CN115863503B - Deep ultraviolet LED epitaxial wafer, preparation method thereof and deep ultraviolet LED - Google Patents
Deep ultraviolet LED epitaxial wafer, preparation method thereof and deep ultraviolet LED Download PDFInfo
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Abstract
The invention discloses a deep ultraviolet LED epitaxial wafer and a preparation method thereof, and a deep ultraviolet LED, wherein the deep ultraviolet LED epitaxial wafer comprises a substrate, and a buffer layer, an undoped AlGaN layer, an N-type AlGaN layer, a multiple quantum well layer, an electron blocking layer, a P-type AlGaN layer and a P-type contact layer which are sequentially laminated on the substrate; the P-type contact layer comprises Mg doped B which is sequentially laminated on the P-type AlGaN layer a Al b Ga 1‑a‑b N layer, B x Al y Ga 1‑x‑y N nanocluster layer/Mg doped B x Al y Ga 1‑x‑y N layers of superlattice layers. The deep ultraviolet LED epitaxial wafer provided by the invention can improve the light extraction efficiency of the deep ultraviolet LED epitaxial wafer.
Description
Technical Field
The invention relates to the technical field of photoelectricity, in particular to a deep ultraviolet LED epitaxial wafer, a preparation method thereof and a deep ultraviolet LED.
Background
The LED emission wavelength is determined by the basic band gap of the device active region material, and the LED made of the III-nitride material covers the whole ultraviolet UV-A, UV-B and UV-C regions from approximately 200nm (corresponding to the band gap width of AlN) to 400 nm (corresponding to the band gap width of InGaN). The deep ultraviolet solid light source is widely applied to the fields of sterilization, water quality purification, biochemistry and medicine, high-density optical storage light source, white light illumination, fluorescence analysis system and related information sensing field, air purification equipment, zero emission automobiles and the like.
The activation energy of the deep ultraviolet LED epitaxial wafer Mg acceptor increases linearly with the increase of the Al component, so that the Mg activation efficiency becomes low, and the low hole concentration makes it difficult to form P-type ohmic contact. In order to improve the P-type ohmic contact, a P-type GaN contact layer can be added, but ultraviolet light can be absorbed by the P-type GaN contact layer, the P-type GaN can generate strong ultraviolet absorption, and the absorption factor of the P-type GaN contact layer is increased along with the decrease of the peak wavelength even if the contact layer is thin.
Therefore, in the prior art, for forming good ohmic contact, mg is heavily doped, but the P-type AlGaN layer has poor crystal quality due to the too high Mg doping concentration, and the narrow forbidden bandwidth of Mg increases light absorption and reduces the external quantum efficiency of the deep ultraviolet LED epitaxial wafer. However, the low doping concentration cannot form good ohmic contact, which results in an increase in the operating voltage of the deep ultraviolet LED epitaxial wafer and affects the aging performance thereof.
Disclosure of Invention
The invention aims to solve the technical problem of providing a deep ultraviolet LED epitaxial wafer, which can improve the activation concentration of Mg, improve the current expansion capability, reduce the contact resistance, improve the light extraction efficiency and improve the photoelectric conversion efficiency of the deep ultraviolet LED epitaxial wafer.
The invention also aims to solve the technical problem of providing a preparation method of the deep ultraviolet LED epitaxial wafer, which has simple process and can stably prepare the deep ultraviolet LED epitaxial wafer with good performance.
In order to solve the technical problems, the invention provides a deep ultraviolet LED epitaxial wafer, which comprises a substrate, and a buffer layer, an undoped AlGaN layer, an N-type AlGaN layer, a multiple quantum well layer, an electron blocking layer, a P-type AlGaN layer and a P-type contact layer which are sequentially laminated on the substrate;
the P-type contact layer comprises Mg doped B which is sequentially laminated on the P-type AlGaN layer a Al b Ga 1-a-b N layer, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N superlattice layers;
the Mg doped B laminated on the P-type AlGaN layer a Al b Ga 1-a-b The Mg doping concentration of the N layer is 1 multiplied by 10 19 atoms/cm 3 -1×10 20 atoms/cm 3 ；
The B is x Al y Ga 1-x-y N nanoclustersThe deposition of the layers was accomplished using the following method: introducing a nitrogen source, a boron source, an aluminum source and a gallium source into the reaction chamber, and completing the process of B by using hydrogen, nitrogen and ammonia as growth atmospheres x Al y Ga 1-x-y Depositing an N nano cluster layer;
wherein, 0 < a < 0.45,0 < b < 0.45,0 < x < 0.45,0 < y < 0.45.
