WO2021032142A1 - 具有啁啾超晶格最终势垒结构的深紫外led及制备方法 - Google Patents

具有啁啾超晶格最终势垒结构的深紫外led及制备方法 Download PDF

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WO2021032142A1
WO2021032142A1 PCT/CN2020/110138 CN2020110138W WO2021032142A1 WO 2021032142 A1 WO2021032142 A1 WO 2021032142A1 CN 2020110138 W CN2020110138 W CN 2020110138W WO 2021032142 A1 WO2021032142 A1 WO 2021032142A1
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layer
final barrier
composition
superlattice
chirped
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French (fr)
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张骏
岳金顺
梁仁瓅
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苏州紫灿科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
    • H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
    • H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/14—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
    • H01L33/145—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure with a current-blocking structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
    • H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
    • H01L33/325—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen characterised by the doping materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/14—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure

Definitions

  • the invention relates to the field of semiconductor optoelectronics, in particular to a deep ultraviolet LED with a chirped superlattice final barrier structure and a preparation method.
  • Group III nitrides as an outstanding representative of wide-bandgap semiconductor materials, have achieved high-efficiency blue-green light-emitting diodes (full name light-emitting diodes, LED for short), lasers and other solid-state light source devices, which are used in flat panel displays, white light lighting, etc. Great success in application. In the past ten years, people expect to apply this efficient luminescent material to the ultraviolet band to meet the growing demand for ultraviolet light sources.
  • the ultraviolet band can generally be divided into: long-wave ultraviolet (ie UVA, wavelength is 320-400nm), medium-wave ultraviolet (ie UVB, wavelength is 280-320nm), short-wave ultraviolet (ie UVC, wavelength is 200-280nm) And vacuum ultraviolet (VUV, the wavelength is 10-200nm).
  • UVA long-wave ultraviolet
  • UVB medium-wave ultraviolet
  • UVC short-wave ultraviolet
  • VUV vacuum ultraviolet
  • the forbidden band width of Al x Ga 1-x N materials can be continuously adjusted from 3.4 eV (GaN) to 6.2 eV (AlN) by changing the Al composition, and can achieve a spectral range from 365 nm to 200 nm. Glow.
  • the band-edge emission wavelength of GaN is about 360 nm, which is usually used as a division mark of the emission band of nitride ultraviolet light-emitting diodes (full name Ultraviolet light-emitting diodes, UV-LED for short).
  • the active area of UV-LEDs with emission wavelengths greater than 360nm adopts a GaN/InGaN quantum well (QWs) structure similar to blue LEDs.
  • QWs quantum well
  • the related research has started as early as the 1990s and has been successfully commercialized.
  • the external quantum efficiency (EQE) has also exceeded 40%, reaching a level comparable to blue LEDs.
  • UV LEDs with emission wavelengths less than 360nm mainly use AlGaN quantum well structures as active regions, and their quantum efficiency is far from satisfactory.
  • One of the main reasons for the low efficiency of high-Al component AlGaN-based deep ultraviolet LEDs is the obvious electron overflow effect.
  • the electrons from the electron injection layer cross the electron barrier layer to the p-type layer, causing the p-type layer to emit light and reduce Improve the internal quantum efficiency. Therefore, it is necessary to propose a new ultraviolet LED solution to solve the problems existing in the prior art.
  • the purpose of the present invention is to provide a deep ultraviolet LED with a chirped superlattice final barrier structure and a preparation method for solving the problem of low efficiency of the deep ultraviolet LED caused by the electronic overflow effect in the prior art.
  • the first solution provided by the present invention is: a deep ultraviolet LED with a chirped superlattice final barrier structure, including a sapphire substrate, an AlN intrinsic layer, an N-type AlGaN layer, and current spreading Layer, quantum well active layer, final barrier layer of the chirped superlattice, electron blocking layer, P-type AlGaN injection layer and P-type GaN contact layer; deposit AlN intrinsic layer and N-type AlGaN layer sequentially on the sapphire substrate , Current spreading layer, quantum well active layer, chirped superlattice final barrier layer, electron blocking layer, P-type AlGaN injection layer and P-type GaN contact layer; the final barrier layer of chirped superlattice is the thickness chirp And a superlattice structure composed of several Al a Ga 1-a N layers and several Al b Ga 1-b N layers alternately.
  • the thicknesses of the a Ga 1-a N layer and the Al b Ga 1-b N layer are x and y, respectively; in the direction from the quantum well active layer to the electron blocking layer, in the Al a Ga 1-a N layer and the Al b n cycles Ga 1-b N layer, consisting of, and the thickness of Al b Ga 1-b N layer is Al a Ga 1-a N layer are x ⁇ n ⁇ t and y ⁇ n ⁇ t, wherein t satisfies 0.1 nm ⁇ t ⁇ 10nm.
  • the Al a Ga 1-a N layer is a single layer structure with a single Al a Ga 1-a N component
  • the Al b Ga 1-b N layer is a single layer structure with a single Al b Ga 1-b N component
  • a and b satisfy 0.4 ⁇ a ⁇ b ⁇ 1.
