CN103972336A - Method for prolonging working life of GaN-based LED device in temperature circulation manner - Google Patents

Method for prolonging working life of GaN-based LED device in temperature circulation manner Download PDF

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Publication number
CN103972336A
CN103972336A CN201410227596.9A CN201410227596A CN103972336A CN 103972336 A CN103972336 A CN 103972336A CN 201410227596 A CN201410227596 A CN 201410227596A CN 103972336 A CN103972336 A CN 103972336A
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temperature
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semiconductor layer
substrate
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CN103972336B (en
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邵春林
汪英杰
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Inner Mongolia Huayan Xinguang Technology Co., Ltd.
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China (beijing) Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005Processes
    • H01L33/0062Processes for devices with an active region comprising only III-V compounds
    • H01L33/0075Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005Processes
    • H01L33/0095Post-treatment of devices, e.g. annealing, recrystallisation or short-circuit elimination

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  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Led Devices (AREA)

Abstract

The invention relates to a method for prolonging the working life of a GaN-based LED device in a temperature circulation manner. The method comprises the following steps: A, growing a GaN buffering layer 2 on a substrate 1 by a low temperature vapor deposition technology, wherein the low temperature is 500 DEG C; B, growing a GaN semiconductor layer 3 on the GaN buffering layer 2 by a high temperature vapor deposition technology, wherein the high temperature is 1050 DEG C; C, carrying out at least one temperature circulation treatment on the GaN semiconductor layer 3, wherein during each temperature circulation, the temperature is reduced from 1050 DEG C to 500 DEG C, increased to 1055 DEG C and then reduced to 1050 DEG C; and D, subsequently growing other layers on the GaN semiconductor layer 3 which is subjected to the temperature circulation treatment. According to the method, the obtained semiconductor device has the beneficial effects that the dislocation density of crystals is lowered, and the light emitting life of the LED device is prolonged.

