WO2016197650A1 - Dopant-free algan-based ultraviolet light emitting diode and preparation method thereof - Google Patents

Dopant-free algan-based ultraviolet light emitting diode and preparation method thereof Download PDF

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WO2016197650A1
WO2016197650A1 PCT/CN2016/076851 CN2016076851W WO2016197650A1 WO 2016197650 A1 WO2016197650 A1 WO 2016197650A1 CN 2016076851 W CN2016076851 W CN 2016076851W WO 2016197650 A1 WO2016197650 A1 WO 2016197650A1
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dopant
algan
layer
type
emitting diode
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PCT/CN2016/076851
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French (fr)
Chinese (zh)
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张连
张韵
王军喜
李晋闽
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中国科学院半导体研究所
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
    • H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
    • H01L33/325—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen characterised by the doping materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
    • H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes

Definitions

  • the invention belongs to the field of semiconductor technology and is applicable to AlGaN-based ultraviolet and deep ultraviolet light-emitting diodes, in particular to a non-dopant-based AlGaN-based ultraviolet light-emitting diode and a preparation method thereof, which can obtain n-type conductivity and p without doping any impurities.
  • both the n-type and p-type conductive layers in the blue-green LED of the GaN/InGaN multiple quantum well and the AlGaN-based ultraviolet LED are implemented by introducing dopant impurities.
  • the n-type GaN doping impurity is Si
  • the p-type GaN doping impurity is Mg.
  • Si or Mg atoms it is necessary to dope a large amount of Si or Mg atoms, which will affect the crystal quality of the GaN material and reduce the mobility of electrons or holes.
  • the diffusion of Mg atoms will seriously affect the quality of the quantum well, resulting in a decrease in luminous efficiency.
  • polarization doping utilizes the relationship between the polarization effect of the GaN-based compound and the composition, and obtains a uniformly distributed net-polarized negative charge or a net-polarized positive charge by gradualizing the composition, thereby inducing the generation of free holes or electrons, thereby realizing n Type or p type conductive.
  • the polarization doping method does not rely on thermal ionization, but relies on the polarization electric field brought about by the composition gradient to ionize the electric field of some inherent defects or impurities in the epitaxial material. Therefore, using the method of polarization doping, high conductivity can be achieved without introducing any dopant.
  • the concentration of electrons and holes in the n-type GaN-based material obtained by the polarization doping method is as high as 1E 18 /cm 3 . This concentration of electrons or holes is sufficient to achieve luminescence of the GaN-based LED.
  • the invention provides a non-dopant AlGaN-based ultraviolet light emitting diode, comprising:
  • n-type layer which is fabricated on a substrate
  • a dopant-free p-type layer is formed over the active region.
  • the invention also provides a method for growing a non-dopant AlGaN-based ultraviolet light-emitting diode, comprising:
  • Step 1 take a substrate
  • Step 2 growing a non-dopant n-type layer of a polar or semi-polar surface along the substrate, without introducing any active dopant during the growth process, and inputting the III-group metal organic source material of the growth reaction chamber
  • the flow rate and the flow rate of the metal organic source material gallium are controlled, and the ratio of TMAl/(TMGa+TMAl) in the reaction chamber is controlled to form a composition-graded non-dopant n-type layer, wherein the Al composition gradually satisfies the direction along the polarization electric field. slowing shrieking;
  • Step 3 growing an active region on the non-dopant n-type layer
  • Step 4 growing a non-dopant p-type layer on the active region, without introducing any active dopant during the growth process, and flowing the flow of the group III metal organic source material Al into the growth reaction chamber and the metal organic source material gallium
  • the flow rate is controlled to control the ratio of TMAl/(TMGa+TMAl) in the reaction chamber to form a p-type AlGaN layer with a gradual composition, wherein the gradual increase of the Al composition gradually increases along the direction of the polarization electric field, and the preparation is completed.
  • the beneficial effect of the present invention is that it can improve the quality of the crystal material and simplify the growth step of the material without introducing any dopant.
  • 1 is a cross-sectional view showing the structure of an AlGaN-based ultraviolet light emitting diode without a dopant.
  • FIG. 2 is a flow chart showing the structural change of a non-dopant AlGaN-based ultraviolet light emitting diode structure during growth.
  • FIG. 3 is a graph showing changes in TMAl and TMGa in a reaction chamber during growth of a non-dopant AlGaN-based ultraviolet light-emitting diode structure along a (0001) polar plane.
  • the present invention provides a dopant-free AlGaN-based ultraviolet light emitting diode, comprising:
  • a non-dopant n-type layer 2 is formed on the substrate 1.
  • the material of the non-dopant n-type layer 2 is a compositionally graded n-type Al L Ga 1-L N having a thickness of 50-500 nm.
  • the L value of the component decreases linearly along the direction of the polarization electric field, from L 1 to L 2 , where 0 ⁇ L 2 ⁇ L 1 ⁇ 1 to ensure linear increase of the polarization electric field, thereby utilizing the non-equilibrium pole
  • the electric field ionizes impurities, defects, and the like to generate electrons, and the layer functions to provide electrons for composite light emission in the active region 3;
  • the material of the well layer is AlGaN, wherein the composition of Al is x, 0 ⁇ x ⁇ 1, and the layer acts to limit carriers, so that carriers are combined to emit light in this region;
  • the undoped p-type layer 4 is a compositionally graded p-type Al M Ga 1-M N having a thickness of 50 to 500 nm.
