CN114843374B - GaN-based light-emitting diode based on C-doped current expansion layer and preparation method thereof - Google Patents
GaN-based light-emitting diode based on C-doped current expansion layer and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 70
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 49
- 239000010980 sapphire Substances 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 230000006911 nucleation Effects 0.000 claims abstract description 34
- 238000010899 nucleation Methods 0.000 claims abstract description 34
- 238000005530 etching Methods 0.000 claims abstract description 16
- 238000003892 spreading Methods 0.000 claims abstract description 14
- 230000007480 spreading Effects 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 382
- 230000008569 process Effects 0.000 claims description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims description 39
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 33
- 229910052733 gallium Inorganic materials 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 230000004888 barrier function Effects 0.000 claims description 14
- 239000002356 single layer Substances 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000000206 photolithography Methods 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 10
- 229910002601 GaN Inorganic materials 0.000 description 228
- 238000006243 chemical reaction Methods 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005121 nitriding Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001259 photo etching Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001534 heteroepitaxy Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 239000012212 insulator Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/01—Manufacture or treatment
- H10H20/011—Manufacture or treatment of bodies, e.g. forming semiconductor layers
- H10H20/013—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials
- H10H20/0137—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials the light-emitting regions comprising nitride materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/01—Manufacture or treatment
- H10H20/011—Manufacture or treatment of bodies, e.g. forming semiconductor layers
- H10H20/013—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials
- H10H20/0133—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials with a substrate not being Group III-V materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/81—Bodies
- H10H20/816—Bodies having carrier transport control structures, e.g. highly-doped semiconductor layers or current-blocking structures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
本发明涉及一种基于C掺杂电流扩展层的GaN基发光二极管及其制备方法，方法包括：在蓝宝石衬底层上生长AlN成核层；在AlN成核层上生长U型GaN层；在U型GaN层上生长第一层n型GaN层；在第一层n型GaN层上生长第二层C掺杂GaN层；在第二层C掺杂GaN层上生长第三层n型GaN层；在第三层n型GaN层上生长多量子阱结构；在多量子阱结构上生长p型GaN层；刻蚀n型电极接触区，以暴露第一层n型GaN层；在n型电极接触区的第一层n型GaN层上沉积n型电极和在p型GaN层上沉积p型电极，以完成GaN基发光二极管的制作。本发明提出一种基于C掺杂的GaN基发光二极管的制备方法，用掺C的GaN层作为电流扩展层，提高LED的性能和可靠性，方法简单，无需引入额外生长源和工艺步骤。
The present invention relates to a GaN-based light-emitting diode based on a C-doped current spreading layer and a preparation method thereof, the method comprising: growing an AlN nucleation layer on a sapphire substrate layer; growing a U-type GaN layer on the AlN nucleation layer; growing a first n-type GaN layer on the U-type GaN layer; growing a second C-doped GaN layer on the first n-type GaN layer; growing a third n-type GaN layer on the second C-doped GaN layer; growing a multi-quantum well structure on the third n-type GaN layer; growing a p-type GaN layer on the multi-quantum well structure; etching an n-type electrode contact region to expose the first n-type GaN layer; depositing an n-type electrode on the first n-type GaN layer in the n-type electrode contact region and depositing a p-type electrode on the p-type GaN layer to complete the production of a GaN-based light-emitting diode. The present invention proposes a preparation method for a GaN-based light-emitting diode based on C-doping, using a C-doped GaN layer as a current spreading layer to improve the performance and reliability of the LED, the method is simple, and no additional growth source and process steps need to be introduced.
Description
Technical Field
The invention belongs to the technical field of microelectronics, and relates to a GaN-based light emitting diode based on a C-doped current expansion layer and a preparation method thereof.
Background
The GaN-based Light Emitting Diode (LED) has advantages of high efficiency, energy saving, environmental protection, long life, small volume, good color rendering and response speed, and the LED-based semiconductor lighting has gradually replaced the conventional lighting.
GaN is currently grown by heteroepitaxy due to the price and size limitations of GaN single crystals. Sapphire is the most commonly used substrate for GaN growth, and has the advantages of mature production technology, moderate price, high mechanical strength, high cost performance and the like. However, since sapphire is an insulator, a device with a vertical structure cannot be manufactured, and an LED with a lateral structure is currently the mainstream. Because the p-type electrode and the n-type electrode of the LED chip with the transverse structure are positioned on the same side, and the conductivity of the p-type material and the conductivity of the n-type material are different, a current congestion effect inevitably exists, so that uneven carrier distribution and local overheating are caused, and the efficiency and the reliability of the device are reduced. Thus, a current spreading layer has been created. The longitudinal resistance of the LED is increased by introducing a layer structure with low resistivity into the structure, so that the current is redistributed, and the transverse current expansion of the chip is improved. The reported current spreading layers include transparent conductive oxide films, current blocking layers under p-type electrodes, alGaN layers in n-type layers, and the like.
