CN103794687A - Gallium nitride LED manufacturing method, gallium nitride LED and chip - Google Patents
Gallium nitride LED manufacturing method, gallium nitride LED and chip Download PDFInfo
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- CN103794687A CN103794687A CN201410042037.0A CN201410042037A CN103794687A CN 103794687 A CN103794687 A CN 103794687A CN 201410042037 A CN201410042037 A CN 201410042037A CN 103794687 A CN103794687 A CN 103794687A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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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- 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
- H01L33/0095—Post-treatment of devices, e.g. annealing, recrystallisation or short-circuit elimination
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- H—ELECTRICITY
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- 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
- H01L33/06—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 within the light emitting region, e.g. quantum confinement structure or tunnel barrier
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- H—ELECTRICITY
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- 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
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
- H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
Abstract
The embodiment of the invention provides a gallium nitride LED manufacturing method, a gallium nitride LED and a chip. The gallium nitride LED manufacturing method comprises the step that a gallium nitride nucleate layer, an undoped gallium nitride layer, an N-doped gallium nitride layer, a quantum well transition layer, a multi-quantum-well layer, a P-doped gallium nitride layer and a contact layer are sequentially grown on a substrate on which the thermal treatment is carried out through a reaction chamber, wherein within the time period from beginning of growing of the N-doped gallium nitride layer to the ending of growing of the multi-quantum-well layer, at least one thermal annealing is carried out. The extensional internal stress can be reduced to the greater extent, the blue shift of the LED is reduced, the anti-static electricity performance of materials is improved, and the lighting efficiency of quantum wells is improved.
Description
Technical field
The embodiment of the present invention relates to semiconductor light-emitting-diode (Light-Emitting Diode, LED) field, relates in particular to a kind of gallium nitride based LED preparation method, gallium nitride based LED and chip.
Background technology
Wide-band gap material take gallium nitride as representative, is the third generation semi-conducting material after silicon Si and GaAs GaAs, can extensive use with the chip of making LED and comprise this LED etc.Owing to obtaining at present, high-quality commercial bulk gallium nitride is more difficult, and general gallium nitride based LED can adopt foreign substrate extension to obtain gallium nitride film.
But gallium nitride and substrate are as having larger lattice mismatch between Sapphire Substrate or Si substrate, can cause epitaxial loayer to produce dislocation, whole epitaxial loayer can be expanded and pass to the dislocation of this epitaxial loayer, and cause the internal stress of the semiconductor device such as gallium nitride based LED excessive, cause band curvature, electron hole greatly reduces at the combined efficiency in the district of having chance with, and then causes material antistatic property low, the low inferior problem of luminous efficiency of quantum well.
Summary of the invention
The embodiment of the present invention provides a kind of gallium nitride based LED preparation method, gallium nitride based LED and chip, can reduce largely extension internal stress, reduces the blue shift of LED, promotes material antistatic property, and can promote the luminous efficiency of quantum well.
First aspect, the embodiment of the present invention provides a kind of gallium nitride based LED preparation method, comprising:
Through growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layer, quantum well transition zone, multiple quantum well layer, P doped gallium nitride layer and contact layer successively on heat treated substrate;
Wherein, starting to grow described N doped gallium nitride layer to the time period of the described multiple quantum well layer that finishes to grow, carry out thermal anneal process at least one times.
Second, the embodiment of the present invention provides a kind of gallium nitride based LED, comprising: gallium nitride based LED prepared by gallium nitride based LED preparation method.
The 3rd, the embodiment of the present invention provides a kind of chip, comprising: the gallium nitride based LED that at least one is above-mentioned.
