CN105449051A - Method for preparing homogeneous LED with novel hole expansion layer structure on GaN substrate or GaN/Al2O3 composite substrate by using MOCVD - Google Patents
Method for preparing homogeneous LED with novel hole expansion layer structure on GaN substrate or GaN/Al2O3 composite substrate by using MOCVD Download PDFInfo
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- CN105449051A CN105449051A CN201410421676.8A CN201410421676A CN105449051A CN 105449051 A CN105449051 A CN 105449051A CN 201410421676 A CN201410421676 A CN 201410421676A CN 105449051 A CN105449051 A CN 105449051A
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Abstract
The invention provides a method for preparing a homogeneous LED with a novel hole expansion layer structure on a GaN substrate or a GaN/Al2O3 composite substrate by using MOCVD. The method comprises designing a hole expansion layer in an optimized way between an InGaN/GaN multi-quantum well active layer and a P-GaN layer, wherein the Al component, the In component, and the p-type doped concentration of the hole expansion layer generate a gradient change varying with an increase in a growth thickness or period, the hole expansion layer may be a single-layer p-AlInGaN hole expansion layer with gradually-changed components and doping, a multi-period p-AlInGaN/AlGaN superlattice-structured hole expansion layer with gradually-changed components and doping, a multi-period p-InGaN/GaN/AlGaN superlattice-structured hole expansion layer with gradually-changed components and doping, or a multi-period p-AlInGaN/InGaN/AlGaN superlattice-structured hole expansion layer with gradually-changed components and doping. The method for growing the hole expansion layer in an optimized way improves an LED current expansion effect and effectively increases the luminous efficiency of an homogeneous LED. The method has good application prospect.
Description
Technical field
The present invention relates to field of semiconductor photoelectron technique, a manufacture method for homo-substrate light-emitting diode, particularly relates to a kind of method adopting the preparation of MOCVD (Metal Organic Vapor extension) technology to have the high brightness homogeneity LED of the p-type extension layer (hole extension layer) of new structure.
Background technology
In recent years, the research and development with the III-nitride material of excellent physical chemical property have become one of the swiftest and the most violent industry of current development, and make substantial progress in blue light and white light emitting diode (LEDs), laser diode (LDs), high density data storage, High Electron Mobility Transistor and high-performance sensitive detection parts etc.But, the heteroepitaxy method being core with two one-step growth methods used till today, lattice mismatch between foreign substrate and epitaxial loayer and thermal mismatching cause there is very high defect concentration in material, seriously constrain the further raising of nitride semi-conductor material quality and device performance and the research and development of new device.According to GaN substrate or GaN/Al
2o
3the homo-substrate such as compound substrate realize homoepitaxy, not only can solve nitride epitaxial fault in material density high, be difficult to cleavage, device reliability difference etc. problem, and the novel homogeneity LED that can develop vertical stratification increases substantially device performance, and avoid the relevant international monopoly barrier of existing two one-step growth methods.Therefore, it is generally acknowledged in the world: who first solves the Science and Technology problem of GaN homo-substrate outer Yanzhong key, and realize industrialization production, the strategic high ground of following III nitride semiconductor research and industrialization will be occupied.For the device of GaN base LED, its quantum well, heterostructure effect of carrier confinement and quantum confined Stark effect (QCSE) play important impact by internal quantum efficiency.The injection efficiency of LED is defined as under certain injection condition, is injected in luminous zone the carrier number producing compound and the ratio injecting carrier population in the unit interval.The method improving Carrier Injection Efficiency mainly improves the injection in hole and reduces the leakage of electronics.For this reason, need main optimization hole extension layer, meanwhile, optimize structure and the interface of quantum well, reduce overflow and surface recombination, reduce leak channel.
Summary of the invention
The invention provides a kind of MOCVD technology that adopts at GaN substrate or GaN/Al
2o
3the method of high brightness homogeneity LED prepared by compound substrate.By designing novel LED structure, between InGaN/GaN multi-quantum well active region and p-GaN, the hole extension layer (p-type extension layer) of Optimal Growing Al component, In component and p doping gradient change, to improve the expansion of horizontal direction hole, makes hole evenly be injected with source region.And then realize the object improving homogeneity LED luminous efficiency.