However, these methods all require an additional growth step, increase process complexity, and the additionally inserted layer structure may affect the crystal quality of the light emitting quantum well layer.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a GaN-based light emitting diode based on a C-doped current expansion layer and a preparation method thereof. The technical problems to be solved by the invention are realized by the following technical scheme:
The embodiment of the invention provides a preparation method of a GaN-based light emitting diode based on a C-doped current expansion layer, which comprises the following steps:
Selecting a sapphire substrate layer;
growing an AlN nucleation layer on the sapphire substrate layer;
growing a U-shaped GaN layer on the AlN nucleation layer;
growing a first n-type GaN layer on the U-type GaN layer;
growing a second C-doped GaN layer on the first n-type GaN layer;
Growing a third n-type GaN layer on the second C-doped GaN layer, wherein the first n-type GaN layer, the second C-doped GaN layer and the third n-type GaN layer form an n-type GaN layer with a three-layer structure;
Growing a multiple quantum well structure on the third N-type GaN layer, wherein the multiple quantum well structure comprises a plurality of periods of quantum wells, and the quantum wells comprise an In xGa1-x N well layer and a GaN barrier layer positioned on the In xGa1-x N well layer;
Growing a p-type GaN layer on the multi-quantum well structure;
etching the n-type electrode contact region to expose the first n-type GaN layer;
And depositing an n-type electrode on the first n-type GaN layer of the n-type electrode contact region and depositing a p-type electrode on the p-type GaN layer to finish the manufacture of the GaN-based light emitting diode.
In one embodiment of the present invention, selecting a sapphire substrate layer includes:
cleaning the sapphire substrate layer;
carrying out heat treatment on the sapphire substrate layer for 5-10min at the temperature of 900-1200 ℃;
And carrying out nitriding treatment on the sapphire substrate layer after heat treatment for 3-5min at the temperature of 1000-1100 ℃.
In one embodiment of the invention, growing an AlN nucleation layer on the sapphire substrate layer comprises:
And growing an AlN nucleating layer with the thickness of 20-50nm on the nitrided sapphire substrate layer by adopting an MOCVD process.
In one embodiment of the present invention, growing a U-shaped GaN layer on the AlN nucleation layer comprises:
And growing a U-shaped GaN layer with the thickness of 2-3 mu m on the AlN nucleation layer by adopting an MOCVD process.
In one embodiment of the present invention, growing a first n-type GaN layer on the U-type GaN layer includes:
Introducing ammonia gas, a gallium source and a silicon source, and growing the first n-type GaN layer on the U-type GaN layer by adopting an MOCVD process.
In one embodiment of the present invention, growing a second layer of C-doped GaN layer on the first layer of n-type GaN layer comprises:
And closing the silicon source, keeping the flow of the ammonia gas and the flow of the gallium source unchanged, and growing a second C doped GaN layer on the first n-type GaN layer by adopting an MOCVD process under a second temperature condition, wherein the second temperature is lower than the first temperature.
In one embodiment of the present invention, growing a third n-type GaN layer on the second C-doped GaN layer includes:
and introducing a silicon source, keeping the flow rates of ammonia gas and gallium source unchanged, and growing a third n-type GaN layer on the second C-doped GaN layer by adopting an MOCVD process under the condition of a first temperature.
In one embodiment of the invention, the thickness of the single-layer In xGa1-x N well layer is 2-5nm, the thickness of the single-layer GaN barrier layer is 9-15nm, and the adjustment range of the In content x is 0.1-0.7.
In one embodiment of the present invention, etching the n-type electrode contact region to expose the first layer of n-type GaN layer includes:
And etching off the p-type GaN layer, the multiple quantum well structure, the third n-type GaN layer, the second C-doped GaN layer and the first n-type GaN layer with partial depth at one end by adopting a photoetching process so as to expose the rest of the first n-type GaN layer.
