CN109659409B - LED epitaxial structure and preparation method thereof - Google Patents
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910002704 AlGaN Inorganic materials 0.000 claims abstract description 47
- 238000002347 injection Methods 0.000 claims abstract description 16
- 239000007924 injection Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 230000000903 blocking effect Effects 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000004065 semiconductor Substances 0.000 claims abstract description 5
- 239000002019 doping agent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- H—ELECTRICITY
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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
- H01L33/14—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
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- 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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- H—ELECTRICITY
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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
- H01L33/14—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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- H—ELECTRICITY
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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
- H01L33/26—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
The invention provides an LED epitaxial structure and a preparation method thereof, wherein the structure comprises a substrate; the semiconductor epitaxial layer positioned on the substrate comprises an AlN layer, an N-type AlGaN layer, a current expansion layer, a quantum well active layer, an electron blocking layer, a P-type AlGaN hole injection layer and a P-type GaN contact layer; an electron deceleration layer is further arranged between the N-type AlGaN layer and the current expansion layer and is made of AlxGa1‑xThe material N, x is more than 40% and less than 100%, the total Al component of the electron deceleration layer is more than that of the N-type AlGaN layer, and the thickness of the electron deceleration layer is 1 nm-200 nm. According to the invention, the electron decelerator with a special structure is added to decelerate electrons entering the quantum well active layer, so that holes can easily enter the first quantum wells close to the N-type AlGaN layer to be subjected to radiation recombination with the electrons, and the luminous efficiency of the deep ultraviolet LED device is improved.
Description
Technical Field
The invention relates to the technical field of photoelectricity, in particular to an LED epitaxial structure and a preparation method thereof.
Background
A Light-Emitting Diode (LED) is a semiconductor electronic component capable of Emitting Light. Such electronic devices appeared as early as 1962, and only low-intensity red light was emitted in the early stage, and other versions of monochromatic light were developed later, and the light emitted so far has spread to visible light, infrared light and ultraviolet light, and the light intensity has been improved to a comparable level. The utility model can be used as an indicator light, a display panel and the like at the beginning; with the continuous progress of the technology, the light emitting diode has been widely applied to displays, television lighting and illumination.
However, the efficiency of the deep ultraviolet LED is low, and one of the main reasons for the low efficiency of the deep ultraviolet LED is that the electron concentration and mobility provided by the n-type AlGaN injection layer are much higher than the hole concentration and mobility provided by the p-type AlGaN injection layer, and on the other hand, the hole injection efficiency is further reduced due to the obstruction of the electron blocking layer. This may result in holes that are difficult to transport into the first few quantum wells of the multi-quantum well active region near the n-type AlGaN injection layer. Therefore, in the multiple quantum well active region, efficient radiative recombination occurs only in the quantum well near the p-type AlGaN injection layer. In order to meet the practical requirements, the light emitting efficiency of the AlGaN-based DUV LED device needs to be improved, and the demand is urgent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an LED epitaxial structure and a preparation method thereof.
The invention is realized by the following steps:
one of the objects of the present invention is to provide an LED epitaxial structure, including:
a substrate;
the semiconductor epitaxial layer positioned on the substrate comprises an AlN layer, an N-type AlGaN layer, a current expansion layer, a quantum well active layer, an electron blocking layer, a P-type AlGaN hole injection layer and a P-type GaN contact layer;
an electron deceleration layer used for decelerating electrons from the N-type AlGaN layer is further arranged between the N-type AlGaN layer and the current expansion layer, and the electron deceleration layer is AlxGa1-xAnd the x is more than 40% and less than 100%, the total Al component of the electron deceleration layer is more than that of the N-type AlGaN layer, and the thickness of the electron deceleration layer is 1 nm-200 nm.
Preferably, the AlxGa1-xThe Al component of the N material is linearly gradually changed from e to f, and the e and the f meet the conditions that the ratio of e is more than 40 percent and the ratio of f is more than 100 percent.
Preferably, the AlxGa1-xThe N material is AlcGa1-cN/AldGa1-dN superlattice structure, wherein c and d respectively satisfy that c is more than 40% and less than 100%, d is more than 40% and less than 100%; al (Al)cGa1-cThe Al component in N is linearly and gradually changed from e to f, and e and f meet the conditions that e is more than 40 percent and f is more than f and d is less than 100 percent; al (Al)dGa1-dThe Al component in N is linearly gradually changed from g to h, and g and h meet the condition that c is more than 40 percent and h is more than h and g is more than 100 percent.
More preferably, e, f, g and h satisfy 40% < e < f < h < g < 100%.
