CN105449051B - One kind is using MOCVD technologies in GaN substrate or GaN/Al2O3The method that high brightness homogeneity LED is prepared in compound substrate - Google Patents
One kind is using MOCVD technologies in GaN substrate or GaN/Al2O3The method that high brightness homogeneity LED is prepared in compound substrate Download PDFInfo
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Abstract
Invention provides one kind using MOCVD technologies in GaN substrate or GaN/Al2O3The method that the homogeneity LED with new hole extension layer structure is prepared in compound substrate.Concrete scheme:Between InGaN/GaN multiple quantum well active layers and p GaN layers, optimization design wherein Al components, In components and p-type doping concentration the hole extension layer of graded with growth thickness or cycle increase：Such as component and the individual layer p AlInGaN holes extension layer of doping gradual change；Or multicycle component and doping gradual change p AlInGaN/AlGaN superlattice structures hole extension layer；Or multicycle component and doping gradual change p InGaN/GaN/AlGaN superlattice structures hole extension layer；Or multicycle component and doping gradual change p AlInGaN/InGaN/AlGaN superlattice structures hole extension layer；By the method for hole extension layer described in Optimal Growing, improve LED current extension effect, effectively improve homogeneity LED luminous efficiencies.The present invention has an optimistic view of its application prospect.
Description
Technical field
The present invention relates to field of semiconductor photoelectron technique, a kind of preparation method of homo-substrate light emitting diode, especially
It is related to a kind of p-type extension layer (sky for being prepared using MOCVD (Metal Organic Vapor extension) technology and there is new structure
Cave extension layer) high brightness homogeneity LED method.
Background technology
In recent years, the research and development of the III-nitride material with excellent physical chemical property have turned into current hair
One of most swift and violent industry of exhibition, and in blue light and white light emitting diode (LEDs), laser diode (LDs), high density information
Storage, HEMT and high-performance sensitive detection parts etc. have made substantial progress.However, use till today
Heteroepitaxy method using two one-step growth methods as core, lattice mismatch and thermal mismatching between foreign substrate and epitaxial layer cause material
The defects of very high density in material be present, seriously constrain nitride semi-conductor material quality and device performance further raising and
The research and development of new device.According to GaN substrates or GaN/Al2O3The homo-substrates such as compound substrate realize homoepitaxy, not only may be used
To solve the problems such as nitride epitaxial fault in material density is high, is difficult to cleavage, device reliability difference, and vertical junction can be developed
The new homogeneity LED of structure increases substantially device performance, and avoids the related international monopoly barrier of existing two one-step growths method.Cause
This, is generally acknowledged that in the world：Who first solves the problems, such as the crucial Science and Technology in the outer Yanzhong of GaN homo-substrates, and realizes industrialization
Production, it will occupy the strategic high ground of following III nitride semiconductor research and industrialization.For GaN base LED device
For, its SQW, heterojunction structure effect of carrier confinement and quantum confined stark effect (QCSE) imitate internal quantum
Rate plays important influence.LED injection efficiency is defined as under certain injection condition, is injected into the unit interval in luminous zone
Compound carrier number is produced with injecting the ratio between carrier population.The method for improving Carrier Injection Efficiency mainly improves hole
Injection and reduce electronics leakage.Therefore, need to mainly optimize hole extension layer, meanwhile, optimize structure and the interface of SQW,
Overflow and surface recombination are reduced, reduces leak channel.
The content of the invention
The present invention provides one kind using MOCVD technologies in GaN substrate or GaN/Al2O3It is same that high brightness is prepared in compound substrate
Matter LED method.By designing new LED structure, between InGaN/GaN multi-quantum well active regions and p-GaN, optimization life
The hole extension layer (p types extension layer) of long Al components, In components and the change of p doping gradients, to improve the expansion of horizontal direction hole
Exhibition, makes hole be uniformly injected into active area.And then realize the purpose for improving homogeneity LED luminous efficiencies.