Description

Utilize temperature cycles method to improve the method for GaN base LED device working life
Technical field
The invention belongs to semiconductor device fabrication field.
Background technology
The band structure of nitride compound semiconductor material belongs to direct gap semiconductor, is suitablely used for manufacturing photoelectric device.The face that the energy gap of nitride semi-conductor material contains is very wide, has the wide 6.2eV of reaching to 0.65eV, and the wavelength of luminescent device can cover the scope from 200 nanometers to nearly 2000 nanometers.
Gallium nitride semiconductor material is material important in nitride semi-conductor material, and the wave-length coverage of the luminescent device made from gallium nitride-based compound semiconductor material is the scope to infrared spectrum by deep ultraviolet.Gallium nitride-based compound semiconductor material has good electrical isolation capabilities, and its resistance to insulated electro field intensity is up to 2x106V/cm.Gallium nitride-based compound semiconductor material has good resistance to elevated temperatures, is applicable to manufacturing high-temperature device.Charge carrier in gallium nitride-based compound semiconductor material has very high saturated velocity, up to 2.7x107cm/s, is the good material of manufacturing high-frequency element.Gallium nitride-based compound semiconductor material has been used for manufacturing the luminescent device of following product: LED, for illumination or indicator light; LED laser, detects for highdensity storage, high-resolution projecting apparatus, surface etc.; Ultraviolet detector, as the detection of flame, burning is controlled, aircraft induction etc.; Electrooptical device, as solar cell, light compositing etc.; Hyperfrequency device, for satellite communication, freeway traffic monitoring command system; Power-type device, for the device such as engine control, high-power inverter.
Gallium nitride-based compound semiconductor material need carry out the growth of material during fabrication on substrate.
At least to consider the crystal structure of material, the factor such as coupling, the coupling of thermal coefficient of expansion of lattice constant at Grown gallium nitride-based compound semiconductor material.
In the time of Grown gallium nitride-based semiconductor material, conventionally use the method for organic metal vapour phase epitaxy.In this method, utilize trimethyl gallium (TMGa) or triethyl-gallium (TEGa) raw material as Ga, raw material using ammonia (NH3) pyrolysis as N, conventionally using materials such as low temperature GaN or AlN as resilient coating, under the high temperature of 1050 DEG C-1150 DEG C, growing gallium nitride base semiconductor material film on resilient coating.
According to the requirement of making device, growth is applicable to the various semiconductor layer structures of device performance again.As GaN based light-emitting diode, will grow thereon n-GaN, GaN/InGaN/GaN quantum well structure, electronic barrier layer and p-GaN layer, the epitaxial loayer of formation LED structure.
Affect nitrogen gallium base LED device working life because have many kinds, for example quality of gallium nitride-based semiconductor material, as number of the integrality of lattice arrangement, dislocation etc. all directly affects the performance of device.Wherein, in the deposition process of GaN semiconductor layer, if there is crystal dislocation, can seriously reduce the luminous efficiency of luminescent device, and cause the luminous easy decay of luminescent device, device working life shortens.Particularly linear dislocation, bad if the condition control of vapor deposition processes obtains, can produce linear dislocation, this linearity dislocation can be extended along the direction of growth of semiconductor layer, even reaches the active layer of device, seriously affects the performance of device.
In practice, people wish the reaction condition by accurately controlling high temperature vapor deposition reaction conventionally, reduce the probability of happening of linear dislocation.But the control of reaction condition is existed to a limit, and too accurately time, higher to precision and the reliability requirement of raw material feed rate control system, temperature and pressure control system, this causes cost to rise.Therefore, the method that still wishes simple possible reduces the dislocation density of GaN semiconductor layer, to improve the crystal mass of GaN semiconductor layer, and then the bulk life time of raising gallium nitride based light emitting diode.
The present invention provides the such dislocation density of minimizing GaN semiconductor layer of simple possible and then the method for the bulk life time of raising gallium nitride based light emitting diode.
Summary of the invention
A first aspect of the present invention relates to the method for utilizing temperature cycles method to improve GaN base LED device working life, comprises the following steps:
A. at the upper low temperature vapor deposition technology growth GaN resilient coating (2) that adopts of substrate (1), wherein said low temperature is 500 DEG C;
B. adopt high temperature gas phase deposition technology at the upper growing GaN semiconductor layer (3) of described GaN resilient coating (2), wherein said high temperature is 1050 DEG C;
C. described GaN semiconductor layer (3) is carried out to temperature cycles processing at least one times, wherein temperature is dropped to 500 DEG C from 1050 DEG C in temperature cycles each time, then be warmed up to 1055 DEG C, then cool to 1050 DEG C;
D. upper through temperature cycles GaN semiconductor layer after treatment (3), follow-up other each layer of continued growth.
Accompanying drawing summary
Fig. 1 is the structural representation of the LED device of the processing object sapphire substrates of method of the present invention.
Fig. 2 is the processing step schematic diagram of method of the present invention, wherein exemplarily shows the step of temperature cycles.
Reference numerals list:
In Fig. 1:
1. substrate; 2.GaN resilient coating; 3.GaN semiconductor layer; 4.n-GaN layer; 5. quantum well layer; 6.AlGaN layer; 7.P-GaN layer;
In Fig. 2:
Oa section: intensification-thermal cleaning-temperature descending section; Ab section: low temperature vapor deposition section, deposition GaN resilient coating; Bc section: section heats up; Cd section: high temperature vapour deposition section, deposition GaN semiconductor layer; De section: temperature cycles processing for the first time; Ef section: temperature cycles processing for the second time; Fg section: temperature cycles processing for the third time; After g point: deposit follow-up other each layer.
