CN111540814A - LED epitaxial growth method for improving quantum efficiency - Google Patents

LED epitaxial growth method for improving quantum efficiency Download PDF

Info

Publication number
CN111540814A
CN111540814A CN202010386169.0A CN202010386169A CN111540814A CN 111540814 A CN111540814 A CN 111540814A CN 202010386169 A CN202010386169 A CN 202010386169A CN 111540814 A CN111540814 A CN 111540814A
Authority
CN
China
Prior art keywords
growing
layer
temperature
doped
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010386169.0A
Other languages
Chinese (zh)
Other versions
CN111540814B (en
Inventor
徐平
谢鹏杰
刘康
尹志哲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiangneng Hualei Optoelectrical Co Ltd
Original Assignee
Xiangneng Hualei Optoelectrical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiangneng Hualei Optoelectrical Co Ltd filed Critical Xiangneng Hualei Optoelectrical Co Ltd
Priority to CN202010386169.0A priority Critical patent/CN111540814B/en
Publication of CN111540814A publication Critical patent/CN111540814A/en
Application granted granted Critical
Publication of CN111540814B publication Critical patent/CN111540814B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C23C16/303—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Led Devices (AREA)

Abstract

The application discloses a light-emitting diode (LED) epitaxial growth method for improving quantum efficiency, which sequentially comprises the following steps of: the method comprises the following steps of treating a substrate, growing a low-temperature GaN buffer layer, growing an undoped GaN layer, growing an N-type GaN layer doped with Si, growing a multi-quantum well layer, growing an AlGaN electronic barrier layer, growing a P-type GaN layer doped with Mg, and cooling, wherein the growing multi-quantum well layer sequentially comprises the steps of growing an InGaN well layer, growing a low-temperature Mg steep-doped AlGaInN layer, growing a high-temperature undoped AlGaInN layer and growing a GaN barrier layer. The method solves the problem of quantum efficiency collapse caused by electron leakage in the existing LED epitaxial growth method, thereby improving the luminous efficiency of the LED, reducing the working voltage and reducing the wavelength drift.

