CN116469981A - High-luminous-efficiency light-emitting diode and preparation method thereof - Google Patents
High-luminous-efficiency light-emitting diode and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- 230000004888 barrier function Effects 0.000 claims abstract description 125
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 86
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000001301 oxygen Substances 0.000 claims abstract description 85
- 239000012535 impurity Substances 0.000 claims abstract description 80
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 150000004767 nitrides Chemical group 0.000 claims abstract description 32
- 229910002704 AlGaN Inorganic materials 0.000 claims abstract description 22
- 230000000903 blocking effect Effects 0.000 claims abstract description 15
- 229910002601 GaN Inorganic materials 0.000 claims description 98
- 238000000151 deposition Methods 0.000 claims description 28
- 230000033228 biological regulation Effects 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 20
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 14
- FGUJWQZQKHUJMW-UHFFFAOYSA-N [AlH3].[B] Chemical compound [AlH3].[B] FGUJWQZQKHUJMW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052582 BN Inorganic materials 0.000 claims description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 22
- 230000006798 recombination Effects 0.000 abstract description 11
- 238000005215 recombination Methods 0.000 abstract description 11
- 239000000969 carrier Substances 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 261
- 239000013078 crystal Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 229910052594 sapphire Inorganic materials 0.000 description 12
- 239000010980 sapphire Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 230000007547 defect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 4
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 4
- 230000005428 wave function Effects 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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 system
- H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
- H01L33/325—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen characterised by the doping materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
Abstract
The invention provides a high-light-efficiency light-emitting diode and a preparation method thereof, wherein the high-light-efficiency light-emitting diode comprises a substrate, a buffer layer, an undoped GaN layer, an n-type GaN layer, an active layer, an electron blocking layer and a P-type GaN layer; wherein the active layer comprises a potential well layer and a composite barrier layer which are alternately deposited on the n-type GaN layer according to a preset period, the composite barrier layer comprises an AlGaN barrier layer and an oxygen impurity regulating barrier layer, and the concentration of oxygen impurities in the oxygen impurity regulating barrier layer is not higher than 5E+16 atoms/cm 3 . According to the invention, the oxygen impurity regulating barrier layer with the boron-doped nitride structure is inserted into the composite barrier layer, so that electrons overflow to the P layer GaN layer to be subjected to non-radiative recombination with holes, and the luminous efficiency of carriers of the active layer is improved.
Description
Technical Field
The invention relates to the technical field of photoelectricity, in particular to a high-light-efficiency light-emitting diode and a preparation method thereof.
Background
At present, in the epitaxial deposition process of the GaN-based epitaxial layer, besides intrinsic defects such as nitrogen vacancies, gallium gaps and the like, impurity elements such as C, H, O and the like are introduced into the unintentional doping. The existence of defects and impurity elements occupies original or located positions in a crystal lattice, and the size of impurity atoms is different from the size of atoms occupying the positions, so that the crystal lattice distortion of a material can be caused, the stress state of the material is changed, the existence of donor and acceptor impurities can influence the doping and carrier concentration in the growth of the material, and some impurity elements can also form a compound with other elements to influence the physical and chemical properties of the material.
The active layer is used as a core area of the layer where the light-emitting diode carrier is compounded, the crystal quality is high and low, and the intensity of polarization effect greatly influences the light-emitting efficiency. Currently, an AlGaN material is generally adopted as a barrier layer, so that electrons overflowing to P-type GaN and holes are reduced to generate non-radiative recombination, and the luminous efficiency of the light-emitting diode is improved.
However, in the AlGaN barrier layer, since an Al source is particularly easy to introduce an oxygen impurity element during the manufacturing process and Al has a strong binding energy with O, it is difficult to remove, and it is introduced into the epitaxial layer during the deposition process. In the AlGaN barrier layer, oxygen mainly occupies nitrogen, so that non-radiative recombination of carriers is increased, and the luminous efficiency of the light-emitting diode is reduced.
