CN110518101B - UV LED epitaxial structure and growth method thereof - Google Patents
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
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- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
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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
- H01L33/005—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
- 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
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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
- H01L33/14—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
- 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
- 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
A UV LED epitaxial structure and a growth method thereof relate to the technical field of LED epitaxial growth and the technical field of near ultraviolet UV LED solidification. Firstly, epitaxially growing a buffer layer, an unintentionally doped AlGaN layer and an n-type doped AlGaN layer on a substrate, then manufacturing a first growth area, a second growth area and a third growth area of a luminescent layer of the multi-quantum well active layer, epitaxially growing a luminescent quantum well and a luminescent quantum barrier in the corresponding areas, finally etching insulating medium mask layers on the first luminescent layer and the second luminescent layer of the multi-quantum well active layer on an epitaxial structure through a photoetching process, and epitaxially growing an electron blocking layer and a p-type doped AlGaN layer. The invention achieves the purpose of manufacturing three UV light sources with different wavelengths on the same LED chip, can reduce the number of the UV light sources and the exposure procedure, simplifies the process manufacturing flow of encapsulation and application, reduces the failure rate of products, improves the power density and improves the curing effect.
Description
Technical Field
The invention relates to the technical field of LED epitaxial growth and the technical field of near Ultraviolet (UV) LED solidification.
Background
Ultraviolet curing is a well-known environment-friendly and energy-saving curing technology, and is a process of finally curing an organic coating by utilizing Ultraviolet (UV) irradiation to perform polymerization reaction. The traditional UV light source uses mercury lamps, and because of the mercury containing toxic substances, the international multi-country has signed a prescription about prohibiting the production and sales of mercury-containing products, and China will also fully execute the 'water convention' in 2020 to prohibit the production and import and export of mercury-containing UV lamps. The UV LED has the advantages of low energy consumption, long service life, no mercury pollution, instant opening, low-voltage safety and the like, so that the UV LED becomes the most suitable light source for replacing a mercury lamp, and is widely used in the curing industry at present.
However, compared with the continuous spectrum of the traditional mercury lamp in the ultraviolet band, the UV LED is extremely narrow in wavelength distribution due to the limitation of the forbidden band spectrum width of the semiconductor material, and is only applied to a plurality of wave bands such as 365nm, 385nm, 395nm, 405nm and the like in the curing industry at present. The organic coating such as ink has different absorptivity to ultraviolet long wave and short wave, so that short wave UV can only work on the surface layer of the coating, and long wave UV works on the deep layer of the coating, therefore, when in curing, a plurality of UV LEDs with different wave bands are generally required to be adopted for mixed exposure, or the UV LEDs are subjected to multiple exposure, and the defects of increased working procedures, increased equipment, increased energy consumption and the like are caused.
Disclosure of Invention
The invention aims to provide a UV LED epitaxial structure integrating three different UV wavelengths on the same LED chip.
The UV LED epitaxial structure comprises the following components from bottom to top: the device comprises a substrate, a buffer layer, an unintentionally doped AlGaN layer, an n-type doped AlGaN layer, a multi-quantum well active layer, an electron blocking layer and a p-type doped AlGaN layer.
The invention is characterized in that:
the multi-quantum well active layer comprises a multi-quantum well active layer first light-emitting layer, a multi-quantum well active layer second light-emitting layer and a multi-quantum well active layer third light-emitting layer; the first light-emitting layer of the multi-quantum well active layer, the second light-emitting layer of the multi-quantum well active layer and the third light-emitting layer of the multi-quantum well active layer are transversely distributed on the n-type doped AlGaN layer; the electron blocking layer is transversely distributed on the first light-emitting layer of the multi-quantum well active layer, the second light-emitting layer of the multi-quantum well active layer and the third light-emitting layer of the multi-quantum well active layer.
The first luminescent layer of the multiple quantum well active layer comprises 5-15 pairs of first luminescent quantum wells In x1 Ga 1-x1 N and first luminescence quantum barrier Al y Ga 1-y N, wherein x1 is 0-0.02, and y is 0-0.2.