Description

LED epitaxial growth method for improving quantum efficiency
Technical Field
The invention belongs to the technical field of LEDs, and particularly relates to an LED epitaxial growth method for improving quantum efficiency.
Background
A Light-Emitting Diode (LED) is a semiconductor electronic device that converts electrical energy into optical energy. When current flows, electrons and holes recombine in the quantum well to emit monochromatic light. As a novel efficient, environment-friendly and green solid-state lighting source, the LED has the advantages of low voltage, low power consumption, small size, light weight, long service life, high reliability, rich colors and the like. At present, the scale of domestic LED production is gradually enlarged, but the LED still has the problem of low luminous efficiency, and the energy-saving effect of the LED is influenced.
In the traditional LED epitaxial InGaN/GaN multi-quantum well layer growing method, electrons in an InGaN/GaN quantum well are easy to leak, so that the quantum efficiency collapses, the radiation efficiency of a light emitting region is low, the light emitting efficiency of an LED is low, and the energy saving effect of the LED is influenced.
Therefore, the problem of quantum efficiency collapse caused by electron leakage in the existing LED multiple quantum well layer is solved, so that the light emitting efficiency of the LED is improved, and a technical problem to be solved in the technical field is urgently solved.
Disclosure of Invention
The invention solves the problem of quantum efficiency collapse caused by electron leakage in the existing LED epitaxial growth method by adopting a new multi-quantum well layer growth method, thereby improving the luminous efficiency of the LED, reducing the working voltage and reducing the wavelength drift.
The LED epitaxial growth method sequentially comprises the following steps: processing a substrate, growing a low-temperature GaN buffer layer, growing an undoped GaN layer, growing an N-type GaN layer doped with Si, growing a multi-quantum well layer, growing an AlGaN electronic barrier layer, growing a P-type GaN layer doped with Mg, and cooling; the growing multiple quantum well layer sequentially comprises: growing an InGaN well layer, growing a low-temperature Mg layer doped with AlGaInN steeply, growing a high-temperature undoped AlGaInN layer and growing a GaN barrier layer, and specifically comprising the following steps:
A. controlling the pressure of the reaction chamber at 200-280mbar, controlling the temperature of the reaction chamber at 900-950 ℃, and introducing NH with the flow rate of 50000-70000sccm320sccm-40sccm of TMGa, 10000-15000sccm of TMIn and 100L/min-130L/min of N2Growing an InGaN well layer with the thickness of 3 nm;
B. keeping the pressure of the reaction chamber unchanged, reducing the temperature of the reaction chamber to 450-520 ℃, and introducing 160-180sccm NH3500-600sccm TMAl, 300-400 sccm TMGa, 100-130L/min N21300-1400sccm of TMIn and Cp2Mg, the doping concentration of Mg is increased by 4E +16atoms/cm per second in the growth process3From 4E +19atoms/cm3Linear ramp increase to 6E +19atoms/cm3And then adding 9E +18atoms/cm per second3From 6E +19atoms/cm3Linear ramp increase to 6E +21atoms/cm3Growing a low-temperature Mg steeply-doped AlGaInN layer with the thickness of 15nm-20 nm;
C. keeping the pressure of the reaction chamber unchanged, raising the temperature of the reaction chamber to 950-3500-600sccm TMAl, 300-400 sccm TMGa, 100-130L/min N21300 and 1400sccm TMIn, and growing a high-temperature undoped AlGaInN layer with the thickness of 15nm-20 nm;
D. reducing the temperature to 800 ℃, keeping the pressure of the reaction cavity at 300mbar-400mbar, and introducing NH with the flow rate of 30000sccm-40000sccm320sccm-60sccm of TMGa and 100L/min-130L/min of N2Growing a 10nm GaN barrier layer;
and repeating the steps A-D, and periodically and sequentially growing an InGaN well layer, a low-temperature Mg steeply-doped AlGaInN layer, a high-temperature undoped AlGaInN layer and a GaN barrier layer, wherein the number of growth cycles is 3-8.
Preferably, the specific process for processing the substrate is as follows:
introducing 100L/min to 130L/min at the temperature of 1000 ℃ to 1100 DEG CH of (A) to (B)2And keeping the pressure of the reaction cavity at 100mbar-300mbar, and processing the sapphire substrate for 5min-10 min.
Preferably, the specific process for growing the low-temperature GaN buffer layer is as follows:
cooling to 500-600 deg.C, maintaining the pressure in the reaction chamber at 300-600mbar, and introducing NH with a flow rate of 10000-20000sccm3TMGa of 50sccm-100sccm and H of 100L/min-130L/min2Growing a low-temperature GaN buffer layer with the thickness of 20nm-40nm on the sapphire substrate;