Disclosure of Invention
Based on this, the present invention is directed to a high light efficiency light emitting diode and a method for manufacturing the same, so as to solve the problems in the prior art.
The first aspect of the invention provides a high-light-efficiency light-emitting diode, which comprises a substrate, and a buffer layer, an undoped GaN layer, an n-type GaN layer, an active layer, an electron blocking layer and a P-type GaN layer which are sequentially deposited on the substrate; the active layer comprises a potential well layer and a composite barrier layer which are alternately deposited on the n-type GaN layer according to a preset period, the composite barrier layer comprises an AlGaN barrier layer and an oxygen impurity regulation barrier layer, the oxygen impurity regulation barrier layer is of a boron-doped nitride structure, and the oxygen impurity regulation potential is of a boron-doped nitride structureThe concentration of oxygen impurities in the barrier layer is not higher than 5E+16 atoms/cm 3 。
The beneficial effects of the invention are as follows: the invention provides a high-light-efficiency light-emitting diode, which is characterized in that an oxygen impurity regulation barrier layer of a boron-doped nitride structure is added into a composite barrier layer, so that the Al component in the composite barrier layer is effectively reduced, and the oxygen in an Al source is further reduced from being brought into a deposited composite barrier layer. In addition, the concentration of oxygen impurities in the oxygen impurity regulating barrier layer is not higher than 5E+16 atoms/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The oxygen impurity concentration of the oxygen impurity regulating barrier layer is low, so that the oxygen occupying nitrogen position is reduced to form shallow donor, and the non-radiative recombination of carriers is increased; the lower oxygen impurity concentration can reduce the polarization effect of the potential well layer caused by stronger electronegativity of oxygen, increase the space wave function separation of electrons and holes, and improve the luminous efficiency of the light-emitting diode. Further, the oxygen impurity regulating barrier layer is of a boron-doped nitride structure, the forbidden bandwidth of boron element in the boron-doped nitride structure is wider, non-radiative recombination of electrons overflowing to the P layer GaN layer and holes is reduced, and the luminous efficiency of carriers of the active layer is improved.
Preferably, the thickness of the composite barrier layer is 1nm-50 nm.
Preferably, the thickness ratio of the AlGaN barrier layer to the oxygen impurity regulation barrier layer is 1:1-1:20.
Preferably, the boron-doped nitride structure is composed of one or more of boron nitride, boron gallium nitride and boron aluminum gallium nitride.
Preferably, the preset period is 1-20.
Preferably, the potential well layer is an InGaN layer, the thickness of the InGaN layer is 1-nm-10 nm, and the in component is 0.01-0.5.
The invention also provides a preparation method for preparing the high-luminous-efficiency light-emitting diode, which comprises the following steps:
providing a substrate;
sequentially depositing a buffer layer, an undoped GaN layer, an n-type GaN layer, an active layer, an electron blocking layer and a P-type GaN layer on the substrate;
wherein the active layer comprises the n-type GaN layers alternately deposited according to a preset periodThe potential well layer and the composite barrier layer comprise an AlGaN barrier layer and an oxygen impurity regulation barrier layer, the oxygen impurity regulation barrier layer is of a boron-doped nitride structure, and the concentration of oxygen impurities in the oxygen impurity regulation barrier layer is not higher than 5E+16 atoms/cm 3 。
Preferably, the deposition growth temperature of the composite barrier layer is 800-1000 ℃.
Preferably, the growth atmosphere in the deposition and growth process of the composite barrier layer is N 2 /H 2 /NH 3 The component ratio of the mixed gas is 1:1:1-1:10:20.
Preferably, the atmosphere pressure for deposition and growth of the composite barrier layer is 50-500 torr.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic diagram of a high-efficiency LED according to the present invention;
FIG. 2 is a schematic diagram of the structure of the active layer in FIG. 1;
fig. 3 is a flowchart of a method for manufacturing a high-efficiency led according to the present invention.