  • the M value of the component increases linearly along the direction of the polarization electric field, from M 1 to M 2 , where 0 ⁇ M 1 ⁇ M 2 ⁇ 1 to ensure linear reduction of the polarization electric field, so that the non-equilibrium polarization electric field can be utilized
  • Ionization impurities, defects, and the like generate holes which function to provide holes for composite light emission in the active region 3.
  • the graded composition n-type dopant-free Al L Ga 1-L N layer 2 and the p-type dopant-free Al M Ga 1-M N Al composition layer 4 is greater than or equal to meet the minimum quantum active region 3
  • the Al composition content of the potential well Al x Ga 1-x N in the well structure is 0 ⁇ x ⁇ L 2 ⁇ L 1 ⁇ 1 and 0 ⁇ x ⁇ M 1 ⁇ M 2 ⁇ 1, thereby securing the active region 3
  • the emitted photons are not absorbed by the non-dopant n-type layer 2 and the non-dopant p-type layer 4.
  • the present invention further provides a method for growing a dopant-free AlGaN-based ultraviolet light emitting diode, comprising:
  • Step 1 Take a substrate 1;
  • Step 2 growing a non-dopant n-type layer 2 of a polar or semi-polar plane along the substrate 1 without introducing any active dopant during the growth process, and a group III metal organic source material for the input growth reaction chamber
  • the flow rate of Al and the flow rate of gallium metal organic material material are controlled, and the ratio of TMAl/(TMGa+TMAl) in the reaction chamber is controlled to form a composition-graded non-dopant n-type layer 2, wherein the Al composition gradient satisfies the edge
  • the direction of the electric field is gradually reduced, and the material of the non-dopant n-type layer 2 is a compositionally graded n-type Al L Ga 1-L N having a thickness of 50-500 nm, and the L value of the component is polarized.
  • the direction of the electric field decreases linearly from L 1 to L 2 , where 0 ⁇ L 2 ⁇ L 1 ⁇ 1;
  • Step 3 growing an active region 3 on the dopant-free n-type layer 2, which is a double heterojunction structure, a single quantum well structure or a multiple quantum well structure, which provides energy to excite the ultraviolet light Radiation output of the diode, the single quantum well structure or the multiple quantum well structure active region 3, the number of quantum well structures is 1 to 15, the thickness of the well layer is 2 to 6 nm, and the thickness of the barrier layer is 5 to 12 nm.
  • the material of the well layer is AlGaN, wherein the composition of Al is x, 0 ⁇ x ⁇ 1;
  • Step 4 growing a non-dopant p-type layer 4 on the active region 3, without introducing any active dopant during the growth process, and flowing the flow rate of the group III metal organic source material Al into the growth reaction chamber and the metal organic source material
  • the flow rate of gallium is controlled to control the ratio of TMAl/(TMGa+TMAl) in the reaction chamber to form a p-type AlGaN layer with a compositional gradation, wherein the gradual increase of the Al composition satisfies the direction of the polarization electric field, the undoped p
  • the type layer 4 is a compositionally graded p-type Al M Ga 1-M N having a thickness of 50 to 500 nm, and the M value of the composition linearly increases along the direction of the polarization electric field, from M 1 to M 2 , wherein 0 ⁇ Preparation was completed by M 1 ⁇ M 2 ⁇ 1.
  • the minimum composition of the non-dopant n-type AlLGa1-LN layer 2 and the non-dopant p-type AlMGa1-MN layer 4 satisfies the potential well Al x Ga 1-x N in the active region 3 quantum well structure.
  • the Al component content is 0 ⁇ x ⁇ L 2 ⁇ L 1 ⁇ 1 and 0 ⁇ x ⁇ M 1 ⁇ M 2 ⁇ 1.
  • Steps 2 and 4 can be exchanged in order, that is, the dopant-free p-type layer 4 is grown, then the active region 3 is grown, and then the long dopant-free n-type layer 2 is regrown.
  • the polarization electric field of the AlGaN material grown in the MOCVD method is opposite to the growth direction. Then the ratio of TMAl/(TMGa+TMAl) gradually increases with the growth time (as shown in Fig. 3, 0 ⁇ t1), and the Al composition can be gradually reduced along the direction of the polarization electric field, and the composition is gradually changed.
  • the active region 3 is grown on the non-dopant n-type layer 2, and the ratio of TMAl to TMGa in the corresponding reaction chamber is in the range of t1 to t2 as shown in FIG. 3;
  • a dopant-free p-type layer 4 is grown on the active region 3, and when the preferred (0001) polar plane is grown, the polarization field of the AlGaN material in the MOCVD growth is opposite to the growth direction, then TMAl/(TMGa+ The ratio of TMAl) gradually decreases with the growth time (as shown in Fig. 3, t2 to t3), and the Al composition gradually increases in the direction of the polarization electric field, and a component-graded non-dopant p-type layer is grown. 4.
  • Steps 1 and 3 can be exchanged in order, that is, a non-dopant p-type layer with a gradual composition of the gradual composition, followed by growth of an AlGaN/AlGaN double heterojunction structure or a quantum well structure, and then regrowth of the long-gradient undoped layer Agent n-type layer.