  • the Al a Ga 1-a N layer has a graded composition single layer structure and the Al composition parameter a is linearly graded from the value c to d, and the Al b Ga 1-b N layer is a single Al b Ga 1-b N Single-layer structure of the components, where b, c and d satisfy 0.4 ⁇ c ⁇ d ⁇ b ⁇ 1.
  • the Al a Ga 1-a N layer is a single layer structure with a single Al a Ga 1-a N composition
  • the Al b Ga 1-b N layer is a composition graded single layer structure
  • the Al composition parameter b is determined by The value e gradually gradually changes to f, where a, e, and f satisfy 0.4 ⁇ a ⁇ f ⁇ e ⁇ 1.
  • the Al a Ga 1-a N layer has a graded composition single layer structure and the Al composition parameter a is linearly graded from g to h, and the Al b Ga 1-b N layer has a graded composition single layer structure.
  • the Al component parameter b linearly changes from the value j to k, where g, h and k satisfy 0.4 ⁇ g ⁇ h ⁇ j ⁇ k ⁇ 1.
  • the dopant used in the P-type AlGaN injection layer and the P-type GaN contact layer is Mg.
  • the second solution provided by the present invention is: a method for preparing a deep ultraviolet LED with a chirped superlattice final barrier structure, which is characterized in that a chirped superlattice final barrier structure
  • the deep ultraviolet LED preparation method adopts a metal organic chemical vapor deposition method to prepare any deep ultraviolet LED with a chirped superlattice final barrier structure in the first solution.
  • the method for preparing a deep ultraviolet LED with a chirped superlattice final barrier structure includes the following steps: growing a buffer layer in an AlN intrinsic layer on a sapphire substrate at a temperature of 400-800°C, with a thickness of 10-50nm; Raise the temperature to 1200 ⁇ 1400°C, grow an AlN intrinsic layer on the buffer layer in the AlN intrinsic layer, the total thickness of the AlN intrinsic layer is 500 ⁇ 4000nm; reduce the temperature to 800 ⁇ 1200°C, grow n on the AlN intrinsic layer Type AlGaN layer, in which the Al composition percentage is 20-90%, and the thickness is 500-4000nm; the temperature is reduced to 700-1100°C, and the current spreading layer and the quantum well active layer are sequentially grown on the n-type AlGaN layer.
  • the barrier thickness of the active layer of the well is 5-30nm and the percentage of Al composition in the barrier is 20-100%, the thickness of the potential well is 0.1-5nm and the percentage of Al composition in the potential well is 0-80%, the preferred potential
  • the percentage of Al in the well is 5 ⁇ 80%; at 700 ⁇ 1100°C, the final barrier layer of the chirped superlattice is grown on the active layer of the quantum well, and the final barrier layer of the chirped superlattice is the thickness Chirped superlattice structure composed of several Al a Ga 1-a N layers and several Al b Ga 1-b N layers alternately, and a ⁇ b, where the thickness of the Al b Ga 1-b N layer is 0.1 ⁇ 5nm and 0.2 ⁇ b ⁇ 1, the thickness of the Al a Ga 1-a N layer is 0.1 to 5 nm and 0 ⁇ a ⁇ 0.8, more preferably 0.05 ⁇ a ⁇ 0.8; under the condition of 700 to 1100 °C, in the chirp
  • An electron blocking layer is grown on the final
  • the beneficial effect of the present invention is: different from the prior art, the present invention provides a deep ultraviolet LED with a chirped superlattice final barrier structure and a preparation method thereof, by introducing a chirped superlattice final barrier layer, The probability of electron tunneling to the P-type AlGaN injection layer is reduced, the electron overflow effect is weakened, and the luminous efficiency of the deep ultraviolet LED is improved.
  • FIG. 1 is a schematic structural view of an embodiment of a deep ultraviolet LED with a chirped superlattice final barrier structure in the present invention
  • FIG. 2 is an energy band comparison diagram of an embodiment of a deep ultraviolet LED with a chirped superlattice final barrier structure in the present invention
  • FIG. 3 is a light output power diagram of an embodiment of a deep ultraviolet LED with a chirped superlattice final barrier structure in the present invention.
  • FIG. 1 is a schematic structural diagram of an embodiment of a deep ultraviolet LED with a chirped superlattice final barrier structure in the present invention.
  • the deep ultraviolet LED with a chirped superlattice final barrier structure in the present invention includes a sapphire substrate 1, an AlN intrinsic layer 2, an N-type AlGaN layer 3, a current spreading layer 4, a quantum well active layer 5, a chirp Superlattice final barrier layer 6, electron blocking layer 7, P-type AlGaN injection layer 8 and P-type GaN contact layer 9; Deposit an AlN intrinsic layer 2, an N-type AlGaN layer 3, and current spreading on the sapphire substrate 1 in sequence Layer 4, quantum well active layer 5, chirped superlattice final barrier layer 6, electron blocking layer 7, P-type AlGaN injection layer 8 and P-type GaN contact layer 9; in addition, the P-type GaN contact layer A P electrode 10 is arranged on 9 and an N electrode 11 is arranged on the side of the N-type Al
  • the electron tunnel is reduced.