Gallium nitride based LED preparation method, gallium nitride based LED and chip that the embodiment of the present invention provides, through growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layer, quantum well transition zone, multiple quantum well layer, P doped gallium nitride layer and contact layer successively on heat treated substrate; Wherein, starting to grow N doped gallium nitride layer to the time period of the multiple quantum well layer that finishes to grow, carry out thermal anneal process at least one times.So, by starting to grow, N doped gallium nitride layer can be released in to carrying out thermal anneal process at least one times in the time period of the multiple quantum well layer that finishes to grow the internal stress that the epitaxial growth of multiple quantum well layer growth before finishing accumulates, reduce largely extension internal stress, the integrated stress of gallium nitride based LED is reduced, and then alleviate the problem of the quantum well band curvature causing because of this stress, reduce the blue shift of gallium nitride based LED, promote material antistatic property, and can promote the luminous efficiency of quantum well.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is gallium nitride based LED preparation method's provided by the invention flow chart;
Fig. 2 is another gallium nitride based LED preparation method's provided by the invention flow chart;
Fig. 3 is a gallium nitride based LED preparation method flow chart more provided by the invention;
Fig. 4 is another gallium nitride based LED preparation method's provided by the invention flow chart;
Fig. 5 is the structural representation of gallium nitride based LED provided by the invention;
Fig. 6 is the structural representation of chip provided by the invention;
Fig. 7 is the brightness contrast figure that gallium nitride based LED provided by the invention makes sample;
Fig. 8 is the blue shift comparison diagram that gallium nitride based LED provided by the invention makes sample.
Embodiment
For making object, technical scheme and the advantage of the embodiment of the present invention clearer, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
It should be noted that, the method can be implemented in as various reative cells at growth apparatus, reative cell can be metal organic chemical vapor deposition equipment (Metal-organic Chemical Vapor Deposition, MOCVD), molecular beam epitaxial device (Molecular Beam Epitaxy, or hydride gas-phase epitaxy equipment (Hydride Vapor Phase Epitaxy MBE), HVPE), preferred, can utilize MOCVD reative cell to prepare gallium nitride based LED.
Fig. 1 is gallium nitride based LED preparation method's provided by the invention flow chart, and as shown in Figure 1, the method comprises:
S101, reative cell are through growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layer, quantum well transition zone, multiple quantum well layer, P doped gallium nitride layer and contact layer successively on heat treated substrate; Wherein, starting to grow N doped gallium nitride layer to the time period of the multiple quantum well layer that finishes to grow, carry out thermal anneal process at least one times.
Further, multiple quantum well layer comprises at least one group of the base layer of growing successively, trap layer and trap coating layer.
Further, the annealing temperature of thermal anneal process can be to be 100 ℃～700 ℃, is preferably 500 ℃～600 ℃; Annealing temperature rate can be 50 ℃/min～100 ℃/min; The time that annealing stops can be 1min～10min, is preferably 3min～5min; The gas of annealing can be H
2, can be N
2, can be also H
2and N
2mist.
For instance, Fig. 2 is another gallium nitride based LED preparation method's provided by the invention flow chart, as shown in Figure 2, starting to grow N doped gallium nitride layer to the time period of the multiple quantum well layer that finishes to grow, carry out thermal anneal process at least one times and can be preferably in the time that growth N doped gallium nitride layer finishes, carry out thermal anneal process.
Preferably, the present embodiment can use the MOCVD reative cell brightness gallium nitride based LED epitaxial wafer that grows tall next life, as adopted high-purity H
2, high-purity N
2, or high-purity H
2with high-purity N
2mist do carrier gas, high-purity N H
3do N source, metallorganic trimethyl gallium TMGa or triethyl-gallium TEGa do gallium source, and trimethyl indium does indium source, and N-type dopant is 200ppm silane SiH
4, P type dopant is two luxuriant magnesium Cp
2mg, substrate is the sapphire PSS of 002, wherein, multiple quantum well layer is built layer, trap layer and trap coating layer for growing successively according to setting cycle.The value of setting cycle can be the arbitrary value in 2-20, and the present embodiment is 7～13 to describe as example take the value of setting cycle.
