + low ammonia gas ratio + high hydrogen gas ratio, and the high hydrogen gas ratio may improve crystal quality. Preferably, the growth temperature of the carbon-doped second nitride layer 132 is 600 ℃ to 800 ℃ in a mode of low temperature, low pressure, low ammonia gas proportion and high hydrogen gas proportion; the growth pressure is less than 250 Torr; the volume fraction of ammonia in the nitrogen source gas is less than 65%, and the volume fraction of hydrogen in the nitrogen source gas is more than 45%.
In the present embodiment, the carbon-doped nitride layer 130 is at least one of a nitride, a ternary mixed crystal nitride, a quaternary mixed crystal nitride, a superlattice structure, and a shallow quantum well structure.
In a specific embodiment, the carbon-doped nitride layer 130 is at least one of GaN, AlN, InN, AlGaN, AlInN, InGaN, AlInGaN, GaN/InN superlattice, GaN/AlN superlattice, InN/GaN superlattice, GaN/AlGaN superlattice, GaN/AlInN superlattice, GaN/InGaN superlattice, GaN/AlInGaN superlattice, InGaN/AlGaN superlattice, InGaN/AlInN superlattice, InGaN/AlInGaN/AlInN superlattice, AlGaN/AlInN superlattice, AlInGaN/AlInGaN superlattice, InGaN/AlInGaN shallow quantum wells, InGaN/AlGaN shallow quantum wells, and InGaN/AlInGaN shallow quantum wells.
In a preferred embodiment, the carbon-doped first nitride layer 131 is preferably GaN and the carbon-doped second nitride layer 133 is preferably AlInGaN.
According to the epitaxial structure of the light emitting diode provided by the embodiment of the invention, the carbon-doped nitride layer is formed in the epitaxial layer, so that the antistatic capability of the light emitting diode can be improved, and the light emitting efficiency of the light emitting diode can be improved.
Furthermore, the carbon-doped first nitride layer formed between the first semiconductor layer of the epitaxial layer and the light emitting layer has crystal defects, namely threading dislocations, due to the lattice mismatch between the substrate 110 and the epitaxial layer 120, so that a leakage current channel is formed, while the carbon-doped first nitride layer of the present invention has a high carbon doping concentration, and is segregated (concentrated) near the threading dislocations, so as to perform the function of compensating an acceptor, thereby causing a nitride compensation mechanism, preventing leakage current, and improving the antistatic capability of the light emitting diode.
Furthermore, a carbon-doped second nitride layer is formed between the light-emitting layer and the electron blocking layer of the epitaxial layer, so that the distribution of electron holes of the light-emitting layer in the light-emitting layer can be regulated and controlled, the injection efficiency of the holes is obviously enhanced, and the repetition probability of the hole and electron wave functions is improved; the electron confinement effect of the luminescent layer is enhanced, and the recombination efficiency of electron holes is enhanced, so that the luminous efficiency of the light-emitting diode is improved.
Second embodiment:
fig. 2 illustrates a cross-sectional view of an epitaxial structure of a light emitting diode provided in accordance with a second embodiment of the present invention. In contrast to the first embodiment of the present invention, the carbon-doped nitride layer 130 includes only the carbon-doped first nitride layer 131, and the carbon-doped first nitride layer 131 is located between the first semiconductor layer 121 and the light emitting layer 122.
According to the epitaxial structure of the light emitting diode of the second embodiment of the present invention, the carbon-doped first nitride layer is formed between the first semiconductor layer of the epitaxial layer and the light emitting layer, and due to the lattice mismatch between the substrate 110 and the epitaxial layer 120, the crystal defect, i.e., threading dislocation, exists in the epitaxial structure of the light emitting diode, so as to form a leakage current channel.
The third embodiment:
fig. 3 illustrates a cross-sectional view of an epitaxial structure of a light emitting diode provided in accordance with a third embodiment of the present invention. In contrast to the first embodiment of the present invention, the carbon-doped nitride layer 130 includes only the carbon-doped second nitride layer 132, and the carbon-doped second nitride layer 132 is located between the light emitting layer 122 and the electron blocking layer 123.