The second luminescent layer of the multiple quantum well active layer is formed by 5-15 pairs of second luminescent quantum wells In x2 Ga 1-x2 N and a second luminescence quantum barrier Al y Ga 1-y N, wherein x2 is 0.02-0.04, and y is 0-0.2.
The third luminescent layer of the multiple quantum well active layer comprises 5-15 pairs of third luminescent quantum wells In x3 Ga 1-x3 N and third luminescence quantum barrier Al y Ga 1-y N, wherein x3 is 0.04-0.07, and y is 0-0.2.
In the invention, x1 is 0-0.02 and is used for adjusting the excitation wavelength of the first luminescence quantum well to be near 365 nm; x2 is 0.02-0.04, and is used for adjusting the excitation wavelength of the second luminescent quantum well to be near 385 nm; x3 is 0.04-0.07, and is used for adjusting the excitation wavelength of the third luminescent quantum well to be about 395 nm; y is 0-0.2, and is used for adjusting the energy band difference between the quantum barrier and the quantum well, so as to play a role in limiting the recombination of electrons and holes in the quantum well.
The invention integrates three UV wavelengths on a single LED chip, and can effectively overcome the defects of the prior art. When the LED chip is conducted in the forward direction, the three groups of quantum well layers emit ultraviolet light with different wavelengths.
The invention has the following excellent effects:
1. the invention integrates the UV light sources with three wavelengths on the same LED chip, is applied to the curing industry, can reduce the number of the UV light sources and the exposure procedure, correspondingly reduces the number of curing equipment and supporting facilities, reduces the energy consumption and saves the cost.
2. Based on the three-wavelength integrated structure, the chip structure can be flexibly designed or the three-wavelength multi-chip integrated structure can be manufactured according to the light intensity requirement of the curing light source, so that the process manufacturing flow of packaging and application is simplified, the product failure rate is reduced, and the development efficiency of a terminal product is improved.
3. Compared with the traditional curing scheme of three or more wavelength package integration, the composite wavelength type multi-quantum well active layer provided by the invention can greatly reduce the package volume, reduce the package consumption, reduce the manufacturing cost, improve the power density and improve the curing effect.
In addition, the invention also provides a growth method of the UV LED epitaxial structure.
The method is characterized by further comprising the following sequential steps of:
1) An insulating medium mask layer is deposited on the n-type doped AlGaN layer for the first time, a growth area of a first luminescent layer of the multi-quantum well active layer is defined through a photoetching process, and then the insulating medium mask layer in the growth area of the first luminescent layer of the multi-quantum well active layer is etched until the n-type doped AlGaN layer is exposed, and the insulating medium mask layer is used as the growth area of the first luminescent layer of the multi-quantum well active layer;
2) Epitaxially growing 5-15 pairs of first luminescent quantum wells In the growth area of the first luminescent layer of the multi-quantum well active layer x1 Ga 1-x1 N and first luminescence quantum barrier Al y Ga 1-y N, wherein x1 is 0-0.02, and y is 0-0.2;
3) Depositing an insulating medium mask layer on the epitaxial structure for the second time, defining a growth area of a second luminescent layer of the multi-quantum well active layer through a photoetching process, and etching the insulating medium mask layer in the growth area of the second luminescent layer of the multi-quantum well active layer until the n-type doped AlGaN layer is exposed to serve as the growth area of the second luminescent layer of the multi-quantum well active layer;
4) Epitaxially growing 5-15 pairs of second light-emitting quantum wells In the growth region of the second light-emitting layer of the multi-quantum well active layer x2 Ga 1-x2 N and a second luminescence quantum barrier Al y Ga 1-y N, wherein x2 is 0.02-0.04, y is 0-0.2;
5) Depositing an insulating medium mask layer on the epitaxial structure for the third time, defining a growth area of a third luminescent layer of the multi-quantum well active layer through a photoetching process, and etching the insulating medium mask layer in the growth area of the third luminescent layer of the multi-quantum well active layer until the n-type doped AlGaN layer is exposed to serve as the growth area of the third luminescent layer of the multi-quantum well active layer;
6) Epitaxially growing 5-15 pairs of third light-emitting quantum wells In the growth region of the third light-emitting layer of the multi-quantum well active layer x3 Ga 1-x3 N and third luminescence quantum barrier Al y Ga 1-y N, wherein x3 is 0.04-0.07, and y is 0-0.2;
7) Etching the insulating medium mask layer on the first luminescent layer of the multiple quantum well active layer and the second luminescent layer of the multiple quantum well active layer on the epitaxial structure through a photoetching process;
8) An electron blocking layer and a p-type doped AlGaN layer are sequentially epitaxially grown on the epitaxial structure.