Another embodiment of the present invention provides a GaN-based light emitting diode based on a C-doped current spreading layer, which is prepared by using the preparation method of the GaN-based light emitting diode according to any one of the above embodiments, and the GaN-based light emitting diode includes:
A sapphire substrate layer;
An AlN nucleation layer positioned on the sapphire substrate layer;
The U-shaped GaN layer is positioned on the AlN nucleation layer;
A first layer of n-type GaN layer located on the U-type GaN layer, wherein the first layer of n-type GaN layer is provided with a first upper surface and a second upper surface, and the second upper surface is located below the first upper surface;
A second layer of C doped GaN layer on the first upper surface of the first layer of n-type GaN layer;
the third n-type GaN layer is positioned on the second C-doped GaN layer;
A multiple quantum well structure on the third N-type GaN layer, the multiple quantum well structure comprising a quantum well of several periods, the quantum well comprising an In xGa1-x N-well layer and a GaN barrier layer on the In xGa1-x N-well layer;
a p-type GaN layer located on the multiple quantum well structure;
An n-type electrode on a second upper surface of the first n-type GaN layer;
and a p-type electrode on the p-type GaN layer.
Compared with the prior art, the invention has the beneficial effects that:
1. the LED has the n-type GaN layers with the three-layer structure, and particularly, the C-doped GaN layer is inserted between the two n-type GaN layers, and the C-doped GaN layer takes C impurities as acceptors to reduce the carrier concentration of the C-doped GaN layer, so that the conductivity of the C-doped GaN layer is reduced, and thus, the insertion of the C-doped GaN layer with poor conductivity can increase the transverse expansion of current, effectively relieve the current congestion effect in the LED with the transverse structure, and improve the efficiency and the reliability of the device.
2. According to the invention, when GaN is grown, the unintentional doping phenomenon of C in the Ga source is utilized, the growth temperature is reduced, the Si source is closed, C doping can be realized, other growth sources are not required to be introduced in the growth process (namely, the C source is not required to be additionally introduced), and the preparation process of the GaN-based light emitting diode is simple and has strong availability.
Other aspects and features of the present invention will become apparent from the following detailed description, which refers to the accompanying drawings. It is to be understood that the drawings are designed solely for purposes of illustration and not as a definition of the limits of the invention, for which reference should be made to the appended claims. It should be further understood that the drawings are not necessarily drawn to scale and that, unless otherwise indicated, they are merely intended to conceptually illustrate the structures and procedures described herein.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a GaN-based light emitting diode based on a C-doped current spreading layer according to an embodiment of the present invention;
fig. 2 is a schematic process diagram of a method for manufacturing a GaN-based light emitting diode based on a C-doped current spreading layer according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a GaN-based light emitting diode based on a C-doped current spreading layer according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
Example 1
Referring to fig. 1 and fig. 2, fig. 1 is a schematic flow chart of a method for preparing a GaN-based light emitting diode based on a C-doped current spreading layer according to an embodiment of the invention, and fig. 2 is a schematic flow chart of a method for preparing a GaN-based light emitting diode based on a C-doped current spreading layer according to an embodiment of the invention. The invention provides a preparation method of a GaN-based light emitting diode based on a C-doped current expansion layer, which comprises the following steps:
Step 1, please refer to fig. 2a, a sapphire substrate layer is selected.
And 1.1, cleaning the sapphire substrate layer.
And 1.2, performing heat treatment on the sapphire substrate layer for 5-10min at the temperature of 900-1200 ℃.
The method comprises the steps of placing the sapphire substrate layer in a metal organic chemical vapor deposition MOCVD reaction chamber, reducing the vacuum degree of the reaction chamber to be less than 2 multiplied by 10 -2 Torr, introducing hydrogen into the reaction chamber, heating the sapphire substrate layer to 900-1200 ℃ under the condition that the pressure of the MOCVD reaction chamber reaches 20-760Torr, and keeping the temperature for 5-10min to finish the heat treatment of the sapphire substrate layer.
And 1.3, nitriding the sapphire substrate layer after heat treatment for 3-5min at the temperature of 1000-1100 ℃.
Specifically, the sapphire substrate layer after heat treatment is placed in a reaction chamber with the temperature of 1000-1100 ℃, ammonia gas with the flow rate of 3000-4000sccm is introduced, and nitriding treatment is continued for 3-5 min.
Step 2, please refer to fig. 2a, an AlN nucleation layer is grown on the sapphire substrate layer.
Specifically, an AlN nucleation layer with the thickness of 20-50nm is grown on the nitrided sapphire substrate layer by adopting an MOCVD process. In order to solve the problem of mismatch between the sapphire substrate layer and the U-shaped GaN layer, an AlN nucleation layer is grown between the sapphire substrate layer and the U-shaped GaN layer.
Step 3, please refer to fig. 2b, a U-shaped GaN layer (unintentionally doped with gallium nitride) is grown on the AlN nucleation layer.
Specifically, a MOCVD process is used to grow a U-shaped GaN layer with a thickness of 2-3 μm on the AlN nucleation layer.