Detailed Description Of The Invention
For the ease of understanding the present invention, now the present invention is described in detail as follows.
" substrate ", has another name called " substrate " or " base material ", refers to tabular a, sheet or film material, and semiconductor device is by carrying out epitaxial growth on this substrate of vapour deposition process.Base material in the present invention, depends on its material, can be sapphire substrate, SiC base material or single crystal silicon substrate.
Before the steps A of method of the present invention, preferably under reducing atmosphere, at the temperature of 1120 DEG C, substrate is carried out to clean, this clean can be called as step e.Then temperature is reduced to 500 DEG C of left and right, starts to carry out steps A of the present invention, in this temperature-fall period, rate of temperature fall is not had to particular/special requirement, as long as can guarantee that substrate is not because cooling is subject to adverse effect.The process of this clean as shown in Figure 2.
In steps A of the present invention, at the upper low temperature vapor deposition technology growth GaN resilient coating (2) that adopts of substrate (1), wherein said low temperature is 500 DEG C; Wherein in this low temperature vapor deposition process, using trimethyl gallium or triethyl-gallium as gallium source, with NH 3as nitrogenous source, after decomposing under above-mentioned low temperature, original position is combined to GaN and is deposited in substrate.The thickness of this GaN resilient coating can be controlled by the condition of vapour deposition, is generally 25nm left and right.Then the high temperature of temperature being brought up to 1050 DEG C of left and right, carries out following steps B.
In step B of the present invention, adopt high temperature gas phase deposition technology at the upper growing GaN semiconductor layer (3) of described GaN resilient coating (2), wherein said high temperature is 1050 DEG C; Wherein in this high temperature vapor deposition processes, using trimethyl gallium or triethyl-gallium as gallium source, with NH 3as nitrogenous source, after decomposing under above-mentioned high temperature, original position is combined to GaN and is deposited on described GaN resilient coating.The thickness of this GaN semiconductor layer can be controlled by the condition of vapour deposition, is generally 2000nm left and right.In this high temperature vapor deposition processes, select suitable Ga/N mol ratio, and control vapor deposition reaction condition, obtain the GaN semiconductor layer 3 of the composition and property with expectation.The speed of growth of this GaN semiconductor layer 3 can be controlled to 2000-3000nm/h.Conventionally, in order to control the crystal mass of the GaN semiconductor layer obtaining by vapour deposition process, do not wish that the speed of growth is too fast, general control is below 2000nm/h.But the present invention is because unique temperature cycles processing can be eliminated the defect of crystals, therefore can not be subject to the restriction of this speed of growth.Then, carry out following steps C.
Step C is key point of the present invention.In this step C, described GaN semiconductor layer (3) is carried out to temperature cycles processing at least one times, wherein temperature is dropped to 500 DEG C from 1050 DEG C in temperature cycles each time, then be warmed up to 1055 DEG C, then cool to 1050 DEG C.Such temperature cycles is preferably carried out more than 3 times.Wherein, heating rate and rate of temperature fall are not had to special requirement, as long as can guarantee that the thermal stress that substrate, GaN resilient coating and GaN semiconductor layer all should not produce because of the cooling that heats up is subject to adverse effect.Heating rate and rate of temperature fall can be linearity or nonlinear, but preferred linearity.In preferred embodiments, rate of temperature fall is not less than 10 DEG C/min, and heating rate is 10 DEG C/sec~20 DEG C/min.In another preferred embodiment, in temperature cycles each time, also described GaN semiconductor layer (3) can be kept being not more than the time of 10 minutes at 1050 DEG C, or, described GaN semiconductor layer (3) is kept being not more than the time of 10 minutes at 500 DEG C, or the two combination.This retention time also can be known as " plateau ", and the length of plateau can be adjusted according to concrete technology condition.Inventor's discovery, to GaN semiconductor layer, after so at least one times temperature cycles is processed, the crystalline quality of GaN semiconductor layer is significantly improved, and this is embodied on the significant prolongation in life-span of semiconductor device, as shown in hereinafter embodiment.
Then, carry out step D of the present invention.In this step D, upper through temperature cycles GaN semiconductor layer after treatment (3), follow-up other each layer of continued growth.Other follow-up material of each layer selects and deposit thickness can be determined as the case may be.In a preferred embodiment, described other each layer comprises n-GaN layer, GaN/GaInN/GaN multiple quantum well layer, electronic barrier layer AlGaN layer, p-GaN material layer successively.In a more preferred embodiment, can also continue to comprise transparent electrode layer or protective layer etc.
The present invention is not only applicable to GaN base semiconductor material, and is applicable to the nitride semi-conductor material of other periodic table III-V family element.
Embodiment
Following examples are only to illustrate of the present invention, do not limit the present invention in any way.
Embodiment 1
By reference to the accompanying drawings 1 and accompanying drawing 2, be illustrated as an example of GaN basic basket light luminescent device example.
In this embodiment, be substrate 1 with sapphire, can adopt the minute surface sapphire substrates without the plane of figure processing; Also can select through the finished PSS sapphire substrates of figure; The face orientation of substrate can be the substrate of polarity C face; Also can select the substrate of the substrate of non-polar m face or semi-polarity face.
The growth of each epitaxial loayer all adopts organic metal CVD (Chemical Vapor Deposition) method (MOCVD) growth.
Detailed process is as follows:
Step e-clean: by putting into MOCVD stove through the sapphire substrates of cleaning, be warmed up to 1120 DEG C to the further clean of substrate surface in reducing atmosphere.Then temperature is reduced to 500 DEG C.