The technical solution of the present invention：Hole extension layer (the p of optimization is introduced between homogeneity LED active layers and p-GaN
Type extension layer).By optimization design p-type extension layer structural parameters (the growth thickness, Al components, In components, Mg such as each layer
The parameters such as doping concentration), Optimal Growing hole extension layer：Such as using Al components and In components and the individual layer p- of p doping gradual changes
AlInGaN holes extension layer；Or Al components and In components and the multicycle p-AlInGaN/AlGaN superlattices of p doping gradual changes
Structure or quantum well structure hole extension layer；Or asymmetric Al components and In components and the multicycle p- of p doping gradual changes
InGaN/GaN/AlGaN superlattice structures or quantum well structure hole extension layer；Or asymmetric Al components and In components and p
Adulterate the multicycle p-AlInGaN/GaN/AlGaN superlattice structure hole extension layer of gradual change.Pass through hole described in Optimal Growing
The method of extension layer (p-type extension layer), improve LED current extension effect, so as to effectively improve homogeneity LED luminous efficiencies.The party
Method comprises the following steps：
Step 1, by GaN substrate or GaN/Al2O3Compound substrate is put into Metal Organic Vapor epitaxial reactor,
In hydrogen (H2) under atmosphere, 700 DEG C are warming up to, NH3 is passed through into reative cell, protects GaN substrate or GaN/Al2O3Compound substrate,
1050 DEG C are warming up to, in chamber pressure 100torr-300torr, in H2Under atmosphere, 2-4 micron thickness n-GaN layers are grown；
Step 2, in nitrogen (N2) under atmosphere, at 820 DEG C, grow the n-In in 5-10 cyclex1Ga1-x1N/GaN(0<x1
≤ x, 0<X≤0.15) superlattices current extending, In components are less than In components in active area wherein in current extending,；
N2Under atmosphere, at 750 DEG C to 850 DEG C, 5-10 cycles In are grownxGa1-xN/GaN(0<X≤0.15) multiple quantum well active layer；
Active layer, in H2、N2Under mixed atmosphere, at 780 DEG C -850 DEG C, growth Al components, In components and the change of p doping gradients
Superlattices hole extension layer, optimization hole extension Rotating fields it is as follows：
(1) hole extension layer is p-Aly1Inx1Ga1-y1-x1N(0<y1≤ 0.15,0<x1≤ x) single layer structure, thickness in monolayer
The gradient change with the increase of hole extension layer growth thickness of 15nm-30nm, wherein Al components, In components and p-type doping concentration
Change.
(2) hole extension layer is multicycle (periodicity is 1 to 10) p-Aly2Inx2Ga1-x2-y2N/Aly2Ga1-y2N(0<y2≤
0.15,0<x2≤ x) superlattice structure, wherein Al components, In components and p-type doping concentration are with hole extension layer growth cycle
Increase and graded.
(3) hole extension layer is multicycle (periodicity is 1 to 10) p-Inx3Ga1-x3N/GaN/Aly3Ga1-y3N(0<x3≤
X, 0<y3≤ 0.15) superlattice structure, wherein Al components, In components and p-type doping concentration are with hole extension layer growth cycle
Increase and graded.
(4) hole extension layer is multicycle (periodicity is 1 to 10) p-Aly4Inx4Ga1-x4-y4N/Ga1N/Aly4Ga1-y4N
(0<y4≤ 0.15,0<x4≤ x) superlattice structure, wherein Al components, In components and p-type doping concentration are with the life of hole extension layer
It is macrocyclic increase and graded.Then in H2Under atmosphere, at 950 DEG C, p-AlGaN electronic barrier layers are grown；
Step 3, in H2Under atmosphere, at 950 DEG C -1040 DEG C, p-GaN layer is grown.
Brief description of the drawings
Fig. 1 is a kind of sectional elevation view of high brightness Light-Emitting Diode in the embodiment of the present invention 1；
Fig. 2 is a kind of sectional elevation view of high brightness Light-Emitting Diode in the embodiment of the present invention 2；
Fig. 3 is to use the high brightness Light-Emitting Diode LED1 of new hole extension layer in the embodiment of the present invention 1, use
The high brightness Light-Emitting Diode LED2 of new hole extension layer in the embodiment of the present invention 2, with the homogeneity without hole extension layer
Substrate LED LED3 PL (photoluminescence, luminescence generated by light) spectrum comparison diagrams.
Embodiment
The present invention provides a kind of method that high brightness homogeneity LED is prepared using MOCVD technologies.By designing new LED
Structure, between InGaN/AlGaN multiple quantum well active layers and p-GaN, growth Al components, In components and p adulterate gradual change
Hole extension layer (p-type extension layer), so as to improve the extension of horizontal direction hole, effectively alleviate active area stress.And then realize and carry
The purpose of high homogeneity LED luminous efficiencies.