Description of main reference numerals:
10. a substrate; 20. a buffer layer; 30. an undoped GaN layer; 40. an n-type GaN layer; 50. an active layer; 51. a potential well layer; 52. a composite barrier layer; 521. an AlGaN barrier layer; 522. an oxygen impurity modulating barrier layer; 60. an electron blocking layer; 70. and a P-type GaN layer.
The invention will be further described in the following detailed description in conjunction with the above-described figures.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Several embodiments of the invention are presented in the figures. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "mounted" on another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like are used herein for illustrative purposes only.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides a high-light-efficiency light-emitting diode and a preparation method thereof, wherein the high-light-efficiency light-emitting diode comprises a substrate, and a buffer layer, an undoped GaN layer, an n-type GaN layer, an active layer, an electron blocking layer and a P-type GaN layer which are sequentially deposited on the substrate; the active layer comprises a potential well layer and a composite barrier layer which are alternately deposited on the n-type GaN layer according to a preset period, the composite barrier layer comprises an AlGaN barrier layer and an oxygen impurity regulation barrier layer, the oxygen impurity regulation barrier layer is of a boron-doped nitride structure, and the concentration of oxygen impurities in the oxygen impurity regulation barrier layer is not higher than 5E+16 atoms/cm 3 . The electron overflow is reduced through the oxygen impurity regulating barrier layer of the boron-doped nitride structure, the oxygen impurity with low concentration in the oxygen impurity regulating barrier layer can reduce the polarization effect of the potential well layer caused by stronger electronegativity of oxygen, the space wave function separation of electrons and holes is increased, and the luminous efficiency of the light-emitting diode is improved.
Specifically, referring to fig. 1 and 2, the high light efficiency light emitting diode provided by the embodiment of the present invention includes a substrate 10, and a buffer layer 20, an undoped GaN layer 30, an n-type GaN layer 40, an active layer 50, an electron blocking layer 60, and a P-type GaN layer 70 sequentially deposited on the substrate 10; wherein the active layer comprises a push buttonThe potential well layer 51 and the composite barrier layer 52 which are alternately deposited on the n-type GaN layer 40 in a preset period, wherein the composite barrier layer 52 comprises an AlGaN barrier layer 521 and an oxygen impurity regulation barrier layer 522, the oxygen impurity regulation barrier layer is of a boron doped nitride structure, and the concentration of oxygen impurities in the oxygen impurity regulation barrier layer is not higher than 5E+16 atoms/cm 3 。
Specifically, the substrate 10 may be a sapphire substrate or an SiO substrate 2 One of a sapphire composite substrate, a silicon carbide substrate, a gallium nitride substrate and a zinc oxide substrate; the sapphire substrate has the advantages of mature preparation process, high cost performance, easy cleaning and processing, good stability at high temperature and wide application range. Therefore, a sapphire substrate is selected, however, the defect of the epitaxial layer deposited directly on the substrate is easy to extend to the active layer, the active layer is an active layer of the light emitting diode, and the defect extending to the active layer directly affects the light emitting effect, so before depositing the epitaxial layer on the substrate, the buffer layer 20 needs to be deposited on the substrate 10 to reduce the defect on the surface of the sapphire substrate to a certain extent, and in particular, the buffer layer 20 may be an AlN buffer layer with a thickness of 10-15 nm.
The undoped GaN layer 30 is deposited on the buffer layer 20, the thickness of the undoped GaN layer 30 is 1-5 μm, and the thicker undoped GaN layer 30 can reduce the effective release of the compressive stress between the light emitting diodes, improve the crystal quality and reduce the reverse leakage. However, the increase of the GaN layer thickness consumes a large amount of Ga source material, which greatly increases the epitaxial cost of a Light Emitting Diode (LED), so further, in order to achieve both the quality and the production cost of the LED, the thickness of the undoped GaN layer 30 is preferably 2-3 μm.
