CN105449052B - A kind of method that high brightness near ultraviolet LED is prepared using MOCVD technologies - Google Patents
A kind of method that high brightness near ultraviolet LED is prepared using MOCVD technologies Download PDFInfo
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- CN105449052B CN105449052B CN201410421706.5A CN201410421706A CN105449052B CN 105449052 B CN105449052 B CN 105449052B CN 201410421706 A CN201410421706 A CN 201410421706A CN 105449052 B CN105449052 B CN 105449052B
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Abstract
The present invention provides a kind of high efficiency near ultraviolet LED method for being prepared using MOCVD technologies and having asymmetrical current extension layer.By designing new LED structure, improve horizontal direction current expansion, to improve the method for near ultraviolet LED luminous efficiency.Concrete scheme is as follows:Asymmetrical n-type current extending is grown between n GaN and InGaN/AlGaN multi-quantum well active regions.It is as follows to optimize current spread layer construction：(1) asymmetric Al components and In components and the n-type AlInGaN current extendings of n doping gradual changes；(2) asymmetric Al components and In components and the multicycle n-type AlInGaN/AlGaN superlattices or quantum well structure current extending of n doping gradual changes；(3) asymmetric Al components and In components and the multicycle n-type InGaN/AlGaN superlattices or quantum well structure current extending of n doping gradual changes；(4) asymmetric Al components In components and the multicycle n-type AlInGaN/GaN/AlGaN superlattices or quantum well structure of n doping gradual changes；Rotating fields are extended by designing New type of current, effectively improve near ultraviolet LED luminous efficiency.
Description
Technical field
The present invention relates to field of semiconductor photoelectron technique, a kind of preparation method of near ultraviolet light emitting diode, especially relate to
And a kind of prepared using MOCVD (Metal Organic Vapor extension) technology has the highlighted of unsymmetric structure current extending
Spend the method for near ultraviolet LED.
Background technology
Ultraviolet semiconductor light source is not only in industrial photocuring, photocatalyst, ultraviolet photolithographic, ultraviolet-sterilization, Water warfare, phototherapy etc.
Aspect will substitute existing mercury lamp ultraviolet source and play bigger effect, but also will develop general illumination, optical tweezer, plant
Growth, petroleum pipeline leak detection, archaeology application, differentiate true and false etc. purposes.Semiconductor ultraviolet source is shone as semiconductor
Another great industry direction after bright, has caused the extensive concern of semiconductor optoelectronic industry.The nothings such as the U.S., Japan, South Korea
Huge strength is not put into the hope of occupying the commanding elevation of industry.Less input in this respect in China, poor with advanced level in the world
Away from larger.In terms of global semiconductor opto-electronics development trend, the formulation that upstream core technologies are equal to grasp industry rule is controlled
Power and industry right of speech, occupy industrial chain enormous profits space, and first chance is captured in model change.China was in 2003
June starts National Semiconductor illuminating engineering, UV-LED research work as one of them important content.In 15 phases
Between, Peking University once undertook the National 863 problem of near ultraviolet LED, developed 380nm~405nm near ultraviolet LEDs under 350mA
Luminous power reaches 110mW.Ultraviolet LED is further studied during 11th Five-Year, 12, obtains emission wavelength 280nm~315nm
Ultraviolet emission.In addition, the unit such as semiconducter research institute of the Chinese Academy of Sciences, Xiamen University, the outstanding life in Qingdao is also just being directed to ultraviolet LED and ground
Study carefully, 300nm ultraviolet LED luminous power has reached mW magnitudes.Different from blue light, ultraviolet LED is in technology period of expansion at present,
The less-restrictive in terms of patent and intellectual property, beneficial to capture, the technology commanding elevation of the Fashion of Future.The domestic dress in ultraviolet LED
There is certain accumulation in terms of standby, material and device, it is currently positive to develop to application module.Formed greatly in UV-LED
Guiding and supporting to be seized the first opportunity in terms of core technology for country is also needed to before industrial scale.
The matter of utmost importance that ultraviolet LED technology faces is that its light efficiency is low.Wavelength 365nm ultraviolet LED power output is only defeated
Enter the 5%-8% of power.It is significantly improved for more than wavelength 385nm ultraviolet LED electricity conversion relative to short wavelength,
But power output only has the 15% of input power.How to effectively improve the light efficiency of ultraviolet LED turns into everybody focus of attention problem.