Abstract

The present invention provides a dopant-free AlGaN-based ultraviolet (UV) light emitting diode (LED) and preparation method thereof. The dopant-free AlGaN-based UV LED comprises: a substrate (1); a dopant-free n-type layer (2) deposited on the substrate (1); an active area (3) deposited on the dopant-free n-type layer (2); and a dopant-free p-type layer (4) deposited on the active area (3). The dopant-free AlGaN-based UV LED does not adopt any dopant, increasing material quality of transistor and simplifying steps of growing layers to form the material.

Description

无掺杂剂的AlGaN基紫外发光二极管及制备方法AlGaN-free ultraviolet light-emitting diode without dopant and preparation method thereof 技术领域Technical field
本发明属于半导体技术领域，适用于AlGaN基紫外和深紫外发光二极管，特别是指一种无掺杂剂的AlGaN基紫外发光二极管及制备方法，其不用掺杂任何杂质而获得n型导电和p型导电，从而实现LED发光的方法。The invention belongs to the field of semiconductor technology and is applicable to AlGaN-based ultraviolet and deep ultraviolet light-emitting diodes, in particular to a non-dopant-based AlGaN-based ultraviolet light-emitting diode and a preparation method thereof, which can obtain n-type conductivity and p without doping any impurities. A method of conducting electricity to achieve LED illumination.
背景技术Background technique
近年来以GaN基LED为核心的半导体照明发展迅猛，白光LED效率有了很大提高，已逐渐成为新一代照明光源。目前，无论在GaN/InGaN多量子阱的蓝绿光LED中，还是在AlGaN基的紫外LED中，其n型和p型导电层均采用引入掺杂杂质的方式来实现。通常n型GaN掺杂杂质为Si，p型GaN的掺杂杂质为Mg。然而，为了获得较高的电子和空穴浓度，势必要掺杂大量的Si或Mg原子，这将对GaN材料的晶体质量造成影响，并降低电子或空穴的迁移率。另外Mg原子的扩散还将严重影响量子阱的质量，从而导致发光效率降低。In recent years, semiconductor lighting with GaN-based LEDs as the core has developed rapidly, and the efficiency of white LEDs has been greatly improved, and has gradually become a new generation of illumination sources. At present, both the n-type and p-type conductive layers in the blue-green LED of the GaN/InGaN multiple quantum well and the AlGaN-based ultraviolet LED are implemented by introducing dopant impurities. Usually, the n-type GaN doping impurity is Si, and the p-type GaN doping impurity is Mg. However, in order to obtain higher electron and hole concentrations, it is necessary to dope a large amount of Si or Mg atoms, which will affect the crystal quality of the GaN material and reduce the mobility of electrons or holes. In addition, the diffusion of Mg atoms will seriously affect the quality of the quantum well, resulting in a decrease in luminous efficiency.
最近，有文献报道了一种新型掺杂方法-极化掺杂。该方法利用GaN基化合物的极化效应与组分的关系，通过使组分渐变获得均匀分布的净极化负电荷或净极化正电荷，并由此诱导产生自由空穴或电子，实现n型或p型导电。极化掺杂方法不依赖与热电离，而是依靠组分梯度带来的极化电场对外延材料中一些固有缺陷或杂质的电场电离。因此使用极化掺杂的方法，无需引入任何掺杂剂即可实现高导电性。据报道，目前利用极化掺杂方法获得的n型GaN基材料中电子和空穴浓度均高达1E18/cm3。此浓度的电子或空穴足以实现GaN基LED的发光。 Recently, a new type of doping method, polarization doping, has been reported in the literature. The method utilizes the relationship between the polarization effect of the GaN-based compound and the composition, and obtains a uniformly distributed net-polarized negative charge or a net-polarized positive charge by gradualizing the composition, thereby inducing the generation of free holes or electrons, thereby realizing n Type or p type conductive. The polarization doping method does not rely on thermal ionization, but relies on the polarization electric field brought about by the composition gradient to ionize the electric field of some inherent defects or impurities in the epitaxial material. Therefore, using the method of polarization doping, high conductivity can be achieved without introducing any dopant. It is reported that the concentration of electrons and holes in the n-type GaN-based material obtained by the polarization doping method is as high as 1E 18 /cm 3 . This concentration of electrons or holes is sufficient to achieve luminescence of the GaN-based LED.
发明内容Summary of the invention
本发明的目的在于，提供一种无掺杂剂的AlGaN基紫外发光二极管结构及制备方法，其不用引入任何掺杂剂，可以提高晶体材料质量，并简化材料的生长步骤。It is an object of the present invention to provide a dopant-free AlGaN-based ultraviolet light emitting diode structure and a method of fabricating the same, which can improve the quality of the crystalline material and simplify the growth step of the material without introducing any dopant.
本发明提供一种无掺杂剂的AlGaN基紫外发光二极管，包括：The invention provides a non-dopant AlGaN-based ultraviolet light emitting diode, comprising:
一衬底；a substrate
一无掺杂剂n型层，其制作在衬底上；a non-dopant n-type layer, which is fabricated on a substrate;
一有源区，其制作在无掺杂剂n型层上；An active region fabricated on the dopant-free n-type layer;
一无掺杂剂p型层，其制作在有源区上。A dopant-free p-type layer is formed over the active region.
