CN116344689B - Light-emitting chip with coating and manufacturing method thereof - Google Patents
Light-emitting chip with coating and manufacturing method thereof Download PDFInfo
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- CN116344689B CN116344689B CN202310602155.1A CN202310602155A CN116344689B CN 116344689 B CN116344689 B CN 116344689B CN 202310602155 A CN202310602155 A CN 202310602155A CN 116344689 B CN116344689 B CN 116344689B
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- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 230000004888 barrier function Effects 0.000 claims abstract description 197
- 239000004065 semiconductor Substances 0.000 claims abstract description 125
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 80
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000758 substrate Substances 0.000 claims abstract description 71
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 claims abstract description 37
- 239000002070 nanowire Substances 0.000 claims abstract description 37
- 230000003247 decreasing effect Effects 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims description 631
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 claims description 53
- 239000011247 coating layer Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 239000012159 carrier gas Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000005922 Phosphane Substances 0.000 claims description 26
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 26
- 229910000064 phosphane Inorganic materials 0.000 claims description 26
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 24
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 19
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 238000005019 vapor deposition process Methods 0.000 claims 1
- 229910002601 GaN Inorganic materials 0.000 description 66
- 239000000243 solution Substances 0.000 description 52
- 238000000605 extraction Methods 0.000 description 43
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 31
- 239000002019 doping agent Substances 0.000 description 16
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 15
- 239000002077 nanosphere Substances 0.000 description 14
- 230000000903 blocking effect Effects 0.000 description 13
- 239000000969 carrier Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005530 etching Methods 0.000 description 12
- 229910052738 indium Inorganic materials 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 9
- 229910052733 gallium Inorganic materials 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 230000006798 recombination Effects 0.000 description 9
- 238000005215 recombination Methods 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 8
- 229910002704 AlGaN Inorganic materials 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 description 5
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 4
- 230000005699 Stark effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- 238000005286 illumination Methods 0.000 description 2
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- 239000007924 injection Substances 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000011807 nanoball Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 230000005428 wave function Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UOSXPFXWANTMIZ-UHFFFAOYSA-N cyclopenta-1,3-diene;magnesium Chemical compound [Mg].C1C=CC=C1.C1C=CC=C1 UOSXPFXWANTMIZ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
- H01L33/025—Physical imperfections, e.g. particular concentration or distribution of impurities
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01L33/12—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 stress relaxation structure, e.g. buffer layer
-
- 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
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Led Devices (AREA)
Abstract
The invention relates to a light-emitting chip with a coating and a manufacturing method thereof, belonging to the technical field of semiconductor devices. The light-emitting chip with the coating comprises a substrate, a first semiconductor layer connected with a first electrode, an active layer, a coating and a second semiconductor layer connected with a second electrode in sequence; the substrate is doped with aluminum, and the aluminum content in the substrate increases gradually to the growth side; the active layer is a plurality of In x Ga 1‑x N layer/Al y Ga 1‑y N barrier layer/GaN barrier layer alternating structure In x Ga 1‑x In the N layer, x is more than or equal to 0.3 and less than or equal to 0.4, and the value of x is unchanged; at each Al y Ga 1‑y In the N barrier layer, y is more than or equal to 0.1 and less than or equal to 0.3, and the value of y is decreased along the growth direction, and the decreasing rate is 10-20%; the coating comprises an InP/InGaAs nanowire coating. The invention effectively improves the luminous efficiency and the stability of the luminous chip.
Description
Technical Field
The invention relates to the technical field of semiconductor devices, in particular to a light-emitting chip with a coating and a manufacturing method thereof.
Background
The light emitting chip is an important semiconductor device, can convert electric energy into light energy, and is widely used in the fields of display, illumination, communication, and the like. The light emitting chip is composed of a plurality of semiconductor material layers and generally comprises a substrate, an n-type semiconductor layer, a quantum well layer, a p-type semiconductor layer, an electrode and other structures.
However, the light emitting chip in the prior art has relatively low light emitting efficiency and stable reliability due to the non-uniform hole distribution, the limited stark effect, energy loss, photon repeated absorption or non-radiative recombination and other factors. For example, the uneven hole distribution can cause different hole densities in different areas, so that the luminous intensity and the wavelength are uneven, and the reliability, the stability and the luminous efficiency of the luminous chip are affected; the stark effect is that in some semiconductor materials, the combination energy between electrons and holes changes, so that the position of a luminescence peak shifts and widens along with the increase of the concentration of injected carriers, which also causes problems of reduced luminescence efficiency, reduced stability and the like of the luminescence chip, and factors such as energy loss, photon repeated absorption or non-radiative recombination and the like of the luminescence chip also cause energy waste and photon loss, thereby reducing the overall luminescence efficiency and stability of the luminescence chip.
In the prior art, the problems of low luminous efficiency and poor stability of the luminous chip are reported to be solved by optimizing the epitaxial structure of the luminous chip, optimizing the process steps or optimizing the design of the electrode and the reflecting layer and the like, and although the problems can be relieved to a certain extent by the methods, the luminous efficiency of the luminous chip is still lower, the stability is still to be further improved, and the high-efficiency and stable luminous chip has great potential and needs in the fields of illumination, display, communication and the like.
In summary, it is highly necessary to provide a light emitting chip with a coating layer and a method for manufacturing the same.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides a light emitting chip with a coating and a manufacturing method thereof. The invention provides a novel light-emitting chip structure, which effectively improves the light-emitting efficiency and the stability of the light-emitting chip.
The present invention provides in a first aspect a light emitting chip with a coating layer, which includes a substrate, a first semiconductor layer, an active layer, a coating layer, and a second semiconductor layer in this order along a growth direction; the light emitting chip with the coating layer further comprises a first electrode electrically connected with the first semiconductor layer and a second electrode electrically connected with the second semiconductor layer; the substrate is doped with aluminum, and the content of the doped aluminum in the substrate is from the first halfOne side of the conductor layer increases gradually towards the side close to the first semiconductor layer; the active layer comprises a plurality of quantum well layers and a plurality of quantum barrier layers which are alternately stacked along the growth direction, wherein the quantum well layers are one more than the quantum barrier layers; the quantum well layer is In x Ga 1-x N layer, x is more than or equal to 0.3 and less than or equal to 0.4, in x Ga 1-x The value of x in the N layers is unchanged; the quantum barrier layer is Al y Ga 1-y N barrier layer/GaN barrier layer, y is more than or equal to 0.1 and less than or equal to 0.3, each Al y Ga 1-y The value of y in the N barrier layer is unchanged, and two adjacent Al layers y Ga 1-y The value of y in the N barrier layer is decreased along the growth direction, and the decreasing rate is 10-20%; the coating comprises an InP/InGaAs nanowire coating.
Preferably, the InP/InGaAs nanowire coating is grown on the basis of an active layer by a metal organic compound vapor deposition method, and the InP/InGaAs nanowire coating is grown by the following steps:
(1) Introducing trimethyl indium to grow for 30-120 s under the conditions that the temperature in the reaction chamber is 300-400 ℃ and the pressure is 50-200 Torr, and then introducing phosphane to grow for 120-600 s under the condition that trimethyl indium is continuously introduced;
(2) Stopping introducing trimethyl indium, then, after the temperature in the reaction chamber is raised to 400-450 ℃, stopping introducing phosphane, and then, simultaneously introducing trimethyl indium, trimethyl gallium and arsine for growing for 30-240 s, thereby obtaining the InP/InGaAs nanowire coating.
Preferably, in the step (1), the volume flow ratio of the trimethylindium to the phosphane is (1.5-2): 1, a step of; and/or in the step (2), the molar flow ratio of the trimethylindium, the trimethylgallium and the arsine is (8-12): 1: (320-350).
Preferably, in the growth process of the step (1) and the step (2), hydrogen and/or nitrogen is used as carrier gas, and the flow rate of the carrier gas is 400-2000 sccm.
Preferably, the Al y Ga 1-y The N barrier layer/GaN barrier layer is made of Al y Ga 1-y The N barrier layer and the GaN barrier layer are arranged layer by layer, and the Al y Ga 1-y An N barrier layer arranged on the In x Ga 1-x And the N layer is arranged between the GaN barrier layer.
Preferably, the Al y Ga 1-y The thickness of the N barrier layer is 2-5 nm, the thickness of the GaN barrier layer is 5-20 nm, and the In x Ga 1-x The thickness of the N layer is 5-20 nm.
Preferably, the preparation of the substrate is as follows: and cleaning and drying the monocrystalline silicon, coating an aluminum doping source solution on one side of the monocrystalline silicon, performing heat treatment at 700-1100 ℃ for 30-120 min, and cooling to obtain the substrate doped with aluminum.