The content of the invention
The present invention provides a kind of method that high brightness near ultraviolet light emitting diode is prepared using MOCVD technologies.Pass through design
New LED structure, growth Al components, In components and n mix between n-GaN and InGaN/AlGaN multi-quantum well active regions
The current extending of miscellaneous gradual change, improve horizontal direction current expansion, effectively alleviate active area stress.And then realize and improve near ultraviolet
The purpose of LED luminous efficiencies.
The technical solution of the present invention：By the n-type electricity that optimization is introduced between near ultraviolet LED n-GaN and active layer
Flow extension layer.By optimizing the structure of n-type current extending as using n-AlInGaN, n-AlInGaN/AlGaN superlattices, n-
InGaN/AlGaN superlattices, n-AlInGaN/GaN/AlGaN multilayer superlattice structures, wherein Al components, In components and n-type
Adulterate gradual change.Optimization design current spread layer construction parameter：The growth thickness of each layer, Al components, In components, Si doping concentration
Etc. parameter.This method comprises the following steps：
Step 1, by Al in Metal Organic Vapor epitaxial reactor2O3Substrate in a hydrogen atmosphere, 1080 DEG C-
Handled 5 minutes at 1100 DEG C, then reduce temperature, at 530-550 DEG C, chamber pressure 500torr, in hydrogen (H2) atmosphere
Under, the GaN cushions of three dimensional growth 20-30 nanometer thickness, then 2-4 micron thickness n-GaN layers are grown at 1000-1500 DEG C；
Step 2, in nitrogen (N2) under atmosphere, asymmetric Al components, In components and n doping are grown at 750-850 DEG C
The n-type current extending of gradual change, optimization current spread layer construction are as follows：
(1) asymmetric Al components and In components and the n-type Al of n doping gradual changesy1Inx1Ga1-y1-x1N current extending (its
In 0<y1≤y；0<X1≤x), thickness in monolayer 15nm-30nm；Wherein Al components and In components is with current extending growth thickness
Increase and it is linearly increasing.
(2) asymmetric Al components and In components and the n-type multicycle Al of n doping gradual changesy2Inx2Ga1-x2-y2N/
Aly2Ga1-y2N superlattices (wherein 0<y2≤y；0<X2≤x), superlattice structure periodicity is 1 to 10；Wherein Al components and In
Component increases and staged increase with current extending growth cycle.
(3) asymmetric Al components and In components and the n-type multicycle In of n doping gradual changesx3Ga1-x3N/Aly3Ga1-y3N surpasses
Lattice or quantum well structure (wherein 0<y3≤y；0<X3≤x), superlattice structure periodicity is 1 to 10；Wherein Al components and
In components increase and staged increase with current extending growth cycle.
(4) asymmetric Al components and In components and the n-type multicycle Al of n doping gradual changesy4Inx4Ga1-x4-y4N/GaN/
Aly4Ga1-y4N superlattices or quantum well structure (wherein 0<y4≤y；0<X4≤x), superlattice structure periodicity is 1 to 10；Wherein
Al components and In components increase and staged increase with current extending growth cycle.
Then 5-10 cycles In are grownxGa1-xN/AlyGa1-yN multi-quantum well active regions, wherein 0<x≤0.05；0<y≤
0.05；On the active area, in a nitrogen atmosphere, p-AlGaN electronic barrier layers are grown at 950 degrees Celsius；
Step 3, in a hydrogen atmosphere, grow p-GaN at 950 DEG C -1040 DEG C.
Improve near ultraviolet LED current expansion effect by optimizing n-type current extending, and then effectively improve near ultraviolet LED
Antistatic effect.
Brief description of the drawings
Fig. 1 is a kind of sectional elevation view of high brightness near ultraviolet light emitting diode in the embodiment of the present invention 1；
Fig. 2 is a kind of sectional elevation view of high brightness near ultraviolet light emitting diode in the embodiment of the present invention 2；
Fig. 3 uses New type of current extension layer near ultraviolet light emitting diode UV-LED1 in the embodiment of the present invention 1, using this hair
New type of current extension layer near ultraviolet light emitting diode UV-LED2 and no current extension layer near ultraviolet light-emitting diodes in bright embodiment 2
Pipe UV-LED luminous powers are with Injection Current change curve.