本发明还提供一种无掺杂剂的AlGaN基紫外发光二极管的生长方法，其包括：The invention also provides a method for growing a non-dopant AlGaN-based ultraviolet light-emitting diode, comprising:
步骤1：取一衬底；Step 1: take a substrate;
步骤2：沿衬底上生长极性面或半极性面的无掺杂剂n型层，生长过程中不引入任何主动掺杂剂，对输入生长反应室的III族金属有机源材料Al的流量和金属有机源材料镓的流量进行控制，控制反应室中TMAl/(TMGa+TMAl)的比例，形成组分渐变的无掺杂剂n型层，其中Al组分渐变满足沿极化电场方向逐渐减小；Step 2: growing a non-dopant n-type layer of a polar or semi-polar surface along the substrate, without introducing any active dopant during the growth process, and inputting the III-group metal organic source material of the growth reaction chamber The flow rate and the flow rate of the metal organic source material gallium are controlled, and the ratio of TMAl/(TMGa+TMAl) in the reaction chamber is controlled to form a composition-graded non-dopant n-type layer, wherein the Al composition gradually satisfies the direction along the polarization electric field. slowing shrieking;
步骤3：在无掺杂剂n型层上生长有源区；Step 3: growing an active region on the non-dopant n-type layer;
步骤4：在有源区上生长无掺杂剂p型层，生长过程中不引入任何主动掺杂剂，对输入生长反应室的III族金属有机源材料Al的流量和金属有机源材料镓的流量进行控制，控制反应室中TMAl/(TMGa+TMAl)的比例，形成组分渐变的p型AlGaN层，其中Al组分渐变满足沿极化电场方向逐渐增加，完成制备。Step 4: growing a non-dopant p-type layer on the active region, without introducing any active dopant during the growth process, and flowing the flow of the group III metal organic source material Al into the growth reaction chamber and the metal organic source material gallium The flow rate is controlled to control the ratio of TMAl/(TMGa+TMAl) in the reaction chamber to form a p-type AlGaN layer with a gradual composition, wherein the gradual increase of the Al composition gradually increases along the direction of the polarization electric field, and the preparation is completed.
本发明的有益效果是，其不用引入任何掺杂剂，可以提高晶体材料质量，并简化材料的生长步骤。The beneficial effect of the present invention is that it can improve the quality of the crystal material and simplify the growth step of the material without introducing any dopant.
附图说明DRAWINGS
为使本发明的目的、技术方案和优点更加清楚明白，以下结合具体 实施例，并参照附图，对本发明做进一步的详细说明，其中：In order to make the objects, technical solutions and advantages of the present invention more clear, the following specific combinations The invention will be further described in detail with reference to the accompanying drawings, in which:
图1为无掺杂剂的AlGaN基紫外发光二极管结构截面图。1 is a cross-sectional view showing the structure of an AlGaN-based ultraviolet light emitting diode without a dopant.
图2为无掺杂剂的AlGaN基紫外发光二极管结构在生长过程中的结构变化流程图。2 is a flow chart showing the structural change of a non-dopant AlGaN-based ultraviolet light emitting diode structure during growth.
图3为无掺杂剂的AlGaN基紫外发光二极管结构沿(0001)极性面生长过程中反应室中的TMAl与TMGa随时间的变化情况。3 is a graph showing changes in TMAl and TMGa in a reaction chamber during growth of a non-dopant AlGaN-based ultraviolet light-emitting diode structure along a (0001) polar plane.
具体实施方式detailed description
请参阅图1所示，本发明提供一种无掺杂剂的AlGaN基紫外发光二极管，包括：Referring to FIG. 1 , the present invention provides a dopant-free AlGaN-based ultraviolet light emitting diode, comprising:
一衬底1；a substrate 1;
一无掺杂剂n型层2，其制作在衬底1上，所述无掺杂剂n型层2的材料为组分渐变的n型AlLGa1-LN，厚度为50～500nm，所述组分的L值沿极化电场方向线性减小，从L1变到L2，其中0≤L2＜L1≤1，以保证极化电场线性增加，从而可利用非平衡极化电场电离杂质、缺陷等产生电子，该层作用为提供用于在有源区3复合发光的电子；A non-dopant n-type layer 2 is formed on the substrate 1. The material of the non-dopant n-type layer 2 is a compositionally graded n-type Al L Ga 1-L N having a thickness of 50-500 nm. The L value of the component decreases linearly along the direction of the polarization electric field, from L 1 to L 2 , where 0 ≤ L 2 <L 1 ≤ 1 to ensure linear increase of the polarization electric field, thereby utilizing the non-equilibrium pole The electric field ionizes impurities, defects, and the like to generate electrons, and the layer functions to provide electrons for composite light emission in the active region 3;
一有源区3，其制作在无掺杂剂n型层2上，所述有源区3是双异质结结构、单量子阱结构或者多量子阱结构，其提供能量以激发该紫外发光二极管的辐射输出，所述单量子阱结构或者多量子阱结构有源区3，量子阱结构的个数为1～15个，阱层的厚度为2～6nm，垒层厚度为5～12nm，该阱层的材料为AlGaN，其中Al的组分为x，0≤x≤1，该层作用为限制载流子，使载流子在此区域复合发光；An active region 3 fabricated on the dopant-free n-type layer 2, the active region 3 being a double heterojunction structure, a single quantum well structure or a multiple quantum well structure providing energy to excite the ultraviolet light Radiation output of the diode, the single quantum well structure or the multiple quantum well structure active region 3, the number of quantum well structures is 1 to 15, the thickness of the well layer is 2 to 6 nm, and the thickness of the barrier layer is 5 to 12 nm. The material of the well layer is AlGaN, wherein the composition of Al is x, 0≤x≤1, and the layer acts to limit carriers, so that carriers are combined to emit light in this region;
