CN103811609A - Oxide semiconductor light-emitting diode epitaxial wafer, device and manufacturing method thereof - Google Patents
Oxide semiconductor light-emitting diode epitaxial wafer, device and manufacturing method thereof Download PDFInfo
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- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
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- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
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Abstract
The invention provides an oxide semiconductor light-emitting diode (LED) epitaxial wafer, a device and a manufacturing method thereof. The oxide semiconductor light-emitting diode epitaxial wafer comprises a substrate, and a template layer, an n type layer, a quantum well active layer, a carrier blocking layer and a p type layer deposited in sequence on the substrate, wherein doping elements in the p type layer at least comprise Mg; the carrier blocking layer is an oxide material containing the element Al, and the element Mg is only permeated into the p type layer at a later period but is not doped in an early depositing process. The non-intentionally-doped carrier blocking layer of a proper thickness is inserted between the active region of a quantum well and the p type layer, thereby the effectively reducing the diffusion effect of a doping agent, namely Mg, in the p type layer in the active region of the quantum well, and increasing the radiation composite efficiency of the quantum well, namely, effectively increasing the internal quantum efficiency of an oxide LED.
Description
Technical field
The present invention relates to semiconductor light-emitting-diode (hereinafter to be referred as LED) technical field, relate in particular to a kind of nitride semiconductor LED epitaxial wafer, device and preparation method thereof.
Background technology
III-V hi-nitride semiconductor material mainly comprises the alloy materials such as the compound-materials such as gallium nitride (GaN), aluminium nitride (AlN), indium nitride (In) and aluminium gallium nitride alloy (AlGaN), InGaN (InGaN), aluminum indium nitride (AlInN), aluminum indium nitride gallium (AlInGaN).Since nineteen nineties Japan scientist Shuji Nakamura invents GaN base blue LED, nitride material and luminescent device are subject to people and more and more pay close attention to, Material growth and the device technology of preparing of GaN base blue-ray LED develop rapidly, nitride white light LED luminous efficiency constantly promotes and realizes industry-wide, at present the power efficiency of nitride blue-ray LED and white light LED part can realize and exceed 50%, and extensive use in the numerous areas such as display screen, liquid crystal backlight, road lighting, Landscape Lighting and even room lighting out of doors.
Along with GaN base visible ray diode technologies reaches its maturity, more short wavelength's ultraviolet band nitride LED receives the concern of increasing research institution and industrial circle.Ultraviolet LED has major application to be worth in fields such as biochemistry detection, sterilizing, polymer cure, non line of sight communication and special lightings.And compared with traditional ultraviolet source mercury lamp, ultraviolet LED has easily tuning, the plurality of advantages such as voltage is low, power consumption is little of small and exquisite portable, environmental protection, wavelength as solid state light emitter.Along with the continuous progress of technology is perfect, be expected to become the main flow of following ultraviolet source.
But compared with GaN base blue-ray LED, at present the luminous power of ultraviolet LED and efficiency also far can not make us satisfied.Especially wavelength is shorter than the deep ultraviolet LED of 300nm, its luminous efficiency generally below 10%, even only have 1% less than.Cause a major reason of this situation to be just that Al component is higher containing the p-type doping that is difficult to realize high conductivity in Al component nitride material, difficulty is larger.In general, more difficult than GaN material containing the epitaxial growth of Al component nitride material, Al component is higher, and difficulty is larger, and in the material that extension goes out, defect concentration is higher, and this causes in the p-type doping of material compensating effect serious; And simultaneously, along with the raising of Al component, the activation energy of p-type dopant Mg in AlGaN and AlInGaN material constantly increases, activation efficiency significantly declines.These reasons cause containing the hole concentration deficiency in Al component nitride material, and conductivity declines, and in the deep ultraviolet LED of high Al contents, situation is particularly serious.
And simultaneously, relatively easy for the N-shaped doping containing Al component nitride material, even if reach 50% high AlGaN material for Al component, still can realize electron concentration and reach 10
18/ cm
2the N-shaped doping of magnitude.That is, in AlGaN and AlInGaN material for same component, N-shaped doping is always easy to p-type doping, and in corresponding N-shaped material, the concentration of electronics will be higher than the hole concentration in same component p-type material.This has just caused an obvious problem: the carrier concentration imbalance in corresponding LED structure in N-shaped layer and p-type layer.Simultaneously, nitride LED operating voltage is often more than 3V, even reach higher, the electronics with higher-energy is crossed the active area quantum well layer of LED possibly, and outside active area, occur non-radiative compound, there is overflow (the electron overflow) of electronics, reduced the radiation recombination efficiency of LED.
