CN109346574A - A kind of epitaxial wafer and growing method improving gallium nitride based LED light-emitting diode luminance - Google Patents

A kind of epitaxial wafer and growing method improving gallium nitride based LED light-emitting diode luminance Download PDF

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CN109346574A
CN109346574A CN201811022401.1A CN201811022401A CN109346574A CN 109346574 A CN109346574 A CN 109346574A CN 201811022401 A CN201811022401 A CN 201811022401A CN 109346574 A CN109346574 A CN 109346574A
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gallium nitride
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CN109346574B (en
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王淑姣
芦玲
祝光辉
陈明
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Huaian Aucksun Optoelectronics Technology Co Ltd
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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
    • 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
    • H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
    • H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
    • 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
    • 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
    • H01L33/14—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 carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
    • H01L33/145—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 carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure with a current-blocking structure

Abstract

The present invention provides a kind of epitaxial wafers and growing method for improving gallium nitride based LED light-emitting diode luminance, using graphic sapphire as substrate, in its surface successively growing AIN buffer layer, intrinsic GaN layer, n-type GaN layer, luminescent layer, low-temperature p-type AlGaN electronic barrier layer, new type high temperature p-type gallium nitride superlattice layer and P type contact layer.New type high temperature P gallium nitride layer of the present invention improves the doping efficiency of magnesium atom by using the superlattice growth method of long fast gradual change, so that hole concentration increases in p-type layer；Using the regular way of gallium source interruption switch, the external quantum efficiency of epitaxial wafer is added somewhat to；The p layer for originating one layer thin of the growth under lower long speed can largely alleviate the stress between p-type AlGaN electronic barrier layer and high temperature p-type gallium nitride layer, promote GaN luminous efficiency；It is passed through the source Al in last 1 section of high temperature superlattice layer, further increases the barrier effect to electronics.

