CN117613158B - GaN-based LD epitaxial structure and preparation method thereof - Google Patents
GaN-based LD epitaxial structure and preparation method thereof Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/12—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a stress relaxation structure, e.g. buffer layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
- H01L33/025—Physical imperfections, e.g. particular concentration or distribution of impurities
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
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- 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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a GaN-based LD epitaxial structure, which comprises a substrate, a composite buffer layer and a composite transition layer, wherein the composite buffer layer comprises a first buffer sub-layer, a second buffer sub-layer and a third buffer sub-layer which are sequentially stacked and grown, the first buffer sub-layer is made of AlN, the second buffer sub-layer is made of Al xGa1‑x N, and the third buffer sub-layer is made of Al yGa1‑y N, wherein x is 0< 0.2, y is 0< 0.2, and x > y; the composite transition layer comprises a first transition sub-layer, a second transition sub-layer, a third transition sub-layer and a fourth transition sub-layer which are sequentially stacked and grown, wherein the first transition sub-layer is a small island forming layer, the second transition sub-layer is a big island forming layer, the third transition sub-layer is a big island merging filling layer, and the fourth transition sub-layer is a superlattice layer. The invention utilizes the growth mode of the composite buffer layer and the composite transition layer to reduce the point defect density and the linear defect extending upwards, improves the crystal quality of epitaxial wafer growth, and further improves the radiation recombination of LD active region.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a GaN-based LD epitaxial structure and a preparation method thereof.
Background
In the photoelectric device prepared by GaN (gallium nitride), the blue light GaN-based LD has the characteristics of low driving energy consumption, large output energy, small volume, stable performance and the like, and has important application value in the fields of data storage, laser display, laser illumination and the like.
However, in the practical application of the blue light GaN-based LD, in-vivo material degradation of the blue light GaN-based LD is one of the most important factors affecting the reliability of the blue light GaN-based LD, and it is considered that the key factors generated by in-vivo degradation of the blue light GaN-based LD are that non-radiative recombination of an active region is increased due to diffusion and proliferation of point defects and dislocation of the active region, so that internal quantum efficiency is reduced, and further performance of the LD such as output optical power, photoelectric conversion efficiency, threshold current and oblique efficiency is reduced with time, thereby causing poor reliability of the device or lamp-dead phenomenon.
Disclosure of Invention
The invention aims to provide a GaN-based LD epitaxial structure which can at least solve part of defects in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The GaN-based LD epitaxial structure comprises a composite buffer layer and a composite transition layer which are sequentially stacked and grown on a substrate, wherein the composite buffer layer comprises a first buffer sub-layer, a second buffer sub-layer and a third buffer sub-layer which are sequentially stacked and grown, the first buffer sub-layer is made of AlN, the second buffer sub-layer is made of Al xGa1-x N, and the third buffer sub-layer is made of Al yGa1-y N, wherein x is 0< 0.2, y is 0< 0.2, and x > y; the composite transition layer comprises a first transition sub-layer, a second transition sub-layer, a third transition sub-layer and a fourth transition sub-layer which are sequentially stacked and grown, wherein the first transition sub-layer is grown on the third buffer sub-layer, the first transition sub-layer is a small island forming layer, the second transition sub-layer is a big island forming layer, the third transition sub-layer is a big island merging filling layer, and the fourth transition sub-layer is a superlattice layer.
Further, the thicknesses of the second buffer sub-layer and the third buffer sub-layer are both larger than the thickness of the first buffer sub-layer.
Further, the thickness of the first transition sub-layer is smaller than the thickness of the second transition sub-layer, and the thickness of the second transition sub-layer is smaller than the thickness of the third transition sub-layer.
Further, the fourth transition sub-layer is a GaN superlattice layer or an AlGaN/n-GaN superlattice layer.
Further, the fourth transition sub-layer is a GaN superlattice layer, the single layer is a Si doped GaN sub-layer, and the Si doping concentration is。
Further, the first transition sub-layer, the second transition sub-layer and the third transition sub-layer are sequentially and circularly overlapped and grown to form the superlattice structure.
Furthermore, an AlN template is arranged between the substrate and the composite buffer layer.