In order to address this problem, people often insert carrier barrier layer (the Electron Blocking Layer of one deck p-type doping between quantum well active area and p-type layer, be called for short EBL), the energy gap of carrier barrier layer is greater than the energy gap of quantum well region material, is often also greater than the energy gap of N-shaped layer and p-type layer material simultaneously.In nitride LED, carrier barrier layer normally has AlGaN or AlInGaN or the AlInN material of higher Al component.This one deck can provide for effectively the stopping of electronics, better electronics was limited in to quantum well region radiation recombination.Meanwhile, as previously mentioned, in the nitride material higher containing Al component, the activation efficiency of p-type dopant Mg is lower, in order to obtain higher hole concentration, and the often Mg that mixes higher concentration in p-type carrier barrier layer, doping content far exceedes 10
19cm
-3and even exceed 10
20cm
-3.
And on the other hand, existing many research reports show, the Mg of the higher dosage of mixing in nitride material can spread, and the reason that causes this diffusion to occur may be the passage that the dislocation in nitride material provides Mg diffusion, may be also the diffusion of the Mg atom that causes due to higher temperature.No matter which kind of reason, in p-type carrier barrier layer, the Mg of higher concentration has suitable dosage and is diffused in the quantum well of closing on, and causes the concentration of Mg atom in this (a bit) quantum well to reach 10
17cm
-3above, so higher.These Mg atoms cause on the contrary more non-radiative recombination centers to occur in quantum well, reduce the radiation recombination efficiency in quantum well, reduce luminous efficiency.In nitride LED, because hole mobility is lower than electron mobility, causing near one of p-type layer or several quantum well is topmost luminescent layers, be vital near one of p-type layer or several quantum well for the luminous efficiency of LED, and due to close p-type carrier barrier layer, Mg in barrier layer is easily diffused into again in these traps, and therefore the problem of Mg diffusion is quite important for the quantum efficiency impact of LED, and is suitable adverse influence.
Summary of the invention
(1) technical problem that will solve
In view of above-mentioned technical problem, the invention provides a kind of nitride semiconductor LED epitaxial wafer, device and preparation method thereof, with in effectively realizing charge carrier and stopping, reduce even to eliminate the adverse effect of Mg diffusion for LED quantum well radiation efficiency.
(2) technical scheme
According to an aspect of the present invention, provide a kind of nitride semiconductor LED epitaxial wafer.This iii-nitride light emitting devices epitaxial wafer comprises: substrate; And be deposited on successively template layer, N-shaped layer, quantum well active area, carrier barrier layer and the p-type layer of the nitride material on substrate; Wherein, in p-type layer, doped chemical at least comprises Mg; Carrier barrier layer is the nitride material that contains Al element, and the Mg element being infiltrated by p-type layer except the later stage, do not mix Mg element in depositing operation its early stage.
According to another aspect of the present invention, also provide a kind of nitride semiconductor LED device.This nitride semiconductor LED device comprises: substrate; Be deposited on successively template layer, N-shaped layer, quantum well active area, carrier barrier layer, the p-type layer of the nitride material on substrate; Reflector and p-type electrode, be deposited on the top of p-type layer; And N-shaped electrode, being formed on a step, this step is by etching p-type layer, carrier barrier layer and quantum well active area from bottom to top, and ends at N-shaped layer and form; Wherein, in p-type layer, doped chemical at least comprises Mg; Carrier barrier layer is the nitride material that contains Al element, and except the Mg element being infiltrated by p-type layer, do not mix Mg element in depositing operation its early stage.