The invention achieves the purpose of manufacturing three UV light sources with different wavelengths on the same LED chip through the processing technical steps, and can be applied to UV curing.
Further, the material of the insulating dielectric mask layer is any one of silicon oxide, silicon nitride, silicon oxynitride or aluminum oxide, but is not limited thereto.
Drawings
Fig. 1 is a schematic diagram of an epitaxial structure of a UV LED according to the present invention.
Fig. 2 to 4 are schematic views of the preparation process, respectively.
Illustration of:
10: a substrate;
20: a buffer layer;
30: unintentionally doping the AlGaN layer;
40: an n-doped AlGaN layer;
41: an insulating medium mask layer;
50: a multi-quantum well active layer first light emitting layer;
51: an insulating medium mask layer;
60: a multi-quantum well active layer second light emitting layer;
61: an insulating medium mask layer;
70: a multi-quantum well active layer third light emitting layer;
80: an electron blocking layer;
90: and a p-type doped AlGaN layer.
Detailed Description
The illustrations provided in the examples below illustrate the basic embodiments of the invention by way of illustration only, in which the shape, size, order of growth, etc. of the materials involved in the invention may vary and the actual structure and process may be more complex.
1. The method comprises the following specific steps:
in the first step, a substrate 10 is provided, and the material of the substrate 10 may be any one of sapphire, silicon carbide, and aluminum nitride, but is not limited thereto.
Step two, gaN or AlN buffer layer 20, unintentionally doped AlGaN layer 30, and n-doped AlGaN layer 40 are sequentially epitaxially grown on substrate 10 using MOCVD.
And thirdly, depositing an insulating medium mask layer 41 on the n-type doped AlGaN layer 40 for the first time by PECVD, etching the insulating medium mask layer of the growth area of the first luminescent layer 50 of the multi-quantum well active layer by a photoetching process until the n-type doped AlGaN layer 40 is exposed.
Step four, in is epitaxially grown In 5-15 pairs by MOCVD In the growth area of the first luminescent layer 50 of the multiple quantum well active layer x1 Ga 1-x1 N quantum well and Al y Ga 1-y N quantum barrier, thereby forming a first light-emitting layer 50 of the multiple quantum well active layer with a thickness of about 250nm, H is introduced during the growth process 2 By changing H 2 Pulse flow rate, regulating In component x1 value to 0-0.02, and regulating Al component y value to 0-0.2 by changing Al flow rate can excite 365nm ultraviolet light, as shown In figure 2.
And fifthly, depositing an insulating medium mask layer 51 on the epitaxial structure obtained after the treatment in the step four for the second time by using PECVD, etching the insulating medium mask layer of the growth area of the second luminescent layer 60 of the multi-quantum well active layer by using a photoetching process until the n-type doped AlGaN layer 40 is exposed.
Step six, in is epitaxially grown In the growth area of the second luminescent layer 60 of the multiple quantum well active layer by MOCVD for 5 to 15 pairs x2 Ga 1-x2 N quantum well and Al y Ga 1-y N quantum barrier, forming a second light-emitting layer 60 of multiple quantum well active layer with thickness of about 250nm, and introducing H during growth 2 By changing H 2 The pulse flow rate is controlled to adjust the x2 value of the In component to be 0.02-0.04, and the y value of the Al component is controlled to be 0-0.2 by changing the Al flow rate, so that ultraviolet light with 385nm can be excited, as shown In figure 3.
And step seven, depositing an insulating medium mask layer 61 for the third time on the epitaxial structure obtained after the step six, wherein the thickness is about 100nm, and etching the insulating medium mask layer of the growth area of the third luminescent layer 70 of the multi-quantum well active layer through a photoetching process until the n-type doped AlGaN layer 40 is exposed.
