CN109346580B - Manufacturing method of light-emitting diode epitaxial wafer - Google Patents
Manufacturing method of light-emitting diode epitaxial wafer Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 230000000737 periodic effect Effects 0.000 claims abstract description 36
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 33
- 239000010980 sapphire Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 239000012159 carrier gas Substances 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 239000002019 doping agent Substances 0.000 claims description 10
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 10
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 6
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims 2
- 229910002601 GaN Inorganic materials 0.000 abstract description 48
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000007771 core particle Substances 0.000 description 14
- 238000004020 luminiscence type Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/20—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 particular shape, e.g. curved or truncated substrate
- H01L33/22—Roughened surfaces, e.g. at the interface between epitaxial layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention discloses a manufacturing method of a light-emitting diode epitaxial wafer, and belongs to the technical field of semiconductors. The manufacturing method comprises the steps of growing a low-temperature buffer layer on a periodic pattern and a concave part of a sapphire substrate; raising the temperature of the reaction chamber, and growing a three-dimensional growth layer on the low-temperature buffer layer on the concave part; keeping the temperature of the reaction chamber unchanged, and introducing hydrogen into the reaction chamber for a period of time to remove the low-temperature buffer layer on the periodic pattern and a part of the three-dimensional growth layer on the concave part. And then raising the temperature of the reaction chamber, and combining the high-temperature undoped GaN layers on the periodic patterns and arranging the high-temperature undoped GaN layers at intervals with the periodic patterns to form cavities. The cavity is filled with air, and the refractive index of the air is smaller than that of the sapphire substrate, and the difference between the refractive indexes of the air and the gallium nitride epitaxial layer is larger, so that light from the multiple quantum well layer is easy to generate total reflection at the cavity and is emitted from the front surface of the light-emitting diode, and the front light-emitting efficiency of the light-emitting diode is improved.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a manufacturing method of a light-emitting diode epitaxial wafer.
Background
Light Emitting Diodes (LEDs) are widely used in electronic devices in many fields due to their advantages of small size, long lifetime, fast response speed, high reliability, etc.
The gallium nitride-based semiconductor material is a new-generation semiconductor material following silicon and gallium arsenide-based materials, is called a third-generation semiconductor material, has wide band gap and excellent physical and chemical properties, and has wide application prospect and research value in the field of photoelectrons. In recent years, gallium nitride-based semiconductors have been receiving much attention. Gallium nitride based light emitting diodes often employ a sapphire substrate.
In the process of implementing the invention, the inventor finds that the prior art has at least the following problems:
for the LED with the normal structure, part of light generated by the multiple quantum well layer can be incident into the sapphire substrate, and the sapphire substrate can absorb part of light, so that the front light-emitting rate of the LED is reduced.
Disclosure of Invention
The embodiment of the invention provides a manufacturing method of an LED epitaxial wafer, which can improve the front light emitting efficiency of an LED. The technical scheme is as follows:
the embodiment of the invention provides a manufacturing method of a light-emitting diode epitaxial wafer, which comprises the following steps:
providing a sapphire substrate, wherein periodic patterns are arranged on the surface of the sapphire substrate, and sunken parts are formed among the periodic patterns;
introducing carrier gas, nitrogen and a Mo source into the reaction chamber, and growing a low-temperature buffer layer on the periodic pattern and the concave part, wherein the low-temperature buffer layer is a GaN layer;
raising the temperature of the reaction chamber, introducing carrier gas, nitrogen and a Mo source into the reaction chamber, and growing a three-dimensional growth layer on the low-temperature buffer layer on the concave part, wherein the three-dimensional growth layer is a GaN layer and the thickness of the three-dimensional growth layer is greater than that of the low-temperature buffer layer;
keeping the temperature of the reaction chamber unchanged, introducing hydrogen into the reaction chamber for a period of time, and removing the low-temperature buffer layer on the periodic graph and a part of the three-dimensional growth layer on the concave part;
raising the temperature of the reaction chamber, introducing carrier gas, nitrogen and a Mo source into the reaction chamber, and growing a high-temperature undoped GaN layer on the three-dimensional growth layer, wherein the high-temperature undoped GaN layer is combined on the periodic pattern and is arranged at intervals with the periodic pattern to form a cavity;
introducing carrier gas, nitrogen, a Mo source and an N-type dopant into the reaction chamber, and growing an N-type layer on the high-temperature undoped GaN layer;
introducing carrier gas, nitrogen and a Mo source into the reaction chamber, and growing a multi-quantum well layer on the N-type layer;
and introducing carrier gas, nitrogen, a Mo source and a P-type dopant into the reaction chamber, and growing a P-type layer on the multi-quantum well layer.