A kind of preparation method of above-mentioned nitride semiconductor LED device is also provided according to a further aspect of the invention.This preparation method comprises: step S202, on substrate, deposit successively template layer, N-shaped layer, quantum well active area, carrier barrier layer, p-type layer, and obtain iii-nitride light emitting devices epitaxial wafer, it is carried out to annealing in process to activate the p-type dopant in p-type layer; Step S204, the predeterminated position on iii-nitride light emitting devices epitaxial wafer etches away p-type layer, carrier barrier layer and quantum well active area, exposes N-shaped layer, to form a step; Step S206 prepares N-shaped electrode on the N-shaped layer of step; Step S208 prepares reflector and p-type electrode on the p-type layer of etching not, thereby forms nitride semiconductor LED device.
According to another aspect of the present invention, also provide a kind of nitride semiconductor LED device.This nitride semiconductor LED device comprises: conductive supporting substrate, its double p-type electrode that does; Be positioned at successively the conductive reflective on conductive supporting substrate, and the p-type layer of nitride material, carrier barrier layer, quantum well active area, N-shaped layer; And be formed at the N-shaped electrode on N-shaped layer; Wherein, in p-type layer, doped chemical at least comprises Mg; Carrier barrier layer is the nitride material that contains Al element, and except the Mg element being infiltrated by p-type layer, does not have in its depositing operation of Mg element and mixes.
A kind of preparation method of above-mentioned nitride semiconductor LED device is also provided according to a further aspect of the invention.This preparation method comprises: step S302, on substrate, form successively template layer, N-shaped layer, quantum well active area, carrier barrier layer, p-type layer, obtain nitride semiconductor LED epitaxial wafer, it is carried out to annealing in process to activate the p-type dopant in p-type layer; Step S304 in preparation reflector, p-type layer surface, electroplates or bonding conductive supporting substrate on reflector; Step 306, peels off substrate and template layer or remove with Ginding process with laser or chemical solution corrosion, exposes N-shaped layer, makes N-shaped electrode, forms nitride semiconductor LED device.
(3) beneficial effect
Can find out from technique scheme, nitride semiconductor LED epitaxial wafer of the present invention, device and preparation method thereof have following beneficial effect:
(1) by insert the non-dosed carrier barrier layer intentionally of suitable thickness between quantum well active area and p-type layer, can effectively reduce dopant Mg in p-type layer toward the diffusion effect in quantum well active area, thereby improve the radiation recombination efficiency of quantum well, effectively improve the internal quantum efficiency of nitride LED;
(2), simultaneously due to described non-carrier barrier layer thinner thickness of having a mind to doping, operating voltage that can't appreciable impact nitride LED, comprehensively can effectively improve the electro-optical efficiency of nitride LED.
Accompanying drawing explanation
Fig. 1 is according to the generalized section of first embodiment of the invention nitride semiconductor LED epitaxial wafer;
Fig. 2 is according to the generalized section of second embodiment of the invention nitride semiconductor LED device:
Fig. 3 is according to the generalized section of third embodiment of the invention nitride semiconductor LED device.
[main element symbol description of the present invention]
101-substrate; 102-template layer;
103-n type layer; 104-quantum well active area;
105-carrier barrier layer (EBL); 106-p type layer;
201-n type electrode; 202-p type electrode;
301-conductive reflective; 302-conductive supporting substrate;
303-n type electrode.
Embodiment
For making the object, 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.It should be noted that, in accompanying drawing or specification description, similar or identical part is all used identical figure number.The implementation that does not illustrate in accompanying drawing or describe is form known to a person of ordinary skill in the art in affiliated technical field.In addition, although the demonstration of the parameter that comprises particular value can be provided herein, should be appreciated that, parameter is without definitely equaling corresponding value, but can in acceptable error margin or design constraint, be similar to corresponding value.The direction term of mentioning in embodiment, for example " on ", D score, 'fornt', 'back', " left side ", " right side " etc., be only the direction with reference to accompanying drawing.Therefore, the direction term of use is to be not used for limiting the scope of the invention for explanation.
The present invention is by introducing a kind of non-carrier barrier layer (uEBL) of having a mind to doping, in effectively realizing charge carrier and stopping, reduce even to eliminate the adverse effect of Mg diffusion for LED quantum well radiation efficiency, thereby effectively improve the quantum efficiency of LED.The advantage of this invention effect in nitride ultraviolet LED is comparatively remarkable, and in nitride deep ultraviolet LED, effect is particularly evident.