In one embodiment, the Mg is doped with B a Al b Ga 1-a-b In the N layer, the component B gradually rises from the direction close to the P-type AlGaN layer to the direction far away from the P-type AlGaN layer;
the Al component gradually decreases from the direction close to the P-type AlGaN layer to the direction far from the P-type AlGaN layer.
In one embodiment, the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The N layers of the superlattice layer are formed by B x Al y Ga 1-x-y N nanocluster layer and Mg-doped B x Al y Ga 1-x-y The N layers are sequentially and alternately laminated, and the repetition period is more than or equal to 1.
In one embodiment, the Mg is doped with B a Al b Ga 1-a-b The thickness of the N layer is 1nm-10 nm;
the B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The thickness of the N layers of the superlattice layers is 1nm-10 nm;
the B is x Al y Ga 1-x-y N nanocluster layer and Mg-doped B x Al y Ga 1-x-y The thickness ratio of the N layers is 1: (1-5).
In one embodiment, the Mg is doped with B a Al b Ga 1-a-b The Mg doping concentration of the N layer is 1 multiplied by 10 19 atoms/cm 3 -1×10 20 atoms/cm 3 ；
The Mg is doped with B x Al y Ga 1-x-y The Mg doping concentration of the N layer is 1 multiplied by 10 20 atoms/cm 3 -1×10 21 atoms/cm 3 。
In order to solve the problems, the invention also provides a preparation method of the deep ultraviolet LED epitaxial wafer, which comprises the following steps:
s1, preparing a substrate;
s2, sequentially depositing a buffer layer, an undoped AlGaN layer, an N-type AlGaN layer, a multiple quantum well layer, an electron blocking layer, a P-type AlGaN layer and a P-type contact layer on the substrate;
the P-type contact layer comprises Mg doped B which is sequentially laminated on the P-type AlGaN layer a Al b Ga 1-a-b N layer, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N layers of superlattice layers, wherein 0 < a < 0.45,0 < b < 0.45,0 < x < 0.45,0 < y < 0.45.
In one embodiment, the Mg is doped with B a Al b Ga 1-a-b The N layer is prepared by the following method:
introducing a nitrogen source, a boron source, an aluminum source, a gallium source and a magnesium source into the reaction chamber, and depositing Mg doped B on the P-type AlGaN layer by using hydrogen and nitrogen as growth atmospheres a Al b Ga 1-a-b And N layers.
In one embodiment, the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The N superlattice layers are prepared by the following steps:
introducing a nitrogen source, a boron source, an aluminum source and a gallium source into the reaction chamber, and completing the process of B by using hydrogen, nitrogen and ammonia as growth atmospheres x Al y Ga 1-x-y Depositing an N nano cluster layer;
introducing a nitrogen source, a boron source, an aluminum source, a gallium source and a magnesium source into the reaction chamber, and completing the Mg doping B by using hydrogen, nitrogen and ammonia as growth atmospheres x Al y Ga 1-x-y Depositing an N layer;
alternately depositing the B x Al y Ga 1-x-y N nanocluster layer and Mg-doped B x Al y Ga 1-x-y N layer to obtain the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N layers of superlattice layers.
In one embodiment, the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y In the deposition process of the N superlattice layers, the temperature in the reaction chamber is 900-1100 ℃;
the pressure in the reaction chamber is 100-300 torr;
in the growth atmosphere, hydrogen: nitrogen gas: ammonia = 1: (5-10): (1-5).
Correspondingly, the invention further provides a deep ultraviolet LED, and the deep ultraviolet LED comprises the deep ultraviolet LED epitaxial wafer.
The implementation of the invention has the following beneficial effects:
the P-type contact layer of the deep ultraviolet LED epitaxial wafer provided by the invention comprises Mg doped B sequentially laminated on the P-type AlGaN layer a Al b Ga 1-a-b N layer, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N layers of superlattice layers. The Mg is doped with B a Al b Ga 1-a-b The N layer can reduce the activation energy of Mg, improve the concentration of activated Mg, and the wider forbidden bandwidth of B, N can reduce the absorption of the P-type contact layer to deep ultraviolet light and reduce the deposition of B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y And the lattice mismatch of N superlattice layers improves the crystal quality. The B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N layers of superlattice layer, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The N-layer superlattice structure is used as a current expansion bridge point, solves the problems of low hole concentration and current expansion deviation caused by low Mg ionization efficiency of the P type, improves the diffusion length of holes of the P type contact layer, improves the expansion capacity of P type current, reduces the accumulation effect of current, improves the ohmic contact between an epitaxial layer and an electrode, reduces the working voltage of a deep ultraviolet LED epitaxial wafer, and improvesAnd the luminous efficiency of the deep ultraviolet LED epitaxial wafer.
