CN112467004B - GaN-based LED epitaxial structure containing electronic storage layer and growth method thereof - Google Patents

GaN-based LED epitaxial structure containing electronic storage layer and growth method thereof Download PDF

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CN112467004B
CN112467004B CN202011195587.8A CN202011195587A CN112467004B CN 112467004 B CN112467004 B CN 112467004B CN 202011195587 A CN202011195587 A CN 202011195587A CN 112467004 B CN112467004 B CN 112467004B
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程立文
张家荣
李侦伟
曾祥华
王俊迪
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    • 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
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    • 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
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Abstract

The invention discloses a GaN-based LED epitaxial structure containing an electronic storage layer and a growth method thereof, In y Ga 1‑y In is arranged between the N/GaN luminescent layer and the AlGaN electron barrier layer x Ga 1‑x N electron storage layer of In x Ga ‑x1In NxThe value was 0.05. In the invention, an In layer is introduced between the last barrier layer of the luminescent layer and the electron barrier layer x Ga ‑x1The N quantum well layer is used as an electronic storage layer. After the electron storage layer is introduced, an electron potential well is formed between the electron blocking layer and the GaN potential barrier due to the introduction of the InGaN material, the potential well can store a large amount of leaked electrons, the Auger recombination efficiency of the device can be effectively reduced, the polarization electric field between the device and the electron blocking layer can be increased, the effective height of the electron blocking layer can be effectively improved, and the electrons can be better limited; and finally, the photoelectric property of the GaN-based LED can be improved.

Description

GaN-based LED epitaxial structure containing electronic storage layer and growth method thereof
Technical Field
The invention relates to the field of LED design and application, in particular to an LED epitaxial growth method for improving the carrier transport and distribution of a light emitting region and a prepared epitaxial layer structure.
Background
The GaN Light Emitting Diode (LED) is used as a novel efficient, energy-saving and environment-friendly illumination light source, is widely applied to backlight illumination, energy-saving illumination and general illumination by virtue of the advantages of high brightness, low power consumption, long service life, low power and the like, and can thoroughly replace the traditional incandescent lamp and fluorescent lamp.
Therefore, factors affecting the photoelectric performance of the LED are focused on, and particularly, the photoelectric performance of the LED is greatly reduced due to the efficiency reduction when the LED is operated under the injection of a large current. At present, researchers propose that the main reasons for the efficiency reduction are the problem of poor carrier injection and the problem of serious electron leakage inside the structure, so a key method for improving the photoelectric performance of the GaN LED is to improve the carrier injection and reduce the electron leakage.
Since holes have a relatively high effective mass and a relatively low mobility with respect to electrons, the number of holes injected from the p-side into the light-emitting layer is much smaller than that of electrons injected from the n-side, and thus, a phenomenon in which a large number of carriers are accumulated near the p-side and electrons leak to the p-side occurs, which eventually leads to a decrease in the radiative recombination efficiency of holes and electrons, and decreases the photoelectric performance of the LED. Therefore, improving the carrier transport to the active layer and the carrier limiting capability of the light emitting layer is an important link for improving the photoelectric performance of the LED.
At present, energy band engineering is generally adopted internationally or an AlGaN electron blocking layer and the like are grown between a light-emitting layer and a p-type GaN layer to improve the transport of carriers and the limiting capability of the carriers, but due to the difference of lattice coefficients of different materials, a large polarization effect occurs in the structure, for example, the AlGaN electron blocking layer is not favorable for injecting holes due to the polarization effect between the AlGaN electron blocking layer and a GaN barrier layer while forming an electron barrier to inhibit electron leakage; in addition, the p-type Mg doping ionization activation rate In the AlGaN electron blocking layer is very low, so that the hole concentration In the AlGaN electron blocking layer is low, and due to the growth conditions, lattice defects and relatively large stress can be generated when the AlGaN electron blocking layer grows, and the distribution uniformity of In components In the quantum well is influenced.
Disclosure of Invention
In order to effectively reduce the problem of efficiency reduction of the GaN-based LED, the invention provides a GaN-based LED epitaxial structure comprising an electronic storage layer and a growth method thereof.
The technical solution for realizing the purpose of the invention is as follows: a GaN-based LED epitaxial structure comprising an electronic storage layer In y Ga 1-y In is arranged between the N/GaN luminescent layer and the AlGaN electron barrier layer x Ga 1-x N electron storage layer of In x Ga -x1In NxThe value was 0.05.