In one exemplary embodiment of the present invention, provide a kind of nitride semiconductor LED epitaxial wafer.Fig. 1 is according to the generalized section of first embodiment of the invention nitride semiconductor LED epitaxial wafer.Please refer to Fig. 1, the present embodiment nitride semiconductor LED comprises: 1, a kind of nitride semiconductor LED epitaxial wafer, it is characterized in that, and comprising: substrate 101; And be deposited on successively template layer 102, N-shaped layer 103, quantum well active area 104, carrier barrier layer 105 and the p-type layer 106 of the nitride material on substrate.Wherein, in p-type layer, doped chemical at least comprises Mg; Carrier barrier layer is the nitride material that contains Al element, and the Mg element being infiltrated by p-type layer except the later stage, does not mix Mg element (hereinafter to be referred as non-carrier barrier layer of having a mind to doping) its early stage in depositing operation.
Below respectively each part of the present embodiment nitride semiconductor LED epitaxial wafer is elaborated.
In the present embodiment, substrate 101 can be sapphire, monocrystalline silicon, carborundum, zinc oxide, gallium nitride or aluminium nitride, but preferably uses sapphire or aluminium nitride substrate material.
Other layers of material except substrate 101 can be prepared by one or more the combination in the technology such as metal-organic chemical vapor deposition equipment (MOCVD), hydride gas-phase epitaxy (HVPE), molecular beam epitaxy (MBE) and deriving technology mode thereof, and preferred technology is MOCVD.
N-shaped layer 103 is Al
ein
fga
1-e-fn material, is grown on template layer 102, wherein, 0<e≤1,0≤f≤0.2, wherein the preferred result of f value is 0, this N-shaped layer material is Al
ega
1-en material, the preferred result of e value is 10%≤e≤90%.This N-shaped layer thickness is 500nm-8 μ m.The preferred dopant of this N-shaped layer is Si.
Quantum well active area 104 is grown on N-shaped layer 103, is the luminescent layer of ultraviolet LED, by one or more groups Al
ain
bga
1-a-bn/Al
cin
dga
1-c-dn structure composition, wherein quantum well layer Al
ain
bga
1-a-bn energy gap E
gabe less than quantum barrier layer Al
cin
dga
1-c-dn energy gap E
gc, and 0≤a<1,0≤b≤0.2,0≤c≤1,0≤d≤0.2.In the time that b value is 0, Al
ain
bga
1-a-bn quantum well is Al
aga
1-an material; In the time that c value is 0, Al
cin
dga
1-c-dn quantum is built and is Al
cga
1-cn material.Preferably value is, 0≤d≤b≤0.03, and 0<a<c≤e, wherein e is N-shaped layer 103Al
ein
fga
1-e-fal component value in N material.Quantum well layer Al
ain
bga
1-a-bthe thickness of N is between 1nm-5nm, quantum barrier layer Al
cin
dga
1-c-dn thickness is between 5nm-20nm.Quantum well layer may be selected to be N-shaped doping or non-doping, and quantum barrier layer also may be selected to be N-shaped doping or non-doping.
In the present embodiment, the peak value of the main glow peak of the luminescent spectrum of described quantum well active area is in the scope of 210nm to 400nm.Preferably, the peak value of the main glow peak of the luminescent spectrum of described quantum well active area is in the scope of 230nm to 300nm.
Non-carrier barrier layer (EBL) 105 of having a mind to doping is grown on quantum well active area 104, and material is Al
xin
yga
1-x-yn, wherein, 0<x≤1,0≤y≤0.2, thickness is between between 2nm to 30nm.In the time of this layer growth, do not have a mind to mix any N-shaped or p-type dopant.Work as Al
xin
yga
1-x-yin N material, y value is 0 o'clock, is Al
xga
1-xn; Work as Al
xin
yga
1-x-yin N material, when x+y=1, be Al
xin
1-xn material.Preferably value is, c<x≤1, and wherein c is the quantum barrier layer Al of quantum well active area 104
cin
dga
1-c-dthe Al component value of N.
