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CN114141615A - High-quality semiconductor epitaxial wafer and preparation method thereof - Google Patents

High-quality semiconductor epitaxial wafer and preparation method thereof Download PDF

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CN114141615A
CN114141615A CN202111427469.XA CN202111427469A CN114141615A CN 114141615 A CN114141615 A CN 114141615A CN 202111427469 A CN202111427469 A CN 202111427469A CN 114141615 A CN114141615 A CN 114141615A
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闫其昂
王国斌
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Jiangsu Third Generation Semiconductor Research Institute Co Ltd
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Abstract

本发明公开了一种高质量半导体外延片及其制备方法。所述制备方法包括：提供包含均匀分散纳米材料的III族金属有机源混合前驱体，并涂覆于衬底上得到III族金属有机源混合前驱体涂覆层，之后进行退火重结晶得到应力释放缓冲层；再生长形成半导体外延结构，制得高质量半导体外延片。本发明在衬底上制备金属有机源涂覆层，同时结合MOCVD反应腔退火重结晶，纳米材料分散的金属有机源涂覆层逐步形成两种晶核分布提供成核中心，外延层应力逐步释放，加强侧向外延生长，抑制外延层位错密度延伸，降低缺陷密度，提高量子阱发光层生长质量，改善漏电性能和发光效率，同时提高发光波长均匀性，可满足适用于Micro‑LED外延均匀性能要求。

Figure 202111427469

The invention discloses a high-quality semiconductor epitaxial wafer and a preparation method thereof. The preparation method includes: providing a group III metal-organic source mixed precursor containing uniformly dispersed nanomaterials, coating it on a substrate to obtain a group III metal-organic source mixed precursor coating layer, and then performing annealing and recrystallization to obtain stress relief. A buffer layer; re-growth to form a semiconductor epitaxial structure, and a high-quality semiconductor epitaxial wafer is obtained. The invention prepares the metal organic source coating layer on the substrate, and combines with MOCVD reaction chamber annealing and recrystallization, the metal organic source coating layer with dispersed nano materials gradually forms two kinds of crystal nuclei distribution to provide nucleation centers, and the stress of the epitaxial layer is gradually released. , strengthen the lateral epitaxial growth, suppress the extension of the dislocation density of the epitaxial layer, reduce the defect density, improve the growth quality of the quantum well light-emitting layer, improve the leakage performance and luminous efficiency, and at the same time improve the uniformity of the luminous wavelength, which can meet the requirements of the Micro-LED epitaxy uniformity performance requirements.

Figure 202111427469

Description

High-quality semiconductor epitaxial wafer and preparation method thereof
Technical Field
The invention relates to a high-quality semiconductor epitaxial wafer and a preparation method thereof, belonging to the technical field of semiconductor material epitaxy.
Background
The III-V group compound semiconductor material is applied to photoelectronic devices, photoelectric integration, ultra-high-speed microelectronic devices, ultra-high-frequency microwave devices and circuits and has wide prospect. Since the III group nitride generally carries out heteroepitaxy on a sapphire or SiC heterogeneous substrate and the like, the crystal lattice between different materials is normal and thermal mismatch can generate dislocation or defect, and the dislocation extends upwards along with the growth of the epitaxial layer, the dislocation is expressed as a non-radiative recombination center when the device works to influence the efficiency of the device, and simultaneously, the dislocation is used as a leakage channel to cause the increase of leakage current so as to lead the rapid aging of the device, influence the working efficiency and the service life of the device and restrict the application of the III group nitride in the field of semiconductor electronics; in addition, with the unprecedented development of the Micro-LED display application field, higher demand is put on the uniformity of the epitaxy.
Disclosure of Invention
The invention mainly aims to provide a high-quality semiconductor epitaxial wafer and a preparation method thereof based on the problem of heterogrowth epitaxial defect of the conventional semiconductor material, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a high-quality semiconductor epitaxial wafer, which comprises the following steps:
providing a mixed precursor of a group III metal organic source containing uniformly dispersed nanomaterial;
coating the mixed precursor of the III-group metal organic source on a substrate to obtain a coating of the mixed precursor of the III-group metal organic source, then placing the substrate with the coating of the mixed precursor of the III-group metal organic source in an MOCVD reaction chamber, introducing the III-group metal organic source, and annealing and recrystallizing in a mixed atmosphere of a V-group element source and a reducing gas to form uniformly distributed nano materials and III-V group compound nano growth structures to obtain a stress release buffer layer;
and growing and forming a semiconductor epitaxial structure on the stress release buffer layer to obtain the high-quality semiconductor epitaxial wafer.
In some embodiments, the nanomaterial comprises a combination of any one or more of a zero-dimensional nanomaterial, a one-dimensional nanomaterial, a two-dimensional nanomaterial, and a three-dimensional nanomaterial.
In some embodiments, the group III metal organic source comprises a group III element including any one or a combination of two or more of indium, gallium, and aluminum.
Further, the group V element source includes any one or a combination of two or more of nitrogen, phosphorus, and arsenic.
Further, the preparation method further comprises the following steps: and growing an unintended doped nitride layer, an n-type nitride layer, a light emitting layer, an electron blocking layer and a p-type nitride layer on the stress release buffer layer in sequence to obtain the high-quality semiconductor epitaxial wafer.
The embodiment of the invention also provides a high-quality semiconductor epitaxial wafer prepared by the method, which comprises a substrate, wherein a stress release buffer layer and a semiconductor epitaxial structure are sequentially formed on the substrate; the stress release buffer layer is formed by annealing and recrystallizing a III-group metal organic source mixed precursor coating layer covered on the surface of the substrate.
Further, the high-quality semiconductor epitaxial wafer comprises a substrate and a stress relief buffer layer, an unintentional doped nitride layer, an n-type nitride layer, a light emitting layer, an electron blocking layer and a p-type nitride layer which are sequentially arranged on the substrate.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and is embodied in the following aspects:
the invention provides an epitaxial wafer obtained by spin-coating a metal organic source with uniformly dispersed nano materials and a preparation method thereof.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart illustrating a process for fabricating a high-quality led epitaxial structure according to an exemplary embodiment of the present invention.
Fig. 2 is a schematic view of a layered structure of an epitaxial structure of a high-quality light emitting diode according to an exemplary embodiment of the present invention.
Description of reference numerals: the LED comprises a substrate 1, a stress release buffer layer 2, an unintended doped nitride layer 3, an n-type nitride layer 4, a light emitting layer 5, an InGaN quantum well layer 51, a GaN quantum barrier layer 52, an electronic barrier layer 6 and a p-type nitride layer 7.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. Based on the embodiments of the present invention, those skilled in the art should understand that: the technical scheme of each embodiment can be modified, or part of technical features can be equivalently replaced; and these modifications or substitutions do not make the essence of the corresponding technical solution depart from the spirit and scope of the technical solution of the embodiments of the present invention, and all other embodiments obtained without inventive labor fall within the scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures. Meanwhile, in the description of the present invention, the directional terms and the sequence terms, etc. are used only for distinguishing the description, and are not to be construed as indicating or implying relative importance.
The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiment of the invention provides a high-quality semiconductor epitaxial wafer, which comprises a substrate, wherein a stress release buffer layer and a semiconductor epitaxial structure are sequentially formed on the substrate; the stress release buffer layer is formed by annealing and recrystallizing a III-group metal organic source mixed precursor coating layer covered on the surface of the substrate.
Further, the thickness of the metal organic source coating layer is 20 nm-2000 nm.
Further, the nano material includes, but is not limited to, any one or combination of zero-dimensional nano material, one-dimensional nano material, two-dimensional nano material and three-dimensional nano material.
Another aspect of the embodiments of the present invention provides a method for preparing a high-quality semiconductor epitaxial wafer, including:
providing a mixed precursor of a group III metal organic source containing uniformly dispersed nanomaterial;
coating the mixed precursor of the III-group metal organic source on a substrate to obtain a coating of the mixed precursor of the III-group metal organic source, then placing the substrate with the coating of the mixed precursor of the III-group metal organic source in an MOCVD reaction chamber, introducing the III-group metal organic source, and annealing and recrystallizing in a mixed atmosphere of a V-group element source and a reducing gas to form uniformly distributed nano materials and III-V group compound nano growth structures to obtain a stress release buffer layer;
and growing and forming a semiconductor epitaxial structure on the stress release buffer layer to obtain the high-quality semiconductor epitaxial wafer.
In some embodiments, the nanomaterials include, but are not limited to, any one or combination of more of zero-dimensional nanomaterials, one-dimensional nanomaterials, two-dimensional nanomaterials, three-dimensional nanomaterials, and the like.
Further, the mass ratio of the nano material to the III group metal organic source in the mixed precursor is less than 1: 1.
In some embodiments, the nano material may be a nano particle, and preferably may be any one or a combination of two or more of a metal nano material, a non-metal inorganic nano material, an organic compound nano material, and the like, and a plurality of nano particles coexist in the dispersion liquid without reacting with each other and still exist in the dispersion liquid as separate nano particles.
Further, the form of the nanomaterial may be any one or a combination of two or more of nanoparticles, nanowires, nanofilms, nanobubbles, and the like, but is not limited thereto.
