CN114823995A - LED epitaxial wafer manufacturing method - Google Patents

LED epitaxial wafer manufacturing method Download PDF

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CN114823995A
CN114823995A CN202210313652.5A CN202210313652A CN114823995A CN 114823995 A CN114823995 A CN 114823995A CN 202210313652 A CN202210313652 A CN 202210313652A CN 114823995 A CN114823995 A CN 114823995A
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徐平
周孝维
许孔祥
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Xiangneng Hualei Optoelectrical Co Ltd
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Xiangneng Hualei Optoelectrical Co Ltd
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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
    • H01L33/005—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 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
    • H01L33/12—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 stress relaxation structure, e.g. buffer layer
    • 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

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Abstract

The application discloses a method for manufacturing an LED epitaxial wafer, which sequentially comprises the following steps: the method comprises the steps of processing a substrate, growing a low-temperature GaN buffer layer, growing a non-doped GaN layer, growing an Si-doped n-type GaN layer, manufacturing a current carrier transition layer, growing a multi-quantum well layer, growing an AlGaN electronic barrier layer, growing an Mg-doped P-type GaN layer, and cooling, wherein the manufacturing of the current carrier transition layer sequentially comprises the steps of sputtering a molybdenum oxide layer, carrying out ozone treatment and manufacturing a nitrogen atom layer. The invention improves the crystal quality of the quantum well by adopting a new manufacturing method, thereby improving the luminous efficiency of the LED.

Description

LED epitaxial wafer manufacturing method
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a manufacturing method of an LED epitaxial wafer.
Background
A Light-Emitting Diode (LED) is a semiconductor electronic device that converts electrical energy into optical energy. When current flows through the LED, electrons and holes in the LED are compounded in the multiple quantum wells 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 energy 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 performance, and the energy-saving effect of the LED is influenced.
The LED epitaxial multi-quantum well prepared by the existing LED epitaxial wafer method has low internal quantum efficiency, seriously hinders the improvement of the LED performance and influences the energy-saving effect of the LED.
In summary, there is an urgent need to develop a new method for fabricating an LED epitaxial wafer, to improve the crystal quality of the quantum well, and to solve the problem of low quantum efficiency in the multiple quantum wells of the existing LED, so as to improve the light emitting efficiency of the LED.
Disclosure of Invention
According to the invention, the crystal quality of the quantum well is improved by adopting a novel epitaxial wafer manufacturing method, so that the luminous efficiency of the LED is improved.
The manufacturing method of the LED epitaxial wafer sequentially comprises the following steps: processing a substrate, growing a low-temperature GaN buffer layer, growing a non-doped GaN layer, growing an Si-doped n-type GaN layer, manufacturing a carrier transition layer, growing a multi-quantum well layer, growing an AlGaN electronic barrier layer, growing an Mg-doped P-type GaN layer and cooling; the method is characterized in that the carrier transition layer is manufactured and sequentially comprises the following steps: sputtering a molybdenum oxide layer, carrying out ozone treatment and manufacturing a nitrogen atom layer, and specifically comprising the following steps:
A. controlling the temperature of a reaction cavity of the magnetron sputtering equipment to be 250-400 ℃, controlling the pressure of the reaction cavity to be 5-18Torr, introducing argon and oxygen into the reaction cavity, sputtering a molybdenum oxide layer with the thickness of 12-25nm on the Si-doped n-type GaN layer, and controlling the sputtering power of the equipment to be gradually increased from 400w to 900w and then gradually decreased from 900w to 600w in the sputtering process;
B. taking the epitaxial wafer sputtered with the molybdenum oxide layer out of the reaction cavity of the magnetron sputtering equipment, placing the epitaxial wafer into the reaction cavity of the plasma equipment, introducing 150-250sccm ozone into the reaction cavity to treat the molybdenum oxide film layer for 2-4min, and gradually increasing the temperature from 200 ℃ to 600 ℃ in the treatment process;
C. controlling the temperature in the reaction cavity of the plasma equipment to be 100-300 ℃, controlling the power to be 40-120w, introducing nitrogen into the reaction cavity in a mode of periodically interrupting a nitrogen source, and forming a nitrogen atom layer on the molybdenum oxide layer through plasma treatment, wherein the time for interrupting the nitrogen and the time for introducing the nitrogen into the reaction cavity are respectively 4s and 8s in the forming process.