The invention also aims to provide a preparation method of the LED epitaxial structure, which specifically comprises the following steps:
and 4, epitaxially growing a current expansion layer, a quantum well active layer, an electron blocking layer, a P-type AlGaN hole injection layer and a P-type GaN contact layer on the electron deceleration layer in sequence.
Preferably, in the step 1, an AlN low-temperature buffer layer is grown on the substrate at 400-800 ℃ and the thickness of the AlN low-temperature buffer layer is 10-50 nm; then heating to 1200-1400 deg.C to grow AlN intrinsic layer with thickness of 500-4000 nm.
Preferably, in the step 2, the temperature is reduced to 800-1200 ℃, and then the N-type AlGaN layer is grown, wherein the Al component of the N-type AlGaN layer is 20-90%, and the thickness is 500-4000 nm.
Preferably, the step 4 specifically includes: (1) firstly, cooling to 700-1100 ℃, and growing a quantum well active layer, wherein the barrier thickness of the quantum well active layer is 5-30 nm, and the Al component is 20-100%; the thickness of a potential well of the quantum well active layer is 0.1 nm-5 nm, and the Al component is 0% -80%; (2) growing an electron blocking layer, wherein the thickness of the electron blocking layer is 5 nm-50 nm, and the Al component is 30% -100%; (3) then growing a P-type AlGaN hole injection layer with the thickness of 1-50nm, using Mg as a P-type dopant, and the growth temperature of the P-type AlGaN hole injection layer is 700-1100 ℃; (4) and then growing a p-type GaN contact layer with the thickness of 1-20nm, using Mg as a p-type dopant and the growth temperature of 400-900 ℃.
The invention has the beneficial effects that:
according to the LED epitaxial structure, the electron deceleration layer with a special structure is added to decelerate electrons entering the multi-quantum well active region, so that holes can enter the first quantum wells close to the N-type AlGaN layer more easily and are subjected to radiation recombination with the electrons, and the luminous efficiency of a deep ultraviolet LED device is improved finally. When the driving current is 350A/cm2Compared with the conventional deep ultraviolet LED device in the prior art, the LED epitaxial structure provided by the optimal embodiment of the invention has the advantage that the luminous efficiency is improved by 1.67 times.
Drawings
Fig. 1 is a schematic structural diagram of an LED epitaxial structure according to an embodiment of the present invention;
fig. 2 is a flowchart of a method for manufacturing an LED epitaxial structure according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of an LED device according to an embodiment of the present invention;
in the figure, a 1-P type GaN contact layer and a 2-P type AlGaN hole injection layer are arranged; 3-an electron blocking layer; 4-quantum well active layer, 5-current spreading layer; 6-electron deceleration layer; a 7-N type AlGaN layer; an 8-AlN layer; 9-a substrate; 10. a P electrode; 11. and an N electrode.
Detailed Description
Example 1
LED epitaxial structure
As shown in fig. 1, an LED epitaxial structure includes:
a substrate 9;
the semiconductor epitaxial layer positioned on the substrate comprises an AlN layer 8, an N-type AlGaN layer 7, a current expansion layer 5, a quantum well active layer 4, an electron blocking layer 3, a P-type AlGaN hole injection layer 2 and a P-type GaN contact layer 1;
an electron decelerating layer 6 for decelerating electrons from the N-type AlGaN layer is further provided between the N-type AlGaN layer 7 and the current spreading layer 5,
and the electron decelerating layer 6 is AlxGa1-xN material, wherein 40% < x < 100%, and the electronsThe total Al component of the deceleration layer is larger than that of the N-type AlGaN layer, and the thickness of the deceleration layer is 1 nm-200 nm.
In particular, the electron-decelerating layer 6 is Al0.5Ga0.5N, the thickness of which is 100 nm.
Second, preparation method of LED epitaxial structure (as shown in FIG. 2)
The epitaxial material growth steps are as follows:
(1) growing an AlN low-temperature buffer layer at 400-800 ℃, wherein the thickness of the AlN low-temperature buffer layer is 10-50 nm; heating to 1200-1400 deg.c to grow AlN intrinsic layer in the thickness of 500-4000 nm;
(2) cooling to 800-1200 ℃, and growing an N-type AlGaN layer, wherein the Al component of the N-type AlGaN layer is 20-90%, and the thickness of the N-type AlGaN layer is 500-4000 nm;
(3) growing the electron decelerating layer;
(4) cooling to 700-1100 deg.c to grow quantum well active area with barrier thickness of 5-30 nm and Al component of 20-100%;
(5) growing an electron blocking layer, wherein the thickness of the electron blocking layer is 5 nm-50 nm, and the Al component is 30% -100%;
(6) and growing a p-type AlGaN hole injection layer with the composition of 0-100% and the thickness of 1-50nm, and using Mg as a p-type dopant. The growth temperature is 700-1100 ℃;
(7) a p-type GaN contact layer is grown to a thickness of 1-20nm using Mg as the p-type dopant. The growth temperature is 400-900 ℃.