Description

A kind of epitaxial wafer and growing method improving gallium nitride based LED light-emitting diode luminance
Technical field
The invention belongs to technical field of semiconductor device preparation, and it is bright to be related to a kind of raising gallium nitride based LED light emitting diode The epitaxial wafer and growing method of degree.
Background technique
Currently, with the raising of LED (light emitting diode) light efficiency, brightness, colour rendering index and reliability, LED is extensive Applied to indoor and outdoor lighting, traffic lights, full-color display and electronic product backlight, automobile lamp and plant illumination etc. Field.Compared with conventional illumination sources, gallium nitride (GaN) base LED have size is small, the service life is long, fast response time, it is low in energy consumption, The advantages that pollution-free, spectral region is wide and adjustable color, is thus contemplated that LED certainly will replace conventional light source in 21 century.
LED operation principle be by electrons and holes in Quantum Well recombination luminescence, wherein electronics is by mixing the n-layer nitrogen of Si Change gallium to provide, hole is provided by the p layer gallium nitride for mixing Mg.Traditional p layers of structure is by low-temperature p-type electronic barrier layer, high temperature p-type nitrogen Change gallium layer and low-temperature p-type contact layer is constituted, it is raw that the growth of high temperature p-type gallium nitride layer generallys use the constant body structure of long speed It is long.Constant speed regular way grows epitaxial structure layer successively in a layered fashion, and epi-layer surface is relatively flat, is emitted from luminous zone Light is easy to be totally reflected at the bed boundary p, reduces light extraction efficiency；Meanwhile in p-type layer p-type dopant magnesium activation energy It is higher, it is not easy to disconnect using Mg-H key in the high temperature p-type gallium nitride of body structure growth, hole concentration is lower.
Summary of the invention
It is an object of the present invention to for above-mentioned conventional high-temperature p-type gallium nitride regular way cause epitaxial wafer light extraction efficiency it is low, The technical problems such as hole concentration is low propose a kind of P type GaN layer growing method for improving GaN base LED luminous efficiency, comprising: blue It is jewel patterned substrate, AlN buffer layer, intrinsic GaN layer, n-type GaN layer, luminescent layer, low-temperature p-type AlGaN electronic barrier layer, new Type high temperature p-type gallium nitride superlattice layer, P type contact layer.
Technical solution of the present invention:
A kind of epitaxial wafer improving gallium nitride based LED light-emitting diode luminance, using graphic sapphire as substrate, at it Surface successively growing AIN buffer layer, intrinsic GaN layer, n-type GaN layer, wherein AlN buffer layer is deposited using magnetically controlled sputter method, n Type GaN layer is with silane (SiH4) it is dopant；The regrowth luminescent layer in n-type GaN layer, luminescent layer by several periods quantum Well layer and quantum barrier layer are constituted；Growing low temperature p-type AlGaN electronic barrier layer, new type high temperature p-type gallium nitride after luminescent layer has been grown Superlattice layer and P type contact layer, wherein p-type dopant is two luxuriant magnesium, and new type high temperature p-type gallium nitride superlattice layer is divided into length again Express delivery increases, tri- sections of superlattice layers of HTP1, HTP2, HTP3 in several periods, in each period using Ga open Mg open/Ga closes Mg and opens Structure growth, HTP3 superlattice layer are passed through a certain proportion of aluminium, and P type contact layer uses body structure growth.
The AlN buffer layer thickness is 10nm~80nm；
The intrinsic GaN layer is with a thickness of 2.0 μm~6.0 μm；
The n-type GaN layer is with a thickness of 2.0 μm~10.0 μm；
The periodicity of the luminescent layer is 5~15, and single quantum well layer thickness is 3nm~6nm, and single quantum is built Layer is with a thickness of 5nm~15nm；
The low-temperature p-type AlGaN electronic barrier layer is with a thickness of 10nm~100nm；
The new type high temperature p-type gallium nitride superlattice layer, MgGaN/MgN:HTP1 periodicity is 3~10, long speed is 0.1nm/s~0.5nm/s, with a thickness of 5nm~25nm, MgGaN/MgN:HTP2 periodicity is 5~15, long speed is 0.15nm/ S~0.8nm/s, with a thickness of 7.5nm~40nm, AlMgGaN/MgN:HTP3 periodicity is 6~18, long speed be 0.2nm/s~ 1.0nm/s, with a thickness of 20nm~100nm；
The P type contact layer is with a thickness of 5nm~50nm；
Improve the optimum condition of the p-type GaN layer growing method of GaN base LED luminous efficiency:
The AlN buffer layer thickness is 20nm~40nm；
The intrinsic GaN layer is with a thickness of 2.5 μm~4.0 μm；
The n-type GaN layer is with a thickness of 3.0 μm~6.0 μm；
The periodicity of the luminescent layer is 7~11, and single quantum well layer thickness is 3nm~6nm, and single quantum is built Layer is with a thickness of 5nm~15nm；
The low-temperature p-type AlGaN electronic barrier layer is with a thickness of 20nm~60nm；
The new type high temperature p-type gallium nitride superlattice layer, MgGaN/MgN:HTP1 periodicity is 4~8, long speed is 0.2nm/s~0.4nm/s, with a thickness of 3nm~15nm, MgGaN/MgN:HTP2 periodicity is 6~12, long speed is 0.3nm/s ~0.6nm/s, with a thickness of 10nm~20nm, AlMgGaN/MgN:HTP3 periodicity is 8~15, long speed be 0.5nm/s~ 0.8nm/s, with a thickness of 30nm~80nm；
The P type contact layer is with a thickness of 10nm~30nm.
A kind of epitaxial wafer growth method improving gallium nitride based LED light-emitting diode luminance, steps are as follows:
Step 1: one layer of AlN buffer layer being deposited on graphical sapphire substrate using magnetically controlled sputter method；
Step 2: the intrinsic gallium nitride layer of unintentional doping is directly grown on AlN buffer layer, growth temperature is 1050 DEG C ~1150 DEG C, growth pressure is 700mbar~900mbar；
Step 3: the n-type GaN layer of Si is mixed in growth on the intrinsic gallium nitride layer that step 2 obtains, and growth temperature is 1020 DEG C ~1100 DEG C, growth pressure is 300mbar~500mbar, and Si concentration is 1*1018/cm3~1*1020/cm3；
Step 4: temperature grows luminescent layer after dropping to 750 DEG C~850 DEG C, and growth pressure is 200mbar~500mbar, hair Quantum well layer and the quantum barrier layer temperature difference in photosphere is at 60 DEG C~90 DEG C；
Step 5: the low-temperature p-type AlGaN electronic barrier layer of Mg, growth temperature are mixed in growth on the luminescent layer that step 4 obtains It is 850 DEG C~900 DEG C, growth pressure is 200mbar~400mbar, and it is 1*10 that Mg, which mixes concentration,18/cm3~1*1021/cm3；
Step 6: being warming up to 1000 DEG C~1020 DEG C growth new type high temperature p-type gallium nitride superlattice layers, growth pressure is Tri- sections of superlattice layer sequences of 200mbar~400mbar, HTP1, HTP2, HTP3 are grown, and long speed is incremented by successively, and Mg mixes concentration and is 1*1017/cm3~1*1020/cm3；
Step 7: temperature grows on the p-type gallium nitride superlattice layer that step 6 obtains after dropping to 750 DEG C~800 DEG C and mixes Mg P type contact layer, growth pressure be 150mbar~300mbar, Mg mix concentration be 1*1018/cm3~1*1021/cm3；
Step 8: finally annealing 15~25 minutes under nitrogen atmosphere, annealing temperature is 700 DEG C~800 DEG C.
The growing technology is metallo-organic compound chemical gaseous phase deposition (MOCVD) growth technology, and metal has Machine source trimethyl gallium (TMGa) or triethyl-gallium (TEGa) are used as gallium source, and trimethyl indium (TMIn) is used as indium source, trimethyl aluminium (TMAl) it is used as silicon source, n-type dopant is silane (SiH4), and p-type dopant is two luxuriant magnesium (CP2Mg)；Carrier gas is high-purity H2、N2 Or the gaseous mixture of the two.
Difference of the invention: new type high temperature P gallium nitride layer of the present invention is by using the superlattice growth for growing fast gradual change Method improves the doping efficiency of magnesium atom, so that hole concentration increases in p-type layer；Simultaneously using the length of gallium source interruption switch Method adds somewhat to the external quantum efficiency of epitaxial wafer；Meanwhile the p layer energy of starting one layer thin of growth under lower long speed The enough stress largely alleviated between p-type AlGaN electronic barrier layer and high temperature p-type gallium nitride layer, promotes GaN and shines Efficiency；It is passed through the source Al in last 1 section of high temperature superlattice layer, further increases the barrier effect to electronics.
Specific embodiment
Below in conjunction with technical solution, a specific embodiment of the invention is further illustrated, the present embodiment is organic using metal Compound chemical vapor deposition device (MOCVD)
Step 1: the AlN buffer layer of one layer of about 25nm is deposited on graphical sapphire substrate using magnetically controlled sputter method, It is placed in MOCVD cavity and carries out epitaxial growth；
Step 2: temperature is risen to about 1050 DEG C~1080 DEG C, under the pressure of 800mbar~900mbar, growth about 20 Minute with a thickness of 2.0 μm~4.0 μm of intrinsic gallium nitride layer；
Step 3: being 1070 DEG C~1090 DEG C in temperature, under the pressure of 300mbar~400mbar, grow a layer thickness The n-type GaN layer of Si is mixed for 3.0 μm~6.0 μm；
Step 4: when temperature is 810 DEG C~840 DEG C, under the pressure of 300mbar~400mbar, growing one layer of 5nm The GaN of~10nm, then one layer of 3nm~5nm of regrowth mixes the InGaN of In on a small quantity, with both this for a superlattices unit knot Structure alternately continuously grows 8~15 periods, this continuous superlattice structure is luminous layer structure；
Step 5: when temperature is 870 DEG C~890 DEG C, under the pressure of 300mbar~400mbar, growing a layer thickness The p-type aluminium gallium nitride alloy electronic barrier layer of Mg is mixed for the low temperature of 20nm~30nm；
Step 6: being warming up to 1000 DEG C~1020 DEG C growth new type high temperature p-type gallium nitride superlattice layers, growth pressure is Tri- sections of superlattice layer sequences of 200mbar~400mbar, HTP1, HTP2, HTP3 are grown, and long speed is incremented by successively, and Mg mixes concentration and is 1*1017/cm3~1*1020/cm3, wherein HTP1/HTP2 super lattice structure layers are MgGaN/MgN, and HTP3 super lattice structure layers are MgAlGaN/MgN；HTP1 periodicity is 4~8, with a thickness of 3nm~15nm, HTP2 periodicity is 6~12, with a thickness of 10nm~20nm, HTP3 periodicity are 8~15, with a thickness of 30nm~80nm；
Step 7: when temperature is 750 DEG C~800 DEG C, under the pressure of 150mbar~300mbar, growing a layer thickness For the p-type contact layer for mixing Mg of 10nm~15nm；
Step 8: finally annealing 15~25 minutes under nitrogen atmosphere.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations； Although present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its It is still possible to modify the technical solutions described in the foregoing embodiments, or special to some or all of technologies Sign is equivalently replaced；And these are modified or replaceed, various embodiments of the present invention that it does not separate the essence of the corresponding technical solution The range of technical solution.