Preferably, the specific process for processing the substrate is as follows:
at the temperature of 1000-1100 ℃, 100-130L/min H is introduced 2 And processing the sapphire substrate for 5-10min by keeping the pressure of the reaction chamber at 100-.
Preferably, the specific process for growing the low-temperature GaN buffer layer is as follows:
cooling to 500- 3 TMGa 50-100sccm and H100-130L/min 2 Growing a low-temperature GaN buffer layer with the thickness of 20-40nm on the sapphire substrate;
raising the temperature to 1000- 3 And H of 100- 2 And preserving the heat for 300-500s to etch 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- 3 200-400sccm TMGa and 100-130L/min H 2 And continuously growing the 2-4 mu m undoped GaN layer.
Preferably, the specific process for growing the Si-doped n-type GaN layer is as follows:
the pressure of the reaction chamber is kept at 300- 3 200-400sccm TMGa, 100-130L/min H 2 And 20-50sccm SiH 4 Continuously growing a 3m-4 μm Si-doped n-type GaN layer, wherein the Si doping concentration is 5E18-5E19atoms/cm 3 。
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 200-400mbar 3 TMGa 30-60sccm, H100-130L/min 2 100 TMAl with 130sccm, 1000 Cp with 1300sccm 2 Growing 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 1E19-1E20atoms/cm 3 。
Preferably, the specific process for growing the Mg-doped P-type GaN layer is as follows:
keeping the pressure of the reaction cavity at 400- 3 20-100sccm of TMGa, 100- 2 And 1000-Cp of 3000sccm 2 Mg, continuously growing a P-type GaN layer doped with Mg with the concentration of 50-200nm, wherein the doping concentration of Mg is 1E19-1E20atoms/cm 3 。
Preferably, the specific process of cooling down is as follows:
cooling to 650 plus 680 ℃, preserving the temperature 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 manufacturing method of the LED epitaxial wafer has the following effects:
according to the invention, the molybdenum oxide layer is inserted between the n-type GaN layer and the multi-quantum well layer, so that a certain compressive stress can be introduced to partially offset the tensile stress generated between the GaN and the sapphire substrate due to large difference of thermal expansion coefficients, and the problem of surface cracking of the GaN epitaxial material layer is relieved to a certain extent. In the process of sputtering the molybdenum oxide film layer, the sputtering power is controlled to be gradually increased and then gradually reduced, so that the molybdenum oxide film with higher quality and uniformity can be obtained, and the high-quality molybdenum oxide film can improve the crystal quality of a subsequently grown multiple quantum well layer.
MoO can be induced by treating the molybdenum oxide film with ozone X Mo inside the crystal lattice 4+ And Mo 5+ Ion conversion to Mo 6+ Ion, Mo 6+ The ions can increase MoO X Increase the work function ofThe number of holes entering the quantum well light-emitting layer can improve the internal quantum efficiency. The temperature is controlled to gradually increase in the ozone treatment process, so that high Mo can be obtained 6+ The molybdenum oxide film with uniform ion content and distribution can further promote the injection of holes into the quantum well luminescent layer, and improve the luminous efficiency of the light-emitting diode.
The polarity of the molybdenum oxide layer is changed by forming the nitrogen atom layer on the molybdenum oxide layer, so that the crystal atoms of the subsequently grown multiple quantum well layer are arranged more neatly, the material growth defects are reduced, the crystal quality of the quantum well layer is improved, and the luminous efficiency of the LED is improved. The nitrogen is introduced in the process of forming the nitrogen atom layer in a mode of periodically interrupting the nitrogen source, on one hand, the nitrogen atom layer with better quality and uniformity is favorably obtained, on the other hand, the crystal grain size of InGaN/GaN which grows next step can be promoted to be reduced, the nucleation density of the crystal grains is increased, and further, when the quantum well grows in a two-dimensional transverse mode, the roughness is reduced, so that the grown quantum well film layer is the most flat and bright, the crystallization quality is higher, and the brightness of the LED is higher.