Preferably, the aluminum doping source solution takes absolute ethyl alcohol as a solvent and aluminum trichloride as a solute; the coating thickness of the aluminum doping source solution is 100-500 nm, and the concentration of aluminum trichloride in the aluminum doping source solution is 0.01-0.1 mol/L.
Preferably, the thickness of the substrate is 300-500 mu m; the thickness of the first semiconductor layer is 100-1000 nm; the thickness of the second semiconductor layer is 50-500 nm; and/or the thickness of the active layer is 50-200 nm.
The present invention provides in a second aspect a method for manufacturing a light emitting chip with a coating layer according to the first aspect of the present invention, the method comprising the steps of:
(a) Preparing the substrate;
(b) Sequentially growing the first semiconductor layer, the active layer, the coating layer and the second semiconductor layer on the substrate;
(c) And arranging the first electrode which is electrically connected on the first semiconductor layer, and arranging the second electrode which is electrically connected on the second semiconductor layer to obtain the light-emitting chip with the coating.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the light-emitting chip with the coating, the substrate is doped with Al, the content of the doped Al in the substrate increases gradually from the side away from the first semiconductor layer to the side close to the first semiconductor layer, and the concentration gradient of the Al can be formed in the substrate, so that the diffusion length of holes at the substrate side is increased, the hole distribution is more uniform, and the light-emitting efficiency and stability of the light-emitting chip are improved.
(2) The light-emitting chip with the coating layer In the invention comprises an active layer which adopts In x Ga 1-x N (0.3.ltoreq.x.ltoreq.0.4) as a quantum well layer has high photoluminescence efficiency and high internal quantum efficiency, while Al y Ga 1-y The addition of the N barrier layer/GaN barrier layer can bring better lattice matching and high electron mobility, and the decrease of the Al content in the barrier layer can reduce stress and defects caused by lattice mismatch, thereby improving the structural stability and the luminous efficiency of the luminous chip, and for the quantum barrier layer, al y Ga 1-y The value range of y of the N barrier layer is more than or equal to 0.1 and less than or equal to 0.3, and each Al y Ga 1-y The value of y in the N barrier layer is unchanged, and two adjacent Al layers y Ga 1-y The value of y in the N barrier layer is decreased along the growth direction, the decreasing rate is 10-20%, the energy band difference of the quantum barrier layer can be increased by the arrangement, so that carriers are more easily grasped in the quantum well layer, energy wave functions can cross among different materials, the binding capacity and photoluminescence efficiency of the carriers are improved, and the quantum confinement Stark effect is effectively restrained; furthermore, decreasing Al y Ga 1-y The N barrier layer can also reduce stress in the light emitting chip, thereby improving stability and lifetime of the light emitting chip.
(3) The light emitting chip with the coating layer further comprises an InP/InGaAs nanowire coating layer, the InP/InGaAs nanowire coating layer can effectively absorb incident light and convert the incident light into electronic excitation, so that the photoelectric conversion efficiency of the light emitting chip can be improved, electric energy can be more effectively converted into light energy, and more carrier generation and transmission channels can be provided due to the fact that the InP/InGaAs nanowire coating layer has a high specific surface area, recombination and scattering of carriers can be reduced, scattering loss of the carriers can be reduced, more carriers can be effectively transmitted, the probability of radiation recombination is increased, and therefore the light emitting efficiency of the light emitting chip can be remarkably improved.
Drawings
The drawings of the present invention are provided for illustrative purposes only and the proportion, the size, and the number of the parts in the drawings do not necessarily coincide with the actual products.
Fig. 1 is a schematic structural diagram of a light emitting chip with a coating layer provided in embodiment 1 of the present invention;
fig. 2 is a schematic structural view of an active layer included in the light emitting chip with a coating layer of the present invention;
fig. 3 is a schematic structural diagram of a light emitting chip with a coating layer according to embodiment 2 of the present invention;
FIG. 4 is a schematic distribution of an array of nanopores in a light extraction layer included in a coated light-emitting chip in some embodiments of the invention;
fig. 5 is a schematic structural diagram of a light emitting chip with a coating layer according to embodiment 3 of the present invention.
In the figure: 1: a substrate; 2: a first semiconductor layer; 3: an active layer; 31: a quantum well layer; 32: a quantum barrier layer; 321: al (Al) y Ga 1-y An N barrier layer; 322: a GaN barrier layer; 4: inP/InGaAs nanowire coating; 5: a second semiconductor layer; 6: a first electrode; 7: a second electrode; 8: a light extraction layer; 81: a nanopore; 9: a carrier blocking layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The present invention provides in a first aspect a light emitting chip with a coating layer, for example, as shown in fig. 1 and 2, which includes a substrate 1, a first semiconductor layer 2, an active layer 3, a coating layer, and a second semiconductor layer 5 in this order along a growth direction; the light-emitting chip with the coating layer further comprises a first electrode 6 electrically connected with the first semiconductor layer 1 and a second electrode electrically connected with the second semiconductor layer 5A pole 7, i.e. the first electrode 6 is electrically connected to the first semiconductor layer 2, the second electrode 7 is electrically connected to the second semiconductor layer 5, in particular the first electrode 6 is electrically connected to a side of the first semiconductor layer 2 remote from the substrate 1, the second electrode 7 is electrically connected to a side of the second semiconductor layer 5 remote from the substrate 1; the first semiconductor layer 2, the second semiconductor layer 5, the first electrode 6 and the second electrode 7 are not particularly limited, and are conventional in the art, for example, the first semiconductor layer 2 is made of a material such as gallium nitride semiconductor doped with n-type dopants, for example, one or more of silicon (Si), germanium (Ge) and tin (Sn), the second semiconductor layer 5 is made of a material such as gallium nitride semiconductor doped with p-type dopants, for example, one or more of magnesium (Mg), zinc (Zn), beryllium (Be), strontium (Sr) and barium (Ba), and the doping concentration of the n-type dopants and/or the p-type dopants may Be 1×10, for example 17 cm -3 Up to 6X 10 18 cm -3 Between them; the light-emitting chip with a coating layer in the present invention may be used as an LED chip, for example.
In the invention, the substrate 1 is doped with aluminum Al, and the content of the doped aluminum in the substrate 1 increases from the side away from the first semiconductor layer 2 to the side close to the first semiconductor layer 2; the active layer 3 includes a plurality of quantum well layers 31 and a plurality of quantum barrier layers 32 which are alternately stacked in a growth direction, the quantum well layers 31 are one more than the quantum barrier layers 32, and in the present invention, "a plurality of" means two or more, in other words, the active layer 3 includes n+1 quantum well layers 31 and n quantum barrier layers 32 in a growth direction, n is a positive integer not less than 2, and n+1 quantum well layers 31 and n quantum barrier layers 32 are alternately stacked; the quantum well layer 31 is In x Ga 1-x N layer, x is more than or equal to 0.3 and less than or equal to 0.4, and x can be 0.3, 0.32, 0.35, 0.38 or 0.40, in x Ga 1-x The value of x in the N layers is fixed along the growth direction; the quantum barrier layer 32 is Al y Ga 1-y The y of the N barrier layer 321/the GaN barrier layer 322,0.1 is more than or equal to 0.3, and each Al y Ga 1-y Y in N barrier 321The value is unchanged, two adjacent Al y Ga 1-y The value of y in the N barrier 321 decreases along the growth direction, and the decreasing rate is 10-20%, namely, the decreasing rate is in the range of 10-20%; in some embodiments of the invention, for example, 6 Al's are provided y Ga 1-y An N barrier layer sequentially comprising Al along the growth direction 0.3 Ga 0.7 N barrier layer, al 0.24 Ga 0.76 N barrier layer, al 0.2 Ga 0.8 N barrier layer, al 0.17 Ga 0.83 N barrier layer, al 0.14 Ga 0.86 N barrier layer, al 0.12 Ga 0.88 An N barrier layer; in some more specific embodiments, the active layer 3 comprises In sequence along the growth direction 0.35 Ga 0.65 N layer, al 0.3 Ga 0.7 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.24 Ga 0.76 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.2 Ga 0.8 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.17 Ga 0.83 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.14 Ga 0.86 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.12 Ga 0.88 N barrier layer, gaN layer and In 0.35 Ga 0.65 An N layer; the coating comprises an InP/InGaAs nanowire coating 4.