Further, an N-type GaN layer, an N-type AlGaN covering layer, an N-type lower waveguide layer, a multiple quantum well layer, an upper waveguide layer, a p-type electron blocking layer, a p-type AlGaN covering layer and a p-type contact layer are sequentially stacked and grown on the composite transition layer.
In addition, the invention also provides a preparation method of the GaN-based LD epitaxial structure, which comprises the following steps:
s1, sequentially growing a first buffer sub-layer, a second buffer sub-layer and a third buffer sub-layer on a substrate to form a composite buffer layer;
the growth temperature of the first buffer sub-layer and the second buffer sub-layer is smaller than that of the third buffer sub-layer, and the growth pressure of the first buffer sub-layer and the second buffer sub-layer is smaller than that of the third buffer sub-layer;
s2, sequentially growing a first transition sub-layer, a second transition sub-layer, a third transition sub-layer and a fourth transition sub-layer on the composite buffer layer to form a composite transition layer;
The growth temperatures of the first transition sub-layer, the second transition sub-layer, the third transition sub-layer and the fourth transition sub-layer are respectively T21, T22, T23 and T24, and T21 is less than T22 and less than or equal to T23 and less than or equal to T24; the growth pressures of the first transition sub-layer, the second transition sub-layer, the third transition sub-layer and the fourth transition sub-layer are respectively P21, P22, P23 and P24, and P21> P22> P23 = P24; the growth carrier gas amounts of the first transition sub-layer, the second transition sub-layer and the third transition sub-layer are F21, F22 and F23 respectively, and F21> F22 and F21> F23.
Further, the gap position when the composite buffer layer is grown is smaller than the gap position when the composite transition layer is grown, and the growth temperature of the composite buffer layer is lower than that of the composite transition layer.
Compared with the prior art, the invention has the beneficial effects that:
The GaN-based LD epitaxial structure provided by the invention is designed to be a composite buffer layer consisting of the AlN layer/the Al xGa1-x N layer/the Al yGa1-y N layer, so that lattice mismatch between a substrate and the buffer layer and thermal mismatch caused by thermal expansion coefficient difference are reduced by utilizing a gradual transition growth mode, a large number of point defects generated by doping high Al components in the epitaxial growth process of an AlGaN material are reduced, the point defect density of the epitaxial structure and dislocation caused by the high Al components are reduced, and the crystal quality of epitaxial structure growth is improved; meanwhile, the gradient temperature rise of the composite transition layer is utilized to firstly improve the crystal quality of crystal nucleus growth, and then the crystal nucleus is continuously filled and grown, so that the linear defects are prevented or reduced from extending upwards in a superlattice growth mode after the epitaxial structure is horizontally grown, the point defect density and the linear defects extending upwards are reduced, the crystal quality of epitaxial wafer growth is improved, the radiation recombination of an LD active region is further improved, the LD is increased along with time, and the performances of the LD such as output light power, photoelectric conversion efficiency, threshold current and oblique efficiency are improved.
The present invention will be described in further detail with reference to the accompanying drawings.