Steps A-low temperature depositing GaN resilient coating: at 500 DEG C, using trimethyl gallium or triethyl-gallium as gallium source, with NH 3as nitrogenous source, with the thick low temperature GaN resilient coating 2 of the about 25nm of low temperature vapor deposition deposition techniques.After having deposited, with suitable programming rate by temperature rise for example, under the needed high temperature of high temperature deposition GaN semiconductor layer, at 1050 DEG C.
Step B-high temperature deposition GaN semiconductor layer: at 1050 DEG C, utilize trimethyl gallium as gallium source, using NH3 pyrolysis as N nitrogenous source, select suitable Ga/N mol ratio, and control raw material and pass into speed and vapor deposition reaction condition, on GaN resilient coating 2, deposit the GaN semiconductor layer 3 that 2000nm is thick, in deposition process, the speed of growth is controlled to 3000nm/h.
Step C-temperature cycles processing: with the rate of temperature fall of 10 DEG C/min, temperature in gas-phase deposition reactor is reduced to 500 DEG C from 1050 DEG C, at 500 DEG C, there is no plateau, be warming up to gradually 1055 DEG C with the heating rate of 10 DEG C/sec at once, and then drop to 1050 DEG C with the rate of temperature fall of 10 DEG C/min, form a temperature cycles.Carry out continuously 3 such temperature cycles.
Step D-deposits other each layer: continue to pass into trimethyl gallium and NH3 in gas-phase deposition reactor, import silane simultaneously, proceed vapor deposition reaction, the GaN layer of continued growth doped silicon on described GaN semiconductor layer 3, be n-GaN layer 4, the about 3000nm of thickness of this n-GaN layer 4.Then, the GaN layer that silicon growth layer doping content is less, as the even diffusion layer of electric current.Then, deposition growing GaN/GaInN/GaN layer successively on the even diffusion layer of electric current, as multi-quantum pit structure layer 5, wherein in InGaN layer, the component of In has determined a light wavelength, wavelength that can be as requested in the time of growing InGaN layer, growth regulation temperature and as supply of the trimethyl indium in indium source etc.Then, growth one deck electronic barrier layer 6, this electronic barrier layer is made up of the larger AlGaN material of energy gap conventionally, and thickness is tens nanometer.Finally, growth p-GaN material layer 7, the p-type dopant material of this pGaN material is Cp2Mg, and holoe carrier is provided after overactivation.
After above-mentioned steps completes, obtain epitaxial wafer, this epitaxial wafer can pass through subsequent treatment, makes the chip of luminescent device, package application.
Comparative example 1
In this comparative example, be substrate 1 with sapphire, can adopt the minute surface sapphire substrates without the plane of figure processing; Also can select through the finished PSS sapphire substrates of figure; The face orientation of substrate can be the substrate of polarity C face; Also can select the substrate of the substrate of non-polar m face or semi-polarity face.
The growth of each epitaxial loayer all adopts organic metal CVD (Chemical Vapor Deposition) method (MOCVD) growth.
Detailed process is as follows:
Step e-clean: by putting into MOCVD stove through the sapphire substrates of cleaning, be warmed up to 1120 DEG C to the further clean of substrate surface in reducing atmosphere.Then temperature is reduced to 500 DEG C.
Steps A-low temperature depositing GaN resilient coating: at 500 DEG C, using trimethyl gallium or triethyl-gallium as gallium source, with NH 3as nitrogenous source, with the thick low temperature GaN resilient coating 2 of the about 25nm of low temperature vapor deposition deposition techniques.After having deposited, with suitable programming rate by temperature rise for example, under the needed high temperature of high temperature deposition GaN semiconductor layer, at 1050 DEG C.
Step B-high temperature deposition GaN semiconductor layer: at 1050 DEG C, utilize trimethyl gallium as gallium source, using NH3 pyrolysis as N nitrogenous source, select suitable Ga/N mol ratio, and control raw material and pass into speed and vapor deposition reaction condition, on GaN resilient coating 2, deposit the GaN semiconductor layer 3 that 2000nm is thick, in deposition process, the speed of growth is controlled to 3000nm/h.
Step C-temperature cycles processing: nothing.
Step D-deposits other each layer: continue to pass into trimethyl gallium and NH3 in gas-phase deposition reactor, import silane simultaneously, proceed vapor deposition reaction, the GaN layer of continued growth doped silicon on described GaN semiconductor layer 3, be n-GaN layer 4, the about 3000nm of thickness of this n-GaN layer 4.Then, the GaN layer that silicon growth layer doping content is less, as the even diffusion layer of electric current.Then, deposition growing GaN/GaInN/GaN layer successively on the even diffusion layer of electric current, as multi-quantum pit structure layer 5, wherein in InGaN layer, the component of In has determined a light wavelength, wavelength that can be as requested in the time of growing InGaN layer, growth regulation temperature and as supply of the trimethyl indium in indium source etc.Then, growth one deck electronic barrier layer 6, this electronic barrier layer is made up of the larger AlGaN material of energy gap conventionally, and thickness is tens nanometer.Finally, growth p-GaN material layer 7, the p-type dopant material of this pGaN material is Cp2Mg, and holoe carrier is provided after overactivation.
After above-mentioned steps completes, obtain epitaxial wafer, this epitaxial wafer uses the technique identical with embodiment 1 through subsequent treatment, makes the chip of luminescent device, package application.
Performance test
Get respectively each 20 of the luminescent device that embodiment 1 and comparative example 1 obtain, measure their data average length of working life under same current condition.The working life of LED luminescent device is defined as follows: under constant operating current, light continuously this luminescent device, until the luminous intensity of this luminescent device lower than its initial maximum emission intensity 80% time while being greater than 20% (or say light decay), the hourage experiencing during this is defined as to its working life.Test is carried out under 30 milliamperes of operating currents, the average life span of the luminescent device of embodiment 1 is 13750 hours, and the luminescent device of comparative example 1 is 11290 hours, life approximately 22%, this illustrates that method of the present invention has significantly improved the average length of working life of luminescent device, indirectly illustrates that temperature cycles method of the present invention has greatly reduced the dislocation density of GaN semiconductor layer.