According to the epitaxial structure of the light emitting diode of the third embodiment of the invention, the carbon-doped second nitride layer is formed between the light emitting layer and the electron blocking layer of the epitaxial layer, so that the distribution of electron holes of the light emitting layer in the light emitting layer can be regulated and controlled, the injection efficiency of the holes is obviously enhanced, and the repetition probability of the hole and electron wave functions is improved; the electron confinement effect of the luminescent layer is enhanced, and the recombination efficiency of electron holes is enhanced, so that the luminous efficiency of the light-emitting diode is improved.
The invention also provides a manufacturing method of the epitaxial structure of the light-emitting diode, which comprises the following steps: forming an epitaxial layer on a substrate, wherein the epitaxial layer comprises a first semiconductor layer, a light emitting layer, an electron blocking layer and a second semiconductor layer which are sequentially stacked on the substrate, the first semiconductor layer is provided with a first doping type, the second semiconductor layer is provided with a second doping type, and the polarities of the first doping type and the second doping type are opposite; a carbon doped nitride layer is formed in the epitaxial layer.
In the present embodiment, the substrate 110 includes, but is not limited to, one of a mirror or micro/nano patterned sapphire substrate, and in the preferred embodiment, the substrate 110 is micro patterned sapphire. In other alternative embodiments, the substrate 110 may also be gallium oxide, zinc oxide, lithium gallate, lithium aluminate.
The epitaxial layer 120 includes a first semiconductor layer 121, a light emitting layer 122, an electron blocking layer 123, and a second semiconductor layer 124, which are sequentially stacked on the substrate 100. The first semiconductor layer 121 is a gallium nitride material layer of a first doping type, and the second semiconductor layer 124 is a gallium nitride material layer of a second doping type, where polarities of the first doping type and the second doping type are opposite. For example, the first doping type is N-type doping, and the second doping type is P-type doping; or the first doping type is P-type doping, and the second doping type is N-type doping.
The light-emitting layer 122 is, for example, a Multi Quantum Well (MQW) structure layer. The MQW multi-quantum well structure includes, for example, GaN/InN/AlN, but is not limited thereto. The electron blocking layer 123 may be AlN or AlGaN, and in this embodiment, AlGaN is preferably used as the electron blocking layer.
Wherein the content of the first and second substances,
the carbon-doped nitride layer 130 includes a carbon-doped first nitride layer 131 and a carbon-doped second nitride layer 132, wherein the carbon-doped first nitride layer 131 is located between the first semiconductor layer 121 and the light emitting layer 122; the carbon-doped second nitride layer 132 is located between the light-emitting layer 122 and the electron blocking layer 123.
In the present embodiment, the carbon doping concentration of the carbon-doped first nitride layer 131 is 1E18cm-3～1E19cm-3The carbon doping concentration of the carbon-doped second nitride layer 132 is 1E18cm-3～1E19cm-3The carbon doping concentration of the carbon-doped first nitride layer 131 and the carbon-doped second nitride layer 132 may be the same or different, and preferably, the carbon-doped first nitride layer 131 is higher than the carbon-doped second nitride layer 132. For example, the carbon-doped first nitride layer 131 preferably has a carbon doping concentration of 1.1E18cm-3The carbon doping concentration of the carbon-doped second nitride layer 132 is 1.05E18 cm-3。
Preferably, the thicknesses of the first and second carbon-doped nitride layers 131 and 132 are different, wherein the thickness of the first carbon-doped nitride layer 131 is 1 to 1000nm, and the thickness of the second carbon-doped nitride layer 132 is 1 to 100 nm. The thicker the thickness of the carbon-doped first nitride layer 131, the more favorable the segregation (concentration) of carbon atoms in the vicinity of threading dislocations. The carbon-doped second nitride layer 132 is used to control the distribution of the electron holes of the light-emitting layer 122 in the light-emitting layer 122.