Further, when the three-dimensional growth layer grows, the temperature of the reaction chamber is controlled to be 1000-1070 ℃.
Further, the step of introducing hydrogen into the reaction chamber for a period of time to remove the low-temperature buffer layer on the periodic pattern and a part of the three-dimensional growth layer on the concave part comprises:
and introducing 60-150L/min hydrogen into the reaction chamber.
Further, the time for introducing hydrogen into the reaction chamber is 1-3 min.
Further, when hydrogen is introduced into the reaction chamber, the temperature of the reaction chamber is controlled to be 1000-1070 ℃.
Further, when hydrogen is introduced into the reaction chamber, the pressure of the reaction chamber is controlled to be 100-500 torr.
Furthermore, when a high-temperature undoped GaN layer grows, the temperature of the reaction chamber is controlled to be 1040-1080 ℃.
Further, the thickness of the low-temperature buffer layer is 20-30 nm.
Further, the thickness of the three-dimensional growth layer grown on the low-temperature buffer layer on the concave part is 0.7-1.1 um.
Further, the carrier gas is high-purity hydrogen or high-purity nitrogen or a mixed gas of the high-purity hydrogen and the high-purity nitrogen, and the Mo source is one or more of trimethyl gallium, trimethyl indium, trimethyl aluminum and triethyl gallium.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
after the three-dimensional growth layer grows, the temperature of the reaction chamber is kept unchanged, hydrogen is introduced into the reaction chamber for a period of time, the temperature of the reaction chamber is higher, GaN is easy to decompose at high temperature, and the low-temperature buffer layer and the three-dimensional growth layer are both GaN layers, so that the low-temperature buffer layer and the three-dimensional growth layer can decompose, and meanwhile, the hydrogen can take GaN decomposition products out of the reaction cavity. And because the thickness of the three-dimensional growth layer is greater than that of the low-temperature buffer layer, hydrogen is introduced for a period of time, the low-temperature buffer layer on the periodic graph and part of the three-dimensional growth layer on the concave part can be removed, and the condition that after the low-temperature buffer layer on the periodic graph of the sapphire substrate is decomposed is ensured, part of the three-dimensional growth layer on the concave part is still not decomposed, so that an undoped GaN layer can be grown on the three-dimensional growth layer subsequently. Further, the temperature of the reaction chamber is increased, and a high-temperature undoped GaN layer grows on the three-dimensional growth layer, and cannot directly grow on the periodic pattern on the surface of the sapphire substrate due to the high growth temperature of the high-temperature undoped GaN layer, so that a cavity is formed between the high-temperature undoped GaN layer and the sapphire substrate. The cavity is filled with air, partial light emitted by the multiple quantum well layer passes through the cavity before being incident on the sapphire substrate, and the refractive index of the air is smaller than that of the sapphire substrate, so that the difference between the refractive indexes of the air and the gallium nitride epitaxial layer is larger, the light from the multiple quantum well layer is easy to generate total reflection at the cavity and is emitted from the front side of the light-emitting diode, and the light-emitting efficiency of the front side of the light-emitting diode is improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a flowchart of a method for manufacturing an epitaxial wafer of a light emitting diode according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of an led epitaxial wafer after step 102 is performed;
fig. 3 is a schematic structural diagram of the led epitaxial wafer after step 103 is performed;
fig. 4 is a schematic structural diagram of the led epitaxial wafer after step 104 is performed;
fig. 5 is a schematic structural diagram of the led epitaxial wafer after step 105 is performed.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
An embodiment of the present invention provides a method for manufacturing a light emitting diode epitaxial wafer, and fig. 1 is a method flowchart of the method for manufacturing the light emitting diode epitaxial wafer according to the embodiment of the present invention, as shown in fig. 1, the method includes:
In this embodiment, the surface of the sapphire substrate is provided with periodic patterns, and recesses are formed between the periodic patterns.