  • the probability of penetrating to the P-type AlGaN injection layer weakens the electron overflow effect, thereby improving the luminous efficiency of the deep ultraviolet LED.
  • the Al a Ga 1-a N layer is a single layer of a single Al a Ga 1-a N composition Structure
  • the Al b Ga 1-b N layer is a single layer structure with a single Al b Ga 1-b N composition, and a and b satisfy 0.4 ⁇ a ⁇ b ⁇ 1
  • Al a Ga 1-a N layer It is a graded composition single layer structure and the Al composition parameter a is linearly graded from the value c to d.
  • the Al b Ga 1-b N layer is a single layer structure with a single Al b Ga 1-b N composition, where b, c And d satisfy 0.4 ⁇ c ⁇ d ⁇ b ⁇ 1; (3)
  • the Al a Ga 1-a N layer is a single layer structure of a single Al a Ga 1-a N composition, and the Al b Ga 1-b N layer is a group A graded single layer structure and the Al composition parameter b linearly graded from e to f, where a, e and f satisfy 0.4 ⁇ a ⁇ f ⁇ e ⁇ 1;
  • Al a Ga 1-a N layer is a group A graded single layer structure and the Al composition parameter a linearly changes from the value g to h
  • the Al b Ga 1-b N layer is a composition graded single layer structure and the Al composition parameter b linearly changes from the value j to k, Where g, h, and k satisfy 0.4 ⁇ g ⁇ h ⁇ j ⁇ k ⁇ 1.
  • the b Ga 1-b N layer is a single -layer structure with a single Al b Ga 1-b N composition; (2) The thickness of the multi-period Al a Ga 1-a N layer and the Al b Ga 1-b N layer increases in sequence, And the Al a Ga 1-a N layer is a single-layer structure with a graded composition, and the Al b Ga 1-b N layer is a single -layer structure with a single Al b Ga 1-b N composition; (3) Multi-period Al a Ga The thicknesses of the 1-a N layer and the Al b Ga 1-b N layer increase sequentially, and the Al a Ga 1-a N layer is a single layer structure with a single Al a Ga 1-a N composition, and the Al b Ga 1-b The N layer is a single-layer structure with a graded composition; (4) The thickness of the multi-period Al a Ga 1-a N layer and the Al b Ga 1-b N layer increase sequentially, and the Al a Ga 1-a N layer is the composition A graded single
  • FIG. 2 is an energy band comparison diagram of an embodiment of a deep ultraviolet LED with a chirped superlattice final barrier structure in the present invention, where a common LB represents the energy band of the traditional final barrier structure , And Figures b, c, d, SLLB-I, SLLB-E, and SLLB-D respectively represent the samples of three different configurations of the deep ultraviolet LED with the final barrier structure of the chirped superlattice in the present invention.
  • the comparison can be seen Compared with the traditional final barrier structure, the chirped superlattice final barrier structure can increase the electron barrier height of the electron blocking layer and reduce the height of the hole injection barrier, thereby blocking electrons from transporting to the p-type layer. Weakened the electron overflow effect.
  • the method for preparing a deep ultraviolet LED with a chirped superlattice final barrier structure includes:
  • the temperature is raised to 1200-1400°C, and an AlN intrinsic layer is grown on the buffer layer in the AlN intrinsic layer.
  • the total thickness of the AlN intrinsic layer is 500-4000 nm.
  • the temperature is lowered to 800-1200 DEG C, and an n-type AlGaN layer is grown on the AlN intrinsic layer, in which the Al composition percentage is 20-90%, and the thickness is 500-4000 nm.
  • the current spreading layer and quantum well active layer are all AlGaN, but the microstructure and composition There is a change in the proportion; for example, the quantum well active layer is an AlGaN film with a multiple quantum well structure, and the quantum well structure is composed of alternating barriers and potential wells. The Al mass fraction of the barrier is relatively high.
  • the Al mass fraction is low; the barrier thickness of the active layer of the quantum well is 5-30nm and the Al composition percentage in the barrier is 20-100%, the thickness of the potential well is 0.1-5nm and the Al composition percentage in the potential well is 0-80%, the preferred Al composition percentage in the potential well is 5-80%; the thickness of the current spreading layer is 20-200 nm, and the Al composition percentage is 20-100%.
  • the final barrier layer of the chirped superlattice is chirped in thickness and consists of several Al a Ga 1 -a superlattice structure composed of a N layer and several Al b Ga 1-b N layers alternately, and a ⁇ b, where the thickness of the Al b Ga 1-b N layer is 0.1-5 nm and 0.2 ⁇ b ⁇ 1,
  • the thickness of the Al a Ga 1-a N layer is 0.1 to 5 nm and 0 ⁇ a ⁇ 0.8, more preferably 0.05 ⁇ a ⁇ 0.8.