raising the temperature to 1000-1100 ℃, keeping the pressure of the reaction cavity at 300mbar-600mbar, and introducing NH with the flow rate of 30000sccm-40000sccm3H of 100L/min-130L/min2And preserving the heat for 300-500 s, and corroding the low-temperature GaN buffer layer into an irregular island shape.
Preferably, the specific process for growing the undoped GaN layer is as follows:
raising the temperature to 1000-1200 ℃, keeping the pressure of the reaction cavity at 300mbar-600mbar, and introducing NH with the flow rate of 30000sccm-40000sccm3TMGa of 200sccm-400sccm and H of 100L/min-130L/min2And continuously growing the undoped GaN layer of 2-4 mu m.
Preferably, the specific process for growing the doped GaN layer is as follows:
keeping the pressure of the reaction cavity at 300mbar-600mbar, keeping the temperature at 1000 ℃ -1200 ℃, and introducing NH with the flow rate of 30000sccm-60000sccm3TMGa of 200sccm-400sccm, H of 100L/min-130L/min2And 20sccm to 50sccm SiH4Continuously growing N-type GaN doped with Si of 3 μm to 4 μm, wherein the doping concentration of Si is 5E18atoms/cm3-1E19atoms/cm3。
Preferably, the specific process for growing the AlGaN electron blocking layer is as follows:
introducing NH of 50000-70000sccm at the temperature of 900-950 ℃ and the pressure of the reaction chamber of 200-400mbar3TMGa 30-60sccm, H100-130L/min2100 TMAl with 130sccm, 1000 Cp with 1300sccm2Growing the AlGaN electron barrier layer under the condition of Mg, wherein the thickness of the AlGaN layer is 40-60nm, and the Mg doping concentration is 1E19atoms/cm3-1E20atoms/cm3。
Preferably, the specific process for growing the Mg-doped P-type GaN layer is as follows:
keeping the pressure of the reaction cavity at 400mbar-900mbar and the temperature at 950-1000 ℃, and introducing NH with the flow rate of 50000sccm-70000sccm320sccm-100sccm of TMGa and 100L/min-130L/min of H2And Cp of 1000sccm to 3000sccm2Mg, continuously growing a P-type GaN layer doped with Mg with the concentration of 1E19atoms/cm and the thickness of 50nm-200nm3-1E20atoms/cm3。
Preferably, the specific process of cooling down is as follows:
cooling to 650-680 ℃, preserving heat for 20-30min, closing the heating system and the gas supply system, and cooling along with the furnace.
Compared with the traditional growth method, the LED epitaxial growth method for improving the quantum efficiency achieves the following effects:
1. according to the invention, the low-temperature Mg steep doping AlGaInN layer structure is introduced into the quantum well, so that a built-in electric field in the quantum well can be provided, the quantum confinement Stark effect is weakened, the fluctuation of a quantum well energy band under different current densities is smaller, and the quantum efficiency is improved. At low temperature, the mobility of electrons and holes is improved, because of the steep doping of Mg, the increased mobility enables the resistance of the quantum well layer to be increased at low temperature, the probability of leakage of electrons out of the active region of the quantum well is greatly reduced, and the leakage of current carriers can be relieved through the steep doping of Mg, so that the problem of quantum efficiency collapse of an LED device is solved, and the luminous efficiency of the LED is improved.
2. According to the invention, the low-temperature Mg doped AlGaInN layer structure is grown in the quantum well firstly, and then the high-temperature undoped AlGaInN layer is grown, so that the whole quantum well layer forms a gradient capacitor structure, the current limiting effect can be achieved, and the light emitting attenuation effect under high current density is reduced to a great extent; the LED light source can block the radial movement of charges, so that the charges are diffused to the periphery, namely, the transverse current expansion capability is enhanced, the LED light emitting efficiency is improved, the forward driving voltage is lower, and the wavelength drift is smaller.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic structural diagram of an LED epitaxy prepared by the method of the present invention;
FIG. 2 is a schematic structural diagram of an LED epitaxy prepared by a conventional method;
the GaN-based LED comprises a sapphire substrate, a low-temperature GaN buffer layer, a non-doped GaN layer, a N-type GaN layer, a multi-quantum well layer, an AlGaN electron barrier layer, a multi-quantum well layer, an InGaN well layer, a low-temperature Mg abrupt doped AlGa.
Detailed Description