Specifically, step 101 further includes;
and annealing the sapphire substrate at 1050 ℃ in a pure hydrogen atmosphere for 5-10 min, and then nitriding the sapphire substrate.
In this embodiment, the manufacturing of the light emitting diode epitaxial wafer can be realized by using a Veeco K465i or C4 MOCVD (Metal Organic chemical vapor Deposition) apparatus. By using high-purity H2(Hydrogen) or high purity N2(Nitrogen) or high purity H2And high purity N2The mixed gas of (2) is used as a carrier gas, high-purity NH3As the N source. The Mo source is one or more of trimethyl gallium (TMGa), trimethyl aluminum (TMAl) and triethyl gallium (TEGa). Trimethyl gallium (TMGa) and triethyl gallium (TEGa) are used as gallium sources, trimethyl indium (TMIn) is used as indium sources, and trimethyl aluminum (TMAl) is used as an aluminum source. Silane (SiH4) as N-type dopant, magnesium diclomelate (CP)2Mg) as a P-type dopant. The pressure in the reaction chamber is 100-600 torr.
And 102, growing a low-temperature buffer layer.
Specifically, the temperature of the reaction chamber is reduced to 540 ℃, the pressure is controlled to be 50-200 torr, carrier gas, ammonia gas and trimethyl gallium are introduced into the reaction chamber, and a GaN layer low-temperature buffer layer with the thickness of 20-30 nm grows on the periodic patterns and the concave parts on the surface of the sapphire substrate. And the growth of the low-temperature GaN buffer layer on the sapphire substrate is facilitated under the low-temperature environment of 540 ℃.
Fig. 2 is a schematic structural diagram of the light emitting diode epitaxial wafer after step 102 is performed, and as shown in fig. 2, the low temperature buffer layer 2 is located on the periodic pattern 1a and the recess 1b on the surface of the sapphire substrate 1.
In the present embodiment, the periodic pattern 1a on the sapphire substrate 1 is conical.
And 103, growing a three-dimensional growth layer.
In this embodiment, the three-dimensional growth layer is a GaN layer.
Specifically, the temperature of the reaction chamber is raised to 1000-1070 ℃, the pressure is controlled to be 100-500 torr, carrier gas, ammonia gas and trimethyl gallium are introduced into the reaction chamber, and a 0.7-1.1 um three-dimensional growth layer grows on the low-temperature buffer layer on the concave part.
In this embodiment, the thickness of the three-dimensional growth layer is 0.7-1.11 um, and the low-temperature buffer layer is 20-30 nm. The thickness of the three-dimensional growth layer is far larger than that of the low-temperature buffer layer, so that after the low-temperature buffer layer on the periodic graph of the sapphire substrate is decomposed, part of the three-dimensional growth layer on the concave part is still not decomposed, and the subsequent growth of the undoped GaN layer is facilitated.
Fig. 3 is a schematic structural diagram of the light emitting diode epitaxial wafer after step 103, and as shown in fig. 3, the three-dimensional growth layer 3 is located on the low-temperature buffer layer 2 on the recess 1 b.
And 104, removing the low-temperature buffer layer on the periodic pattern and part of the three-dimensional growth layer on the concave part.
Specifically, the temperature of the reaction chamber is kept unchanged, the pressure of the reaction chamber is controlled to be 100-500 torr, hydrogen is introduced into the reaction chamber for a period of time, and the low-temperature buffer layer on the periodic graph and a part of the three-dimensional growth layer on the concave part are removed.
Wherein, the temperature of the reaction chamber is kept to be 1000-1070 ℃, so that the reaction chamber is kept at a high temperature, and the high temperature is favorable for the decomposition of the GaN layer.