一无掺杂剂p型层4，其制作在有源区3上，所述无掺杂p型层4为组分渐变的p型AlMGa1-MN，厚度为50～500nm，所述组分的M值沿极化电场方向线性增加，从M1变到M2，其中0≤M1＜M2≤1，以保证极化电场线性减小，从而可利用非平衡极化电场电离杂质、缺陷等产生空穴，该层作用为提供用于在有源区3复合发光的空穴。a dopant-free p-type layer 4, which is formed on the active region 3, the undoped p-type layer 4 is a compositionally graded p-type Al M Ga 1-M N having a thickness of 50 to 500 nm. The M value of the component increases linearly along the direction of the polarization electric field, from M 1 to M 2 , where 0 ≤ M 1 <M 2 ≤ 1 to ensure linear reduction of the polarization electric field, so that the non-equilibrium polarization electric field can be utilized Ionization impurities, defects, and the like generate holes which function to provide holes for composite light emission in the active region 3.
其中组分渐变的无掺杂剂n型AlLGa1-LN层2和无掺杂剂p型 AlMGa1-MN层4的Al组分最小值满足大于等于有源区3量子阱结构中势阱AlxGa1-xN的Al组分含量，既是0≤x≤L2＜L1≤1且0≤x≤M1＜M2≤1，以此保障有源区3发出的光子不会被无掺杂剂n型层2和无掺杂剂p型层4吸收。Wherein the graded composition n-type dopant-free Al L Ga 1-L N layer 2 and the p-type dopant-free Al M Ga 1-M N Al composition layer 4 is greater than or equal to meet the minimum quantum active region 3 The Al composition content of the potential well Al x Ga 1-x N in the well structure is 0 ≤ x ≤ L 2 < L 1 ≤ 1 and 0 ≤ x ≤ M 1 < M 2 ≤ 1, thereby securing the active region 3 The emitted photons are not absorbed by the non-dopant n-type layer 2 and the non-dopant p-type layer 4.
请参阅图2，并结合参阅图1本发明还提供一种无掺杂剂的AlGaN基紫外发光二极管的生长方法，其包括：Referring to FIG. 2 , and in conjunction with FIG. 1 , the present invention further provides a method for growing a dopant-free AlGaN-based ultraviolet light emitting diode, comprising:
步骤1：取一衬底1；Step 1: Take a substrate 1;
步骤2：沿衬底1上生长极性面或半极性面的无掺杂剂n型层2，生长过程中不引入任何主动掺杂剂，对输入生长反应室的III族金属有机源材料Al的流量和金属有机源材料镓的流量进行控制，控制反应室中TMAl/(TMGa+TMAl)的比例，形成组分渐变的无掺杂剂n型层2，其中Al组分渐变满足沿极化电场方向逐渐减小，所述无掺杂剂n型层2的材料为组分渐变的n型AlLGa1-LN，厚度为50～500nm，所述组分的L值沿极化电场方向线性减小，从L1变到L2，其中0≤L2＜L1≤1；Step 2: growing a non-dopant n-type layer 2 of a polar or semi-polar plane along the substrate 1 without introducing any active dopant during the growth process, and a group III metal organic source material for the input growth reaction chamber The flow rate of Al and the flow rate of gallium metal organic material material are controlled, and the ratio of TMAl/(TMGa+TMAl) in the reaction chamber is controlled to form a composition-graded non-dopant n-type layer 2, wherein the Al composition gradient satisfies the edge The direction of the electric field is gradually reduced, and the material of the non-dopant n-type layer 2 is a compositionally graded n-type Al L Ga 1-L N having a thickness of 50-500 nm, and the L value of the component is polarized. The direction of the electric field decreases linearly from L 1 to L 2 , where 0 ≤ L 2 < L 1 ≤ 1;
步骤3：在无掺杂剂n型层2上生长有源区3，所述有源区3是双异质结结构、单量子阱结构或者多量子阱结构，其提供能量以激发该紫外发光二极管的辐射输出，所述单量子阱结构或者多量子阱结构有源区3，量子阱结构的个数为1～15个，阱层的厚度为2～6nm，垒层厚度为5～12nm，该阱层的材料为AlGaN，其中Al的组分为x，0≤x≤1；Step 3: growing an active region 3 on the dopant-free n-type layer 2, which is a double heterojunction structure, a single quantum well structure or a multiple quantum well structure, which provides energy to excite the ultraviolet light Radiation output of the diode, the single quantum well structure or the multiple quantum well structure active region 3, the number of quantum well structures is 1 to 15, the thickness of the well layer is 2 to 6 nm, and the thickness of the barrier layer is 5 to 12 nm. The material of the well layer is AlGaN, wherein the composition of Al is x, 0≤x≤1;
步骤4：在有源区3上生长无掺杂剂p型层4，生长过程中不引入任何主动掺杂剂，对输入生长反应室的III族金属有机源材料Al的流量和金属有机源材料镓的流量进行控制，控制反应室中TMAl/(TMGa+TMAl)的比例，形成组分渐变的p型AlGaN层，其中Al组分渐变满足沿极化电场方向逐渐增加，所述无掺杂p型层4为组分渐变的p型AlMGa1-MN，厚度为50～500nm，所述组分的M值沿极化电场方向线性增加，从M1变到M2，其中0≤M1＜M2≤1，完成制备。Step 4: growing a non-dopant p-type layer 4 on the active region 3, without introducing any active dopant during the growth process, and flowing the flow rate of the group III metal organic source material Al into the growth reaction chamber and the metal organic source material The flow rate of gallium is controlled to control the ratio of TMAl/(TMGa+TMAl) in the reaction chamber to form a p-type AlGaN layer with a compositional gradation, wherein the gradual increase of the Al composition satisfies the direction of the polarization electric field, the undoped p The type layer 4 is a compositionally graded p-type Al M Ga 1-M N having a thickness of 50 to 500 nm, and the M value of the composition linearly increases along the direction of the polarization electric field, from M 1 to M 2 , wherein 0 ≤ Preparation was completed by M 1 <M 2 ≤1.
