CN102881790A - LED quantum well structure and growth method - Google Patents
LED quantum well structure and growth method Download PDFInfo
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Abstract
The invention provides a semiconductor light emitting diode quantum well structure which comprises a shallow base layer, a shallow well layer, a quantum base layer and a quantum well layer. The shallow base layer is made of gallium nitride, and the shallow well layer, the quantum base layer and the quantum well layer are all made of indium gallium nitride alloy. The invention further provides a growth method of the semiconductor light emitting diode quantum well structure. The growth method includes alternative growth of the shallow base layer, the shallow well layer, the quantum base layer and the quantum well layer. The invention provides a GaN extension structure comprising a substrate, a GaN buffer layer, an N type GaN layer, a lighting layer multi-quantum well, a P-type GaN layer, a P type Al GaN layer, a P type GaN layer and a P type contact layer, wherein the lighting layer multi-quantum well is of the semiconductor light emitting diode quantum well structure. The semiconductor light emitting diode quantum well structure has the advantages that capture efficiency of electrons or holes of each quantum well layer in an active layer can be effectively improved.
Description
Technical field
The present invention relates to gallium nitride based technical field of material, relate in particular to quantum well structure and the growing method thereof of a kind of LED.
Background technology
Semiconductor light-emitting-diode (LED) is that to utilize the injected electrons hole to carry out radiation recombination at the active area that is sandwiched in n-type doped region and p-type doped region luminous.The electric current injection efficiency is higher, and electron hole radiation recombination probability is larger, and the semiconductor light-emitting-diode luminous efficiency is just higher.
In order to increase electric current injection efficiency and electron hole radiation recombination probability, various structures has been proposed in the prior art.For example, adopt quantum well structure, add electronics or hole blocking layer and adopt electron capture emission layer etc., these structures respectively have its advantage, and its limitation is also respectively arranged.
For quantum well structure, the material that utilizes different band gap in certain space, can increase its radiation recombination probability with electronics or hole confinement greatly.But, in gallium nitrate based blue-green light LED, because there is very strong electric field in polarity effect in quantum well, electronics is separated with the space, hole, cause the radiation recombination probability significantly to reduce.People usually adopt narrower quantum well structure to increase the radiation recombination probability of electron hole, however narrower quantum well structure cause electronics and hole to capture probability lower, cause the led current injection efficiency to reduce.
For adding electronic barrier layer, although can increase the electric current injection efficiency, but as the material of electronic barrier layer generally difficult obtain and quality lower, may reduce electron hole radiation recombination probability, for example the AlGaN electronic barrier layer in the gallium nitrate based blue-green light LED.
The electron capture emission layer that adopts in order to increase the electron capture probability, between N-shaped doped layer and mqw active layer, to insert the lower material of energy bandgaps, to reduce the kinetic energy of electronics, then by potential barrier tunnelling thinner between this layer and the quantum well, increase quantum well to the probability of capturing of electronics.Its shortcoming has two, one, and this layer only has remarkable result to adjacent quantum well, because potential barrier is thicker, tunnelling probability reduces to a plurality of quantum well structures, and the quantum well after leaning on can significantly not increase owing to the existence of this layer the electron capture probability; But the existence of this layer may cause the quantum well layer crystal mass to reduce, and produces the V-type defective, increases leakage current, reduces the radiation recombination probability.
Summary of the invention
The technical problem to be solved in the present invention provides quantum well structure and the growing method thereof of a kind of LED, by novel quantum well structure, effectively increases the electronics of each quantum well layer in the active layer or the capture efficiency in hole.
According to one aspect of the invention, a kind of semiconductor light-emitting-diode quantum well structure is provided, comprising:
Shallow base layer, its material is gallium nitride;
Shallow well layer, its material are that indium nitride is sowed alloy;
Quantum barrier layer, its material are that indium nitride is sowed alloy; With
Quantum well layer, its material are that indium nitride is sowed alloy.
Optionally, the four-layer structure of described shallow base layer, shallow well layer, quantum barrier layer and quantum well layer composition arranged sequentially have a plurality of.
Optionally, described tactic four-layer structure is 1-12.
Optionally, the component of shallow well layer and thickness are arranged so that the energy level of the electronics in the shallow well layer and the high excitation level resonance in the quantum well layer.
Optionally, shallow barrier layer thickness is 5-25nm, and the thickness of shallow well layer is 1-3nm, and quantum barrier layer thickness is 1-1.5nm, and the thickness of quantum well layer is 1-5nm.
Optionally, in the shallow well layer, the indium component is between 3%-8%; In the quantum barrier layer, doped indium and aluminium, the indium component is controlled at 1%-5%, and al composition is controlled at 1%-5%; In the quantum well layer, the indium component is between 15%-30%.
According to a further aspect of the present invention, provide a kind of growing method of semiconductor light-emitting-diode quantum well structure, comprising:
Adopt the alternating growth of the structure of shallow base layer+shallow well layer+one a quantum barrier layer+quantum well layer, wherein,
The thickness of shallow well layer is between 1-3nm, and the shallow thickness of building layer is at 5-25nm, and growth temperature is between 690-890 ℃, and pressure is between 100-600 Torr, and V/III mol ratio is between 300-5000;
The thickness of quantum well layer is between 1-5nm, and growth temperature is between 720-820 ℃, and pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000;
Quantum barrier layer thickness is between 1-1.5nm, and growth temperature is between 820-920 ℃, and pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000.
Optionally, the growth temperature of shallow well layer is controlled at the scope that is lower than 10 degrees centigrade of quantum barrier layer growth temperatures, thereby reduces stress.
Optionally, doped indium and aluminium in quantum barrier layer, thus reduce polarity effect in the structure, improve crystal mass.
Optionally, in quantum barrier layer, the indium component is controlled at 1%-5%, and al composition is controlled at 1%-5%.
Another aspect according to the present invention provides a kind of GaN epitaxial structure, comprising:
Substrate, GaN resilient coating, N-type GaN layer, luminescent layer Multiple Quantum Well, P type GaN layer, P type AlGaN layer, P type GaN layer and P type contact layer;
Wherein, the luminescent layer Multiple Quantum Well is described semiconductor light-emitting-diode quantum well structure.
Optionally, described GaN resilient coating comprises two-layer, is respectively low temperature GaN resilient coating and high temperature GaN resilient coating.
Optionally, the four-layer structure of described shallow base layer, shallow well layer, quantum barrier layer and quantum well layer composition arranged sequentially have a plurality of.
Optionally, described tactic four-layer structure is 3-12.
Another aspect according to the present invention provides a kind of growing method of GaN epitaxial structure, comprising:
Substrate is annealed in hydrogen atmosphere, clean described substrate surface, temperature is controlled between 1030-1200 ℃, then carries out nitrogen treatment;
With drop in temperature between 500-650 ℃, the thick low temperature GaN resilient coating of growth 20-30 nm, in this growth course, growth pressure is controlled between the 300-760 Torr, V/III mol ratio is between 500-3200;
Described low temperature GaN buffer growth stops to pass into TMGa after finishing, and substrate 1 temperature is increased between 900-1200 ℃, and low temperature GaN resilient coating original position is carried out thermal anneal process, and annealing time is between 5-30min;
After the annealing, between 1000-1200 ℃, epitaxial growth thickness is the high temperature GaN resilient coating between 0.5-2 μ m with adjustment, and growth pressure is between 100-500 Torr, and V/III mol ratio is between 300-3000;
After described high temperature GaN buffer growth finishes, the stable N-type GaN layer of growth one deck doping content, thickness is at 1.2-4.2 μ m, and growth temperature is between 1000-1200 ℃, and pressure is between 100-600 Torr, and V/III mol ratio is between 300-3000;
The luminescent layer Multiple Quantum Well adopts the alternating growth of the structure of shallow base layer+shallow well layer+one a quantum barrier layer+quantum well layer, wherein, the thickness of shallow well layer is between 1-3nm, the shallow thickness of layer of building is at 5-25nm, growth temperature is between 690-890 ℃, pressure is between 100-600 Torr, and V/III mol ratio is between 300-5000; The thickness of quantum well layer is between 1-5nm, and growth temperature is between 720-820 ℃, and pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000; Quantum barrier layer thickness is between 1-1.5nm, and growth temperature is between 820-920 ℃, and pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000;
After described luminescent layer multiple quantum well layer growth finishes, the P type GaN layer between the growth thickness 10-100nm, growth temperature is between 620-820 ℃, and growth time is between 5-35min, and pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000.In the process of growing P-type layer, N2 is as carrier gas;
After described P type GaN layer finishes, the P type AlGaN layer between the growth thickness 10-50nm, growth temperature is between 900-1100 ℃, growth time is between 5-15min, pressure is between 50-500 Torr, and V/III mol ratio is between 1000-20000, and the component of Al is controlled between the 10%-30%;
After described P type AlGaN layer growth finishes, the P type GaN layer between the growth thickness 100-800nm, growth temperature is between 850-950 ℃, and growth time is between 5-30min, and pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000; With
After described P type GaN layer growth finishes, the P type contact layer between the growth thickness 5-20nm, growth temperature is between 850-1050 ℃, and growth time is between 1-10min, and pressure is between 100-500 Torr, and V/III mol ratio is between 1000-20000.
Optionally, the growing method of described GaN epitaxial structure also comprises:
After above-mentioned each layer epitaxially grown finishes, the temperature of reative cell is down between 650-800 ℃, adopts the pure nitrogen gas atmosphere to carry out annealing in process 2-15min, be down to subsequently room temperature; With
Described epitaxial structure is made single small-size chips through subsequent machining technologies such as cleaning, deposition, photoetching and etchings.
Optionally, as carrier gas, with trimethyl gallium, triethyl-gallium, trimethyl aluminium, trimethyl indium and ammonia be respectively as Ga, Al, In and N source with high-purity hydrogen or nitrogen, with silane and two luxuriant magnesium respectively as n, p-type dopant.
Optionally, the growth temperature of shallow well layer is controlled at the scope that is lower than 10 degrees centigrade of quantum barrier layer growth temperatures, thereby reduces stress.
Optionally, doped indium and aluminium in quantum barrier layer, thus reduce polarity effect in the structure, improve crystal mass.
Optionally, in quantum barrier layer, the indium component is controlled at 1%-5%, and al composition is controlled at 1%-5%.
According to a further aspect of the present invention, provide a kind of epitaxial structure and growth course as described below:
Substrate 1: backing material is annealed in hydrogen atmosphere, the clean substrate surface, temperature is controlled between 1030-1200 ℃, then carries out nitrogen treatment; Substrate 1 is the material that is fit to GaN and semiconductor epitaxial Material growth thereof, such as sapphire, and GaN monocrystalline, monocrystalline silicon, single-crystal silicon carbide etc.;
Low temperature buffer layer 2: with drop in temperature between 500-650 ℃, the thick low temperature GaN resilient coating of growth 20-30 nm, in this growth course, growth pressure is controlled between the 300-760 Torr, V/III mol ratio is between 500-3200;
High temperature buffer layer 3: after low temperature buffer layer 2 growths finish, stop to pass into TMGa, underlayer temperature is increased between 900-1200 ℃, low temperature buffer layer 2 original positions are carried out thermal anneal process, annealing time is between 5-30min; After the annealing, between 1000-1200 ℃, epitaxial growth thickness is high temperature between the 0.5-2um GaN that undopes under lower V/III mol ratio condition, in this growth course with adjustment, growth pressure is between 100-500 Torr, and V/III mol ratio is between 300-3000;
N-type layer 4: after high temperature buffer layer 3 growths finish, the stable N-type layer 4 of growth one deck doping content, thickness is at 1.2-4.2um, and growth temperature is between 1000-1200 ℃, and pressure is between 100-600 Torr, and V/III mol ratio is between 300-3000;
Luminescent layer multi-quantum pit structure SW+MQW(shallow well and quantum well) 5: adopt shallow base+one shallow well+quantum to build the alternating growth of the structure of (mixing In and Al)+quantum well, wherein the thickness of shallow well is between 1-3nm, the thickness at shallow base is at 5-25nm, growth temperature is between 690-890 ℃, pressure is between 100-600 Torr, and V/III mol ratio is between 300-5000; The thickness of quantum well is between 1-5nm, and growth temperature is between 720-820 ℃, and pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000; Quantum barrier layer thickness is between 1-1.5nm, and growth temperature is between 820-920 ℃, and pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000.This kind structure replaces repeated growth.Periodicity suits to be chosen in 3-12 cycle.
P type layer 6: after 5 growths of luminescent layer multiple quantum well layer finish, P type GaN layer between the growth thickness 10-100nm, growth temperature is between 620-820 ℃, and growth time is between 5-35min, pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000.In the process of growing P-type layer, N2 is as carrier gas.
After 6 growth of P type layer 7:P type layer finish, P type AlGaN layer between the growth thickness 10-50nm, growth temperature is between 900-1100 ℃, growth time is between 5-15min, pressure is between 50-500 Torr, V/III mol ratio is between 1000-20000, and the component of Al is controlled between the 10%-30%.
After 7 growth of P type layer 8:P type layer finish, the P type GaN layer between the growth thickness 100-800nm, growth temperature is between 850-950 ℃, and growth time is between 5-30min, and pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000.
After 8 growth of P type layer 9:P type layer finish, the P type contact layer between the growth thickness 5-20nm, growth temperature is between 850-1050 ℃, and growth time is between 1-10min, and pressure is between 100-500 Torr, and V/III mol ratio is between 1000-20000.
Epitaxial growth is down to the temperature of reative cell between 650-800 ℃ after finishing, and adopts the pure nitrogen gas atmosphere to carry out annealing in process 2-15min, is down to subsequently room temperature, finishes epitaxial growth.
Epitaxial wafer is made single small-size chips through subsequent machining technologies such as cleaning, deposition, photoetching and etchings.
Compared with prior art, the invention has the advantages that:
(1) novel quantum well structure adopts shallow base+one shallow well+quantum to build the alternating growth of the structure of (mixing indium In and aluminium Al)+quantum well, and this structure can increase the electronics of each quantum well layer in the active layer or the capture efficiency in hole effectively.
(2) this novel quantum well structure can improve interior quantum combined efficiency, thereby obtains the GaN series LED of high luminous intensity.
(3) can avoid the generation of V-type defective by reasonable control shallow well.
Description of drawings
Fig. 1 is the schematic diagram of the LED epitaxial structure that provides of one embodiment of the invention;
Fig. 2 is the quantum well structure schematic diagram of the LED epitaxial structure among Fig. 1;
Fig. 3 be among Fig. 1 the LED epitaxial structure can be with schematic diagram.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing, the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The inventor finds through research, quantum well structure with blue-green light LED of electron capture emission layer of the prior art, the electron capture emission layer only is positioned at mqw active layer foremost, less to the quantum well layer contribution by the rear end, and because this layer or form or formed by the thinner gallium indium nitride layer of multilayer by the thicker gallium indium nitride layer of individual layer, cause that easily V-type defective produces, increase device creepage, reduce the radiation recombination probability.
According to one embodiment of the invention, the schematic diagram of LED epitaxial structure comprises as shown in Figure 1:
Low temperature GaN(gallium nitride) resilient coating 2,
High temperature GaN resilient coating 3,
N-type GaN layer 4,
Luminescent layer Multiple Quantum Well 5,
P type GaN layer 6,
P type AlGaN(aluminum gallium nitride) layer 7,
P type GaN layer 8, and
P type contact layer 9.
The forming process of this LED epitaxial structure comprises:
With drop in temperature between 500-650 ℃, the thick low temperature GaN resilient coating 2 of growth 20-30 nm, in this growth course, growth pressure is controlled between the 300-760 Torr, V/III mol ratio is between 500-3200;
After described low temperature GaN resilient coating 2 growths finish, stop to pass into the TMGa(trimethyl gallium), substrate 1 temperature is increased between 900-1200 ℃, low temperature GaN resilient coating 2 original positions are carried out thermal anneal process, annealing time is between 5-30min;
After the annealing, between 1000-1200 ℃, epitaxial growth thickness is the high temperature GaN resilient coating 3 between 0.5-2 μ m with adjustment, and growth pressure is between 100-500 Torr, and V/III mol ratio is between 300-3000;
After described high temperature GaN resilient coating 3 growths finish, the stable N-type GaN layer 4 of growth one deck doping content, thickness is at 1.2-4.2 μ m, and growth temperature is between 1000-1200 ℃, and pressure is between 100-600 Torr, and V/III mol ratio is between 300-3000.
With reference to quantum well structure schematic diagram 2 and can be with schematic diagram 3, see that from top to bottom layer 1,2,3 and 4 forms one-periods, can carry out repetition, amount of cycles can select from 1 to 12.
The forming process of this LED epitaxial structure also comprises:
After described luminescent layer multiple quantum well layer 5 growths finish, P type GaN layer 6 between the growth thickness 10-100nm, growth temperature is between 620-820 ℃, and growth time is between 5-35min, pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000.In the process of growing P-type layer, N2 is as carrier gas;
After described P type GaN layer 6 finishes, the P type AlGaN layer 7 between the growth thickness 10-50nm, growth temperature is between 900-1100 ℃, growth time is between 5-15min, pressure is between 50-500 Torr, and V/III mol ratio is between 1000-20000, and the component of Al is controlled between the 10%-30%;
After described P type AlGaN layer 7 growth finish, the P type GaN layer 8 between the growth thickness 100-800nm, growth temperature is between 850-950 ℃, and growth time is between 5-30min, and pressure is between 100-500 Torr, and V/III mol ratio is between 300-5000; With
After described P type GaN layer 8 growth finish, the P type contact layer 9 between the growth thickness 5-20nm, growth temperature is between 850-1050 ℃, and growth time is between 1-10min, and pressure is between 100-500 Torr, and V/III mol ratio is between 1000-20000.
The forming process of this LED epitaxial structure also comprises:
After above-mentioned each layer epitaxially grown finishes, the temperature of reative cell is down between 650-800 ℃, adopts the pure nitrogen gas atmosphere to carry out annealing in process 2-15min, be down to subsequently room temperature;
Epitaxial structure (epitaxial wafer) is made single small-size chips through subsequent machining technologies such as cleaning, deposition, photoetching and etchings.
Above-described embodiment with high-purity hydrogen or nitrogen as carrier gas, with trimethyl gallium (TMGa), triethyl-gallium (TEGa), trimethyl aluminium (TMAl), trimethyl indium (TMIn) and ammonia (NH3) use silane (SiH4) and two luxuriant magnesium (Cp2Mg) respectively as n, p-type dopant respectively as Ga, Al, In and N source.
Above-described embodiment has reduced the stress in the structure by reducing shallow quantum well temperature; By mixing In and Al in the quantum base, reduced the polarity effect in the structure to improve crystal mass; Finally the combining structure with shallow quantum well+quantum well has improved epitaxial wafer brightness.
Still with reference to figure 1, wherein also provide a kind of quantum well structure that increases the semiconductor light-emitting-diode of internal quantum efficiency, comprising:
Original position electron capture emission layer 102 is connected with quantum well layer 104 by having high tunneling barrier layer 103, and layer 101,102,103 and 104 forms one-period and carries out repeated growth, and periodicity can select from 1 to 12; The growth temperature of shallow well is controlled at the scope that is lower than 10 degrees centigrade of quantum base growth temperatures, thereby reduces stress; In quantum is built, mix In and Al, reduce the polarity effect in the structure, improve crystal mass, thereby reach the purpose that improves brightness.
The present invention is by providing the quantum well mechanism of the semiconductor light-emitting-diode that increases internal quantum efficiency, this structure is as active layer, can effectively improve the probability of capturing in electronics or hole, thereby improve gallium nitride blue light-emitting diode internal quantum efficiency, increase its luminous efficiency.
Should be noted that and understand, in the situation that does not break away from the desired the spirit and scope of the present invention of accompanying claim, can make to the present invention of foregoing detailed description various modifications and improvement.Therefore, the scope of claimed technical scheme is not subjected to the restriction of given any specific exemplary teachings.
Claims (7)
1. semiconductor light-emitting-diode quantum well structure comprises:
Shallow base layer, its material is gallium nitride;
Shallow well layer, its material are that indium nitride is sowed alloy;
Quantum barrier layer, its material are that indium nitride is sowed alloy; With
Quantum well layer, its material are that indium nitride is sowed alloy.
2. semiconductor light-emitting-diode quantum well structure as claimed in claim 1, wherein, the four-layer structure of described shallow base layer, shallow well layer, quantum barrier layer and quantum well layer composition is arranged sequentially have a plurality of.
3. semiconductor light-emitting-diode quantum well structure as claimed in claim 2, wherein, described tactic four-layer structure is 1-12.
4. semiconductor light-emitting-diode quantum well structure as claimed in claim 1, wherein, the component of shallow well layer and thickness are arranged so that the energy level of the electronics in the shallow well layer and the high excitation level resonance in the quantum well layer.
5. the growing method of a semiconductor light-emitting-diode quantum well structure as claimed in claim 1 comprises: the alternating growth that adopts the structure of shallow base layer+shallow well layer+one a quantum barrier layer+quantum well layer.
6. the growing method of semiconductor light-emitting-diode quantum well structure as claimed in claim 5 wherein, is controlled at the scope that is lower than 10 degrees centigrade of quantum barrier layer growth temperatures with the growth temperature of shallow well layer, thereby reduces stress.
7. the growing method of semiconductor light-emitting-diode quantum well structure as claimed in claim 5, wherein, doped indium and aluminium in quantum barrier layer, thus polarity effect in the structure reduced, improve crystal mass.
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| CN103746053A (en) * | 2014-01-14 | 2014-04-23 | 圆融光电科技有限公司 | Purple LED (light-emitting diode) preparation method, purple LED and chip |
| CN105895768A (en) * | 2016-06-16 | 2016-08-24 | 厦门乾照光电股份有限公司 | Well-doped light emitting diode |
| CN106057996A (en) * | 2016-06-22 | 2016-10-26 | 华灿光电(苏州）有限公司 | Epitaxial wafer of light-emitting diode and growing method thereof |
| CN106098883A (en) * | 2016-06-27 | 2016-11-09 | 山东浪潮华光光电子股份有限公司 | A kind of quantum well structure, a kind of LED epitaxial structure and growing method thereof |
| CN106756875A (en) * | 2015-12-24 | 2017-05-31 | 中国科学院苏州纳米技术与纳米仿生研究所 | The preparation method of InAlGaN series alloy materials |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103746053A (en) * | 2014-01-14 | 2014-04-23 | 圆融光电科技有限公司 | Purple LED (light-emitting diode) preparation method, purple LED and chip |
| CN103746053B (en) * | 2014-01-14 | 2016-08-17 | 圆融光电科技有限公司 | A kind of purple LED preparation method, purple LED and chip |
| CN106756875A (en) * | 2015-12-24 | 2017-05-31 | 中国科学院苏州纳米技术与纳米仿生研究所 | The preparation method of InAlGaN series alloy materials |
| CN106756875B (en) * | 2015-12-24 | 2020-02-04 | 杭州增益光电科技有限公司 | Preparation method of InAlGaN series alloy material |
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| CN106057996A (en) * | 2016-06-22 | 2016-10-26 | 华灿光电(苏州）有限公司 | Epitaxial wafer of light-emitting diode and growing method thereof |
| CN106098883A (en) * | 2016-06-27 | 2016-11-09 | 山东浪潮华光光电子股份有限公司 | A kind of quantum well structure, a kind of LED epitaxial structure and growing method thereof |
| CN106098883B (en) * | 2016-06-27 | 2018-04-13 | 山东浪潮华光光电子股份有限公司 | A kind of quantum well structure, a kind of LED epitaxial structure and its growing method |
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Application publication date: 20130116 |