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 view of an epitaxial LED prepared in example 1;
FIG. 2 is a schematic view of the epitaxial structure of the LED prepared in comparative example 1;
the GaN-based light-emitting diode comprises a sapphire substrate, a low-temperature GaN buffer layer, a non-doped GaN layer, a n-type GaN layer, a molybdenum oxide layer, a nitrogen atom layer, a multi-quantum well layer, an AlGaN electron barrier layer, a P-type GaN layer, an InGaN well layer, an InGaN barrier layer, a GaN barrier layer and a P-type GaN layer, wherein the sapphire substrate is 1, the low-temperature GaN buffer layer is 2, the non-doped GaN layer is 3, the n-type GaN layer is 4, the n-type GaN layer is 5, the molybdenum oxide layer is 6, the nitrogen atom layer is 7, the multi-quantum well layer is 8, the AlGaN electron barrier layer is 9, the P-type GaN layer is 71, the InGaN well layer is 72, and the GaN barrier layer is.
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, the structural order, the order of adjoining, and the manufacturing method 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 this embodiment, the method for manufacturing the LED epitaxial wafer provided by the present invention uses MOCVD to grow the GaN-based LED epitaxial wafer, and uses high-purity H 2 Or high purity N 2 Or high purity H 2 And high purity N 2 The mixed gas of (2) is used as a carrier gas, high-purity NH 3 As 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 dopant 2 Mg), the reaction pressure is between 70mbar and 600 mbar. The specific growth method is as follows (please refer to fig. 1 for the epitaxial structure):
the manufacturing method of the LED epitaxial wafer sequentially comprises the following steps: processing a sapphire substrate 1, growing a low-temperature GaN buffer layer 2, growing a non-doped GaN layer 3, growing an Si-doped n-type GaN layer 4, sputtering a molybdenum oxide layer 5, carrying out ozone treatment, manufacturing a nitrogen atom layer 6, growing a multi-quantum well layer 7, growing an AlGaN electronic barrier layer 8, growing an Mg-doped P-type GaN layer 9, and cooling; wherein,
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 100-300mbar 2 The 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 300-600mbar 3 TMGa 50-100sccm, H100-130L/min 2 Growing the low-temperature GaN buffer layer 2 on the sapphire substrate 1 under the condition (1), 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 300-600mbar 3 And H of 100- 2 Under the condition of (1), keeping the temperature for 300-.
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 300-600mbar 3 200-400sccm TMGa and 100-130L/min H 2 The non-doped 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:
the pressure of the reaction chamber is kept at 300- 3 、20TMGa of 0-400sccm, H of 100-130L/min 2 And 20-50sccm SiH 4 Continuously growing a 3-4 μm Si-doped n-type GaN layer 4 in which the Si doping concentration is 5E18-1E19atoms/cm 3 。
And 5: a molybdenum oxide layer 5 is sputtered.
Specifically, the step 5 further includes:
controlling the temperature of a reaction cavity of the magnetron sputtering equipment to be 250-400 ℃, controlling the pressure of the reaction cavity to be 5-18Torr, introducing argon and oxygen into the reaction cavity, sputtering the molybdenum oxide layer 5 with the thickness of 12-25nm on the Si-doped n-type GaN layer 4, and controlling the sputtering power of the equipment to be gradually increased from 400w to 900w and then gradually decreased from 900w to 600w in the sputtering process.
Step 6: and (4) carrying out ozone treatment.
Specifically, the step 6 further includes:
taking the epitaxial wafer sputtered with the molybdenum oxide layer 5 out of the reaction cavity of the magnetron sputtering equipment and placing the epitaxial wafer into the reaction cavity of the plasma equipment, introducing 150-250sccm ozone into the reaction cavity to treat the molybdenum oxide layer 5 for 2-4min, and gradually increasing the temperature from 200 ℃ to 600 ℃ in the treatment process.
And 7, manufacturing a nitrogen atom layer 6.
Specifically, the step 7 is further:
controlling the temperature in the reaction cavity of the plasma equipment to be 100-300 ℃, controlling the power to be 40-120w, introducing nitrogen into the reaction cavity in a mode of periodically interrupting a nitrogen source, forming a nitrogen atom layer 6 on the molybdenum oxide layer 5 through plasma treatment, wherein the time for interrupting the nitrogen and the time for introducing the nitrogen into the reaction cavity are 4s and 8s respectively in the forming process.