其中无掺杂剂n型AlLGa1-LN层2和无掺杂剂p型AlMGa1-MN层4的Al组分最小值满足大于等于有源区3量子阱结构中势阱AlxGa1-xN的Al组分含量，既是0≤x≤L2＜L1≤1且0≤x≤M1＜M2≤1。 The minimum composition of the non-dopant n-type AlLGa1-LN layer 2 and the non-dopant p-type AlMGa1-MN layer 4 satisfies the potential well Al x Ga 1-x N in the active region 3 quantum well structure. The Al component content is 0 ≤ x ≤ L 2 < L 1 ≤ 1 and 0 ≤ x ≤ M 1 < M 2 ≤ 1.
其中步骤2和步骤4可以交换顺序，即先生长无掺杂剂p型层4，接着生长有源区3，然后再生长无掺杂剂n型层2。 Steps 2 and 4 can be exchanged in order, that is, the dopant-free p-type layer 4 is grown, then the active region 3 is grown, and then the long dopant-free n-type layer 2 is regrown.
参阅图3，给出了本发明一优选实施例中所述无掺杂剂的AlGaN基紫外发光二极管结构沿(0001)极性面制作过程中反应室中的TMAl与TMGa随时间的变化情况。Referring to FIG. 3, the change of TMAl and TMGa in the reaction chamber during the fabrication of the (0001) polar plane in the non-dopant AlGaN-based ultraviolet light-emitting diode structure according to a preferred embodiment of the present invention is shown.
取一个衬底1，在衬底1上生长无掺杂剂n型层2，如在优选的(0001)极性面生长时，由于MOCVD法生长中AlGaN材料的极化电场与生长方向相反，则TMAl/(TMGa+TMAl)的比例随生长时间逐渐增加(如图3中所示0～t1段)，便能实现Al组分沿极化电场方向逐渐减小，生长出组分渐变的无掺杂剂n型层2；Taking a substrate 1 and growing a non-dopant n-type layer 2 on the substrate 1, as in the growth of the preferred (0001) polar plane, the polarization electric field of the AlGaN material grown in the MOCVD method is opposite to the growth direction. Then the ratio of TMAl/(TMGa+TMAl) gradually increases with the growth time (as shown in Fig. 3, 0~t1), and the Al composition can be gradually reduced along the direction of the polarization electric field, and the composition is gradually changed. Dopant n-type layer 2;
在无掺杂剂n型层2上生长有源区3，相应的反应室中TMAl与TMGa的比例随生长时间如图3中所示t1～t2段；The active region 3 is grown on the non-dopant n-type layer 2, and the ratio of TMAl to TMGa in the corresponding reaction chamber is in the range of t1 to t2 as shown in FIG. 3;
在有源区3上生长无掺杂剂p型层4，在优选的(0001)极性面生长时，由于MOCVD法生长中AlGaN材料的极化电场与生长方向相反，则TMAl/(TMGa+TMAl)的比例随生长时间逐渐减小(如图3中所示t2～t3段)，便能实现Al组分沿极化电场方向逐渐增加，生长出组分渐变的无掺杂剂p型层4。A dopant-free p-type layer 4 is grown on the active region 3, and when the preferred (0001) polar plane is grown, the polarization field of the AlGaN material in the MOCVD growth is opposite to the growth direction, then TMAl/(TMGa+ The ratio of TMAl) gradually decreases with the growth time (as shown in Fig. 3, t2 to t3), and the Al composition gradually increases in the direction of the polarization electric field, and a component-graded non-dopant p-type layer is grown. 4.