As used in the specification and in the claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
Furthermore, the present description does not limit the components and method steps disclosed in the claims to those of the embodiments. In particular, the dimensions, materials, shapes, structural and adjacent orders, manufacturing methods, and the like of the components described in the embodiments are merely illustrative examples, and the scope of the present invention is not limited thereto, unless otherwise specified. The sizes and positional relationships of the structural members shown in the drawings are exaggerated for clarity of illustration.
The present application will be described in further detail below with reference to the accompanying drawings, but the present application is not limited thereto.
Example 1
In the embodiment, the LED epitaxial growth method for improving the quantum efficiency provided by the invention is adopted, MOCVD is adopted to grow the GaN-based LED epitaxial wafer, and high-purity H is adopted2Or high purity N2Or high purity H2And high purity N2The mixed gas of (2) is used as a carrier gas, high-purity NH3As the N source, a metal organic source, trimethyl gallium (TMGa) as the gallium source, trimethyl indium (TMIn) as the indium source, and an N-type dopant, Silane (SiH)4) Trimethylaluminum (TMAl) as the aluminum source and magnesium diclomelate (CP) as the P-type dopant2Mg), the reaction pressure is between 70mbar and 900 mbar. The specific growth method is as follows (please refer to fig. 1 for the epitaxial structure):
an LED epitaxial growth method for improving quantum efficiency sequentially comprises the following steps: processing a sapphire substrate 1, growing a low-temperature GaN buffer layer 2, growing an undoped GaN layer 3, growing an N-type GaN layer 4 doped with Si, growing a multi-quantum well layer 5, growing an AlGaN electronic barrier layer 6, growing a P-type GaN layer 7 doped with Mg, and cooling; wherein the content of the first and second substances,
step 1: the sapphire substrate 1 is processed.
Specifically, the step 1 further includes:
introducing 100-130L/min H at the temperature of 1000-1100 ℃ and the pressure of the reaction cavity of 100-300mbar2The sapphire substrate was processed for 5 to 10 minutes under the conditions of (1).
Step 2: and growing the low-temperature GaN buffer layer 2, and forming irregular islands on the low-temperature GaN buffer layer 2.
Specifically, the step 2 further includes:
introducing 10000-20000sccm NH into the reaction chamber at the temperature of 500-600 ℃ and the pressure of 300-600mbar3TMGa 50-100sccm, H100-130L/min2Under the conditions of (1), growing the low-temperature GaN buffer layer 2 on the sapphire substrate, the low-temperature GaN buffer layer 2The thickness is 20-40 nm;
introducing NH of 30000-40000sccm at the temperature of 1000-1100 ℃ and the pressure of the reaction chamber of 300-600mbar3H of 100L/min-130L/min2Under the conditions of (1), the irregular islands are formed on the low-temperature GaN buffer layer 2.
And step 3: an undoped GaN layer 3 is grown.
Specifically, the step 3 further includes:
introducing NH of 30000-40000sccm at the temperature of 1000-1200 ℃ and the pressure of the reaction chamber of 300-600mbar3200-400sccm TMGa, 100-130L/min H2The undoped GaN layer 3 grown under the condition of (a); the thickness of the undoped GaN layer 3 is 2-4 μm.
And 4, step 4: a Si doped N-type GaN layer 4 is grown.
Specifically, the step 4 is further:
keeping the pressure of the reaction cavity at 300mbar-600mbar, keeping the temperature at 1000 ℃ -1200 ℃, and introducing NH with the flow rate of 30000sccm-60000sccm3TMGa of 200sccm-400sccm, H of 100L/min-130L/min2And 20sccm to 50sccm SiH4Continuously growing a 3 μm-4 μm Si-doped N-type GaN layer 4 in which the Si doping concentration is 5E18atoms/cm3-1E19atoms/cm3。
And 5: the multiple quantum well layer 5 is grown.
The multiple quantum well layer 5 is further grown by:
(1) controlling the pressure of the reaction chamber at 200-280mbar, controlling the temperature of the reaction chamber at 900-950 ℃, and introducing NH with the flow rate of 50000-70000sccm320sccm-40sccm of TMGa, 10000-15000sccm of TMIn and 100L/min-130L/min of N2Growing an InGaN well layer 51 with a thickness of 3 nm; (2) keeping the pressure of the reaction chamber unchanged, reducing the temperature of the reaction chamber to 450-520 ℃, and introducing 160-180sccm NH3500-600sccm TMAl, 300-400 sccm TMGa, 100-130L/min N21300-1400sccm of TMIn and Cp2Mg, the doping concentration of Mg is increased by 4E +16atoms/cm per second in the growth process3From 4E +19atoms/cm3Linear ramp increase to 6E +19atoms/cm3And then