And 8: the multiple quantum well layer 7 is grown.
The multiple quantum well layer 7 is further grown by:
keeping the pressure of the reaction cavity at 300- 3 20-40sccm of TMGa, 10000- 2 Growing an In-doped InGaN well layer 71 with a thickness of 3 nm;
raising the temperature to 800 ℃, and keeping the pressure of the reaction cavity at 300-4 DEG C00mbar, NH with the flow rate of 50000- 3 20-100sccm of TMGa and 100-130L/min of N 2 Growing a 10nm GaN barrier layer 72;
and repeatedly and alternately growing the InGaN well layer 71 and the GaN barrier layer 72 to obtain the InGaN/GaN multi-quantum well light-emitting layer, wherein the number of the alternate growth cycles of the InGaN well layer 71 and the GaN barrier layer 72 is 7-13.
And step 9: an AlGaN electron blocking layer 8 is grown.
Specifically, the step 9 is further:
introducing NH of 50000-70000sccm at the temperature of 900-950 ℃ and the pressure of the reaction chamber of 200-400mbar 3 TMGa 30-60sccm, H100-130L/min 2 100-TMAl of 130sccm and 1000-Cp of 1300sccm 2 Growing the AlGaN electron barrier layer 8 under the condition of Mg, wherein the thickness of the AlGaN layer 8 is 40-60nm, and the Mg doping concentration is 1E19-1E20atoms/cm 3 。
Step 10: a P-type GaN layer 9 doped with Mg is grown.
Specifically, the step 10 is further:
introducing NH of 50000-70000sccm at the temperature of 950-1000 ℃ and the pressure of the reaction chamber of 400-900mbar 3 20-100sccm of TMGa, 100- 2 1000-Cp of 3000sccm 2 Growing a P-type GaN layer 9 doped with Mg with a thickness of 50-200nm under the condition of Mg and a Mg doping concentration of 1E19-1E20atoms/cm 3 。
Step 11: 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.
Comparative example 1
A comparative example, a method for growing a conventional LED epitaxial structure, is provided below (see fig. 2 for an epitaxial structure).
Step 1: introducing 100-130L/min H at the temperature of 1000-1100 ℃ and the pressure of the reaction cavity of 100-300mbar 2 The 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 300-600mbar 3 TMGa 50-100sccm, H100-130L/min 2 Growing the low-temperature GaN buffer layer 2 on the sapphire substrate 1 under the condition (1), 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 300-600mbar 3 100-130L/min H 2 Under the condition of (1), keeping the temperature for 300-.
And 3, 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 300-600mbar 3 200-400sccm TMGa and 100-130L/min H 2 Under the conditions of (a), growing the undoped GaN layer; 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 300-600mbar 3 200-400sccm TMGa, 100-130L/min H 2 20-50sccm SiH 4 Under the conditions of (1) growing a Si-doped n-type GaN layer 4, the thickness of the n-type GaN layer 4 being 3-4 μm, the concentration of Si doping being 5E18-1E19atoms/cm 3 。
And 5: an InGaN/GaN MQW layer 7 is grown.
Specifically, the multiple quantum well layer 7 is grown, and further:
keeping the pressure of the reaction cavity at 300- 3 20-40sccm of TMGa, 10000- 2 Growing an In-doped InGaN well layer 71 with a thickness of 3 nm;
the temperature is raised to 800 ℃,keeping the pressure of the reaction cavity at 300- 3 20-100sccm of TMGa and 100-130L/min of N 2 Growing a 10nm GaN barrier layer 72;
and repeatedly and alternately growing the InGaN well layer 71 and the GaN barrier layer 72 to obtain the InGaN/GaN multi-quantum well light-emitting layer, wherein the number of the alternate growth cycles of the InGaN well layer 71 and the GaN barrier layer 72 is 7-13.