Preferably, In y Ga 1-y The N/GaN light emitting layer is formed of In y Ga -y1N quantum well layers and GaN barrier layers formed alternately, In x Ga 1- x The N electron storage layer is disposed on the GaN barrier layer of the light emitting layer.
Preferably, In x Ga 1-x The thickness of the N-electron storage layer was 1 nm.
Preferably, the thickness of the light-emitting layer is 70 to 75 nm.
Preferably, the AlGaN electron blocking layer has a thickness of 90-100 nm.
The growth method of the electronic storage layer comprises the following steps:
under the conditions that the pressure of a reaction cavity is 100 Torr-500 Torr and the temperature is 700 ℃ -800 ℃, TEGa, TMIn and SiH are used4As MO source, In doped with In is grown x Ga 1-x An N electron storage layer is formed on the substrate,xis 0.05.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, an In layer is introduced between the last barrier layer of the luminescent layer and the electron barrier layer x Ga -x1N quantum well layer (x0.05) as an electron storage layer. After the electron storage layer is introduced, an electron potential well is formed between the electron blocking layer and the GaN potential barrier due to the introduction of the InGaN material, a large number of leaked electrons can be stored in the potential well, and the Auger recombination efficiency of the device can be effectively reduced. In addition, in the traditional GaN-based LED, the interface between the last potential barrier of the light-emitting layer and the electron blocking layer is a GaN-AlGaN interface, after the electron storage layer is introduced, the interface between the storage layer and the electron blocking layer is an InGaN-AlGaN interface, and compared with the GaN-AlGaN interface, the polarization electric field between the storage layer and the electron blocking layer can be increased, the effective height of the electron blocking layer can be effectively improved, and electrons can be better limited; and finally, the photoelectric property of the GaN-based LED can be improved.
Drawings
Fig. 1 is a band diagram of a general GaN-based LED.
FIG. 2 is the bookInvention contains In x Ga 1-x Energy band diagram of GaN-based LED of N electron storage layer.
Fig. 3 is a schematic flow chart of an epitaxial growth method of a GaN-based LED epitaxial structure including an electron storage layer according to the present invention.
Detailed Description
The invention is further elucidated with reference to the figures and embodiments.
Fig. 1 is an energy band diagram of a general GaN-based LED. FIG. 2 shows that In is contained In the present invention x Ga 1-x Energy band diagram of GaN-based LED of N electron storage layer.
As can be seen from fig. 1 and fig. 2, after the electron storage layer according to the present invention is introduced into the device, the layer can not only store electrons, but also increase the effective barrier height of the electron blocking layer in the GaN-based LED.
With reference to fig. 3, the method for growing the epitaxial structure of the GaN-based LED according to the present invention is as follows:
the invention uses VEECO MOCVD to grow the high-brightness GaN-based LED epitaxial wafer. Using high-purity H2Or high purity N2Or high purity H2And high purity N2As a carrier gas, high purity NH3（NH3Purity 99.999%) as an N source, a metallo-organic source of trimethylgallium (TMGa) and a metallo-organic source of triethylgallium (TEGa), trimethylindium (TMIn) as an indium source, and an N-type dopant of Silane (SiH)4) Trimethylaluminum (TMAl) as the aluminum source and magnesium diclomelate (CP) as the P-type dopant2Mg), the substrate is (0001) plane sapphire, the reaction pressure is between 100 Torr and 1000 Torr, and the specific growth mode is as follows:
101, annealing the sapphire substrate in a hydrogen atmosphere at 1050-1150 ℃, and cleaning the surface of the substrate.
102, introducing ammonia gas and TMGa at the temperature of 500-610 ℃ and the pressure of a reaction cavity of 400-650 Torr, and growing a low-temperature nucleation layer GaN with the thickness of 20-40 nm on a sapphire substrate;
103, keeping the pressure of the reaction cavity at 1050-1200 ℃ to be 100-500 Torr, introducing ammonia gas and TMGa, and continuously growing the non-doped u-GaN layer with the thickness of 1-3 mu m.