Claims (3)

1. it is a kind of improve gallium nitride based LED light-emitting diode luminance epitaxial wafer, which is characterized in that with graphic sapphire be lining Bottom, in its surface successively growing AIN buffer layer, intrinsic GaN layer, n-type GaN layer, wherein AlN buffer layer uses magnetically controlled sputter method Deposition, n-type GaN layer is with silane (SiH4) it is dopant；The regrowth luminescent layer in n-type GaN layer, luminescent layer is by several periods Quantum well layer and quantum barrier layer are constituted；Growing low temperature p-type AlGaN electronic barrier layer, the nitridation of new type high temperature p-type after luminescent layer has been grown Gallium superlattice layer and P type contact layer, wherein p-type dopant is two luxuriant magnesium, and new type high temperature p-type gallium nitride superlattice layer is divided into length again Express delivery increases, tri- sections of superlattice layers of HTP1, HTP2, HTP3 in several periods, in each period using Ga open Mg open/Ga closes Mg and opens knot Structure growth, HTP3 superlattice layer are passed through a certain proportion of aluminium, and P type contact layer uses body structure growth；
The AlN buffer layer thickness is 10nm~80nm；
The intrinsic GaN layer is with a thickness of 2.0 μm~6.0 μm；
The n-type GaN layer is with a thickness of 2.0 μm~10.0 μm；
The periodicity of the luminescent layer is 5~15, and single quantum well layer thickness is 3nm~6nm, single quantum barrier layer thickness For 5nm~15nm；
The low-temperature p-type AlGaN electronic barrier layer is with a thickness of 10nm~100nm；
The new type high temperature p-type gallium nitride superlattice layer, MgGaN/MgN:HTP1 periodicity is 3~10, long speed is 0.1nm/s~0.5nm/s, with a thickness of 5nm~25nm, MgGaN/MgN:HTP2 periodicity is 5~15, long speed is 0.15nm/s ~0.8nm/s, with a thickness of 7.5nm~40nm, AlMgGaN/MgN:HTP3 periodicity is 6~18, long speed be 0.2nm/s~ 1.0nm/s, with a thickness of 20nm~100nm；
The P type contact layer is with a thickness of 5nm~50nm.
2. the epitaxial wafer according to claim 1 for improving gallium nitride based LED light-emitting diode luminance, which is characterized in that
The AlN buffer layer thickness is 20nm~40nm；
The intrinsic GaN layer is with a thickness of 2.5 μm~4.0 μm；
The n-type GaN layer is with a thickness of 3.0 μm~6.0 μm；
The periodicity of the luminescent layer is 7~11, and single quantum well layer thickness is 3nm~6nm, single quantum barrier layer thickness For 5nm~15nm；
The low-temperature p-type AlGaN electronic barrier layer is with a thickness of 20nm~60nm；
The new type high temperature p-type gallium nitride superlattice layer, MgGaN/MgN:HTP1 periodicity is 4~8, long speed is 0.2nm/ S~0.4nm/s, with a thickness of 3nm~15nm, MgGaN/MgN:HTP2 periodicity is 6~12, long speed be 0.3nm/s~ 0.6nm/s, with a thickness of 10nm~20nm, AlMgGaN/MgN:HTP3 periodicity is 8~15, long speed be 0.5nm/s~ 0.8nm/s, with a thickness of 30nm~80nm；
The P type contact layer is with a thickness of 10nm~30nm.
3. a kind of epitaxial wafer growth method for improving gallium nitride based LED light-emitting diode luminance, which is characterized in that steps are as follows:
Step 1: one layer of AlN buffer layer being deposited on graphical sapphire substrate using magnetically controlled sputter method；
Step 2: directly grow the intrinsic gallium nitride layer of unintentional doping on AlN buffer layer, growth temperature is 1050 DEG C~ 1150 DEG C, growth pressure is 700mbar~900mbar；
Step 3: the n-type GaN layer of Si is mixed in growth on the intrinsic gallium nitride layer that step 2 obtains, and growth temperature is 1020 DEG C~ 1100 DEG C, growth pressure is 300mbar~500mbar, and Si concentration is 1*1018/cm3~1*1020/cm3；
Step 4: temperature grows luminescent layer after dropping to 750 DEG C~850 DEG C, and growth pressure is 200mbar~500mbar, luminescent layer In quantum well layer and the quantum barrier layer temperature difference at 60 DEG C~90 DEG C；
Step 5: the low-temperature p-type AlGaN electronic barrier layer of Mg, growth temperature 850 are mixed in growth on the luminescent layer that step 4 obtains DEG C~900 DEG C, growth pressure is 200mbar~400mbar, and it is 1*10 that Mg, which mixes concentration,18/cm3~1*1021/cm3；
Step 6: being warming up to 1000 DEG C~1020 DEG C growth new type high temperature p-type gallium nitride superlattice layers, growth pressure 200mbar Tri- sections of superlattice layer sequences of~400mbar, HTP1, HTP2, HTP3 are grown, and long speed is incremented by successively, and it is 1*10 that Mg, which mixes concentration,17/cm3 ~1*1020/cm3；
Step 7: temperature grows the p-type for mixing Mg after dropping to 750 DEG C~800 DEG C on the p-type gallium nitride superlattice layer that step 6 obtains Contact layer, growth pressure are 150mbar~300mbar, and it is 1*10 that Mg, which mixes concentration,18/cm3~1*1021/cm3；
Step 8: finally annealing 15~25 minutes under nitrogen atmosphere, annealing temperature is 700 DEG C~800 DEG C.
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