Drawings
Fig. 1 is a schematic view of a GaN-based LD epitaxial structure of the present invention;
FIG. 2 is a schematic diagram of the composite buffer layer of FIG. 1;
FIG. 3 is a schematic structural view of the composite transition layer of FIG. 1;
Reference numerals illustrate: 1. a substrate; 2. a composite buffer layer; 3. a composite transition layer; 4. an N-type GaN layer; 5. an n-type AlGaN cladding layer; 6. an N-type lower waveguide layer; 7. a multiple quantum well layer; 8. an upper waveguide layer; 9. a p-type electron blocking layer; 10. a p-type AlGaN cladding layer; 11. a p-type contact layer; 201. a first buffer sub-layer; 202. a second buffer sub-layer; 203. a third buffer sub-layer; 301. a first transition sublayer; 302. a second transition sub-layer; 303. a third transition sub-layer; 304. and a fourth transition sublayer.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be understood that the terms "center," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate orientations or positional relationships based on the orientation or positional relationships shown in the drawings, merely to facilitate describing the present invention and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or by an abutting connection or integrally connected; the specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
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", "a second" may include one or more such features, either explicitly or implicitly; in the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
As shown in fig. 1,2 and 3, the present embodiment provides a GaN-based LD epitaxial structure, which includes a composite buffer layer 2 and a composite transition layer 3 sequentially grown on a substrate 1, where the composite buffer layer 2 includes a first buffer sub-layer 201, a second buffer sub-layer 202 and a third buffer sub-layer 203 sequentially grown in a stacked manner, the first buffer sub-layer 201 is made of AlN (i.e., aluminum nitride) and the second buffer sub-layer 202 is made of Al xGa1-x N (i.e., aluminum gallium nitride), and the third buffer sub-layer 203 is made of Al yGa1-y N (i.e., aluminum gallium nitride), where 0< x <0.2, 0< y <0.2, and x > y; the composite transition layer 3 comprises a first transition sub-layer 301, a second transition sub-layer 302, a third transition sub-layer 303 and a fourth transition sub-layer 304 which are sequentially stacked and grown, the first transition sub-layer 301 is grown on the third buffer sub-layer 203, the first transition sub-layer 301 is a small island forming layer, the second transition sub-layer 302 is a big island forming layer, the third transition sub-layer 303 is a big island merging filling layer, and the fourth transition sub-layer 304 is a superlattice layer.
The specific manufacturing process of the GaN-based LD epitaxial structure of this embodiment is as follows:
First, a first buffer sub-layer 201, a second buffer sub-layer 202, and a third buffer sub-layer 203 are sequentially grown on a substrate 1 to form a composite buffer layer 2. In the growth process, the growth temperature of the first buffer sub-layer 201 and the second buffer sub-layer 202 is smaller than that of the third buffer sub-layer 203, and the growth temperatures of the first buffer sub-layer 201 and the second buffer sub-layer 202 can be the same or different; the growth pressure of the first buffer sub-layer 201 and the second buffer sub-layer 202 is smaller than that of the third buffer sub-layer 203, and the growth pressures of the first buffer sub-layer 201 and the second buffer sub-layer 202 may be the same or different.
Then, the first transition sublayer 301, the second transition sublayer 302, the third transition sublayer 303 and the fourth transition sublayer 304 are sequentially grown on the composite buffer layer 2 to form a composite transition layer 3. In the growth process of the composite transition layer 3, the growth temperatures of the first transition sublayer 301, the second transition sublayer 302, the third transition sublayer 303 and the fourth transition sublayer 304 are respectively T21, T22, T23 and T24, and T21 is less than T22 and less than or equal to T23 and less than or equal to T24; the growth pressures of the first transition sublayer 301, the second transition sublayer 302, the third transition sublayer 303 and the fourth transition sublayer 304 are P21, P22, P23, P24, respectively, and p21> p22> p23=p24; the growth carrier amounts of the first transition sublayer 301, the second transition sublayer 302 and the third transition sublayer 303 are F21, F22 and F23 respectively, and F21> F22 and F21> F23.
In this embodiment, the buffer layer is designed into a composite buffer layer structure composed of a first buffer sub-layer 201 made of AlN material, a second buffer sub-layer 202 made of Al xGa1-x N material, and a third buffer sub-layer 203 made of Al yGa1-y N material, the Al content in each buffer sub-layer is gradually reduced, and by designing the buffer layer to be grown in a gradual transition manner, lattice mismatch between the substrate 1 and the buffer layer and thermal mismatch caused by thermal expansion coefficient difference are reduced, so that a large number of point defects generated by doping high Al component in the epitaxial growth process of AlGaN material are reduced, and the point defect density and dislocation caused by the epitaxial structure are reduced, thereby improving the crystal quality of epitaxial structure growth. After the composite buffer layer 2 is grown, a composite transition layer 3 consisting of a first transition sublayer 301, a second transition sublayer 302, a third transition sublayer 303 and a fourth transition sublayer 