CN106876540B - A kind of epitaxial growth method improving GaN base LED internal quantum efficiency - Google Patents
A kind of epitaxial growth method improving GaN base LED internal quantum efficiency Download PDFInfo
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- CN106876540B CN106876540B CN201710140872.1A CN201710140872A CN106876540B CN 106876540 B CN106876540 B CN 106876540B CN 201710140872 A CN201710140872 A CN 201710140872A CN 106876540 B CN106876540 B CN 106876540B
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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
- H01L33/0066—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
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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
- 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
- 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
- H01L33/26—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 invention discloses it is a kind of improve GaN base LED internal quantum efficiency epitaxial growth method, the material structure include stack gradually on a sapphire substrate growing low temperature nucleating layer, unintentional doped gan layer, n-type GaN layer, two methods of InGaN/ low temperature GaN/ high temperature GaN composition multiple quantum well layer, electronic barrier layer, p-type GaN layer and P type contact layer.Wherein the low temperature GaN cap rock of two methods includes that the low temperature GaN growth of first stage is not passed through H in the process2Gas；H is passed through in the low temperature GaN cap rock growth course of second stage2Gas.The present invention can not only effectively avoid H using the low temperature GaN of two methods2Etching of the gas directly to In atom, avoids the reduction of In content in InGaN well layer, additionally it is possible to reduce dislocation in low temperature cap rock, impurity, the defects of V-arrangement is cheated density, crystal quality is improved, to improve the purpose of the internal quantum efficiency of GaN base LED.
Description
Technical field
The invention belongs to field of optoelectronic devices, and in particular to a kind of epitaxial growth for improving GaN base LED internal quantum efficiency
Method.
Background technique
Gallium nitride based light emitting diode (Light Emitting Diode, LED) have high brightness, low energy consumption, the long-life,
The features such as fast response time and environmental protection, is widely used in indoor and street lighting, traffic signals and outdoor display, Automobile
The multiple fields such as lamp illumination, liquid crystal backlight.Therefore, large power white light LED is considered as the lighting source of 21 century.
Current commercialized GaN base LED epitaxial structure is mostly different along [0001] direction (c-axis) on a sapphire substrate
Matter extension.Due to Sapphire Substrate and wurtzite structure GaN on lattice constant, thermal expansion coefficient there are biggish difference, make
Obtain the defect density in GaN body material up to 108cm-2.Due to the hereditary effect of defect in epitaxial growth, can defect be prolonged
Extend to multiple quantum wells region.Secondly, in order to improve the incorporation efficiency of In, the growth temperature of InGaN well layer not above 800 DEG C,
And the growth temperature of the ingredient of In more high request is lower, however NH at low temperature3Crack insufficient, therefore the meeting in epitaxial growth
Many defects are formed, such as the vacancy N, antistructure defect etc., so that crystal quality declines, LED luminous efficiency is seriously reduced.In order to improve
Crystal quality, the growth temperature of GaN barrier layer are generally higher than the growth temperature of InGaN well layer, this just needs to introduce low temperature GaN lid
Layer is come the loss of In when preventing heating.It is brilliant since growth temperature is low although GaN cap rock can effectively prevent the loss of In
Weight is poor.It is located at the defect of multi-quantum well active region, such as In cluster, misfit dislocation, threading dislocation, stacked layers in a word
Mistake, surface crater and V-arrangement hole etc., will form non-radiative recombination center, so that carrier is largely reduced due to non-radiative recombination,
Seriously reduce the internal quantum efficiency of LED.
Summary of the invention
It is an object of the invention in view of the above-mentioned problems, providing a kind of extension life for improving GaN base LED internal quantum efficiency
Long method.This method can not only reduce quantum well region defect concentration, and preparation method is simple, and preparation cost is lower.
