CN102185056B - Gallium-nitride-based light emitting diode capable of improving electron injection efficiency - Google Patents
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Abstract
The invention discloses a gallium-nitride-based light emitting diode capable of improving electron injection efficiency. The gallium-nitride-based light emitting diode comprises a substrate, a gallium nitride nucleation layer, a buffer layer, an n-type contact layer, a lower multicycle n-type electron coupling layer, a lower tunneling potential barrier layer, an upper multicycle n-type electron coupling layer, an upper tunneling potential barrier layer, a multicycle active luminous layer, a negative electrode, a p-type electron blocking layer, a p-type contact layer and a positive electrode, wherein the gallium nitride nucleation layer is manufactured on the substrate; the buffer layer is manufactured on the gallium nitride nucleation layer; the n-type contact layer is manufactured on the buffer layer; a table top is formed on one side of the upper surface of the n-type contact layer; the lower multicycle n-type electron coupling layer is manufactured on the other side of the table top on the n-type contact layer; the lower tunneling potential barrier layer is manufactured on the lower multicycle n-type electron coupling layer; the upper multicycle n-type electron coupling layer is manufactured on the lower tunneling potential barrier layer; the upper tunneling potential barrier layer is manufactured on the upper multicycle n-type electron coupling layer; the multicycle active luminous layer is manufactured on the upper tunneling potential barrier layer; the negative electrode is manufactured on the table top of the n-type contact layer; the p-type electron blocking layer is manufactured on the multicycle active luminous layer; the p-type contact layer is manufactured on the p-type electron blocking layer; and the positive electrode is manufactured on the p-type contact layer to form the structure of the gallium-nitride-based light emitting diode.
Description
Technical field
The present invention relates to a kind of gallium nitride (GaN) series LED, particularly relate to a kind of GaN series LED of the n type electronics coupled layer by two or more sets different indium components.
Background technology
III-V family photoelectric semiconductor material is described as third generation semi-conducting material at present.And the GaN series LED, owing to can produce the light-emitting diode (abbreviating " LED " as) of various coloured light (blue light or the purple light that especially need high energy gap) through the composition of control material, and become the emphasis of industry research.
With GaN is the main at present MOCVD of the employing technology of epitaxial growth of the semi-conducting material or the device on basis.In the technology of utilizing MOCVD technology growth nitride-based semiconductor (GaN, AlN, InN and their alloy nitride) and since not with the backing material of GaN lattice match, so the employing sapphire carries out heteroepitaxy as substrate usually.Yet, between sapphire and nitride-based semiconductor, have the bigger lattice mismatch (13.8%) and the difference of thermal coefficient of expansion, so growth does not have the high-quality nitride-based semiconductor of be full of cracks, surfacing very difficult.At present the most effectively epitaxial growth method adopt usually two step epitaxial growth methods (referring to H.Amano, N.Sawaki and Y.Toyoda etc., " using the metal organic vapor of the high-quality GaN film of AlN resilient coating to grow "; Appl.Phys.Lett.48; 1986,353), though crystal mass improve to a certain extent; But because there is very big stress in the lattice mismatch between sapphire and the nitride in the epitaxial loayer.Simultaneously, exist bigger thermal mismatching in the active luminescent layer between indium gallium nitrogen and the gallium nitride too, promptly when temperature changes, also can produce certain strain in the active layer.Because the III group-III nitride has the compressive strain characteristic, these strain meetings produce very big compression in InGaN/GaN MQW active area.Thereby in the MQW active area, form bigger compressive strain electric field (being piezoelectric field effect (piezo-electrical field effect)); And the existence of piezoelectric field effect makes electronics spatially separate with the wave function in hole on the one hand, thereby causes weakening of radiation recombination intensity; Owing to the existence of piezoelectric field, make the n district Fermi level of LED raise, even be higher than p district Fermi level (Appl.Phys.Lett., 94,2009,231123) on the other hand, cause electronics to cross active area from the n district and directly arrive the non-radiation recombination of p district generation.In order to reduce the overshoot of electronics; Early stage method is that the indium gallium nitrogen of the low indium component that growth one deck is thick before active luminescent layer inserts layer as electronics savings layer; But, in research afterwards, this layer indium gallium nitrogen changed into the SQW or the superlattice structure (referring to patent CN1552104A and patent CN101174662A) of indium gallium nitrogen and gallium nitride because the quality of indium gallium nitrogen layer reduces rapidly along with the increase of thickness.These two kinds of structures to reducing the overshoot of electronics, increase the injection efficiency of electronics under the condition that little electric current injects, play a good role.But, along with the increase of injected current density,, causing the further raising of n district Fermi level because extra electric field is consistent with the compressive strain direction of an electric field in the active layer, the overshoot behavior of electronics increases the weight of, and still has a large amount of electronics to cross active layer and directly arrives the p district.