The main role of the n-type GaN layer 40 in the LED is to further reduce defects between crystals and provide enough electrons for the LED to emit light and to allow the electrons to smoothly move to the active layer 50, and to undergo radiative recombination with holes in the active layer 50; further reducing the defect of the crystal can improve the quality of the crystal, providing enough electrons to be combined with holes in the active layer can effectively improve the overall luminous efficiency of the LED, and the more electrons and holes are combined in radiation, the better the luminous effect of the LED is. Specifically, the thickness of the n-type GaN layer 40 is 2 μm to 3 μm, and the n-type GaN layer can effectively release stress and improve the light emitting efficiency of the light emitting diode.
Specifically, the active layer 50 includes a potential well layer 51 and a composite barrier layer 52 alternately deposited on the n-type GaN layer 40 according to a preset period, optionally, the potential well layer 51 is an InGaN layer, the thickness of the InGaN layer is 1nm to 10nm, and the in composition is 0.01 to 0.5; in addition, the period in which the potential well layer 51 and the composite barrier layer 52 are alternately deposited may be 1 to 20; the thickness of the composite barrier layer 52 is 1nm-50nm, the composite barrier layer 52 comprises an AlGaN barrier layer 521 and an oxygen impurity regulation barrier layer 522, and optionally, the thickness ratio of the AlGaN barrier layer 521 to the oxygen impurity regulation barrier layer 522 is 1:1-1:20. The oxygen impurity regulating barrier layer is of a boron-doped nitride structure, and optionally, the boron-doped nitride structure can be formed by one or a combination of a plurality of boron nitride, boron gallium nitride and boron aluminum gallium nitride, namely, the boron-doped nitride structure can be of a single-layer structure or a multi-layer structure; the concentration of oxygen impurities in the oxygen impurity regulating barrier layer is not higher than 5E+16 atoms/cm 3 。
Specifically, the oxygen impurity regulating barrier layer 522 is in a boron doped nitride structure, which can effectively reduce the Al component in the composite barrier layer 52, and further reduce the oxygen in the Al source from being carried into the deposited composite barrier layer. The concentration of oxygen impurity in the conventional AlGaN barrier layer is 1E+17 atoms/cm 3 ~1E+18atoms/cm 3 In between, the concentration of oxygen impurities in the oxygen impurity regulating barrier layer is controlled to be 5E+16 atoms/cm 3 The following are set forth; oxygen impurities in the composite barrier layer regulate and control the lower oxygen impurity concentration of the barrier layer, so that the oxygen is reduced to occupy nitrogen to form shallow donors, and the non-radiative recombination of carriers is increased. The lower oxygen impurity concentration can reduce the polarization effect of the potential well layer caused by stronger electronegativity of oxygen, increase the space wave function separation of electrons and holes, and improve the luminous efficiency of the light-emitting diode. Further, the forbidden bandwidth of boron element of the oxygen impurity regulation barrier layer is wider, electrons overflowing to the P layer GaN layer and holes are reduced to generate non-radiative recombination, and the luminous efficiency of carriers of the active layer is improved.
The electron blocking layer 60 is Al a In b A GaN layer with a thickness of 10 nm-40 nm, whereinA is a value Fan Wei of 0.005-0.1, b is a value Fan Wei 0.01.01-0.2; the thickness of the P-type GaN layer 70 is 10 nm-50nm, and Mg can be adopted for doping, and the doping concentration of the Mg is 1E+19 atoms/cm 3 ~1E+21atoms/cm 3 。
Referring to fig. 3, a method for manufacturing a light emitting diode with high light efficiency according to an embodiment of the present invention is used for manufacturing the light emitting diode, and specifically, the method for manufacturing a light emitting diode provided by the present invention includes steps S10 to S80.