The present invention is achieved by the following technical solutions: a kind of epitaxial growth side for improving GaN base LED internal quantum efficiency
Method includes the following steps:
One substrate is provided and surface cleaning is carried out to substrate；
GaN nucleating layer and the high temperature anneal are grown on substrate after the cleaning；
Unintentional doped gan layer is grown on GaN nucleating layer after annealing；
The growing n-type GaN layer in unintentional doped gan layer；
Grow multi-quantum well luminescence layer in n-type GaN layer, the multi-quantum well luminescence layer is several pairs of InGaN well layer/low
Warm GaN cap rock/high temperature GaN barrier layer is successively alternately stacked composition from bottom to top, and the growth of every layer of low temperature GaN cap rock is divided into two
Stage, first stage are not to be passed through H in growth course2Gas, second stage are to be passed through H in growth course2Gas；
P-AlGaN electronic barrier layer is grown in multi-quantum well luminescence layer；
P-GaN layer and p-GaN contact layer are grown on p-AlGaN electronic barrier layer.
When growing GaN nucleating layer and the high temperature anneal in the present invention, the temperature of the high temperature anneal is 950-
1110℃。
When concrete application, NH is first passed through in a growth cycle of the multi-quantum well luminescence layer3Gas, the source In, the source Ga,
Grow InGaN well layer；After well layer has been grown, it is simply turned off the source In, grows the GaN cap rock of first stage；Then pass to small flow
H2, grow the GaN cap rock of second stage；After cap rock has been grown, the source Ga and H are closed2Gas simultaneously starts to warm up, and reaches barrier layer to temperature
Growth temperature and after stablizing, then the source Ga is opened, grow GaN barrier layer.It grows and completes to barrier layer, close the source Ga and start to cool down, to temperature
After degree reaches well layer growth temperature and stablizes, then the source Ga and the source In are opened, grows the well layer of next cycle.
The growth temperature of low temperature GaN cap rock of the present invention is consistent with the growth temperature of InGaN well layer, the life of high temperature GaN barrier layer
Long temperature is higher than the growth temperature of InGaN well layer and GaN cap rock.Low temperature cap rock is used to protect the In atom in InGaN well layer, prevents
Only In atom is evaporated and is desorbed in temperature-rise period.
Further, during growing multiple quantum wells, H only is passed through in the second stage of low temperature GaN cap rock growth2, and
H is not passed through in the growth course of InGaN well layer, the first stage of low temperature GaN cap rock growth and GaN barrier layer2Gas.
Technical solution of the present invention it is further preferred that the H2The flow of gas is that low temperature GaN cap rock was grown
The 0.1%-20% for all gas total flow being passed through in journey.The all gas only contains NH3Gas, H2Gas and N2Gas.
Further, the thickness proportion of the first stage of every layer of low temperature GaN cap rock is more than or equal to 10% and is less than or equal to 90%.It should
Thickness proportion is first stage and two stage ratio.If wherein the thickness proportion of first stage does not have protective layer less than 10%
Effect；If the thickness proportion of first stage is greater than 90%, improvement is unobvious.
In addition, in the multi-quantum well luminescence layer InGaN well layer with a thickness of 1-6nm, the overall thickness of low temperature GaN cap rock is
0.2-6nm, high temperature GaN barrier layer with a thickness of 5-20nm.
When it is implemented, In component is 5-40% in mole percent in the InGaN well layer.
Preferably, InGaN well layer/low temperature GaN cap rock/high temperature GaN barrier layer periodicity in the multi-quantum well luminescence layer
It is 1-20 pairs.
The epitaxial growth method through the invention is covered when growing the low temperature cap rock of multicycle Quantum Well in growth
The first stage of layer is not passed through H2Gas is because of H2Gas understands etch away sections In atom, and In's contains in reduction InGaN well layer
Amount；And the H of small flow is passed through in second stage2Gas is because there are many dislocations, impurity in low temperature cap rock, V-arrangement hole etc. is lacked
It falls into, and small flow H2The addition of gas partially can remove or be passivated these defects, improve crystal quality, additionally it is possible to etch away
Excessive In atom reduces the cluster of In atom, improves the uniformity of In component, forms precipitous trap and builds interface.Therefore, pass through
The present invention can achieve the purpose for improving the internal quantum efficiency of GaN base LED.