The substrate included in the light-emitting chip with the coating layer is doped with Al, the content of the doped Al in the substrate increases gradually from one side away from the first semiconductor layer to one side close to the first semiconductor layer, and a concentration gradient of the Al can be formed in the substrate, so that the diffusion length of holes at the substrate side is increased, the hole distribution is more uniform, and the light-emitting efficiency and stability of the light-emitting chip are improved; the light-emitting chip with the coating layer In the invention comprises an active layer which adopts In x Ga 1-x N (0.3.ltoreq.x.ltoreq.0.4) as a quantum well layer has high photoluminescence efficiency and high internal quantum efficiency, while Al y Ga 1-y The addition of the N/GaN barrier layer can lead to better lattice matching and high electron mobility, and the decrease of the Al content in the barrier layer can Stress and defect caused by lattice mismatch are reduced, so that the structural stability and luminous efficiency of the luminous chip are improved, and for the quantum barrier layer, al y Ga 1-y The value range of y of the N barrier layer is more than or equal to 0.1 and less than or equal to 0.3, and each Al y Ga 1-y The value of y in the N barrier layer is unchanged, and two adjacent Al layers y Ga 1-y The value of y in the N barrier layer is decreased along the growth direction, the decreasing rate is 10-20%, the energy band difference of the quantum barrier layer can be increased by the arrangement, so that carriers are more easily grasped in the quantum well layer, energy wave functions can cross among different materials, the binding capacity and photoluminescence efficiency of the carriers are improved, and the quantum confinement Stark effect is effectively restrained; furthermore, decreasing Al y Ga 1-y The N barrier layer can also reduce the stress in the light-emitting chip, so that the stability and the service life of the light-emitting chip are improved; the light emitting chip with the coating layer further comprises an InP/InGaAs nanowire coating layer, the InP/InGaAs nanowire coating layer can effectively absorb incident light and convert the incident light into electronic excitation, so that the photoelectric conversion efficiency of the light emitting chip can be improved, electric energy can be more effectively converted into light energy, and more carrier generation and transmission channels can be provided due to the fact that the InP/InGaAs nanowire coating layer has a high specific surface area, recombination and scattering of carriers can be reduced, scattering loss of the carriers can be reduced, more carriers can be effectively transmitted, the probability of radiation recombination is increased, and therefore the light emitting efficiency of the light emitting chip can be remarkably improved.
In the present invention x Ga 1-x In the N layer, x is more than or equal to 0.3 and less than or equal to 0.4, and the In is prepared by a metal organic chemical vapor deposition method (MOCVD method) x Ga 1-x The N layer is conventional in the art, and may be, for example, triethylindium (TEI) as the indium source, triethylgallium (TEGa) as the gallium source, ammonia (NH) 3 ) Is a nitrogen source, nitrogen (N) 2 ) The indium source and the gallium source are used as carrier gases and grown under the conditions that the temperature is 750-850 ℃ and the pressure is 350-500 Torr, and In with different x values can be obtained by regulating and controlling the flow rates of the indium source and the gallium source x Ga 1-x An N layer; the flow rate of the gallium source can be, for exampleThe flow rate of the indium source may be 600 to 1200sccm, the flow rate of the nitrogen source may be 25000 to 35000sccm, and the flow rate of the carrier gas may be 4000 to 5000sccm, for example; to grow In 0.35 Ga 0.65 For example, the N layer may be formed on a nitrogen source (NH) by MOCVD equipment 3 ) Maintaining flow at 28000sccm, temperature at 850deg.C, pressure at 380Torr, gallium source (triethylgallium) flow at 340sccm, indium source (triethylindium) flow at 1000sccm, and nitrogen flow at 4000sccm, and growing to obtain In with thickness of 5-20 nm 0.35 Ga 0.65 And N layers.
Al in the present invention y Ga 1-y In the N barrier layer, y is more than or equal to 0.1 and less than or equal to 0.3, and Al is prepared by an MOCVD method y Ga 1-y The N barrier layer is conventional in the art, and specifically, for example, triethylaluminum (TMAL) as an aluminum source, triethylgallium (TEGa) as a gallium source, ammonia (NH) 3 ) Is nitrogen source, nitrogen (N) 2 ) The Al with different y values can be obtained by controlling the flow rates of an aluminum source and a gallium source as carrier gas and growing at the temperature of 800-1100 ℃ and the pressure of 100-400 Torr y Ga 1-y An N barrier layer; to grow Al 0.3 Ga 0.7 For example, the N barrier layer may be grown by MOCVD equipment at a temperature of 900 ℃, a reaction chamber pressure of 300Torr, a TEGa flow of 120sccm, a TMAL flow of 500sccm, and NH 3 Growing to obtain Al under the condition of 30000sccm and 4000sccm of nitrogen 0.3 Ga 0.7 An N barrier layer, and for obtaining Al with other value of y y Ga 1-y The N barrier layer can be obtained by controlling the flow rate of the growth source during the growth process on the basis of the above, and of course, al can be obtained under other conditions according to conventional control by those skilled in the art 0.3 Ga 0.7 N barrier layer and other y-valued Al y Ga 1-y And an N barrier layer.
According to some preferred embodiments, the material used for the first electrode 6 and/or the second electrode 7 may be, for example, one or more of chromium, nickel, aluminum, titanium, gold, platinum, tungsten, lead, rhodium, zinc, copper, silver; the first semiconductor layer 2 is an n-type GaN layer; the second semiconductor layer 5 is a p-type GaN layer; in the present invention, when the first semiconductor is an n-type GaN layer and the n-type dopant is silicon, the preparation of the n-type GaN layer is, for example: growing n-type GaN by using MOCVD equipment, controlling the temperature of a reaction chamber to be 1100 ℃, controlling the pressure to be 300Torr, simultaneously introducing ammonia gas with the flow rate of 25000sccm, a silicon source (monosilane) with the flow rate of 8sccm, a gallium source (triethylgallium) with the flow rate of 340sccm and nitrogen gas (carrier gas) with the flow rate of 4000sccm, and growing to obtain an n-type GaN layer with the thickness of 100-1000 nm as a first semiconductor layer; in the present invention, when the second semiconductor layer is a p-type GaN layer and the p-type dopant is magnesium, the p-type GaN layer is prepared, for example, by: and growing the P-type GaN by using MOCVD equipment, controlling the temperature of a reaction chamber to 980 ℃, controlling the pressure to 150Torr, simultaneously introducing ammonia gas with the flow rate of 35000sccm, a gallium source (triethylgallium) with the flow rate of 38sccm, a magnesium source (magnesium dicyclopentadiene) with the flow rate of 1800sccm and nitrogen gas (carrier gas) with the flow rate of 4000sccm, and growing to obtain the P-type GaN layer with the thickness of 50-500 nm.
According to some preferred embodiments, the InP/InGaAs nanowire coating 4 is grown on the basis of the active layer 3 by a metal organic compound vapor deposition method (MOVCD method), the growth of the InP/InGaAs nanowire coating comprising the steps of:
(1) Growing by introducing trimethyl indium (TMI) for 30-120 s (for example, 30, 40, 50, 60, 70, 80, 90, 100, 110 or 120 s) under the conditions that the temperature in the reaction chamber is 300-400 ℃ (for example, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃ or 400 ℃) and the pressure is 50-200 Torr (for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 Torr), and then simultaneously introducing Phosphane (PH) under the condition that the trimethyl indium (TMI) is continuously introduced 3 ) Growing for 120-600 s (e.g., 120, 150, 200, 250, 300, 350, 400, 450, 500, 550, or 600 s);
(2) Stopping introducing trimethyl indium, heating the reaction chamber to 400-450deg.C (400 deg.C, 410 deg.C, 420 deg.C, 430 deg.C, 440 deg.C or 450 deg.C), stopping introducing phosphane, and introducing trimethyl indium (TMI)) Trimethylgallium (TMGa) and arsine (AsH) 3 ) Growing for 30-240 s (such as 30, 60, 90, 120, 150, 180, 200 or 240 s) to obtain InP/InGaAs nanowire coating; in the step (2), the pressure in the reaction chamber is kept at 50-200 Torr; in some preferred embodiments, the InP/InGaAs nanowire coating has a thickness of 50-250 nm.
According to some preferred embodiments, in step (1), the volume flow ratio of the trimethylindium to the phosphane is (1.5-2): 1 (e.g., 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1); and/or in the step (2), the molar flow ratio of the trimethylindium, the trimethylgallium and the arsine is (8-12): 1: (320-350) (e.g., 8:1:320, 9:1:320, 10:1:320, 11:1:320, 12:1:320, 8:1:330, 9:1:330, 10:1:330, 11:1:330, 12:1:330, 8:1:340, 9:1:340, 10:1:340, 11:1:340, 12:1:340, 8:1:350, 9:1:350, 10:1:350, 11:1:350, or 12:1:350).