P-type layer 106 is grown on non-carrier barrier layer (EBL) 105 of having a mind to doping, can be one or more the combination in the materials such as p-GaN, p-AlGaN, p-AlInN, p-AlInGaN; This p-type layer can be made up of one deck homogenous material, also can comprise multiple layers of different materials; Thickness is between 30nm-1 μ m.The preferred material of p-type layer 106 is the combination of p-AlInGaN or p-AlGaN and p-GaN, wherein p-AlInGaN or p-AlGaN layer are long on non-carrier barrier layer (EBL) 105 of having a mind to adulterate, and p-GaN material length is on p-AlInGaN or p-AlGaN layer.The dopant of p-type layer 106 can be Mg, C or its combination, is preferably Mg.
In the extension of nitride material, conventionally epitaxial temperature is more than 500 ℃ and even more than 1000 ℃, dopant under high temperature in p-type layer 106 has higher activity, easily diffuse into quantum well active area, core luminous zone 104, once these dopants are easy to become non-radiative radiation center after entering in quantum well active area 104, reduce LED luminous efficiency.But not have a mind to 105 of the carrier barrier layers (EBL) of doping effectively played stop reduce Mg from p-type layer 106 toward the diffusion in quantum well active area 104, there is non-radiative compound probability thereby reduce charge carrier, raising LED luminous efficiency.
Nitride semiconductor LED epitaxial wafer based on above-mentioned, in another exemplary embodiment of the present invention, also provides a kind of nitride semiconductor LED device.Fig. 2 is according to the generalized section of second embodiment of the invention nitride semiconductor LED device.Please refer to Fig. 2, this nitride semiconductor LED device comprises:
Be deposited on successively template layer 102, N-shaped layer 103, quantum well active area 104, non-carrier barrier layer (EBL) 105, p-type layer 106 of having a mind to doping on described substrate;
P-type electrode, is deposited on the top of described p-type layer 106; And
N-shaped electrode, is formed on a step, and this step is by p-type layer 106, non-carrier barrier layer 105 and quantum well active area 104 of having a mind to doping described in etching from bottom to top, and ends at N-shaped layer 103 and form.
Below introduce the preparation method of this nitride semiconductor LED device.This preparation method comprises:
Step S202, utilize epitaxial growth of semiconductor material technology on backing material 101, to form successively template layer 102, N-shaped layer 103, quantum well active area 104, non-carrier barrier layer (EBL) 105, p-type layer 106 of having a mind to doping, obtain nitride semiconductor LED epitaxial wafer, and nitride semiconductor LED epitaxial wafer is carried out to annealing in process to activate the p-type dopant in p-type layer 106;
Step S204, adopt photoresist to carry out graphically to nitride semiconductor LED epitaxial wafer, then partly etch away the p-type layer 106 of predeterminated position, non-carrier barrier layer 105 and quantum well active area 104 of having a mind to doping by dry method or wet process, until expose N-shaped layer 103, form ledge structure;
Step S206, on the N-shaped layer 103 of ledge structure, prepare N-shaped electrode 201, this electrode layer can be the Multi-layer metal alloys such as Ti/Al/Ti/Au, Ti/Al/Ni/Au, Ti/Al/Pt/Au, V/Au/V/Au or V/Au/Ni/Au, thickness is 200-900nm, and electrode can form by the mode of sputter or electron beam evaporation;
Step S208, on the p-type layer 106 of etching not, prepare reflector and p-type electrode 202, this electrode layer can be the metal alloys such as Ni/Au, Ni/Ag, Ni/Ag/Au, Ni/Ag/Pt, Al/Ti/Au, thickness is 20-500nm, electrode can form by the mode of sputter or electron beam evaporation, thereby forms nitride semiconductor LED device.
Nitride semiconductor LED epitaxial wafer based on above-mentioned, in another exemplary embodiment of the present invention, also provides a kind of nitride semiconductor diode device.Fig. 3 is according to the generalized section of third embodiment of the invention nitride semiconductor LED device.Please refer to Fig. 3, this nitride semiconductor LED device comprises:
Conductive supporting substrate 302, its double p-type electrode that does;
Be positioned at successively conductive reflective 301, p-type layer 106, non-carrier barrier layer (EBL) 105, quantum well active area 104, N-shaped layer 103 of having a mind to doping on conductive supporting substrate 302; And
Be formed at the N-shaped electrode 303 on N-shaped layer 103.