Detailed description of the invention
Fig. 1 is the epitaxial wafer flow chart of conventional method growth.
Fig. 2 is the epitaxial wafer flow chart of prior art growth.
Fig. 3 is the present invention using InGaN well layer/two-step method low temperature GaN cap rock/high temperature GaN barrier layer composition Multiple-quantum
The room temperature of the epitaxial wafer and tradition InGaN well layer/low temperature GaN cap rock of well structure/high temperature GaN barrier layer composition multi-quantum pit structure
(300K) photoluminescence spectrum comparison diagram.Wherein only the growth conditions of low temperature GaN cap rock is different, and the low temperature depth of cover of traditional structure is
1.0nm is not passed through H in growth course2Gas.And the low temperature GaN cap rock first stage of two-step method with a thickness of 0.5nm, second
Stage is with a thickness of the H for being passed through 200sccm in 0.5nm and second stage2Gas (the 2.5% of all gas total flow), other
Structure and parameter are identical.It can be seen that the present invention is built using InGaN well layer/two-step method low temperature GaN cap rock/high temperature GaN
The epitaxial wafer emission wavelength and tradition InGaN well layer/low temperature GaN cap rock/high temperature GaN barrier layer group of the multi-quantum pit structure of layer composition
At multi-quantum pit structure epitaxial wafer emission wavelength compared to being basically unchanged, only blue shift 1.0nm, and strong light at room temperature
Degree about enhances 2 times.The contrast test of above-mentioned photoluminescence spectrum is using He-Cd laser, the PL light of excitation wavelength 325nm
Spectrometer.
Fig. 4 is the present invention using InGaN well layer/two-step method low temperature GaN cap rock/high temperature GaN barrier layer composition Multiple-quantum
The extension of the epitaxial wafer and tradition InGaN well layer/low temperature GaN cap rock of well structure/high temperature GaN barrier layer composition multi-quantum pit structure
The internal quantum efficiency comparison diagram of piece.Wherein only the growth conditions of low temperature GaN cap rock is different, and the low temperature GaN cap rock of traditional structure is thick
Degree is 1.0nm, is not passed through H in growth course2Gas.And the low temperature GaN cap rock first stage of two-step method with a thickness of 0.5nm,
Second stage is with a thickness of the H for being passed through 200sccm in 0.5nm and second stage2Gas (2.5vol%), other structures and ginseng
It counts up to exactly the same.Internal quantum efficiency value uses following calculation formula:.Wherein I10KAnd I300KRespectively in 10K and
The integrated intensity of the photoluminescence spectrum measured when 300K.It can be seen that the present invention uses the low temperature GaN/ high temperature of two methods of InGaN/
The epitaxial wafer internal quantum efficiency of the multi-quantum pit structure of GaN composition about improves 1.3 times.The survey of photoluminescence spectrum when 10K and 300K
What is used is the PL spectrometer of He-Cd laser, excitation wavelength 325nm.
Fig. 5 is the present invention using InGaN well layer/two-step method low temperature GaN cap rock/high temperature GaN barrier layer composition Multiple-quantum
The low temperature GaN cap rock of epitaxial wafer and InGaN well layer/one-step method of well structure/high temperature GaN barrier layer composition multi-quantum pit structure
Room temperature (300K) photoluminescence spectrum comparison diagram of epitaxial wafer.Wherein only the growth conditions of low temperature GaN cap rock is different, the low temperature of one-step method
GaN depth of cover is 1.0nm, and the H of 200sccm is passed through in growth course2Gas (2.5vol%).And the low temperature GaN lid of two-step method
The layer first stage, second stage was with a thickness of 0.5nm with a thickness of the H for being passed through 200sccm in 0.5nm and second stage2Gas
(the 2.5% of all gas total flow), other structures and parameter are identical.It can be seen that the present invention uses two methods of InGaN/
The epitaxial wafer luminous intensity at room temperature of multi-quantum pit structure of low temperature GaN/ high temperature GaN composition about improve 1.5 times.The room
Temperature under photoluminescence intensity be Nd-YAG laser, excitation wavelength 266nm PL spectrometer measured.
