CN102891229A - Nitride semiconductor material light emitting diode and preparation method thereof - Google Patents
Nitride semiconductor material light emitting diode and preparation method thereof Download PDFInfo
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- CN102891229A CN102891229A CN2012103751446A CN201210375144A CN102891229A CN 102891229 A CN102891229 A CN 102891229A CN 2012103751446 A CN2012103751446 A CN 2012103751446A CN 201210375144 A CN201210375144 A CN 201210375144A CN 102891229 A CN102891229 A CN 102891229A
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Abstract
The invention provides a nitride semiconductor material light emitting diode and a preparation method of the nitride semiconductor material light emitting diode. The nitride semiconductor material light emitting diode comprises a substrate, an n-type contact layer, an active luminous layer and a p-type contact layer, wherein the n-type contact layer is made from nitride semiconductor materials and is formed on the substrate; the active luminous layer is made from nitride semiconductor materials and is formed on the n-type contact layer; the p-type contact layer is made from p-type nitride semiconductor materials and is formed on the active luminous layer; and the active luminous layer is in a multiple periodic quantum well structure made from at least two different nitride semiconductor materials, and at least parts of nitride semiconductor materials of a quantum well layer in the multiple periodic quantum well structure are of p-type dopings. The nitride semiconductor material light emitting diode provided by the invention can improve the distribution of holes of nitride semiconductor materials in an active area.
Description
Technical field
The present invention relates to technical field of semiconductors, relate in particular to a kind of nitride semi-conductor material light-emitting diode and preparation method thereof.
Background technology
III-V family photoelectric semiconductor material is described as third generation semi-conducting material, and the nitride semi-conductor material light-emitting diode is owing to can realize that the spectral emissions from the blue light to ruddiness becomes the emphasis of industry research by the composition of modulation material.
At present, the MOCVD technology is mainly adopted in the epitaxial growth of nitride semi-conductor material or device, but because the backing material of shortage and gallium nitride Lattice Matching, the main sapphire that adopts carries out heteroepitaxy as substrate, yet owing to lattice mismatch larger between sapphire and the nitride material and the difference of thermal coefficient of expansion, the difficult quality guarantee of epitaxial loayer also exists larger stress and thermal mismatching in addition in the epitaxial loayer.
In traditional nitride semi-conductor material light-emitting diode active area, because the effective mass in hole is larger, mobility is low, therefore the hole in the nitride semi-conductor material light-emitting diode mainly is distributed near in several quantum well of p-type nitride semi-conductor material contact layer, distributes very inhomogeneous.In addition, owing to the reasons such as lattice mismatch between quantum well in the active area and the barrier layer can form larger polarized electric field at multiquantum well region, this polarized electric field makes that electronics separates with the wave function in hole in the quantum well, affects radiation recombination efficiency and luminous intensity.
Summary of the invention
The technical problem that (one) will solve
In view of this, the invention provides a kind of nitride semi-conductor material light-emitting diode and preparation method thereof, to improve the distribution in hole in the nitride semi-conductor material light-emitting diode active area.
(2) technical scheme
According to an aspect of the present invention, provide a kind of nitride semi-conductor material light-emitting diode, having comprised: substrate; The N-shaped contact layer, its material is the nitride semi-conductor material of N-shaped, is formed on the substrate; Active luminescent layer, its material is nitride semi-conductor material, is formed on the N-shaped contact layer; And the p-type contact layer, its material is the nitride semi-conductor material of p-type, is formed on the active luminescent layer; Wherein, the active luminescent layer multicycle quantum well structures that at least two kinds of different nitride semi-conductor materials consist of of serving as reasons, the nitride semi-conductor material of at least part of quantum well layer is that p-type is mixed in this multicycle quantum well structure.
According to another aspect of the present invention, also provide a kind of preparation method of nitride semi-conductor material light-emitting diode, having comprised: form the N-shaped contact layer at substrate, its material is the nitride semi-conductor material of N-shaped; Form the active luminescent layer of the multicycle quantum well structure that is made of two kinds of different nitride semi-conductor materials at the N-shaped contact layer, the nitride semi-conductor material of at least part of quantum well layer is that p-type is mixed in this multicycle quantum well structure; And at active luminescent layer formation p-type contact layer, its material is the nitride semi-conductor material of p-type.