As a further preference, the carbon concentration in the carbon-doped nitride layer 130 varies in a gradient along the thickness direction of the nitride layer 130. Specifically, the carbon concentration in the carbon-doped nitride layer 130 changes according to a gradual gradient, or the carbon concentration in the carbon-doped nitride layer 130 changes according to a transition gradient; wherein, in the gradual gradient change, the carbon concentration is a numerical value which is continuously changed in sequence; in the transition type gradient change, the change value of the carbon concentration is a fixed value. In a preferred embodiment, the carbon concentration in the carbon-doped nitride layer 130 is gradually increased or gradually decreased, so as to obtain better spreading of electrons and holes, thereby facilitating uniform distribution of electrons and holes in the quantum well.
In other embodiments, the carbon concentration in the carbon-doped nitride layer 130 is constant along the thickness direction of the nitride layer, and is a fixed value.
The carbon-doped nitride layer 130 is formed by at least one of reducing a growth temperature, doping aluminum or other metals, reducing a growth pressure, reducing a volume fraction of ammonia gas introduced into a nitrogen source gas, and increasing a volume fraction of hydrogen gas introduced into the nitrogen source gas during an epitaxial growth process. The nitrogen source gas introduced comprises at least one of hydrogen, ammonia and nitrogen. Specifically, since the cracking of ammonia gas is not facilitated at low temperature and low pressure, the carbon doping concentration of the carbon-doped nitride layer can be increased at low temperature and low pressure.
The carbon-doped first nitride layer 131 may be formed in any one of a low-temperature + low-pressure ratio, a low-temperature + low ammonia ratio, or a low-temperature + low-pressure + low ammonia ratio. Preferably, the growth temperature of the carbon-doped first nitride layer 131 is 600-800 ℃ in a low temperature + low pressure + low ammonia gas ratio mode; the growth pressure is less than 250 Torr; the volume fraction of ammonia in the nitrogen source gas is less than 65%.
The carbon-doped second nitride layer 133 may be formed in any one of a low temperature + low pressure, a low temperature + low ammonia gas ratio, a low temperature + high hydrogen gas ratio, or a low temperature + low pressure + low ammonia gas ratio + high hydrogen gas ratio, and the high hydrogen gas ratio may improve crystal quality. Preferably, the growth temperature of the carbon-doped second nitride layer 132 is 600 ℃ to 800 ℃ in a mode of low temperature, low pressure, low ammonia gas proportion and high hydrogen gas proportion; the growth pressure is less than 250 Torr; the volume fraction of ammonia in the nitrogen source gas is less than 65%, and the volume fraction of hydrogen in the nitrogen source gas is more than 45%.
In the present embodiment, the carbon-doped nitride layer 130 is at least one of a nitride, a ternary mixed crystal nitride, a quaternary mixed crystal nitride, a superlattice structure, and a shallow quantum well structure.
In a preferred embodiment, the carbon-doped nitride layer 130 is at least one of GaN, AlN, InN, AlGaN, AlInN, InGaN, AlInGaN, GaN/InN superlattices, GaN/AlN superlattices, InN/GaN superlattices, GaN/AlGaN superlattices, GaN/AlInN superlattices, GaN/InGaN superlattices, GaN/AlInGaN superlattices, InGaN/AlInN superlattices, InGaN/AlInGaN superlattices, AlGaN/AlInN superlattices, AlInGaN/AlInGaN superlattices, InGaN/GaN shallow quantum wells, InGaN/AlGaN shallow quantum wells, InGaN/AlInGaN shallow quantum wells.
According to the manufacturing method of the epitaxial structure of the light emitting diode provided by the embodiment of the invention, the carbon-doped nitride layer is formed in the epitaxial layer, so that the antistatic capability of the light emitting diode can be improved, and the light emitting efficiency of the light emitting diode can be improved.
Furthermore, a carbon-doped first nitride layer is formed between the first semiconductor layer of the epitaxial layer and the light emitting layer, and crystal defects, namely threading dislocations, exist in the epitaxial structure of the light emitting diode due to the fact that lattice mismatch exists between the substrate and the epitaxial layer, so that a leakage current channel is formed.