In this embodiment, step 104 includes:
introducing 60-150L/min hydrogen into the reaction chamber for 1-3 min. The hydrogen is introduced for 1-3 min in the high-temperature environment, so that the low-temperature GaN buffer layer on the pattern of the sapphire substrate can be completely decomposed. Meanwhile, 60-150L/min of hydrogen is introduced and can be used as carrier gas to take the decomposition products of the GaN out of the reaction chamber. If the time for introducing the hydrogen is too long, the three-dimensional growth layer is decomposed too much, the crystal quality of the three-dimensional growth layer is reduced, and the growth of the epitaxial structure is influenced. If the time for introducing hydrogen is too short, the low-temperature buffer layer on the pattern of the sapphire substrate cannot be completely decomposed, and the generation of voids is influenced.
Fig. 4 is a schematic structural diagram of the light emitting diode epitaxial wafer after step 104 is performed, and as shown in fig. 4, the low-temperature buffer layer 2 on the periodic pattern 1a of the sapphire substrate 1 and a part of the three-dimensional growth layer 3 on the recess 1b are decomposed.
And 105, growing a high-temperature undoped GaN layer.
Specifically, the temperature of the reaction chamber is increased to 1040-1080 ℃, the pressure is controlled at 100-300 torr, carrier gas, nitrogen and trimethyl gallium are introduced into the reaction chamber, and a high-temperature undoped GaN layer with the thickness of 1.5um is grown on the three-dimensional growth layer.
Fig. 5 is a schematic structural view of the light emitting diode epitaxial wafer after step 105 is performed, and as shown in fig. 5, the high temperature undoped GaN layer 4 does not grow on the periodic pattern 1a of the sapphire substrate 1 because the growth temperature of the high temperature undoped GaN layer 4 is high and the GaN layer is not lattice-matched with the sapphire substrate 1. The high-temperature undoped GaN layer 4 is merged on the periodic pattern 1a and spaced apart from the periodic pattern 1a to form a void 4 a.
And 106, growing an N-type layer.
Controlling the temperature of the reaction chamber at 1040-1070 ℃ and the pressure at 100-300 torr, introducing carrier gas, nitrogen, trimethyl gallium and an N-type dopant into the reaction chamber, and growing a Si-doped GaN layer with the thickness of 2um on the high-temperature undoped GaN layer.
In this embodiment, after performing step 105, the manufacturing method may further include:
and step 107, growing the multiple quantum well layer.
In the present embodiment, the multiple quantum well layer includes a plurality of InGaN well layers and GaN barrier layers alternately grown in cycles.
Specifically, step 107 comprises:
controlling the temperature of the reaction chamber at 730-830 ℃, controlling the pressure at 100-400 torr, introducing carrier gas, nitrogen, triethyl gallium and trimethyl indium into the reaction chamber, and growing an InGaN well layer with the thickness of 2.5 nm;
controlling the temperature of the reaction chamber to be 850-930 ℃ and the pressure to be 100-400 torr, introducing carrier gas, nitrogen and triethyl gallium into the reaction chamber, and growing a GaN barrier layer with the thickness of 15 nm.
In this embodiment, step 108 may be further performed after step 107 is performed.
And step 108, growing an electron blocking layer.
In the present embodiment, the electron blocking layer is an AlGaN layer doped with Mg.
Specifically, step 108 includes:
controlling the temperature of the reaction chamber to be 900-1000 ℃, controlling the pressure to be 50-200 torr, introducing carrier gas, nitrogen, triethyl gallium, trimethyl indium and a P-type dopant into the reaction chamber, and growing an electronic barrier layer with the thickness of 80nm on the multi-quantum well layer.
And step 109, growing a P type layer.
In this embodiment, the P-type layer is a Mg-doped GaN layer.
Controlling the temperature of the reaction chamber to 870-970 ℃, controlling the pressure to 100-500 torr, introducing carrier gas, nitrogen, triethyl gallium and a P-type dopant into the reaction chamber, and growing a P-type GaN layer with the thickness of 15nm on the electron blocking layer.
In this embodiment, after step 109 is executed, step 110 may also be executed.
And step 110, growing a P-type contact layer.
In this embodiment, the P-type contact layer is a heavily Mg-doped GaN layer.