According to some preferred embodiments, in the growth process of step (1) and step (2), hydrogen and/or nitrogen is used as a carrier gas, and the flow rate of the carrier gas is 400-2000 sccm (e.g. 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900 or 2000 sccm).
According to some specific embodiments, the InP/InGaAs nanowire coatings described in the present invention are prepared, for example:
(1) Introducing trimethylindium to grow for 60s under the conditions that the temperature in the reaction chamber is 330 ℃ and the pressure is 100Torr, and then introducing phosphane to grow for 480s under the condition that trimethylindium is continuously introduced; in the step (1), hydrogen is used as carrier gas to be introduced into trimethyl indium and phosphane, the flow rate of the carrier gas is 1500sccm, the flow rate of the trimethyl indium is 60sccm, and the flow rate of the phosphane is 32sccm;
(2) Stopping introducing trimethyl indium, then stopping introducing phosphane after the temperature in the reaction chamber is raised to 410 ℃, and simultaneously introducing trimethyl indium, trimethyl gallium and arsine for 180 seconds to obtain an InP/InGaAs nanowire coating with the thickness of 100 nm; in step (2), the pressure in the reaction chamber is maintained at 100Torr; in the step (2), trimethylindium, trimethylgallium and arsine are introduced by taking hydrogen as carrier gas, wherein the flow rate of the carrier gas is 1500sccm, the molar flow rate of the trimethylindium is 2.79 mu mol/min, the molar flow rate of the trimethylgallium is 0.274 mu mol/min, and the molar flow rate of the arsine is 91.92 mu mol/min.
According to some preferred embodiments, the Al y Ga 1-y The N barrier layer/GaN barrier layer is made of Al y Ga 1-y The N barrier layer 321 and the GaN barrier layer 322 are laminated, and the Al y Ga 1-y An N barrier 321 is provided on the In x Ga 1-x Between the N layer and the GaN barrier layer 322, for example, as shown in fig. 2.
According to some preferred embodiments, the Al y Ga 1-y The N barrier layer 321 has a thickness of 2-5 nm (e.g., 2, 3, 4, or 5 nm), the GaN barrier layer 322 has a thickness of 5-20 nm (e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm), the In x Ga 1-x The thickness of the N layer is 5-20 nm (e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm).
According to some preferred embodiments, the preparation of the substrate is: cleaning and drying monocrystalline silicon, coating an aluminum doping source solution on one side of the monocrystalline silicon, performing heat treatment at 700-1100 ℃ (such as 700 ℃, 800 ℃, 900 ℃, 1000 ℃ or 1100 ℃) for 30-120 min (such as 30, 40, 50, 60, 70, 80, 90, 100, 110 or 120 min), and cooling to obtain an aluminum doped substrate; the method and the conditions of the coating are not particularly limited, and the conventional selection in the field can enable the aluminum doping source solution to be uniformly coated on one side of the monocrystalline silicon, for example, a spin coating mode can be adopted to enable the aluminum doping source solution to be uniformly coated on one side of the monocrystalline silicon; in the invention, in the heat treatment process, the aluminum doping source moves from side to side in the substrate through diffusion, because the aluminum doping source solution is coated on one side of the monocrystalline silicon, the diffusion concentration of aluminum is large on the side of the monocrystalline silicon coated with the aluminum doping source solution, and the diffusion concentration of aluminum is small on the side far away from the side coated with the aluminum doping source solution, so that the concentration gradient doping of aluminum can be realized; in the invention, the cooling is natural cooling, for example, natural cooling to room temperature of 15-35 ℃ to obtain the substrate doped with aluminum.
According to some preferred embodiments, the aluminum doping source solution uses absolute ethanol as a solvent and aluminum trichloride as a solute; the coating thickness of the aluminum doping source solution is 100-500 nm (for example, 100, 150, 200, 250, 300, 350, 400, 450 or 500 nm), and the concentration of aluminum trichloride in the aluminum doping source solution is 0.01-0.1 mol/L (for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1 mol/L); in some embodiments of the invention, the substrate is prepared by: cleaning and drying monocrystalline silicon, coating an aluminum doping source solution on one side of the monocrystalline silicon, performing heat treatment at 900 ℃ for 50min, and naturally cooling to obtain an aluminum doped substrate; the aluminum doping source solution takes absolute ethyl alcohol as a solvent and aluminum trichloride as a solute; the concentration of aluminum trichloride in the aluminum doping source solution is 0.08mol/L, and the coating thickness of the aluminum doping source solution is 400nm.
According to some preferred embodiments, the thickness of the substrate is 300-500 μm (e.g. 300, 350, 400, 450 or 500 μm); the thickness of the first semiconductor layer is 100-1000 nm (for example, 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1000 nm); the thickness of the second semiconductor layer is 50-500 nm (e.g. 50, 100, 150, 200, 250, 300, 350, 400, 450 or 500 nm); and/or the thickness of the active layer is 50-200 nm (e.g. 50, 100, 150 or 200 nm).
According to some preferred embodiments, the light emitting chip with a coating further comprises a light extraction layer 8 arranged between the first semiconductor layer 2 and the active layer 3, for example as shown in fig. 3; the light extraction layer 8 is an aluminum nitride layer, a nanopore array is arranged on one side, close to the active layer 3, of the light extraction layer 8, and the depth of a nanopore 81 in the nanopore array is 40-60% of the thickness of the light extraction layer 8; in the invention, preferably, the light emitting chip with a coating further comprises a light extraction layer, the light extraction layer is provided with a nanopore array, the light extraction layer with the nanopore array is arranged and can be used as a light guide channel to help photons escape from the inside of the light emitting chip as much as possible instead of being absorbed in the inside, the nanopore array structure of the light extraction layer can change the propagation path and the emergent angle of light, so that the radiation angle of the light emitted from the light emitting chip can be increased, the light can be more widely propagated and radiated, the escape efficiency of photons can be higher by controlling the depth of the nanopore to 40% -60% of the thickness of the light extraction layer, and meanwhile, the energy of the light can not be excessively lost, thereby improving the brightness and the efficiency of the whole light emitting chip; according to the invention, the nanopore array is arranged on one side of the aluminum nitride layer, which is close to the active layer, compared with the situation that the nanopore array is arranged in the n-type gallium nitride layer, the luminous efficiency of the luminous chip can be improved more effectively, and the possible reason is that the light extraction layer is arranged, so that light can be transmitted from the active layer to the aluminum nitride layer and transmitted through the nanopore array, and can be extracted and radiated out effectively, and the situation that part of light is reflected or absorbed is possible due to the fact that the nanopore array is arranged in the n-type gallium nitride layer directly, so that the improvement of the luminous efficiency is not obvious is possible. In addition, aluminum nitride also has high thermal stability and corrosion resistance, and can improve the reliability and stability of the light emitting chip.
In the present invention, the preparation of the light extraction layer may be, for example: growing an aluminum nitride layer (AlN layer) by using a metal organic compound chemical vapor deposition method (MOCVD method), and coating the aluminum nitride layer by using a pulling method to obtain an aluminum nitride layer with a nanosphere array on the surface, wherein in the process, silica nanospheres are used as masks, the concentration of a nanosphere solution used for coating is 5-15 wt%, and water is used as a dispersing agent for the nanosphere solution; in the present invention, the nanosphere solution is also referred to as a nanosphere aqueous solution; etching the aluminum nitride layer with the nanosphere array on the surface by utilizing an ICP etching technology, and forming a hole structure in the aluminum nitride layer to obtain the aluminum nitride layer with the nanopore array (also called as a nanopillar array); the etching thickness is such that the depth of the nano holes is 40-60% of the thickness of the light extraction layer, and after etching, cleaning is performed in a photoresist removing solution and a configured HF acid solution to obtain a light extraction layer with a nano hole array on one side; of course, other methods may be used in the present invention to form the light extraction layer with one side provided with the nanopore array.
According to some preferred embodiments, the thickness of the light extraction layer 8 is 50-400 nm (e.g. 50, 100, 150, 200, 250, 300, 350 or 400 nm).