Three, LED device (as shown in figure 3)
The P-type GaN contact layer 1 is connected with a P electrode 10, and the N-type AlGaN layer 7 is connected with an N electrode 11.
Example 2
An LED epitaxial structure, as in embodiment 1, except that the electron-decelerating layer 6 is Al0.99Ga0.01N, the thickness of which is 200 nm. The preparation method of the LED epitaxial structure is the same as that of example 1.
Example 3
An LED epitaxial structure, as in embodiment 1, except that the electron-decelerating layer 6 is Al0.41Ga0.49N, the thickness of which is 1 nm;the preparation method of the LED epitaxial structure is the same as that of example 1.
Example 4
An LED epitaxial structure, as in embodiment 1, except that the electron-decelerating layer 6 is Al0.99Ga0.01N, the thickness of which is 200 nm; al (Al)0.99Ga0.01The Al component in N is linearly gradually changed from 0.99 to 0.70; the preparation method of the LED epitaxial structure is the same as that of example 1.
Example 5
An LED epitaxial structure, as in embodiment 1, except that the electron-decelerating layer 6 is Al0.41Ga0.49N, the thickness of which is 1 nm; al (Al)0.41Ga0.49The preparation method of the LED epitaxial structure is the same as that of the embodiment 1, wherein the Al component in N is linearly gradually changed from 0.41 to 0.69.
Comparative example 1 a conventional deep ultraviolet LED device (without an electron retarding layer);
comparative example 2 ultraviolet LED device having an electron decelerating layer, and the electron decelerating layer is AlxGa1-xN material, wherein x is less than 40%;
experimental examples measurement of luminous efficiency
Adopting an integrating sphere to drive the current to be 35A/cm2The deep ultraviolet LED devices of examples 1 to 5 and comparative examples 1 to 2 were tested under the conditions for luminous efficiency. The results are shown in table 1 below.
TABLE 1
The experimental result shows that the driving current is 35A/cm2In comparison with the deep ultraviolet LED device of comparative example 1, the light emitting efficiency of the LEDs of examples 1-3 is improved, and the light emitting efficiency of the LED epitaxial structure of example 5 is improved by 1.67 times; the electron entering the multi-quantum well active region is decelerated by adding the deceleration layer, so that holes can enter the first quantum wells close to the N-type AlGaN layer more easily and are subjected to radiation recombination with the electrons, and finally, the luminous efficiency of the deep ultraviolet LED device is improved.
Compared with the deep ultraviolet LED device of the comparative example 1, the deep ultraviolet LED device of the comparative example 2 is improved to a small extent;
compared with the deep ultraviolet LED device of the comparative example 2, the LED devices of the examples 1 to 3 have greatly improved luminous efficiency; showing the electron-decelerating layer Al of the present inventionxGa1-xIn the N material, x must satisfy 40% < x < 100%, and the luminous efficiency of the deep ultraviolet LED device can be obviously improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. An LED epitaxial structure, comprising:
a substrate;
the semiconductor epitaxial layer positioned on the substrate comprises an AlN layer, an N-type AlGaN layer, a current expansion layer, a quantum well active layer, an electron blocking layer, a P-type AlGaN hole injection layer and a P-type GaN contact layer;
an electron deceleration layer used for decelerating electrons from the N-type AlGaN layer is further arranged between the N-type AlGaN layer and the current expansion layer, and the electron deceleration layer is AlxGa1-xAnd the x is more than 40% and less than 100%, the total Al component of the electron deceleration layer is more than that of the N-type AlGaN layer, and the thickness of the electron deceleration layer is 1 nm-200 nm.
2. LED epitaxial structure according to claim 1, characterized in that the Al isxGa1-xThe Al component of the N material is linearly gradually changed from e to f, and the e and the f meet the conditions that the ratio of e is more than 40 percent and the ratio of f is more than 100 percent.
3. LED epitaxial structure according to claim 1, characterized in that the Al isxGa1-xThe N material is AlcGa1-cN/AldGa1-dN superlattice structure, wherein c and d respectively satisfy that c is more than 40% and less than 100%, d is more than 40% and less than 100%; al (Al)cGa1-cThe Al component in N is linearly and gradually changed from e to f, and e and f meet the conditions that e is more than 40 percent and f is more than f and d is less than 100 percent; al (Al)dGa1-dThe Al component in N is linearly gradually changed from g to h, and g and h meet the condition that c is more than 40 percent and h is more than h and g is more than 100 percent.
