CN104485399B - Epitaxial growth method for improving epitaxial crystal quality - Google Patents

Epitaxial growth method for improving epitaxial crystal quality Download PDF

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Publication number
CN104485399B
CN104485399B CN201410720665.XA CN201410720665A CN104485399B CN 104485399 B CN104485399 B CN 104485399B CN 201410720665 A CN201410720665 A CN 201410720665A CN 104485399 B CN104485399 B CN 104485399B
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layer
gan
gan layer
pss
growth
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CN104485399A (en
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商毅博
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XI'AN SHENGUANG HAORUI PHOTOELECTRIC TECHNOLOGY Co Ltd
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XI'AN SHENGUANG HAORUI PHOTOELECTRIC 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
    • H01L33/025—Physical imperfections, e.g. particular concentration or distribution of impurities
    • 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
    • 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 provides an epitaxial growth method for improving epitaxial crystal quality, which is capable of effectively improving the epitaxial crystal quality of an LED (light emitting diode). The epitaxial growth method comprises the following steps of (1) taking a conical PSS (patterned sapphire substrate) as a growth substrate, and growing a first buffer layer at low temperature; (2) growing a first U-GaN layer at high temperature, wherein the growth thickness meets the condition that the first U-GaN layer incompletely covers the PSS pattern, namely, the tip part of the PSS is higher than the surface of the first U-GaN layer; (3) performing high-temperature annealing in an NH3 environment, cooling to low temperature, and then growing a second buffer layer; (4) growing a second U-GaN layer at high temperature, wherein the growth thickness meets the condition that the second U-GaN layer completely covers the PSS pattern; (5) sequentially growing a SiH4-doped n-GaN layer, a multi-quantum well active layer, a doped p-type AlGaN barrier layer and a doped p-type GaN layer, and finally annealing under nitrogen atmosphere.