According to some preferred embodiments, the aperture of the nanopores 81 in the nanopore array is 10-30 nm (e.g. 10, 12, 15, 18, 20, 22, 25, 28 or 30 nm), the pore spacing between two adjacent nanopores 81 is 80-150 nm (e.g. 80, 90, 100, 110, 120, 130, 140 or 150 nm), and in the present invention, the nanopore array is schematically distributed in the light extraction layer, for example, as shown in fig. 4; in the invention, the aperture of the nano holes is preferably 10-30 nm, and the hole spacing between two adjacent nano holes is 80-150 nm, so that the light extraction efficiency is improved more favorably; according to the invention, a large number of creative experiments show that the smaller the aperture of the nano holes is, the light extraction efficiency can be improved, but the manufacturing cost can be increased, the directivity of escaping light can be influenced by the spacing between the nano holes, the angle of escaping light can become more random due to the overlarge spacing, and the light is difficult to escape due to the overlarge spacing, so that in the invention, the aperture of the nano holes is preferably 10-30 nm, and the hole spacing between two adjacent nano holes is preferably 80-150 nm.
According to some preferred embodiments, the light emitting chip with the coating layer further comprises a carrier blocking layer 9 arranged between the coating layer and the second semiconductor layer 5, for example as shown in fig. 5; the carrier blocking layer 9 is In z Al 1-z N layer, 0.1.ltoreq.z.ltoreq.0.3, in the present invention, the In z Al 1-z N layer is, for example, in 0.1 Al 0.9 N layer, in 0.15 Al 0.85 N layer, in 0.2 Al 0.8 N、In 0.25 Al 0.75 N or In 0.3 Al 0.7 N; in the present invention, it is preferable that the light emitting chip having a coating layer further includes the carrier blocking layer provided between the coating layer and the second semiconductor layer, the carrier blocking layer being due to In z Al 1-z The energy band structure of the N material contains proper In content and Al content, so that the flow of electrons and holes can be blocked, non-radiative recombination is reduced, and the luminous efficiency is improved; specifically, when current passes through the light-emitting chip, a large amount of injection recombination can be generated due to the high carrier concentration of the first semiconductor layer and the second semiconductor layer, so that the light-emitting efficiency can be reduced, and the invention can effectively prevent the injection of partial carriers, reduce the occurrence of non-radiative recombination and improve the light-emitting efficiency by arranging the proper carrier blocking layer; in addition, the carrier blocking layer can also help to form a reflecting interface, promote the escape of photons and further improve the luminous efficiency.
In the present invention, the In may be grown by an MOCVD method z Al 1-z The N layer is not particularly limited to specific growth conditions and is a conventional technology in the field; in preparing the In z Al 1-z In the N layer, triethylaluminum (TMAL) is used as aluminum source, triethylindium (TEI) is used as indium source, and ammonia (NH) 3 ) Is nitrogen source, nitrogen (N) 2 ) Is used as carrier gas, grows under the conditions of the temperature of 800-900 ℃ and the pressure of 100-400 Torr, and can obtain In with different z values by regulating and controlling the flow of an aluminum source and an indium source z Al 1-z An N layer; to grow In 0.15 Al 0.85 For example, the N layer may be prepared by setting the temperature of the reaction chamber to 900℃and the pressure of the reaction chamber to 100Torr, simultaneously introducing three gases, namely, an ammonia gas at a flow rate of 5000sccm, an indium source at a flow rate of 10sccm and an aluminum source at a flow rate of 80sccm, into the reaction chamber, and using nitrogen gas as a carrier gas at a flow rate of 400sccm to obtain In 0.15 Al 0.85 And N layers.
According to some preferred embodiments, the carrier blocking layer 9 has a thickness of 5-20 nm (e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm).
The present invention provides in a second aspect a method for manufacturing a light emitting chip with a coating layer according to the first aspect of the present invention, the method comprising the steps of:
(a) Preparing the substrate;
(b) Sequentially growing the first semiconductor layer, the active layer, the coating layer and the second semiconductor layer on the substrate;
(c) And arranging the first electrode which is electrically connected on the first semiconductor layer, and arranging the second electrode which is electrically connected on the second semiconductor layer to obtain the light-emitting chip with the coating.
According to some preferred embodiments, step (b) is: sequentially growing the first semiconductor layer, the light extraction layer, the active layer, the coating layer and the second semiconductor layer on the substrate; the light extraction layer is an aluminum nitride layer, a nanopore array is arranged on one side, close to the active layer, of the light extraction layer, and the depth of a nanopore in the nanopore array is 40-60% of the thickness of the light extraction layer.
According to some preferred embodiments, step (b) is: sequentially growing the first semiconductor layer, the light extraction layer, the active layer, the coating layer, the carrier blocking layer and the second semiconductor layer on the substrate; the carrier blocking layer is In z Al 1-z N layer, z is more than or equal to 0.1 and less than or equal to 0.3; in the invention, when the light-emitting chip with the coating is manufactured, the growth process conditions of the first semiconductor layer, the light extraction layer, the active layer, the carrier blocking layer, the second semiconductor layer and the like are not particularly limited, and the conventional operation is adopted; the invention is not particularly limited in terms of the process conditions for arranging the first electrode electrically connected on the first semiconductor layer and arranging the second electrode electrically connected on the second semiconductor layer, and the conventional operation is adopted.
According to some specific embodiments, the preparation of the light emitting chip with a coating according to the present invention comprises:
(1) cleaning and drying monocrystalline silicon, coating an aluminum doping source solution on one side of the monocrystalline silicon, performing heat treatment at 900 ℃ for 50min, and naturally cooling to obtain an aluminum doped substrate; the aluminum doping source solution takes absolute ethyl alcohol as a solvent and aluminum trichloride as a solute; the concentration of aluminum trichloride in the aluminum doping source solution is 0.08mol/L, and the coating thickness of the aluminum doping source solution is 400nm.
(2) Growing an n-type GaN layer on the side, with higher aluminum doping content, of the substrate obtained in the step (1) by using an MOCVD method, wherein the n-type dopant is silicon and is used as a first semiconductor layer; the thickness of the n-type GaN layer is 100-1000 nm.
(3) Growing an active layer by an MOCVD method on the basis of the first semiconductor layer obtained in the step (2), wherein the active layer comprises 7 quantum well layers and 6 quantum barrier layers which are alternately stacked along the growth direction; the quantum well layer is In 0.35 Ga 0.65 An N layer, the quantum barrier layer is Al y Ga 1-y An N barrier layer/GaN barrier layer, the Al y Ga 1-y The N barrier layer/GaN barrier layer is made of Al y Ga 1-y The N barrier layer and the GaN barrier layer are arranged layer by layer, and Al y Ga 1-y The N barrier layer is arranged on In x Ga 1-x The N layer is arranged between the GaN barrier layer; the Al is y Ga 1-y The thickness of the N barrier layer is 2-5 nm, the thickness of the GaN barrier layer is 5-20 nm, and the In x Ga 1-x The N layer is 5-20 nm;6 Al y Ga 1-y The N barrier layer is sequentially Al along the growth direction 0.3 Ga 0.7 N barrier layer, al 0.24 Ga 0.76 N barrier layer, al 0.2 Ga 0.8 N barrier layer, al 0.17 Ga 0.83 N barrier layer, al 0.14 Ga 0.86 N barrier layer, al 0.12 Ga 0.88 An N barrier layer; that is, in is grown sequentially by MOCVD method on the basis of the first semiconductor layer obtained In step (2) 0.35 Ga 0.65 N layer, al 0.3 Ga 0.7 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.24 Ga 0.76 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.2 Ga 0.8 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.17 Ga 0.83 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.14 Ga 0.86 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.12 Ga 0.88 N barrier layer, gaN layer and In 0.35 Ga 0.65 And N layers.
(4) And (3) growing the InP/InGaAs nanowire coating by an MOCVD method on the basis of the active layer obtained in the step (3).
(5) Growing a p-type GaN layer by an MOCVD method on the basis of the InP/InGaAs nanowire coating obtained in the step (4), wherein a p-type doping agent is magnesium and is used as a second semiconductor layer, and the thickness of the p-type GaN layer is 50-500 nm; and then, treating for 15min in a nitrogen atmosphere at 750 ℃, and naturally cooling to room temperature to obtain the epitaxial structure of the light-emitting chip with the coating.
(6) And (3) arranging a first electrode electrically connected to a first semiconductor layer included in the epitaxial structure obtained in the step (5), and arranging a second electrode electrically connected to a second semiconductor layer included in the epitaxial structure, so as to obtain the light-emitting chip with the coating.