  • the light output power of the above-mentioned deep ultraviolet LED with the chirped superlattice final barrier structure was tested, and compared with the deep ultraviolet LED with the traditional final barrier structure, as shown in Fig. 3, and calculated according to Fig. 3 ,
  • the light output power of the deep ultraviolet LED with the chirped superlattice final barrier structure in the present invention is 16.3% higher than that of the traditional deep ultraviolet LED, which proves that the present invention has a chirped superlattice final barrier
  • the structure of the deep ultraviolet LED can significantly improve the luminous efficiency of the device.
  • the present invention provides a deep ultraviolet LED with a chirped superlattice final barrier structure and a preparation method thereof.
  • a deep ultraviolet LED with a chirped superlattice final barrier structure and a preparation method thereof.

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Abstract

一种具有啁啾超晶格最终势垒结构的深紫外LED及制备方法，该深紫外LED包括蓝宝石衬底（1）、AlN本征层（2）、N型AlGaN层（3）、电流扩展层（4）、量子阱有源层（5）、啁啾超晶格最终势垒层（6）、电子阻挡层（7）、P型AlGaN注入层（8）和P型GaN接触层（9）；其中啁啾超晶格最终势垒层（6）为厚度啁啾且由若干AlaGa1-aN层和若干AlbGa1-bN层周期交替组成的超晶格结构。通过引入啁啾超晶格最终势垒层，降低了电子隧穿至P型AlGaN注入层的概率，削弱了电子溢流效应，从而提高了深紫外LED的发光效率。

Description

具有啁啾超晶格最终势垒结构的深紫外LED及制备方法 技术领域
本发明涉及半导体光电领域，特别是一种具有啁啾超晶格最终势垒结构的深紫外LED及制备方法。
背景技术
Ⅲ族氮化物作为宽禁带半导体材料中的杰出代表，已经实现了高效的蓝绿光发光二极管(全称light-emitting diodes，简称LED)、激光器等固态光源器件，其在平板显示、白光照明等应用方面取得了巨大成功。近十年来，人们期望将这种高效的发光材料应用于紫外波段，以满足日益增长的紫外光源需求。紫外波段根据其生物效应通常可分为：长波紫外(即UVA，波长为320～400nm)、中波紫外(即UVB，波长为280～320nm)、短波紫外(即UVC，波长为200～280nm)以及真空紫外(即VUV，波长为10～200nm)。紫外线虽然不能被人类眼睛所感知，但其应用却非常广泛。长波紫外光源在医学治疗、紫外固化、紫外光刻、信息存储、植物照明等领域有着巨大的应用前景；而深紫外光包含中波紫外和短波紫外，则在杀菌消毒、水净化、生化探测、非视距通信等方面有着不可替代的作用。目前，传统紫外光源主要是汞灯，具有体积大、功耗高、电压高、污染环境等缺点，不利于其在日常生活及特殊环境下的应用。因此，人们迫切希望研制出一种高效的半导体紫外光源器件以替代传统的汞灯。现有研究表明Ⅲ族氮化物中的AlGaN是制备半导体紫外光源器件的最佳候选材料，AlGaN基紫外LED具有无毒环保、小巧便携、低功耗、低电压、易集成、寿命长、波长可调等诸多优势，有望在未来几年取得突破性进展以及广泛应用，并逐步取代传统紫外汞灯。