304 is grown on the composite buffer layer 2, wherein the first transition sublayer 301 converts a seed crystal of a low-temperature buffer layer from two-dimensional growth (2D) to three-dimensional growth (3D) to form a small island, the crystal quality of the seed crystal is improved by heating growth, the seed crystal is combined to form the small island, the point defect density is reduced by combining the seed crystal, the growth temperature of the second transition sublayer 302 is continuously increased, the combination of the small island and the small island is accelerated, the island is formed by growth, the process mainly grows in the 3D direction, the defect density is continuously reduced, the growth temperature of the third transition sublayer 303 is higher than the growth temperature of the first two transition sublayers 301 and the second transition sublayer 302, the growth rate is higher than that of the first transition sublayer 301 and the second transition sublayer 302, the islands are combined and the filling speed is increased, so that the 3D growth is accelerated to 2D, the decomposition of epitaxial layers by high temperature is reduced, the growth is promoted to be a GaN epitaxial structure with better crystal quality, then a fourth transition sub-layer 304 of a superlattice layer structure is grown on a GaN film layer which is already grown in 2D, the temperature of the superlattice layer is slightly higher than the temperature of the three previous transition sub-layers, the crystal quality of materials can be further improved, and linear defects extending upwards are turned at the interface of the superlattice layer or annihilated inside the superlattice structure due to the superlattice layer, so that the design of the fourth transition sub-layer 304 of the superlattice layer structure further reduces the defect density of materials, thereby improving the crystal quality of materials, improving the radiation recombination of an LD active area, further leading to the increase of LD with time, the output light power, the photoelectric conversion efficiency, the output light power of the LD and the photoelectric conversion efficiency of the LD, and the threshold current, the slope efficiency and other performances are improved.
Because the parasitic reaction of the Al atoms not only forms a coating on the surface of the cavity in the reaction chamber, but also may drop off to the wafer to form large particle defects, and may also form lattice point introduction point defects on the surface of the wafer, the gap position (i.e., the distance between the graphite disc base and the cavity cover of the reaction chamber) when the composite buffer layer 2 is grown is preferably designed to be smaller than the gap position when the composite transition layer 3 is grown, so that the distance between the graphite disc base and the cavity cover is shortened when the composite buffer layer 2 is grown, the pre-reaction with NH 3 is reduced when the Al atoms grow, the density of the point defects is reduced, and the crystal quality is improved.
Further, after the composite buffer layer 2 is grown, the carrier gas amount is increased, and the NH 3 in the reaction chamber is increased to 5-10 times of that when the composite buffer layer is grown, so that the carrier gas is further reacted with the Al source remained in the reaction chamber and the parasitic reaction Al, the residual Al in the reaction chamber is reduced, the possibility of introducing Al point defects is reduced, the crystal quality is further improved, and after the reaction process, the composite transition layer 3 is grown on the composite buffer layer 2.
As a specific embodiment, the thickness d2 of the second buffer sub-layer 202 is greater than the thickness d1 of the first buffer sub-layer 201, that is, d1< d2, the thickness d3 of the third buffer sub-layer 203 is greater than the thickness d1 of the first buffer sub-layer 201, that is, d1< d3, and the thickness d2 of the second buffer sub-layer may be the same as or different from the thickness d3 of the third buffer sub-layer, and the thickness of each buffer sub-layer may be designed according to specific requirements in the actual growth process. Specifically, in the present embodiment, the thickness d1 of the first buffer sub-layer 201 is not greater than 20nm, the thickness d2 of the second buffer sub-layer 202 is 5-30 nm, and the thickness d3 of the third buffer sub-layer 203 is 5-30 nm.
In the growth process of the composite buffer layer 2, pure hydrogen is used as carrier gas for the growth of the first buffer sublayer 201 and the second buffer sublayer 202, and hydrogen can be used as carrier gas for the growth of the third buffer sublayer 203, or a mixed gas of H 2 and N 2 can be used as carrier gas.
As a specific embodiment, the thickness D1 of the first transition sub-layer 301 is designed to be smaller than the thickness D2 of the second transition sub-layer 302, the thickness D2 of the second transition sub-layer 302 is designed to be smaller than the thickness D3 of the third transition sub-layer 303, and the thicknesses of the third transition sub-layer 303 and the fourth transition sub-layer 304 may be the same or different, and the thicknesses of the transition sub-layers may be designed according to specific requirements in the actual growth process. Specifically, in the present embodiment, the thickness D1 of the first transition sub-layer 301 is not greater than 1um, the thickness D2 of the second transition sub-layer 302 is not greater than 1um, the thickness D3 of the third transition sub-layer 303 is not greater than 2um, and the thickness D4 of the fourth transition sub-layer 304 is not greater than 2um.