adding 9E +18atoms/cm per second3From 6E +19atoms/cm3Linear ramp increase to 6E +21atoms/cm3Growing a low-temperature Mg steeply doped AlGaInN layer 52 with the thickness of 15nm-20 nm; (3) keeping the pressure of the reaction chamber unchanged, raising the temperature of the reaction chamber to 950-3500-600sccm TMAl, 300-400 sccm TMGa, 100-130L/min N21300 and 1400sccm TMIn, and growing a high-temperature undoped AlGaInN layer 53 with the thickness of 15nm-20 nm; (4) reducing the temperature to 800 ℃, keeping the pressure of the reaction cavity at 300mbar-400mbar, and introducing NH with the flow rate of 30000sccm-40000sccm320sccm-60sccm of TMGa and 100L/min-130L/min of N2Growing a 10nm GaN barrier layer 54;
repeating the steps A-D, and periodically and sequentially growing an InGaN well layer 51, a low-temperature Mg steeply-doped AlGaInN layer 52, a high-temperature undoped AlGaInN layer 53 and a GaN barrier layer 54 with the growth period number of 3-8.
Specifically, the step 6 further includes:
introducing NH of 50000-70000sccm at the temperature of 900-950 ℃ and the pressure of the reaction chamber of 200-400mbar3TMGa 30-60sccm, H100-130L/min2100 TMAl with 130sccm, 1000 Cp with 1300sccm2Growing the AlGaN electron barrier layer 6 under the condition of Mg, wherein the thickness of the AlGaN layer 6 is 40-60nm, and the Mg doping concentration is 1E19atoms/cm3-1E20atoms/cm3。
And 7: a Mg doped P-type GaN layer 7 is grown.
Specifically, the step 7 is further:
introducing NH of 50000-70000sccm at the temperature of 950-1000 ℃ and the pressure of the reaction chamber of 400-900mbar320-100sccm of TMGa, 100-21000-Cp of 3000sccm2Growing a Mg-doped P-type GaN layer 7 with the thickness of 50-200nm under the condition of Mg, wherein the Mg doping concentration is 1E19atoms/cm3-1E20atoms/cm3。
And 8: keeping the temperature for 20-30min at 650-680 ℃, then closing the heating system and the gas supply system, and cooling along with the furnace.
Example 2
The following provides a comparative example, an existing conventional LED epitaxial growth method.
Step 1: introducing 100-130L/min H at the temperature of 1000-1100 ℃ and the pressure of the reaction cavity of 100-300mbar2The sapphire substrate was processed for 5 to 10 minutes under the conditions of (1).
Step 2: and growing the low-temperature GaN buffer layer 2, and forming irregular islands on the low-temperature GaN buffer layer 2.
Specifically, the step 2 further includes:
introducing 10000-20000sccm NH into the reaction chamber at the temperature of 500-600 ℃ and the pressure of 300-600mbar3TMGa 50-100sccm, H100-130L/min2Growing the low-temperature GaN buffer layer 2 on the sapphire substrate under the condition (2), wherein the thickness of the low-temperature GaN buffer layer 2 is 20-40 nm;
introducing NH of 30000-40000sccm at the temperature of 1000-1100 ℃ and the pressure of the reaction chamber of 300-600mbar3H of 100L/min-130L/min2Under the conditions of (1), the irregular islands are formed on the low-temperature GaN buffer layer 2.
And step 3: an undoped GaN layer 3 is grown.
Specifically, the step 3 further includes:
introducing NH of 30000-40000sccm at the temperature of 1000-1200 ℃ and the pressure of the reaction chamber of 300-600mbar3200-400sccm TMGa, 100-130L/min H2The undoped GaN layer 3 grown under the condition of (a); the thickness of the undoped GaN layer 3 is 2-4 μm.
And 4, step 4: a Si doped N-type GaN layer 4 is grown.
Specifically, the step 4 is further:
introducing NH of 30000-60000sccm at the temperature of 1000-1200 ℃ and the pressure of the reaction chamber of 300-600mbar3200-400sccm TMGa, 100-130L/min H220-50sccm SiH4Under the conditions of (1) growing a Si-doped N-type GaN layer 4, the thickness of the N-type GaN layer being 3-4 μm, the concentration of the Si-doping being 5E18atoms/cm3-1E19atoms/cm3。
And 5: an InGaN/GaN MQW layer 5 is grown.
Specifically, the multiple quantum well layer is grown, and further:
keeping the pressure of the reaction cavity at 300mbar-400mbar and the temperature at 720 ℃, and introducing NH with the flow rate of 50000sccm-70000sccm320sccm-40sccm of TMGa, 10000-15000sccm of TMIn and 100L/min-130L/min of N2Growing an In-doped InGaN well layer 51 with a thickness of 3 nm;
raising the temperature to 800 ℃, keeping the pressure of the reaction cavity at 300mbar-400mbar, and introducing NH with the flow rate of 50000sccm-70000sccm320sccm to 100sccm of TMGa and 100L/min to 130L/min of N2Growing a 10nm GaN barrier layer 54;
and repeatedly and alternately growing the InGaN well layer 51 and the GaN barrier layer 54 to obtain an InGaN/GaN multi-quantum well layer, wherein the number of the alternate growth cycles of the InGaN well layer 51 and the GaN barrier layer 54 is 7-13.