目前，Al xGa 1-xN材料的禁带宽度可通过改变Al组分实现从3.4eV(GaN)到 6.2eV(AlN)范围内的连续可调，能够实现从365nm到200nm光谱范围内的发光。其中，GaN的带边发光波长约为360nm，通常作为氮化物紫外发光二极管(全称Ultraviolet light-emitting diodes,简称UV-LED)发光波段的一个划分标志。发光波长大于360nm的UV-LED的有源区采用和蓝光LED类似的GaN/InGaN量子阱(QWs)结构。其相关研究早在上世纪90年代就已开始，目前已成功商业化，外量子效率(EQE)也已超过40％，达到了与蓝光LED相比拟的水平。
相比之下，发光波长小于360nm的UV LED则主要采用AlGaN量子阱结构作为有源区，其量子效率远没有这么令人满意。导致高Al组分AlGaN基深紫外LED效率偏低的一个主要原因是存在明显的电子溢流效应，来源于电子注入层的电子越过电子阻挡层至p型层，造成了p型层发光，降低了内量子效率。故需要提出一种新的紫外LED方案用于解决现有技术中存在的问题。
发明内容
本发明的目的在于，提供一种具有啁啾超晶格最终势垒结构的深紫外LED及制备方法，用于解决现有技术中由于电子溢流效应而导致深紫外LED效率低的问题。
为解决上述技术问题，本发明提供的第一解决方案为：一种具有啁啾超晶格最终势垒结构的深紫外LED，包括蓝宝石衬底、AlN本征层、N型AlGaN层、电流扩展层、量子阱有源层、啁啾超晶格最终势垒层、电子阻挡层、P型AlGaN注入层和P型GaN接触层；于蓝宝石衬底上依次沉积AlN本征层、N型AlGaN层、电流扩展层、量子阱有源层、啁啾超晶格最终势垒层、电子阻挡层、P型AlGaN注入层和P型GaN接触层；啁啾超晶格最终势垒层为厚度啁啾且由若干Al aGa 1-aN层和若干Al bGa 1-bN层周期交替组成的超晶格结构。
其中，啁啾超晶格最终势垒层中包含由Al aGa 1-aN层和Al bGa 1-bN层组成的n个周期，n≥1；在n＝1的周期中，Al aGa 1-aN层和Al bGa 1-bN层的厚度分别为x和y；沿量子阱有源层至电子阻挡层的方向上，在Al aGa 1-aN层和Al bGa 1-bN层组成的n个周期中，Al aGa 1-aN层和Al bGa 1-bN层的厚度分别为x±n·t和y±n·t， 其中t满足0.1nm≤t≤10nm。
优选的，Al aGa 1-aN层为单一Al aGa 1-aN组分的单层结构，Al bGa 1-bN层为单一Al bGa 1-bN组分的单层结构，且a和b满足0.4＜a＜b＜1。
优选的，Al aGa 1-aN层为组分渐变式单层结构且Al组分参数a由数值c线性渐变至d，Al bGa 1-bN层为单一Al bGa 1-bN组分的单层结构，其中b、c和d满足0.4＜c＜d＜b＜1。
优选的，Al aGa 1-aN层为单一Al aGa 1-aN组分的单层结构，Al bGa 1-bN层为组分渐变式单层结构且Al组分参数b由数值e线性渐变至f，其中a、e和f满足0.4＜a＜f＜e＜1。
优选的，Al aGa 1-aN层为组分渐变式单层结构且Al组分参数a由数值g线性渐变至h，Al bGa 1-bN层为组分渐变式单层结构且Al组分参数b由数值j线性渐变至k，其中g、h和k满足0.4＜g＜h＜j＜k＜1。
优选的，P型AlGaN注入层和P型GaN接触层中所采用的掺杂剂为Mg。
为解决上述技术问题，本发明提供的第二解决方案为：一种具有啁啾超晶格最终势垒结构的深紫外LED制备方法，其特征在于，具有啁啾超晶格最终势垒结构的深紫外LED制备方法采用金属有机化学气相沉积法制备前述第一解决方案中任一具有啁啾超晶格最终势垒结构的深紫外LED。
其中，具有啁啾超晶格最终势垒结构的深紫外LED制备方法步骤包括：在400～800℃条件下，于蓝宝石衬底上生长AlN本征层中的缓冲层，厚度为10～50nm；升温至1200～1400℃，于AlN本征层中的缓冲层上生长AlN本征层，AlN本征层的总厚度为500～4000nm；降温至800～1200℃，于AlN本征层上生长n型AlGaN层，其中Al组分百分数为20～90％，厚度为500～4000nm；降温至700～1100℃，于n型AlGaN层上一侧依次生长电流扩展层和量子阱有源层，其中量子阱有源层的势垒厚度为5～30nm且势垒中Al组分百分数为20～100％，势阱厚度为0.1～5nm且势阱中Al组分百分数为0～80％，优选的势阱中Al组分百分数为5～80％；在700～1100℃条件下，于的量子阱有源层上生长啁啾超晶格最终势垒层，啁啾超晶格最终势垒层为厚度啁啾且由若干Al aGa 1-aN层和若干 Al bGa 1-bN层周期交替组成的超晶格结构，且a＜b，其中Al bGa 1-bN层的厚度为0.1～5nm且0.2＜b＜1，Al aGa 1-aN层的厚度为0.1～5nm且0＜a＜0.8，进一步优选的0.05＜a＜0.8；在700～1100℃条件下，于啁啾超晶格最终势垒层上生长电子阻挡层，厚度为5～50nm，Al组分百分数为30～100％；在700～1100℃条件下，于电子阻挡层上生长p型AlGaN注入层，Al组分百分数为0～100％，进一步优选的Al组分百分数为5～100％，厚度为1～50nm，并采用Mg作为p型掺杂剂；在400～900℃条件下，于p型AlGaN注入层上生长p型GaN接触层，厚度为1～20nm，并采用Mg作为p型掺杂剂。