Technical solution of the present invention: the hole extension layer (p-type extension layer) introducing optimization between homogeneity LED active layer and p-GaN.By optimal design p-type extension layer structural parameters (parameter such as doping content as the growth thickness of each layer, Al component, In component, Mg), Optimal Growing hole extension layer: to adulterate the individual layer p-AlInGaN hole extension layer of gradual change as adopted Al component and In component and p; Or Al component and In component and p adulterate the multicycle p-AlInGaN/AlGaN superlattice structure of gradual change or quantum well structure hole extension layer; Or asymmetric Al component and In component and p adulterate the multicycle p-InGaN/GaN/AlGaN superlattice structure of gradual change or quantum well structure hole extension layer; Or the multicycle p-AlInGaN/GaN/AlGaN superlattice structure hole extension layer of asymmetric Al component and In component and p doping gradual change.By the method for hole extension layer described in Optimal Growing (p-type extension layer), improve LED current expansion effect, thus effectively improve homogeneity LED luminous efficiency.The method comprises the following steps:
Step one, by GaN substrate or GaN/Al
2o
3compound substrate puts into Metal Organic Vapor epitaxial reactor, at hydrogen (H
2) under atmosphere, be warming up to 700 DEG C, in reative cell, pass into NH3, protection GaN substrate or GaN/Al
2o
3compound substrate, is warming up to 1050 DEG C, at chamber pressure 100torr-300torr, at H
2under atmosphere, growth 2-4 micron thickness n-GaN layer;
Step 2, at nitrogen (N
2) under atmosphere, at 820 DEG C, the n-In in 5-10 cycle of growth
x1ga
1-x1n/GaN (0<x
1≤ x, 0<x≤0.15) superlattice current extending, wherein in current extending, In component is less than In component in active area; At N
2under atmosphere, at 750 DEG C to 850 DEG C, growth 5-10 cycle In
xga
1-xn/GaN (0<x≤0.15) multiple quantum well active layer; In active layer, at H
2, N
2under mixed atmosphere, at 780 DEG C-850 DEG C, the superlattice hole extension layer that growth Al component, In component and p doping gradient change, the hole extension layer structure of optimization is as follows:
(1) hole extension layer is p-Al
y1in
x1ga
1-y1-x1n (0<y
1≤ 0.15,0<x
1≤ x) single layer structure, thickness in monolayer 15nm-30nm, wherein Al component, In component and p-type doping content with the increase of hole extension layer growth thickness graded.
(2) hole extension layer is multicycle (periodicity is 1 to 10) p-Al
y2in
x2ga
1-x2-y2n/Al
y2ga
1-y2n (0<y
2≤ 0.15,0<x
2≤ x) superlattice structure, wherein Al component, In component and p-type doping content with the increase of hole extension layer growth cycle graded.
(3) hole extension layer is multicycle (periodicity is 1 to 10) p-In
x3ga
1-x3n/GaN/Al
y3ga
1-y3n (0<x
3≤ x, 0<y
3≤ 0.15) superlattice structure, wherein Al component, In component and p-type doping content with the increase of hole extension layer growth cycle graded.
(4) hole extension layer is multicycle (periodicity is 1 to 10) p-Al
y4in
x4ga
1-x4-y4n/Ga
1n/Al
y4ga
1-y4n (0<y
4≤ 0.15,0<x
4≤ x) superlattice structure, wherein Al component, In component and p-type doping content with the increase of hole extension layer growth cycle graded.Then at H
2under atmosphere, at 950 DEG C, growth p-AlGaN electronic barrier layer;
Step 3, at H
2under atmosphere, at 950 DEG C-1040 DEG C, growth p-GaN layer.
Accompanying drawing explanation
Fig. 1 is the sectional elevation view of a kind of high brightness Light-Emitting Diode in the embodiment of the present invention 1;
Fig. 2 is the sectional elevation view of a kind of high brightness Light-Emitting Diode in the embodiment of the present invention 2;
Fig. 3 adopts the high brightness Light-Emitting Diode LED1 of novel hole extension layer in the embodiment of the present invention 1, adopts the high brightness Light-Emitting Diode LED2 of novel hole extension layer in the embodiment of the present invention 2, comparison diagram is composed with the PL (photoluminescence, luminescence generated by light) of the homo-substrate LED 3 without hole extension layer.