Step 6: an AlGaN electron blocking layer 6 is grown.
Specifically, the step 6 further includes:
introducing NH of 50000-70000sccm at the temperature of 900-950 ℃ and the pressure of the reaction chamber of 200-400mbar3TMGa 30-60sccm, H100-130L/min2100 TMAl with 130sccm, 1000 Cp with 1300sccm2Growing the AlGaN electron barrier layer 6 under the condition of Mg, wherein the thickness of the AlGaN layer is 40-60nm, and the concentration of Mg doping is 1E19atoms/cm3-1E20atoms/cm3。
And 7: a Mg doped P-type GaN layer 7 is grown.
Specifically, the step 7 is further:
introducing NH of 50000-70000sccm at the temperature of 950-1000 ℃ and the pressure of the reaction chamber of 400-900mbar320-100sccm of TMGa, 100-21000-Cp of 3000sccm2Growing a Mg-doped P-type GaN layer 7 with the thickness of 50-200nm under the condition of Mg, wherein the Mg doping concentration is 1E19atoms/cm3-1E20atoms/cm3。
And 8: keeping the temperature for 20-30min at 650-680 ℃, then closing the heating system and the gas supply system, and cooling along with the furnace.
Samples 1 and 2 were prepared according to the above examples 1 and 2, respectively, with sample 1 and 2 being about 150nm coated with an ITO layer under the same pre-process conditions, about 1500nm coated with a Cr/Pt/Au electrode under the same conditions, and a protective layer of SiO coated under the same conditions2About 100nm, the sample was then ground and cut under the same conditions into 635 μm by 635 μm (25mil by 25mil) chip particles, and then 100 dies were picked from the same positions of sample 1 and sample 2, respectively, and packaged into a white LED under the same packaging process. The photoelectric properties of sample 1 and sample 2 were tested using an integrating sphere at a drive current of 350 mA.
TABLE 1 comparison of electrical parameters of sample 1 and sample 2
Figure BDA0002483911830000091
The data obtained by the integrating sphere are analyzed and compared, and as can be seen from table 1, the luminous efficiency of the LED (sample 1) prepared by the LED epitaxial growth method provided by the invention is obviously improved, the work is lower, and the wavelength drift is smaller, because the technical scheme of the invention solves the problem of quantum efficiency collapse caused by electron leakage in the existing LED epitaxial growth method, the luminous efficiency of the LED is improved, the working voltage is reduced, and the wavelength drift is reduced.
Compared with the traditional growth method, the LED epitaxial growth method for improving the quantum efficiency achieves the following effects:
1. according to the invention, the low-temperature Mg steep doping AlGaInN layer structure is introduced into the quantum well, so that a built-in electric field in the quantum well can be provided, the quantum confinement Stark effect is weakened, the fluctuation of a quantum well energy band under different current densities is smaller, and the quantum efficiency is improved. At low temperature, the mobility of electrons and holes is improved, because of the steep doping of Mg, the increased mobility enables the resistance of the quantum well layer to be increased at low temperature, the probability of leakage of electrons out of the active region of the quantum well is greatly reduced, and the leakage of current carriers can be relieved through the steep doping of Mg, so that the problem of quantum efficiency collapse of an LED device is solved, and the luminous efficiency of the LED is improved.
2. According to the invention, the low-temperature Mg doped AlGaInN layer structure is grown in the quantum well firstly, and then the high-temperature undoped AlGaInN layer is grown, so that the whole quantum well layer forms a gradient capacitor structure, the current limiting effect can be achieved, and the light emitting attenuation effect under high current density is reduced to a great extent; the LED light source can block the radial movement of charges, so that the charges are diffused to the periphery, namely, the transverse current expansion capability is enhanced, the LED light emitting efficiency is improved, the forward driving voltage is lower, and the wavelength drift is smaller.
Since the method has already been described in detail in the embodiments of the present application, the expanded description of the structure and method corresponding parts related to the embodiments is omitted here, and will not be described again. The description of specific contents in the structure may refer to the contents of the method embodiments, which are not specifically limited herein.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.