本发明的有益效果是：区别于现有技术的情况，本发明提供一种具有啁啾超晶格最终势垒结构的深紫外LED及制备方法，通过引入啁啾超晶格最终势垒层，降低了电子隧穿至P型AlGaN注入层的概率，削弱了电子溢流效应，从而提高了深紫外LED的发光效率。
附图说明
图1是本发明中具有啁啾超晶格最终势垒结构的深紫外LED一实施方式的结构示意图；
图2是本发明中具有啁啾超晶格最终势垒结构的深紫外LED一实施方式的能带对比图；
图3是本发明中具有啁啾超晶格最终势垒结构的深紫外LED一实施方式的出光功率图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，均属于本发明保护的范围。
对于本发明中提出的第一解决方案，请参阅图1，图1是本发明中具有啁 啾超晶格最终势垒结构的深紫外LED一实施方式的结构示意图。本发明中具有啁啾超晶格最终势垒结构的深紫外LED，包括蓝宝石衬底1、AlN本征层2、N型AlGaN层3、电流扩展层4、量子阱有源层5、啁啾超晶格最终势垒层6、电子阻挡层7、P型AlGaN注入层8和P型GaN接触层9；于蓝宝石衬底1上依次沉积AlN本征层2、N型AlGaN层3、电流扩展层4、量子阱有源层5、啁啾超晶格最终势垒层6、电子阻挡层7、P型AlGaN注入层8和P型GaN接触层9；此外，还可在P型GaN接触层9上设置P电极10，在N型AlGaN层3远离电流扩展层4的一侧设置N电极11，以构成完整的深紫外LED器件；其中，啁啾超晶格最终势垒层6为厚度啁啾且由若干Al aGa 1-aN层和若干Al bGa 1-bN层周期交替组成的超晶格结构，通过引入厚度啁啾的超晶格结构作为最终势垒，降低了电子隧穿至P型AlGaN注入层的概率，削弱了电子溢流效应，从而提高了深紫外LED的发光效率。
具体地，对上述啁啾超晶格最终势垒层的结构设置进行详细描述。对于啁啾超晶格最终势垒层的厚度设置方面，啁啾超晶格最终势垒层中包含由Al aGa 1-aN层和Al bGa 1-bN层组成的n个周期，n≥1；在n＝1的周期中，Al aGa 1-aN层和Al bGa 1-bN层的厚度分别为x和y；沿量子阱有源层至电子阻挡层的方向上，在Al aGa 1-aN层和Al bGa 1-bN层组成的n个周期中，Al aGa 1-aN层和Al bGa 1-bN层的厚度分别为x±n·t和y±n·t，其中t满足0.1nm≤t≤10nm，即本方案中多周期Al aGa 1-aN层和Al bGa 1-bN层的厚度既可以是同步线性递增的方式，也可以是同步线性递减的方式，这两种设置方式可根据实际情况进行选择，在此不作限定。
对于啁啾超晶格最终势垒层的组分比例设置方面，可存在以下四种设置方式：(1)Al aGa 1-aN层为单一Al aGa 1-aN组分的单层结构，Al bGa 1-bN层为单一Al bGa 1-bN组分的单层结构，且a和b满足0.4＜a＜b＜1；(2)Al aGa 1-aN层为组分渐变式单层结构且Al组分参数a由数值c线性渐变至d，Al bGa 1-bN层为单一Al bGa 1-bN组分的单层结构，其中b、c和d满足0.4＜c＜d＜b＜1；(3)Al aGa 1-aN层为单一Al aGa 1-aN组分的单层结构，Al bGa 1-bN层为组分渐变式单层结构且Al组分参数b由数值e线性渐变至f，其中a、e和f满足0.4＜a＜f＜e＜1；(4) Al aGa 1-aN层为组分渐变式单层结构且Al组分参数a由数值g线性渐变至h，Al bGa 1-bN层为组分渐变式单层结构且Al组分参数b由数值j线性渐变至k，其中g、h和k满足0.4＜g＜h＜j＜k＜1。
综合啁啾超晶格最终势垒层的厚度和组份比例两方面的设置情况，可知本方案中啁啾超晶格最终势垒层的具体设置方式总有八种，依次为：(1)多周期Al aGa 1-aN层和Al bGa 1-bN层的厚度依次递增，且Al aGa 1-aN层为单一Al aGa 1-aN组分的单层结构，Al bGa 1-bN层为单一Al bGa 1-bN组分的单层结构；(2)多周期Al aGa 1-aN层和Al bGa 1-bN层的厚度依次递增，且Al aGa 1-aN层为组分渐变式单层结构，Al bGa 1-bN层为单一Al bGa 1-bN组分的单层结构；(3)多周期Al aGa 1-aN层和Al bGa 1-bN层的厚度依次递增，且Al aGa 1-aN层为单一Al aGa 1-aN组分的单层结构，Al bGa 1-bN层为组分渐变式单层结构；(4)多周期Al aGa 1-aN层和Al bGa 1-bN层的厚度依次递增，且Al