Specific embodiment
Further description is carried out to the present invention below by embodiment.As mentioned in working as in specification in the whole text
" only containing " or " only " is a closed term, therefore should be construed to " only "." about " refer in acceptable error range
Interior, those skilled in the art can solve the technical problem within a certain error range, basically reach the technical effect.
A kind of epitaxial growth method improving GaN base LED internal quantum efficiency, includes the following steps:
One substrate is provided and surface cleaning is carried out to substrate；
GaN nucleating layer and the high temperature anneal are grown on substrate after the cleaning；
Unintentional doped gan layer is grown on GaN nucleating layer after annealing；
The growing n-type GaN layer in unintentional doped gan layer；
Grow multi-quantum well luminescence layer in n-type GaN layer, the multi-quantum well luminescence layer is several pairs of InGaN well layer/low
Warm GaN cap rock/high temperature GaN barrier layer is successively alternately stacked composition from bottom to top, and the growth of every layer of low temperature GaN cap rock is divided into two
Stage, first stage are not to be passed through H in growth course2Gas, second stage are to be passed through H in growth course2Gas；
P-AlGaN electronic barrier layer is grown in multi-quantum well luminescence layer；
P-GaN layer and p-GaN contact layer are grown on p-AlGaN electronic barrier layer.
Further, as a kind of specific embodiment of epitaxial growth method provided by the invention: extension of the invention is raw
Long method is realized in the instrument of MOCVD board model Aixtron TS300.When wherein growing multi-quantum well luminescence layer,
Keep reaction cavity pressure 200-600mBar, be passed through flow to be the optional range 2000-6000sccm of 4000sccm()
NH3The flow of gas, the source In and the source Ga is by carrier gas N2It conveys into reaction chamber, wherein In source flux is the source 20-400sccm, Ga
Flow is 5-100sccm.InGaN well layer is grown in the range of temperature is 650-800 DEG C, in growth course pressure, temperature with
And it is passed through NH3Gas, the source In, the source Ga flow constant；After well layer has been grown, it is simply turned off the source In, grows the first stage
GaN cap rock pressure, temperature and is passed through NH in growth course3Gas, the source Ga flow constant；Then pass to total gas
The H of flow 2.5%2(workable range is 0.1%-20%), grows the GaN cap rock of second stage, pressure, temperature in growth course
Spend and be passed through NH3Gas, the source Ga flow constant；After cap rock has been grown, the source Ga and H are closed2Gas and start to warm up to
750-950 DEG C, keep the pressure of reaction chamber constant, ammonia flow is constant, and Ga source flux is 10-100sccm, and temperature is opened after stablizing
Begin growth GaN barrier layer, pressure, temperature and is passed through NH in growth course3Gas, the source In, the source Ga flow constant.Wait build
Layer growth is completed, and is closed the source Ga and is started to cool down, and is 20- being passed through flow after temperature reaches well layer growth temperature and stablizes
The In of 400sccm, the source Ga that flow is 5-100sccm, grow the well layer of next cycle, repeat the above steps.Periodicity is
1-20 pairs.Wherein N2The total flow of reaction chamber is maintained to protect substantially during entire quantum trap growth as carrier gas and compensation gas
Hold constant, N2Flow can be selected 2000-6000sccm, during the growth process can be according to NH3, the source In, the source Ga, H2Flow become
Change is compensated accordingly.