104, keeping the pressure of the reaction cavity at 1050-1200 ℃ to be 100-600 Torr, and introducing ammonia gas, TMGa and SiH4Continuously growing a Si-doped n-GaN layer with a stable doping concentration and a thickness of 2-4 mu m, wherein the doping concentration of Si is 8 multiplied by 1018 atoms/cm3~2×1019atoms/cm3。
105, at the temperature of 800-950 ℃, at the pressure of 100-500 Torr in the reaction chamber, and using TEGa, TMIn and SiH as MO sources4Growing a GaN barrier layer with the thickness of 8 nm-15 nm, and doping Si in the GaN barrier layer with the Si doping concentration of 8 multiplied by 1016 atoms/cm3~6×1017 atoms/cm3. Keeping the pressure of the reaction cavity at 100-500 Torr and the temperature at 700-800 ℃, and using TEGa, TMIn and SiH4As MO source, In doped with In and having a thickness of 2 nm was grown y Ga -y1An N quantum well layer is formed on the substrate,y0.1 to 0.3. Repeatedly growing GaN barrier layer and then repeating In y Ga -y1Growth of N Quantum well layer, alternatively growing In y Ga 1-y N/GaN light emitting layer for controlling In y Ga -y1The growth period of the N quantum well layer was 6.
106, using TEGa, TMIn and SiH at the reaction cavity pressure of 100 Torr-500 Torr and the temperature of 700 ℃ -800 DEG C4As MO source, In y Ga 1-y In with the thickness of 1nm is grown on the GaN barrier layer of the N/GaN luminous layer x Ga -x1An N electron storage layer is formed on the substrate,xand was 0.05.
107, keeping the pressure of the reaction cavity at 20 Torr-200 Torr and the temperature at 900 ℃ -1100 ℃, and introducing MO sources TMA1, TMGa and CP2Mg In x Ga -x1Continuously growing a P-type AlGaN electron barrier layer with the thickness of 50 nm-200 nm on the N electron storage layer for 3 min-100 min, wherein the molar component of Al is 10% -30%, and the doping concentration of Mg is 1 multiplied by 1018atoms/cm3~1×1021 atoms/cm3。
108, keeping the pressure of the reaction cavity at 100-500 Torr and the temperature at 850-1050 ℃, and introducing MO sources of TEGa and CP2Mg, continuously growing a P-type GaN contact layer doped with Mg with the thickness of 200 nm on the AlGaN electron barrier layer, wherein the doping concentration of the Mg is 1 multiplied by 1019 atoms/cm3~1×1022 atoms/cm3；
And 109, after the epitaxial growth is finished, reducing the reaction temperature to 650-800 ℃, annealing for 5-10 min in a pure nitrogen atmosphere, and then reducing the temperature to room temperature to finish the growth.
Sample 1 prepared by the method described in example 1, i.e., the growth method of the present invention, and sample 2 grown by the method described in example 2 are described below, respectively.
Example 1
This embodiment provides a LED epitaxial structure, and this epitaxial structure includes in proper order: processing a substrate (1), growing a low-temperature nucleation layer (2), growing an undoped low-temperature u-GaN layer (3), growing an Si-doped n-GaN layer (4), and growing In y Ga 1-y N/GaN light-emitting layer (5) for growing In x Ga 1-x And an N electronic storage layer (6), an AlGaN electronic barrier layer (7), a P-type GaN contact layer (8) and cooling (9). As shown in fig. 3, the epitaxial layer of the above structure is grown as follows,
step 101, processing the substrate (1):
and annealing the sapphire substrate in a hydrogen atmosphere at the temperature of 1100 ℃, and cleaning the surface of the substrate.
Step 102, growing a low-temperature nucleation layer GaN (2):
introducing ammonia gas and TMGa at 550 ℃ and the pressure of a reaction cavity of 500 Torr, growing a low-temperature nucleation layer GaN with the thickness of 30 nm on the sapphire substrate, stopping introducing the TMGa, and carrying out in-situ annealing treatment, wherein the annealing temperature is raised to 1100 ℃ and the annealing time is 10 min;
step 103, growing undoped u-GaN (3):
and keeping the pressure of the reaction cavity at 1100 ℃ at 500 Torr, introducing ammonia gas and TMGa, and continuously growing an undoped u-GaN layer with the thickness of 2 mu m on the low-temperature nucleation layer GaN.