Temperature is risen to 1080 ℃ by S201, MOCVD reative cell, under 200Torr pressure, substrate carried out to the high-temperature process of 5min.
S202, MOCVD reative cell are by greenhouse cooling to 530 ℃, under 200Torr pressure, at the gallium nitride nucleating layer of Grown 35nm.
Temperature is warmed up to 1080 ℃ by S203, MOCVD reative cell, under 200Torr pressure, and the undoped gallium nitride layer of the 1.7 μ m that grow on gallium nitride nucleating layer.
S204, MOCVD reative cell decline temperature and remain on 1070 ℃, under 200Torr pressure, and the N doped gallium nitride layer of the 3.2 μ m that grow on undoped gallium nitride layer, wherein N doping content is 5E+18atom/cm
3.
S205, MOCVD reative cell reduce the temperature to 500 ℃ in 300s, stop 3min and carry out thermal anneal process.
S206, MOCVD reative cell are raised to temperature 850 ℃ in 250s, under 200Torr pressure, and the quantum well transition zone of the 300nm that grows in the N doped gallium nitride layer after thermal annealing, wherein N doping content is 8E+17atom/cm
3, In component is multiple quantum well layer 30%.
Temperature is raised to 870 ℃ by S207, MOCVD reative cell, under 200Torr pressure, and the base layer of growth 13.5nm.
S208, MOCVD reative cell reduce the temperature to 760 ℃, under 200Torr pressure, and the trap layer of the 2.5nm that grows on the layer of base.
S209, MOCVD reative cell holding temperature be at 760 ℃, under 200Torr pressure, and the trap coating layer of the 2nm that grows on trap layer.
Repeat successively S207, S208 and S209, number of repetition 7～13.
It should be noted that, the base layer of growth is in the growth of quantum well transition zone for the first time, and the base layer of growth is to grow on the trap coating layer of growth for the first time for the second time, and the base layer of growth by that analogy later.
Temperature is elevated to 870 ℃ by S210, MOCVD reative cell, under 200Torr pressure, and the last base layer of the 8nm that grows on trap coating layer.
It should be noted that, can be used as multiple quantum well layer by S207 to this part that completes that S210 forms.
Temperature is elevated to 980 ℃ by S211, MOCVD reative cell, under 200Torr pressure, in the end builds the P doped gallium nitride layer of the upper growth of layer 250nm.
S212, MOCVD reaction chamber temperature drop to 750 ℃, under 200Torr pressure, and the contact layer of 2nm of growing in P doped gallium nitride layer, and maintain 10min, do last thermal anneal process.
For instance, contact layer can be metal contact layer.
Again for instance, Fig. 3 is a gallium nitride based LED preparation method flow chart more provided by the invention, as shown in Figure 3, starting to grow N doped gallium nitride layer to the time period of the multiple quantum well layer that finishes to grow, carrying out thermal anneal process at least one times can be preferably in the time that grown quantum trap transition zone finishes, the value of carrying out thermal anneal process setting cycle can be the arbitrary value in 2-20, and the present embodiment is 7～13 to describe as example take the value of setting cycle.
Preferably, the present embodiment also can use the MOCVD reative cell brightness gallium nitride based LED epitaxial wafer that grows tall next life, as adopted high-purity H
2, high-purity N
2, or high-purity H
2with high-purity N
2mist do carrier gas, high-purity N H
3do N source, metallorganic trimethyl gallium TMGa or triethyl-gallium TEGa do gallium source, and trimethyl indium does indium source, and N-type dopant is 200ppm silane SiH4, and P type dopant is two luxuriant magnesium Cp
2mg, substrate is the sapphire PSS of 002.
Further, the present embodiment also illustrates take setting cycle number as combination layer of 1 growth, but does not do any restriction with this.
S301, MOCVD reaction chamber temperature rise to 1080 ℃, under 200Torr pressure, substrate are carried out to the high-temperature process of 5min.