Fig. 1 is that the embodiment of the present invention 1 is a kind of prepares the high brightness with new hole extension layer structure using MOCVD technologies
Homogeneity LED sectional elevation view.Fig. 1 includes GaN substrate (or GaN/Al2O3Compound substrate) 101；N-GaN layers 102；It is more
The n-In in cyclex1Ga1-x1N/GaN(0<x1≤ x, 0<X≤0.15) superlattices current extending 103；The In of multicyclexGa1-xN/
GaN(0<X≤0.15) multiple quantum well active layer 104；Multicycle p-Inx3Ga1-x3N/GaN/Aly3Ga1-y3N(0<x3≤ x, 0<y3≤
0.15) superlattices hole extension layer 105, wherein Al components, In components and p-type doping concentration are with hole extension layer growth cycle
Increase and graded；P-AlGaN electronic barrier layers 106；P-GaN layer 107.Fig. 2, which is that the embodiment of the present invention 2 is a kind of, to be used
MOCVD technologies prepare the sectional elevation view of the high brightness homogeneity LED with new hole extension layer structure.Fig. 2 includes
GaN substrate (or GaN/Al2O3Compound substrate) 201；N-GaN layers 202；The n-In of multicyclex1Ga1-x1N/GaN(0<x1≤ x, 0<
X≤0.15) superlattices current extending 203；The In of multicyclexGa1-xN/GaN(0<X≤0.15) multiple quantum well active layer
204；Multicycle p-Aly3Inx3Ga1-x3-y3N/GaN/Aly3Ga1-y3N(0<y3≤ 0.15,0<x3≤ x) superlattices hole extension layer
205, wherein Al components, In components and p-type doping concentration with the increase of hole extension layer growth cycle graded；p-
AlGaN electronic barrier layers 206；P-GaN layer 207.In Fig. 1, Fig. 2, n-type current extending (electronic current extension layer) (103,
203) and hole extension layer (p-type extension layer) (105,205) In components be less than InGaN/GaN multiple quantum well active layers (104,
204) In components.The hole extension layer (105,205), it can also use individual layer p-Aly1Inx1Ga1-y1-x1N(0<y1≤
0.15,0<x1≤ x) structure, its thickness 15nm-30nm；Or multicycle p-Aly2Inx2Ga1-x2-y2N/Aly2Ga1-y2N (wherein 0<y2
≤ 0.15,0<x2≤ x) superlattices (or SQW) structure；Or other structures；As long as meet wherein Al components, In components and p
Doping concentration principle of graded with hole extension layer growth thickness or the increase in cycle, then all in the model of this patent protection
Within enclosing.
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 GaN substrate (or GaN/Al2O3Compound substrate) 101
It is put into Metal Organic Vapor epitaxial reactor, in hydrogen (H2) under atmosphere, 700 DEG C are warming up to, lead into reative cell
Enter NH3, protection GaN substrates (or GaN/Al2O3Compound substrate), 1050 DEG C are warming up to, in chamber pressure 100torr-
300torr, in H2Under atmosphere, growth 2-4 micron thickness n-GaN layers 102；In nitrogen (N2) under atmosphere, grow 5 under 820 degrees Celsius
N- (3nm) In in individual cycle0.05Ga0.95N/ (3nm) GaN current extendings 103, electron concentration 1018cm-3；Then 10 are grown
Cycle (3nm) In0.15Ga0.85N/ (12nm) GaN multiple quantum well active layers 104, on the active layer, 10 are grown at 820 DEG C
P- (3nm) In in cyclex3Ga1-x3N/(3nm)GaN/(3nm)Aly3Ga1-y3N superlattices hole extension layer 105, wherein In components
x3Increase with hole extension layer periodicity from 0.1 gradient and reduce to 0.01 (by controlling TMIn flow, In components x3With the cycle
Counting increase is respectively：0.1、0.09、0.08、0.07、0.06、0.05、0.04、 0.03、0.02、0.01)；Wherein Al components y3
Increase with hole extension layer periodicity from 0.05 gradient and increase to 0.14 (by controlling TMAl flow, Al components y3With the cycle
Counting increase is respectively：0.05、0.06、 0.07、0.08、0.09、0.1、0.11、0.12、0.13、0.14)；Hole concentration is with sky
Cave extension layer periodicity increases from 1017cm-3Gradient increases to 1018cm-3；Then in N2Under atmosphere, grown under 950 degrees Celsius
20 nanometer thickness, hole concentration 1018cm-3P-Al0.15Ga0.85N electronic barrier layers 106, finally in H2Under atmosphere, in 950-
Growth thickness is 200 nanometers of p-GaN layer 107 at 1040 DEG C.