In an alternative embodiment, the first transition sub-layer 301, the second transition sub-layer 302 and the third transition sub-layer 303 are all GaN layers. For the growth of the composite transition layer 3, in some embodiments, the first transition sub-layer 301, the second transition sub-layer 302, and the third transition sub-layer 303 may be grown sequentially, i.e., the second transition sub-layer 302 is grown after the first transition sub-layer 301 is grown to the design thickness, and the third transition sub-layer 303 is grown after the second transition sub-layer 302 is grown to the design thickness. In other embodiments, the first transition sublayer 301, the second transition sublayer 302 and the third transition sublayer 303 may also be grown in the form of a superlattice, that is, a single layer of the first transition sublayer 301, the second transition sublayer 302 and the third transition sublayer 303 are used as one cycle period, and a plurality of cycle periods are sequentially and cyclically stacked to form a superlattice structure, and then a fourth transition sublayer 304 is grown on the superlattice structure.
In an alternative embodiment, the fourth transition sub-layer 304 may be a GaN superlattice layer, or may be an AlGaN (i.e. aluminum gallium nitride) superlattice layer, or may be an AlGaN/n-GaN superlattice layer formed by circularly stacking an AlGaN layer and an n-GaN (i.e. n-type gallium nitride) layer; wherein, for AlGaN superlattice layer or AlGaN/n-GaN superlattice layer, al composition of AlGaN layer can be constant or variable.
Specifically, when the fourth transition sub-layer 304 is a GaN superlattice layer, the GaN superlattice layer is formed by circularly stacking and growing a GaN layer and an n-GaN layer for 10-50 periods, wherein the n-GaN layer of the single layer is a Si doped GaN sub-layer, and the Si doping concentration isThe growth thickness of the single-layer GaN layer and the single-layer n-GaN layer is 10-500 nm, the growth temperature of the single-layer GaN layer and the single-layer n-GaN layer are different, and the specific growth period, the single-layer growth thickness and the growth temperature are optimal values according to the specific actual requirements and the collocation in the growth process.
In an alternative embodiment, an AlN (i.e., aluminum nitride) template is disposed between the substrate 1 and the composite buffer layer 2, where the AlN template is formed on the substrate 1 by PVD (i.e., physical vapor deposition) coating, and the thickness of the AlN template is 0-50 nm.
In an alternative embodiment, the N-type GaN layer 4, the N-type AlGaN cladding layer 5, the N-type lower waveguide layer 6, the multiple quantum well layer 7, the upper waveguide layer 8, the p-type electron blocking layer 9, the p-type AlGaN cladding layer 10 and the p-type contact layer 11 are sequentially stacked and grown on the composite transition layer 3.
The following describes the preparation process of the GaN-based LD epitaxial structure of the present invention by specific examples.
Example 1:
High-purity hydrogen (H 2) or nitrogen (N 2) is used as carrier gas, trimethylgallium (TMGa), trimethylaluminum (TMAL) and ammonia (NH 3) are respectively used as Ga source, al source and N source, silane (SiH 4) and magnesium dicyclopentadiene (Cp 2 Mg) are respectively used as N-type and p-type doping agents, and a metal organic chemical vapor deposition method is adopted to prepare an epitaxial structure; the method comprises the following specific steps:
S1, adopting a PVD (physical vapor deposition) film plating AlN template on a sapphire substrate 1, and heating to 1030 ℃ and stabilizing for 5min in a pure hydrogen atmosphere to clean the surface, wherein the heating and stabilizing time can be long or short so as to match the growth value of an epitaxial wafer to be an optimal value.
S2, firstly cooling to 870 ℃, setting the gap position of the reaction chamber to 9mm, introducing NH 3 and TMGa source under the condition of 100mbar pressure, and growing a first buffer sub-layer 201 with the thickness of 5nm under the condition that carrier gas is pure hydrogen; growing a second buffer sub-layer 202 with the thickness of 10nm under the condition of being heated to 890 ℃, wherein the pressure and atmosphere conditions are the same as those of the first buffer sub-layer 201; then, the temperature was raised to 910℃and the pressure was 150mbar to grow a third buffer sub-layer 203 in a mixed gas of nitrogen and hydrogen at a thickness of 20nm.