Below introduce the preparation method of this nitride semiconductor LED device.This preparation method comprises:
Step S302, utilize epitaxial growth of semiconductor material technology on backing material 101, to form successively template layer 102, N-shaped layer 103, quantum well active area 104, non-carrier barrier layer (EBL) 105, p-type layer 106 of having a mind to doping, obtain nitride semiconductor LED epitaxial wafer, and nitride semiconductor LED epitaxial wafer is carried out to annealing in process to activate p-type dopant.
Step S304, in p-type layer 106 preparation reflector 301, surface, this reflector can be Ag, Al or both alloys, can form by the mode of sputter or electron beam evaporation.
Step S306 prepares conductive supporting substrate 302 on reflector 301, and conductive supporting substrate can be prepared by plated metal, and preferred metal is Cu; Also can pass through other existing electrically-conductive backing plates such as bonding Si, GaAs, ZnO.
Step S308, gets rid of backing material 101 and template layer 102, can adopt that high power density laser is peeled off, the method for the either method such as dry etching, chemical solution corrosion or cmp or combination removes, and exposes N-shaped layer 103.
Step S310 makes N-shaped electrode 303, and this electrode can be the metal such as Al or Al/Ti/Au, and electrode can form by the mode of sputter or electron beam evaporation, thereby forms nitride semiconductor LED device.
Based on above-mentioned three embodiment, below introduce the concrete nitride semiconductor LED epitaxial wafer of three profits and describe the present invention in detail.
1, the first nitride semiconductor LED epitaxial wafer
Utilize MOCVD equipment order in Sapphire Substrate to form the template layer being made up of multilayer material, described template layer comprises: low temperature AI N resilient coating, high temperature AlN layer, AlN/AlGaN superlattice structure; Wherein
Described low temperature AI N buffer growth is in Sapphire Substrate, and growth temperature is between 600-700 ℃, thickness 20-80nm;
Described high temperature AlN layer growth is on low temperature AI N resilient coating, and growth temperature is between 1200-1400 ℃, thickness 500nm-1.5 μ m;
Described AlN/AlGaN superlattice structure grows on high temperature AlN layer, growth temperature is 1050-1150 ℃, in superlattice, AlN and AlGaN thickness in monolayer are 10-20nm, and wherein the Al component in AlGaN layer is between 40%-70%, and superlattice period is 20 cycles.
N-shaped AlGaN Material growth on described AlN/AlGaN superlattice, growth temperature 1000-1100 ℃, Al component between 45%-55%, thickness 3-4 μ m, dopant is Si, doping content 10
18-10
19/ cm
3.
Quantum well active area is grown on described N-shaped AlGaN material, by 5 groups of Al
aga
1-an/Al
cga
1-cn Multiple Quantum Well forms, and wherein quantum is built Al
cga
1-cthe Al amount of component b of N between 40%-50%, thickness 8-12nm, quantum well Al
aga
1-athe Al component a of N between 35%-40%, thickness 1-3nm, quantum well active area growth temperature and described N-shaped AlGaN Material growth temperature are consistent, front 4 groups of quantum are built and quantum well is all adulterated Si, doping content 10
17-10
18/ cm
3, last group quantum builds and quantum well undopes, and the plain quantum of in the end growing after a quantum well layer is built the growth that finishes quantum well active area; The main glow peak wavelength of quantum well active area is between 280-300nm.
Non-carrier barrier layer of having a mind to doping is grown on described quantum well active area, material is AlGaN, wherein Al component is 60-70%, thickness is 10-20nm, growth temperature is identical with described quantum well active area growth temperature, in growth course, in MOCVD reative cell, only have a mind to pass into Al, Ga and N source, other source and dopant all keep closing, and keep the flow in the source that passes into constant in growth course.
P-type AlGaN layer growth is on described non-carrier barrier layer of having a mind to adulterate, Al component is between 40%-55%, and thickness is 30-70nm, and growth temperature is identical with described quantum well active area growth temperature, p-type dopant is Mg, and p-type dopant doping content is between 4 × 10
19-3 × 10
20/ cm
3.
P-type GaN ohmic contact layer is grown on described p-type AlGaN layer, and thickness is 50-80nm, and growth temperature is 950-1050 ℃, and is no more than the growth temperature of described quantum well, and p-type dopant is Mg, and p-type dopant doping content is between 4 × 10
19-3 × 10
20/ cm
3.Complete after the growth of deep ultraviolet LED epitaxial wafer, carry out high annealing, to activate p-type dopant.