Step 104, growing a Si-doped n-GaN layer (4):
at 1100 ℃, the pressure of the reaction chamber is kept at 500 Torr, and ammonia gas, TMGa and SiH are introduced4Continuously growing a Si-doped n-GaN layer with a thickness of 3 μm and a stable Si doping concentration on the undoped u-GaN layer, wherein the Si doping concentration is 1 × 1019atoms/cm3。
Step 105 of growing In y Ga 1-y N/GaN light-emitting layer (5):
maintaining the pressure of a reaction cavity at 950 ℃ and 500 Torr, and growing a GaN barrier layer with the thickness of 15 nm by using an MO source of TEGa, TMIn and SiH 4;
in a reaction chamber at a pressure of 300 Torr and a temperature of 750 ℃ using TEGa, TMIn and SiH4As MO source, In doped with In and having a thickness of 2 nm was grown on the n-GaN layeryGa1-yAn N quantum well layer, y is 0.2;
repeatedly growing GaN barrier layer and then repeating InyGa1-yGrowth of N Quantum well layer, alternatively growing InyGa1-yN/GaN light emitting layer for controlling InyGa1-yThe growth period of the N quantum well layer was 6.
Step 106, growing In x Ga 1-x N-electron storage layer (6):
in a reaction chamber at a pressure of 500 Torr and a temperature of 800 ℃ using TEGa, TMIn and SiH4As MO source, InyGa1-yIn with the thickness of 1nm is grown on the GaN barrier layer of the N/GaN luminous layerxGa1-xN electron storage layer, x is 0.05.
Step 107, growing an AlGaN electron blocking layer (7):
the pressure of the reaction cavity is kept at 200 Torr and the temperature is kept at 1100 ℃, and MO sources are introduced into the reaction cavity, wherein the MO sources are TMA1, TMGa and CP2Mg InxGa1-xContinuously growing a 200 nm-thick P-type AlGaN electron blocking layer on the N electron storage layer for 100 min, wherein the molar composition of Al is 20%, and the doping concentration of Mg is 1 multiplied by 1021 atoms/cm3。
Step 108, growing a P-type GaN contact layer (8):
keeping the pressure of the reaction cavity at 500 Torr and the temperature at 1000 ℃, and introducing MO sources of TEGa and CP2Mg, continuously growing a P-type GaN contact layer with the thickness of 20 nm and doped with Mg on the AlGaN electron barrier layer, wherein the doping concentration of the Mg is 1 multiplied by 1021atoms/cm3；
Step 109, cooling:
and after the epitaxial growth is finished, reducing the reaction temperature to 750 ℃, annealing for 10 min in a pure nitrogen atmosphere, then reducing the temperature to room temperature, and finishing the growth to obtain a sample 1.
The invention adopts the InGaN electronic storage layer, thereby effectively reducing the electronic leakage and reducing the efficiency reduction problem. The chip quality is improved to a great extent, and the hole injection is further improved.
Example 2
This embodiment provides a conventional LED epitaxial structure, which in turn comprises: processing a substrate (1), growing a low-temperature nucleation layer (2), growing an undoped low-temperature u-GaN layer (3), growing an Si-doped n-GaN layer (4), and growing In y Ga 1-y The N/GaN luminescent layer (5), an AlGaN electron barrier layer (6), a P-type GaN contact layer (7) and cooling (8). A conventional LED epitaxial growth method is adopted, and the specific steps are as follows:
step 201, processing a substrate (1):
and annealing the sapphire substrate in a hydrogen atmosphere at the temperature of 1100 ℃, and cleaning the surface of the substrate.
Step 202, growing a low-temperature nucleation layer GaN (2):
introducing ammonia gas and TMGa at 550 ℃ and the pressure of a reaction cavity of 500 Torr, growing a low-temperature nucleation layer GaN with the thickness of 30 nm on the sapphire substrate, stopping introducing the TMGa, and carrying out in-situ annealing treatment, wherein the annealing temperature is raised to 1100 ℃ and the annealing time is 10 min;
step 203, growing undoped u-GaN (3):
and keeping the pressure of the reaction cavity at 1100 ℃ at 500 Torr, introducing ammonia gas and TMGa, and continuously growing an undoped u-GaN layer with the thickness of 2 mu m on the low-temperature nucleation layer GaN.