Step 4, please refer to fig. 2c, a first n-type GaN layer is grown on the U-type GaN layer.
Specifically, ammonia gas, a gallium source and a silicon source are introduced, and a MOCVD process is adopted to grow a first n-type GaN layer on the U-type GaN layer under a first temperature condition.
Preferably, the first temperature is 1050 ℃.
Preferably, the Si doping concentration is 10 18-1019cm-3.
Further, ammonia gas, a gallium source and a silicon source are simultaneously introduced under the condition that the temperature of a reaction chamber is 1050 ℃, and a MOCVD process is adopted to grow a first n-type GaN layer with the thickness of 1-1.5 mu m on a U-type GaN layer, so that the second C-doped GaN layer can achieve the effect of effectively reducing current congestion, and the thickness of the first n-type GaN layer is set to be 1-1.5 mu m under the condition that the cost is not increased.
Step 5, please refer to fig. 2d, a second C-doped GaN layer is grown on the first n-type GaN layer.
Specifically, the silicon source is turned off, the flow of ammonia gas and gallium source is kept unchanged (i.e. the same as step 4), and a second layer of C-doped GaN layer is grown on the first layer of n-type GaN layer by using an MOCVD process under a second temperature condition, wherein the second temperature is lower than the first temperature, so that the second layer of C-doped GaN layer is capable of effectively reducing conductivity, and therefore the silicon source needs to be turned off, and meanwhile, the second temperature is lower than the first temperature in order to enable more C-doping.
Preferably, the second temperature is 600-850 ℃, because too high a temperature results in less C doping, thereby not effectively reducing conductivity, while too low a temperature is detrimental to GaN growth, and thus the second temperature is set to 600-850 ℃.
Further, the silicon source is closed, the flow of ammonia gas and gallium source is kept unchanged, the growth temperature is reduced from 1050 ℃ to 600-850 ℃, a second C doped GaN layer with the thickness of 50-200nm is grown on the first n-type GaN layer by adopting an MOCVD process, the effect of effectively reducing conductivity is not achieved when the thickness of the second C doped GaN layer is too thin, the overall conductivity is affected when the thickness of the second C doped GaN layer is too thick, and the second C doped GaN layer with the thickness of 50-200nm can ensure that the conductivity is effectively reduced and meanwhile the overall conductivity is kept good.
The Ga source of this embodiment may be from trimethylgallium or triethylgallium, since there is carbon in the Ga source, and thus there is C impurity doped into the material when growing the second C-doped GaN layer, thus making the second temperature lower than the first temperature, so that more C is doped by lowering the growth temperature.
Step 6, please refer to fig. 2e, a third n-type GaN layer is grown on the second C-doped GaN layer, and the first n-type GaN layer, the second C-doped GaN layer and the third n-type GaN layer form an n-type GaN layer with a three-layer structure.
Specifically, a silicon source is introduced, the flow rates of ammonia gas and gallium source are kept unchanged (namely the flow rate is the same as that of the step 4), and a third n-type GaN layer is grown on the second C-doped GaN layer by adopting an MOCVD process under the condition of a first temperature.
Further, a silicon source is introduced, the flow rates of ammonia gas and gallium source are kept unchanged, the growth temperature is increased from 600-850 ℃ to 1050 ℃, and a second C doped GaN layer with the thickness of 300-500nm is grown on the first n-type GaN layer by adopting an MOCVD process.
In step 7, referring to fig. 2f, a multiple quantum well structure is grown on the third N-type GaN layer, where the multiple quantum well structure includes a quantum well with a number of periods, and the quantum well includes an In xGa1-x N well layer and a GaN barrier layer on the In xGa1-x N well layer, for example, the number of periods may be 8-12, specifically, for example, 9.
Preferably, the thickness of the single-layer In xGa1-x N well layer is 2-5nm, and the thickness of the single-layer GaN barrier layer is 9-15nm, wherein the adjustment range of the In content x is 0.1-0.7.
Step 8, please refer to fig. 2g, a p-type GaN layer is grown on the multiple quantum well structure.
Specifically, a Mg source is introduced, a p-type GaN layer with the thickness of 100-200nm is grown on a multi-quantum well structure by adopting an MOCVD process, the doping concentration of Mg is 10 19-1022cm-3, the temperature of a reaction chamber is maintained at 800-1100 ℃, and annealing is carried out for 5-10min under the atmosphere of H 2.
Step 9, please refer to fig. 2h, etching the n-type electrode contact region to expose the first n-type GaN layer.
Specifically, a p-type GaN layer, a multiple quantum well structure, a third n-type GaN layer, a second C-doped GaN layer and a first n-type GaN layer with partial depth at one end are etched by adopting a photoetching process, so that the rest of the first n-type GaN layer is exposed.