Step 6: an AlGaN electron blocking layer 8 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 200-400mbar 3 TMGa 30-60sccm, H100-130L/min 2 100 TMAl with 130sccm, 1000 Cp with 1300sccm 2 Growing the AlGaN electron barrier layer 8 under the condition of Mg, wherein the thickness of the AlGaN layer 8 is 40-60nm, and the Mg doping concentration is 1E19-1E20atoms/cm 3 。
And 7: a P-type GaN layer 9 doped with Mg 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 400-900mbar 3 20-100sccm of TMGa, 100- 2 1000-Cp of 3000sccm 2 Growing a P-type GaN layer 9 doped with Mg with a thickness of 50-200nm under the condition of Mg and a Mg doping concentration of 1E19-1E20atoms/cm 3 。
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 example 1 and comparative example 1, respectively, with samples 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 conditions 2 About 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 1000 dies were individually picked at the same position for sample 1 and sample 2, and packaged into a white LED under the same packaging process. By integrating sphereThe photoelectric properties of sample 1 and sample 2 were tested under a drive current of 350 mA.
TABLE 1 comparison of electrical parameters of sample 1 and sample 2
Figure BDA0003568079190000091
The data obtained by the integrating sphere are analyzed and compared, and as can be seen from table 1, the luminous flux of the LED (sample 1) prepared by the growth method is obviously improved, and the voltage, the antistatic capacity and other electrical parameters of the LED become better, because the technical scheme of the invention improves the quality of the quantum well, improves the luminous efficiency and improves the photoelectric properties of other LEDs.
The manufacturing method of the LED epitaxial wafer achieves the following effects:
according to the invention, the molybdenum oxide layer is inserted between the n-type GaN layer and the multi-quantum well layer, so that a certain compressive stress can be introduced to partially offset the tensile stress generated between the GaN and the sapphire substrate due to large difference of thermal expansion coefficients, and the problem of surface cracking of the GaN epitaxial material layer is relieved to a certain extent. In the process of sputtering the molybdenum oxide film layer, the sputtering power is controlled to be gradually increased and then gradually reduced, so that the molybdenum oxide film with higher quality and uniformity can be obtained, and the high-quality molybdenum oxide film can improve the crystal quality of a subsequently grown multiple quantum well layer.
MoO can be induced by treating the molybdenum oxide film with ozone X Mo inside the crystal lattice 4+ And Mo 5+ Ion conversion to Mo 6+ Ion, Mo 6+ The ions can increase MoO X The work function of (2) increases the number of holes entering the quantum well light-emitting layer, thereby improving the internal quantum efficiency. The temperature is controlled to gradually increase in the ozone treatment process, so that high Mo can be obtained 6+ The molybdenum oxide film with uniform ion content and distribution can further promote the injection of holes into the quantum well luminescent layer, and improve the luminous efficiency of the light-emitting diode.
The polarity of the molybdenum oxide layer is changed by forming the nitrogen atom layer on the molybdenum oxide layer, so that the crystal atoms of the subsequently grown multiple quantum well layer are arranged more neatly, the material growth defects are reduced, the crystal quality of the quantum well layer is improved, and the luminous efficiency of the LED is improved. The nitrogen is introduced in the process of forming the nitrogen atom layer in a mode of periodically interrupting the nitrogen source, on one hand, the nitrogen atom layer with better quality and uniformity is favorably obtained, on the other hand, the crystal grain size of InGaN/GaN which grows next step can be promoted to be reduced, the nucleation density of the crystal grains is increased, and further, when the quantum well grows in a two-dimensional transverse mode, the roughness is reduced, so that the grown quantum well film layer is the most flat and bright, the crystallization quality is higher, and the brightness of the LED is higher.