Description

A kind of epitaxial growth method improving epitaxial crystal quality
Technical field：
The invention belongs to semi-conductor electronic device technology of preparing, particularly to a kind of new growth LED epitaxial growth method.
Background technology：
As the representative of third generation semi-conducting material, GaN material has many superiority such as energy gap is big, high temperature resistant Energy.Therefore, GaN semiconductor device show in light, optical storage, laser printing, white-light illuminating and the field such as medical and military all There is wide application.GaN base light emitting (LED) is wherein the most strikingly utilized to add that fluorescent material synthesis white light is realized White-light illuminating.
Mostly GaN is grown on a sapphire substrate using MOCVD device at present, however, Sapphire Substrate and GaN material There is larger mismatch (16%) in lattice paprmeter, lead to Grown on Sapphire Substrates GaN crystal to have very high dislocation density, brilliant Weight is very poor, causes Carrier Leakage and the harmful effect such as non-radiative recombination center increases is so that under device internal quantum efficiency Fall.Updating with technique, people begin with patterned substrate technology (PSS), that is, pass through in sapphire substrate surface Make the figure with fine structure, change the growth course of GaN, in the artificial nucleation in substrate surface manufacturing cycle property The heart, can effectively suppress the generation of material Dislocations, improve crystal mass, so that the internal quantum efficiency of device is got a promotion.
For example, first using taper PSS as growth substrate, low temperature-grown buffer layer；Then high growth temperature U-GaN layer, growth Thickness ensures that U-GaN layer is completely covered PSS figure；Grow doping SiH more successively4N-GaN layer, multiple quantum well active layer, mix Miscellaneous p-type AlGaN barrier layer, doped p type GaN layer, finally anneal under nitrogen atmosphere.
But, although the nuclearing centre of artificial manufacture at present decreases the generation of dislocation to a certain extent, in PSS figure Between region still suffer from a large amount of dislocations (as Fig. 1), this is by the huge lattice mismatch between saphire substrate material and GaN material Cause.
Content of the invention：
The present invention proposes a kind of new LED epitaxial growth method, can effectively lift the crystal mass of LED extension.
The solution of the present invention is as follows：
This epitaxial growth method, comprises the following steps：
1) using taper PSS as growth substrate, low-temperature epitaxy first buffer layer；
2) high growth temperature the U-GaN layer, growth thickness should ensure that a U-GaN layer is not completely covered PSS figure, that is, have PSS tip exceeds a U-GaN layer surface；
3) in NH3Carry out high annealing in environment, be then down to low temperature, regrowth second buffer layer；
4) high growth temperature the 2nd U-GaN layer, growth thickness should ensure that the 2nd U-GaN layer is completely covered PSS figure；
5) grow doping SiH successively4N-GaN layer, multiple quantum well active layer, doped p type AlGaN barrier layer, doped p type GaN layer, finally anneals under nitrogen atmosphere.
Alleged " high temperature ", " low temperature " is the technical term with its meaning in this area above.
Based on such scheme, the present invention also makees following optimization further and limits：
First U-GaN thickness degree is 0.5um-2.0um, and second buffer layer thickness is 5nm-40nm, the 2nd U-GaN thickness degree For 1.0um-2.0um.
Step 3) in annealing temperature be 1000 DEG C -1200 DEG C, the time be 1min-10min.
First buffer layer and second buffer layer are AlxGa1-xN, 0≤x≤1.I.e. during X=0, first buffer layer and second Cushion is GaN；During x=1, cushion is AlN；When x is between 0 to 1, cushion is AlGaN.
The LED being obtained using above-mentioned epitaxial growth method, including taper PSS substrate, cushion, U-GaN layer, is mixed The n-GaN layer of miscellaneous SiH4, multiple quantum well active layer, doped p type AlGaN barrier layer and doped p type GaN layer；Compare existing LED structure, it is characterized in that：Described cushion and U-GaN layer be divided on the whole the first buffer layer growing successively, First U-GaN layer, second buffer layer and the 2nd U-GaN layer, the wherein the first U-GaN layer is not completely covered PSS figure, the 2nd U- GaN layer is completely covered PSS figure.
The invention has the advantages that：
1st, grown after U-GaN-1 in NH3In environment, sample is annealed, in high temperature, U-GaN-1 surface interface There is desorption in crystal grain that can be larger, migration Reorganization in surface atom, so that the defect of U-GaN-1 is reduced, surface flattens Whole.
2nd, the U-GaN-1 of thinner thickness remains part PSS figure outside GaN film layer, for follow-up buffer-2 and U- GaN-2 epitaxial growth provides periodic nuclearing centre, improves crystal mass.
3rd, grow buffer-2 layer on U-GaN-1 layer, compared to the buffer-1 layer growing on a sapphire substrate, In GaN material substrate, the buffer-2 layer of growth is provided that there is less defect, less internal stress and less crystal orientation difference Crystal grain.Thus providing preferably basis for the U-GaN-2 of subsequent growth, effectively reducing the defect concentration of crystal, improving crystal Quality.
Brief description：
Fig. 1 causes the schematic diagram of a large amount of dislocations for prior art region between PSS figure.
Fig. 2 is the extension overall structure figure of the LED of the present invention.
Specific embodiment：
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is further described.
The present invention carries out epitaxial growth using taper PSS as growth substrate, grows one layer on a sapphire substrate first Buffer-1, then the non-impurity-doped U-GaN-1 of high growth temperature layer again, makes GaN layer that PSS figure is not completely covered, that is, has PSS tip exceeds U-GaN-1 plane, afterwards in NH3In environment, high annealing is carried out to sample, then be down to low temperature, regrowth Two layers of buffer-2, the undoped high temperature U-GaN-2 of one layer of regrowth afterwards, then one layer of doping SiH of regrowth4N-GaN, Regrowth multiple quantum well active layer afterwards, then grows doped p type AlGaN barrier layer, then grows one layer of doped p type GaN layer. As Fig. 2.
The present invention uses metallo-organic compound chemical gaseous phase deposition (MOCVD) growth technology, using trimethyl gallium
(TMGa), triethyl-gallium (TEGa), and trimethyl indium (TMIn), trimethyl aluminium (TMAl) and ammonia (NH3) silane (SiH4) and two luxuriant magnesium (cp2mg) provide the gallium source required for growth, indium source, silicon source, and nitrogen source, silicon source, magnesium source respectively.
Embodiment one：The concrete growth course of LED extension of the present invention and preferable example of parameters are as follows：
1. the Sapphire Substrate after cleaning is put in MOCVD device, toast 10 minutes at 1100 DEG C.
2. being cooled to 620 DEG C of growth a layer thickness is the low temperature GaN buffer-1 layer of 20nm, generally AlxGa1-xN (0 ＜ x ＜ 1) growth pressure be 500torr.
3. it is warming up to the non-impurity-doped U-GaN-1 layer of one layer of about thickness 1.3um of 1165 DEG C of growths, growth pressure is 200torr.
4. in NH3In environment, it is warming up to 1170 DEG C, anneal 5min, pressure is 200torr.
5. being cooled to 620 DEG C of growth a layer thickness is the low temperature GaN buffer-2 layer of 10nm, and growth pressure is 500torr.
6. it is warming up to the non-impurity-doped U-GaN-2 layer of one layer of about thickness 1.0um of 1165 DEG C of growths again, growth pressure is 200torr.
7. it is warming up to 1170 DEG C, growth a layer thickness for the n-GaN layer of 2.0um doping silane, growth pressure is 200torr.
8. switch carrier gas, nitrogen is changed into from hydrogen, pressure is 200torr, grows multiple quantum well layer.
9. switch carrier gas, hydrogen be changed into from nitrogen, temperature to 1185 DEG C, 150torr, grow one layer of p-type AlGaN layer, thick Degree 20nm, growth pressure is 100torr.
10. 1080 DEG C of temperature, growth thick layer is p-type GaN of 150nm doping Mg, and growth pressure is 100torr.
11. switching gases, are changed into nitrogen from hydrogen, and anneal in 1200 DEG C 20min under nitrogen atmosphere.
This growth course terminates.
Embodiment two (traditional scheme)：
1. the Sapphire Substrate after cleaning is put in MOCVD device, toast 10 minutes at 1100 DEG C.
2. being cooled to 620 DEG C of growth a layer thickness is the low temperature GaN buffer-1 layer of 20nm, and growth pressure is 500torr.
3. it is warming up to the non-impurity-doped U-GaN-2 layer of one layer of about thickness 2.0um of 1165 DEG C of growths again, growth pressure is 200torr.
4. it is warming up to 1170 DEG C, growth a layer thickness for the n-GaN layer of 2.0um doping silane, growth pressure is 200torr.
5. switch carrier gas, nitrogen is changed into from hydrogen, pressure is 200torr, grows multiple quantum well layer.
6. switch carrier gas, hydrogen be changed into from nitrogen, temperature to 1185 DEG C, 150torr, grow one layer of p-type AlGaN layer, thick Degree 20nm, growth pressure is 100torr.
7. 1080 DEG C of temperature, growth thick layer is p-type GaN of 150nm doping Mg, growth pressure position 100torr.
8. switch gas, nitrogen is changed into from hydrogen, anneal in 1200 DEG C 20min under nitrogen atmosphere.
This growth course terminates.
The crystal mass of epitaxial wafer can be characterized by XRD, contrast epitaxial growth method of the present invention (embodiment one) The XRD result of the epitaxial wafer (embodiment two) prepared with conventional epitaxial growth method, wherein 002 testing result is respectively 274 With 350 (numerical value is less, represents crystal mass higher), the present invention is compared with traditional method hence it is evident that improve the crystal matter of LED extension Amount.
Give the design parameter that can reach best-of-breed technology effect in above example, but these concrete numerical values should not regard It is the restriction to the claims in the present invention protection domain.The improved principle of the technology of the present invention, this area skill is elaborated in description Art personnel are it should be realized that the adjustment that under basic scheme, each design parameter is done with appropriateness remains able to substantially realize this Bright purpose.