S302, MOCVD reative cell are by greenhouse cooling to 530 ℃, under 200Torr pressure, at the gallium nitride nucleating layer of Grown 35nm.
Temperature is warmed up to 1080 ℃ by S303, MOCVD reative cell, under 200Torr pressure, and the undoped gallium nitride layer of the 1.7 μ m that grow on gallium nitride nucleating layer.
S304, MOCVD reative cell decline temperature and remain on 1070 ℃, under 200Torr pressure, and the N doped gallium nitride layer of the 3.2 μ m that grow on undoped gallium nitride layer, wherein N doping content is 5E+18atom/cm
3.
S305, MOCVD reative cell reduce the temperature to 850 ℃ in 250s, under 200Torr pressure, and the quantum well transition zone of the 300nm that grows in N doped gallium nitride layer, wherein N doping content is 8E+17atom/cm
3, In component is multiple quantum well layer 30%.
S306, MOCVD reative cell reduce the temperature to 500 ℃ in 300s, stop 3min and carry out thermal anneal process.
S307, MOCVD reative cell are raised to temperature 870 ℃ in 100～300s, under 200Torr pressure, and the base layer of growth 13.5nm.
S308, MOCVD reative cell reduce the temperature to 760 ℃, under 200Torr pressure, and the trap layer of the 2.5nm that grows on the layer of base.
S309, MOCVD reative cell holding temperature be at 760 ℃, under 200Torr pressure, and the trap coating layer of the 2nm that grows on trap layer.
Repeat successively S307, S308 and S309, number of repetition 7～13.
Temperature is elevated to 870 ℃ by S310, MOCVD reative cell, under 200Torr pressure, and the last base layer of the 8nm that grows on trap coating layer.
Temperature is elevated to 980 ℃ by S311, MOCVD reative cell, under 200Torr pressure, in the end builds the P doped gallium nitride layer of the upper growth of layer 250nm.
S312, MOCVD reaction chamber temperature drop to 750 ℃, under 200Torr pressure, and the contact layer of 2nm of growing in P doped gallium nitride layer, and maintain 10min, do last thermal anneal process.
Again for instance, Fig. 4 is another gallium nitride based LED preparation method's provided by the invention flow chart, as shown in Figure 4, starting to grow N doped gallium nitride layer to the time period of the multiple quantum well layer that finishes to grow, carrying out thermal anneal process at least one times can be preferably in growth multiple quantum well layer, while finishing to grow trap coating layer, carry out one time thermal anneal process, wherein, multiple quantum well layer comprises at least one group of the base layer of growing successively, trap layer and trap coating layer at every turn.The value of setting cycle can be the arbitrary value in 2-20, and the present embodiment is 7～13 to describe as example take the value of setting cycle.
Preferably, the present embodiment also can use the MOCVD reative cell brightness gallium nitride based LED epitaxial wafer that grows tall next life, as adopted high-purity H
2, high-purity N
2, or high-purity H
2with high-purity N
2mist do carrier gas, high-purity N H
3do N source, metallorganic trimethyl gallium TMGa or triethyl-gallium TEGa do gallium source, and trimethyl indium does indium source, and N-type dopant is 200ppm silane SiH
4, P type dopant is two luxuriant magnesium Cp
2mg, substrate is the sapphire PSS of 002.
S401, MOCVD reaction chamber temperature rise to 1080 ℃, under 200Torr pressure, substrate are carried out to the high-temperature process of 5min.
S402, MOCVD reative cell are by greenhouse cooling to 530 ℃, under 200Torr pressure, at the gallium nitride nucleating layer of Grown 35nm.
Temperature is warmed up to 1080 ℃ by S403, MOCVD reative cell, under 200Torr pressure, and the undoped gallium nitride layer of the 1.7 μ m that grow on gallium nitride nucleating layer.