Furthermore, a carbon-doped second nitride layer is formed between the light-emitting layer and the electron blocking layer of the epitaxial layer, so that the distribution of electron holes of the light-emitting layer in the light-emitting layer can be regulated and controlled, the injection efficiency of the holes is obviously enhanced, and the repetition probability of the hole and electron wave functions is improved; the electron confinement effect of the luminescent layer is enhanced, and the recombination efficiency of electron holes is enhanced, so that the luminous efficiency of the light-emitting diode is improved.
While embodiments in accordance with the invention have been described above, these embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments described. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated. The scope of the invention should be determined from the following claims.

Claims (23)

1. An epitaxial structure of a light emitting diode, comprising:
a substrate;
the epitaxial layer is positioned on the substrate and comprises a first semiconductor layer, a light emitting layer, an electron blocking layer and a second semiconductor layer which are sequentially stacked on the substrate, the first semiconductor layer is provided with a first doping type, the second semiconductor layer is provided with a second doping type, and the polarities of the first doping type and the second doping type are opposite;
a carbon-doped nitride layer in the epitaxial layer;
the carbon-doped nitride layer comprises a carbon-doped first nitride layer, the carbon-doped first nitride layer is positioned between the first semiconductor layer and the light-emitting layer, and the carbon-doped first nitride layer has a carbon doping concentration of 1E18cm-3～1E19cm-3。
2. An epitaxial structure for a light emitting diode according to claim 1, wherein the carbon-doped nitride layer further comprises a carbon-doped second nitride layer, the carbon-doped second nitride layer being located between the light emitting layer and the electron blocking layer.
3. An epitaxial structure of a light emitting diode according to claim 2, wherein the carbon doping concentration of the carbon-doped second nitride layer is 1E18cm-3～1E19cm-3。
4. The epitaxial structure of the light emitting diode of claim 2, wherein the thickness of the carbon-doped second nitride layer is 1 to 100 nm.
5. The epitaxial structure of the light emitting diode of claim 1, wherein the thickness of the carbon-doped first nitride layer is 1 to 1000 nm.
6. An epitaxial structure for a light emitting diode according to claim 1, wherein the carbon concentration in the carbon-doped nitride layer varies according to a gradient along the thickness direction of the nitride layer.
7. An epitaxial structure of a light emitting diode according to claim 6, wherein the carbon concentration in the carbon-doped nitride layer varies according to a gradual gradient, or the carbon concentration in the carbon-doped nitride layer varies according to a transition gradient; wherein, in the gradual gradient change, the carbon concentration is a numerical value which is continuously changed in sequence; in the transition type gradient change, the change value of the carbon concentration is a fixed value.
8. Epitaxial structure of a light emitting diode according to claim 1, wherein the carbon concentration in the carbon doped nitride layer is constant along the thickness direction of the nitride layer.
9. The epitaxial structure of the light emitting diode of any of claims 1-8, wherein the carbon-doped nitride layer is at least one of a nitride, a ternary mixed crystal nitride, a quaternary mixed crystal nitride, a superlattice structure, a shallow quantum well structure.
10. Epitaxial structure of a light emitting diode according to any of claims 1-8, wherein the carbon doped nitride layer is at least one of GaN, AlN, InN, AlGaN, AlInN, InGaN, AlInGaN, GaN/InN superlattices, GaN/AlN superlattices, InN/GaN superlattices, GaN/AlGaN superlattices, GaN/AlInN superlattices, GaN/InGaN superlattices, InGaN/AlGaN superlattices, InGaN/AlInN superlattices, InGaN/AlInGaN superlattices, AlGaN/AlInN superlattices, AlGaN/AlInGaN superlattices, AlInGaN/AlInGaN superlattices, InGaN/GaN shallow quantum wells, AlGaN/AlGaN shallow quantum wells, InGaN/AlInGaN shallow quantum wells.