Step 204, growing a Si-doped n-GaN layer (4):
at 1100 ℃, the pressure of the reaction chamber is kept at 500 Torr, and ammonia gas, TMGa and SiH are introduced4Continuously growing a Si-doped n-GaN layer with a thickness of 3 μm and a stable Si doping concentration on the undoped u-GaN layer, wherein the Si doping concentration is 1 × 1019atoms/cm3。
Step 205, growing In y Ga 1-y N/GaN light-emitting layer (5):
maintaining the pressure of a reaction cavity at 950 ℃ and 500 Torr, and growing a GaN barrier layer with the thickness of 15 nm by using an MO source of TEGa, TMIn and SiH 4;
in a reaction chamber at a pressure of 300 Torr and a temperature of 750 ℃ using TEGa, TMIn and SiH4As MO source, In doped with In and having a thickness of 2 nm was grown on the n-GaN layeryGa1-yAn N quantum well layer, y is 0.2;
repeatedly growing GaN barrier layer and then repeating InyGa1-yGrowth of N Quantum well layer, alternatively growing InyGa1-yN/GaN light emitting layer for controlling InyGa1-yThe growth period of the N quantum well layer was 6.
Step 206, growing an AlGaN electron blocking layer (6):
the pressure of the reaction cavity is kept at 200 Torr and the temperature is kept at 1100 ℃, and MO sources are introduced into the reaction cavity, wherein the MO sources are TMA1, TMGa and CP2Mg In y Ga 1-y Continuously growing a 200 nm-thick P-type AlGaN electron blocking layer on a GaN barrier layer of the N/GaN light-emitting layer for 100 min, wherein the molar component of Al is 20%, and the Mg doping concentration is 1 multiplied by 1021 atoms/cm3。
Step 207, growing a P-type GaN contact layer (7):
keeping the pressure of a reaction cavity at 500 Torr and the temperature at 1000 ℃, and introducing MO sources of TEGa and CP2Mg, continuously growing a P-type GaN contact layer with the thickness of 20 nm and doped with Mg on the AlGaN electron barrier layer, wherein the doping concentration of the Mg is 1 multiplied by 1021atoms/cm3；
Step 208, cooling:
and after the epitaxial growth is finished, reducing the reaction temperature to 750 ℃, annealing for 10 min in a pure nitrogen atmosphere, then reducing the temperature to room temperature, and finishing the growth to obtain a sample 2.
Sample 2 differs from sample 1 in that: the epitaxial structure of sample 1 had an In layer x Ga 1-x The N electron storage layer, but not sample 2, the other epitaxial layer growth conditions were completely identical.
Respectively plating ITO layer with thickness of 200 nm on sample 1 and sample 2, plating Cr/Pt/Au electrode with thickness of about 170 nm, and plating protective layer SiO on the same condition2About 50 nm thick, then the sample was ground and cut into 762 μm × 762 μm (30 mi × 30 mil) chip particles, then 150 grains were individually selected from the sample 1 and the sample 2 at the same position, and the photoelectric properties of the sample 1 and the sample 2 were spot-measured by the same LED spot-measuring machine under the condition of 100 mA driving current.
By definition of the efficiency drop, the efficiency drop is the ratio of the maximum IQE minus the IQE at the current operating current to the maximum IQE, the efficiency drop for the typical LED epitaxial structure, sample 2, is 30.1%, whereas the efficiency drop for sample 1 designed by the present invention is only 14.2%.
The invention shows that the GaN-based LED epitaxial growth method with the electronic storage layer can effectively reduce the efficiency attenuation of the GaN-based LED.

Claims (4)

1. A GaN-based LED epitaxial structure containing an electronic storage layer is characterized In that In y Ga 1-y In is arranged between the N/GaN luminescent layer and the AlGaN electron barrier layer x Ga 1-x N electron storage layer, In x Ga 1-x An N electron storage layer is disposed on the GaN barrier layer In the light emitting layer, wherein In x Ga -x1In NxValue of 0.05, In x Ga 1-x The thickness of the N electronic storage layer is 1 nm; in y Ga 1-y The N/GaN light emitting layer is formed of In y Ga -y1N quantum well layers and GaN barrier layers formed alternately, In y Ga -y1In N quantum well layersyThe value is 0.1 to 0.3.
2. The GaN-based LED epitaxial structure of claim 1, wherein the light emitting layer has a thickness of 70-75 nm.
3. The GaN-based LED epitaxial structure of claim 1, wherein the AlGaN electron blocking layer has a thickness of 90 to 100 nm.
4. A method of growing an epitaxial structure for a GaN-based LED according to any of claims 1 to 3, wherein the electron storage layer in the epitaxial structure is prepared by the steps of: under the conditions that the pressure of a reaction cavity is 100 Torr-500 Torr and the temperature is 700 ℃ -800 ℃, TEGa, TMIn and SiH are used4As MO source, In doped with In is grown x Ga 1-x An N-electron storage layer is formed on the substrate,xis 0.05.
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