S404, MOCVD reative cell decline temperature and remain on 1070 ℃, under 200Torr pressure, and the N doped gallium nitride layer of the 3.2 μ m that grow on undoped gallium nitride layer, wherein N doping content is 5E+18atom/cm
3.
S405, MOCVD reative cell reduce the temperature to 850 ℃, under 200Torr pressure, and the quantum well transition zone of the 300nm that grows in N doped gallium nitride layer, wherein N doping content is 8E+17atom/cm
3, In component is multiple quantum well layer 30%.
Temperature is raised to 870 ℃ by S406, MOCVD reative cell, under 200Torr pressure, and the base layer of growth 13.5nm.
S407, MOCVD reative cell reduce the temperature to 760 ℃, under 200Torr pressure, and the trap layer of the 2.5nm that grows on the layer of base.
S408, MOCVD reative cell holding temperature be at 760 ℃, under 200Torr pressure, and the trap coating layer of the 2nm that grows on trap layer.
S409, MOCVD reative cell reduce the temperature to 500 ℃ in 300s, stop 3min and carry out thermal anneal process.
Repeat successively S406, S407, S408 and S409, number of repetition 7～13.
Temperature is elevated to 870 ℃ by S410, MOCVD reative cell, under 200Torr pressure, and the last base layer of the 8nm that grows on trap coating layer.
Temperature is elevated to 980 ℃ by S411, MOCVD reative cell, under 200Torr pressure, in the end builds the P doped gallium nitride layer of the upper growth of layer 250nm.
S412, MOCVD reaction chamber temperature drop to 750 ℃, under 200Torr pressure, and the contact layer of 2nm of growing in P doped gallium nitride layer, and maintain 10min, do last thermal anneal process.
In the gallium nitride based LED preparation method that the gallium nitride based LED preparation method that above-mentioned Fig. 1 provides and Fig. 2～Fig. 4 enumerate, thermal anneal process is simple, can on any epitaxial device, all can realize, because thermal annealing can have influence on the angularity of epitaxial wafer, therefore can control epitaxial wafer angularity in the time growing multiple quantum well layer by control annealing time, annealing temperature rate, thereby improve wavelength uniformity.Topmost, by thermal annealing can effectively discharge multiple quantum well layer grow completely finish before the extension internal stress of accumulation, the integrated stress of gallium nitride based LED is reduced, and then the quantum well band curvature that stress causes alleviates, and promotes the luminous efficiency of quantum well; And the reduction of extension internal stress can reduce the blue shift of gallium nitride based LED, promote material antistatic property and ageing properties.Generally speaking, the method can effectively reduce the internal stress of device, has promoted the luminous efficiency of quantum well, reduces the blue shift of gallium nitride based LED, promotes material antistatic property and ageing properties.
Fig. 5 is the structural representation of gallium nitride based LED provided by the invention, and as shown in Figure 5, gallium nitride based LED 50 comprises:
Through growing gallium nitride nucleating layer 502, undoped gallium nitride layer 503, N doped gallium nitride layer 504, quantum well transition zone 505, multiple quantum well layer 506, P doped gallium nitride layer 507 and contact layer 508 successively on heat treated substrate 501, wherein, multiple quantum well layer 506 is built layer 5061, trap layer 5062 and trap coating layer 5063 for growing successively according to setting cycle.The value of setting cycle is N, and N can be the arbitrary value in 2-20.
It should be noted that, gallium nitride based LED 50 is that the method for utilizing above-mentioned Fig. 1～Fig. 4 to provide prepares.