Step S10, providing a substrate;
specifically, the substrate can be sapphire substrate or SiO 2 One of a sapphire composite substrate, a silicon carbide substrate, a gallium nitride substrate and a zinc oxide substrate. Sapphire is the most commonly used GaN-based LED substrate material at present, and the sapphire substrate has the greatest advantages of mature technology, good stability, easy cleaning and processing and low production cost. Therefore, in this embodiment mode, sapphire is used as a substrate.
Step S20, depositing a buffer layer on a substrate;
specifically, physical vapor deposition (Physical Vapor Deposition, PVD) can be adopted to deposit a buffer layer on the substrate, the thickness of the buffer layer is 15-20 nm, in the embodiment, an AlN buffer layer is adopted, the AlN buffer layer provides a nucleation center with the same orientation as the substrate, stress generated by lattice mismatch between an epitaxial GaN material and the substrate and thermal stress generated by thermal expansion coefficient mismatch are released, a flat nucleation surface is provided for epitaxial growth, and the contact angle of nucleation growth is reduced to enable island-shaped GaN grains to be connected into a plane in a smaller thickness, so that the island-shaped GaN grains are converted into two-dimensional epitaxial growth.
Step S30, preprocessing the substrate on which the buffer layer is deposited.
Specifically, the sapphire substrate on which the buffer layer has been deposited is transferred to a Metal-organic vapor deposition (MOCVD) device, wherein high-purity H can be adopted in the MOCVD device 2 (Hydrogen), high purity N 2 (Nitrogen) high purity H 2 And high purity N 2 One of the mixed gases of (a) is used as carrier gas, highPure NH 3 As N source, trimethylgallium (TMGa) and triethylgallium (TEGa) as gallium source, trimethylindium (TMIn) as indium source, trimethylaluminum (TMAL) as aluminum source, silane (SiH) 4 ) As an N-type dopant, magnesium dicyclopentadiene (CP 2 Mg) as P-type dopant.
Specifically, the substrate on which the buffer layer has been deposited is subjected to a process of H 2 The atmosphere is treated for 1-10 min, the treatment temperature is 1000-1200 ℃, and then nitriding treatment is carried out on the GaN epitaxial layer, so that the crystal quality of the buffer layer is improved, and the crystal quality of the GaN epitaxial layer deposited subsequently can be effectively improved.
In step S40, an undoped GaN layer is deposited on the buffer layer.
After nitriding the substrate on which the buffer layer is deposited, depositing an undoped GaN layer in MOCVD equipment by adopting high-purity NH 3 As an N source, trimethylgallium (TMGa) and triethylgallium (TEGa) as a gallium source; the growth temperature of the undoped GaN layer is 1050-1200 ℃, the pressure is 50-500 torr, and the thickness is 1-5 μm; preferably, the growth temperature of the undoped GaN layer is 1100 ℃, the growth pressure is 150 torr, the growth temperature of the undoped GaN layer is higher, the pressure is lower, the quality of the prepared GaN crystal is better, along with the increase of the thickness of GaN, the compressive stress in the undoped GaN layer can be released through stacking faults, the line defect is reduced, the quality of the crystal is improved, the reverse leakage current is reduced, but the consumption of Ga source materials is larger by improving the thickness of the GaN layer, the epitaxial cost of an LED is greatly improved, and preferably, the growth thickness of the undoped GaN layer is 2-3 mu m, the production cost is saved, and the GaN material has higher crystal quality.
And S50, depositing an n-type GaN layer on the undoped GaN layer.
Specifically, after the undoped GaN layer is deposited, the n-type GaN layer is continuously deposited in MOCVD equipment, optionally, the growth temperature of the n-type GaN layer is 1050 ℃ -1200 ℃, the pressure is 100-600 torr, the thickness is 2-3 mu m, and the doping concentration of Si is 1E+19 atoms/cm 3 ~5E+19atoms/cm 3 . Preferably, the growth temperature of the n-type GaN layer is 1120 ℃, the growth pressure is 100torr, the growth thickness is 2.5 mu m, and the doping concentration of Si is 2.5E+19 atoms/cm 3 Head of a machineThe n-type GaN layer provides sufficient electrons for LED luminescence, and the resistivity of the n-type GaN layer is higher than that of the transparent electrode on the p-GaN layer, so that the n-type GaN layer can be doped with enough Si, the resistivity of the n-type GaN layer can be effectively reduced, the n-type GaN layer can effectively release stress, and the luminous efficiency of the LED is improved.