Claims (6)

1. a kind of epitaxial growth method improving epitaxial crystal quality, comprises the following steps：
1) using taper PSS as growth substrate, low-temperature epitaxy first buffer layer；
2) high growth temperature the U-GaN layer, growth thickness should ensure that a U-GaN layer is not completely covered PSS figure, that is, have PSS Tip exceeds a U-GaN layer surface；
3) in NH3Carry out high annealing, annealing temperature is 1000 DEG C -1200 DEG C, the time is 1min-10min in environment；Then drop To low temperature, regrowth second buffer layer；
4) high growth temperature the 2nd U-GaN layer, growth thickness should ensure that the 2nd U-GaN layer is completely covered PSS figure；
5) grow doping SiH successively4N-GaN layer, multiple quantum well active layer, doped p type AlGaN barrier layer, doped p type GaN Layer, finally anneals under nitrogen atmosphere.
2. according to claim 1 improve epitaxial crystal quality epitaxial growth method it is characterised in that：First U-GaN Thickness degree is 0.5um-2.0um, and second buffer layer thickness is 5nm-40nm, and the 2nd U-GaN thickness degree is 1.0um-2.0um.
3. according to claim 1 improve epitaxial crystal quality epitaxial growth method it is characterised in that：First buffer layer It is AlxGa1-xN with second buffer layer, 0≤x≤1.
4. adopt method as claimed in claim 1 be obtained LED, including taper PSS substrate, cushion, U-GaN layer, Doping SiH4N-GaN layer, multiple quantum well active layer, doped p type AlGaN barrier layer and doped p type GaN layer；Its feature exists In：Described cushion and U-GaN layer be divided on the whole the first buffer layer growing successively, a U-GaN layer, second buffer layer with And the 2nd U-GaN layer, the wherein the first U-GaN layer is not completely covered PSS figure, and the 2nd U-GaN layer is completely covered PSS figure.
5. LED according to claim 4 it is characterised in that：First U-GaN thickness degree is 0.5um-2.0um, the Two buffer layer thicknesses are 5nm-40nm, and the 2nd U-GaN thickness degree is 1.0um-2.0um.
6. LED according to claim 4 it is characterised in that：First buffer layer and second buffer layer all adopt AlxGa1-xN, 0≤x≤1.
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CN104900769B (en) * 2015-04-09 2017-10-17 映瑞光电科技(上海)有限公司 GaN base LED epitaxial structure and preparation method thereof
CN104900774B (en) * 2015-05-07 2017-05-17 西北工业大学明德学院 Transverse epitaxial growth method for double buffer layers for improving brightness of LED (Light Emitting Diode)
CN116207196A (en) * 2023-05-05 2023-06-02 江西兆驰半导体有限公司 LED epitaxial wafer, preparation method thereof and LED chip

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CN103456852A (en) * 2012-05-30 2013-12-18 比亚迪股份有限公司 LED epitaxial wafer and production method thereof
CN103824916A (en) * 2014-03-12 2014-05-28 合肥彩虹蓝光科技有限公司 Growing method of composite nucleating layer for enhancing quality of gallium nitride crystal

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CN101847673A (en) * 2009-03-27 2010-09-29 大连美明外延片科技有限公司 GaN-based LED epitaxial wafer and growing method thereof
CN103456852A (en) * 2012-05-30 2013-12-18 比亚迪股份有限公司 LED epitaxial wafer and production method thereof
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