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 GaN substrate (or GaN/Al2O3Compound substrate) 201
It is put into Metal Organic Vapor epitaxial reactor, in hydrogen (H2) under atmosphere, 700 DEG C are warming up to, lead into reative cell
Enter NH3, protection GaN substrates (or GaN/Al2O3Compound substrate), 1050 DEG C are warming up to, in chamber pressure 100torr-
300torr, in H2Under atmosphere, growth 2-4 micron thickness n-GaN layers 202；In nitrogen (N2) under atmosphere, grow 5 under 820 degrees Celsius
N- (3nm) In in individual cycle0.05Ga0.95N/ (3nm) GaN current extendings 203, electron concentration 1018cm-3；Then in nitrogen
(N2) under atmosphere, 10 cycles (3nm) In is grown at 750 degrees c0.15Ga0.85N/ (12nm) GaN multiple quantum well active layers
204, on the active layer, p- (3nm) Al in 10 cycles is grown at 820 DEG Cy3Inx3Ga1-x3-y3N/(3nm)GaN/(3nm)
Aly3Ga1-y3N superlattices hole extension layer 205, wherein In components x3Reduced with the increase of hole extension layer periodicity from 0.1 gradient
To 0.01 (by controlling TMIn flow, In components x3It is respectively with periodicity increase：0.1、0.09、0.08、0.07、0.06、
0.05、0.04、0.03、0.02、0.01)；Wherein Al components y3Increase with hole extension layer periodicity from 0.05 gradient and increase to
0.14 (by controlling TMAl flow, Al components y3It is respectively with periodicity increase： 0.05、0.06、0.07、0.08、0.09、
0.1、0.11、0.12、0.13、0.14)；Hole concentration increases from 10 with hole extension layer periodicity17cm-3Gradient increases to
1018cm-3；Then in N2Under atmosphere, 20 nanometer thickness, hole concentration 10 are grown under 950 degrees Celsius18cm-3P-
Al0.15Ga0.85N electronic barrier layers 206, finally in H2Under atmosphere, growth thickness is 200 nanometers of p-GaN at 950-1040 DEG C
Layer 207.
Superlattice structure hole extension layer is except using p-Al in embodiment 2y3Inx3Ga1-x3-y3N/GaN/Aly3Ga1-y3N
, can be using other structures in patent specification such as beyond superlattice structure：p-Aly2Inx2Ga1-x2-y2N/Aly2Ga1-y2N(0<y2≤
0.15,0<x2≤ x) superlattice structure； p-Inx3Ga1-x3N/GaN/Aly3Ga1-y3N(0<x3≤ x, 0<y3≤ 0.15) superlattices knot
Structure；Luminous efficiency can be effectively improved using the hole extension layer of these structures, reach with LED chip in embodiment 2 similar in
Effect.As shown in figure 3, the high brightness homogeneity LED chip made using Example 1 and Example 2 of the present invention technical scheme
(LED1 and LED2), compared with the homo-substrate LED chip (LED3) of no hole extension layer, excellent photoelectric property is shown,
Its luminous efficiency significantly improves.
Embodiment described above technological thought only to illustrate the invention and feature, its describe it is more specific and in detail,
Its purpose, which is only that, to be enable one of ordinary skill in the art to understand present disclosure and implements accordingly, rather than is limited with this
The scope of the claims of the fixed present invention.It should be pointed out that for the person of ordinary skill of the art, structure of the present invention is not being departed from
On the premise of think of, various modifications and improvements can be made, as long as according to thinking improvements introduced of the present invention and mutation, cover
In the scope of the claims of the present invention.