Step S60, depositing an active layer on the n-type GaN layer.
Specifically, the active layer comprises a potential well layer and a composite barrier layer which are alternately deposited on the n-type GaN layer according to a preset period, the composite barrier layer comprises an AlGaN barrier layer and an oxygen impurity regulating barrier layer, the oxygen impurity regulating barrier layer is of a boron doped nitride structure, and the concentration of oxygen impurities in the oxygen impurity regulating barrier layer is not higher than 5E+16 atoms/cm 3 . Preferably, the deposition period of the potential well layer and the composite barrier layer is 1-20; preferably, the potential well layer is an InGaN layer, the deposition growth temperature of the InGaN layer is 700-900 ℃, the deposition thickness is 1 nm-10 nm, the growth atmosphere pressure is 50-500 torr, and the In component In the InGaN layer is 0.01-0.5. The deposition growth temperature of the composite barrier layer is 800-1000 ℃ and the growth atmosphere is N 2 /H 2 /NH 3 The component ratio of the mixed gas is 1:1:1-1:10:20, and the deposition and growth atmosphere pressure is 50-500 torr. Preferably, the deposition thickness of the composite barrier layer is 1nm-50nm, wherein the thickness ratio of the deposited AlGaN barrier layer to the oxygen impurity regulating barrier layer is 1:1-1:20; the oxygen impurity regulating barrier layer is a boron-doped nitride structure, and optionally, the boron-doped nitride structure is formed by one or a combination of a plurality of boron nitride, boron gallium nitride and boron aluminum gallium nitride.
Specifically, the deposited oxygen impurity regulating barrier layer is of a boron doped nitride structure, so that the Al component in the composite barrier layer can be effectively reduced, the Al source is reduced to be brought into the deposited epitaxial layer, and in addition, the concentration of oxygen impurities in the oxygen impurity regulating barrier layer is controlled to be 5E+16 atoms/cm 3 The following are set forth; oxygen impurities in the composite barrier layer regulate and control the lower concentration of the oxygen impurities of the barrier layer, so that the situation that oxygen mainly occupies nitrogen sites to form shallow donors and cause non-radiative recombination increase of carriers is avoided. The lower oxygen impurity concentration can reduce the polarization effect of the potential well layer caused by stronger electronegativity of oxygen, increase the space wave function separation of electrons and holes,the luminous efficiency of the light emitting diode is improved. Further, the forbidden bandwidth of boron element of the oxygen impurity regulation barrier layer is wider, electrons overflowing to the P layer GaN layer and holes are reduced to generate non-radiative recombination, and the luminous efficiency of carriers of the active layer is improved.
In step S70, an electron blocking layer is deposited on the active layer.
Specifically, the electron blocking layer is Al a In b The thickness of the GaN layer is 10 nm-40 nm, the growth deposition temperature is 900-1000 ℃, the pressure is 100-300 torr, the Al component is 0.005-0.1, and the in component is 0.01-0.2. Preferably, the electron blocking layer has a thickness of 15nm, a growth deposition temperature of 965 ℃ and a pressure of 200torr, the Al component concentration is gradually changed from 0.01 to 0.05 and the in component is 0.01 along the growth direction of the epitaxial layer. The electron blocking layer can not only effectively limit electron overflow, but also reduce blocking of holes, improve injection efficiency of holes to the quantum well, reduce carrier auger recombination, and improve luminous efficiency of the light emitting diode.
In step S80, a P-type GaN layer is deposited on the electron blocking layer.