S3, after the low-temperature composite buffer layer 2 is deposited, the gap position of the reaction chamber is adjusted from 9mm to 11mm, the temperature is raised to 1160 ℃, 3-10 times of the quantity of the composite buffer layer 2NH 3 is introduced under the condition that the pressure is 200mbar, the carrier gas is mixed gas of H 2 and N 2, the gas quantity is the most suitable condition for matching the quantity of the growing composite transition layer 3, the pre-passage is carried out for 60 seconds, the parasitic reaction Al and the residual Al source in the reaction chamber are pre-treated, the migration rate of the parasitic reaction Al is improved, the parasitic reaction Al enters into crystal lattice points, and the formation of point defects is reduced; after pretreatment, introducing proper NH 3 and TMGa source to grow for 200-500 s, and growing a first transition sub-layer 301 with the thickness of 10-30 nm; after the first transition sub-layer 301 is grown, continuously heating to 1180 ℃, wherein the growth pressure is 300mbar, the NH 3 amount is reduced by 30-50%, the TMGa flow is increased by 10-30%, the second transition sub-layer 302 with the thickness of 50-100 nm is grown, continuously heating to 1210 ℃ after the second transition sub-layer 302 is grown, the NH 3 amount and the TMGa flow are the same as the second transition sub-layer 302 flow, the growth pressure is 300mbar, and the third transition sub-layer 303 with the thickness of about 600-1000 um is grown; the third transition sub-layer 303 is grown and the fourth transition sub-layer 304 is grown. The fourth transition sub-layer 304 is formed by GaN/n-GaN cyclic superposition growth for 20 periods, the growth temperature of the single-layer GaN layer is 1225 ℃, the thickness of the single-layer GaN layer is 15nm, the growth pressure is 240mbar, the growth temperature of the single-layer n-GaN layer is 1210 ℃, the thickness of the single-layer n-GaN layer is 10nm, the growth pressure is 240mbar, and the Si doping concentration is 5×10 18cm-3.
And S4, after the composite transition layer 3 is grown, the temperature is raised to 1240 ℃ to deposit an N-type GaN layer 4 doped with Si with the thickness of 1.0 mu m, wherein the doping concentration of Si is 3.0X10 18cm-3, and the N-type GaN layer is used as an N-type contact layer.
S5, growing an N-type AlGaN covering layer 5 with the thickness of 1.5um at the temperature of 1200 ℃, wherein the Si doping concentration is 1.5X10 18cm-3, the N-type AlGaN covering layer 5 is an Al 0.08Ga0.92N/Al0.12Ga0.88 N superlattice layer, the thickness of a single Al 0.08Ga0.92 N layer is 12nm, the thickness of an Al 0.12Ga0.88 N layer is 8nm, the growth is carried out for 60 cycles, the temperature is reduced to 1100 ℃ after the growth of the superlattice layer, and a transition layer AlGaN layer with the Al component gradually changing from 0.12 to 0.005 is grown, and the thickness is 300nm.
S6, cooling to 960 ℃ to grow a 150 nm-thick Si-doped N-type lower waveguide layer 6, wherein the doping concentration of Si is 5.0X10 17cm-3, the N-type lower waveguide layer 6 is In 0.05Ga0.95 N/GaN and is In a superlattice structure, the thickness of a single-layer In 0.05Ga0.95 N layer is 1.2nm, the thickness of a single-layer GaN layer is 3.0nm, and the cyclic growth is carried out for 32 cycles.
S7, next cooling to grow the Si doped multiple quantum well layer 7, wherein the Si doping concentration is 1.0X10 18cm-3; the multi-quantum well layer 7 comprises a first quantum barrier layer and a second quantum barrier layer, wherein the first quantum barrier layer and the second quantum barrier layer both comprise In xGa1-x N/GaN superlattice layers of indium gallium nitride and gallium nitride, and the indium element proportion In the first quantum barrier layer is larger than the indium element proportion In the second quantum barrier layer; the thickness of the single-layer In xGa1-x N is 5.0nm, the growth temperature is 900 ℃, the thickness of the single-layer GaN layer is 12nm, and the growth temperature is 960 ℃.