Embodiment
The invention provides a kind of method that the MOCVD of employing technology prepares high brightness homogeneity LED.By designing novel LED structure, between InGaN/AlGaN multiple quantum well active layer and p-GaN, grow the hole extension layer (p-type extension layer) of Al component, In component and p doping gradual change, thus improve the expansion of horizontal direction hole, effectively alleviate active area stress.And then realize the object improving homogeneity LED luminous efficiency.
Fig. 1 is that the embodiment of the present invention 1 one kinds adopts MOCVD technology to prepare the sectional elevation view with the high brightness homogeneity LED of novel hole extension layer structure.Fig. 1 comprises GaN substrate (or GaN/Al
2o
3compound substrate) 101; N-GaN layer 102; Multiply periodic n-In
x1ga
1-x1n/GaN (0<x
1≤ x, 0<x≤0.15) superlattice current extending 103; Multiply periodic In
xga
1-xn/GaN (0<x≤0.15) multiple quantum well active layer 104; Multicycle p-In
x3ga
1-x3n/GaN/Al
y3ga
1-y3n (0<x
3≤ x, 0<y
3≤ 0.15) superlattice hole extension layer 105, wherein Al component, In component and p-type doping content with the increase of hole extension layer growth cycle graded; P-AlGaN electronic barrier layer 106; P-GaN layer 107.Fig. 2 is that the embodiment of the present invention 2 one kinds adopts MOCVD technology to prepare the sectional elevation view with the high brightness homogeneity LED of novel hole extension layer structure.Fig. 2 comprises GaN substrate (or GaN/Al
2o
3compound substrate) 201; N-GaN layer 202; Multiply periodic n-In
x1ga
1-x1n/GaN (0<x
1≤ x, 0<x≤0.15) superlattice current extending 203; Multiply periodic In
xga
1-xn/GaN (0<x≤0.15) multiple quantum well active layer 204; Multicycle p-Al
y3in
x3ga
1-x3-y3n/GaN/Al
y3ga
1-y3n (0<y
3≤ 0.15,0<x
3≤ x) superlattice hole extension layer 205, wherein Al component, In component and p-type doping content with the increase of hole extension layer growth cycle graded; P-AlGaN electronic barrier layer 206; P-GaN layer 207.In Fig. 1, Fig. 2, N-shaped current extending (electronic current extension layer) (103,203) and hole extension layer (p-type extension layer) (105,205) In component is less than the In component of InGaN/GaN multiple quantum well active layer (104,204).Described hole extension layer (105,205), also can adopt individual layer p-Al
y1in
x1ga
1-y1-x1n (0<y
1≤ 0.15,0<x
1≤ x) structure, its thickness 15nm-30nm; Or multicycle p-Al
y2in
x2ga
1-x2-y2n/Al
y2ga
1-y2n (wherein 0<y
2≤ 0.15,0<x
2≤ x) superlattice (or quantum well) structure; Or other structure; As long as satisfied wherein Al component, In component and p doping content be the principle of graded with hole extension layer growth thickness or the increase in cycle, then all within the scope of this patent protection.
Embodiment 1
Use Aixtron company, close coupling vertical reative cell MOCVD growing system.Use trimethyl gallium (TMGa) in growth course, trimethyl indium (TMIn), trimethyl aluminium (TMAl) as III source, ammonia (NH
3) as group V source, silane (SiH
4) as N-shaped doped source, two luxuriant magnesium (Cp
2mg) as p-type doped source, first by GaN substrate (or GaN/Al
2o
3compound substrate) 101 put into Metal Organic Vapor epitaxial reactor, at hydrogen (H
2) under atmosphere, be warming up to 700 DEG C, in reative cell, pass into NH
3, protection GaN substrate (or GaN/Al
2o
3compound substrate), be warming up to 1050 DEG C, at chamber pressure 100torr-300torr, at H
2under atmosphere, growth 2-4 micron thickness n-GaN layer 102; At nitrogen (N
2) under atmosphere, under 820 degrees Celsius, grow n-(3nm) In in 5 cycles
0.05ga
0.95n/ (3nm) GaN current extending 103, electron concentration is 10
18cm
-3; Then 10 cycles (3nm) In is grown
0.15ga
0.85n/ (12nm) GaN multiple quantum well active layer 104, on this active layer, grows p-(3nm) In in 10 cycles at 820 DEG C
x3ga
1-x3n/ (3nm) GaN/ (3nm) Al
y3ga
1-y3n superlattice hole extension layer 105, wherein In component x
3with hole extension layer periodicity increase from 0.1 gradient be reduced to 0.01 (by the flow of control TMIn, In component x
3be 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 component y
3with hole extension layer periodicity increase from 0.05 gradient be increased to 0.14 (by the flow of control TMAl, Al component y
3be 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 periodicity
17cm
-3gradient is increased to 10
18cm
-3; Then at N
2under atmosphere, grow 20 nanometer thickness under 950 degrees Celsius, hole concentration is 10
18cm
-3p-Al
0.15ga
0.85n electronic barrier layer 106, finally at H
2under atmosphere, at 950-1040 DEG C, growth thickness is the p-GaN layer 107 of 200 nanometers.