aGa 1-aN层为组分渐变式单层结构，Al bGa 1-bN层为组分渐变式单层结构；(5)多周期Al aGa 1-aN层和Al bGa 1-bN层的厚度依次递减，且Al aGa 1-aN层为单一Al aGa 1-aN组分的单层结构，Al bGa 1-bN层为单一Al bGa 1-bN组分的单层结构；(6)多周期Al aGa 1-aN层和Al bGa 1-bN层的厚度依次递减，且Al aGa 1-aN层为组分渐变式单层结构，Al bGa 1-bN层为单一Al bGa 1-bN组分的单层结构；(7)多周期Al aGa 1-aN层和Al bGa 1-bN层的厚度依次递减，且Al aGa 1-aN层为单一Al aGa 1-aN组分的单层结构，Al bGa 1-bN层为组分渐变式单层结构；(8)多周期Al aGa 1-aN层和Al bGa 1-bN层的厚度依次递减，且Al aGa 1-aN层为组分渐变式单层结构，Al bGa 1-bN层为组分渐变式单层结构。可根据实际需求采用适宜的设置方案，在此不作限定。
请参阅图2，图2是本发明中具有啁啾超晶格最终势垒结构的深紫外LED一实施方式的能带对比图，其中a图common LB代表的是传统最终势垒结构的能带，而b、c、d图SLLB-I、SLLB-E、SLLB-D分别代表的是本发明中啁啾超晶格最终势垒结构的深紫外LED三个不同设置方式的样品，对比可以看出，相比于传统最终势垒结构，啁啾超晶格最终势垒结构可以提高电子阻挡层电子势垒高度，降低空穴注入势垒高度，从而阻挡电子向p型层进行输运，从而削弱 了电子溢流效应。
对于本发明提出的第二解决方案，具有啁啾超晶格最终势垒结构的深紫外LED制备方法步骤包括：
(1)在400～800℃条件下，于蓝宝石衬底上生长AlN本征层中的缓冲层，厚度为10～50nm。
(2)升温至1200～1400℃，于AlN本征层中的缓冲层上生长AlN本征层，AlN本征层的总厚度为500～4000nm。
(3)降温至800～1200℃，于AlN本征层上生长n型AlGaN层，其中Al组分百分数为20～90％，厚度为500～4000nm。
(4)降温至700～1100℃，于n型AlGaN层上一侧依次生长电流扩展层和量子阱有源层，电流扩展层和量子阱有源层的成分均为AlGaN，但微观结构和组分比例存在变化；如量子阱有源层是具有多量子阱结构的AlGaN膜层，而量子阱结构由势垒和势阱交替构成，势垒的Al质量分数较高，相对的，势阱的Al质量分数较低；其中量子阱有源层的势垒厚度为5～30nm且势垒中Al组分百分数为20～100％，势阱厚度为0.1～5nm且势阱中Al组分百分数为0～80％，优选的势阱中Al组分百分数为5～80％；电流扩展层厚度为20～200nm，Al组分百分数为20～100％。
(5)在700～1100℃条件下，于的量子阱有源层上生长啁啾超晶格最终势垒层，啁啾超晶格最终势垒层为厚度啁啾且由若干Al aGa 1-aN层和若干Al bGa 1-bN层周期交替组成的超晶格结构，且a＜b，其中Al bGa 1-bN层的厚度为0.1～5nm且0.2＜b＜1，Al aGa 1-aN层的厚度为0.1～5nm且0＜a＜0.8，进一步优选的0.05＜a＜0.8。
(6)在700～1100℃条件下，于啁啾超晶格最终势垒层上生长电子阻挡层，厚度为5～50nm，Al组分百分数为30～100％。
(7)在700～1100℃条件下，于电子阻挡层上生长p型AlGaN注入层，Al组分百分数为0～100％，进一步优选的Al组分百分数为5～100％，厚度为1～50nm，并采用Mg作为p型掺杂剂。
(8)在400～900℃条件下，于p型AlGaN注入层上生长p型GaN接触层，厚度为1～20nm，并采用Mg作为p型掺杂剂。
由于第二解决方案中的具有啁啾超晶格最终势垒结构的深紫外LED制备方法用于制备前述第一解决方案中的具有啁啾超晶格最终势垒结构的深紫外LED，故两个方案中的具有啁啾超晶格最终势垒结构的深紫外LED的结构和功能应保持一致。
进一步地，对上述具有啁啾超晶格最终势垒结构的深紫外LED的出光功率进行测试，并与传统最终势垒结构的深紫外LED进行对比，如图3所示，根据图3进行计算，得到本发明中具有啁啾超晶格最终势垒结构的深紫外LED的出光功率较传统深紫外LED的出光功率有16.3％的提升，即证明本发明中具有啁啾超晶格最终势垒结构的深紫外LED能够器件的发光效率显著提高。
区别于现有技术的情况，本发明提供一种具有啁啾超晶格最终势垒结构的深紫外LED及制备方法，通过引入啁啾超晶格最终势垒层，降低了电子隧穿至P型AlGaN注入层的概率，削弱了电子溢流效应，从而提高了深紫外LED的发光效率。
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (9)