Step 10, please refer to fig. 2i, in which an n-type electrode is deposited on the first n-type GaN layer of the n-type electrode contact region and a p-type electrode is deposited on the p-type GaN layer, so as to complete the fabrication of the GaN-based light emitting diode.
Specifically, an n-type electrode is respectively deposited on the first n-type GaN layer by adopting a metal sputtering method, and a p-type electrode is deposited on the p-type GaN layer, so that the manufacturing of the GaN-based light emitting diode is completed.
Because of the current structure, in the process that current flows from the p-type electrode to the n-type electrode, a current collecting edge (also called current congestion) effect exists, because the first n-type GaN layer and the third n-type GaN layer are conductive layers and have a plurality of current carriers, a C-doped GaN layer is added between the first n-type GaN layer and the third n-type GaN layer, thereby partial electrons can be neutralized, the conductivity of the C-doped GaN layer is reduced, and thus, the lateral expansion of the current can be increased by inserting a C-doped GaN layer with poor conductivity, thereby effectively relieving the current congestion effect in the LED with a lateral structure and improving the efficiency and the reliability of the device.
2. According to the method, when GaN is grown, the unintentional doping phenomenon of C in the Ga source is utilized, the growth temperature is reduced, so that when the C doped GaN layer is grown, the Si source is closed, C doping can be realized, and therefore, the C doping can be realized without introducing other growth sources (namely, without additionally introducing the C source) in the growth process, and therefore, the effect of relieving the current congestion effect in the LED with the transverse structure is achieved under the condition that the process flow is not increased, and meanwhile, the process for preparing the GaN-based light-emitting diode is simple and has strong usability.
Example two
The invention also provides a preparation method of the C-doped blue light LED with the light emitting wavelength of 450nm based on the first embodiment, which comprises the following steps:
And step one, heat treatment.
And then introducing hydrogen into the reaction chamber, heating the sapphire substrate layer to 900 ℃ under the condition that the pressure of the MOCVD reaction chamber reaches 20Torr, and keeping the temperature for 10min to finish the heat treatment of the sapphire substrate layer.
And step two, nitriding at high temperature.
And placing the sapphire substrate layer after heat treatment in a reaction chamber with the temperature of 1000 ℃, introducing ammonia with the flow of 3500sccm, and nitriding for 5min to complete nitriding.
And thirdly, growing an AlN nucleation layer.
Referring to FIG. 2a, under the condition that the temperature of the reaction chamber is 1000 ℃, ammonia gas with the flow rate of 3000sccm and an aluminum source with the flow rate of 40sccm are simultaneously introduced, and an AlN nucleation layer with the thickness of 20nm is grown on the nitrided sapphire substrate layer by adopting an MOCVD process.
And step four, growing a U-shaped GaN layer.
Referring to FIG. 2b, under the condition that the temperature of the reaction chamber is 950 ℃, ammonia gas with flow rate of 2500sccm and gallium source with flow rate of 150sccm are simultaneously introduced, and a MOCVD process is adopted to grow a U-shaped GaN layer with thickness of 2 μm on the AlN nucleation layer under the condition that the pressure is kept at 20 Torr.
And step five, growing an n-type GaN layer with a three-layer structure.
5A) Referring to fig. 2C, under the condition that the temperature of the reaction chamber is 1050 ℃, ammonia gas with flow rate of 2500sccm, a gallium source with flow rate of 150sccm and a silicon source with flow rate of 40sccm are simultaneously introduced, and under the condition that the maintaining pressure is 20Torr, a first n-type GaN layer with thickness of 1 μm and Si doping concentration of 1×10 18cm-3 is grown on the U-type GaN layer by adopting an MOCVD process.
5B) Referring to fig. 2d, the Si source is turned off, the flow rates of the ammonia gas and the gallium source are kept unchanged, the growth temperature is reduced to 850 ℃, and a second C-doped GaN layer with a thickness of 50nm is grown on the first n-type GaN layer;
5c) Referring to fig. 2e, a silicon source with a flow rate of 40sccm is introduced, the flow rates of ammonia and gallium source are kept unchanged, the growth temperature is raised to 1050 ℃, and a third n-type GaN layer with a thickness of 300nm and a Si doping concentration of 1×10 18cm-3 is grown on the second C-doped GaN layer.
Step six, please refer to fig. 2f, an In 0.15Ga0.85 N/GaN multiple quantum well structure with a light emission wavelength of 450nm is grown.