The gallium nitride based LED that the embodiment of the present invention provides, preparation method comprises: through growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layer, quantum well transition zone, multiple quantum well layer, P doped gallium nitride layer and contact layer successively on heat treated substrate; Wherein, starting to grow N doped gallium nitride layer to the time period of the multiple quantum well layer that finishes to grow, carry out thermal anneal process at least one times.So, by starting to grow, N doped gallium nitride layer can be released in to carrying out thermal anneal process at least one times in the time period of the multiple quantum well layer that finishes to grow the internal stress that the epitaxial growth of multiple quantum well layer growth before finishing accumulates, reduce largely extension internal stress, the integrated stress of gallium nitride based LED is reduced, and then alleviate the problem of the quantum well band curvature causing because of this stress, reduce the blue shift of gallium nitride based LED, promote material antistatic property, and can promote the luminous efficiency of quantum well.
Again further, the structural representation that Fig. 6 is chip provided by the invention, as shown in Figure 6, chip 1 comprises the gallium nitride based LED 50 that at least one Fig. 5 provides.
For instance, can utilize the gallium nitride based LED preparation method that Fig. 2 provides to obtain structure as the gallium nitride based LED 50 of Fig. 5, called after sample a; Can utilize the gallium nitride based LED preparation method that Fig. 3 provides to obtain structure as the gallium nitride based LED 50 of Fig. 5, called after sample b; Can utilize the gallium nitride based LED preparation method that Fig. 4 provides to obtain structure as the gallium nitride based LED 50 of Fig. 5, called after sample c.
It is as a comparison sample in the gallium nitride based LED of Fig. 5 that recycling prior art is prepared a structure under equal environment, called after sample d.Use the MOCVD reative cell brightness gallium nitride based LED epitaxial wafer that grows tall next life, as adopted high-purity H
2, high-purity N
2, or high-purity H
2with high-purity N
2mist do carrier gas, high-purity N H
3do N source, metallorganic trimethyl gallium TMGa or triethyl-gallium TEGa do gallium source, and trimethyl indium does indium source, and N-type dopant is 200ppm silane SiH
4, P type dopant is two luxuriant magnesium Cp
2mg, substrate is the sapphire PSS of 002.Concrete growth pattern is as follows: MOCVD reaction chamber temperature rises to 1080 ℃, under 200Torr pressure, substrate is carried out to the high-temperature process of 5min; By greenhouse cooling to 530 ℃, under 200Torr pressure, at the gallium nitride nucleating layer of Grown 35nm; Temperature is warmed up to 1080 ℃, under 200Torr pressure, the undoped gallium nitride layer of the 1.7 μ m that grow on gallium nitride nucleating layer; Temperature is declined and remain on 1070 ℃, under 200Torr pressure, the N doped gallium nitride layer of the 3.2 μ m that grow on undoped gallium nitride layer, wherein N doping content is 5E+18atom/cm
3; Reduce the temperature to 850 ℃, under 200Torr pressure, the quantum well transition zone of the 300nm that grows in N doped gallium nitride layer, wherein N doping content is 8E+17atom/cm
3, In component is multiple quantum well layer 30%; Temperature is raised to 870 ℃, under 200Torr pressure, the base layer of growth 13.5nm; Reduce the temperature to 760 ℃, under 200Torr pressure, the trap layer of the 2.5nm that grows on the layer of base; Holding temperature is at 760 ℃, under 200Torr pressure, and the trap coating layer of the 2nm that grows on trap layer; Repeat successively S403, S407, S408 and S409, number of repetition 7～13; Temperature is elevated to 870 ℃, under 200Torr pressure, the last base layer of the 8nm that grows on trap coating layer; Temperature is elevated to 980 ℃, under 200Torr pressure, in the end builds the P doped gallium nitride layer of the upper growth of layer 250nm; Temperature drops to 750 ℃, under 200Torr pressure, and the contact layer of 2nm of growing in P doped gallium nitride layer, and maintain 10min, do last thermal anneal process.