According to other specific embodiments, before the growth of the active layer, firstly growing an aluminum nitride layer by an MOCVD method on the basis of the first semiconductor layer obtained in the step (2), and then coating the aluminum nitride layer by a pulling method to obtain aluminum nitride with a nanosphere array on the surface, wherein in the process, silicon dioxide nanospheres are used as masks, and the concentration of a nanosphere aqueous solution adopted in coating is 5-15wt%; etching the aluminum nitride layer with the nanosphere array on the surface by utilizing an ICP etching technology to obtain the aluminum nitride layer with the nanopore array, wherein the aluminum nitride layer is used as a light extraction layer, and then the active layer is grown on the basis of the light extraction layer; the thickness of the etched nano holes is 40-60% of the thickness of the light extraction layer, and the etched nano holes are cleaned in a photoresist removing solution and a configured HF acid solution to obtain the light extraction layer with the nano hole array on one side.
According to other specific embodiments, prior to performing step (5) above, in is grown by MOCVD on the basis of the InP/InGaAs nanowire coating obtained In step (4) 0.15 Al 0.85 N layer is again In 0.15 Al 0.85 And growing a p-type GaN layer on the basis of the N layer.
The invention is further illustrated below with reference to examples. These examples are merely illustrative of preferred embodiments of the present invention and the scope of the present invention should not be construed as being limited to these examples only.
Example 1
The embodiment provides a light-emitting chip with a coating, as shown in fig. 1, which sequentially comprises a substrate, a first semiconductor layer, an active layer, an InP/InGaAs nanowire coating and a second semiconductor layer along a growth direction; the light emitting chip with the coating layer further comprises a first electrode electrically connected to the first semiconductor layer and a second electrode electrically connected to the second semiconductor layer; the first semiconductor layer is an n-type GaN layer, the n-type dopant is silicon, and the thickness of the first semiconductor layer is 500nm; the second semiconductor layer is a p-type GaN layer, the p-type dopant is magnesium, and the thickness of the second semiconductor layer is 150nm.
In this embodiment, the substrate is doped with aluminum, and the content of the doped aluminum in the substrate increases from a side away from the first semiconductor layer to a side close to the first semiconductor layer; the preparation of the substrate comprises the following steps: cleaning and drying monocrystalline silicon with the thickness of 400 mu m, coating an aluminum doping source solution on one side of the monocrystalline silicon, performing heat treatment at 900 ℃ for 50min, and naturally cooling to obtain a substrate doped with aluminum; the aluminum doping source solution takes absolute ethyl alcohol as a solvent and aluminum trichloride hexahydrate as a solute; the concentration of aluminum trichloride in the aluminum doping source solution is 0.08mol/L, and the coating thickness of the aluminum doping source solution is 400nm; the active layer sequentially comprises In along the growth direction 0.35 Ga 0.65 N layer, al 0.3 Ga 0.7 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.24 Ga 0.76 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.2 Ga 0.8 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.17 Ga 0.83 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.14 Ga 0.86 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.12 Ga 0.88 N barrier layer, gaN layer and In 0.35 Ga 0.65 An N layer; each In 0.35 Ga 0.65 The thickness of the N layer is 8nm, the thickness of each GaN layer is 10nm, al 0.3 Ga 0.7 N barrier layer, al 0.24 Ga 0.76 N barrier layer, al 0.2 Ga 0.8 N barrier layer, al 0.17 Ga 0.83 N barrier layer, al 0.14 Ga 0.86 N barrier layer, al 0.12 Ga 0.88 The thickness of the N barrier layers was 3nm.
In this embodiment, the InP/InGaAs nanowire coating is prepared by: (1) Introducing trimethylindium to grow for 60s under the conditions that the temperature in the reaction chamber is 330 ℃ and the pressure is 100Torr, and then introducing phosphane to grow for 480s under the condition that trimethylindium is continuously introduced; in the step (1), hydrogen is used as carrier gas to be introduced into trimethyl indium and phosphane, the flow rate of the carrier gas is 1500sccm, the flow rate of the trimethyl indium is 60sccm, and the flow rate of the phosphane is 32sccm; (2) Stopping introducing trimethyl indium, then stopping introducing phosphane after the temperature in the reaction chamber is raised to 410 ℃, and simultaneously introducing trimethyl indium, trimethyl gallium and arsine for 180 seconds to obtain an InP/InGaAs nanowire coating with the thickness of 100 nm; in step (2), the pressure in the reaction chamber is maintained at 100Torr; in the step (2), trimethylindium, trimethylgallium and arsine are introduced by taking hydrogen as carrier gas, wherein the flow rate of the carrier gas is 1500sccm, the molar flow rate of the trimethylindium is 2.79 mu mol/min, the molar flow rate of the trimethylgallium is 0.274 mu mol/min, and the molar flow rate of the arsine is 91.92 mu mol/min.
Example 2
The embodiment provides a light emitting chip with a coating, as shown in fig. 3, which sequentially comprises a substrate, a first semiconductor layer, a light extraction layer, an active layer, an InP/InGaAs nanowire coating and a second semiconductor layer along a growth direction; the light emitting chip with the coating layer further comprises a first electrode electrically connected to the first semiconductor layer and a second electrode electrically connected to the second semiconductor layer; the first semiconductor layer is an n-type GaN layer, the n-type dopant is silicon, and the thickness of the first semiconductor layer is 500nm; the second semiconductor layer is a p-type GaN layer, the p-type dopant is magnesium, and the thickness of the second semiconductor layer is 150nm.
In this embodiment, the substrate is doped with aluminum, and the content of the doped aluminum in the substrate increases from a side away from the first semiconductor layer to a side close to the first semiconductor layer; the preparation of the substrate comprises the following steps: cleaning and drying monocrystalline silicon with the thickness of 400 mu m, coating an aluminum doping source solution on one side of the monocrystalline silicon, performing heat treatment at 900 ℃ for 50min, and naturally cooling to obtain a substrate doped with aluminum; the aluminum doping source solution takes absolute ethyl alcohol as a solvent and aluminum trichloride hexahydrate as a solute; the concentration of aluminum trichloride in the aluminum doping source solution is 0.08mol/L, and the coating thickness of the aluminum doping source solution is 400nm; the light extraction layer is an aluminum nitride layer with the thickness of 100nm, a nanopore array is arranged on one side, close to the active layer, of the light extraction layer, and the depth of a nanopore in the nanopore array is 50% of the thickness of the light extraction layer; the aperture of the nano holes in the nano hole array is 20nm, and the hole spacing between two adjacent nano holes is 100nm; the preparation of the nanopore array in the light extraction layer comprises the following steps: coating an aluminum nitride layer by using a pulling method to obtain aluminum nitride with a nanosphere array on the surface, wherein in the process, silicon dioxide nanospheres are used as masks, and the concentration of a nanosphere aqueous solution adopted in coating is 10wt%; etching the aluminum nitride layer with the nano ball array on the surface by utilizing an ICP etching technology to obtain the aluminum nitride layer with the nano hole array, and cleaning the aluminum nitride layer with the nano hole array in a photoresist removing solution and a configured HF acid solution after etching to obtain a light extraction layer with one side provided with the nano hole array; the active layer sequentially comprises In along the growth direction 0.35 Ga 0.65 N layer, al 0.3 Ga 0.7 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.24 Ga 0.76 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.2 Ga 0.8 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.17 Ga 0.83 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.14 Ga 0.86 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.12 Ga 0.88 N barrier layer, gaN layer and In 0.35 Ga 0.65 An N layer; each In 0.35 Ga 0.65 The thickness of the N layer is 8nm, the thickness of each GaN layer is 10nm, al 0.3 Ga 0.7 N barrier layer, al 0.24 Ga 0.76 N barrier layer, al 0.2 Ga 0.8 N barrier layer, al 0.17 Ga 0.83 N barrier layer, al 0.14 Ga 0.86 N barrier layer, al 0.12 Ga 0.88 The thickness of the N barrier layers was 3nm.
In this embodiment, the InP/InGaAs nanowire coating is prepared by: (1) Introducing trimethylindium to grow for 60s under the conditions that the temperature in the reaction chamber is 330 ℃ and the pressure is 100Torr, and then introducing phosphane to grow for 480s under the condition that trimethylindium is continuously introduced; in the step (1), hydrogen is used as carrier gas to be introduced into trimethyl indium and phosphane, the flow rate of the carrier gas is 1500sccm, the flow rate of the trimethyl indium is 60sccm, and the flow rate of the phosphane is 32sccm; (2) Stopping introducing trimethyl indium, then stopping introducing phosphane after the temperature in the reaction chamber is raised to 410 ℃, and simultaneously introducing trimethyl indium, trimethyl gallium and arsine for 180 seconds to obtain an InP/InGaAs nanowire coating with the thickness of 100 nm; in step (2), the pressure in the reaction chamber is maintained at 100Torr; in the step (2), trimethylindium, trimethylgallium and arsine are introduced by taking hydrogen as carrier gas, wherein the flow rate of the carrier gas is 1500sccm, the molar flow rate of the trimethylindium is 2.79 mu mol/min, the molar flow rate of the trimethylgallium is 0.274 mu mol/min, and the molar flow rate of the arsine is 91.92 mu mol/min.