Embodiment
The present invention provides a kind of method that high brightness near ultraviolet LED is prepared using MOCVD technologies.It is new by designing
LED structure, Al components, In components and n doping gradual changes are grown between n-GaN and InGaN/AlGaN multi-quantum well active regions
Current extending, improve horizontal direction current expansion, effectively alleviate active area stress.And then realize and improve near ultraviolet LED hair
The purpose of light efficiency.
Fig. 1 is that the embodiment of the present invention 1 is a kind of prepares highlighting with unsymmetric structure current extending using MOCVD technologies
Spend the sectional elevation view of near ultraviolet LED.Fig. 1 includes Al2O3Substrate 101, n-GaN102, n-AlInGaN current extendings
103, InGaN/AlGaN multiple quantum well active layers 104, p-AlGaN electronic barrier layers 105, p-GaN 106.Wherein n-type electric current expands
Exhibition layer In components, Al components are less than InGaN/AlGaN multi-quantum well active region In components and Al components；Fig. 2 is of the invention real
Apply a kind of vertical throwing face that the high brightness near ultraviolet LED with unsymmetric structure current extending is prepared using MOCVD technologies of example 2
View.Fig. 2 includes Al2O3Substrate 201, n-GaN 202, n-AlInGaN/AlGaN superlattice structures current extending 203,
InGaN/AlGaN multiple quantum well active layers 204, p-AlGaN electronic barrier layers 205, p-GaN 206.Wherein n-type current extending
In components, Al components are less than InGaN/AlGaN multi-quantum well active region In components and Al components；N-type current extending uses
N-AlInGaN, n-AlInGaN/AlGaN superlattices or quantum well structure, n- of Al components, In components and n doping gradual changes
As long as AlInGaN/GaN/AlGaN superlattices or quantum well structure or other structures meet Al components, In components and n doping
The principle of gradual change is all within the scope of this patent protection.
Embodiment 1
Using Aixtron companies, the vertical reative cell MOCVD growing systems of close coupling.Trimethyl gallium is used in growth course
(TMGa), trimethyl indium (TMIn), trimethyl aluminium (TMAl) are used as group III source, ammonia (NH3) it is used as group V source, silane (SiH4)
As n-shaped doped source, two luxuriant magnesium (Cp2Mg p-type doped source) is used as, first by Al in MOCVD reative cells2O3Substrate 101 heats
To 1080-1100 degrees Celsius, in H2Lower processing 5 minutes, is then cooled at 530-550 degrees Celsius in Al2O3On substrate, reaction
Chamber pressure 500torr, under hydrogen (H2) atmosphere, the GaN cushions after three dimensional growth 20-30 nanometers are Celsius in 1000-1500
The lower growth 2-4 micron thickness n-GaN 102 of degree, in nitrogen (N2) under atmosphere, 15-30 nanometer thickness is grown under 750-850 degrees Celsius
N-AlxInyGa1-x-yN current extendings 103, electron concentration increase from 10 with current extending growth thickness17cm-3It is linear to increase
It is added to 1018cm-3, wherein Al components x span is 0<X≤0.05, In component y span are 0<y≤0.05；Connect
Growth 5-10 cycles In0.05Ga0.95N/Al0.05Ga0.95N multiple quantum well active layers 104, on the active layer, in nitrogen (N2)
Under atmosphere, 15-30 nanometer thickness is grown under 950 degrees Celsius, hole concentration is more than 1018cm-3P-Al0.15Ga0.85N electronic blockings
Layer 105, finally in H2Under atmosphere, in the p-GaN 106 that 950-1040 degrees Celsius of lower growth thickness is 100-500 nanometers.