Step eight, epitaxially growing 5 to 15 pairs of In by MOCVD In the growth region of the third luminescent layer 70 of the multiple quantum well active layer x3 Ga 1-x3 N quantum well and Al y Ga 1-y N quantum barrier, therebyForming a third light-emitting layer 70 of the multiple quantum well active layer with the thickness of about 250nm, and introducing H during the growth process 2 By changing H 2 Pulse flow rate, regulating In component x3 value to 0.04-0.07, and regulating Al component y value to 0-0.2 by changing Al flow rate can excite 395nm ultraviolet light, as shown In figure 4.
Step nine, etching the insulating medium mask layers 51 and 61 on the first light emitting layer 50 of the multiple quantum well active layer and the second light emitting layer 60 of the multiple quantum well active layer on the epitaxial structure obtained after the treatment in step eight through a photolithography process.
Step ten, epitaxially growing an electron blocking layer 80 and a p-type doped AlGaN layer 90 in sequence on the epitaxial structure obtained after the treatment in step nine, as shown in fig. 1.
The material of the insulating dielectric mask layer in the above manufacturing process may be any one of silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide, but is not limited thereto.
2. The structure of the formed product is described as follows:
as shown in fig. 1, the epitaxial structure includes, from bottom to top: a substrate 10, a buffer layer 20, an unintentionally doped AlGaN layer 30, an n-type doped AlGaN layer 40, a multiple quantum well active layer (multiple quantum well active layer first light emitting layer 50, multiple quantum well active layer second light emitting layer 60 and multiple quantum well active layer third light emitting layer 70), an electron blocking layer 80 and a p-type doped AlGaN layer 90.
The multiple quantum well active layer first light emitting layer 50, the multiple quantum well active layer second light emitting layer 60, and the multiple quantum well active layer third light emitting layer 70 are laterally distributed over the n-doped AlGaN layer 40, and the electron blocking layer 80 is laterally distributed over the multiple quantum well active layer first light emitting layer 50, the multiple quantum well active layer second light emitting layer 60, and the multiple quantum well active layer third light emitting layer 70.
Multiple quantum well active layer first light emitting layer 50 consists of 5-15 pairs of first light emitting quantum wells In x1 Ga 1-x1 N and first luminescence quantum barrier Al y Ga 1-y N, wherein x1 is 0-0.02, and y is 0-0.2.
Multiple quantum well active layer second light emitting layer 60 comprises 5-15 pairs of second light emitting quantum wells In x2 Ga 1-x2 N and a second luminescence quantum barrier Al y Ga 1-y N, wherein x2 is 0.02-0.04, and y is 0-0.2.
Multiple quantum well active layer third light emitting layer 70 is composed of 5-15 pairs of third light emitting quantum wells In x3 Ga 1-x3 N and third luminescence quantum barrier Al y Ga 1-y N, wherein x3 is 0.04-0.07, and y is 0-0.2.
Claims (3)
1. A UV LED epitaxial structure comprising, from bottom to top: the device comprises a substrate, a buffer layer, an unintentionally doped AlGaN layer, an n-type doped AlGaN layer, a multi-quantum well active layer, an electron blocking layer and a p-type doped AlGaN layer;
the method is characterized in that: the multi-quantum well active layer comprises a multi-quantum well active layer first light-emitting layer, a multi-quantum well active layer second light-emitting layer and a multi-quantum well active layer third light-emitting layer;
the first light-emitting layer of the multi-quantum well active layer, the second light-emitting layer of the multi-quantum well active layer and the third light-emitting layer of the multi-quantum well active layer are transversely distributed on the n-type doped AlGaN layer;
the electron blocking layer is transversely distributed on the first light-emitting layer of the multi-quantum well active layer, the second light-emitting layer of the multi-quantum well active layer and the third light-emitting layer of the multi-quantum well active layer;
the first luminescent layer of the multiple quantum well active layer comprises 5-15 pairs of first luminescent quantum wells In x1 Ga 1-x1 N and first luminescence quantum barrier Al y Ga 1-y N is composed, wherein x1 is 0-0.02, y is 0-0.2;
the second luminescent layer of the multiple quantum well active layer is formed by 5-15 pairs of second luminescent quantum wells In x2 Ga 1-x2 N and a second luminescence quantum barrier Al y Ga 1-y N, wherein x2 is 0.02-0.04, y is 0-0.2;
the third luminescent layer of the multiple quantum well active layer comprises 5-15 pairs of third luminescent quantum wells In x3 Ga 1-x3 N and third luminescence quantum barrier Al y Ga 1-y N, wherein x3 is 0.04-0.07, and y is 0-0.2.