Embodiment 2
Use Aixtron company, close coupling vertical reative cell MOCVD growing system.Use trimethyl gallium (TMGa) in growth course, trimethyl indium (TMIn), trimethyl aluminium (TMAl) as III source, ammonia (NH
3) as group V source, silane (SiH
4) as N-shaped doped source, two luxuriant magnesium (Cp
2mg) as p-type doped source, first by GaN substrate (or GaN/Al
2o
3compound substrate) 201 put into Metal Organic Vapor epitaxial reactor, at hydrogen (H
2) under atmosphere, be warming up to 700 DEG C, in reative cell, pass into NH
3, protection GaN substrate (or GaN/Al
2o
3compound substrate), be warming up to 1050 DEG C, at chamber pressure 100torr-300torr, at H
2under atmosphere, growth 2-4 micron thickness n-GaN layer 202; At nitrogen (N
2) under atmosphere, under 820 degrees Celsius, grow n-(3nm) In in 5 cycles
0.05ga
0.95n/ (3nm) GaN current extending 203, electron concentration is 10
18cm
-3; Then at nitrogen (N
2) under atmosphere, grow 10 cycles (3nm) In at 750 degrees c
0.15ga
0.85n/ (12nm) GaN multiple quantum well active layer 204, on this active layer, grows p-(3nm) Al in 10 cycles at 820 DEG C
y3in
x3ga
1-x3-y3n/ (3nm) GaN/ (3nm) Al
y3ga
1-y3n superlattice hole extension layer 205, wherein In component x
3with hole extension layer periodicity increase from 0.1 gradient be reduced to 0.01 (by the flow of control TMIn, In component x
3be 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 component y
3with hole extension layer periodicity increase from 0.05 gradient be increased to 0.14 (by the flow of control TMAl, Al component y
3be 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 periodicity
17cm
-3gradient is increased to 10
18cm
-3; Then at N
2under atmosphere, grow 20 nanometer thickness under 950 degrees Celsius, hole concentration is 10
18cm
-3p-Al
0.15ga
0.85n electronic barrier layer 206, finally at H
2under atmosphere, at 950-1040 DEG C, growth thickness is the p-GaN layer 207 of 200 nanometers.
In embodiment 2, superlattice structure hole extension layer is except adopting p-Al
y3in
x3ga
1-x3-y3n/GaN/Al
y3ga
1-y3beyond N superlattice structure, other structures can be adopted in patent specification as p-Al
y2in
x2ga
1-x2-y2n/Al
y2ga
1-y2n (0<y
2≤ 0.15,0<x
2≤ x) superlattice structure; P-In
x3ga
1-x3n/GaN/Al
y3ga
1-y3n (0<x
3≤ x, 0<y
3≤ 0.15) superlattice structure; Adopt the hole extension layer of these structures effectively can improve luminous efficiency, reach the effect close with LED chip in embodiment 2.As shown in Figure 3, adopt the high brightness homogeneity LED chip (LED1 and LED2) that the embodiment of the present invention 1 and embodiment 2 technical scheme make, compared with the homo-substrate LED chip (LED3) not having hole extension layer, the photoelectric property that display is excellent, its luminous efficiency significantly improves.
Above-described embodiment is only and technological thought of the present invention and feature is described, it describes comparatively concrete and detailed, its object is only to enable those of ordinary skill in the art understand content of the present invention and implement accordingly, instead of limits the scope of the claims of the present invention with this.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made, as long as the improvement done according to thinking of the present invention and mutation, be all encompassed in the scope of the claims of the present invention.