Embodiment 2
Using Aixtron companies, the vertical reative cell MOCVD growing systems of close coupling.Trimethyl gallium is used in growth course
(TMGa), trimethyl indium (TMIn), trimethyl aluminium (TMAl) are used as group III source, ammonia (NH3) it is used as group V source, silane (SiH4)
As n-shaped doped source, two luxuriant magnesium (Cp2Mg p-type doped source) is used as, first by Al in MOCVD reative cells2O3Substrate 201 heats
To 1080-1100 degrees Celsius, in H2Lower processing 5 minutes, is then cooled at 530-550 degrees Celsius in Al2O3On substrate, reaction
Chamber pressure 500torr, hydrogen (H2) under atmosphere, the GaN cushions after three dimensional growth 20-30 nanometers, at 1000-1500 degrees Celsius
Lower growth 2-4 micron thickness n-GaN 202, in nitrogen (N2) under atmosphere, the n- in 10 cycles is grown under 750-850 degrees Celsius
(3nm)AlxInyGa1-x-yN/(3nm)AlxGa1-xN current extendings 203, electron concentration is with current extending number of superlattice cycles
Increase from 1017cm-3Staged increases to 1018cm-3, wherein Al components x span is 0<X≤0.05, In component y's takes
It is 0 to be worth scope<y≤0.05；In components x is respectively with periodicity increase：0.01、0.01、0.02、0.02、0.03、0.03、
0.04、0.04、0.05、0.05；Wherein Al components y is respectively with current extending periodicity increase：0.01、0.01、0.02、
0.02、0.03、0.03、0.04、0.04、0.05、0.05；Then 5-10 cycles In are grown0.05Ga0.95N/Al0.05Ga0.95N volumes
Sub- trap active layer 204, on the active layer, in nitrogen (N2) under atmosphere, 15-30 nanometer thickness, hole are grown under 950 degrees Celsius
Concentration is more than 1018cm-3P-Al0.15Ga0.85N electronic barrier layers 205, finally in H2Under atmosphere, under 950-1040 degrees Celsius
Growth thickness is the p-GaN 206 of 100-500 nanometers.
Superlattice structure current extending 203 is except using n-Al in embodiment 2xInyGa1-x-yN/AlxGa1-xN superlattices
, can be using other structures in patent specification such as beyond structure：N-type multicycle Inx3Ga1-x3N/Aly3Ga1-y3N superlattice structures
(wherein 0<y3≤y；0<x3≤x)；N-type multicycle Aly4Inx4Ga1-x4-y4N/GaN/Aly4Ga1-y4N superlattice structures (wherein 0<
y4≤y；0<x4≤x)；Luminous efficiency can be effectively improved using the current extending of these superlattice structures, reach and implement
Effect similar in LED in example 2.As shown in figure 3, the black light LED chip made using the technical scheme of embodiment 1 in the present invention
(UV-LED1) show excellent photoelectric property, light efficiency as shown in Figure 3 relative to no current extending black light LED core
Piece (UV-LED) improves 50%；The black light LED chip (UV-LED2) made using the technical scheme of embodiment in the present invention 2
The black light LED chip sample made relative to the technical scheme of embodiment 1 improves 20%.
Embodiment described above technological thought only to illustrate the invention and feature, its describe it is more specific and in detail,
Its object is to enable one of ordinary skill in the art to understand present disclosure and implement according to this, therefore can not be only with this
To limit the scope of the claims of the present invention, but therefore it can not be interpreted as limitation of the scope of the invention.It should be pointed out that pair
For one of ordinary skill in the art, without departing from the inventive concept of the premise, some deformations can also be made and changed
Enter, i.e., all changes made according to disclosed spirit, should cover in the scope of the claims of the present invention.
Claims (5)
- A kind of 1. method that high brightness near ultraviolet LED is prepared using MOCVD technologies, it is characterised in that in n-GaN and InGaN/ The n-type electric current that new asymmetric Al components, In components and n doping gradual changes are grown between AlGaN multi-quantum well active regions expands Layer is opened up, this method comprises the following steps：Step 1, by Al in Metal Organic Vapor epitaxial reactor2O3Substrate in a hydrogen atmosphere, 1080 DEG C -1100 Handled 5 minutes at DEG C, then reduce temperature, at 530-550 DEG C, chamber pressure 500torr, in hydrogen（H2）Under atmosphere, three The GaN cushions of dimension growth 20-30 nanometer thickness, then 2-4 micron thickness n-GaN layers are grown at 1000-1500 DEG C；Step 2, in nitrogen（N2）Under atmosphere, asymmetric Al components, In components and n doping gradual changes are grown at 750-850 DEG C N-type current extending, then grow 5-10 cycles InxGa1-xN/AlyGa1-yN multi-quantum well active regions, wherein 0<x≤0.05； 0<y≤0.05；On the active area, in a nitrogen atmosphere, p-AlGaN electronic barrier layers are grown at 950 degrees Celsius；Step 3, in a hydrogen atmosphere, grow p-GaN at 950 DEG C -1040 DEG C.