And growing nine periods of In 0.15Ga0.85 N/GaN multi-quantum well structures on the third N-type GaN layer by adopting an MOCVD process under the condition that the pressure of a reaction chamber is 40Torr, wherein:
The thickness of the single-layer In 0.15Ga0.85 N well layer In each period is 2nm, the growth temperature is 750 ℃, the flow of a nitrogen source is 1100sccm, the flow of a gallium source is 50sccm, and the flow of an indium source is 200sccm In the growth process;
The thickness of the single-layer GaN barrier layer in each period is 9nm, the growth temperature is 850 ℃, the flow rate of the nitrogen source is kept to be 2000sccm in the growth process, and the flow rate of the gallium source is 150sccm.
Step seven, please refer to fig. 2g, a p-type GaN layer is grown.
7A) Simultaneously introducing ammonia gas with flow rate of 2500sccm, a gallium source with flow rate of 150sccm and a magnesium source with flow rate of 100sccm under the condition that the reaction chamber temperature is 1060 ℃, and growing a p-type GaN layer with thickness of 100nm and Mg doping concentration of 1 multiplied by 10 19cm-3 on an In 0.15Ga0.85 N/GaN multi-quantum well structure by adopting an MOCVD process under the condition that the pressure is kept at 20 Torr;
7b) The reaction chamber temperature was maintained at 860 ℃ and annealed under an H 2 atmosphere for 5min.
Step eight, please refer to fig. 2h, etching the n-type electrode contact region.
And etching part of GaN by adopting a photoetching process to expose the first n-type GaN layer, and etching the second C-doped GaN layer and part of the first n-type GaN layer to a depth.
Step nine, please refer to fig. 2i, deposit the electrode.
And respectively depositing n-type electrodes on the first n-type GaN layer by adopting a metal sputtering method, and depositing p-type electrodes on the p-type GaN layer to finish the manufacture of the blue light LED device.
Example III
The invention also provides a preparation method of the green LED based on C doping with the luminous wavelength of 520nm based on the first embodiment, which comprises the following steps:
And step one, heat treatment.
And then introducing hydrogen into the reaction chamber, heating the sapphire substrate layer to 1000 ℃ under the condition that the pressure of the MOCVD reaction chamber reaches 400Torr, and keeping for 7min to finish the heat treatment of the sapphire substrate layer.
And step two, nitriding at high temperature.
And placing the sapphire substrate layer after heat treatment in a reaction chamber with the temperature of 1050 ℃, introducing ammonia with the flow of 3500sccm, and nitriding for 4min to complete nitriding.
And thirdly, growing an AlN nucleation layer.
Referring to FIG. 2a, under the condition that the temperature of the reaction chamber is 1000 ℃, ammonia gas with the flow rate of 3000sccm and an aluminum source with the flow rate of 40sccm are simultaneously introduced, and an AlN nucleation layer with the thickness of 30nm is grown on the nitrided sapphire substrate layer by adopting an MOCVD process.
And step four, growing a U-shaped GaN layer.
Referring to FIG. 2b, at a reaction chamber temperature of 950 ℃, ammonia gas at a flow rate of 2500sccm and a gallium source at a flow rate of 150sccm were simultaneously introduced, and a MOCVD process was used to grow a U-shaped GaN layer with a thickness of 2.5 μm on the AlN nucleation layer while maintaining a pressure of 20 Torr.
And step five, growing an n-type GaN layer with a three-layer structure.
5A) Referring to fig. 2C, under the condition that the temperature of the reaction chamber is 1050 ℃, ammonia gas with flow rate of 2500sccm, a gallium source with flow rate of 150sccm and a silicon source with flow rate of 50sccm are simultaneously introduced, and under the condition that the maintaining pressure is 20Torr, a first n-type GaN layer with thickness of 1.3 μm and Si doping concentration of 5×10 18cm-3 is grown on the U-type GaN layer by adopting an MOCVD process.
5B) Referring to fig. 2d, the Si source is turned off, the flow rates of the ammonia gas and the gallium source are kept unchanged, the growth temperature is reduced to 700 ℃, and a second C-doped GaN layer with a thickness of 100nm is grown on the first n-type GaN layer;
5c) Referring to fig. 2e, a silicon source with a flow rate of 50sccm is introduced, the flow rates of ammonia and gallium source are kept unchanged, the growth temperature is raised to 1050 ℃, and a third n-type GaN layer with a thickness of 400nm and a Si doping concentration of 5×10 18cm-3 is grown on the second C-doped GaN layer.
Step six, please refer to fig. 2f, an In 0.32Ga0.68 N/GaN multiple quantum well structure with a light emission wavelength of 520nm is grown.