11. A method for manufacturing an epitaxial structure of a light emitting diode comprises the following steps:
forming an epitaxial layer on a substrate, wherein the epitaxial layer comprises a first semiconductor layer, a light emitting layer, an electron blocking layer and a second semiconductor layer which are sequentially stacked on the substrate, the first semiconductor layer is provided with a first doping type, the second semiconductor layer is provided with a second doping type, and the polarities of the first doping type and the second doping type are opposite;
epitaxially growing a carbon-doped nitride layer in the epitaxial layer;
wherein the carbon-doped nitride layer comprises a first carbon-doped nitride layer, the first carbon-doped nitride layer is positioned between the first semiconductor layer and the light-emitting layer, and the carbon-doped first nitride layer has a carbon doping concentration of 1E18cm-3～1E19cm-3。
12. A method of fabricating an epitaxial structure for a light emitting diode according to claim 11, wherein the carbon-doped nitride layer further comprises a carbon-doped second nitride layer, the carbon-doped second nitride layer being located between the light emitting layer and the electron blocking layer.
13. The method for manufacturing an epitaxial structure of a light-emitting diode according to claim 12, wherein the carbon doping concentration of the carbon-doped second nitride layer is 1E 18-1E 19cm-3。
14. A method for fabricating an epitaxial structure for a light emitting diode according to claim 12, wherein the thickness of the carbon-doped second nitride layer is 1 to 100 nm.
15. A method for fabricating an epitaxial structure for a light emitting diode according to claim 11, wherein the thickness of the carbon-doped first nitride layer is 1 to 1000 nm.
16. A method for fabricating an epitaxial structure for a light emitting diode according to claim 11, wherein a nitrogen source gas comprising at least one of hydrogen, ammonia and nitrogen is introduced during the epitaxial growth of the carbon-doped nitride layer.
17. A method of fabricating an epitaxial structure for a light emitting diode according to claim 11, wherein the growth temperature of the carbon-doped first nitride layer is 600 ℃ to 800 ℃; the growth pressure is less than 250 Torr; the volume fraction of ammonia in the introduced nitrogen source gas is less than 65 percent.
18. A method of fabricating an epitaxial structure for a light emitting diode according to claim 12, wherein the growth temperature of the carbon-doped second nitride layer is 600 ℃ to 800 ℃; the growth pressure is less than 250 Torr; the volume fraction of ammonia in the introduced nitrogen source gas is less than 65%, and the volume fraction of hydrogen in the introduced nitrogen source gas is more than 45%.
19. A method of fabricating an epitaxial structure for a light emitting diode according to claim 11, wherein the carbon concentration in the carbon-doped nitride layer is varied in a gradient along a thickness direction of the nitride layer.
20. A method of fabricating an epitaxial structure for a light emitting diode according to claim 19, wherein the carbon concentration in the carbon-doped nitride layer is graded in a gradual manner, or the carbon concentration in the carbon-doped nitride layer is graded in a transition manner; wherein, in the gradual gradient change, the carbon concentration is a numerical value which is continuously changed in sequence; in the transition type gradient change, the change value of the carbon concentration is a fixed value.
21. A method of fabricating an epitaxial structure for a light-emitting diode according to claim 11, wherein a carbon concentration in the carbon-doped nitride layer is constant along a thickness direction of the nitride layer.
22. A method of fabricating an epitaxial structure for a light emitting diode according to any one of claims 11 to 21, wherein the carbon-doped nitride layer is at least one of a nitride, a ternary mixed crystal nitride, a quaternary mixed crystal nitride, a superlattice structure, a shallow quantum well structure.
23. Method of manufacturing an epitaxial structure of a light emitting diode according to any of the claims 11-21, wherein the carbon doped nitride layer is at least one of GaN, AlN, InN, AlGaN, AlInN, InGaN, AlInGaN, GaN/InN superlattices, GaN/AlN superlattices, InN/GaN superlattices, GaN/AlGaN superlattices, GaN/AlInN superlattices, GaN/InGaN superlattices, GaN/AlInGaN superlattices, InGaN/AlGaN superlattices, InGaN/AlInN superlattices, InGaN/AlInGaN superlattices, AlGaN/AlInN superlattices, AlGaN/AlInGaN superlattices, AlInGaN/AlInGaN superlattices, InGaN/AlInGaN shallow quantum wells, AlGaN/InGaN shallow quantum wells, InGaN/AlInGaN shallow quantum wells.
CN202111140799.0A 2021-09-28 2021-09-28 Epitaxial structure of light emitting diode and manufacturing method thereof Pending CN114038954A (en)

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Application publication date: 20220211