  1. 一种具有啁啾超晶格最终势垒结构的深紫外LED，其特征在于，包括蓝宝石衬底、AlN本征层、N型AlGaN层、电流扩展层、量子阱有源层、啁啾超晶格最终势垒层、电子阻挡层、P型AlGaN注入层和P型GaN接触层；
    于所述蓝宝石衬底上依次沉积所述AlN本征层、N型AlGaN层、电流扩展层、量子阱有源层、啁啾超晶格最终势垒层、电子阻挡层、P型AlGaN注入层和P型GaN接触层；
    所述啁啾超晶格最终势垒层为厚度啁啾且由若干Al aGa 1-aN层和若干Al bGa 1-bN层周期交替组成的超晶格结构。
  2. 根据权利要求1中所述的具有啁啾超晶格最终势垒结构的深紫外LED，其特征在于，所述啁啾超晶格最终势垒层中包含由所述Al aGa 1-aN层和Al bGa 1-bN层组成的n个周期，n≥1；
    在n＝1的周期中，Al aGa 1-aN层和Al bGa 1-bN层的厚度分别为x和y；
    沿所述量子阱有源层至所述电子阻挡层的方向上，在所述Al aGa 1-aN层和Al bGa 1-bN层组成的n个周期中，所述Al aGa 1-aN层和Al bGa 1-bN层的厚度分别为x±n·t和y±n·t，其中t满足0.1nm≤t≤10nm。
  3. 根据权利要求2中所述的具有啁啾超晶格最终势垒结构的深紫外LED，其特征在于，所述Al aGa 1-aN层为单一Al aGa 1-aN组分的单层结构，Al bGa 1-bN层为单一Al bGa 1-bN组分的单层结构，且a和b满足0.4＜a＜b＜1。
  4. 根据权利要求2中所述的具有啁啾超晶格最终势垒结构的深紫外LED，其特征在于，所述Al aGa 1-aN层为组分渐变式单层结构且Al组分参数a由数值c线性渐变至d，所述Al bGa 1-bN层为单一Al bGa 1-bN组分的单层结构，其中b、c和d满足0.4＜c＜d＜b＜1。
  5. 根据权利要求2中所述的具有啁啾超晶格最终势垒结构的深紫外LED，其特征在于，所述Al aGa 1-aN层为单一Al aGa 1-aN组分的单层结构，所述Al bGa 1-bN层为组分渐变式单层结构且Al组分参数b由数值e线性渐变至f，其中a、e和f满足0.4＜a＜f＜e＜1。
  6. 根据权利要求2中所述的具有啁啾超晶格最终势垒结构的深紫外LED，其特征在于，所述Al aGa 1-aN层为组分渐变式单层结构且Al组分参数a由数值g线性渐变至h，所述Al bGa 1-bN层为组分渐变式单层结构且Al组分参数b由数值j线性渐变至k，其中g、h和k满足0.4＜g＜h＜j＜k＜1。
  7. 根据权利要求1中所述的具有啁啾超晶格最终势垒结构的深紫外LED，其特征在于，所述P型AlGaN注入层和P型GaN接触层中所采用的掺杂剂为Mg。
  8. 一种具有啁啾超晶格最终势垒结构的深紫外LED制备方法，其特征在于，所述具有啁啾超晶格最终势垒结构的深紫外LED制备方法采用金属有机化学气相沉积法制备权利要求1～7中任一所述具有啁啾超晶格最终势垒结构的深紫外LED。
  9. 根据权利要求8中所述的具有啁啾超晶格最终势垒结构的深紫外LED制备方法，其特征在于，步骤包括：
    在400～800℃条件下，于蓝宝石衬底上生长AlN本征层中的缓冲层，厚度为10～50nm；
    升温至1200～1400℃，于AlN本征层中的缓冲层上生长AlN本征层，所述AlN本征层的总厚度为500～4000nm；
    降温至800～1200℃，于所述AlN本征层上生长n型AlGaN层，其中Al组分百分数为20～90％，厚度为500～4000nm；
    降温至700～1100℃，于所述n型AlGaN层上一侧依次生长电流扩展层和量子阱有源层，其中所述量子阱有源层的势垒厚度为5～30nm且势垒中Al组分百分数为20～100％，势阱厚度为0.1～5nm且势阱中Al组分百分数为0～80％；
    在700～1100℃条件下，于所述的量子阱有源层上生长啁啾超晶格最终势垒层，所述啁啾超晶格最终势垒层为厚度啁啾且由若干Al aGa 1-aN层和若干Al bGa 1-bN层周期交替组成的超晶格结构，且a＜b，其中所述Al bGa 1-bN层的厚度为0.1～5nm且0.2＜b＜1，Al aGa 1-aN层的厚度为0.1～5nm且0＜a＜0.8；
    在700～1100℃条件下，于所述啁啾超晶格最终势垒层上生长电子阻挡层， 厚度为5～50nm，Al组分百分数为30～100％；
    在700～1100℃条件下，于所述电子阻挡层上生长p型AlGaN注入层，Al组分百分数为0-100％，厚度为1～50nm，并采用Mg作为p型掺杂剂；
    在400～900℃条件下，于所述p型AlGaN注入层上生长p型GaN接触层，厚度为1～20nm，并采用Mg作为p型掺杂剂。
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