Claims (5)
1. one kind adopts MOCVD technology at GaN substrate or GaN/Al
2o
3the method of high brightness homogeneity LED prepared by compound substrate, it is characterized in that, between InGaN/GaN multiple quantum well active layer and p-GaN, the hole extension layer (p-type extension layer) of Al component, In component and the p doping gradient change that Optimal Growing is novel, the method comprises the following steps:
Step one, by GaN substrate or GaN/Al
2o
3compound substrate puts into Metal Organic Vapor epitaxial reactor, at hydrogen (H
2) under atmosphere, be warming up to 700 DEG C, in reative cell, pass into NH3, protection GaN substrate or GaN/Al
2o
3compound substrate, is warming up to 1050 DEG C, at chamber pressure 100torr-300torr, at H
2under atmosphere, growth 2-4 micron thickness n-GaN layer;
Step 2, at nitrogen (N
2) under atmosphere, at 820 DEG C, the n-In in 5-10 cycle of growth
x1ga
1-x1n/GaN (0<x
1≤ x, 0<x≤0.15) superlattice current extending, wherein in current extending, In component is less than In component in active area; At N
2under atmosphere, at 750 DEG C to 850 DEG C, growth 5-10 cycle In
xga
1-xn/GaN (0<x≤0.15) multiple quantum well active layer; In active layer, at H
2, N
2under mixed atmosphere, at 780 DEG C-850 DEG C, the superlattice hole extension layer (p-type extension layer) that growth Al component, In component and p doping gradient change; Then at H
2under atmosphere, at 950 DEG C, growth p-AlGaN electronic barrier layer;
Step 3, at H
2under atmosphere, at 950 DEG C-1040 DEG C, growth p-GaN layer.
2. one according to claim 1 adopts MOCVD technology at GaN substrate or GaN/Al
2o
3the method of high brightness homogeneity LED prepared by compound substrate, it is characterized in that: described hole extension layer is p-Al
y1in
x1ga
1-y1-x1n (0<y
1≤ 0.15,0<x
1≤ x) single layer structure, thickness in monolayer 15nm-30nm, wherein Al component, In component and p-type doping content with the increase of hole extension layer growth thickness graded.
3. one according to claim 1 adopts MOCVD technology at GaN substrate or GaN/Al
2o
3the method of high brightness homogeneity LED prepared by compound substrate, it is characterized in that: described hole extension layer is multicycle (periodicity is 1 to 10) p-Al
y2in
x2ga
1-x2-y2n/Al
y2ga
1-y2n (0<y
2≤ 0.15,0<x
2≤ x) superlattice structure, wherein Al component, In component and p-type doping content with the increase of hole extension layer growth cycle graded.
4. one according to claim 1 adopts MOCVD technology at GaN substrate or GaN/Al
2o
3the method of high brightness homogeneity LED prepared by compound substrate, it is characterized in that: described hole extension layer is multicycle (periodicity is 1 to 10) p-In
x3ga
1-x3n/GaN/Al
y3ga
1-y3n (0<x
3≤ x, 0<y
3≤ 0.15) superlattice structure, wherein Al component, In component and p-type doping content with the increase of hole extension layer growth cycle graded.
5. one according to claim 1 adopts MOCVD technology at GaN substrate or GaN/Al
2o
3the method of high brightness homogeneity LED prepared by compound substrate, it is characterized in that: described hole extension layer is multicycle (periodicity is 1 to 10) p-Al
y4in
x4ga
1-x4-y4n/Ga
1n/Al
y4ga
1-y4n (0<y
4≤ 0.15,0<x
4≤ x) superlattice structure, wherein Al component, In component and p-type doping content with the increase of hole extension layer growth cycle graded.
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|---|---|---|---|
| CN201410421676.8A CN105449051B (en) | 2014-08-25 | 2014-08-25 | One kind is using MOCVD technologies in GaN substrate or GaN/Al2O3The method that high brightness homogeneity LED is prepared in compound substrate |
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|---|---|---|---|
| CN201410421676.8A CN105449051B (en) | 2014-08-25 | 2014-08-25 | One kind is using MOCVD technologies in GaN substrate or GaN/Al2O3The method that high brightness homogeneity LED is prepared in compound substrate |
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| 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 |
| CN111341892A (en) * | 2020-03-17 | 2020-06-26 | 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 |
| CN111370545A (en) * | 2020-03-30 | 2020-07-03 | 福建兆元光电有限公司 | Epitaxial structure for improving antistatic performance of LED and preparation method thereof |
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| 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 |
| CN117691019B (en) * | 2024-02-02 | 2024-04-30 | 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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