Claims (8)

1. utilize temperature cycles method to improve a method for GaN base LED device working life, comprise the following steps:
A. at the upper low temperature vapor deposition technology growth GaN resilient coating (2) that adopts of substrate (1), wherein said low temperature is 500 DEG C;
B. adopt high temperature gas phase deposition technology at the upper growing GaN semiconductor layer (3) of described GaN resilient coating (2), wherein said high temperature is 1050 DEG C;
C. described GaN semiconductor layer (3) is carried out to temperature cycles processing at least one times, wherein temperature is dropped to 500 DEG C from 1050 DEG C in temperature cycles each time, then be warmed up to 1055 DEG C, then cool to 1050 DEG C;
D. upper through temperature cycles GaN semiconductor layer after treatment (3), follow-up other each layer of continued growth.
2. according to the process of claim 1 wherein in described temperature cycles, rate of temperature fall is not less than 10 DEG C/min, and heating rate is 10 DEG C/sec~20 DEG C/min.
3. according to the method for claim 1, wherein in temperature cycles each time, described GaN semiconductor layer (3) is kept being not more than the time of 10 minutes at 1050 DEG C, or, described GaN semiconductor layer (3) is kept being not more than the time of 10 minutes at 500 DEG C, or the two combination.
4. according to the process of claim 1 wherein that described substrate is sapphire substrates or monocrystal silicon substrate.
5. according to the process of claim 1 wherein that described other each layer comprises n-GaN layer, GaN/GaInN/GaN multiple quantum well layer, electronic barrier layer AlGaN layer, p-GaN material layer successively.
6. according to the process of claim 1 wherein that described temperature cycles carries out more than 3 times.
7. according to the process of claim 1 wherein in described high temperature vapour deposition process, using trimethyl gallium or triethyl-gallium as gallium source, with NH 3as nitrogenous source, through pyrolysis and pyroreaction, generate described GaN semiconductor layer (3).
8. before described steps A, be also included in the step e of substrate being carried out clean under reducing atmosphere at the temperature of 1120 DEG C according to the process of claim 1 wherein.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109004073A (en) * 2018-07-31 2018-12-14 湘能华磊光电股份有限公司 A kind of epitaxial growth method improving GaN base LED chip luminous efficiency

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Publication number Priority date Publication date Assignee Title
CN101060076A (en) * 2007-05-14 2007-10-24 武汉大学 A manufacture method for GaN insulation or semi-insulation epitaxy layer
US20100258912A1 (en) * 2009-04-08 2010-10-14 Robert Beach DOPANT DIFFUSION MODULATION IN GaN BUFFER LAYERS
CN103811601A (en) * 2014-03-12 2014-05-21 合肥彩虹蓝光科技有限公司 Method for GaN base LED multi-stage buffer layer growth with sapphire substrate serving as substrate

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Publication number Priority date Publication date Assignee Title
CN101060076A (en) * 2007-05-14 2007-10-24 武汉大学 A manufacture method for GaN insulation or semi-insulation epitaxy layer
US20100258912A1 (en) * 2009-04-08 2010-10-14 Robert Beach DOPANT DIFFUSION MODULATION IN GaN BUFFER LAYERS
CN103811601A (en) * 2014-03-12 2014-05-21 合肥彩虹蓝光科技有限公司 Method for GaN base LED multi-stage buffer layer growth with sapphire substrate serving as substrate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109004073A (en) * 2018-07-31 2018-12-14 湘能华磊光电股份有限公司 A kind of epitaxial growth method improving GaN base LED chip luminous efficiency

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