And growing nine periods of In 0.32Ga0.68 N/GaN multi-quantum well structures on the third N-type GaN layer by adopting an MOCVD process under the condition that the pressure of a reaction chamber is 40Torr, wherein:
the thickness of the single-layer In 0.32Ga0.68 N well layer In each period is 3nm, the growth temperature is 750 ℃, the flow of a nitrogen source is 1100sccm, the flow of a gallium source is 50sccm, and the flow of an indium source is 250sccm In the growth process;
The thickness of the single-layer GaN barrier layer in each period is 12nm, the growth temperature is 850 ℃, the flow rate of the nitrogen source is kept to be 2000sccm in the growth process, and the flow rate of the gallium source is 150sccm.
Step seven, please refer to fig. 2g, a p-type GaN layer is grown.
7A) Simultaneously introducing ammonia gas with flow rate of 2500sccm, a gallium source with flow rate of 150sccm and a magnesium source with flow rate of 150sccm under the condition that the reaction chamber temperature is 1060 ℃, and growing a p-type GaN layer with thickness of 150nm and Mg doping concentration of 1 multiplied by 10 20cm-3 on an In 0.32Ga0.68 N/GaN multi-quantum well structure by adopting an MOCVD process under the condition that the pressure is kept at 20 Torr;
7b) The reaction chamber temperature was maintained at 900 ℃ and annealed under an H 2 atmosphere for 8min.
Step eight, please refer to fig. 2h, etching the n-type electrode contact region.
And etching part of GaN by adopting a photoetching process to expose the first n-type GaN layer, and etching the second C-doped GaN layer and part of the first n-type GaN layer to a depth.
Step nine, please refer to fig. 2i, deposit the electrode.
And respectively depositing n-type electrodes on the first n-type GaN layer by adopting a metal sputtering method, and depositing p-type electrodes on the p-type GaN layer to finish the manufacture of the green LED device.
Example IV
The invention also provides a preparation method of the C-doped yellow LED with the light emitting wavelength of 600nm based on the first embodiment, which comprises the following steps:
And step one, heat treatment.
And then introducing hydrogen into the reaction chamber, heating the sapphire substrate layer to 1200 ℃ under the condition that the pressure of the MOCVD reaction chamber reaches 760Torr, and keeping for 10min to finish the heat treatment of the sapphire substrate layer.
And step two, nitriding at high temperature.
And placing the sapphire substrate layer after heat treatment in a reaction chamber with the temperature of 1100 ℃, introducing ammonia with the flow of 4000sccm, and nitriding for 5min to complete nitriding.
And thirdly, growing an AlN nucleation layer.
Referring to FIG. 2a, under the condition that the temperature of the reaction chamber is 1000 ℃, ammonia gas with the flow rate of 3000sccm and an aluminum source with the flow rate of 40sccm are simultaneously introduced, and an AlN nucleation layer with the thickness of 50nm is grown on the nitrided sapphire substrate layer by adopting an MOCVD process.
And step four, growing a U-shaped GaN layer.
Referring to FIG. 2b, under the condition that the temperature of the reaction chamber is 950 ℃, ammonia gas with the flow rate of 2500sccm and a gallium source with the flow rate of 150sccm are simultaneously introduced, and a MOCVD process is adopted to grow a U-shaped GaN layer with the thickness of 3 μm on the AlN nucleation layer under the condition that the pressure is kept at 20 Torr.
And step five, growing an n-type GaN layer with a three-layer structure.
5A) Referring to FIG. 2C, under the condition that the temperature of the reaction chamber is 1050 ℃, a gallium source with the flow rate of 2500sccm and a silicon source with the flow rate of 60sccm are simultaneously introduced, and under the condition that the maintaining pressure is 20Torr, a first n-type GaN layer with the thickness of 1.5 μm and the Si doping concentration of 1×10 19cm-3 is grown on the U-type GaN layer by adopting an MOCVD process.
5B) Referring to fig. 2d, the Si source is turned off, the flow rates of the ammonia gas and the gallium source are kept unchanged, the growth temperature is reduced to 600 ℃, and a second C-doped GaN layer with a thickness of 200nm is grown on the first n-type GaN layer;
5c) Referring to fig. 2e, a silicon source with a flow rate of 60sccm is introduced, the flow rates of ammonia and gallium source are kept unchanged, the growth temperature is raised to 1050 ℃, and a third n-type GaN layer with a thickness of 500nm and a Si doping concentration of 1×10 19cm-3 is grown on the second C-doped GaN layer.
Step six, please refer to fig. 2f, an In 0.4Ga0.6 N/GaN multiple quantum well structure with a light emission wavelength of 600nm is grown.