Claims (8)

1. An LED epitaxial growth method for improving quantum efficiency is characterized by sequentially comprising the following steps: processing a substrate, growing a low-temperature GaN buffer layer, growing an undoped GaN layer, growing an N-type GaN layer doped with Si, growing a multi-quantum well layer, growing an AlGaN electronic barrier layer, growing a P-type GaN layer doped with Mg, and cooling; the growing multiple quantum well layer sequentially comprises: growing an InGaN well layer, growing a low-temperature Mg layer doped with AlGaInN steeply, growing a high-temperature undoped AlGaInN layer and growing a GaN barrier layer, and specifically comprising the following steps:
A. the pressure of the reaction chamber is controlled at 200-280mbar, the temperature of the reaction chamber is controlled at 900-950 ℃, and the flow rate is 50000-70000sccmNH320sccm-40sccm of TMGa, 10000-15000sccm of TMIn and 100L/min-130L/min of N2Growing an InGaN well layer with the thickness of 3 nm;
B. keeping the pressure of the reaction chamber unchanged, reducing the temperature of the reaction chamber to 450-520 ℃, and introducing 160-180sccm NH3500-600sccm TMAl, 300-400 sccm TMGa, 100-130L/min N21300-1400sccm of TMIn and Cp2Mg, the doping concentration of Mg is increased by 4E +16atoms/cm per second in the growth process3From 4E +19atoms/cm3Linear ramp increase to 6E +19atoms/cm3And then adding 9E +18atoms/cm per second3From 6E +19atoms/cm3Linear ramp increase to 6E +21atoms/cm3Growing a low-temperature Mg steeply-doped AlGaInN layer with the thickness of 15nm-20 nm;
C. keeping the pressure of the reaction chamber unchanged, raising the temperature of the reaction chamber to 950-3500-600sccm TMAl, 300-400 sccm TMGa, 100-130L/min N21300 and 1400sccm TMIn, and growing a high-temperature undoped AlGaInN layer with the thickness of 15nm-20 nm;
D. reducing the temperature to 800 ℃, keeping the pressure of the reaction cavity at 300mbar-400mbar, and introducing NH with the flow rate of 30000sccm-40000sccm320sccm-60sccm of TMGa and 100L/min-130L/min of N2Growing a 10nm GaN barrier layer;
and repeating the steps A-D, and periodically and sequentially growing an InGaN well layer, a low-temperature Mg steeply-doped AlGaInN layer, a high-temperature undoped AlGaInN layer and a GaN barrier layer, wherein the number of growth cycles is 3-8.
2. The LED epitaxial growth method for improving quantum efficiency according to claim 1, wherein 100L/min-130L/min of H is introduced at a temperature of 1000 ℃ -1100 ℃2And keeping the pressure of the reaction cavity at 100mbar-300mbar, and processing the sapphire substrate for 5min-10 min.
3. The LED epitaxial growth method for improving quantum efficiency according to claim 1, wherein the specific process for growing the low-temperature GaN buffer layer is as follows:
cooling to 500-600 deg.C, maintaining the pressure in the reaction chamber at 300-600mbar, and introducing NH with a flow rate of 10000-20000sccm3TMGa of 50sccm-100sccm and H of 100L/min-130L/min2Growing a low-temperature GaN buffer layer with the thickness of 20nm-40nm on the sapphire substrate;
raising the temperature to 1000-1100 ℃, keeping the pressure of the reaction cavity at 300mbar-600mbar, and introducing NH with the flow rate of 30000sccm-40000sccm3H of 100L/min-130L/min2And preserving the heat for 300-500 s, and corroding the low-temperature GaN buffer layer into an irregular island shape.
4. The LED epitaxial growth method for improving quantum efficiency according to claim 1, wherein the specific process for growing the undoped GaN layer is as follows:
raising the temperature to 1000-1200 ℃, keeping the pressure of the reaction cavity at 300mbar-600mbar, and introducing NH with the flow rate of 30000sccm-40000sccm3TMGa of 200sccm-400sccm and H of 100L/min-130L/min2And continuously growing the undoped GaN layer of 2-4 mu m.
5. The LED epitaxial growth method for improving quantum efficiency according to claim 1, wherein the specific process for growing the Si-doped N-type GaN layer is as follows:
keeping the pressure of the reaction cavity at 300mbar-600mbar, keeping the temperature at 1000 ℃ -1200 ℃, and introducing NH with the flow rate of 30000sccm-60000sccm3TMGa of 200sccm-400sccm, H of 100L/min-130L/min2And 20sccm to 50sccm SiH4Continuously growing N-type GaN doped with Si of 3 μm to 4 μm, wherein the doping concentration of Si is 5E18atoms/cm3-1E19atoms/cm3。
6. The LED epitaxial growth method for improving quantum efficiency according to claim 1, wherein the specific process for growing the AlGaN electron blocking layer is as follows:
introducing NH of 50000-70000sccm at the temperature of 900-950 ℃ and the pressure of the reaction chamber of 200-400mbar3TMGa 30-60sccm, H100-130L/min2、1TMAl of 00-130sccm, Cp of 1000-1300sccm2Growing the AlGaN electron barrier layer under the condition of Mg, wherein the thickness of the AlGaN layer is 40-60nm, and the Mg doping concentration is 1E19atoms/cm3-1E20atoms/cm3。
7. The LED epitaxial growth method for improving quantum efficiency according to claim 1, wherein the specific process for growing the Mg-doped P-type GaN layer is as follows:
keeping the pressure of the reaction cavity at 400mbar-900mbar and the temperature at 950-1000 ℃, and introducing NH with the flow rate of 50000sccm-70000sccm320sccm-100sccm of TMGa and 100L/min-130L/min of H2And Cp of 1000sccm to 3000sccm2Mg, continuously growing a P-type GaN layer doped with Mg with the concentration of 1E19atoms/cm and the thickness of 50nm-200nm3-1E20atoms/cm3。
8. The LED epitaxial growth method for improving quantum efficiency according to claim 1, wherein the specific process of cooling down is as follows:
cooling to 650-680 ℃, preserving heat for 20-30min, closing the heating system and the gas supply system, and cooling along with the furnace.
CN202010386169.0A 2020-05-09 2020-05-09 LED epitaxial growth method for improving quantum efficiency Active CN111540814B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010386169.0A CN111540814B (en) 2020-05-09 2020-05-09 LED epitaxial growth method for improving quantum efficiency