Example 3
The embodiment provides a light emitting chip with a coating, as shown in fig. 5, which sequentially includes a substrate, a first semiconductor layer, a light extraction layer, an active layer, an InP/InGaAs nanowire coating, a carrier blocking layer, and a second semiconductor layer along a growth direction; the light emitting chip with the coating layer further comprises a first electrode electrically connected to the first semiconductor layer and a second electrode electrically connected to the second semiconductor layer; the first semiconductor layer is an n-type GaN layer, the n-type dopant is silicon, the first semiconductor layerIs 500nm thick; the second semiconductor layer is a p-type GaN layer, the p-type dopant is magnesium, and the thickness of the second semiconductor layer is 150nm; the carrier blocking layer is In with the thickness of 10nm 0.15 Al 0.85 And N layers.
In this embodiment, the substrate is doped with aluminum, and the content of the doped aluminum in the substrate increases from a side away from the first semiconductor layer to a side close to the first semiconductor layer; the preparation of the substrate comprises the following steps: cleaning and drying monocrystalline silicon with the thickness of 400 mu m, coating an aluminum doping source solution on one side of the monocrystalline silicon, performing heat treatment at 900 ℃ for 50min, and naturally cooling to obtain a substrate doped with aluminum; the aluminum doping source solution takes absolute ethyl alcohol as a solvent and aluminum trichloride hexahydrate as a solute; the concentration of aluminum trichloride in the aluminum doping source solution is 0.08mol/L, and the coating thickness of the aluminum doping source solution is 400nm; the light extraction layer is an aluminum nitride layer with the thickness of 100nm, a nanopore array is arranged on one side, close to the active layer, of the light extraction layer, and the depth of a nanopore in the nanopore array is 50% of the thickness of the light extraction layer; the aperture of the nano holes in the nano hole array is 20nm, and the hole spacing between two adjacent nano holes is 100nm; the preparation of the nanopore array in the light extraction layer comprises the following steps: coating an aluminum nitride layer by using a pulling method to obtain aluminum nitride with a nanosphere array on the surface, wherein in the process, silicon dioxide nanospheres are used as masks, and the concentration of a nanosphere aqueous solution adopted in coating is 10wt%; etching the aluminum nitride layer with the nano ball array on the surface by utilizing an ICP etching technology to obtain the aluminum nitride layer with the nano hole array, and cleaning the aluminum nitride layer with the nano hole array in a photoresist removing solution and a configured HF acid solution after etching to obtain a light extraction layer with one side provided with the nano hole array; the active layer sequentially comprises In along the growth direction 0.35 Ga 0.65 N layer, al 0.3 Ga 0.7 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.24 Ga 0.76 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.2 Ga 0.8 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.17 Ga 0.83 N barrier layer, GaN layer, in 0.35 Ga 0.65 N layer, al 0.14 Ga 0.86 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.12 Ga 0.88 N barrier layer, gaN layer and In 0.35 Ga 0.65 An N layer; each In 0.35 Ga 0.65 The thickness of the N layer is 8nm, the thickness of each GaN layer is 10nm, al 0.3 Ga 0.7 N barrier layer, al 0.24 Ga 0.76 N barrier layer, al 0.2 Ga 0.8 N barrier layer, al 0.17 Ga 0.83 N barrier layer, al 0.14 Ga 0.86 N barrier layer, al 0.12 Ga 0.88 The thickness of the N barrier layers was 3nm.
In this embodiment, the InP/InGaAs nanowire coating is prepared by: (1) Introducing trimethylindium to grow for 60s under the conditions that the temperature in the reaction chamber is 330 ℃ and the pressure is 100Torr, and then introducing phosphane to grow for 480s under the condition that trimethylindium is continuously introduced; in the step (1), hydrogen is used as carrier gas to be introduced into trimethyl indium and phosphane, the flow rate of the carrier gas is 1500sccm, the flow rate of the trimethyl indium is 60sccm, and the flow rate of the phosphane is 32sccm; (2) Stopping introducing trimethyl indium, then stopping introducing phosphane after the temperature in the reaction chamber is raised to 410 ℃, and simultaneously introducing trimethyl indium, trimethyl gallium and arsine for 180 seconds to obtain an InP/InGaAs nanowire coating with the thickness of 100 nm; in step (2), the pressure in the reaction chamber is maintained at 100Torr; in the step (2), trimethylindium, trimethylgallium and arsine are introduced by taking hydrogen as carrier gas, wherein the flow rate of the carrier gas is 1500sccm, the molar flow rate of the trimethylindium is 2.79 mu mol/min, the molar flow rate of the trimethylgallium is 0.274 mu mol/min, and the molar flow rate of the arsine is 91.92 mu mol/min.
Example 4
Example 4 is substantially the same as example 2 except that:
the light extraction layer in this embodiment is an aluminum nitride layer, and no nanopore array is formed on a side of the aluminum nitride, which is close to the active layer.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that:
the substrate in this comparative example was a single crystal silicon substrate having a thickness of 400 μm, and aluminum was not doped in the single crystal silicon substrate.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that:
the active layers are arranged differently, and the active layers in this comparative example are sequentially: first AlGaN-GaN barrier layer, in 0.15 Ga 0.85 N quantum well layer, second AlGaN-GaN barrier layer, in 0.15 Ga 0.85 N quantum well layer, third AlGaN-GaN barrier layer, in 0.15 Ga 0.85 N quantum well layer, fourth AlGaN-GaN barrier layer, in 0.15 Ga 0.85 N quantum well layer, fifth AlGaN-GaN barrier layer, in 0.15 Ga 0.85 An N quantum well layer, a sixth GaN barrier layer; wherein the first AlGaN-GaN barrier layer comprises Al with thickness of 3nm 0.1 Ga 0.9 An N barrier layer, an AlGaN barrier layer with a thickness of 7nm and an Al component which is continuously reduced from 0.1 to 0 along the growth direction, and a GaN barrier layer with a thickness of 5 nm; the second AlGaN-GaN barrier layer comprises Al with thickness of 4nm 0.08 Ga 0.92 An N barrier layer, an AlGaN barrier layer with a 6nm Al composition decreasing from 0.08 to 0 continuously along the growth direction, and a GaN barrier layer with a 5nm thickness; the third AlGaN-GaN barrier layer comprises Al with thickness of 5nm 0.06 Ga 0.94 An N barrier layer, an AlGaN barrier layer with a thickness of 5nm and an Al component with a thickness of 5nm continuously reduced from 0.06 to 0 along the growth direction, and a GaN barrier layer with a thickness of 5 nm; the fourth AlGaN-GaN barrier layer comprises Al with thickness of 6nm 0.04 Ga 0.96 An N barrier layer, an AlGaN barrier layer with a thickness of 4nm and an Al component with a thickness of 5nm, the AlGaN barrier layer being continuously reduced from 0.04 to 0 along the growth direction; the fifth AlGaN-GaN barrier layer comprises Al with thickness of 7nm 0.02 Ga 0.98 An N barrier layer, an AlGaN barrier layer with a thickness of 5nm and an Al component with a thickness of 5nm continuously reduced from 0.02 to 0 along the growth direction, and a GaN barrier layer with a thickness of 5 nm; in (In) 0.15 Ga 0.85 The thicknesses of the N quantum well layers are 5nm, and the thicknesses of the sixth GaN barrier layers are 15nm.