(3) beneficial effect
Can find out from technique scheme, nitride semi-conductor material light-emitting diode of the present invention and preparation method thereof has following beneficial effect:
(1) in the active luminescent layer, the quantum well of the bottom back cavitation that mixes no longer is confined near in the quantum well of p-type nitride semi-conductor material contact layer, electronics can be modulated different quantum well radiations from hole composite strengthening in the quantum well of bottom;
(2) in the active luminescent layer, p-type is mixed can produce more hole, the composite strengthening in electronics and hole, and the lumination of light emitting diode intensity enhancing is conducive to suppress overflowing of electronics simultaneously, establishment droop effect.
Description of drawings
Fig. 1 is the structural representation according to the nitride semi-conductor material light-emitting diode of the embodiment of the invention;
Fig. 2 is the flow chart according to the nitride semi-conductor material light-emitting diodes tube preparation method of the embodiment of the invention;
Fig. 3 is traditional semiconductor diode and semiconductor diode electroluminescence test result of the present invention.
[main element symbol description]
The 11-substrate; The 12-nucleating layer;
The 13-resilient coating; 14-n type contact layer;
The active luminescent layer of 15-; 151-indium gallium nitrogen sublayer;
152-gallium nitrogen sublayer; 16-p type electronic barrier layer;
17-p type contact layer.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
The object of the present invention is to provide a kind of nitride semi-conductor material light-emitting diode and preparation method thereof, mix by the p-type to quantum well layer in the active area, not only can produce more hole but also can shield the impact of polarized electric field, thereby improve the injection efficiency in hole, improve the distribution in hole.
Fig. 1 is the structural representation according to the nitride semi-conductor material light-emitting diode of the embodiment of the invention.Please refer to Fig. 1, this nitride semi-conductor material light-emitting diode comprises: substrate 11, and nucleating layer 12, resilient coating 13, N-shaped contact layer 14, active luminescent layer 15, p-type electronic barrier layer 16 and the p-type contact layer 17 of growing successively on this substrate; Wherein, the multicycle quantum well structure of active luminescent layer 15 for being consisted of by two kinds of different nitride semi-conductor materials, the nitride semi-conductor material of at least part of quantum well layer is that p-type is mixed in this multicycle quantum well structure.Wherein, the material of nucleating layer, resilient coating, N-shaped contact layer and p-type contact layer is nitride semi-conductor material.
When preparation nitride semi-conductor material light-emitting diode, the Sapphire Substrate of (0001) direction is the most frequently used substrate.Certainly, those skilled in the art can select other equally, with the lattice mismatch of gallium nitrogen material less than 20% monocrystalline oxide, such as r-face, m-or a-surface sapphire, 6H-SiC, 4H-SiC or Si etc.
The effect that it will be apparent to those skilled in the art that nucleating layer 12 and resilient coating 13 is the quality that improves later stage gallium nitrogen crystal, also can omit in actual fabrication process.In addition, p-type electronic barrier layer 16 is block electrons overflowing from active area to the p-type contact layer, and it can omit equally.
In the present embodiment, nitride semi-conductor material can be selected a kind of in the following material: gallium nitrogen (being gallium nitride), indium nitrogen (being indium nitride), aluminium nitrogen (being aluminium nitride), indium gallium nitrogen, aluminum gallium nitride and aluminium gallium nitrogen etc.For example, the material of N-shaped contact layer 14 can be N-shaped gallium nitrogen material, and the material of p-type contact layer can be p-type gallium nitrogen material.
In nitride semi-conductor material light-emitting diode shown in Figure 1, the multicycle quantum well structure of active luminescent layer 15 for being formed by indium gallium nitrogen sublayer 151 and gallium nitrogen layer 152 overlapping depositions, wherein indium gallium nitrogen sublayer is that p-type is mixed, the doping scope can be some or whole quantum well, doping way can be that isoconcentration mixes or modulation doping, and this modulation doping for example is that doping content increases gradually or reduces gradually.And those skilled in the art can select the number of plies of multicycle quantum well structure and the nitride semi-conductor material of each layer equally as required, equally should be within protection scope of the present invention.
In the present embodiment, mix by the p-type to quantum well layer in the active area, both can produce more hole, can shield again the impact of polarized electric field, thereby improve the injection efficiency in hole, improve the distribution in hole.