Drawings
Fig. 1 is a schematic structural diagram of a deep ultraviolet LED epitaxial wafer provided by the present invention.
Wherein: substrate 1, buffer layer 2, undoped AlGaN layer 3, N-type AlGaN layer 4, multiple quantum well layer 5, electron blocking layer 6, P-type AlGaN layer 7, P-type contact layer 8, mg-doped B a Al b Ga 1-a-b N layers 81 and B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N superlattice layers 82.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and advantages of the present invention more apparent.
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
in the present invention, "preferred" is merely to describe embodiments or examples that are more effective, and it should be understood that they are not intended to limit the scope of the present invention.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, the numerical range is referred to, and both ends of the numerical range are included unless otherwise specified.
In order to solve the above problems, the present invention provides a deep ultraviolet LED epitaxial wafer, as shown in fig. 1, comprising a substrate 1, and a buffer layer 2, an undoped AlGaN layer 3, an N-type AlGaN layer 4, a multiple quantum well layer 5, an electron blocking layer 6, a P-type AlGaN layer 7 and a P-type contact layer 8 sequentially stacked on the substrate 1;
the P-type contact layer 8 comprises Mg doped B sequentially laminated on the P-type AlGaN layer 7 a Al b Ga 1-a-b N layer 81, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N superlattice layers 82, wherein 0 < a < 0.45,0 < b < 0.45,0 < x < 0.45，0＜y＜0.45。
The P-type contact layer 8 of the deep ultraviolet LED epitaxial wafer provided by the invention comprises Mg doped B which is sequentially laminated on the P-type AlGaN layer 7 a Al b Ga 1-a-b N layer 81, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N superlattice layers 82. The Mg is doped with B a Al b Ga 1-a-b The N layer 81 can reduce the activation energy of Mg, improve the concentration of activated Mg, and the wider forbidden bandwidth of B, N can reduce the absorption of the P-type contact layer 8 to deep ultraviolet light and reduce the deposition of B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The lattice mismatch in the N superlattice layer 82 improves crystal quality. The B is x Al y Ga 1-x- y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The N-layer superlattice layer 82 is used as a current expansion bridge point, solves the problems of low hole concentration and current expansion deviation caused by low Mg ionization efficiency of the P-type contact layer, improves the diffusion length of holes of the P-type contact layer, improves the expansion capability of P-type current, reduces the accumulation effect of current, improves the ohmic contact between an epitaxial layer and an electrode, reduces the working voltage of a deep ultraviolet LED epitaxial wafer, and improves the luminous efficiency of the deep ultraviolet LED epitaxial wafer.
In one embodiment, the Mg is doped with B a Al b Ga 1-a-b In the N layer 81, the B component gradually increases from the direction close to the P-type AlGaN layer 7 to the direction away from the P-type AlGaN layer 7; the Al composition gradually decreases from the vicinity of the P-type AlGaN layer 7 to the direction away from the P-type AlGaN layer 7. Preferably, the Mg is doped with B a Al b Ga 1-a-b In the N layer 81, the B composition increases from 0.1 to 0.4 from the vicinity of the P-type AlGaN layer 7 to the direction away from the P-type AlGaN layer 7, and the al composition decreases from 0.45 to 0.2 from the vicinity of the P-type AlGaN layer 7 to the direction away from the P-type AlGaN layer 7.
It should be noted that the activation energy of Mg gradually decreases with the increase of Al component, so that when the Al component doping of the deep ultraviolet P-type contact layer is higher, the concentration of activated Mg is lower, and the current is expandedPoor. The B component and the Al component are distributed according to the rule, so that the activation energy of Mg can be reduced, the concentration of activated Mg is improved, the absorption of the P-type contact layer to deep ultraviolet light can be reduced due to wider forbidden band width of B, N, and the deposition of B with the rear surface can be reduced x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y And the lattice mismatch of N superlattice layers improves the crystal quality.
In one embodiment, the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The N-layer superlattice layer 82 is composed of B x Al y Ga 1-x-y N nanocluster layer and Mg-doped B x Al y Ga 1-x-y The N layers are sequentially and alternately laminated, and the repetition period is more than or equal to 1, namely the superlattice period number is more than or equal to 1. Wherein B is x Al y Ga 1-x-y The N nano-cluster layer is not doped with Mg, the absorption of deep ultraviolet light is reduced, the light reflection is increased by the structure of the N nano-cluster layer, the light emitting efficiency of the deep ultraviolet light is improved, and the Mg is doped with B x Al y Ga 1-x-y The N layer can provide better ohmic contact due to higher activated Mg concentration, and the contact resistance of the deep ultraviolet LED epitaxial wafer is reduced. Preferably, said B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y In the N superlattice layer 82, x is more than 0.1 and less than 0.45,0.1 and y is more than 0.3; more preferably, x is 0.4 and y is 0.2.