In order to reduce the overshoot behavior of electronics under big electric current injection condition; Improve the injection efficiency of electronics; We add two or more sets multi-quantum pit structures that is made up of the indium gallium nitrogen and the aluminium indium gallium nitrogen of different indium components below the active area active layer, with this as the electronics coupled layer.Indium component in each group quantum well structure is not wait, and the closer to active luminescent layer, the indium component in the indium gallium nitrogen is high more.Along with the increase of indium component, indium gallium nitrogen SQW strengthens the restriction of electronics, and it is inner that more electronics will be bound in the electronics coupled layer, reduces the overshoot of electronics with this.Pass through aluminium indium gallium nitrogen thin layer between the electronics coupled layer as the tunneling barrier layer.Width through regulating indium gallium nitrogen quantum well layer in each electronics coupled layer comes the energy level in the quantum well, and finally reaches electronics between the different coupling layers and the energy level between coupling layer and active luminescent layer resonance; Through regulating the thickness of aluminium indium gallium nitrogen tunneling barrier layer, improve the tunnelling probability of electronics between resonance level.
Summary of the invention
The object of the present invention is to provide a kind of GaN series LED, can increase big electric current injection down to the restriction of electronics, reduce the overshoot of electronics, thereby improve the injection efficiency of electronics, improve the luminous efficiency of light-emitting diode with this through this structural design.
The present invention provides a kind of GaN series LED that improves electron injection efficiency, and it comprises:
One substrate;
One gallium nitride nucleating layer, this gallium nitride nucleating layer is produced on the substrate;
One resilient coating, this resilient coating are produced on the gallium nitride nucleating layer;
One n type contact layer, this n type contact layer is produced on the resilient coating, forms a table top in this side above n type contact layer, and this n type contact layer is made up of n type gallium nitride;
Multicycle n type electronics coupled layer once, this following multicycle n type electronics coupled layer be produced on n type contact layer upper table surface opposite side above;
Tunneling barrier layer once, this time tunneling barrier layer is produced on n of the following multicycle type electronics coupled layer;
One n of last multicycle type electronics coupled layer, multicycle n type electronics coupled layer is produced on down on the tunneling barrier layer on this;
Tunneling barrier layer on one, tunneling barrier layer is produced on the multicycle n type electronics coupled layer on this;
Active luminescent layer of one multicycle, this activity luminescent layer is produced on the tunneling barrier layer;
One negative electrode, this negative electrode are produced on the table top of n type contact layer;
One p type electronic barrier layer, this p type electronic barrier layer are produced on the active luminescent layer of multicycle;
One p type contact layer, this p type contact layer is produced on the p type electronic barrier layer, and this p type contact layer is made up of p type gallium nitride;
One positive electrode, this positive electrode are produced on the p type contact layer, form the structure of GaN series LED.
Description of drawings
For further specifying technology contents of the present invention, the present invention will be described in more detail below in conjunction with accompanying drawing and embodiment, wherein:
Fig. 1 is the GaN series LED according to the n of having type electronics coupled layer of the present invention.
Fig. 2 is existing and according to the PL luminous intensity curve of GaN series LED of the present invention, and wherein the triangle lines are the gallium nitride based LED with n type electronics coupled layer structure of the present invention; Circular lines are the gallium nitride based LED of traditional structure.
Embodiment
See also shown in Figure 1ly, the present invention provides a kind of GaN series LED, and it comprises:
One substrate 11, with (0001) to sapphire (Al
2O
3) be substrate 11, other materials that can be used for substrate 11 comprise that also alumina single crystal, 6H-SiC, 4H-SiC or the lattice constant of R-face or A-face approach the monocrystalline oxide of nitride-based semiconductor.Adopt high-purity N H in the preparation
3Do the N source, high-purity H
2And N
2Mist do carrier gas; Trimethyl gallium or triethyl-gallium are done the Ga source, and trimethyl indium is done the In source, and trimethyl aluminium is done the Al source; N type dopant is a silane, and p type dopant is two luxuriant magnesium.
One gallium nitride nucleating layer 12, this gallium nitride nucleating layer 12 is produced on the substrate 11.Growth parameter(s) comprises: 500 ℃ to 800 ℃ of reaction temperatures, reaction chamber pressure 200 be to 500Torr, carrier gas flux 10-30 liter/minute, trimethyl gallium flow 20-250 micromole/minute, ammonia flow 20-80 moles/min, growth time 1-10 minute;
One resilient coating 13, this resilient coating 13 is produced on the nucleating layer 12.Growth parameter(s) comprises: reaction temperature 950-1180 ℃, reaction chamber pressure 76-250Torr, carrier gas flux 5-20 liter/minute, the trimethyl gallium flow be the 80-400 micromole/minute, ammonia flow is the 200-800 moles/min, growth time 20-60 minute;
One n type contact layer 14, this n type contact layer 14 is produced on the resilient coating 13, and this n type contact layer 14 is made up of n type gallium nitride.Growth parameter(s) comprises: reaction temperature 950-1150 ℃, and reaction chamber pressure 76-250Torr, carrier gas flux 5-20 liter/minute; Trimethyl gallium flow 80-400 micromole/minute; Ammonia flow 200-800 moles/min, silane flow rate 0.2-2.0 nanomole/minute, growth time 10-40 minute;
Once multicycle n type electronics coupled layer 15, this following multicycle n type electronics coupled layer 15 be produced on n type contact layer 14 upper table surfaces 141 opposite sides above.Said electronics coupled layer of following multicycle 15 is to be made up of the multiply periodic quantum well structure that indium gallium nitrogen (InGaN) thin layer 151 and aluminium indium gallium nitrogen (AlInGaN) thin layer 152 interaction cascadings form.Growth parameter(s) comprises: AlInGaN thin layer (promptly building layer 152): reaction temperature 700-900 ℃, and reaction chamber pressure 100-500Torr, carrier gas flux 5-20 liter/minute; Ammonia flow 200-800 moles/min; Trimethyl indium flow 10-50 micromole/minute, trimethyl gallium flow 0.1-1.0 micromole/minute, trimethyl aluminium flow 20-100 micromole/minute; Silane flow rate 0-2.0 nanomole/minute, time 0.1-5 minute; InGaN thin layer (being trap layer 151): reaction temperature 700-850 ℃; Reaction chamber pressure 100-500Torr; Carrier gas flux 5-20 liter/minute, ammonia flow 200-800 moles/min, trimethyl gallium flow 0.1-1.0 micromole/minute; Trimethyl indium flow 10-50 micromole/minute, time 0.1-5 minute; The structural cycle number is 3 to 20;
Once the tunneling barrier layer 16, and this time tunneling barrier layer 16 is produced on n of the following multicycle type electronics coupled layer 15, is made up of aluminium indium gallium nitrogen (AlInGaN) thin layer.Contact-making surface is the indium gallium nitrogen thin layer 151 of n of following multicycle type electronics coupled layer 15 under it.Growth parameter(s) comprises: reaction temperature 700-900 ℃, and reaction chamber pressure 100-500Torr, carrier gas flux 5-20 liter/minute; Ammonia flow 200-800 moles/min; Trimethyl indium flow 10-50 micromole/minute, trimethyl gallium flow 0.1-1.0 micromole/minute, trimethyl aluminium flow 20-100 micromole/minute; Silane flow rate 0-2.0 nanomole/minute, time 0.1-5 minute;
One n of last multicycle type electronics coupled layer 17; Should be produced on down on the tunneling barrier layer 16 by n of last multicycle type electronics coupled layer 17, said n of last multicycle type electronics coupled layer 17 is to be made up of the multiply periodic quantum well structure that indium gallium nitrogen (InGaN) thin layer 171 and aluminium indium gallium nitrogen (AlInGaN) thin layer 172 interaction cascadings form.Growth parameter(s) comprises: AlInGaN thin layer (promptly building layer 172): reaction temperature 700-900 ℃, and reaction chamber pressure 100-500Torr, carrier gas flux 5-20 liter/minute; Ammonia flow 200-800 moles/min; Trimethyl indium flow 10-50 micromole/minute, trimethyl gallium flow 0.1-1.0 micromole/minute, trimethyl aluminium flow 20-100 micromole/minute; Silane flow rate 0-2.0 nanomole/minute, time 0.1-5 minute; InGaN thin layer (being trap layer 171): reaction temperature 700-850 ℃; Reaction chamber pressure 100-500Torr; Carrier gas flux 5-20 liter/minute, ammonia flow 200-800 moles/min, trimethyl gallium flow 0.1-1.0 micromole/minute; Trimethyl indium flow 10-50 micromole/minute, time 0.1-5 minute; The structural cycle number is 3 to 20;
One active luminescent layer 19, this activity luminescent layer 19 is produced on the tunneling barrier layer 18, and said active luminescent layer 19 is to be made up of the multiply periodic quantum well structure that indium gallium nitrogen (InGaN) thin layer 191 and aluminium indium gallium nitrogen (AlInGaN) thin layer 192 interaction cascadings form.Growth parameter(s) comprises: AlInGaN thin layer (promptly building layer 192): reaction temperature 700-900 ℃, and reaction chamber pressure 100-500Torr, carrier gas flux 5-20 liter/minute; Ammonia flow 200-800 moles/min; Trimethyl indium flow 10-50 micromole/minute, trimethyl gallium flow 0.1-1.0 micromole/minute, trimethyl aluminium flow 20-100 micromole/minute; Silane flow rate 0-2.0 nanomole/minute, time 0.1-5 minute; InGaN thin layer (being trap layer 191): reaction temperature 700-850 ℃; Reaction chamber pressure 100-500Torr; Carrier gas flux 5-20 liter/minute, ammonia flow 200-800 moles/min, trimethyl gallium flow 0.1-1.0 micromole/minute; Trimethyl indium flow 10-50 micromole/minute, time 0.1-5 minute; The MQW periodicity is 4 to 15;
The growth temperature of indium gallium nitrogen thin layer 151 is preferably 600-900 ℃ in n of the following multicycle type electronics coupled layer 15 among the present invention; Be lower than the growth temperature of indium gallium nitrogen thin layer 171 in n of the last multicycle type electronics coupled layer 17, and the growth temperature of this two-layer indium gallium nitrogen thin layer 151,171 all is lower than the growth temperature of indium gallium nitrogen thin layer 191 in the active luminescent layer 19.
The indium component of indium gallium nitrogen thin layer should be in 0＜x＜0.3 in the n type electronics coupled layer among the present invention.And by the indium gallium nitrogen thin layer 191 in the active luminescent layer 19 again of indium gallium nitrogen thin layer 171 in indium gallium nitrogen 151 to last multicycle of the thin layer n type electronics coupled layer 17 in n of the following multicycle type electronics coupled layer 15, its indium component increases gradually.
The thickness of the aluminium indium gallium nitrogen tunneling barrier layer 16/18 among the present invention is preferably the 2-20 nanometer.
The present invention has many group n type electronics coupled layers 15/17 through growth below active luminescent layer 19, obtained the GaN series LED that luminous intensity obtains bigger raising.Main cause is as follows:
The many groups of growth electronics coupled layer 15,17 below active luminescent layer 19; And the indium component of indium gallium nitrogen thin layer is by the indium gallium nitrogen thin layer 191 in the active luminescent layer 19 again of indium gallium nitrogen thin layer 171 in indium gallium nitrogen 151 to last multicycle of the thin layer n type electronics coupled layer 17 in n of the following multicycle type electronics coupled layer 15 in the electronics coupled layer, and its indium component increases gradually.Owing to have higher indium component in the electronics coupled layer, to the constraint ability enhancing of electronics, it is inner that so more electronics will be bound in the electronics coupled layer, reduces the overshoot of electronics under the big electric current injection condition.Indium component and trap through regulating in the indium gallium nitrogen thin layer 151,171 are wide; Realize energy level resonance between n of following multicycle type electronics coupled layer 15 and the last multicycle n type electronics coupled layer 17, and the final energy level resonance that realizes between the indium gallium nitrogen thin layer 191 in n of last multicycle type electronics coupled layer 17 and the active luminescent layer 19; Through regulating the thickness of tunneling barrier layer aluminium indium gallium nitrogen layer 16,18, realize the energy level resonance tunnel-through between n of following multicycle type electronics coupled layer 15 and last multicycle n type electronics coupled layer 17 and the active luminescent layer 19.Thereby reach the purpose that improves the charge carrier injection efficiency.
One negative electrode 22, this negative electrode 22 are produced on the table top 141 of n type contact layer 14, are made up of chromium platinum or titanium aluminium titanium.
One p type electronic barrier layer 20, this p type electronic barrier layer 20 is produced on the active luminescent layer 19, and this p type electronic barrier layer 20 is made up of aluminium indium gallium nitrogen.The thickness of said p type electronic barrier layer 20 is 10-50nm, and the lower surface of said p type electronic barrier layer contacts with aluminium indium gallium nitrogen thin layer 192 in the said active luminescent layer.Growth parameter(s) comprises: reaction temperature 700-1000 ℃, and reaction chamber pressure 50-200Torr, carrier gas flux 5-20 liter/minute; Ammonia flow 100-400 moles/min; Trimethyl indium flow 10-50 micromole/minute, trimethyl aluminium flow 20-100 micromole/minute, trimethyl gallium flow 80-200 micromole/minute; Two luxuriant magnesium flows be the 150-400 nanomole/minute, time 1-10 minute.
Wherein said p type electronic barrier layer 20 is a p type dopant with two luxuriant magnesium, and the doping content of two luxuriant magnesium is 10
19-10
21Cm
-3
One p type contact layer 21, this p type contact layer 21 is produced on the p type electronic barrier layer 20, and this p type contact layer 21 is made up of p type gallium nitride.Growth parameter(s) comprises: reaction temperature 950-1100 ℃, and reaction chamber pressure 200-500Torr, carrier gas flux 5-20 liter/minute; Ammonia flow 200-800 moles/min; Trimethyl gallium flow 80-400 micromole/minute, two luxuriant magnesium flows be the 0.5-5 micromole/minute, time 10-50 minute.
One positive electrode 23, this positive electrode 23 is produced on the p type contact layer 21, is made up of the chromium platinum.Accomplish the making of GaN series LED.
Photoluminescence property for the GaN series LED that do not have n type electronics coupled layer according to GaN series LED and the traditional handicraft of the n of having type electronics coupled layer of the present invention shown in Figure 2 contrasts.Wherein the triangle lines are the gallium nitride based LED with n type electronics coupled layer structure of the present invention; Circular lines are the gallium nitride based LED of traditional structure.By finding out among Fig. 2, compare with the LED of traditional structure, under same injection current condition, the luminous intensity of LED structure of the present invention increases, and explains that the internal quantum efficiency of light-emitting diode has obtained effective raising.
The above; Be merely the embodiment among the present invention, but protection scope of the present invention is not limited thereto, anyly is familiar with this technological people in the technical scope that the present invention disclosed; The conversion that can expect easily or replacement all should be encompassed in of the present invention comprising within the scope.Therefore, protection scope of the present invention should be as the criterion with the protection range of claims.
Claims (8)
1. GaN series LED that improves electron injection efficiency, it comprises:
One substrate;
One gallium nitride nucleating layer, this gallium nitride nucleating layer is produced on the substrate;
One resilient coating, this resilient coating are produced on the gallium nitride nucleating layer;
One n type contact layer, this n type contact layer is produced on the resilient coating, forms a table top in this side above n type contact layer, and this n type contact layer is made up of n type gallium nitride;
Multicycle n type electronics coupled layer once; This following multicycle n type electronics coupled layer be produced on n type contact layer upper table surface opposite side above; This following multicycle in each cycle of n type electronics coupled layer comprises: an indium gallium nitrogen thin layer and the aluminium indium gallium nitrogen thin layer of making above that, and the top of this following multicycle n type electronics coupled layer makes one deck indium gallium nitrogen thin layer again;
Tunneling barrier layer once, this time tunneling barrier layer is produced on n of the following multicycle type electronics coupled layer:
One n of last multicycle type electronics coupled layer, multicycle n type electronics coupled layer is produced on down on the tunneling barrier layer on this;
Tunneling barrier layer on one, tunneling barrier layer is produced on the multicycle n type electronics coupled layer on this;
Active luminescent layer of one multicycle, this activity luminescent layer is produced on the tunneling barrier layer;
One negative electrode, this negative electrode are produced on the table top of n type contact layer;
One p type electronic barrier layer, this p type electronic barrier layer are produced on the active luminescent layer of multicycle;
One p type contact layer, this p type contact layer is produced on the p type electronic barrier layer, and this p type contact layer is made up of p type gallium nitride;
One positive electrode, this positive electrode are produced on the p type contact layer, form the structure of GaN series LED.
2. the GaN series LED of raising electron injection efficiency as claimed in claim 1, each cycle of wherein going up multicycle n type electronics coupled layer comprises:
One indium gallium nitrogen thin layer and the aluminium indium gallium nitrogen thin layer of making above that, the top of multicycle n type electronics coupled layer makes one deck indium gallium nitrogen thin layer again on this.
3. the GaN series LED of raising electron injection efficiency as claimed in claim 1, each cycle of wherein said active luminescent layer comprises:
One indium gallium nitrogen thin layer and the aluminium indium gallium nitrogen thin layer of making above that, the top of this activity luminescent layer makes one deck indium gallium nitrogen thin layer again.
4. the GaN series LED of raising electron injection efficiency as claimed in claim 1, wherein the periodicity of n of following multicycle type electronics coupled layer is 3-20, the thickness of every layer of aluminum indium gallium nitrogen thin layer is 2-20nm; The thickness of each layer indium gallium nitrogen thin layer is 1-4nm.
5. the GaN series LED of raising electron injection efficiency as claimed in claim 2, the periodicity of wherein going up multicycle n type electronics coupled layer is 3-20, the thickness of every layer of aluminum indium gallium nitrogen thin layer is 2-20nm; The thickness of each layer indium gallium nitrogen thin layer is 1-4nm.
6. the GaN series LED of raising electron injection efficiency as claimed in claim 3, wherein the periodicity of active luminescent layer is 4-15, the thickness of every layer of aluminum indium gallium nitrogen thin layer is 4-20nm; The thickness of each layer indium gallium nitrogen thin layer is 1-4nm.
7. according to claim 1 or claim 2 the GaN series LED of raising electron injection efficiency; Wherein the indium component in n of following multicycle type electronics coupled layer and the last multicycle n type electronics coupled layer indium gallium nitrogen thin layer from bottom to up is increase gradually, but can not surpass the indium component in the indium gallium nitrogen thin layer in the said active luminescent layer.
8. the GaN series LED of raising electron injection efficiency as claimed in claim 1, the thickness that wherein descends tunneling barrier layer and last tunneling barrier layer is 2-20nm.
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| CN1921157A (en) * | 2005-08-26 | 2007-02-28 | 中国科学院半导体研究所 | High efficiency deep ultraviolet light-emitting diode |
| CN101174662A (en) * | 2006-10-30 | 2008-05-07 | 璨圆光电股份有限公司 | Multiple quantum well nitride light emitting diode with carrier supplying layer |
| CN101540364A (en) * | 2009-04-23 | 2009-09-23 | 厦门大学 | Nitride luminescent device and production method thereof |
| WO2011007637A1 (en) * | 2009-07-15 | 2011-01-20 | 住友電気工業株式会社 | Nitride-based semiconductor light-emitting element |
| CN101931036A (en) * | 2010-07-21 | 2010-12-29 | 中国科学院半导体研究所 | Gallium nitride luminous diode |
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| US9780255B2 (en) | 2012-11-19 | 2017-10-03 | Genesis Photonics Inc. | Nitride semiconductor structure and semiconductor light emitting device including the same |
| CN103972343A (en) * | 2013-01-25 | 2014-08-06 | 新世纪光电股份有限公司 | Nitride semiconductor structure and semiconductor light-emitting component |
| CN103972343B (en) * | 2013-01-25 | 2017-09-22 | 新世纪光电股份有限公司 | Nitride semiconductor structure and semiconductor light-emitting elements |
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