In addition, as shown in Figure 1, for the electric excitation with the external world conducts to active area, the N-shaped contact layer 14 of the p-type contact layer 17 of predeterminable area, p-type electronic barrier layer 16, active luminescent layer 15 and part is etched to form table top, and positive and negative electrode lays respectively on this table top and the predeterminable area p-type contact layer 17 outward.
Fig. 2 is the flow chart according to the preparation nitride semi-conductor material light-emitting diode method of the embodiment of the invention.Please refer to Fig. 2, this preparation method comprises:
Steps A selects (0001) direction sapphire as substrate 11;
Step B makes nucleating layer 12 and the resilient coating 13 of nitride semi-conductor material successively on substrate 11;
The growth parameter(s) of this nucleating layer 12 comprises: reaction temperature is 500-850 ℃, reaction chamber pressure is 150-500Torr, carrier gas flux 10-30 liter/min clock, the flow of trimethyl gallium be the 20-250 micromole/minute, ammonia flow is the 20-80 moles/min, and growth time is 1-10 minute.
The growth parameter(s) of this resilient coating 13 comprises: growth temperature 900-1200 ℃, reaction chamber pressure 75-250Torr, carrier gas flux are 5-20 liter/min of clock, the flow of trimethyl gallium be the 80-400 micromole/minute, ammonia flow is the 200-800 moles/min, and growth time is 20-60 minute.
Step C makes N-shaped gallium nitrogen contact layer 14 at resilient coating 13, and wherein, this N-shaped gallium nitrogen contact layer 14 is take silane as the N-shaped dopant;
These N-shaped gallium nitrogen contact layer 14 growth parameter(s)s comprise: growth temperature: 950-1150 ℃, reaction chamber pressure 75-250Torr, carrier gas flux 5-20 liter/min clock, TMGa flow rate 80-400 micromole/minute, ammonia flow 200-800 moles/min, silane flow rate 0.2-2.0 nanomole/minute, growth time 10-40 minute.
Step D, overlapping deposition indium gallium nitrogen sublayer 151 and gallium nitrogen sublayer 152, thereby the active luminescent layer 15 of formation multicycle quantum well structure on the surface of N-shaped gallium nitrogen contact layer 14;
Wherein, indium gallium nitrogen sublayer is that p-type is mixed, and the doping scope can be some or whole quantum well, and doping way can be that isoconcentration mixes or modulation doping.P-type is mixed can produce more hole, the composite strengthening in electronics and hole, and the lumination of light emitting diode intensity enhancing is conducive to suppress overflowing of electronics simultaneously, establishment droop effect.
After mixing, quantum well layer in the Multiple Quantum Well zone can produce the hole, charge carrier quantity is increased, thereby produced simultaneously charge carrier can improve luminous intensity by the partly shielding effect polarized electric field with the ionization acceptor, while is along with the raising of doping content in the quantum well layer, the charge carrier quantity that produces also can cause the variation of active area band structure when increasing, especially the variation of valence band structure is conducive to transporting and distributing of hole.
In active luminescent layer, the quantum well of the bottom back cavitation that mixes no longer is confined near in the quantum well of p-type nitride semi-conductor material contact layer, electronics can be modulated different quantum well radiations from hole composite strengthening in the quantum well of bottom.
Step e, growing p-type electronic barrier layer 16 on active luminescent layer 15;
In this step, p-type electronic barrier layer 16 is made of aluminum gallium nitride, and its thickness is 10-50nm, and its lower surface contacts with gallium nitrogen layer 152 in the described active luminescent layer.Growth parameter(s) comprises: growth temperature: 700-1000 ℃, and reaction chamber pressure 50-200Torr, carrier gas flux 5-20 liter/min clock, ammonia flow 100-400 moles/min, TMGa flow rate 80-200 micromole/minute, two luxuriant magnesium flows be the 150-400 nanomole/minute, the time is 1-10 minute.