2. The method of claim 1, further comprising the sequential steps of:
1) An insulating medium mask layer is deposited on the n-type doped AlGaN layer for the first time, a growth area of a first luminescent layer of the multi-quantum well active layer is defined through a photoetching process, and then the insulating medium mask layer in the growth area of the first luminescent layer of the multi-quantum well active layer is etched until the n-type doped AlGaN layer is exposed, and the insulating medium mask layer is used as the growth area of the first luminescent layer of the multi-quantum well active layer;
2) Epitaxially growing 5-15 pairs of first luminescent quantum wells In the growth area of the first luminescent layer of the multi-quantum well active layer x1 Ga 1-x1 N and first luminescence quantum barrier Al y Ga 1-y N, wherein x1 is 0-0.02, and y is 0-0.2;
3) Depositing an insulating medium mask layer on the epitaxial structure for the second time, defining a growth area of a second luminescent layer of the multi-quantum well active layer through a photoetching process, and etching the insulating medium mask layer in the growth area of the second luminescent layer of the multi-quantum well active layer until the n-type doped AlGaN layer is exposed to serve as the growth area of the second luminescent layer of the multi-quantum well active layer;
4) Epitaxially growing 5-15 pairs of second light-emitting quantum wells In the growth region of the second light-emitting layer of the multi-quantum well active layer x2 Ga 1-x2 N and a second luminescence quantum barrier Al y Ga 1-y N, wherein x2 is 0.02-0.04, y is 0-0.2;
5) Depositing an insulating medium mask layer on the epitaxial structure for the third time, defining a growth area of a third luminescent layer of the multi-quantum well active layer through a photoetching process, and etching the insulating medium mask layer in the growth area of the third luminescent layer of the multi-quantum well active layer until the n-type doped AlGaN layer is exposed to serve as the growth area of the third luminescent layer of the multi-quantum well active layer;
6) Epitaxially growing 5-15 pairs of third light-emitting quantum wells In the growth region of the third light-emitting layer of the multi-quantum well active layer x3 Ga 1-x3 N and third luminescence quantaPotential barrier Al y Ga 1-y N, wherein x3 is 0.04-0.07, and y is 0-0.2;
7) Etching the insulating medium mask layer on the first luminescent layer of the multiple quantum well active layer and the second luminescent layer of the multiple quantum well active layer on the epitaxial structure through a photoetching process;
8) An electron blocking layer and a p-type doped AlGaN layer are sequentially epitaxially grown on the epitaxial structure.
3. The method of growing a UV LED epitaxial structure of claim 2, wherein: the insulating medium mask layer is made of any one of silicon oxide, silicon nitride, silicon oxynitride or aluminum oxide.
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| 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 |
| CN111223968A (en) * | 2020-01-17 | 2020-06-02 | 湘能华磊光电股份有限公司 | LED epitaxial growth method for realizing different light-emitting wavelengths on same epitaxial wafer |
| CN111146316B (en) * | 2020-02-21 | 2021-08-27 | 湘能华磊光电股份有限公司 | Preparation method of RGB LED integrated display array |
| CN111312867B (en) * | 2020-02-21 | 2023-12-15 | 湘能华磊光电股份有限公司 | Preparation method of single-chip white light LED |
| CN114038967B (en) * | 2021-07-27 | 2023-05-16 | 重庆康佳光电技术研究院有限公司 | LED epitaxial structure, manufacturing method thereof and LED device |
| CN114203864B (en) * | 2021-10-19 | 2023-12-05 | 闽都创新实验室 | Method for preparing multifunctional luminous triode device |
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