In the outer Yanzhong of conventional deep ultraviolet LED, conventionally adopt the carrier barrier layer of p-type doping, adopt doping content to exceed 10
19/ cm
3p-type dopant Mg, carrier barrier layer growth temperature reaches 1000 ℃ or higher, because Mg atom is comparatively active, at so high temperature, be highly susceptible to spreading, enter into the quantum well of closing on, become non-radiative recombination center, reduce quantum well luminous efficiency.Described non-carrier barrier layer of having a mind to doping can effectively stop/slow down that Mg in p-type AlGaN layer is toward the diffusion in quantum well; Simultaneously because the operating voltage of deep ultraviolet LED generally exceedes 5V, what adopt suitable thickness non-ly has a mind to the operating voltage that doping blocking layer can't appreciable impact device, integrate, non-carrier barrier layer of having a mind to doping can effectively promote the electro-optical efficiency of deep ultraviolet LED.
2, the second nitride semiconductor LED epitaxial wafer
Utilize MOCVD equipment at extension AlN template layer on AlN substrate, growth temperature is between 1200-1400 ℃, thickness 100-200nm;
The non-doped with Al GaN graded bedding of extension on described AlN template layer, growth temperature 1050-1150 ℃, Al component is reduced to 65%, growth thickness 200-300nm from 95% gradually along the direction of growth;
Extension N-shaped AlGaN material on described non-doped with Al GaN graded bedding, growth temperature 1000-1100 ℃, Al component between 60%-65%, thickness 2-3 μ m, dopant is Si, doping content 10
18-10
19/ cm
3.
Quantum well active area is grown on described N-shaped AlGaN material, by 4 groups of Al
ain
bga
1-an/Al
cga
1-c-dn Multiple Quantum Well forms, and wherein quantum is built Al
cga
1-cthe Al amount of component b of N between 50%-60%, thickness 8-12nm, quantum well Al
ain
bga
1-athe Al component a of N between 45%-50%, between In component 0.5-3%, thickness 1-3nm, quantum well active area growth temperature 900-950 ℃, front 4 groups of quantum are built the Si that all adulterates, doping content 10
17-10
18/ cm
3, all quantum well all undope, and the plain quantum of in the end growing after a quantum well layer is built the growth that finishes quantum well active area; The main glow peak wavelength of quantum well active area is between 260-290nm.
Non-carrier barrier layer of having a mind to doping is grown on described quantum well active area, by 3 groups of Al
ain
bga
1-an/Al
cga
1-c-dn superlattice layer forms.Wherein Al in every group of superlattice
ain
bga
1-an layer thickness is 3-5nm, and Al component is 65-80%, between In component 0.5-2%, and keeps Al
ain
bga
1-an layer energy gap is greater than the energy gap of quantum barrier layer; Al
cga
1-c-dn layer Al component is 70-85%, and keeps Al
cga
1-c-dn layer energy gap is greater than the energy gap of N-shaped layer, and thickness is 5-8nm.Al
ain
bga
1-an/Al
cga
1-c-dn superlattice layer growth temperature is identical with described quantum well active area growth temperature, only has a mind to pass into Al, Ga, In and N source in growth course in MOCVD reative cell, and other source and dopant all keep closing.
P-type AlGaN layer growth is on described non-carrier barrier layer of having a mind to adulterate, Al component is between 60%-65%, and thickness is 30-70nm, and growth temperature is identical with described quantum well active area growth temperature, p-type dopant is Mg, and p-type dopant doping content is between 4 × 10
19-3 × 10
20/ cm
3.
P-type GaN ohmic contact layer is grown on described p-type AlGaN layer, and thickness is 100-150nm, and growth temperature is 900-950 ℃, and is no more than the growth temperature of described quantum well, and p-type dopant is Mg, and p-type dopant doping content is between 4 × 10
19-3 × 10
20/ cm
3.Complete after the growth of deep ultraviolet LED epitaxial wafer, carry out high annealing, to activate p-type dopant.