Specifically, the P-type GaN layer mainly serves to provide holes for the active layer, so that electrons and holes are radiative and combined in the active layer to emit light. The growth temperature of the P-type GaN layer is 900-1050 ℃, the thickness is 10-50 nm, the growth pressure is 100-600 torr, mg is adopted for doping, and the doping concentration is 1 E+10 19 ~1 E+10 21 atoms/cm 3 Too high a Mg doping concentration can damage crystal quality, while too low a doping concentration can affect hole concentration. Preferably, the growth temperature of the P-type GaN layer is 985 ℃, the thickness is 15nm, the growth pressure is 200torr, and the doping concentration of Mg is 2E+10 20 atoms/cm 3 . Meanwhile, for the LED structure with the V-shaped pits, the higher growth temperature of the P-type GaN layer is favorable for combining the V-shaped pits, so that the LED epitaxial wafer with a smooth surface is obtained.
Example 1
In this embodiment, a sapphire substrate is used. Wherein the thickness of the composite barrier layer is 10 nm; the thickness ratio of the AlGaN barrier layer to the oxygen impurity regulating barrier layer is 1:5, a step of; the boron-doped nitride structure is composed of boron nitrideForming; the preset period is 1; the potential well layer is an InGaN layer, the thickness of the InGaN layer is 10nm, and the in component is 0.01. The concentration of oxygen impurity in the boron doped nitride structure is 5E+16 atoms/cm 3 . The deposition growth temperature of the composite barrier layer is 800 ℃. The growth atmosphere in the deposition and growth process of the composite barrier layer is N 2 /H 2 /NH 3 A mixed gas with the component ratio of 1:1:2. The atmosphere pressure for deposition and growth of the composite barrier layer is 150 torr.
Example 2
The light emitting diode in this embodiment is different from the light emitting diode in embodiment 1 in that the thickness of the composite barrier layer is 50nm; the thickness ratio of the AlGaN barrier layer to the oxygen impurity regulating barrier layer is 1:20. The boron-doped nitride structure is composed of boron gallium nitride; the preset period is 20.
Example 3
The light emitting diode in this embodiment is different from the light emitting diode in embodiment 1 in that the thickness of the composite barrier layer is 1nm; the thickness ratio of the AlGaN barrier layer to the oxygen impurity regulating barrier layer is 1:1. The boron-doped nitride structure is composed of boron aluminum gallium nitride; the preset period is 10.
Example 4
The light emitting diode in this embodiment is different from the light emitting diode in embodiment 1 in that the InGaN layer thickness is 5nm and the in composition is 0.05; the concentration of oxygen impurity in the boron doped nitride structure is 2E+16 atoms/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The boron-doped nitride structure is formed by combining boron nitride and boron gallium nitride.
Example 5
The light emitting diode in this embodiment is different from the light emitting diode in embodiment 1 in that the InGaN layer thickness is 1nm and the in composition is 0.03; the concentration of oxygen impurity in the boron doped nitride structure is 1E+16 atoms/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The boron-doped nitride structure is formed by combining boron nitride and boron aluminum gallium nitride.
Example 6
The light emitting diode in this example is different from the light emitting diode in example 1 in that the temperature at which the composite barrier layer is deposited and grown is 850 ℃. The growth atmosphere in the deposition and growth process of the composite barrier layer is N 2 /H 2 /NH 3 A mixed gas with the component ratio of 1:1:1. The atmosphere pressure for the deposition and growth of the composite barrier layer is 50 torr, and the boron-doped nitride structure is formed by combining boron gallium nitride and boron aluminum gallium nitride.
Example 7
The light emitting diode in this example is different from the light emitting diode in example 1 in that the temperature at which the composite barrier layer is deposited and grown is 1000 ℃. The growth atmosphere in the deposition and growth process of the composite barrier layer is N 2 /H 2 /NH 3 A mixed gas with the component ratio of 1:10:20. The atmosphere pressure for the deposition and growth of the composite barrier layer is 500torr, and the boron-doped nitride structure is formed by combining boron nitride, boron gallium nitride and boron aluminum gallium nitride.