- 2. a kind of method that high brightness near ultraviolet LED is prepared using MOCVD technologies according to claim 1, its feature are existed In：The n-type current extending adulterates the n-Al of gradual change using asymmetric Al components, In components and ny1Inx1Ga1-y1-x1N is mono- Rotating fields, thickness in monolayer 15nm-30nm；Wherein Al components increase and increased with current extending growth thickness；In components are with electricity Stream extension layer growth thickness increases and increased.
- 3. a kind of method that high brightness near ultraviolet LED is prepared using MOCVD technologies according to claim 1, its feature are existed In：The n-type current extending adulterates the multicycle n- of gradual change using asymmetric Al components, In components and n Aly2Inx2Ga1-x2-y2N/Aly2Ga1-y2N superlattice structures, superlattice structure periodicity are 1 to 10；Wherein Al components expand with electric current Opening up layer growth cycle increases and staged increase；In components increase and staged increase with current extending growth cycle.
- 4. a kind of method that high brightness near ultraviolet LED is prepared using MOCVD technologies according to claim 1, its feature are existed In：The n-type current extending adulterates the multicycle n-In of gradual change using asymmetric Al components, In components and nx3Ga1-x3N/ Aly3Ga1-y3N superlattice structures, superlattice structure periodicity are 1 to 10；Wherein Al components increase with current extending growth cycle Add and staged increase；In components increase and staged increase with current extending growth cycle.
- 5. a kind of method that high brightness near ultraviolet LED is prepared using MOCVD technologies according to claim 1, its feature are existed In：The n-type current extending adulterates the multicycle n- of gradual change using asymmetric Al components, In components and n Aly4Inx4Ga1-x4-y4N/GaN/Aly4Ga1-y4N superlattice structures, superlattice structure periodicity are 1 to 10；Wherein Al components are with electricity Flowing extension layer growth cycle increases and staged increase；In components increase and staged increase with current extending growth cycle.
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| CN106784188B (en) * | 2016-12-23 | 2018-09-25 | 东莞市中镓半导体科技有限公司 | A kind of preparation method of the near ultraviolet LED with composite electron barrier layer |
| CN108470803B (en) * | 2018-03-20 | 2019-11-12 | 华灿光电（浙江）有限公司 | A kind of epitaxial wafer and production method of light emitting diode |
| CN108987544B (en) * | 2018-05-31 | 2020-04-14 | 华灿光电（浙江）有限公司 | Light emitting diode epitaxial wafer and manufacturing method thereof |
| CN109360878B (en) * | 2018-08-27 | 2020-04-14 | 华灿光电（浙江）有限公司 | Epitaxial wafer of light emitting diode and preparation method thereof |
| CN109346583B (en) * | 2018-08-31 | 2021-04-27 | 华灿光电（浙江）有限公司 | Light emitting diode epitaxial wafer and preparation method thereof |
| CN110112269B (en) * | 2019-03-29 | 2020-10-16 | 华灿光电股份有限公司 | Light emitting diode epitaxial wafer and preparation method thereof |
| CN111146318A (en) * | 2020-01-20 | 2020-05-12 | 江苏晶曌半导体有限公司 | Based on MoS2Thin layer ultraviolet light-emitting diode and manufacturing method thereof |
| CN114335278B (en) * | 2022-03-16 | 2022-08-05 | 至芯半导体(杭州)有限公司 | Epitaxial structure of UVB chip and application thereof |
| CN117855352B (en) * | 2024-03-04 | 2024-05-14 | 山西中科潞安紫外光电科技有限公司 | LED epitaxial structure based on gradual change superlattice strain control and preparation method |
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