S8, growing an upper waveguide layer 8 with the thickness of 150nm at 960 ℃, wherein the upper waveguide layer 8 is of an In 0.05Ga0.95 N/GaN superlattice structure, the thickness of a single-layer In 0.05Ga0.95 N/GaN is 1.2nm, the thickness of a single-layer GaN layer is 3.0nm, and the cyclic growth is carried out for 32 cycles, wherein the components and the thickness of the upper waveguide layer are the same as those of the N-type lower waveguide layer 6.
And S9, growing a p-type electron blocking layer 9 with the thickness of 15nm on the upper waveguide layer 8, wherein the growth temperature is 1115 ℃, and the p-type electron blocking layer 9 is a p-type AlGaN electron blocking layer.
S10, growing a p-type AlGaN covering layer 10 on the p-type electron blocking layer 9, wherein the thickness of the p-type AlGaN covering layer 10 is 430nm.
S11, growing a p-type contact layer 11 at 1100 ℃, wherein the growth thickness is 30nm, and the p-type contact layer 11 is a p-type GaN contact layer.
After the epitaxial structure is finished, the grown epitaxial structure is subjected to semiconductor processing technologies such as cleaning, deposition, photoetching and etching to manufacture a single chip.
Example 2:
The preparation process of the epitaxial structure in this embodiment is substantially the same as that of embodiment 1, except that when the fourth transition sub-layer 304 of the composite transition layer 3 is grown in this embodiment, the fourth transition sub-layer 304 is grown for 20 cycles of AlGaN/n-GaN cycle stack, the growth temperature of the single-layer AlGaN layer is 1200 ℃, the thickness is 5nm, the growth pressure is 200mbar, the growth temperature of the single-layer n-GaN layer is 1215 ℃, the thickness is 20nm, the growth pressure is 240mbar, and the si doping concentration is 5×10 18cm-3.
Example 3:
The preparation process of the epitaxial structure in this embodiment is approximately the same as that of the above embodiment 1, and is different in that the first transition sublayer 301, the second transition sublayer 302 and the third transition sublayer 303 of the composite transition layer 3 are grown in this embodiment in a superlattice mode, after the composite buffer layer 2 at low temperature is deposited, the gap position of the reaction chamber is adjusted from 9mm to 11mm, the temperature is raised to 1160 ℃, 3-10 times of the NH 3 of the composite buffer layer 2 is introduced under the condition of 200mbar pressure, the carrier gas is the mixed gas of H 2 and N 2, the gas amount is the most suitable condition for matching the amount of the composite transition layer to be grown, the Al and the residual Al source of parasitic reaction in the reaction cavity are pre-passed for 60s, the mobility of the parasitic reaction Al is improved, and the formation of point defects is reduced; after pretreatment, introducing proper NH 3 and TMGa source to grow for 200-500 s, and growing a first transition sub-layer 301 with the thickness of 2-5 nm; after the first transition sub-layer 301 is grown, continuously heating to 1180 ℃, wherein the growth pressure is 300mbar, the NH 3 amount is reduced by 30-50%, the TMGa flow is increased by 10-30%, the second transition sub-layer 302 with the thickness of 10-20 nm is grown, after the second transition sub-layer 302 is grown, continuously heating to 1210 ℃, the NH 3 amount and the TMGa flow are the same as the second transition sub-layer 302 flow, the growth pressure is 300mbar, and the third transition sub-layer 303 with the thickness of about 50-100 nm is grown; and then the first transition sub-layer 301, the second transition sub-layer 302 and the third transition sub-layer 303 are repeatedly overlapped and circularly grown for 10-50 periods in sequence to form a superlattice structure, and then a fourth transition sub-layer 304 is grown on the superlattice structure. The fourth transition sub-layer 304 is formed by GaN/n-GaN cyclic superposition growth for 20 periods, the growth temperature of the single-layer GaN layer is 1225 ℃, the thickness of the single-layer GaN layer is 15nm, the growth pressure is 240mbar, the growth temperature of the single-layer n-GaN layer is 1210 ℃, the thickness of the single-layer n-GaN layer is 10nm, the growth pressure is 240mbar, and the Si doping concentration is 5×10 18cm-3.