Comparative example
The light emitting diode in this comparative example is different from the light emitting diode in embodiment 1 in that in this comparative example, the barrier layer of the active layer is a 10nm AlGaN barrier layer having an oxygen impurity concentration of 1e+17 atoms/cm 3 -1E+18 atoms/cm 3 。
Referring to table 1, the results of comparing the parameters and the corresponding light transmittance of the above examples and comparative examples are shown.
TABLE 1
As can be seen from Table 1, the light-emitting diode epitaxial wafer provided by the invention has the advantage that the photoelectric efficiency is improved by 0.8% -4.5% compared with the light-emitting diode epitaxial wafer prepared by mass production at present.
It should be noted that the foregoing implementation procedure is only for illustrating the feasibility of the present application, but this does not represent that the led of the present application has only a few implementation procedures, and instead, the led of the present application may be incorporated into the feasible implementation of the present application as long as it can be implemented. In addition, in the embodiment of the present invention, the structural part of the high-light-efficiency light-emitting diode corresponds to the part of the method for preparing the high-light-efficiency light-emitting diode according to the present invention, and the specific implementation details are the same, which is not described herein.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The high-light-efficiency light-emitting diode is characterized by comprising a substrate, and a buffer layer, an undoped GaN layer, an n-type GaN layer, an active layer, an electron blocking layer and a P-type GaN layer which are sequentially deposited on the substrate;
the active layer comprises a potential well layer and a composite barrier layer which are alternately deposited on the n-type GaN layer according to a preset period, the composite barrier layer comprises an AlGaN barrier layer and an oxygen impurity regulation barrier layer, the oxygen impurity regulation barrier layer is of a boron-doped nitride structure, and the concentration of oxygen impurities in the oxygen impurity regulation barrier layer is not higher than 5E+16 atoms/cm 3 。
2. The high light efficiency light emitting diode of claim 1, wherein the composite barrier layer has a thickness of 1nm to 50 nm.
3. The high light efficiency light emitting diode of claim 1, wherein the AlGaN barrier layer and the oxygen impurity modulation barrier layer have a thickness ratio of 1:1 to 1:20.
4. The high light efficiency light emitting diode of claim 1, wherein the boron doped nitride structure is comprised of one or more combinations of boron nitride, boron gallium nitride, boron aluminum gallium nitride.
5. The high light efficiency led of claim 1 wherein the predetermined period is 1-20.
6. The high-efficiency light emitting diode of claim 1, wherein the potential well layer is an InGaN layer having a thickness of 1 nm-10 nm and an in composition of 0.01-0.5.
7. A method for manufacturing a high light efficiency light emitting diode according to any one of claims 1 to 6, comprising the steps of:
providing a substrate;
sequentially depositing a buffer layer, an undoped GaN layer, an n-type GaN layer, an active layer, an electron blocking layer and a P-type GaN layer on the substrate;
the active layer comprises a potential well layer and a composite barrier layer which are alternately deposited on the n-type GaN layer according to a preset period, the composite barrier layer comprises an AlGaN barrier layer and an oxygen impurity regulation barrier layer, the oxygen impurity regulation barrier layer is of a boron-doped nitride structure, and the concentration of oxygen impurities in the oxygen impurity regulation barrier layer is not higher than 5E+16 atoms/cm 3 。
8. The method of manufacturing according to claim 7, wherein: the deposition and growth temperature of the composite barrier layer is 800-1000 ℃.
9. The method of manufacturing according to claim 7, wherein: the growth atmosphere in the deposition and growth process of the composite barrier layer is N 2 /H 2 /NH 3 The component ratio of the mixed gas is 1:1:1-1:10:20.
10. The method of manufacturing according to claim 7, wherein: the atmosphere pressure for deposition and growth of the composite barrier layer is 50-500 torr.
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