When it is implemented, the thickness proportion of the first stage of every layer of low temperature GaN cap rock is more than or equal to 10% and is less than or equal to
90%。
Further, in the multi-quantum well luminescence layer InGaN well layer with a thickness of 1-6nm, the overall thickness of low temperature GaN cap rock
For 0.2-6nm, high temperature GaN barrier layer with a thickness of 5-20nm.
Preferably, In component is 5-40% in mole percent in the InGaN well layer.
Claims (6)
1. a kind of epitaxial growth method for improving GaN base LED internal quantum efficiency, which comprises the steps of:
One substrate is provided and surface cleaning is carried out to substrate；
GaN nucleating layer and the high temperature anneal are grown on substrate after the cleaning；
Unintentional doped gan layer is grown on GaN nucleating layer after annealing；
The growing n-type GaN layer in unintentional doped gan layer；
Multi-quantum well luminescence layer is grown in n-type GaN layer, the multi-quantum well luminescence layer is several pairs of InGaN well layer/low temperature
GaN cap rock/high temperature GaN barrier layer is successively alternately stacked composition, the growth temperature and InGaN well layer of low temperature GaN cap rock from bottom to top
Growth temperature it is consistent, the growth temperature of high temperature GaN barrier layer is higher than the growth temperature of InGaN well layer and low temperature GaN cap rock, and often
The growth of layer low temperature GaN cap rock is divided into two stages, and the first stage is not to be passed through H in growth course2Gas, second stage are made a living
H is passed through in growth process2Gas；
P-AlGaN electronic barrier layer is grown in multi-quantum well luminescence layer；
P-GaN layer and p-GaN contact layer are grown on p-AlGaN electronic barrier layer.
2. a kind of epitaxial growth method for improving GaN base LED internal quantum efficiency according to claim 1, which is characterized in that
The H2The flow of gas is the 0.1%-20% for all gas total flow being passed through in low temperature GaN cap rock growth course.
3. a kind of epitaxial growth method for improving GaN base LED internal quantum efficiency according to claim 2, which is characterized in that
The thickness proportion of the first stage of every layer of low temperature GaN cap rock is more than or equal to 10% and is less than or equal to 90%.
4. a kind of epitaxial growth method for improving GaN base LED internal quantum efficiency according to claim 3, which is characterized in that
In the multi-quantum well luminescence layer InGaN well layer with a thickness of 1-6nm, the overall thickness of low temperature GaN cap rock is 0.2-6nm, high temperature
GaN barrier layer with a thickness of 5-20nm.
5. a kind of epitaxial growth method for improving GaN base LED internal quantum efficiency according to claim 4, which is characterized in that
In component is 5-40% in mole percent in the InGaN well layer.
6. a kind of epitaxial growth method for improving GaN base LED internal quantum efficiency according to claim 5, which is characterized in that
InGaN well layer/low temperature GaN cap rock/high temperature GaN barrier layer periodicity is 1-20 pairs in the multi-quantum well luminescence layer.
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| CN109300850A (en) * | 2018-09-03 | 2019-02-01 | 淮安澳洋顺昌光电技术有限公司 | A kind of blue-ray LED epitaxial structure and preparation method |
| CN109888069B (en) * | 2019-01-10 | 2020-12-25 | 中国科学院半导体研究所 | InGaN/GaN quantum well structure and LED epitaxial wafer preparation method |
| CN110518096A (en) * | 2019-07-05 | 2019-11-29 | 华灿光电(苏州）有限公司 | The preparation method of LED epitaxial slice |
| CN111081828B (en) * | 2019-10-21 | 2021-01-12 | 华灿光电(苏州）有限公司 | Growth method of Micro LED epitaxial wafer and Micro LED epitaxial wafer |
| CN113675304A (en) * | 2021-08-20 | 2021-11-19 | 江西兆驰半导体有限公司 | Gallium nitride-based light emitting diode and manufacturing method thereof |
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