The foregoing examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention, and all designs that are the same or similar to the present invention are within the scope of the present invention.
Claims (10)
1. A GaN-based LD epitaxial structure is characterized in that: the composite buffer layer comprises a first buffer sub-layer, a second buffer sub-layer and a third buffer sub-layer which are sequentially stacked and grown on a substrate, wherein the first buffer sub-layer is made of AlN, the second buffer sub-layer is made of Al xGa1-x N, and the third buffer sub-layer is made of Al yGa1-y N, wherein x is 0< 0.2, y is 0< 0.2, and x > y; the composite transition layer comprises a first transition sub-layer, a second transition sub-layer, a third transition sub-layer and a fourth transition sub-layer which are sequentially stacked and grown, wherein the first transition sub-layer is grown on the third buffer sub-layer, the first transition sub-layer is a small island forming layer, the second transition sub-layer is a big island forming layer, the third transition sub-layer is a big island merging filling layer, and the fourth transition sub-layer is a superlattice layer.
2. The GaN-based LD epitaxial structure of claim 1, wherein: the thicknesses of the second buffer sub-layer and the third buffer sub-layer are both larger than that of the first buffer sub-layer.
3. The GaN-based LD epitaxial structure of claim 1, wherein: the thickness of the first transition sub-layer is smaller than that of the second transition sub-layer, and the thickness of the second transition sub-layer is smaller than that of the third transition sub-layer.
4. The GaN-based LD epitaxial structure of claim 1, wherein: the fourth transition sub-layer is a GaN superlattice layer or an AlGaN/n-GaN superlattice layer.
5. The GaN-based LD epitaxial structure of claim 4, wherein: the fourth transition sublayer is a GaN superlattice layer, the single layer is a Si doped GaN sublayer, and the Si doping concentration is。
6. The GaN-based LD epitaxial structure of claim 1, wherein: and the first transition sub-layer, the second transition sub-layer and the third transition sub-layer are sequentially and circularly overlapped and grown to form the superlattice structure.
7. The GaN-based LD epitaxial structure of claim 1, wherein: an AlN template is arranged between the substrate and the composite buffer layer.
8. The GaN-based LD epitaxial structure of claim 1, wherein: and the composite transition layer is sequentially laminated and grown with an N-type GaN layer, an N-type AlGaN covering layer, an N-type lower waveguide layer, a multiple quantum well layer, an upper waveguide layer, a p-type electron blocking layer, a p-type AlGaN covering layer and a p-type contact layer.
9. The method for manufacturing a GaN-based LD epitaxial structure of any one of claims 1 to 8, characterized by: the method comprises the following steps:
s1, sequentially growing a first buffer sub-layer, a second buffer sub-layer and a third buffer sub-layer on a substrate to form a composite buffer layer;
the growth temperature of the first buffer sub-layer and the second buffer sub-layer is smaller than that of the third buffer sub-layer, and the growth pressure of the first buffer sub-layer and the second buffer sub-layer is smaller than that of the third buffer sub-layer;
s2, sequentially growing a first transition sub-layer, a second transition sub-layer, a third transition sub-layer and a fourth transition sub-layer on the composite buffer layer to form a composite transition layer;
The growth temperatures of the first transition sub-layer, the second transition sub-layer, the third transition sub-layer and the fourth transition sub-layer are respectively T21, T22, T23 and T24, and T21 is less than T22 and less than or equal to T23 and less than or equal to T24; the growth pressures of the first transition sub-layer, the second transition sub-layer, the third transition sub-layer and the fourth transition sub-layer are respectively P21, P22, P23 and P24, and P21> P22> P23 = P24; the growth carrier gas amounts of the first transition sub-layer, the second transition sub-layer and the third transition sub-layer are F21, F22 and F23 respectively, and F21> F22 and F21> F23.
10. The method for manufacturing a GaN-based LD epitaxial structure of claim 9, wherein: the gap position when the composite buffer layer is grown is smaller than the gap position when the composite transition layer is grown, and the growth temperature of the composite buffer layer is lower than that of the composite transition layer.
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