The light emitting chip in this comparative example is significantly inferior in light emitting efficiency and stability to the light emitting chip in embodiment 1 of the present invention; possible, areThe reason is that the active layer In embodiment 1 of the present invention sequentially includes In the growth direction 0.35 Ga 0.65 N layer, al 0.3 Ga 0.7 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.24 Ga 0.76 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.2 Ga 0.8 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.17 Ga 0.83 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.14 Ga 0.86 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.12 Ga 0.88 N barrier layer, gaN layer and In 0.35 Ga 0.65 The N layer, the arrangement of the active layer in embodiment 1 of the present invention has a higher energy band bending, which is helpful to enhance the confinement effect of electrons and holes in the quantum well, and the Al component in the active layer in embodiment 1 of the present invention is higher, which is helpful to reduce defect density and improve crystal quality, and in addition, the arrangement of the active layer in embodiment 1 of the present invention can effectively prevent the inward leakage of carriers, thereby reducing the influence of leakage current, which is also helpful to improve the light emitting efficiency and stability of the light emitting chip; the light-emitting chip prepared by the embodiment 1 of the invention can obtain higher light-emitting efficiency and lower leakage current, and has higher stability and reliability.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that:
the light emitting chip in this comparative example does not include the InP/InGaAs nanowire coating, i.e., the light emitting chip in this comparative example includes a substrate, a first semiconductor layer, an active layer, and a second semiconductor layer in this order along the growth direction; the light emitting chip further comprises a first electrode electrically connected to the first semiconductor layer and a second electrode electrically connected to the second semiconductor layer; the first semiconductor layer is an n-type GaN layer, the n-type dopant is silicon, and the thickness of the first semiconductor layer is 500nm; the second semiconductor layer is a p-type GaN layer, the p-type dopant is magnesium, and the thickness of the second semiconductor layer is 150nm.
In this comparative example, the substrate was doped with aluminumAnd the content of doped aluminum in the substrate increases from the side away from the first semiconductor layer to the side close to the first semiconductor layer; the preparation of the substrate comprises the following steps: cleaning and drying monocrystalline silicon with the thickness of 400 mu m, coating an aluminum doping source solution on one side of the monocrystalline silicon, performing heat treatment at 900 ℃ for 50min, and naturally cooling to obtain a substrate doped with aluminum; the aluminum doping source solution takes absolute ethyl alcohol as a solvent and aluminum trichloride hexahydrate as a solute; the concentration of aluminum trichloride in the aluminum doping source solution is 0.08mol/L, and the coating thickness of the aluminum doping source solution is 400nm; the active layer sequentially comprises In along the growth direction 0.35 Ga 0.65 N layer, al 0.3 Ga 0.7 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.24 Ga 0.76 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.2 Ga 0.8 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.17 Ga 0.83 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.14 Ga 0.86 N barrier layer, gaN layer, in 0.35 Ga 0.65 N layer, al 0.12 Ga 0.88 N barrier layer, gaN layer and In 0.35 Ga 0.65 An N layer; each In 0.35 Ga 0.65 The thickness of the N layer is 8nm, the thickness of each GaN layer is 10nm, al 0.3 Ga 0.7 N barrier layer, al 0.24 Ga 0.76 N barrier layer, al 0.2 Ga 0.8 N barrier layer, al 0.17 Ga 0.83 N barrier layer, al 0.14 Ga 0.86 N barrier layer, al 0.12 Ga 0.88 The thickness of the N barrier layers was 3nm.
The chips obtained in examples 1 to 4 and comparative examples 1 to 3 were fabricated to have a size of 45×45mil, and the optical power was measured at a current of 350mA, and the optical power results were shown in table 1; the invention also carries out 1000h aging test under normal temperature and 350mA current, and the result of the 1000h optical power maintenance rate is shown in table 1.
TABLE 1
As can be seen from the results in table 1, the substrate doped with aluminum, the active layer and the coating layer (InP/InGaAs nanowire coating) are provided, so that the light-emitting chip with the coating layer is provided with high light-emitting efficiency, good stability and reliability, the light power of the light-emitting chip with the coating layer in embodiments 1 to 4 of the present invention is as high as 489mW or more, and the light power maintenance rate of 1000h is not lower than 99%, which indicates that the light-emitting chip with the coating layer in the present invention has high light-emitting efficiency, good stability and reliability, and long service life; the light power value of the chip is measured to be larger, so that the luminous efficiency of the chip is higher, the light power maintenance rate of 1000h is measured to be higher, the stability and the reliability of the chip are better, and the service life is longer.
The invention is not described in detail in a manner known to those skilled in the art.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A light emitting chip with a coating, characterized by:
the light-emitting chip with the coating comprises a substrate, a first semiconductor layer, an active layer, a coating and a second semiconductor layer in sequence along the growth direction;
the light emitting chip with the coating layer further comprises a first electrode electrically connected with the first semiconductor layer and a second electrode electrically connected with the second semiconductor layer;
the substrate is doped with aluminum, and the content of the doped aluminum in the substrate increases gradually from the side away from the first semiconductor layer to the side close to the first semiconductor layer;
the active layer comprises a plurality of quantum well layers and a plurality of quantum barrier layers which are alternately stacked along the growth direction, wherein the quantum well layers are one more than the quantum barrier layers; the quantum well layer is In x Ga 1-x N layer, x is more than or equal to 0.3 and less than or equal to 0.4, in x Ga 1-x The value of x in the N layers is unchanged;
the quantum barrier layer is Al y Ga 1-y N barrier layer/GaN barrier layer, y is more than or equal to 0.1 and less than or equal to 0.3, each Al y Ga 1-y The value of y in the N barrier layer is unchanged, and two adjacent Al layers y Ga 1-y The value of y in the N barrier layer is decreased along the growth direction, and the decreasing rate is 10-20%;
the coating is an InP/InGaAs nanowire coating.
2. The coated light emitting chip of claim 1 wherein the InP/InGaAs nanowire coating is grown on the basis of an active layer by a metal organic compound vapor deposition process, the InP/InGaAs nanowire coating growth comprising the steps of:
(1) Introducing trimethyl indium to grow for 30-120 s under the conditions that the temperature in the reaction chamber is 300-400 ℃ and the pressure is 50-200 Torr, and then introducing phosphane to grow for 120-600 s under the condition that trimethyl indium is continuously introduced;
(2) Stopping introducing trimethyl indium, then, after the temperature in the reaction chamber is raised to 400-450 ℃, stopping introducing phosphane, and then, simultaneously introducing trimethyl indium, trimethyl gallium and arsine for growing for 30-240 s, thereby obtaining the InP/InGaAs nanowire coating.
3. The coated light emitting chip of claim 2, wherein:
in the step (1), the volume flow ratio of the trimethylindium to the phosphane is (1.5-2): 1, a step of; and/or
In the step (2), the molar flow ratio of the trimethylindium, the trimethylgallium and the arsine is (8-12): 1: (320-350).
4. The coated light emitting chip of claim 2, wherein:
in the growth process of the step (1) and the step (2), hydrogen and/or nitrogen is used as carrier gas, and the flow rate of the carrier gas is 400-2000 sccm.
5. The coated light emitting chip of claim 1, wherein:
the Al is y Ga 1-y The N barrier layer/GaN barrier layer is made of Al y Ga 1-y The N barrier layer and the GaN barrier layer are arranged layer by layer, and the Al y Ga 1-y An N barrier layer arranged on the In x Ga 1-x And the N layer is arranged between the GaN barrier layer.
6. The coated light-emitting chip of claim 5, wherein:
the Al is y Ga 1-y The thickness of the N barrier layer is 2-5 nm, the thickness of the GaN barrier layer is 5-20 nm, and the In x Ga 1-x The thickness of the N layer is 5-20 nm.
7. The coated light emitting chip of claim 1, wherein:
the preparation of the substrate comprises the following steps: and cleaning and drying the monocrystalline silicon, coating an aluminum doping source solution on one side of the monocrystalline silicon, performing heat treatment at 700-1100 ℃ for 30-120 min, and cooling to obtain the substrate doped with aluminum.
8. The coated light emitting chip of claim 7, wherein:
The aluminum doping source solution takes absolute ethyl alcohol as a solvent and aluminum trichloride as a solute; the coating thickness of the aluminum doping source solution is 100-500 nm, and the concentration of aluminum trichloride in the aluminum doping source solution is 0.01-0.1 mol/L.
9. The coated light-emitting chip according to any one of claims 1 to 8, wherein:
the thickness of the substrate is 300-500 mu m;
the thickness of the first semiconductor layer is 100-1000 nm;
the thickness of the second semiconductor layer is 50-500 nm; and/or
The thickness of the active layer is 50-200 nm.
10. The method of manufacturing a light-emitting chip with a coating layer according to any one of claims 1 to 9, characterized in that the method of manufacturing comprises the steps of:
(a) Preparing the substrate;
(b) Sequentially growing the first semiconductor layer, the active layer, the coating layer and the second semiconductor layer on the substrate;
(c) And arranging the first electrode which is electrically connected on the first semiconductor layer, and arranging the second electrode which is electrically connected on the second semiconductor layer to obtain the light-emitting chip with the coating.
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| US20080296148A1 (en) * | 2007-06-04 | 2008-12-04 | National Tsing Hua University | Method for fabricating concentration-gradient high-frequency ferromagnetic films |
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