In some embodiments, the nanomaterial (i.e., nanoparticles) may be Si3N4、SiO2、GaN、AlN、InN、SiC、ScAlN、Al2O3、Si、C、TiC、TiN、WC、WC-CO、B4C、BN、TiB2、LaF3、MoS2、ZrB2、ZnS、ZnSe、ZnO、Fe3O4、Ta2O5、SnO2、TiO2、ZrO2Ni, Au, Ag, Fe, Co, Mn, Ti, Mg, Al, Ga, In, polystyrene, perovskite,Graphene, etc., may be any one or a combination of two or more of them, but is not limited thereto, and may be any other possible nanoparticles.
Further, the nano material may preferably include SiN, SiO2、GaN、AlN、InN、SiC、ScAlN、Al2O3、Si、C、TiC、TiN、BN、ZnS、ZnSe、ZnO、TiO2And any one or a combination of two or more of Ni, Au, Ag, Fe, Co, Mn, Ti, Mg, Al, graphene, and the like.
Still further, the nanomaterial may preferably include SiN, GaN, AlN, SiC, ScAlN, Al2O3、TiO2Any one or a combination of two or more of Ni, Al, Ga, graphene, and the like.
Furthermore, the diameter of the nano material is 5-500 nm.
In some embodiments, the group III metal organic source comprises a group III element including any one or a combination of two or more of indium (In), gallium (Ga), and aluminum (Al).
Further, the group III metal organic source includes a group III organic compound source including any one of an indium source, a gallium source, and an aluminum source or a combination of two or more thereof.
Wherein, the indium (In) source comprises one or a combination of two or more of trimethyl indium, triethyl indium and dimethyl ethyl indium, the gallium (Ga) source comprises one or a combination of two or more of trimethyl gallium (TMG), triethyl gallium and triisopropyl gallium, and the aluminum source comprises any one or a combination of two or more of trimethyl aluminum, triethyl aluminum, dimethyl alkyl aluminum, dimethyl aluminum hydride and alane complex, but is not limited thereto.
In some embodiments, the group V element source includes a group V element including any one or a combination of two or more of nitrogen (N), phosphorus (P), and arsenic (As).
Further, the group V element source includes any one or a combination of two or more of a nitrogen source, a phosphorus source, and an arsenic source.
Wherein the nitrogen source comprises NH3Organic amine compounds, trap compounds and the likeAny one or a combination of two or more of (a) and (b), but not limited thereto. Wherein the organic amine compound may be an alkylamine such as t-butylamine, n-propylamine, etc., and the trap compound may be a dimethyl trap, but is not limited thereto.
Wherein the phosphorus source comprises PH3And/or an organophosphorous source including, but not limited to, tert-butylphosphorus.
Wherein the arsenic source comprises AsH3And/or an organic arsenic source including, but not limited to, tert-butyl arsenic.
Further, the reducing gas preferably includes H2But is not limited thereto.
Further, the flow ratio of the V group element source to the reducing gas in the mixed atmosphere is 10: 1-100: 1.
Further, the thickness of the III-group metal organic source mixed precursor coating layer is 20-2000 nm.
In some embodiments, the method of making further comprises: and growing an unintended doped nitride layer, an n-type nitride layer, a light emitting layer, an electron blocking layer and a p-type nitride layer on the stress release buffer layer in sequence to obtain the high-quality semiconductor epitaxial wafer.
Further, the substrate may be sapphire, silicon carbide, silicon, zinc oxide, gallium nitride, gallium arsenide, or the like, but is not limited thereto.
In some embodiments, the method for preparing a mixed group III metal-organic source precursor with uniformly dispersed nanomaterials by spin coating on a substrate comprises the steps of:
1) preparation of nanomaterial dispersion
Adding the nano material into a dispersing solvent for mixing, adding a dispersing agent to prevent the spontaneous agglomeration phenomenon of the nano particles due to high surface energy, and uniformly dispersing the nano particles in the solvent to form nano material dispersion liquid under the ultrasonic condition at a certain temperature;
2) preparation of mixed precursors of group III metal organic sources containing homogeneously dispersed nanomaterials
Separating the nano material from the solvent, quickly drying, mixing the nano material with a proper amount of a III-group metal organic source, and obtaining a III-group metal organic source mixed precursor containing the uniformly dispersed nano material under the ultrasonic condition at a certain temperature;
3) spin coating of mixed group III metal organic source precursors containing uniformly dispersed nanomaterials
And spin-coating a III-group metal organic source mixed precursor containing uniformly dispersed nano materials on the substrate to obtain a III-group metal organic source mixed precursor coating layer.
Specifically, the step 2) specifically comprises the following steps: uniformly mixing the nano material and the III-group metal organic source, and carrying out ultrasonic treatment at 5-40 ℃ for 10-60 min to obtain the III-group metal organic source mixed precursor containing uniformly dispersed nano material.
Specifically, before the step 1), uniformly dispersing the nano material in a dispersing solvent, performing ultrasonic treatment to form a nano material dispersion liquid, then separating the nano material from the dispersing solvent, and drying, wherein the dispersing solvent comprises ethanol, and the ultrasonic treatment time is 0.5-2 h; the nano material dispersion liquid also comprises a dispersing agent.
Further, the high-quality semiconductor epitaxial wafer is a Light Emitting Diode (LED) epitaxial wafer.
In some more specific embodiments, referring to fig. 1, the method for preparing the high-quality light emitting diode epitaxial wafer specifically includes the following steps:
1) providing a substrate, which may be sapphire, silicon carbide, silicon, zinc oxide or gallium nitride;
2) in a glove box N2In the atmosphere, spin-coating a III-group metal organic source mixed precursor containing uniformly dispersed nano materials on a substrate by adopting a spin-coating method, and forming a III-group metal organic source mixed precursor coating layer with the thickness of 20-2000 nm on the substrate;
3) placing the substrate with the group III metal organic source mixed precursor coating layer into a reaction chamber of MOCVD growth equipment, and growing an epitaxial layer by adopting an epitaxial growth process as follows:
placing a substrate with a mixed precursor coating of a group III metal organic source in a reaction chamber of MOCVD growth equipment, introducing the group III metal organic source under the pressure of 100-600 torr in the reaction chamber, heating the reaction chamber to 500-1200 ℃, introducing a group V element source and reducing gas for annealing and recrystallization for 10-100 s, and then growing to obtain a stress release buffer layer with the thickness of 10-100 nm;
4) growing an unintentional doped nitride layer with the thickness of 1-4 mu m on the stress release buffer layer, wherein the unintentional doped nitride layer is an unintentional doped GaN layer, a Ga source required by growth is a TMG source, and the growth atmosphere is H2The growth temperature is 1000-1200 ℃, and the growth pressure is 100-600 torr;
5) growing an n-type nitride layer with the thickness of 1-4 mu m on the unintended doped nitride layer, wherein the n-type nitride layer is an n-type GaN layer, and the doping concentration of Si is 2 multiplied by 1018 cm-3～5×1019cm-3(ii) a The Ga source required by the growth is TMG source, and the growth atmosphere is H2The growth temperature is 1000-1200 ℃, and the growth pressure is 100-600 torr;
6) growing a light emitting layer on the N-type nitride layer, wherein the light emitting layer is grown by 1-20 pairs of InGaN/GaN multiple quantum well light emitting layers In a co-growth mode, each InGaN/GaN multiple quantum well light emitting layer comprises an InGaN quantum well layer and a GaN quantum barrier layer which are periodically and repeatedly grown In an alternating mode, the repetition period is 1-20, the thickness of each InGaN quantum well layer is 2-6 nm, a Ga source required by growth is a TEG source, an In source is a TMIn source, and the growth atmosphere is N2The growth temperature is 700-900 ℃, and the growth pressure is 200-500 torr; the thickness of the GaN quantum barrier layer is 6-20 nm, the Ga source required by growth is a TEG source, and the growth atmosphere is H2The growth temperature is 750-950 ℃, and the growth pressure is 200-500 torr;
7) growing an electron blocking layer with the thickness of 15-150 nm on the luminous layer, wherein the electron blocking layer is a p-type AlGaN electron blocking layer, a Ga source required by growth is a TMG source, an Al source is a TMAl source, and the growth atmosphere is N2The growth temperature is 950-1050 ℃ and the growth pressure is 100-200 torr；
8) Growing a p-type nitride layer with the thickness of 20-200 nm on the electron blocking layer, wherein the p-type nitride layer is a p-type GaN layer, and the doping concentration of Mg is 1 multiplied by 1018 em-3～5×1020cm-3(ii) a The Ga source required by the growth is TMG source, and the growth atmosphere is H2The growth temperature is 950-1050 ℃ and the growth pressure is 200-600 torr.
Another aspect of embodiments of the present invention also provides a high-quality semiconductor epitaxial wafer prepared by the foregoing method.
Specifically, the high-quality semiconductor epitaxial wafer comprises a substrate, wherein a stress release buffer layer and a semiconductor epitaxial structure are sequentially formed on the substrate; the stress release buffer layer is formed by annealing and recrystallizing a III-group metal organic source mixed precursor coating layer covered on the surface of the substrate.
Further, the high-quality semiconductor epitaxial wafer is a Light Emitting Diode (LED) epitaxial wafer.
Further, the thickness of the group III metal organic source mixed precursor coating layer is 20 nm-2000 nm.
Further, the high-quality semiconductor epitaxial wafer comprises a substrate and a stress relief buffer layer, an unintentional doped nitride layer, an n-type nitride layer, a light emitting layer, an electron blocking layer and a p-type nitride layer which are sequentially arranged on the substrate.
Further, the substrate may be sapphire, silicon carbide, silicon, zinc oxide, gallium nitride, gallium arsenide, or the like, but is not limited thereto.
Further, the unintentionally doped nitride layer is an unintentionally doped GaN layer with a thickness of 1-4 μm.
Further, the n-type nitride layer is an n-type GaN layer with the thickness of 1-4 mu m, and the doping concentration of Si is 2 multiplied by 1018em-3～5×1019cm-3。
Further, the light emitting layer is an InGaN/GaN multi-quantum well light emitting layer, the InGaN/GaN multi-quantum well light emitting layer comprises InGaN quantum well layers and GaN quantum barrier layers which are periodically and repeatedly and alternately grown, the repetition period is 1-20, the thickness of the InGaN quantum well layers is 2-6 nm, and the thickness of the GaN quantum barrier layers is 6-20 nm.
Furthermore, the electron blocking layer is a p-type AlGaN electron blocking layer with the thickness of 15-150 nm.
Further, the p-type nitride layer is a p-type GaN layer with the thickness of 20-200 nm, and the doping concentration of Mg is 1 multiplied by 1018 cm-3～5×1020cm-3。
Specifically, as shown in fig. 2, the high-quality semiconductor epitaxial wafer of the present invention includes a substrate 1, and a stress relief buffer layer 2, an unintentionally doped nitride layer 3, an n-type nitride layer 4, a light emitting layer 5, an electron blocking layer 6, and a p-type nitride layer 7 sequentially disposed thereon.
The substrate 1 is a sapphire, silicon carbide, silicon, zinc oxide, gallium nitride, gallium arsenide or other material substrate.
Further, the stress release buffer layer 2 is formed by annealing and recrystallizing a group III metal organic source mixed precursor coating layer obtained by spin coating a group III metal organic source mixed precursor containing uniformly dispersed nano materials, wherein the thickness of the group III metal organic source mixed precursor coating layer is 20-2000 nm.
Further, the unintentionally doped nitride layer 3 is an unintentionally doped GaN layer with a thickness of 1-4 μm.
Further, the n-type nitride layer 4 is an n-type GaN layer with a thickness of 1-4 μm, and the doping concentration of Si is 2 × 1018cm-3～5×1019cm-3。
Further, the light emitting layer 5 is a cycle growth 1-20 pairs of InGaN/GaN multiple quantum well light emitting layers, the thickness of the InGaN quantum well layer 51 is 2-6 nm, and the thickness of the GaN quantum barrier layer 52 is 6-20 nm.
Furthermore, the electron blocking layer 6 is a p-type AlGaN electron blocking layer with the thickness of 15-150 nm.
Further, the p-type nitride layer 7 is a p-type GaN layer with a thickness of 20-200 nm, and the doping concentration of Mg is 1 × 1018cm-3～5×1020cm-3。
The technical solutions, implementation processes, principles, and the like of the embodiments of the present invention will be further explained with reference to the embodiments and the accompanying drawings.
Example 1
1) Preparation of Ni nanoparticle dispersion
Adding 30 mass percent of nano Ni powder with the diameter of 30-80 nm into absolute ethyl alcohol, adding 0.15 mass percent of citric acid dispersing agent, and performing ultrasonic treatment for 2 hours at room temperature;
2) preparation of Ni nanoparticle TMG source
Separating the Ni nano particles from the solvent, quickly drying and immediately mixing with a high-purity TMG source, wherein the mass fraction of the Ni nano particles is 40%, and performing ultrasonic treatment at 40 ℃ for 60min to obtain a TMG source mixed precursor for uniformly dispersing the Ni nano particles;
3) spin-coating Ni nanoparticle TMG source mixed precursor
In a glove box N2In the atmosphere, spin-coating a TMG source mixed precursor of the Ni nanoparticles on a sapphire substrate by a spin-coating method of a spin coater at the rotating speed of 4000rpm to form a TMG source mixed precursor coating layer with the thickness of 30nm and uniformly dispersing the Ni nanoparticles on the substrate;
4) growth of LED epitaxial wafer on TMG source mixed precursor coating layer
Putting a substrate 1 with a TMG source mixed precursor coating layer for dispersing Ni nano particles into an MOCVD reaction chamber, setting the pressure to be 500torr, introducing a TMG source, heating to be 1060 ℃, and introducing NH3And H2Annealing and recrystallizing for 10s, NH3And H2The flow ratio of the GaN layer to the buffer layer is 10: 1, and a GaN stress release buffer layer 2 is grown;
② on the GaN stress release buffer layer 2, under the conditions of 1080 deg.C of temperature and 200torr of growth pressure, an unintentional doped nitride layer 3 with a thickness of 4 μm is grown, and is an unintentional doped GaN layer, the required Ga source is TMG source, and the growth atmosphere is H2An atmosphere;
thirdly, an n-type nitride layer 4 with a thickness of 1 μm is grown on the unintentionally doped nitride layer 3 at a temperature of 1060 ℃ and a growth pressure of 200torr, the n-type nitride layer is an n-type GaN layer, and the doping concentration of Si is 8 x 1018 cm-3Required for growthThe Ga source of (A) is TMG source, and the growth atmosphere is H2An atmosphere;
fourthly, on the N-type nitride layer 4, a light emitting layer 5 is grown, 6 pairs of InGaN/GaN multiple quantum well light emitting layers are repeatedly grown, the thickness of an InGaN quantum well layer 51 is 3nm, the growth temperature is 750 ℃, the growth pressure is 200torr, and the growth atmosphere is switched to N2Atmosphere, the thickness of the GaN quantum barrier layer 52 is 11nm, the growth temperature is 810 ℃, and the growth atmosphere is switched to H2The atmosphere, the growth pressure is 200torr, the Ga source required by growth is TEGa, and the In source is TMIn;
fifthly, growing an electron blocking layer 6 with the thickness of 25nm on the InGaN/GaN multi-quantum well light-emitting layer 5 at the temperature of 950 ℃ and the growth pressure of 200torr, wherein the electron blocking layer is a p-type A1GaN electron blocking layer, the Ga source required by growth is a TMG source, the Al source is TMAl, and the growth atmosphere is N2An atmosphere;
sixthly, growing a p-type nitride layer 7 with the thickness of 50nm on the electron blocking layer 6 at the temperature of 950 ℃ and the growth pressure of 200torr, wherein the p-type nitride layer is a p-type GaN layer, and the Mg doping concentration is 5 multiplied by 1019 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is switched to H2An atmosphere.
Example 2
1) Preparation of Ni nanoparticle dispersion
Adding 30 mass percent of nano Ni powder with the diameter of 30-80 nm into absolute ethyl alcohol, adding 0.15 mass percent of citric acid dispersing agent, and performing ultrasonic treatment for 2 hours at room temperature;
2) preparation of Ni nanoparticle TMG source
Separating the Ni nano particles from the solvent, quickly drying and immediately mixing with a high-purity TMG source, wherein the mass fraction of the Ni nano particles is 40%, and performing ultrasonic treatment at 40 ℃ for 60min to obtain a TMG source mixed precursor for uniformly dispersing the Ni nano particles;
3) spin-coating Ni nanoparticle TMG source mixed precursor
In a glove box N2In the atmosphere, spin-coating the TMG source mixed precursor of the Ni nanoparticles on the sapphire substrate at the rotation speed of 4000rpm by a spin coating method of a spin coater to form a TMG source mixed precursor coating with the thickness of 800nm and uniformly dispersing the Ni nanoparticles on the substrateA layer;
4) growth of LED epitaxial wafer on TMG source mixed precursor coating layer
Putting a substrate 1 with a TMG source mixed precursor coating layer for dispersing Ni nano particles into an MOCVD reaction chamber, setting the pressure to be 300torr, introducing a TMG source, heating to be 1200 ℃, and introducing NH3And H2Annealing and recrystallizing for 40s, NH3And H2The flow ratio of the GaN layer to the buffer layer is 20: 1, and a GaN stress release buffer layer 2 is grown;
② on the GaN stress release buffer layer 2, under the conditions of 1080 deg.C of temperature and 200torr of growth pressure, an unintentionally doped nitride layer 3 with a thickness of 2.5 μm is grown, and is an unintentionally doped GaN layer, the required Ga source is TMG source, and the growth atmosphere is H2An atmosphere;
thirdly, an n-type nitride layer 4 with a thickness of 2.5 μm is grown on the unintentionally doped nitride layer 3 at a temperature of 1060 ℃ and a growth pressure of 200torr, the n-type nitride layer is an n-type GaN layer, and the doping concentration of Si is 8 x 1018 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is H2An atmosphere;
fourthly, on the N-type nitride layer 4, a light emitting layer 5 is grown, 6 pairs of InGaN/GaN multi-quantum well light emitting layers are repeatedly grown, the thickness of an InGaN quantum well layer 51 is 3nm, the growth temperature is 750 ℃, and the growth atmosphere is switched to N2The growth pressure is 200torr, the thickness of the GaN quantum barrier layer 52 is 11nm, the growth temperature is 810 ℃, and the growth atmosphere is switched to H2The atmosphere, the growth pressure is 200torr, the Ga source required by growth is TEGa, and the In source is TMIn;
fifthly, growing an electron blocking layer 6 with the thickness of 25nm on the InGaN/GaN multi-quantum well light-emitting layer 5 at the temperature of 950 ℃ and the growth pressure of 200torr, wherein the electron blocking layer is a p-type AlGaN electron blocking layer, the Ga source required by the growth is TMG source, the Al source is TMAl source, and the growth atmosphere is N2An atmosphere;
sixthly, growing a p-type nitride layer 7 with the thickness of 50nm on the electron blocking layer 6 at the temperature of 950 ℃ and the growth pressure of 200torr, wherein the p-type nitride layer is a p-type GaN layer, and the Mg doping concentration is 5 multiplied by 1019 cm-3The Ga source required for growth is TMG sourceThe growth atmosphere is switched to H2An atmosphere.
Example 3
1) Preparation of Ni nanoparticle dispersion
Adding 30 mass percent of nano Ni powder with the diameter of 30-80 nm into absolute ethyl alcohol, adding 0.15 mass percent of citric acid dispersing agent, and performing ultrasonic treatment for 2 hours at room temperature;
2) preparation of Ni nanoparticle TMG source
Separating the Ni nano particles from the solvent, quickly drying and immediately mixing with a high-purity TMG source, wherein the mass fraction of the Ni nano particles is 40%, and performing ultrasonic treatment at 25 ℃ for 30min to obtain a TMG source mixed precursor for uniformly dispersing the Ni nano particles;
3) spin-coating Ni nanoparticle TMG source mixed precursor
In a glove box N2In the atmosphere, spin-coating a TMG source mixed precursor of the Ni nanoparticles on a sapphire substrate by a spin-coating method of a spin coater at the rotating speed of 4000rpm to form a TMG source mixed precursor coating layer with the thickness of 1800nm and uniformly dispersing the Ni nanoparticles on the substrate;
4) growth of LED epitaxial wafer on TMG source mixed precursor coating layer
Putting a substrate 1 with a TMG source mixed precursor coating layer for dispersing Ni nano particles into an MOCVD reaction chamber, setting the pressure to be 200torr, introducing a TMG source, heating to be 1200 ℃, and introducing NH3And H2Annealing and recrystallizing for 100s, NH3And H2The flow ratio of the GaN layer to the buffer layer is 50: 1, and a GaN stress release buffer layer 2 is grown;
② on the GaN stress release buffer layer 2, under the conditions of 1080 deg.C of temperature and 200torr of growth pressure, an unintentional doped nitride layer 3 with a thickness of 1 μm is grown, and is an unintentional doped GaN layer, the required Ga source is TMG source, and the growth atmosphere is H2An atmosphere;
thirdly, an n-type nitride layer 4 with a thickness of 4 μm is grown on the unintentionally doped nitride layer 3 at a temperature of 1060 ℃ and a growth pressure of 200torr, the n-type nitride layer is an n-type GaN layer, and the doping concentration of Si is 8 x 1018 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is H2An atmosphere;
fourthly, on the N-type nitride layer 4, a light emitting layer 5 is grown, in order to repeatedly grow 8 pairs of InGaN/GaN multiple quantum well light emitting layers, the thickness of the InGaN quantum well layer 51 is 3nm, the growth temperature is 750 ℃, and the growth atmosphere is switched to N2The growth pressure is 300torr, the thickness of the GaN quantum barrier layer 52 is 11nm, the growth temperature is 810 ℃, and the growth atmosphere is switched to H2The atmosphere, the growth pressure is 300torr, the Ga source required by growth is TEGa, and the In source is TMIn;
fifthly, growing an electron blocking layer 6 with the thickness of 25nm on the InGaN/GaN multi-quantum well light-emitting layer 5 at the temperature of 950 ℃ and the growth pressure of 200torr, wherein the electron blocking layer is a p-type A1GaN electron blocking layer, the Ga source required by growth is a TMG source, the Al source is TMAl, and the growth atmosphere is N2An atmosphere;
sixthly, growing a p-type nitride layer 7 with the thickness of 50nm on the electron blocking layer 6 at the temperature of 950 ℃ and the growth pressure of 200torr, wherein the p-type nitride layer is a p-type GaN layer, and the Mg doping concentration is 5 multiplied by 1019 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is switched to H2An atmosphere.
The surface roughness Ra of the LED epitaxial wafers obtained in the embodiments 1, 2 and 3 is less than 0.7, the thickness uniformity of the epitaxial layers is less than 2%, the half-peak width of 470nm blue light wave in a photoluminescence PL test is less than 18nm, the wavelength uniformity std is less than 1.0nm, and the requirement of miro-LED on the wavelength uniformity can be met.
The experiment shows that the surface defect of the epitaxial wafer is increased from 5 multiplied by 10 along with the increase of the thickness of the unintentional doped nitride layer from the embodiment 1 to the embodiment 38cm-2Down to 1 x 108cm-2Experiments show that as the electroluminescent point-measurement brightness of the epitaxial wafer is increased from 132 to 256 in example 1 and the point-measurement voltage is reduced from 4.5V to 3.2V as the thickness of the n-type nitride layer is increased from 132 to 256 in example 1 to 3 in example 3, the thicknesses of the unintentionally doped nitride layer and the n-type nitride layer can be matched by controlling the annealing recrystallization of the TMG source mixed precursor coating layer in combination with practical application, and different requirements of surface defects and photoelectric properties of the epitaxial wafer are met.
The inventor also takes different uniformly dispersed metal nano-particles (such as Au, Ag, Fe, Co, Mn, Ti, Mg, Al, Ga, In and the like) TMG source precursor layers as stress release buffer layers by spin coating, tests show that the TMG source precursor layers can reduce dislocation density and residual stress when taken as stress release, improve the growth quality of a quantum well luminous layer, improve the electric leakage performance and the luminous efficiency, simultaneously improve the uniformity of luminous wavelength, and can meet the requirement of being suitable for the uniformity performance of Micro-LED epitaxy.
Example 4
1)Si3N4Preparation of nanoparticle dispersions
Adding 10 mass percent of Si with the diameter of 30-80 nm into absolute ethyl alcohol3N4Adding 0.15% citric acid dispersant into the nanometer powder, and performing ultrasonic treatment at room temperature for 30 min;
2)Si3N4preparation of nanoparticle TMG source
Mixing Si3N4Separating the nanoparticles from the solvent, rapidly drying and immediately mixing with a high purity TMG source, Si3N4The mass fraction of the nano particles is 10 percent, and the uniform dispersion Si is obtained by ultrasonic treatment for 30min at 25 DEG C3N4TMG source mixed precursor of nano particles;
3) spin-on Si3N4Nanoparticle TMG source mixed precursor
In a glove box N2In the atmosphere, Si is coated by spin coating at 4000rpm by a spin coater3N4The nano-particle TMG source mixed precursor is coated on a sapphire substrate in a spinning way to form uniformly dispersed Si with the thickness of 80nm on the substrate3N4A TMG source mixed precursor coating layer of nanoparticles;
4) LED epitaxial wafer growth on MO source coating layer
Will have dispersed Si3N4Placing the sapphire substrate of the TMG source mixed precursor coating layer of the nano particles in an MOCVD reaction chamber, setting the pressure to 300torr, introducing the TMG source, heating to 1200 ℃, and introducing NH3And H2Annealing and recrystallizing for 15s, NH3And H2The flow ratio of the GaN layer to the buffer layer is 80: 1, and a GaN stress release buffer layer 2 is prepared;
stress release buffer in GaNOn the strike layer 2, an unintentionally doped nitride layer 3 with a thickness of 3 μm is grown at a temperature of 1080 ℃ and a growth pressure of 200torr, the unintentionally doped nitride layer is an unintentionally doped GaN layer, the required Ga source is a TMG source, and the growth atmosphere is H2An atmosphere;
thirdly, an n-type nitride layer 4 with a thickness of 3 μm is grown on the unintentionally doped nitride layer 3 at a temperature of 1060 ℃ and a growth pressure of 200torr, the n-type nitride layer is an n-type GaN layer, and the doping concentration of Si is 8 x 1018 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is H2An atmosphere;
fourthly, on the N-type nitride layer 4, a light emitting layer 5 is grown, in order to repeatedly grow 6 pairs of InGaN/GaN multiple quantum well light emitting layers, the thickness of the InGaN quantum well layer 51 is 3nm, the growth temperature is 770 ℃, and the growth atmosphere is switched to N2The growth pressure is 300torr, the thickness of the GaN quantum barrier layer 52 is 11nm, the growth temperature is 825 ℃, and the growth atmosphere is switched to H2The atmosphere, the growth pressure is 300torr, the Ga source required by growth is TEGa, and the In source is TMIn;
fifthly, growing an electron blocking layer 6 with the thickness of 15nm on the InGaN/GaN multi-quantum well light-emitting layer 5 at the temperature of 1000 ℃ and the growth pressure of 200torr, wherein the electron blocking layer is a p-type A1GaN electron blocking layer, the Ga source required by growth is a TMG source, the Al source is TMAl, and the growth atmosphere is N2An atmosphere;
sixthly, growing a p-type nitride layer 7 with the thickness of 20nm on the electron blocking layer 6 at the temperature of 950 ℃ and the growth pressure of 300torr, wherein the p-type nitride layer is a p-type GaN layer, and the Mg doping concentration is 5 multiplied by 1019 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is switched to H2An atmosphere.
The thickness uniformity of the epitaxial layer of the LED epitaxial wafer obtained in this example is less than 2%, the half-peak width of the blue light wave at 470nm in photoluminescence PL test is 18.7nm, the wavelength uniformity std is 0.85nm, and the yield of the leakage IR at 0405 chip size test is 98.5%.
Example 5
1)Al2O3Preparation of nanoparticle dispersions
Adding absolute ethyl alcohol, wherein the mass fraction of the absolute ethyl alcohol is 15 percent, and the diameter of the absolute ethyl alcohol is 5 percent0to 200nm of Al2O3Adding 0.15% citric acid dispersant into the nanometer powder, and performing ultrasonic treatment at room temperature for 30 min;
2)Al2O3preparation of nanoparticle TMG source
Mixing Al2O3The nanoparticles are separated from the solvent, quickly dried and immediately mixed with a high purity TMG source, Al2O3The mass fraction of the nano particles is 15 percent, and the uniform dispersion Al is obtained by ultrasonic treatment for 60min at 15 DEG C2O3TMG source mixed precursor of nano particles;
3) spin-on Al2O3Nanoparticle TMG source mixed precursor
In a glove box N2In the atmosphere, Al is coated by spin coating at 2000rpm2O3The nano-particle TMG source mixed precursor is coated on the sapphire substrate 1 in a spinning way, and uniformly dispersed Al with the thickness of 80nm is formed on the substrate2O3A TMG source mixed precursor coating layer of nanoparticles;
4) LED epitaxial wafer growth on MO source coating layer
Will have dispersed Al2O3Placing the sapphire substrate of the TMG source mixed precursor coating layer of the nano particles in an MOCVD reaction chamber, setting the pressure to be 200torr, introducing a TMG source, heating to be 1200 ℃, and introducing NH3And H2Annealing and recrystallizing for 30s, NH3And H2The flow ratio of the GaN layer to the buffer layer is 100: 1, and a GaN stress release buffer layer 2 is prepared;
② on the GaN stress release buffer layer 2, under the conditions of 1080 deg.C of temperature and 200torr of growth pressure, an unintentional doped nitride layer 3 with a thickness of 3 μm is grown, and is an unintentional doped GaN layer, the required Ga source is TMG source, and the growth atmosphere is H2An atmosphere;
thirdly, an n-type nitride layer 4 with a thickness of 3 μm is grown on the unintentionally doped nitride layer 3 at a temperature of 1060 ℃ and a growth pressure of 200torr, the n-type nitride layer is an n-type GaN layer, and the doping concentration of Si is 8 x 1018 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is H2An atmosphere;
n type nitrogenOn the compound layer 4, a light emitting layer 5 was grown by repeating 6 pairs of InGaN/GaN multiple quantum well light emitting layers, the thickness of the InGaN quantum well layer 51 was 3nm, the growth temperature was 730 ℃, and the growth atmosphere was switched to N2The growth pressure is 400torr, the thickness of the GaN quantum barrier layer 52 is 11nm, the growth temperature is 805 ℃, and the growth atmosphere is switched to H2The atmosphere, the growth pressure is 400torr, the Ga source required by growth is TEGa, and the In source is TMIn;
fifthly, growing an electron blocking layer 6 with the thickness of 150nm on the InGaN/GaN multi-quantum well light-emitting layer 5 at the temperature of 1050 ℃ and the growth pressure of 100torr, wherein the electron blocking layer is a p-type AlGaN electron blocking layer, the Ga source required by the growth is TMG source, the Al source is TMAl source, and the growth atmosphere is N2An atmosphere;
sixthly, growing a p-type nitride layer 7 with the thickness of 200nm on the electron blocking layer 6 at the temperature of 1050 ℃ and the growth pressure of 200torr, wherein the p-type nitride layer is a p-type GaN layer, and the Mg doping concentration is 5 multiplied by 1019 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is switched to H2An atmosphere.
Through tests, the photoluminescence PL test of the LED epitaxial wafer obtained in the embodiment has the 470nm blue light wave half-peak width of 18.5nm, the wavelength uniformity std of 0.98nm and the surface defects of 2 multiplied by 108cm-2The different uniformly dispersed nano particle TMG source precursor layers are spin-coated to serve as stress release buffer layers, dislocation density and residual stress can be reduced as stress release, the growth quality of a quantum well light-emitting layer is improved, electric leakage performance and light-emitting efficiency are improved, light-emitting wavelength uniformity is improved, and the requirement of being suitable for Micro-LED epitaxial uniformity performance can be met.
Example 6
1) Preparation of graphene dispersion
Adding 5% by mass of graphene nano powder with the diameter of 300-500 nm into absolute ethyl alcohol, adding 0.15% by mass of citric acid dispersing agent, and performing ultrasonic treatment for 30min at room temperature;
2) preparation of graphene nanoparticle TMG source
Separating the graphene nanoparticles from the solvent, quickly drying and immediately mixing the graphene nanoparticles with a high-purity TMG source, wherein the mass fraction of the graphene nanoparticles is 5%, and performing ultrasonic treatment at 25 ℃ for 45min to obtain a TMG source mixed precursor for uniformly dispersing the graphene nanoparticles;
3) spin-coated graphene nanoparticle TMG source mixed precursor
In a glove box N2In the atmosphere, spin-coating a mixed precursor of a graphene nano particle TMG source on a sapphire substrate by a spin coating method of a spin coater at the rotating speed of 4000rpm to form a TMG source mixed precursor coating layer with the thickness of 2000nm and uniformly dispersing the graphene nano particles on the substrate;
4) LED epitaxial wafer growth on MO source coating layer
Putting a sapphire substrate with a TMG source mixed precursor coating layer for dispersing graphene nanoparticles in an MOCVD reaction chamber, setting the pressure as 100torr, introducing a TMG source, heating to 1200 ℃, and introducing NH3And H2Annealing and recrystallizing for 100s, NH3And H2The flow ratio of the GaN layer to the buffer layer is 50: 1, and a GaN stress release buffer layer 2 is prepared;
② on the GaN stress release buffer layer 2, under the conditions of 1080 deg.C of temperature and 200torr of growth pressure, an unintentional doped nitride layer 3 with a thickness of 3 μm is grown, and is an unintentional doped GaN layer, the required Ga source is TMG source, and the growth atmosphere is H2An atmosphere;
thirdly, an n-type nitride layer 4 with a thickness of 3 μm is grown on the unintentionally doped nitride layer 3 at a temperature of 1060 ℃ and a growth pressure of 200torr, the n-type nitride layer is an n-type GaN layer, and the doping concentration of Si is 8 x 1018 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is H2An atmosphere;
fourthly, on the N-type nitride layer 4, a light emitting layer 5 is grown, in order to repeatedly grow 10 pairs of InGaN/GaN multiple quantum well light emitting layers, the thickness of the InGaN quantum well layer 51 is 6nm, the growth temperature is 800 ℃, and the growth atmosphere is switched to N2The growth pressure is 200torr, the thickness of the GaN quantum barrier layer 52 is 6nm, the growth temperature is 900 ℃, and the growth atmosphere is switched to H2The atmosphere, the growth pressure is 200torr, the Ga source required by growth is TEGa, and the In source is TMIn;
fifth on the InGaN/GaN multi-quantum well light-emitting layer 5Growing an electron barrier layer 6 with a thickness of 25nm as a p-type AlGaN electron barrier layer under the conditions of a temperature of 950 ℃ and a growth pressure of 200torr, wherein a Ga source required by the growth is a TMG source, an Al source is TMAl, and a growth atmosphere is N2An atmosphere;
sixthly, growing a p-type nitride layer 7 with the thickness of 50nm on the electron blocking layer 6 at the temperature of 950 ℃ and the growth pressure of 600torr, wherein the p-type nitride layer is a p-type GaN layer, and the Mg doping concentration is 5 multiplied by 1019 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is switched to H2An atmosphere.
Example 7
1)TiO2Preparation of nanoparticle dispersions
Adding 30 mass percent of TiO with the diameter of 30-80 nm into absolute ethyl alcohol2Adding 0.15 mass percent of citric acid dispersant into the nano powder, and performing ultrasonic treatment for 2 hours at room temperature;
2)TiO2preparation of nanoparticle TMG source
Adding TiO into the mixture2Separating the nanoparticles from the solvent, rapidly drying and immediately mixing with a high purity TMG source, TiO2The mass fraction of the nano particles is 28 percent, and the uniform dispersion TiO is obtained by ultrasonic treatment for 50min at the temperature of 5 DEG C2TMG source mixed precursor of nano particles;
3) spin coating TiO2Nanoparticle TMG source mixed precursor
In a glove box N2In the atmosphere, TiO is coated by spin coating of a spin coater at the rotating speed of 4000rpm2The mixed precursor of the nano-particle TMG source is coated on a sapphire substrate in a spinning way to form uniformly dispersed TiO with the thickness of 2000nm on the substrate2A TMG source mixed precursor coating layer of nanoparticles;
4) LED epitaxial wafer growth on MO source coating layer
Will have dispersed TiO2Placing the sapphire substrate of the TMG source mixed precursor coating layer of the nano particles in an MOCVD reaction chamber, setting the pressure to be 600torr, introducing a TMG source, heating to be 1200 ℃, and introducing NH3And H2Annealing and recrystallizing for 100s, NH3And H2The flow ratio of (1) to (30) to obtain the GaN stress release bufferPunching a layer 2;
the rest of the procedure was the same as in example 6.
Example 5 and example 6 ultraviolet light epitaxial wafers with wavelengths of 400nm and 415nm are respectively prepared, the wavelength uniformity std of the photoluminescence PL test of the LED epitaxial wafers is 0.52 and 0.65nm, the half-peak width is less than 15nm, and the surface defects are 2.2 multiplied by 108cm-2The surface roughness Ra of the epitaxial wafer is less than 0.7.
The inventors also spin-coat different uniformly dispersed metal oxide nanoparticles (e.g., ZnO, Fe)3O4、Ta2O5、SnO2、ZrO2And the like) the TMG source precursor layer is used as a stress release buffer layer, and the dislocation density and the residual stress can be reduced by using the TMG source precursor layer as the stress release, so that the growth quality of a quantum well light-emitting layer is improved, the electric leakage performance and the light-emitting efficiency are improved, the uniformity of the light-emitting wavelength is improved, and the requirement on the uniformity performance of Micro-LED epitaxy can be met.
Example 8
1) Preparation of GaN nanoparticle dispersion
Adding 30% by mass of GaN nano powder with the diameter of 30-80 nm into absolute ethyl alcohol, adding 0.15% by mass of citric acid dispersing agent, and performing ultrasonic treatment for 2 hours at room temperature;
2) preparation of GaN nanoparticle TMG source
Separating the GaN nano particles from the solvent, quickly drying and immediately mixing with a high-purity TMG source, wherein the mass fraction of the GaN nano particles is 24%, and performing ultrasonic treatment at 5 ℃ for 50min to obtain a TMG source mixed precursor for uniformly dispersing the GaN nano particles;
3) spin-coated GaN nanoparticle TMG source mixed precursor
In a glove box N2In the atmosphere, spin-coating a TMG source mixed precursor of the GaN nano particles on a sapphire substrate by a spin-coating method of a spin coater at the rotating speed of 4000rpm to form a TMG source mixed precursor coating layer with the thickness of 2000nm and capable of uniformly dispersing the GaN nano particles on the substrate;
4) LED epitaxial wafer growth on MO source coating layer
Placing a sapphire substrate with a TMG source mixed precursor coating layer for dispersing GaN nano particles onSetting the pressure in the MOCVD reaction chamber to 300torr, introducing a TMG source, heating to 1200 ℃, and introducing NH3And H2Annealing and recrystallizing for 100s, NH3And H2The flow ratio of the GaN layer to the buffer layer is 60: 1, and a GaN stress release buffer layer 2 is prepared;
the rest of the procedure was the same as in example 6.
Example 9
1) Preparation of Si Dispersion
Adding 5% by mass of Si nano powder with the diameter of 5000-800 nm into absolute ethyl alcohol, adding 0.15% by mass of citric acid dispersing agent, and performing ultrasonic treatment for 30min at room temperature;
2) preparation of Si nanoparticle TMG source
Separating Si nanoparticles from a solvent, quickly drying and immediately mixing the Si nanoparticles with a high-purity TMG source, wherein the mass fraction of the Si nanoparticles is 5%, and performing ultrasonic treatment at 25 ℃ for 10min to obtain a TMG source mixed precursor for uniformly dispersing the Si nanoparticles;
3) spin-coated Si nanoparticle TMG source mixed precursor
In a glove box N2In the atmosphere, spin-coating a TMG source mixed precursor of Si nanoparticles on a sapphire substrate by a spin-coating method of a spin coater at the rotating speed of 4000rpm to form a TMG source mixed precursor coating layer with the thickness of 2000nm and uniformly dispersing the Si nanoparticles on the substrate;
4) LED epitaxial wafer growth on MO source coating layer
Putting a sapphire substrate with a TMG source mixed precursor coating layer for dispersing Si nano particles in an MOCVD reaction chamber, setting the pressure to be 500torr, introducing a TMG source, heating to be 1125 ℃, and introducing NH3And H2Annealing and recrystallizing for 10s, NH3And H2The flow ratio of the GaN layer to the buffer layer is 100: 1, and a GaN stress release buffer layer 2 is prepared;
the rest of the procedure was the same as in example 6.
The inventor also spin-coats different uniformly dispersed non-metal nanoparticles (such as C, SiC and B)4C. BN, etc.) TMG source precursor layer as stress release buffer layer for reducing dislocation density and residual stress and improving growth quality of quantum well light-emitting layerThe leakage performance and the luminous efficiency are improved, the uniformity of the luminous wavelength (std is less than 1nm) is improved, the number of particles on the surface of the epitaxial wafer is less than 10, and the defect density is less than 5 multiplied by 108cm-2And the requirement of uniform epitaxial performance of the Micro-LED can be met.
Accordingly, the inventors also tested the effect of using a TMG source precursor layer of uniformly dispersed organic compound nanoparticles, such as polystyrene, as a buffer layer by spin coating, substantially as in the previous examples.
Example 10
1) Preparation of Ni nanoparticle dispersion
Adding 30 mass percent of nano Ni powder with the diameter of 30-80 nm into absolute ethyl alcohol, adding 0.15 mass percent of citric acid dispersing agent, and performing ultrasonic treatment for 2 hours at room temperature;
2) preparation of Ni nanoparticle TMG source
Separating the Ni nano particles from the solvent, quickly drying and immediately mixing with a high-purity TMG source, wherein the mass fraction of the Ni nano particles is 40%, and performing ultrasonic treatment at 40 ℃ for 30min to obtain a TMG source mixed precursor for uniformly dispersing the Ni nano particles;
3) spin-coating Ni nanoparticle TMG source mixed precursor
In a glove box N2In the atmosphere, spin-coating a TMG source mixed precursor of the Ni nanoparticles on a silicon substrate by a spin coating machine at the rotating speed of 4000rpm to form a TMG source mixed precursor coating layer with the thickness of 25nm and uniformly dispersing the Ni nanoparticles on the substrate;
4) LED epitaxial wafer growth on group III metal organic source coating layer
Putting a silicon substrate with a TMG source mixed precursor coating layer for dispersing Ni nano particles into an MOCVD reaction chamber, setting the pressure to be 200torr, introducing a TMG source, heating to be 650 ℃, and introducing AsH3And H2Annealing and recrystallizing for 10s, AsH3And H2The flow ratio of (1) to (15) to obtain GaAsA stress release buffer layer 2;
② in GaAsOn the stress release buffer layer 2, an unintentional doped nitride layer with a thickness of 3 μm is grown at 1200 deg.C under a growth pressure of 100torrLayer 3, which is an unintentionally doped GaN layer, the required Ga source is TMG source, and the growth atmosphere is H2An atmosphere;
thirdly, an n-type nitride layer 4 with a thickness of 3 μm is grown on the unintentionally doped nitride layer 3 at a temperature of 1000 ℃ and a growth pressure of 600torr, the n-type nitride layer is an n-type GaN layer, and the doping concentration of Si is 8 x 1018 Gm-3The Ga source required by the growth is TMG source, and the growth atmosphere is H2An atmosphere;
fourthly, on the N-type nitride layer 4, a light emitting layer 5 is grown, 6 pairs of InGaN/GaN multi-quantum well light emitting layers are repeatedly grown, the thickness of an InGaN quantum well layer 51 is 3nm, the growth temperature is 750 ℃, and the growth atmosphere is switched to N2The growth pressure is 500torr, the thickness of the GaN quantum barrier layer 52 is 11nm, the growth temperature is 810 ℃, and the growth atmosphere is switched to H2The atmosphere, the growth pressure is 500torr, the Ga source required by growth is TEGa, and the In source is TMIn;
fifthly, growing an electron blocking layer 6 with the thickness of 25nm on the InGaN/GaN multi-quantum well light-emitting layer 5 at the temperature of 850 ℃ and the growth pressure of 200torr, wherein the electron blocking layer is a p-type A1GaN electron blocking layer, the Ga source required by growth is a TMG source, the Al source is TMAl, and the growth atmosphere is N2An atmosphere;
sixthly, growing a p-type nitride layer 7 with the thickness of 50nm on the electron blocking layer 6 at the temperature of 950 ℃ and the growth pressure of 200torr, wherein the p-type nitride layer is a p-type GaN layer, and the Mg doping concentration is 5 multiplied by 1019 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is switched to H2An atmosphere.
Example 11
1) Preparation of Ni nanoparticle dispersion
Adding 30 mass percent of nano Ni powder with the diameter of 30-80 nm into absolute ethyl alcohol, adding 0.15 mass percent of citric acid dispersing agent, and performing ultrasonic treatment for 2 hours at room temperature;
2) preparation of Ni nano-particle dimethyl ethyl indium
Separating Ni nano particles from a solvent, quickly drying and immediately mixing the Ni nano particles with a high-purity dimethylethyl indium source, wherein the mass fraction of the Ni nano particles is 40%, and performing ultrasonic treatment at 40 ℃ for 30min to obtain a dimethylethyl indium source mixed precursor for uniformly dispersing the Ni nano particles;
3) spin-coating Ni nanoparticle trimethyl indium source mixed precursor
In a glove box N2In the atmosphere, a spin coating method of a spin coater is used for spin-coating a mixed precursor of the dimethyl ethyl indium source of the Ni nanoparticles on a silicon substrate at the rotating speed of 4000rpm, and a coating layer of the mixed precursor of the dimethyl ethyl indium source with the thickness of 20nm and uniformly dispersed Ni nanoparticles is formed on the substrate;
4) LED epitaxial wafer growth on group III metal organic source coating layer
Putting a gallium arsenide substrate with a dimethyl ethyl indium source mixed precursor coating layer for dispersing Ni nano particles into an MOCVD reaction chamber, setting the pressure to be 400torr, heating to be 500 ℃, and introducing tert-butyl arsenic (TBA) and H2Annealing for recrystallization for 10s, TBA and H2The flow ratio of the InAs stress release buffer layer to the InAs stress release buffer layer is 15: 1, and the InAs stress release buffer layer is prepared by introducing dimethyl ethyl indium;
② on the InAs stress release buffer layer 2, under the conditions of 1000 deg.C of temperature and 600torr of growth pressure, an unintentional doped nitride layer 3 with thickness of 3 μm is grown, and is an unintentional doped GaN layer, the required Ga source is TMG source, and its growth atmosphere is H2An atmosphere;
thirdly, an n-type nitride layer 4 with a thickness of 3 μm is grown on the unintentionally doped nitride layer 3 at a temperature of 1200 ℃ and a growth pressure of 100torr, the n-type nitride layer is an n-type GaN layer, and the doping concentration of Si is 8 x 1018 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is H2An atmosphere;
fourthly, on the N-type nitride layer 4, a light emitting layer 5 is grown, 6 pairs of InGaN/GaN multi-quantum well light emitting layers are repeatedly grown, the thickness of the InGaN quantum well layer 51 is 2nm, the growth temperature is 700 ℃, and the growth atmosphere is switched to N2The growth pressure is 200torr, the thickness of the GaN quantum barrier layer 52 is 20nm, the growth temperature is 950 ℃, and the growth atmosphere is switched to H2The atmosphere, the growth pressure is 200torr, the Ga source required by growth is TEGa, and the In source is TMIn;
fifthly, growing on the InGaN/GaN multi-quantum well light-emitting layer 5 at 950 DEG CUnder the condition of the long pressure of 200torr, an electron blocking layer 6 with the thickness of 25nm is grown and is a p-type A1GaN electron blocking layer, a Ga source required by growth is a TMG source, an Al source is TMAl, and the growth atmosphere is N2An atmosphere;
sixthly, growing a p-type nitride layer 7 with the thickness of 50nm on the electron blocking layer 6 at the temperature of 950 ℃ and the growth pressure of 200torr, wherein the p-type nitride layer is a p-type GaN layer, and the Mg doping concentration is 5 multiplied by 1019 cm-3The Ga source required by the growth is TMG source, and the growth atmosphere is switched to H2An atmosphere.
Example 12
1) Preparation of Ni nanoparticle dispersion
Adding 30 mass percent of nano Ni powder with the diameter of 30-80 nm into absolute ethyl alcohol, adding 0.15 mass percent of citric acid dispersing agent, and performing ultrasonic treatment for 2 hours at room temperature;
2) preparation of Ni nano-particle dimethyl ethyl indium
Separating Ni nano particles from a solvent, quickly drying and immediately mixing the Ni nano particles with high-purity dimethylethyl indium immediately, wherein the mass fraction of the Ni nano particles is 40%, and performing ultrasonic treatment at 20 ℃ for 30min to obtain a dimethylethyl indium source mixed precursor for uniformly dispersing the Ni nano particles;
3) spin-coating Ni nano particle dimethyl ethyl indium mixed precursor
In a glove box N2In the atmosphere, a spin coating method of a spin coater is used for spin-coating a mixed precursor of the dimethyl ethyl indium source of the Ni nanoparticles on a silicon substrate at the rotating speed of 4000rpm, and a coating layer of the mixed precursor of the dimethyl ethyl indium source with the thickness of 100nm and uniformly dispersed Ni nanoparticles is formed on the substrate;
4) LED epitaxial wafer growth on group III metal organic source coating layer
Putting a gallium arsenide substrate with a dimethyl ethyl indium source mixed precursor coating layer for dispersing Ni nano particles into an MOCVD reaction chamber, setting the pressure to be 500torr, introducing dimethyl ethyl indium, heating to be 650 ℃, and introducing tert-butyl phosphorus (TBP) and H2Annealing to recrystallize 100s, TBP and H2The flow ratio is 20: 1, and an InP stress release buffer layer 2 is prepared;
the rest of the procedure was the same as in example 11.
In the above embodiment 10, embodiment 11, and embodiment 12, the nitride LED epitaxial layers are respectively prepared on the GaAs substrate by spin-coating different uniformly dispersed mixed precursor layers of the metal nanoparticle source as stress release buffer layers, because the GaAs substrate has high quality, easy to understand and low cost, and the process is mature, the practicality of the GaAs substrate nitride material is expanded, and the GaAs substrate is easy to p-type dope to improve the light extraction efficiency, compared with the nitride LED prepared by the GaAs substrate using the conventional buffer layer method, the PL test intensity of epitaxy is improved by more than 10 times, and the point measurement luminescence intensity is improved by more than 6 times under the 20mA condition.
Example 13
1) Preparation of Ni nanoparticle dispersion
Adding 30 mass percent of nano Ni powder with the diameter of 30-80 nm into absolute ethyl alcohol, adding 0.15 mass percent of citric acid dispersing agent, and performing ultrasonic treatment for 2 hours at room temperature;
2) preparation of Ni nano particle trimethyl aluminum source
Separating the Ni nanoparticles from the solvent, quickly drying and immediately mixing the Ni nanoparticles with a high-purity trimethyl aluminum source, wherein the mass fraction of the Ni nanoparticles is 45%, and performing ultrasonic treatment at 40 ℃ for 40min to obtain a trimethyl aluminum source mixed precursor for uniformly dispersing the Ni nanoparticles;
3) spin-coating Ni nanoparticle trimethyl aluminum source mixed precursor
In a glove box N2In the atmosphere, spin-coating a Ni nanoparticle trimethyl aluminum source mixed precursor on a sapphire substrate by a spin-coating machine at the rotating speed of 4000rpm to form a 60 nm-thick trimethyl aluminum source mixed precursor coating layer for uniformly dispersing Ni nanoparticles on the substrate;
4) LED epitaxial wafer growth on group III metal organic source coating layer
Putting a sapphire substrate with a trimethyl aluminum source mixed precursor coating layer for dispersing Ni nano particles in an MOCVD reaction chamber, setting the pressure to be 100torr, introducing a trimethyl aluminum source, heating to be 1200 ℃, and introducing NH3And H2Annealing and recrystallizing for 10s, NH3And H2The flow ratio of (A) to (B) is 50: 1Obtaining an AlN stress release buffer layer 2;
the rest of the procedure was the same as in example 11.
Comparative example 1
The comparative example differs from example 1 in that: no Ni nanoparticles were added to the TMG source.
The surface roughness Ra of the epitaxial wafer obtained in the comparative example is 0.8, the thickness uniformity of the epitaxial layer is 2.5%, the half-width of a blue light wave with the wavelength of 470nm in a photoluminescence PL test is 20nm, the wavelength uniformity std is 1.5nm, and the surface defect of the epitaxial wafer is 7 multiplied by 108cm-2The electroluminescence spot measurement luminance was 125, and the spot measurement voltage was 5.2V.
Comparative example 2
The comparative example differs from example 1 in that: the GaN buffer layer is directly epitaxially grown by adopting the conventional MOCVD without adopting TMG source spin coating.
The surface roughness Ra of the epitaxial wafer obtained in the comparative example is 1, the uniformity of the thickness of the epitaxial layer is 3%, the half-peak width of a 470nm blue light wave in a photoluminescence PL test is 22nm, the wavelength uniformity std is 2nm, and the surface defect of the epitaxial wafer is 8 multiplied by 108cm-2The electroluminescence spot measurement luminance was 118, and the spot measurement voltage was 5.9V.
Tests on final manufacturing of LED chips with the same size in embodiment 1, comparative example 1 and comparative example 2 of the invention show that the brightness of embodiment 1 of the invention is improved by more than 2% compared with comparative example 1, and the yield of leakage IR is improved by 4%, and the results are shown in Table 1.
Watch (A)
Figure BDA0003377941020000221
Figure BDA0003377941020000231
According to the invention, different uniformly dispersed metal nanoparticle coating layers are spin-coated, and simultaneously annealing recrystallization is combined with an MOCVD reaction cavity, the metal organic source coating layers dispersed by the nano material gradually form two crystal nucleus distributions to provide a nucleation center, the stress of the epitaxial layer is gradually released, lateral epitaxial growth is enhanced, dislocation density extension of the epitaxial layer is inhibited, the defect density is reduced, the growth quality of a quantum well light-emitting layer is improved, the electric leakage performance and the light-emitting efficiency are improved, the uniformity of the light-emitting wavelength is improved, and the requirement on the uniformity of the extension of the Micro-LED can be met.
It should be understood that the method for preparing an LED epitaxial wafer in the present invention is not limited to the above embodiment, which is a preferred embodiment of the present invention, but it is within the scope of the present invention to epitaxially grow the underlying structure by spin-coating the nanoparticle precursor.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. A method for preparing a high-quality semiconductor epitaxial wafer is characterized by comprising the following steps:
providing a mixed precursor of a group III metal organic source containing uniformly dispersed nanomaterial;
coating the mixed precursor of the III group metal organic source on a substrate (1) to obtain a coating layer of the mixed precursor of the III group metal organic source, then placing the substrate with the coating layer of the mixed precursor of the III group metal organic source in an MOCVD reaction chamber, introducing the III group metal organic source, and carrying out annealing recrystallization in a mixed atmosphere of a V group element source and reducing gas to form uniformly distributed nano materials and III-V group compound nano growth structures to obtain a stress release buffer layer (2);
and growing and forming a semiconductor epitaxial structure on the stress release buffer layer (2) to obtain the high-quality semiconductor epitaxial wafer.
2. The method of claim 1, wherein: the nano material comprises any one or combination of more of a zero-dimensional nano material, a one-dimensional nano material, a two-dimensional nano material and a three-dimensional nano material; and/or the mass ratio of the nano material to the III group metal organic source in the mixed precursor is less than 1: 1; and/or the form of the nanometer material comprises any one or the combination of more than two of nanometer particles, nanometer wires, nanometer films and nanometer blocks; and/or the nano material comprises any one or the combination of more than two of metal nano materials, non-metal inorganic nano materials and organic compound nano materials.
3. The method of claim 2, wherein: the nanomaterial comprises Si3N4、SiO2、GaN、AlN、InN、SiC、ScAlN、Al2O3、Si、C、TiC、TiN、WC、WC-Co、B4C、BN、TiB2、LaF3、MoS2、ZrB2、ZnS、ZnSe、ZnO、Fe3O4、Ta2O5、SnO2、TiO2、ZrO2Any one or combination of more than two of Ni, Au, Ag, Fe, Co, Mn, Ti, Mg, Al, Ga, In, polystyrene, perovskite and graphene; and/or the diameter of the nano material is 5-500 nm.
4. The production method according to claim 3, characterized in that: the nano material comprises SiN and SiO2、GaN、AlN、InN、SiC、ScAlN、Al2O3、Si、C、TiC、TiN、BN、ZnS、ZnSe、ZnO、TiO2Any one or combination of more than two of Ni, Au, Ag, Fe, Co, Mn, Ti, Mg, Al and graphene.
5. The production method according to claim 3, characterized in that: the nanomaterial comprises Si3N4、SiO2、GaN、AlN、SiC、ScAlN、Al2O3、TiO2Any one or combination of more than two of Ni, Al, Ga and graphene;
and/or the group III element contained in the group III metal organic source comprises any one or the combination of more than two of indium, gallium and aluminum; the III group metal organic source comprises a III group organic compound source, and the III group organic compound source comprises any one or a combination of more than two of an indium source, a gallium source and an aluminum source; the indium source comprises any one or the combination of more than two of trimethyl indium, triethyl indium and dimethyl ethyl indium, the gallium source comprises any one or the combination of more than two of trimethyl gallium, triethyl gallium and triisopropyl gallium, and the aluminum source comprises any one or the combination of more than two of trimethyl aluminum, triethyl aluminum, dimethyl alkyl aluminum, dimethyl aluminum hydride and alane complex;
and/or the group V element contained in the group V element source comprises any one or the combination of more than two of nitrogen, phosphorus and arsenic; the V group element source comprises any one or the combination of more than two of a nitrogen source, a phosphorus source and an arsenic source; the nitrogen source comprises NH3Any one or combination of more than two of organic amine compounds and trap compounds; the organic amine compound comprises alkylamine, the alkylamine comprises tert-butylamine and/or n-propylamine, and the trap compound comprises a dimethyl trap; the phosphorus source comprises PH3And/or an organophosphorous source comprising tert-butylphosphorus; the arsenic source comprises AsH3And/or an organic arsenic source comprising tert-butyl arsenic;
and/or the reducing gas comprises H2(ii) a And/or the flow ratio of the V group element source to the reducing gas in the mixed atmosphere is 10: 1-100: 1.
6. The method of claim 1, further comprising: and growing an unintended doped nitride layer (3), an n-type nitride layer (4), a light-emitting layer (5), an electron blocking layer (6) and a p-type nitride layer (7) on the stress release buffer layer (2) in sequence to obtain the high-quality semiconductor epitaxial wafer.
7. The method of claim 6, comprising the steps of:
1) providing a substrate (1), wherein the substrate (1) is sapphire, silicon carbide, silicon, zinc oxide, gallium nitride or gallium arsenide;
2) in N2In the atmosphere, coating the mixed precursor of the III group metal organic source on a substrate (1) by adopting a spin coating method, and forming a coating layer of the mixed precursor of the III group metal organic source with the thickness of 20 nm-2000 nm on the substrate (1);
3) placing a substrate with a mixed precursor coating of a group III metal organic source in a reaction chamber of MOCVD growth equipment, introducing the group III metal organic source under the pressure of 100-600 torr in the reaction chamber, heating the reaction chamber to 500-1200 ℃, introducing a group V element source and reducing gas for annealing and recrystallization for 10-100 s, and then growing to obtain a stress release buffer layer (2) with the thickness of 10-100 nm;
4) growing an unintended doped nitride layer (3) on the stress release buffer layer (2), wherein the unintended doped nitride layer (3) is an unintended doped GaN layer, a Ga source required by growth is a TMG source, and the growth atmosphere is H2The growth temperature is 1000-1200 ℃, and the growth pressure is 100-600 torr;
5) growing an n-type nitride layer (4) on the unintentionally doped nitride layer (3), wherein the n-type nitride layer (4) is an n-type GaN layer, and the doping concentration of Si is 2 x 1018cm-3～5×1019cm-3(ii) a The Ga source required by the growth is TMG source, and the growth atmosphere is H2The growth temperature is 1000-1200 ℃, and the growth pressure is 100-600 torr;
6) growing a light emitting layer (5) on the n-type nitride layer (4), growing 1-20 pairs of InGaN/GaN multi-quantum well light emitting layers In a co-growth mode, wherein the InGaN/GaN multi-quantum well light emitting layers comprise InGaN quantum well layers (51) and GaN quantum barrier layers (52) which are periodically and repeatedly and alternately grown, the thickness of each InGaN quantum well layer (51) is 2-6 nm, a Ga source required by growth is a TEG source, an In source is a TMIn source,growth atmosphere is N2The growth temperature is 700-900 ℃, and the growth pressure is 200-500 torr; the thickness of the GaN quantum barrier layer (52) is 6-20 nm, the Ga source required by growth is a TEG source, and the growth atmosphere is H2The growth temperature is 750-950 ℃, and the growth pressure is 200-500 torr;
7) growing an electron blocking layer (6) on the light emitting layer (5), wherein the electron blocking layer (6) is a p-type AlGaN electron blocking layer, a Ga source required by growth is a TMG source, an A1 source is a TMA1 source, and the growth atmosphere is N2The growth temperature is 950-1050 ℃ and the growth pressure is 100-200 torr;
8) growing a p-type nitride layer (7) on the electron blocking layer (6), wherein the p-type nitride layer (7) is a p-type GaN layer, and the doping concentration of Mg is 1 multiplied by 1018cm-3～5×1020cm-3(ii) a The Ga source required by the growth is TMG source, and the growth atmosphere is H2The growth temperature is 950-1050 ℃ and the growth pressure is 200-600 torr.
8. High quality semiconductor epitaxial wafer produced by the method according to any of claims 1 to 7, comprising a substrate (1), characterized in that: a stress release buffer layer (2) and a semiconductor epitaxial structure are sequentially formed on the substrate (1); the stress release buffer layer (2) is formed by annealing and recrystallizing a III-group metal organic source mixed precursor coating layer coated on the surface of the substrate (1).
9. A high quality semiconductor epitaxial wafer according to claim 8, characterized in that: the high-quality semiconductor epitaxial wafer is a light-emitting diode epitaxial wafer, and the light-emitting diode epitaxial wafer comprises a substrate (1), and a stress release buffer layer (2), an unintended doped nitride layer (3), an n-type nitride layer (4), a light-emitting layer (5), an electron blocking layer (6) and a p-type nitride layer (7) which are sequentially arranged on the substrate.
10. A high quality semiconductor epitaxial wafer according to claim 9, characterized in that: the unintentional doped nitride layer (3) is an unintentional doped GaN layer with the thickness of 1-4 mu m;
and/or the n-type nitride layer (4) is an n-type GaN layer with the thickness of 1-4 mu m, and the doping concentration of Si is 2 multiplied by 1018cm-3～5×1019cm-3：
And/or the light emitting layer (5) is an InGaN/GaN multi-quantum well light emitting layer, the InGaN/GaN multi-quantum well light emitting layer comprises InGaN quantum well layers (51) and GaN quantum barrier layers (52) which are periodically and repeatedly and alternately grown, the repetition period is 1-20, the thickness of the InGaN quantum well layers (51) is 2-6 nm, and the thickness of the GaN quantum barrier layers (52) is 6-20 nm;
and/or the electron blocking layer (6) is a p-type AlGaN electron blocking layer with the thickness of 15-150 nm;
and/or the p-type nitride layer (7) is a p-type GaN layer with the thickness of 20-200 nm, and the doping concentration of Mg is 1 multiplied by 1018cm-3～5×1020cm-3。
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CN115050860A (en) * 2022-06-15 2022-09-13 江苏第三代半导体研究院有限公司 Semiconductor light-emitting structure preparation method and device based on III-group nitride quantum dots
CN115810697A (en) * 2023-02-10 2023-03-17 江西兆驰半导体有限公司 Silicon-based ultraviolet LED epitaxial structure, preparation method thereof and ultraviolet LED
CN116885067A (en) * 2023-09-06 2023-10-13 江西兆驰半导体有限公司 Light-emitting diode epitaxial wafer and preparation method thereof

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CN115050860A (en) * 2022-06-15 2022-09-13 江苏第三代半导体研究院有限公司 Semiconductor light-emitting structure preparation method and device based on III-group nitride quantum dots
CN115050860B (en) * 2022-06-15 2023-09-22 江苏第三代半导体研究院有限公司 Preparation method and device of semiconductor light-emitting structure based on III nitride quantum dots
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