Specifically, step 110 includes:
controlling the temperature of the reaction chamber to 870-970 ℃ and the pressure to 100-500 torr, introducing carrier gas, nitrogen, triethyl gallium and a P-type dopant into the reaction chamber, and growing a P-type contact layer with the thickness of 15nm on the P-type layer.
After the steps are completed, the temperature of the reaction chamber is reduced to 600-850 ℃, annealing treatment is carried out for 5-15 min in a nitrogen atmosphere, then the temperature is gradually reduced to the room temperature, and the epitaxial growth of the light emitting diode is finished.
Plating an N-type electrode and a P-type electrode on the first sample and the second sample under the same process conditions, and grinding and cutting the processed first sample and the second sample into 245 x 619 mu m2Crystal grains of (1), whichThe first sample was obtained by a conventional manufacturing method, and the second sample was obtained by the manufacturing method of example one.
Core particles with the light-emitting wavelengths of 451-452 nm, 452-453 nm and 453-454 nm are respectively selected from the first sample and the second sample, and the light-emitting brightness of the core particles with the three wave bands from the first sample and the second sample is respectively tested under the condition of 120mA driving current.
As a result, the emission luminance of the core particles having an emission wavelength of 451 to 452nm in the first sample was 199.4mW, and the emission luminance of the core particles having an emission wavelength of 451 to 452nm in the second sample was 203.5 mW. The luminescence brightness of the core particle with the luminescence wavelength of 452-453 nm of the first sample is 199.4mW, and the luminescence brightness of the core particle with the luminescence wavelength of 452-453 nm of the second sample is 203.6 mW. The luminescence brightness of the core particles with the luminescence wavelength of 452-453 nm of the first sample is 199.3mW, and the luminescence brightness of the core particles with the luminescence wavelength of 452-453 nm of the second sample is 203.5 mW.
Further, under the same process conditions, the crystal grains of the first sample and the crystal grains of the second sample were encapsulated, and the light emission luminance of the core grains of the three wavelength bands from the first sample and the second sample were respectively tested under the condition that the driving current was 120 mA.
As a result, the emission luminance of the core particles having an emission wavelength of 451 to 452nm in the first sample was 192.8mW, and the emission luminance of the core particles having an emission wavelength of 451 to 452nm in the second sample was 196.5 mW. The luminous brightness is improved by 1.92%. The luminance of the core particle with the light-emitting wavelength of 452-453 nm of the first sample is 192.1mW, the luminance of the core particle with the light-emitting wavelength of 452-453 nm of the second sample is 196mW, and the luminance is improved by 2.03%. The luminance of the core particle with the light-emitting wavelength of 452-453 nm of the first sample is 190.6mW, the luminance of the core particle with the light-emitting wavelength of 452-453 nm of the second sample is 194.5mW, and the luminance is improved by 2.05%.
Therefore, the light-emitting diode manufactured by the manufacturing method provided by the embodiment of the invention has higher luminous brightness and better luminous effect.