4. An LED epitaxial structure according to claim 3 wherein e, f, g and h satisfy 40% < e < f < h < g < 100%.
5. LED epitaxial structure according to claim 1, characterized in that the Al of the electron-decelerating layerxGa1-xThe N-type dopant in the N material is Si.
6. The LED epitaxial structure of claim 1 wherein the P-type AlGaN hole injection layer is AlpGa1-pThe N material comprises the components of more than 0 percent and less than 100 percent, and the thickness is 1 nm-600 nm.
7. A method for preparing an LED epitaxial structure according to any one of claims 1 to 6, characterized in that it comprises in particular the following steps:
step 1, epitaxially growing an AlN layer on a substrate, wherein the AlN layer comprises an AlN low-temperature buffer layer and an AlN intrinsic layer;
step 2, epitaxially growing an N-type AlGaN layer on the AlN layer;
step 3, epitaxially growing an electronic deceleration layer on the N-type AlGaN layer;
and 4, epitaxially growing a current expansion layer, a quantum well active layer, an electron blocking layer, a P-type AlGaN hole injection layer and a P-type GaN contact layer on the electron deceleration layer in sequence.
8. The method for preparing an LED epitaxial structure according to claim 7, wherein in step 1, an AlN low-temperature buffer layer is grown on a substrate at 400 to 800 ℃ to a thickness of 10 to 50 nm; then heating to 1200-1400 deg.C to grow AlN intrinsic layer with thickness of 500-4000 nm.
9. The method for preparing an LED epitaxial structure according to claim 7, wherein in the step 2, the temperature is reduced to 800-1200 ℃, and then an N-type AlGaN layer is grown, wherein the N-type AlGaN layer has an Al component of 20-90% and a thickness of 500-4000 nm.
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| CN110165030B (en) * | 2019-04-24 | 2022-04-22 | 华南师范大学 | Deep ultraviolet LED illuminator based on AlGaN |
| CN110112270A (en) * | 2019-05-10 | 2019-08-09 | 马鞍山杰生半导体有限公司 | Deep ultraviolet LED epitaxial wafer and preparation method thereof and deep ultraviolet LED |
| CN111223969B (en) * | 2020-01-10 | 2021-07-20 | 武汉深紫科技有限公司 | Deep ultraviolet LED device with visible light wave band and preparation method thereof |
| CN111244237B (en) * | 2020-01-15 | 2021-04-30 | 圆融光电科技股份有限公司 | Ultraviolet LED epitaxial structure and growth method thereof |
| CN112242466B (en) * | 2020-09-29 | 2022-01-28 | 苏州紫灿科技有限公司 | Deep ultraviolet LED with in-situ V-shaped nanopore structure and preparation method thereof |
| CN112331752A (en) * | 2020-12-03 | 2021-02-05 | 至芯半导体(杭州)有限公司 | Deep ultraviolet LED epitaxial manufacturing method with low-resistivity P-type layer |
| CN112993102A (en) * | 2021-05-11 | 2021-06-18 | 东南大学 | Ultraviolet light-emitting diode with electronic speed reduction layer structure |
| CN114050104B (en) * | 2021-11-12 | 2022-09-30 | 松山湖材料实验室 | Processing method of aluminum nitride single crystal substrate and preparation method of ultraviolet light-emitting device |
| CN114203868A (en) * | 2021-12-13 | 2022-03-18 | 苏州紫灿科技有限公司 | Deep ultraviolet chip with n-type low-resistance ohmic contact structure and preparation method thereof |
| CN114361308A (en) * | 2021-12-28 | 2022-04-15 | 芜湖启迪半导体有限公司 | Deep ultraviolet light-emitting device with double electron blocking layers and preparation method thereof |
| CN114335278B (en) * | 2022-03-16 | 2022-08-05 | 至芯半导体(杭州)有限公司 | Epitaxial structure of UVB chip and application thereof |
| CN115832136B (en) * | 2023-02-22 | 2023-06-06 | 江西兆驰半导体有限公司 | AlGaN-based ultraviolet light-emitting diode and preparation method thereof |
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| CN103681985B (en) * | 2013-11-21 | 2016-05-25 | 华灿光电(苏州）有限公司 | Epitaxial wafer of a kind of light emitting diode and preparation method thereof |
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| CN106025032A (en) * | 2016-06-21 | 2016-10-12 | 华灿光电(苏州）有限公司 | Epitaxial wafer of light-emitting diode and growing method thereof |
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| CN105845797A (en) * | 2016-05-26 | 2016-08-10 | 聚灿光电科技股份有限公司 | Light-emitting diode (LED) epitaxial structure and fabrication method thereof |
| CN108400133A (en) * | 2018-05-11 | 2018-08-14 | 广东工业大学 | A kind of the deep ultraviolet LED epitaxial structure and preparation method of same side structure |
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