Step F, the p-type contact layer 17 of continued growth nitride semi-conductor material on p-type electronic barrier layer 16, wherein, dopant can be two luxuriant magnesium;
This p-type contact layer 17 is produced on the p-type electronic barrier layer 16, and this layer is made of p-type gallium nitrogen.Concrete growth parameter(s) comprises: growth temperature 950-1100 ℃, reaction chamber pressure 200-500Torr, carrier gas flux 5-20 liter/min clock, ammonia flow 200-800 moles/min, TMGa flow rate be the 80-400 micromole/minute, two luxuriant magnesium flows be the 0.5-5 micromole/minute, the time is 10-60 minute.
Except adopting two luxuriant magnesium as the dopant, can also adopt diethyl zinc as dopant.
Step G, etching under a side direction of p-type contact layer 17 upper surfaces, etching depth arrives in the N-shaped gallium nitrogen contact layer 14 always, forms table top 141;
Lithographic method is such as being dry etching, induction even summation plasma etching or reactive ion etching etc.
Step H, making positive electrode 19 on p-type contact layer 17; Table top 141 at N-shaped contact layer 14 is made negative electrode 18, finishes the preparation of nitride semi-conductor material light-emitting diode.
In the present embodiment, the method for growing nitride semi-conducting material is metal-organic chemical vapor deposition equipment, i.e. MOCVD can certainly adopt other growth pattern, such as molecular beam epitaxy, i.e. and MBE, or hydride gas-phase epitaxy, i.e. HVPE.
Need to prove, a kind of concrete nitride semi-conductor material light-emitting diode of above usefulness is that example illustrates preparation method of the present invention.For the nitride semi-conductor material light-emitting diode of other types, its preparation process similarly, difference only is the material of equivalent layer, repeats no more herein.
Fig. 3 is traditional semiconductor diode and semiconductor diode electroluminescence test result of the present invention.And in the active luminescent layer 15 of semiconductor diode of the present invention, the first indium gallium nitrogen sublayer of transmitting green light is positioned at the upper strata, and near p-type electronic barrier layer 16 1 sides, the second indium gallium nitrogen sublayer of emission blue light is positioned at lower floor, near N-shaped contact layer 14 1 sides.
But the first indium gallium nitrogen sublayer and the second indium gallium nitrogen sublayer be all the content of indium gallium nitrogen layer indium different can cause different luminous.In this test, used the indium gallium nitrogen active layer of different indium components.Indium gallium nitrogen sublayer 151 both can be identical indium component also can be every layer in the indium component different.
Can find out from test result, under the identical current strength, only has single green luminescence peak in the unadulterated sample, faint blue light peak appears in the sample after mixing in part indium gallium nitrogen sublayer, and all the sample that mixes of indium gallium nitrogen sublayers not only occurs obviously bimodal but also luminous intensity that send blue light indium gallium nitrogen sublayer bottom is stronger.This explanation the distribution of p-type doping back cavitation is carried out in the part or all of indium gallium nitrogen sublayer of the active luminescent layer of nitride semi-conductor material light-emitting diode and transport be improved significantly.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (14)
1. a nitride semi-conductor material light-emitting diode is characterized in that, comprising:
Substrate;
The N-shaped contact layer, its material is the nitride semi-conductor material of N-shaped, is formed on the described substrate;
Active luminescent layer, its material is nitride semi-conductor material, is formed on the described N-shaped contact layer; And
The p-type contact layer, its material is the nitride semi-conductor material of p-type, is formed on the described active luminescent layer;
Wherein, the described active luminescent layer at least two kinds of multicycle quantum well structures that the overlapping deposition of different nitride semi-conductor materials forms of serving as reasons, the nitride semi-conductor material of at least part of quantum well layer is that p-type is mixed in this multicycle quantum well structure.
2. nitride semi-conductor material light-emitting diode according to claim 1 is characterized in that, described nitride semi-conductor material is a kind of in the following material: gallium nitrogen, indium gallium nitrogen, aluminum gallium nitride, aluminium gallium nitrogen, indium nitrogen and aluminium nitrogen.
3. nitride semi-conductor material light-emitting diode according to claim 2 is characterized in that: the multicycle quantum well structure of described active luminescent layer for being formed by the overlapping deposition in indium gallium nitrogen sublayer and gallium nitrogen sublayer;
In this multicycle quantum well structure, partly or entirely the indium gallium nitrogen sublayer of quantum well is that p-type is mixed.