Above-mentioned sample a, sample b, sample c and sample d are made as respectively to the chip of 350 μ m × 430 μ m, Fig. 7 is the brightness contrast figure that gallium nitride based LED provided by the invention makes sample, as shown in Figure 7, the sample a sample b that three embodiment of the present invention provide and sample c brightness ratio sample d have improved 1%～2%.Fig. 8 is the blue shift comparison diagram that gallium nitride based LED provided by the invention makes sample, and as shown in Figure 8, the sample a sample b that three embodiment of the present invention provide and sample c brightness ratio sample d have reduced 0.2nm～0.5nm.Therefore can illustrate, the present invention can effectively discharge the internal stress of gallium nitride based LED epitaxial material by thermal anneal process method, reduce the quantum well band curvature that causes because of internal stress, reduces the blue shift of LED, promote material antistatic property, and can promote the luminous efficiency of quantum well.
The chip of what the embodiment of the present invention provided comprise at least one gallium nitride based LED, through growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layer, quantum well transition zone, multiple quantum well layer, P doped gallium nitride layer and contact layer successively on heat treated substrate; Wherein, starting to grow N doped gallium nitride layer to the time period of the multiple quantum well layer that finishes to grow, carry out thermal anneal process at least one times.So, by starting to grow, N doped gallium nitride layer can be released in to carrying out thermal anneal process at least one times in the time period of the multiple quantum well layer that finishes to grow the internal stress that the epitaxial growth of multiple quantum well layer growth before finishing accumulates, reduce largely extension internal stress, the integrated stress of gallium nitride based LED is reduced, and then alleviate the problem of the quantum well band curvature causing because of this stress, reduce the blue shift of gallium nitride based LED, promote material antistatic property, and can promote the luminous efficiency of quantum well.
Finally it should be noted that: above each embodiment, only in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to aforementioned each embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or some or all of technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (9)
1. a gallium nitride based LED preparation method, is characterized in that, comprising:
Through growing gallium nitride nucleating layer, undoped gallium nitride layer, N doped gallium nitride layer, quantum well transition zone, multiple quantum well layer, P doped gallium nitride layer and contact layer successively on heat treated substrate;
Wherein, starting to grow described N doped gallium nitride layer to the time period of the described multiple quantum well layer that finishes to grow, carry out thermal anneal process at least one times.
2. method according to claim 1, is characterized in that, described starting to grow described N doped gallium nitride layer to the time period of the described multiple quantum well layer that finishes to grow, and carries out thermal anneal process at least one times and comprises:
In the time that the described N doped gallium nitride layer of growth finishes, carry out described thermal anneal process.
3. method according to claim 1, is characterized in that, described starting to grow described N doped gallium nitride layer to the time period of the described multiple quantum well layer that finishes to grow, and carries out thermal anneal process at least one times and comprises:
In the time that the described quantum well transition zone of growth finishes, carry out described thermal anneal process.
4. method according to claim 1, is characterized in that, described starting to grow described N doped gallium nitride layer to the time period of the described multiple quantum well layer that finishes to grow, and carries out thermal anneal process at least one times and comprises:
In the described multiple quantum well layer of growth, while finishing to grow trap coating layer, carry out once described thermal anneal process at every turn, wherein, described multiple quantum well layer comprises at least one group of the base layer of growing successively, trap layer and trap coating layer.
5. according to the method described in claim 1～4 any one, it is characterized in that,
The annealing temperature of described thermal anneal process is 100 ℃～700 ℃, and annealing temperature rate is 50 ℃/min～100 ℃/min, and annealing time is 1min～10min, and the gas of annealing is hydrogen H
2and/or nitrogen N
2.
6. method according to claim 5, is characterized in that,
The annealing temperature of described thermal anneal process is 500 ℃～600 ℃, and annealing time is 3min～5min.
7. method according to claim 4, is characterized in that, described setting cycle number is arbitrary value in 2-20.
8. a gallium nitride based LED, is characterized in that, comprises the gallium nitride based LED of preparing according to the gallium nitride based LED preparation method described in claim 1～7 any one.
9. a chip, is characterized in that, comprises at least one gallium nitride based LED claimed in claim 8.
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