And growing nine periods of In 0.4Ga0.6 N/GaN multi-quantum well structures on the third N-type GaN layer by adopting an MOCVD process under the condition that the pressure of a reaction chamber is 40Torr, wherein:
The thickness of the single-layer In 0.4Ga0.6 N well layer In each period is 5nm, the growth temperature is 750 ℃, the flow of a nitrogen source is 1100sccm, the flow of a gallium source is 50sccm, and the flow of an indium source is 300sccm In the growth process;
The thickness of the single-layer GaN barrier layer in each period is 15nm, the growth temperature is 850 ℃, the flow rate of the nitrogen source is kept to be 2000sccm in the growth process, and the flow rate of the gallium source is 150sccm.
Step seven, please refer to fig. 2g, a p-type GaN layer is grown.
7A) Simultaneously introducing ammonia gas with flow rate of 2500sccm, a gallium source with flow rate of 150sccm and a magnesium source with flow rate of 300sccm under the condition that the temperature of a reaction chamber is 1060 ℃, and growing a p-type GaN layer with thickness of 200nm and Mg doping concentration of 1 multiplied by 10 22cm-3 on an In 0.4Ga0.6 N/GaN multi-quantum well structure by adopting an MOCVD process under the condition that the pressure is kept at 20 Torr;
7b) The reaction chamber temperature was maintained at 1100 ℃, and annealed under an H 2 atmosphere for 10min.
Step eight, please refer to fig. 2h, etching the n-type electrode contact region.
And etching part of GaN by adopting a photoetching process to expose the first n-type GaN layer, and etching the second C-doped GaN layer and part of the first n-type GaN layer to a depth.
Step nine, please refer to fig. 2i, deposit the electrode.
And respectively depositing n-type electrodes on the first n-type GaN layer by adopting a metal sputtering method, and depositing p-type electrodes on the p-type GaN layer to finish the manufacture of the yellow LED device.
Example five
Referring to fig. 3, fig. 3 is a schematic structural diagram of a GaN-based light emitting diode based on a C-doped current spreading layer according to an embodiment of the present invention. The present invention also provides a GaN-based light emitting diode based on a C-doped current spreading layer based on the above embodiment, the GaN-based light emitting diode comprising:
A sapphire substrate layer;
the AlN nucleation layer is positioned on the sapphire substrate layer;
the U-shaped GaN layer is positioned on the AlN nucleation layer;
the first n-type GaN layer is positioned on the U-type GaN layer and is provided with a first upper surface and a second upper surface, and the second upper surface is positioned below the first upper surface;
a second layer of C doped GaN layer on the first upper surface of the first layer of n-type GaN layer;
The third n-type GaN layer is positioned on the second C-doped GaN layer;
The multi-quantum well structure is positioned on the third N-type GaN layer and comprises a plurality of periods of quantum wells, wherein each quantum well comprises an In xGa1-x N well layer and a GaN barrier layer positioned on the In xGa1-x N well layer;
the p-type GaN layer is positioned on the multi-quantum well structure;
an n-type electrode on the second upper surface of the first n-type GaN layer;
and a p-type electrode on the p-type GaN layer.
Preferably, the AlN nucleation layer has a thickness in the range of 20-50nm.
Preferably, the thickness of the U-shaped GaN layer ranges from 2 μm to 3 μm.
Preferably, the first n-type GaN layer has a thickness ranging from 1 to 1.5 μm and a Si doping concentration of 10 18-1019cm-3, the second C-doped GaN layer has a thickness ranging from 50 to 200nm, and the third n-type GaN layer has a thickness ranging from 300 to 500nm and a Si doping concentration of 10 18-1019cm-3.
Preferably, the multi-quantum well structure includes a total of nine cycles of quantum wells, each cycle of quantum wells including an In xGa1- x N well layer and a GaN barrier layer on the In xGa1-x N well layer, and each cycle of In xGa1-x N well layer and GaN barrier layer having thicknesses ranging from 2-5nm and 9-15nm, respectively.
Preferably, the adjustment range of In content parameter x In the In xGa1-x N well layer is 0.1-0.7, and quantum wells with different In content can be used for preparing LEDs with different light-emitting wavelengths
Preferably, the thickness of the p-type GaN layer ranges from 100 to 200nm.
In the description of the present invention, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic point described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristic data points described may be combined in any suitable manner in any one or more embodiments or examples. Further, one skilled in the art can engage and combine the different embodiments or examples described in this specification.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (7)
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| CN111987198A (en) * | 2020-08-31 | 2020-11-24 | 西安电子科技大学 | Fe-doped GaN-based lateral structure light-emitting diode and fabrication method |
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