According to the embodiment of the invention, after the growth of the three-dimensional growth layer is finished, the temperature of the reaction chamber is kept unchanged, hydrogen is introduced into the reaction chamber for a period of time, at the moment, the temperature of the reaction chamber is higher, GaN is easy to decompose at high temperature, and the low-temperature buffer layer and the three-dimensional growth layer are both GaN layers, so that the low-temperature buffer layer and the three-dimensional growth layer can decompose, and meanwhile, the hydrogen can take GaN decomposition products out of the reaction chamber. And because the thickness of the three-dimensional growth layer is greater than that of the low-temperature buffer layer, hydrogen is introduced for a period of time, the low-temperature buffer layer on the periodic graph and part of the three-dimensional growth layer on the concave part can be removed, and the condition that after the low-temperature buffer layer on the periodic graph of the sapphire substrate is decomposed is ensured, part of the three-dimensional growth layer on the concave part is still not decomposed, so that an undoped GaN layer can be grown on the three-dimensional growth layer subsequently. Further, the temperature of the reaction chamber is increased, and a high-temperature undoped GaN layer grows on the three-dimensional growth layer, and cannot directly grow on the periodic pattern on the surface of the sapphire substrate due to the high growth temperature of the high-temperature undoped GaN layer, so that a cavity is formed between the high-temperature undoped GaN layer and the sapphire substrate. The cavity is filled with air, partial light emitted by the multiple quantum well layer passes through the cavity before being incident on the sapphire substrate, and the refractive index of the air is smaller than that of the sapphire substrate, so that the difference between the refractive indexes of the air and the gallium nitride epitaxial layer is larger, the light from the multiple quantum well layer is easy to generate total reflection at the cavity and is emitted from the front side of the light-emitting diode, and the light-emitting efficiency of the front side of the light-emitting diode is improved.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent replacements, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A manufacturing method of a light emitting diode epitaxial wafer is characterized by comprising the following steps:
providing a sapphire substrate, wherein periodic patterns are arranged on the surface of the sapphire substrate, and sunken parts are formed among the periodic patterns;
introducing carrier gas, nitrogen and a Mo source into the reaction chamber, and growing a low-temperature buffer layer on the periodic pattern and the concave part, wherein the low-temperature buffer layer is a GaN layer;
raising the temperature of the reaction chamber, introducing carrier gas, nitrogen and a Mo source into the reaction chamber, and growing a three-dimensional growth layer on the low-temperature buffer layer on the concave part, wherein the three-dimensional growth layer is a GaN layer and the thickness of the three-dimensional growth layer is greater than that of the low-temperature buffer layer;
keeping the temperature of the reaction chamber unchanged, introducing hydrogen into the reaction chamber for a period of time, and removing the low-temperature buffer layer on the periodic graph and a part of the three-dimensional growth layer on the concave part;
raising the temperature of the reaction chamber, introducing carrier gas, nitrogen and a Mo source into the reaction chamber, and growing a high-temperature undoped GaN layer on the three-dimensional growth layer, wherein the high-temperature undoped GaN layer is combined on the periodic pattern and is arranged at intervals with the periodic pattern to form a cavity;
introducing carrier gas, nitrogen, a Mo source and an N-type dopant into the reaction chamber, and growing an N-type layer on the high-temperature undoped GaN layer;
introducing carrier gas, nitrogen and a Mo source into the reaction chamber, and growing a multi-quantum well layer on the N-type layer;
and introducing carrier gas, nitrogen, a Mo source and a P-type dopant into the reaction chamber, and growing a P-type layer on the multi-quantum well layer.
2. The method of claim 1, wherein the temperature of the reaction chamber is controlled to be 1000 to 1070 ℃ when growing the three-dimensional growth layer.
3. The method of claim 1, wherein the flowing hydrogen gas into the reaction chamber for a period of time to remove the low-temperature buffer layer on the periodic pattern and a portion of the three-dimensionally grown layer on the recesses comprises:
and introducing 60-150L/min hydrogen into the reaction chamber.
4. The method according to claim 3, wherein the time for introducing hydrogen gas into the reaction chamber is 1 to 3 min.
5. The method according to claim 1, wherein the temperature of the reaction chamber is controlled to 1000 to 1070 ℃ when the hydrogen gas is introduced into the reaction chamber.
6. The method according to claim 1, wherein the pressure in the reaction chamber is controlled to 100 to 500torr when the hydrogen gas is introduced into the reaction chamber.
7. The method of claim 1, wherein the temperature of the reaction chamber is controlled to 1040-1080 ℃ when growing the high-temperature undoped GaN layer.
8. The method according to claim 1, wherein the low-temperature buffer layer has a thickness of 20 to 30 nm.
9. The method of manufacturing according to claim 1, wherein the thickness of the three-dimensional growth layer grown on the low-temperature buffer layer on the recess is 0.7 to 1.1 um.
10. The production method according to any one of claims 1 to 9, wherein the carrier gas is high-purity hydrogen gas or high-purity nitrogen gas or a mixed gas of high-purity hydrogen gas and high-purity nitrogen gas, and the Mo source is one or more of trimethyl gallium, trimethyl indium, trimethyl aluminum, and triethyl gallium.
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