Claims (5)
1. one kind is using MOCVD technologies in GaN substrate or GaN/Al2O3The method that high brightness homogeneity LED is prepared in compound substrate,
Characterized in that, between InGaN/GaN multiple quantum well active layers and p-GaN, the new Al components of Optimal Growing, In components with
And the hole extension layer of p doping gradients change, this method comprise the following steps：
Step 1, by GaN substrate or GaN/Al2O3Compound substrate is put into Metal Organic Vapor epitaxial reactor, in hydrogen
Gas（H2）Under atmosphere, 700 DEG C are warming up to, NH3 is passed through into reative cell, protects GaN substrate or GaN/Al2O3Compound substrate, heating
To 1050 DEG C, in chamber pressure 100torr-300torr, in H2Under atmosphere, 2-4 micron thickness n-GaN layers are grown；
Step 2, in nitrogen（N2）Under atmosphere, at 820 DEG C, the n-In in 5-10 cycle is grownx1Ga1-x1N/GaN superlattices electric currents
In components are less than In components in active area in extension layer, wherein current extending；In N2It is raw at 750 DEG C to 850 DEG C under atmosphere
Long 5-10 cycles InxGa1-xN/GaN multiple quantum well active layers；In active layer, in H2 、N2Under mixed atmosphere, 780 DEG C-
850 DEG C, the superlattices hole extension layer of growth Al components, In components and the change of p doping gradients；Then in H2Under atmosphere,
950 DEG C, grow p-AlGaN electronic barrier layers；
Step 3, in H2Under atmosphere, at 950 DEG C -1040 DEG C, p-GaN layer is grown.
2. one kind according to claim 1 is using MOCVD technologies in GaN substrate or GaN/Al2O3Prepared in compound substrate high
Brightness homogeneity LED method, it is characterised in that：The hole extension layer is p-Aly1Inx1Ga1-y1-x1N single layer structures, single monolayer thick
Degree 15nm-30nm, wherein Al components, In components and p-type the doping concentration gradient with the increase of hole extension layer growth thickness
Change.
3. one kind according to claim 1 is using MOCVD technologies in GaN substrate or GaN/Al2O3Prepared in compound substrate high
Brightness homogeneity LED method, it is characterised in that：The hole extension layer is multicycle p-Aly2Inx2Ga1-x2-y2N/Aly2Ga1-y2N
The gradient change with the increase of hole extension layer growth cycle of superlattice structure, wherein Al components, In components and p-type doping concentration
Change.
4. one kind according to claim 1 is using MOCVD technologies in GaN substrate or GaN/Al2O3Prepared in compound substrate high
Brightness homogeneity LED method, it is characterised in that：The hole extension layer is multicycle p-Inx3Ga1-x3N/GaN/Aly3Ga1-y3N
The gradient change with the increase of hole extension layer growth cycle of superlattice structure, wherein Al components, In components and p-type doping concentration
Change.
5. one kind according to claim 1 is using MOCVD technologies in GaN substrate or GaN/Al2O3Prepared in compound substrate high
Brightness homogeneity LED method, it is characterised in that：The hole extension layer is multicycle p-Aly4Inx4Ga1-x4-y4N/Ga1N/
Aly4Ga1-y4N superlattice structures, wherein Al components, In components and p-type doping concentration with hole extension layer growth cycle increasing
Add and graded.
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| CN106784210B (en) * | 2016-11-24 | 2019-03-01 | 华灿光电（浙江）有限公司 | A kind of epitaxial wafer of light emitting diode and preparation method thereof |
| 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 |
| CN107180899B (en) * | 2017-07-21 | 2023-11-14 | 广东工业大学 | Deep ultraviolet LED |
| CN108550676B (en) * | 2018-05-29 | 2020-07-07 | 华灿光电（浙江）有限公司 | Light emitting diode epitaxial wafer and manufacturing method thereof |
| CN110085712B (en) * | 2019-04-30 | 2021-07-30 | 芜湖德豪润达光电科技有限公司 | Light emitting diode and forming method thereof |
| CN111341892B (en) * | 2020-03-17 | 2021-11-02 | 厦门乾照半导体科技有限公司 | LED epitaxial structure, manufacturing method thereof and LED chip |
| CN111370545B (en) * | 2020-03-30 | 2021-04-30 | 福建兆元光电有限公司 | Epitaxial structure for improving antistatic performance of LED and preparation method thereof |
| CN115347097B (en) * | 2022-10-18 | 2023-03-14 | 江西兆驰半导体有限公司 | Light emitting diode epitaxial wafer and preparation method thereof |
| CN117691019A (en) * | 2024-02-02 | 2024-03-12 | 江西兆驰半导体有限公司 | P-type GaN layer light-emitting diode epitaxial wafer and preparation method thereof |
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