4. nitride semi-conductor material light-emitting diode according to claim 3 is characterized in that, in the described multicycle quantum well structure, all the indium gallium nitrogen sublayer in the quantum well is that p-type is mixed;
The p-type of indium gallium nitrogen sublayer is doped to isoconcentration doping or modulation doping in each quantum well.
5. nitride semi-conductor material light-emitting diode according to claim 1 is characterized in that, also comprises:
Nucleating layer, its material is nitride semi-conductor material, is formed on the described substrate;
Resilient coating, its material is nitride semi-conductor material, is formed between nucleating layer and the described N-shaped contact layer;
The p-type electronic barrier layer is formed between described active luminescent layer and the described p-type contact layer.
6. nitride semi-conductor material light-emitting diode according to claim 5 is characterized in that:
The described N-shaped contact layer of the described p-type contact layer of predeterminable area, p-type electronic barrier layer, active luminescent layer and part is etched to form table top;
Positive electrode and negative electrode lay respectively on this table top and the predeterminable area p-type contact layer outward.
7. each described nitride semi-conductor material light-emitting diode in 6 according to claim 1 is characterized in that, the material of described N-shaped contact layer is N-shaped gallium nitrogen material, and the material of described p-type contact layer is p-type gallium nitrogen material.
8. the preparation method of a nitride semi-conductor material light-emitting diode is characterized in that, comprising:
Form the N-shaped contact layer at substrate, its material is the nitride semi-conductor material of N-shaped;
Form the active luminescent layer of the multicycle quantum well structure that is made of two kinds of different nitride semi-conductor materials at described N-shaped contact layer, the nitride semi-conductor material of at least part of quantum well layer is that p-type is mixed in this multicycle quantum well structure; And
Form the p-type contact layer at described active luminescent layer, its material is the nitride semi-conductor material of p-type.
9. the preparation method of nitride semi-conductor material light-emitting diode according to claim 8 is characterized in that, described nitride semi-conductor material is a kind of in the following material: gallium nitrogen, indium gallium nitrogen, aluminum gallium nitride, aluminium gallium nitrogen, indium nitrogen and aluminium nitrogen.
10. nitride semi-conductor material light-emitting diode according to claim 9 is characterized in that, described step at the active luminescent layer of N-shaped contact layer formation comprises:
Overlapping deposition indium gallium nitrogen sublayer and gallium nitrogen sublayer, to form described multicycle quantum well structure, wherein, the indium gallium nitrogen sublayer in the part or all of quantum well is that p-type is mixed.
11. nitride semi-conductor material light-emitting diode according to claim 9 is characterized in that, in the step of described overlapping deposition indium gallium nitrogen sublayer and gallium nitrogen sublayer:
All the indium gallium nitrogen sublayer in the quantum well is that p-type is mixed, and the p-type of indium gallium nitrogen sublayer is doped to isoconcentration doping or modulation doping in each quantum well.
12. the preparation method of nitride semi-conductor material light-emitting diode according to claim 8 is characterized in that:
Also comprise before the described step that forms the N-shaped contact layer at substrate: on described substrate, be formed into successively stratum nucleare and resilient coating, described N-shaped contact layer is formed on the described resilient coating, wherein, the material of described nucleating layer and resilient coating is nitride semi-conductor material;
Also comprised before the step of described active luminescent layer formation p-type contact layer: form the p-type electronic barrier layer at described active luminescent layer, described p-type contact layer is formed on the described p-type electronic barrier layer.
13. the preparation method of nitride semi-conductor material light-emitting diode according to claim 12 is characterized in that, describedly also comprises after active luminescent layer forms the step of p-type contact layer:
Etching under a side direction of p-type contact layer upper surface, etching depth arrive in the N-shaped contact layer always, form table top;
Making positive electrode on described p-type contact layer; Table top at described N-shaped contact layer is made negative electrode.
14. the preparation method of each described nitride semi-conductor material light-emitting diode in 13 is characterized in that according to claim 8,
Described in the step of substrate formation N-shaped contact layer, the material of described N-shaped contact layer is N-shaped gallium nitrogen material;
Described in the step of active luminescent layer formation p-type contact layer, the material of described p-type contact layer is p-type gallium nitrogen material.
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| CN104716239A (en) * | 2013-12-11 | 2015-06-17 | 比亚迪股份有限公司 | LED structure and forming method thereof |
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