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. A manufacturing method of an LED epitaxial wafer sequentially comprises the following steps: processing a substrate, growing a low-temperature GaN buffer layer, growing a non-doped GaN layer, growing an Si-doped n-type GaN layer, manufacturing a carrier transition layer, growing a multi-quantum well layer, growing an AlGaN electronic barrier layer, growing an Mg-doped P-type GaN layer and cooling; the method is characterized in that the carrier transition layer is manufactured and sequentially comprises the following steps: sputtering a molybdenum oxide layer, carrying out ozone treatment and manufacturing a nitrogen atom layer, and specifically comprising the following steps:
A. controlling the temperature of a reaction cavity of the magnetron sputtering equipment to be 250-400 ℃, controlling the pressure of the reaction cavity to be 5-18Torr, introducing argon and oxygen into the reaction cavity, sputtering a molybdenum oxide layer with the thickness of 12-25nm on the Si-doped n-type GaN layer, and controlling the sputtering power of the equipment to be gradually increased from 400w to 900w and then gradually decreased from 900w to 600w in the sputtering process;
B. taking the epitaxial wafer sputtered with the molybdenum oxide layer out of the reaction cavity of the magnetron sputtering equipment, placing the epitaxial wafer into the reaction cavity of the plasma equipment, introducing 150-250sccm ozone into the reaction cavity to treat the molybdenum oxide film layer for 2-4min, and gradually increasing the temperature from 200 ℃ to 600 ℃ in the treatment process;
C. controlling the temperature in the reaction cavity of the plasma equipment to be 100-300 ℃, controlling the power to be 40-120w, introducing nitrogen into the reaction cavity in a mode of periodically interrupting a nitrogen source, and forming a nitrogen atom layer on the molybdenum oxide layer through plasma treatment, wherein the time for interrupting the nitrogen and the time for introducing the nitrogen into the reaction cavity are respectively 4s and 8s in the forming process.
2. The method for fabricating the LED epitaxial wafer of claim 1, wherein 100- 2 And processing the sapphire substrate for 5-10min by keeping the pressure of the reaction chamber at 100-.
3. The method for manufacturing the LED epitaxial wafer according to claim 2, wherein the specific process for growing the low-temperature GaN buffer layer is as follows:
cooling to 500- 3 TMGa of 50-100sccm and H of 100- 2 Growing a low-temperature GaN buffer layer with the thickness of 20-40nm on the sapphire substrate;
raising the temperature to 1000- 3 And H of 100- 2 And preserving the heat for 300-500s to etch the low-temperature GaN buffer layer into an irregular island shape.
4. The method for manufacturing the LED epitaxial wafer according to claim 1, wherein the specific process for growing the non-doped GaN layer is as follows:
raising the temperature toThe temperature is increased to 1200 ℃ at 1000 ℃, the pressure of the reaction cavity is kept at 300- 3 200-400sccm TMGa and 100-130L/min H 2 And continuously growing the 2-4 mu m undoped GaN layer.
5. The method for manufacturing the LED epitaxial wafer according to claim 1, wherein the specific process for growing the Si-doped n-type GaN layer is as follows:
the pressure of the reaction chamber is kept at 300- 3 200-400sccm TMGa, 100-130L/min H 2 And 20-50sccm SiH 4 Continuously growing a 3-4 μm Si-doped n-type GaN layer, wherein the Si doping concentration is 5E18-1E19atoms/cm 3 。
6. The method for manufacturing the LED epitaxial wafer 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 200-400mbar 3 TMGa 30-60sccm, H100-130L/min 2 100-TMAl of 130sccm and 1000-Cp of 1300sccm 2 Growing the AlGaN electron barrier layer under the condition of Mg, wherein the thickness of the AlGaN layer is 40-60nm, and the doping concentration of Mg is 1E19-1E20atoms/cm 3 。
7. The method for manufacturing the LED epitaxial wafer 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 400- 3 20-100sccm of TMGa, 100- 2 And 1000-Cp of 3000sccm 2 Mg, continuously growing a P-type GaN layer doped with Mg with the concentration of 50-200nm, wherein the doping concentration of Mg is 1E19-1E20atoms/cm 3 。
8. The method for manufacturing the LED epitaxial wafer according to claim 1, wherein the specific process of cooling down is as follows:
cooling to 650 plus 680 ℃, preserving the temperature for 20-30min, closing the heating system and the gas supply system, and cooling along with the furnace.
CN202210313652.5A 2022-03-28 2022-03-28 LED epitaxial wafer manufacturing method Pending CN114823995A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116130572A (en) * 2023-04-18 2023-05-16 江西兆驰半导体有限公司 Light-emitting diode epitaxial wafer, preparation method thereof and light-emitting diode

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116130572A (en) * 2023-04-18 2023-05-16 江西兆驰半导体有限公司 Light-emitting diode epitaxial wafer, preparation method thereof and light-emitting diode

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