其中步骤1和步骤3可以交换顺序，即先生长组分渐变的无掺杂剂p型层，接着生长AlGaN/AlGaN双异质结结构或量子阱结构，然后再生长组分渐变的无掺杂剂n型层。 Steps 1 and 3 can be exchanged in order, that is, a non-dopant p-type layer with a gradual composition of the gradual composition, followed by growth of an AlGaN/AlGaN double heterojunction structure or a quantum well structure, and then regrowth of the long-gradient undoped layer Agent n-type layer.
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 The specific embodiments of the present invention have been described in detail, and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims (13)

  1. 一种无掺杂剂的AlGaN基紫外发光二极管，包括：A dopant-free AlGaN-based ultraviolet light emitting diode comprising:
    一衬底；a substrate
    一无掺杂剂n型层，其制作在衬底上；a non-dopant n-type layer, which is fabricated on a substrate;
    一有源区，其制作在无掺杂剂n型层上；An active region fabricated on the dopant-free n-type layer;
    一无掺杂剂p型层，其制作在有源区上。A dopant-free p-type layer is formed over the active region.
  2. 如权利要求1所述的无掺杂剂的AlGaN基紫外发光二极管，其中所述有源区是双异质结结构、单量子阱结构或者多量子阱结构，其提供能量以激发该紫外发光二极管的辐射输出。The dopant-free AlGaN-based ultraviolet light emitting diode of claim 1 wherein said active region is a double heterojunction structure, a single quantum well structure or a multiple quantum well structure that provides energy to excite the ultraviolet light emitting diode Radiation output.
  3. 如权利要求2所述的无掺杂剂的AlGaN基紫外发光二极管，其中所述单量子阱结构或者多量子阱结构有源区，量子阱结构的个数为1～15个，阱层的厚度为2～6nm，垒层厚度为5～12nm，该阱层的材料为AlGaN，其中Al的组分为x，0≤x≤1。The dopant-free AlGaN-based ultraviolet light-emitting diode according to claim 2, wherein the single quantum well structure or the multiple quantum well structure active region has a number of quantum well structures of 1 to 15, and a thickness of the well layer. The thickness of the barrier layer is 5 to 12 nm, and the material of the well layer is AlGaN, wherein the composition of Al is x, 0≤x≤1.
  4. 如权利要求1所述的无掺杂剂的AlGaN基紫外发光二极管，其中所述无掺杂剂n型层的材料为组分渐变的n型AlLGa1-LN，厚度为50～500nm，所述组分的L值沿极化电场方向线性减小，从L1变到L2，其中0≤L2＜L1≤1。The dopant-free AlGaN-based ultraviolet light-emitting diode according to claim 1, wherein the material of the non-dopant n-type layer is a compositionally graded n-type Al L Ga 1-L N having a thickness of 50 to 500 nm. The L value of the component decreases linearly in the direction of the polarization electric field, from L 1 to L 2 , where 0 ≤ L 2 < L 1 ≤ 1.
  5. 如权利要求1所述的无掺杂剂的AlGaN基紫外发光二极管，其中所述无掺杂p型层为组分渐变的p型AlMGa1-MN，厚度为50～500nm，所述组分的M值沿极化电场方向线性增加，从M1变到M2，其中0≤M1＜M2≤1。The dopant-free AlGaN-based ultraviolet light-emitting diode according to claim 1, wherein the undoped p-type layer is a compositionally graded p-type Al M Ga 1-M N having a thickness of 50 to 500 nm. The M value of the component increases linearly in the direction of the polarization electric field, from M 1 to M 2 , where 0 ≤ M 1 < M 2 ≤ 1.
  6. 如权利要求1所述的无掺杂剂的AlGaN基紫外发光二极管，其中组分渐变的n型AlLGa1-LN层和p型AlMGa1-MN层的Al组分最小值满足大于等于有源区量子阱结构中势阱AlxGa1-xN的Al组分含量，既是0≤x≤L2＜L1≤1且0≤x≤M1＜M2≤1。The dopant-free AlGaN-based ultraviolet light-emitting diode according to claim 1, wherein an Al composition minimum of the compositionally graded n-type Al L Ga 1-L N layer and the p-type Al M Ga 1-M N layer The content of the Al component satisfying the potential well Al x Ga 1-x N in the quantum well structure of the active region is equal to 0 ≤ x ≤ L 2 < L 1 ≤ 1 and 0 ≤ x ≤ M 1 < M 2 ≤ 1.
  7. 一种无掺杂剂的AlGaN基紫外发光二极管的生长方法，其包括：A method for growing a non-dopant AlGaN-based ultraviolet light emitting diode, comprising:
    步骤1：取一衬底；Step 1: take a substrate;
    步骤2：沿衬底上生长极性面或半极性面的无掺杂剂n型层，生长过程中不引入任何主动掺杂剂，对输入生长反应室的III族金属有机源材 料Al的流量和金属有机源材料镓的流量进行控制，控制反应室中TMAl/(TMGa+TMAl)的比例，形成组分渐变的无掺杂剂n型层，其中Al组分渐变满足沿极化电场方向逐渐减小；Step 2: growing a non-dopant n-type layer of a polar or semi-polar surface along the substrate, without introducing any active dopant during the growth process, and a group III metal organic source for the input growth reaction chamber The flow rate of Al and the flow rate of gallium metal organic material are controlled to control the ratio of TMAl/(TMGa+TMAl) in the reaction chamber to form a composition-graded non-dopant n-type layer, wherein the Al composition gradually satisfies the edge The direction of the electric field is gradually reduced;
    步骤3：在无掺杂剂n型层上生长有源区；Step 3: growing an active region on the non-dopant n-type layer;
    步骤4：在有源区上生长无掺杂剂p型层，生长过程中不引入任何主动掺杂剂，对输入生长反应室的III族金属有机源材料Al的流量和金属有机源材料镓的流量进行控制，控制反应室中TMAl/(TMGa+TMAl)的比例，形成组分渐变的p型AlGaN层，其中Al组分渐变满足沿极化电场方向逐渐增加，完成制备。Step 4: growing a non-dopant p-type layer on the active region, without introducing any active dopant during the growth process, and flowing the flow of the group III metal organic source material Al into the growth reaction chamber and the metal organic source material gallium The flow rate is controlled to control the ratio of TMAl/(TMGa+TMAl) in the reaction chamber to form a p-type AlGaN layer with a gradual composition, wherein the gradual increase of the Al composition gradually increases along the direction of the polarization electric field, and the preparation is completed.
  8. 如权利要求7所述的无掺杂剂的AlGaN基紫外发光二极管的生长方法，其中所述有源区是双异质结结构、单量子阱结构或者多量子阱结构，其提供能量以激发该紫外发光二极管的辐射输出。The method of growing a dopant-free AlGaN-based ultraviolet light emitting diode according to claim 7, wherein said active region is a double heterojunction structure, a single quantum well structure or a multiple quantum well structure, which provides energy to excite the Radiation output of the UV LED.
  9. 如权利要求8所述的无掺杂剂的AlGaN基紫外发光二极管的生长方法，其中所述单量子阱结构或者多量子阱结构有源区，量子阱结构的个数为1～15个，阱层的厚度为2～6nm，垒层厚度为5～12nm，该阱层的材料为AlGaN，其中Al的组分为x，0≤x≤1。The method of growing a dopant-free AlGaN-based ultraviolet light-emitting diode according to claim 8, wherein the single quantum well structure or the multiple quantum well structure active region has a number of quantum well structures of 1 to 15, and a well The thickness of the layer is 2-6 nm, the thickness of the barrier layer is 5-12 nm, and the material of the well layer is AlGaN, wherein the composition of Al is x, 0≤x≤1.
  10. 如权利要求7所述的无掺杂剂的AlGaN基紫外发光二极管的生长方法，其中所述无掺杂剂n型层的材料为组分渐变的n型AlLGa1-LN，厚度为50～500nm，所述组分的L值沿极化电场方向线性减小，从L1变到L2，其中0≤L2＜L1≤1。The method of growing AlGaN-based ultraviolet light emitting diode undoped agent according to claim 7, wherein the non-dopant n-type layer of material is n-type composition graded Al L Ga 1-L N, having a thickness of 50 to 500 nm, the L value of the component linearly decreases in the direction of the polarization electric field, from L 1 to L 2 , where 0 ≤ L 2 < L 1 ≤ 1.
  11. 如权利要求7所述的无掺杂剂的AlGaN基紫外发光二极管的生长方法，其中所述无掺杂p型层为组分渐变的p型AlMGa1-MN，厚度为50～500nm，所述组分的M值沿极化电场方向线性增加，从M1变到M2，其中0≤M1＜M2≤1。The method of growing a dopant-free AlGaN-based ultraviolet light-emitting diode according to claim 7, wherein said undoped p-type layer is a compositionally graded p-type Al M Ga 1-M N having a thickness of 50 to 500 nm. The M value of the component increases linearly in the direction of the polarization electric field, from M 1 to M 2 , where 0 ≤ M 1 < M 2 ≤ 1.
  12. 如权利要求7所述的无掺杂剂的AlGaN基紫外发光二极管的生长方法，其中组分渐变的n型AlLGa1-LN层和p型AlMGa1-MN层的Al组分最小值满足大于等于有源区量子阱结构中势阱AlxGa1-xN的Al组分含量，既是0≤x≤L2＜L1≤1且0≤x≤M1＜M2≤1。A method of growing a dopant-free AlGaN-based ultraviolet light-emitting diode according to claim 7, wherein the compositionally graded n-type Al L Ga 1-L N layer and the p-type Al M Ga 1-M N layer Al group The minimum value satisfies the content of the Al component greater than or equal to the potential well Al x Ga 1-x N in the quantum well structure of the active region, which is 0 ≤ x ≤ L 2 < L 1 ≤ 1 and 0 ≤ x ≤ M 1 < M 2 ≤1.
  13. 如权利要求7所述的无掺杂剂的AlGaN基紫外发光二极管的生 长方法，其中步骤2和步骤4可以交换顺序，及先生长无掺杂剂组分渐变p型AlGaN层，接着生长AlGaN/AlGaN双异质结结构或量子阱结构，然后再生长无掺杂剂组分渐变n型AlGaN层。 The raw material of the dopant-free AlGaN-based ultraviolet light emitting diode of claim 7 a long method in which steps 2 and 4 can be exchanged in sequence, and a non-dopant component is gradually graded with a p-type AlGaN layer, followed by an AlGaN/AlGaN double heterojunction structure or a quantum well structure, and then a regrowth-free dopant The composition is graded with an n-type AlGaN layer.
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