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010386169.0A CN111540814B (en) 2020-05-09 2020-05-09 LED epitaxial growth method for improving quantum efficiency

Publications (2)

Publication Number Publication Date
CN111540814A true CN111540814A (en) 2020-08-14
CN111540814B CN111540814B (en) 2023-03-21

Family

ID=71980353

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010386169.0A Active CN111540814B (en) 2020-05-09 2020-05-09 LED epitaxial growth method for improving quantum efficiency

Country Status (1)

Country Link
CN (1) CN111540814B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001044209A (en) * 1999-07-27 2001-02-16 Furukawa Electric Co Ltd:The MANUFACTURE OF GaN-BASED SEMICONDUCTOR DEVICE
US20080042121A1 (en) * 2006-08-16 2008-02-21 Michael Iza METHOD FOR DEPOSITION OF MAGNESIUM DOPED (Al, In, Ga, B)N LAYERS
CN103985797A (en) * 2014-05-05 2014-08-13 湘能华磊光电股份有限公司 Multi-quantum-well structure, growing method and LED chip with structure
CN104091872A (en) * 2014-07-30 2014-10-08 湘能华磊光电股份有限公司 LED epitaxial wafer diffused through Mg, growing method and LED structure
CN104241464A (en) * 2014-09-05 2014-12-24 西安神光皓瑞光电科技有限公司 Epitaxial growth method increasing P-type gallium nitride doping concentration
CN105869994A (en) * 2016-04-14 2016-08-17 湘能华磊光电股份有限公司 Growth method for superlattice layer and LED epitaxial structure comprising superlattice layer
CN105932118A (en) * 2016-06-13 2016-09-07 湘能华磊光电股份有限公司 LED epitaxial growth method for improving hole injection
CN107394018A (en) * 2017-08-10 2017-11-24 湘能华磊光电股份有限公司 A kind of LED epitaxial growth methods
CN108336198A (en) * 2017-12-26 2018-07-27 华灿光电（浙江）有限公司 Light emitting diode epitaxial wafer and manufacturing method thereof
CN110629197A (en) * 2019-09-24 2019-12-31 湘能华磊光电股份有限公司 LED epitaxial structure growth method

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001044209A (en) * 1999-07-27 2001-02-16 Furukawa Electric Co Ltd:The MANUFACTURE OF GaN-BASED SEMICONDUCTOR DEVICE
US20080042121A1 (en) * 2006-08-16 2008-02-21 Michael Iza METHOD FOR DEPOSITION OF MAGNESIUM DOPED (Al, In, Ga, B)N LAYERS
CN103985797A (en) * 2014-05-05 2014-08-13 湘能华磊光电股份有限公司 Multi-quantum-well structure, growing method and LED chip with structure
CN104091872A (en) * 2014-07-30 2014-10-08 湘能华磊光电股份有限公司 LED epitaxial wafer diffused through Mg, growing method and LED structure
CN104241464A (en) * 2014-09-05 2014-12-24 西安神光皓瑞光电科技有限公司 Epitaxial growth method increasing P-type gallium nitride doping concentration
CN105869994A (en) * 2016-04-14 2016-08-17 湘能华磊光电股份有限公司 Growth method for superlattice layer and LED epitaxial structure comprising superlattice layer
CN105932118A (en) * 2016-06-13 2016-09-07 湘能华磊光电股份有限公司 LED epitaxial growth method for improving hole injection
CN107394018A (en) * 2017-08-10 2017-11-24 湘能华磊光电股份有限公司 A kind of LED epitaxial growth methods
CN108336198A (en) * 2017-12-26 2018-07-27 华灿光电（浙江）有限公司 Light emitting diode epitaxial wafer and manufacturing method thereof
CN110629197A (en) * 2019-09-24 2019-12-31 湘能华磊光电股份有限公司 LED epitaxial structure growth method

Also Published As

Publication number Publication date
CN111540814B (en) 2023-03-21

Similar Documents

Publication Publication Date Title
CN111223764A (en) LED epitaxial growth method for improving radiation recombination efficiency
CN110629197B (en) LED epitaxial structure growth method
CN109411573B (en) LED epitaxial structure growth method
CN114284406B (en) Preparation method of nitride light-emitting diode
CN110957403B (en) LED epitaxial structure growth method
CN111370540B (en) LED epitaxial growth method for improving luminous efficiency
CN110620168B (en) LED epitaxial growth method
CN112048710A (en) LED epitaxial growth method for reducing blue shift quantity of LED light-emitting wavelength
CN113328015B (en) Method for manufacturing light emitting diode chip with improved brightness
CN112687770B (en) LED epitaxial growth method
CN112941490B (en) LED epitaxial quantum well growth method
CN111952418B (en) LED multi-quantum well layer growth method for improving luminous efficiency
CN111769181B (en) LED epitaxial growth method suitable for small-spacing display screen
CN113540296A (en) Manufacturing method of LED epitaxial wafer suitable for small-spacing display screen
CN111276579B (en) LED epitaxial growth method
CN112420884B (en) LED epitaxial multi-quantum well layer growth method
CN111769180B (en) LED epitaxial growth method suitable for small-spacing display screen
CN111540814B (en) LED epitaxial growth method for improving quantum efficiency
CN112599647B (en) LED epitaxial multi-quantum well layer growth method
CN111952420A (en) LED epitaxial growth method suitable for manufacturing small-spacing display screen
CN111628056B (en) LED multi-quantum well layer growth method for improving crystal quality
CN111276578B (en) LED epitaxial structure growth method
CN114122206B (en) Manufacturing method of light-emitting diode
CN113972304B (en) LED epitaxial wafer manufacturing method
CN113036005B (en) LED epitaxial quantum well growth method for improving internal quantum efficiency

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant