CN103066174A - Epitaxial structure and growing method for improving gallium nitride (GaN) based light-emitting diode (LED) lighting efficiency - Google Patents

Epitaxial structure and growing method for improving gallium nitride (GaN) based light-emitting diode (LED) lighting efficiency Download PDF

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CN103066174A
CN103066174A CN201310008822XA CN201310008822A CN103066174A CN 103066174 A CN103066174 A CN 103066174A CN 201310008822X A CN201310008822X A CN 201310008822XA CN 201310008822 A CN201310008822 A CN 201310008822A CN 103066174 A CN103066174 A CN 103066174A
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李刚
郭丽彬
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Hefei Irico Epilight Technology Co Ltd
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Abstract

The invention discloses an epitaxial structure and a growing method for improving gallium nitride (GaN) based light-emitting diode (LED) lighting efficiency. The order of the epitaxial structure from bottom to up is that a substrate, a low-temperature GaN buffer layer, a GaN non-doping layer, a N-shaped GaN layer, a multiple quantum well (MQW) structure, a multiple quantum well active layer, a low-temperature P-shaped GaN layer, a P-shaped aluminum (AL) GaN layer, a high-temperature P-shaped GaN layer and a P-shaped contact layer, wherein the order of the multiple quantum well active layer from bottom to up comprises a InyGa1-yN potential well layer, a InN layer and a barrier layer in sequence. The growing method of the multiple quantum well active layer structure is that by inserting the InN layer and a low-temperature annealing step in the growing process of a InyGa1 potential well layer and a GaN barrier layer, so that the composition of In quantum dot in the barrier layer is advanced and crystalline quality of the quantum well is improved, therefore, gallium nitride based LED lighting efficiency is improved.

Description

A kind of epitaxial structure and growing method that improves GaN base LED luminous efficiency
 
Technical field
The present invention relates to III group nitride material preparing technical field, particularly a kind of novel multiple quantum well active layer structure, epitaxial growth method that can Effective Raise gallium nitride based light emitting diode luminous efficiency.
Background technology
Light-emitting diode (LED, Light Emitting Diode) is a kind of semiconductor solid luminescence device, and it utilizes semiconductor PN as luminescent material, can directly electricity be converted to light.After the two ends of semiconductor PN add forward voltage, inject the minority carrier of PN junction and majority carrier and occur compoundly, emit superfluous energy and cause photo emissions, directly send versicolor light.
III group-III nitride take gallium nitride as representative is the semiconductor material with wide forbidden band of direct band gap, has electronics drift saturated velocity high, and thermal conductivity is good, strong chemical bond, the premium properties such as high temperature resistant and anticorrosive.Its ternary alloy three-partalloy indium gallium nitrogen (InGaN) band gap is adjustable continuously to 3.4eV gallium nitride (GaN) from 0.7eV indium nitride (InN), and emission wavelength has covered the whole zone of visible light and black light.The distinguishing features such as the light-emitting diode take the InGaN/GaN Multiple Quantum Well as active layer has efficiently, environmental protection, energy-conservation, the life-span is long are considered to the most potential a kind of New Solid cold light source that enters the general lighting field.
In the InGaN/GaN multiple quantum well active layer, the local effect of charge carrier is very large on luminous efficiency impact, and this localization is since in the InGaN potential well layer space uneven distribution of In component cause.Be limited in the rich In district of InGaN potential well layer nanoscale quantum-dot structure by the charge carrier that electricity injects or optical excitation produces, charge carrier is played three-dimensional restriction, make charge carrier be difficult to move to non-radiative recombination center, thereby greatly improve the radiation recombination luminous efficiency.Studies show that, mix Si in the GaN barrier layer, can impel the In in the InGaN potential well layer to be condensed into In group, luminous efficiency is strengthened.After but the growth of InGaN potential well layer finishes, often adopt high growth temperature GaN barrier layer, this will cause volatilization and the variation on the potential well layer thickness direction of In, thereby cause the reduction of In quantum dot composition and the expansion of emission wavelength.In addition, the Si atom is diffused into the InGaN potential well layer, also will cause the deterioration of quantum well crystal mass, and so that the luminous efficiency reduction of device.
Given this, be necessary to provide a kind of new multiple quantum well active layer structure and method thereof to overcome above-mentioned shortcoming.
 
Summary of the invention
The present invention is directed to above-mentioned problems of the prior art, a kind of epitaxial structure and growing method of the GaN of raising base LED luminous efficiency are provided, increase a kind of novel multiple quantum well active layer structure and and specific growing method, improve the composition of In quantum dot in the potential well layer, improve the crystal mass of quantum well, to strengthen the luminous efficiency of gallium nitride based LED.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of epitaxial structure that improves GaN base LED luminous efficiency, this epitaxial structure order from bottom to top is followed successively by: substrate, low temperature GaN resilient coating, GaN non-doped layer, N-type GaN layer, multi-quantum pit structure MQW, multiple quantum well active layer, low temperature P type GaN layer, P type AlGaN layer, high temperature P type GaN layer and P type contact layer.
The structure of described multiple quantum well active layer order from bottom to top comprises successively: In yGa 1-yN potential well layer, InN layer, barrier layer.
A kind of growing method that improves the epitaxial structure of above-mentioned GaN base LED luminous efficiency, wherein, the growth of described multiple quantum well active layer was divided into for three steps:
(1) In that grows first yGa 1-yThe N potential well layer, wherein, x＜y＜1, described In yGa 1-yThe molar constituent content of In remains unchanged in the N potential well layer;
(2) In yGa 1-yAfter the growth of N potential well layer finishes, stop to pass into the TEGa(triethyl-gallium), continue to pass into the TMIn(trimethyl indium), under the condition that the technique growth conditions remains unchanged, growth InN layer, thickness is 0.1-0.5nm;
(3) after the InN layer growth finishes, stop to pass into the TMIn(trimethyl indium), under the condition that growth temperature remains unchanged, carry out in-situ annealing 5-40s, and then the growth barrier layer that heats up.
Described growth In yGa 1-yThe growth temperature of N potential well layer is between 720-820 ℃, and pressure is between 100-500Torr, and V/III is than being 300-5000, and thickness is between 2-5nm.
The growth temperature of described growth barrier layer is between 820-920 ℃, and pressure is between 100-500Torr, and V/III is than being 300-5000, and thickness is between 8-15nm.
The present invention is with high-purity hydrogen (H 2) or nitrogen (N 2) as carrier gas, respectively as Ga, Al, In and N source, use silane (SiH4) and two luxuriant magnesium (CP2Mg) respectively as N, P type dopant with trimethyl gallium (TMGa), triethyl-gallium (TEGa), trimethyl aluminium (TMAl), trimethyl indium (TMIn) and ammonia (NH3).
The invention has the advantages that, by in InGaN potential well layer and GaN barrier layer growth course, inserting InN layer and process annealing step, on the one hand, the InN layer can reduce the variation of In composition on the potential well layer thickness direction, improve the roughness at quantum well interface and the broadening effect of emission wavelength, thereby guarantee the stability of device spectrum; On the other hand, the InN layer can the Effective Raise potential well layer in the composition of In quantum dot, simultaneously, the process annealing step can be eliminated stress and the crystal defect in the Multiple Quantum Well, improve the crystal mass of quantum well, thereby improve internal quantum efficiency and the luminous efficiency of gallium nitride based LED.
Description of drawings
Fig. 1 is LED epitaxial structure schematic diagram provided by the present invention;
Fig. 2 is the growth schematic diagram of multiple quantum well active layer among Fig. 1.
Embodiment
The below elaborates to embodiments of the invention: the present embodiment is implemented under take technical solution of the present invention as prerequisite, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
LED epitaxial structure as shown in Figure 1, order from bottom to top comprises successively: substrate 1, low temperature GaN resilient coating 2, GaN non-doped layer 3, N-type GaN layer 4, multi-quantum pit structure MQW5, multiple quantum well active layer 6, low temperature P type GaN layer 7, P type AlGaN layer 8, high temperature P type GaN layer 9, P type contact layer 10.
A kind of growing method that improves the epitaxial structure of above-mentioned gallium nitride based LED luminous efficiency comprises following concrete steps:
Step 1 is carried out high-temperature cleaning with substrate 1 and is processed 5-20min in 1000-1200 ℃ of hydrogen atmosphere, then carry out nitrogen treatment, and substrate 1 is the material that is fit to the growth of GaN base semiconductor epitaxial material, such as sapphire, GaN and carborundum (SiC) monocrystalline etc.;
Step 2, between 500-650 ℃, growth thickness is the low temperature GaN resilient coating 2 of 20-30nm with drop in temperature, and growth pressure is controlled between the 300-760Torr, and V/III is than being 50-1000;
Step 3, after described low temperature GaN resilient coating 2 growths finish, stop to pass into trimethyl gallium (TMGa), underlayer temperature is increased between 900-1200 ℃, and described low temperature GaN resilient coating 2 is carried out the original position thermal anneal process, annealing time is at 5-30min, after the annealing, between 1000-1200 ℃, epitaxial growth thickness is the GaN non-doped layer 3 of 0.5-2 μ m with adjustment, growth pressure is between 100-500Torr, and V/III is than being 100-3000;
Step 4, after described GaN non-doped layer 3 growths finish, the stable N-type GaN layer 4 of growth one deck doping content, thickness is 1.2-4.2 μ m, and growth temperature is between 1000-1200 ℃, and pressure is between 100-600Torr, and V/III is than being 100-3000;
Step 5, after described N-type GaN layer 4 growth finish, growth multi-quantum pit structure MQW5, described multi-quantum pit structure MQW5 is by the In in 2-15 cycle xGa 1-xN/GaN (0＜x＜0.4) Multiple Quantum Well forms, the In in 1 cycle xGa 1-xN/GaN quantum well thickness is between 2-5nm, and growth temperature is 720-920 ℃, and pressure is between 100-600Torr, and V/III is than being 300-5000;
Step 6, after described multi-quantum pit structure MQW5 growth finishes, growth multiple quantum well active layer 6, described multiple quantum well active layer 6 comprise successively overlapping quantum well structure of 3-15, and described quantum well structure is grown successively by potential well layer 6a and barrier layer 6b and formed, the growth of described potential well layer 6a was divided into for three steps, as shown in Figure 2, among the figure, " on " expression reaction raw material pass into the reaction chamber reaction, " off " expression reaction raw material stop to pass into the reaction chamber reaction, and In grows first (1) yGa 1-yN (x＜y＜1) potential well layer 11, growth temperature are between 720-820 ℃, and pressure is between 100-500Torr, and V/III is than being 300-5000, thickness between 2-5nm, described In yGa 1-yThe molar constituent content of In remains unchanged in the N potential well layer; (2) In yGa 1-yAfter the growth of N potential well layer finishes, stop to pass into triethyl-gallium (TEGa) 12, continue to pass into trimethyl indium (TMIn) 13, other technique growth conditions remains unchanged, growth InN layer 14, and thickness is 0.1-0.5nm; (3) after 4 growth of InN layer finish, stop to pass into trimethyl indium (TMIn), carry out in-situ annealing 5-40s under the condition that growth temperature remains unchanged, growth barrier layer 6b then heats up; The growth temperature of described barrier layer 6b is between 820-920 ℃, and pressure is between 100-500Torr, and V/III is than being 300-5000, and thickness is between 8-15nm;
Step 7, after described multiple quantum well active layer 6 growths finished, growth thickness was the low temperature P type GaN layer 7 of 10-100nm, and growth temperature is between 620-820 ℃, and growth time is 5-35min, and pressure is between 100-500Torr, and V/III is than being 300-5000;
Step 8, after described low temperature P type GaN layer 7 growth finish, growth thickness is the P type AlGaN layer 8 of 10-50nm, growth temperature is between 900-1100 ℃, growth time is 5-15min, pressure is between 50-500Torr, and V/III is than being 10-1000, and the molar constituent content of Al is controlled between the 10%-30% in the P type AlGaN layer 8;
Step 9, after described P type AlGaN layer 8 growth finished, growth thickness was the high temperature P type GaN layer 9 of 100-800nm, and growth temperature is between 850-950 ℃, and growth time is 5-30min, and pressure is between 100-500Torr, and V/III is than being 300-5000;
Step 10, after described high temperature P type GaN layer 9 growth finish, the P type contact layer 10 of growth thickness between 5-20nm, growth temperature is between 850-1050 ℃, and growth time is 1-10min, and pressure is between 100-500Torr, and V/III is than being 1000-20000;
Step 11, epitaxial growth is down to the temperature of reative cell between 650-800 ℃ after finishing, and adopts pure nitrogen gas atmosphere to carry out annealing in process 2-15min, then is down to room temperature, namely gets LED epitaxial structure as shown in Figure 1.
Subsequently, make single small-size chips through subsequent machining technologies such as cleaning, deposition, photoetching and etchings.
The present embodiment with high-purity hydrogen (H2) or nitrogen (N2) as carrier gas, respectively as Ga, Al, In and N source, use silane (SiH4) and two luxuriant magnesium (CP2Mg) respectively as N, P type dopant with trimethyl gallium (TMGa), triethyl-gallium (TEGa), trimethyl aluminium (TMAl), trimethyl indium (TMIn) and ammonia (NH3).
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (5)

1. epitaxial structure that improves GaN base LED luminous efficiency, it is characterized in that, this epitaxial structure order from bottom to top is followed successively by: substrate, low temperature GaN resilient coating, GaN non-doped layer, N-type GaN layer, multi-quantum pit structure MQW, multiple quantum well active layer, low temperature P type GaN layer, P type AlGaN layer, high temperature P type GaN layer and P type contact layer.
2. the epitaxial structure of raising GaN base LED luminous efficiency according to claim 1 is characterized in that, the structure of described multiple quantum well active layer order from bottom to top comprises successively: In yGa 1-yN potential well layer, InN layer, barrier layer.
3. the growing method of the epitaxial structure of raising GaN base LED luminous efficiency according to claim 2 is characterized in that, the growth of described multiple quantum well active layer was divided into for three steps:
(1) In that grows first yGa 1-yThe N potential well layer, wherein, x＜y＜1, described In yGa 1-yThe molar constituent content of In remains unchanged in the N potential well layer;
(2) In yGa 1-yAfter the growth of N potential well layer finishes, stop to pass into the TEGa(triethyl-gallium), continue to pass into the TMIn(trimethyl indium), under the condition that the technique growth conditions remains unchanged, growth InN layer, thickness is 0.1-0.5nm;
(3) after the InN layer growth finishes, stop to pass into the TMIn(trimethyl indium), under the condition that growth temperature remains unchanged, carry out in-situ annealing 5-40s, and then the growth barrier layer that heats up.
4. the growing method of the epitaxial structure of raising GaN base LED luminous efficiency according to claim 3 is characterized in that described growth In yGa 1-yThe growth temperature of N potential well layer is between 720-820 ℃, and pressure is between 100-500Torr, and V/III is than being 300-5000, and thickness is between 2-5nm.
5. the growing method of the epitaxial structure of raising according to claim 3 GaN base LED luminous efficiency, it is characterized in that, the growth temperature of described growth barrier layer is between 820-920 ℃, and pressure is between 100-500Torr, V/III is than being 300-5000, and thickness is between 8-15nm.
CN201310008822XA 2013-01-10 2013-01-10 Epitaxial structure and growing method for improving gallium nitride (GaN) based light-emitting diode (LED) lighting efficiency Pending CN103066174A (en)

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Application publication date: 20130424