Further, mg is doped with B a Al b Ga 1-a-b N layer 81 and B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x- y The proper thickness of the N-layer superlattice layer 82 and the proper number of superlattice periods may reduce the thickness of the P-type contact layer and reduce the absorption of deep ultraviolet light. In one embodiment, the Mg is doped with B a Al b Ga 1-a-b The thickness of the N layer 81 is 1nm-10 nm; the B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The thickness of the N superlattice layer 82 is 1nm-10 nm; the saidB x Al y Ga 1-x-y Thickness of N nanocluster layer: the Mg is doped with B x Al y Ga 1-x-y Thickness of N layer = 1: (1-5). Preferably, the Mg is doped with B a Al b Ga 1-a-b The thickness of the N layer 81 is 7nm; the B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The thickness of the N superlattice layer 82 is 6nm; the B is x Al y Ga 1-x-y Thickness of N nanocluster layer: the Mg is doped with B x Al y Ga 1-x-y Thickness of N layer = 1:2.
in addition, the doping concentration of Mg in a proper range is favorable for current expansion, the current expansion is poor when the doping concentration of Mg is too low, the contact resistance is increased sharply, and the doping concentration is too high, which also causes Mg complex and reduces the activated Mg concentration. In one embodiment, the Mg is doped with B a Al b Ga 1-a-b The N layer 81 has a Mg doping concentration of 1×10 19 atoms/cm 3 -1×10 20 atoms/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The Mg is doped with B x Al y Ga 1-x-y The Mg doping concentration of the N layer is 1 multiplied by 10 20 atoms/cm 3 -1×10 21 atoms/cm 3 . Preferably, the Mg is doped with B a Al b Ga 1-a-b The Mg doping concentration of the N layer 81 is 7×10 19 atoms/cm 3 -8×10 19 atoms/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The Mg is doped with B x Al y Ga 1-x-y The Mg doping concentration of the N layer is 3×10 20 atoms/cm 3 -4×10 20 atoms/cm 3 。
In order to solve the problems, the invention also provides a preparation method of the deep ultraviolet LED epitaxial wafer, which comprises the following steps:
s1, preparing a substrate 1;
in one embodiment, the substrate may be selected from (0001) plane sapphire substrate, alN substrate, si (111) substrate, siC (0001) substrate, and the like. Preferably, the substrate is a sapphire substrate, which is the most commonly used substrate material at present, and has the advantages of mature preparation process, low price, easy cleaning and processing and good stability at high temperature.
S2, a buffer layer 2, an undoped AlGaN layer 3, an N-type AlGaN layer 4, a multiple quantum well layer 5, an electron blocking layer 6, a P-type AlGaN layer 7 and a P-type contact layer 8 are sequentially deposited on the substrate 1.
In one embodiment, the step S2 includes the steps of:
s21, depositing an AlN buffer layer 2 on the substrate 1, wherein the thickness is 20nm-200nm.
Preferably, an AlN buffer layer is deposited in PVD, with a thickness of 100 a nm a. The AlN buffer layer is adopted to provide a nucleation center which is the same as the substrate in orientation, so that stress generated by lattice mismatch between AlGaN and the substrate and thermal stress generated by thermal expansion coefficient mismatch are released, a flat nucleation surface is provided by further growth, the contact angle of nucleation growth is reduced, so that GaN grains growing in an island shape can be connected into a plane in a smaller thickness, the GaN grains are converted into two-dimensional epitaxial growth, the crystal quality of a subsequent deposited AlGaN layer is improved, the dislocation density is reduced, and the radiation recombination efficiency of the multi-quantum well layer is improved.
In one embodiment, a MOCVD (Metal-organic chemical vapor deposition) apparatus, MOCVD (MOCVD for short), is used to obtain high purity H 2 (Hydrogen), high purity N 2 (Nitrogen) high purity H 2 And high purity N 2 Is used as carrier gas, high-purity NH 3 As N source, trimethylgallium (TMGa) and triethylgallium (TEGa) as gallium source, trimethylaluminum (TMAL) as aluminum source, silane (SiH) 4 ) As an N-type dopant, magnesium dicyclopentadiene (CP 2 Mg) as P-type dopant.
S22, depositing an undoped AlGaN layer 3 on the buffer layer 2.
Preferably, the undoped AlGaN layer is deposited on the AlN buffer layer by adopting a metal organic vapor deposition (MOCVD) method, wherein the growth temperature is 1000-1300 ℃, the growth pressure is 50-500 torr, and the thickness is 1-5 mu m.
More preferably, the undoped AlGaN layer is grown at 1200 ℃ under a growth pressure of 100torr and a thickness of 2 μm-3 μm. The undoped AlGaN layer has higher growth temperature and lower pressure, the prepared GaN crystals have better quality, meanwhile, the thickness is increased along with the increase of the AlGaN thickness, the compressive stress can be released through stacking faults, the line defects are reduced, the crystal quality is improved, the reverse leakage current is reduced, but the consumption of MO source (metal organic source) materials by improving the AlGaN layer thickness is larger, and the epitaxial cost of the light-emitting diode is greatly improved, so that the conventional undoped AlGaN epitaxial wafer for the light-emitting diode usually grows to 2-3 mu m, the production cost is saved, and the GaN materials have higher crystal quality.
S23, depositing an N-type AlGaN layer 4 on the undoped AlGaN layer 3.
Preferably, an N-type AlGaN layer is deposited on the undoped AlGaN layer, the growth temperature is 1000-1300 ℃, and the doping concentration is 1 multiplied by 10 19 atoms/cm 3 -5×10 20 atoms/cm 3 The thickness is 1 μm-5 μm.
More preferably, the growth temperature of the N-type AlGaN layer is 1200 ℃, the growth pressure is 100torr, the growth thickness is 2 μm-3 μm, and the Si doping concentration is 2.5X10 19 atoms/cm 3 . Firstly, an N-type doped AlGaN layer provides sufficient electrons and holes for ultraviolet LED luminescence to be combined; secondly, the resistivity of the N-type doped AlGaN layer is higher than that of the transparent electrode on the P-type GaN layer, so that the enough Si doping can effectively reduce the resistivity of the N-type GaN layer; finally, the N-type doped AlGaN layer has enough thickness to effectively release stress and improve the luminous efficiency of the light emitting diode.
And S24, depositing a multi-quantum well layer 5 on the N-type AlGaN layer 4.
Preferably, the multiple quantum well layers are alternately stacked Al m Ga 1-m N quantum well layer and Al n Ga 1-n N quantum barrier layers, and stacking cycle number is 3-15. Wherein Al is m Ga 1-m The growth temperature of the N quantum well layer is 950-1150 ℃, the thickness is 2-5 nm, the growth pressure is 50-300 torr, and the Al component is 0.2-0.6; al (Al) n Ga 1-n The growth temperature of the N quantum barrier layer is 1000-1300 ℃, the thickness is 5-15 nm, the growth pressure is 50-300 torr, and the Al component is 0.4-0.8.
More preferably, the stacking cycle number of the multiple quantum well layers is 9, the Al m Ga 1-m The growth temperature of the N quantum well layer is 1050 ℃ and the thickness of the N quantum well layer is equal to3.5nm, a pressure 200torr, an Al composition of 0.55; the Al is n Ga 1-n The growth temperature of the N quantum barrier layer is 1150 ℃, the thickness is 11nm, the growth pressure is 200torr, and the Al component is 0.7. The multi-quantum well is an electron and hole composite region, and the reasonable structural design can remarkably increase the overlapping degree of electron and hole wave functions, so that the luminous efficiency of the LED device is improved.
And S25, depositing an electron blocking layer 6 on the multiple quantum well layer 5.
Preferably, the electron blocking layer is an AlGaN electron blocking layer with the thickness of 10nm-100nm, the growth temperature of 1000-1100 ℃ and the pressure of 100-300 torr, wherein the Al component is 0.4-0.8.
More preferably, the AlGaN electron blocking layer has a thickness of 30nm, wherein the Al component is 0.75, and the growth temperature is 1050 ℃, and the growth pressure is 200torr. The AlGaN electron blocking layer can not only effectively limit electron overflow, but also reduce blocking of holes, improve injection efficiency of the holes to the quantum well, reduce carrier auger recombination and improve luminous efficiency of the light-emitting diode.
S26, depositing a P-type AlGaN layer 7 on the electron blocking layer 6.
Preferably, the growth temperature of the P-type AlGaN layer is 1000-1100 ℃, the thickness is 20-200 nm, the growth pressure is 100-600 torr, and the doping concentration of Mg is 1X 10 19 atoms/cm 3 -1×10 20 atoms/cm 3 。
More preferably, the growth temperature of the P-type AlGaN layer is 1050 ℃, the thickness is 100nm, the growth pressure is 200torr, and the doping concentration of Mg is 5 multiplied by 10 19 atoms/cm 3 . Too high a Mg doping concentration can damage the crystal quality, while a lower doping concentration can affect the hole concentration. Meanwhile, the P-type doped AlGaN layer can effectively fill up the epitaxial layer to obtain the deep ultraviolet LED epitaxial wafer with a smooth surface.
And S27, depositing a P-type contact layer 8 on the P-type AlGaN layer 7.
The P-type contact layer 8 comprises Mg doped B sequentially laminated on the P-type AlGaN layer 7 a Al b Ga 1-a-b N layer 81, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N-layer superLattice layer 82, wherein 0 < a < 0.45,0 < b < 0.45,0 < x < 0.45,0 < y < 0.45.
In one embodiment, the Mg is doped with B a Al b Ga 1-a-b The N layer is prepared by the following method:
introducing a nitrogen source, a boron source, an aluminum source, a gallium source and a magnesium source into the reaction chamber, and depositing Mg doped B on the P-type AlGaN layer by using hydrogen and nitrogen as growth atmospheres a Al b Ga 1-a-b And N layers.
In one embodiment, the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The N superlattice layers are prepared by the following steps:
introducing a nitrogen source, a boron source, an aluminum source and a gallium source into the reaction chamber, and completing the process of B by using hydrogen, nitrogen and ammonia as growth atmospheres x Al y Ga 1-x-y Depositing an N nano cluster layer;
introducing a nitrogen source, a boron source, an aluminum source, a gallium source and a magnesium source into the reaction chamber, and completing the Mg doping B by using hydrogen, nitrogen and ammonia as growth atmospheres x Al y Ga 1-x-y Depositing an N layer;
alternately depositing the B x Al y Ga 1-x-y N nanocluster layer and Mg-doped B x Al y Ga 1-x-y N layer to obtain the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N layers of superlattice layers.
In one embodiment, the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y In the deposition process of the N superlattice layers, the temperature in the reaction chamber is 900-1100 ℃; the pressure in the reaction chamber is 100-300 torr; in the growth atmosphere, hydrogen: nitrogen gas: ammonia = 1: (5-10): (1-5). Preferably, said B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y In the deposition process of the N superlattice layers, the temperature in a reaction chamber is 1050 ℃; the pressure in the reaction chamber is200torr; in the growth atmosphere, hydrogen: nitrogen gas: ammonia = 1:6:3.
in the above preparation method, the Mg-doped B is used as a growth atmosphere a Al b Ga 1-a-b The N layer growth atmosphere has no ammonia gas, so that nitrogen atoms are prevented from being introduced; the B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y Hydrogen of N-layer superlattice layer: nitrogen gas: ammonia = 1: (5-10): (1-5) the binding energy of Mg-H is low, and the Mg-H can be broken by annealing to activate the Mg.
In terms of growth temperature, the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The growth temperature of the N-layer superlattice layer is 900-1100 ℃, and the higher temperature ensures the crystal quality of the P-type contact layer. The growth pressure is 100-300 torr, the mobility of Mg atoms is improved by low pressure, and the Mg doping is uniform.
Correspondingly, the invention further provides a deep ultraviolet LED, and the deep ultraviolet LED comprises the deep ultraviolet LED epitaxial wafer. The photoelectric efficiency of the deep ultraviolet LED is effectively improved, and other items have good electrical properties.
The invention is further illustrated by the following examples:
example 1
The embodiment provides a deep ultraviolet LED epitaxial wafer, which comprises a substrate, and a buffer layer, an undoped AlGaN layer, an N-type AlGaN layer, a multiple quantum well layer, an electron blocking layer, a P-type AlGaN layer and a P-type contact layer which are sequentially laminated on the substrate;
the P-type contact layer comprises Mg doped B which is sequentially laminated on the P-type AlGaN layer a Al b Ga 1-a-b N layer, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N superlattice layers;
the Mg is doped with B a Al b Ga 1-a-b N layers: the B component is increased from 0.1 to 0.4 from the direction close to the P-type AlGaN layer to the direction far away from the P-type AlGaN layer, and the Al component is increased from the direction close to the P-type AThe lGaN layer is reduced from 0.45 to 0.2 towards the direction far away from the P-type AlGaN layer; the thickness is 7nm; mg doping concentration of 7.5×10 19 atoms/cm 3 。
The B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y In the N layers of superlattice layers: x is 0.4 and y is 0.2; the thickness of the whole layer is 6nm, the B x Al y Ga 1-x-y Thickness of N nanocluster layer: the Mg is doped with B x Al y Ga 1-x-y Thickness of N layer = 1:3, a step of; the superlattice period number is 3; the Mg is doped with B x Al y Ga 1-x-y The doping concentration of the N layer is 3.5X10 20 atoms/cm 3 。
Example 2
The present embodiment provides a deep ultraviolet LED epitaxial wafer, which is different from embodiment 1 in that: the Mg is doped with B a Al b Ga 1-a-b The thickness of the N layer is 10nm; the B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The thickness of the N layers of the superlattice layers is 8nm. The remainder was the same as in example 1.
Example 3
The present embodiment provides a deep ultraviolet LED epitaxial wafer, which is different from embodiment 1 in that: the Mg is doped with B a Al b Ga 1-a-b The thickness of the N layer is 5nm; the B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The thickness of the N layers of the superlattice layers is 4nm. The remainder was the same as in example 1.
Example 4
The present embodiment provides a deep ultraviolet LED epitaxial wafer, which is different from embodiment 1 in that: the B is x Al y Ga 1-x-y Thickness of N nanocluster layer: the Mg is doped with B x Al y Ga 1-x-y Thickness of N layer = 1:1. the remainder was the same as in example 1.
Example 5
The present embodiment provides a deep ultraviolet LED epitaxial wafer, which is different from embodiment 1 in that: the B is x Al y Ga 1-x-y Thickness of N nanocluster layer: the Mg is doped with B x Al y Ga 1-x-y Thickness of N layer = 1:5. the remainder was the same as in example 1.
Example 6
The present embodiment provides a deep ultraviolet LED epitaxial wafer, which is different from embodiment 1 in that: the B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The number of superlattice periods of the N superlattice layers is 5. The remainder was the same as in example 1.
Example 7
The present embodiment provides a deep ultraviolet LED epitaxial wafer, which is different from embodiment 1 in that: x is 0.2 and y is 0.4. The remainder was the same as in example 1.
Example 8
The present embodiment provides a deep ultraviolet LED epitaxial wafer, which is different from embodiment 1 in that: the Mg is doped with B a Al b Ga 1-a-b The Mg doping concentration of the N layer is 1 multiplied by 10 19 atoms/cm 3 . The remainder was the same as in example 1.
Example 9
The present embodiment provides a deep ultraviolet LED epitaxial wafer, which is different from embodiment 1 in that: the Mg is doped with B x Al y Ga 1-x-y The Mg doping concentration of the N layer is 8 multiplied by 10 20 atoms/cm 3 . The remainder was the same as in example 1.
Comparative example 1
The embodiment provides a deep ultraviolet LED epitaxial wafer, which comprises a substrate, and a buffer layer, an undoped AlGaN layer, an N-type AlGaN layer, a multiple quantum well layer, an electron blocking layer, a P-type AlGaN layer and a P-type contact layer which are sequentially laminated on the substrate;
the P-type contact layer is an Mg-doped P-type AlGaN contact layer, and the thickness is 20nm.
The deep ultraviolet LED epitaxial wafers prepared in example 1-example 9 and comparative example 1 were prepared into 15 mil×15 mil chips using the same chip process conditions, 300 LED chips were extracted, and the photoelectric efficiency was tested at 120mA/60mA current. The optical efficiency improvement ratio of example 1-example 9 compared to the comparative example was calculated, and the specific test results are shown in table 1.
TABLE 1 example 1-example 9 Performance test results for deep ultraviolet LEDs
From the above results, the deep ultraviolet LED epitaxial wafer provided by the invention has a P-type contact layer comprising Mg doped B sequentially laminated on the P-type AlGaN layer a Al b Ga 1-a-b N layer, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N layers of superlattice layers. The Mg is doped with B a Al b Ga 1-a-b The N layer can reduce the activation energy of Mg, improve the concentration of activated Mg, and the wider forbidden bandwidth of B, N can reduce the absorption of the P-type contact layer to deep ultraviolet light and reduce the deposition of B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y And the lattice mismatch of N superlattice layers improves the crystal quality. The B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N layers of superlattice layer, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The N-layer superlattice structure is used as a current expansion bridging point, so that the problems of low hole concentration and current expansion deviation caused by low Mg ionization efficiency of a P type are solved, the diffusion length of holes of a P type contact layer is improved, the expansion capacity of P type current is improved, the accumulation effect of current is reduced, the ohmic contact between an epitaxial layer and an electrode is improved, the working voltage of a deep ultraviolet LED epitaxial wafer is reduced, and the luminous efficiency of the deep ultraviolet LED epitaxial wafer is improved.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (10)
1. The deep ultraviolet LED epitaxial wafer is characterized by comprising a substrate, and a buffer layer, an undoped AlGaN layer, an N-type AlGaN layer, a multiple quantum well layer, an electron blocking layer, a P-type AlGaN layer and a P-type contact layer which are sequentially laminated on the substrate;
the P-type contact layer comprises Mg doped B which is sequentially laminated on the P-type AlGaN layer a Al b Ga 1-a-b N layer, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N superlattice layers;
the Mg doped B laminated on the P-type AlGaN layer a Al b Ga 1-a-b The Mg doping concentration of the N layer is 1 multiplied by 10 19 atoms/cm 3 -1×10 20 atoms/cm 3 ；
The B is x Al y Ga 1-x-y The N nanocluster layer is deposited by the following method: introducing a nitrogen source, a boron source, an aluminum source and a gallium source into the reaction chamber, and completing the process of B by using hydrogen, nitrogen and ammonia as growth atmospheres x Al y Ga 1-x-y Depositing an N nano cluster layer;
wherein, 0 < a < 0.45,0 < b < 0.45,0 < x < 0.45,0 < y < 0.45.
2. The deep ultraviolet LED epitaxial wafer of claim 1, wherein Mg is doped with B a Al b Ga 1-a-b In the N layer, the component B gradually rises from the direction close to the P-type AlGaN layer to the direction far away from the P-type AlGaN layer;
the Al component gradually decreases from the direction close to the P-type AlGaN layer to the direction far from the P-type AlGaN layer.
3. The deep ultraviolet LED epitaxial wafer of claim 1, wherein B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The N layers of the superlattice layer are formed by B x Al y Ga 1-x-y N nanocluster layer and Mg-doped B x Al y Ga 1-x-y The N layers are sequentially and alternately laminated, and the repetition period is more than or equal to 1.
4. The deep ultraviolet LED epitaxial wafer of any one of claims 1-3, wherein Mg is doped with B a Al b Ga 1-a- b The thickness of the N layer is 1nm-10 nm;
the B is x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The thickness of the N layers of the superlattice layers is 1nm-10 nm;
the B is x Al y Ga 1-x-y N nanocluster layer and Mg-doped B x Al y Ga 1-x-y The thickness ratio of the N layers is 1: (1-5).
5. The deep ultraviolet LED epitaxial wafer of any one of claims 1-3, wherein Mg is doped with B x Al y Ga 1-x- y The Mg doping concentration of the N layer is 1 multiplied by 10 20 atoms/cm 3 -1×10 21 atoms/cm 3 。
6. A method for preparing the deep ultraviolet LED epitaxial wafer according to any one of claims 1 to 5, comprising the steps of:
s1, preparing a substrate;
s2, sequentially depositing a buffer layer, an undoped AlGaN layer, an N-type AlGaN layer, a multiple quantum well layer, an electron blocking layer, a P-type AlGaN layer and a P-type contact layer on the substrate;
the P-type contact layer comprises Mg doped B which is sequentially laminated on the P-type AlGaN layer a Al b Ga 1-a-b N layer, B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N layers of superlattice layers, wherein 0 < a < 0.45,0 < b < 0.45,0 < x < 0.45,0 < y < 0.45.
7. The method for preparing a deep ultraviolet LED epitaxial wafer according to claim 6, characterized in thatIn that the Mg is doped with B a Al b Ga 1-a-b The N layer is prepared by the following method:
introducing a nitrogen source, a boron source, an aluminum source, a gallium source and a magnesium source into the reaction chamber, and depositing Mg doped B on the P-type AlGaN layer by using hydrogen and nitrogen as growth atmospheres a Al b Ga 1-a-b And N layers.
8. The method for preparing deep ultraviolet LED epitaxial wafer according to claim 6, wherein the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y The N superlattice layers are prepared by the following steps:
introducing a nitrogen source, a boron source, an aluminum source and a gallium source into the reaction chamber, and completing the process of B by using hydrogen, nitrogen and ammonia as growth atmospheres x Al y Ga 1-x-y Depositing an N nano cluster layer;
introducing a nitrogen source, a boron source, an aluminum source, a gallium source and a magnesium source into the reaction chamber, and completing the Mg doping B by using hydrogen, nitrogen and ammonia as growth atmospheres x Al y Ga 1-x-y Depositing an N layer;
alternately depositing the B x Al y Ga 1-x-y N nanocluster layer and Mg-doped B x Al y Ga 1-x-y N layer to obtain the B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y N layers of superlattice layers.
9. The method for preparing deep ultraviolet LED epitaxial wafer according to claim 8, wherein B x Al y Ga 1-x-y N nanocluster layer/Mg doped B x Al y Ga 1-x-y In the deposition process of the N superlattice layers, the temperature in the reaction chamber is 900-1100 ℃;
the pressure in the reaction chamber is 100-300 torr;
in the growth atmosphere, hydrogen: nitrogen gas: ammonia = 1: (5-10): (1-5).
10. A deep ultraviolet LED, characterized in that the deep ultraviolet LED comprises a deep ultraviolet LED epitaxial wafer according to any one of claims 1-5.
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