In the outer Yanzhong of conventional deep ultraviolet LED, conventionally adopt the carrier barrier layer of p-type doping, adopt doping content to exceed 10
19/ cm
3p-type dopant Mg, because Mg atom is comparatively active, be at high temperature highly susceptible to spreading, enter into the quantum well of closing on, become non-radiative recombination center, reduce quantum well luminous efficiency.Described by 3 groups of Al
ain
bga
1-an/Al
cga
1-c-dthe non-carrier barrier layer of having a mind to doping that N superlattice layer forms, can effectively stop/slow down that Mg in p-type AlGaN layer is toward the diffusion in quantum well; Pass through Al simultaneously
ain
bga
1-an and Al
cga
1-c-dthe interface that two kinds of different materials of N form contributes to further to stop the diffusion of Mg atom.Because the operating voltage of deep ultraviolet LED generally exceedes 5V, adopt the Al of suitable groups number and thickness
ain
bga
1-an/Al
cga
1-c-dn superlattice are non-has a mind to the operating voltage that doping blocking layer can't appreciable impact device, integrates, and described non-carrier barrier layer of having a mind to doping can effectively promote the electro-optical efficiency of deep ultraviolet LED.
3, the third nitride semiconductor LED epitaxial wafer
Utilize MOCVD equipment on template layer, to form N-shaped AlGaN material, growth temperature 1000-1100 ℃, Al component between 25%-35%, thickness 3-4 μ m, dopant is Si, doping content 10
18-10
19/ cm
3.
Quantum well active area is grown on described N-shaped AlGaN material, by 3 groups of Al
aga1
-an/Al
cin
dga
1-c-dn Multiple Quantum Well forms.Wherein quantum is built Al
cin
dga
1-c-dthe Al amount of component b of N between 20%-30%, between In component 0.5-2%, thickness 6-10nm, and keep quantum build Al
cin
dga
1-c-dthe energy gap of N is no more than the energy gap of N-shaped layer; Quantum well Al
aga
1-athe Al component a of N is between 15%-20%, and maintenance quantum well Al
aga
1-athe energy gap of N is less than Al
cin
dga
1-c-dthe energy gap that N quantum is built, quantum well thickness 1-3nm.Quantum well active area growth temperature 900-950 ℃, front 2 groups of quantum are built and trap all adulterates Si, doping content 10
17-10
18/ cm
3, the 3rd group of quantum built and trap all undopes, and the plain quantum of in the end growing after a quantum well layer is built the growth of end quantum well active area; The main glow peak wavelength of quantum well active area is between 320-340nm.
Non-carrier barrier layer of having a mind to doping is grown on described quantum well active area, material is AlInN, wherein Al component is 75-85%, and the energy gap that keeps described AlInN layer is greater than the energy gap of N-shaped layer, thickness is 10-20nm, and growth temperature is identical with described quantum well active area growth temperature, only has a mind to pass into Al, In and N source in growth course in MOCVD reative cell, other source and dopant all keep closing, and keep the flow in the source that passes into constant in growth course.
P-type AlGaN layer growth is on described non-carrier barrier layer of having a mind to adulterate, Al component is between 40%-55%, and thickness is 30-70nm, and growth temperature is identical with described quantum well active area growth temperature, p-type dopant is Mg, and p-type dopant doping content is between 4 × 10
19-3 × 10
20/ cm
3.
P-type GaN ohmic contact layer is grown on described p-type AlGaN layer, and thickness is 50-80nm, and growth temperature is 900-950 ℃, and is no more than the growth temperature of described quantum well, and p-type dopant is Mg, and p-type dopant doping content is between 4 × 10
19-3 × 10
20/ cm
3.Complete after the growth of deep ultraviolet LED epitaxial wafer, carry out high annealing, to activate p-type dopant.
So far, by reference to the accompanying drawings the multiple embodiment of the present invention be have been described in detail.Describe according to above, those skilled in the art should have clearly understanding to the present invention.
In sum, the invention provides a kind of nitride semiconductor LED epitaxial wafer, device and preparation method thereof.This nitride semiconductor LED epitaxial wafer is by introducing a kind of non-carrier barrier layer (uEBL) of having a mind to doping, in effectively realizing charge carrier and stopping, reduce even to eliminate the adverse effect of Mg diffusion for LED quantum well radiation efficiency, thereby effectively improve the quantum efficiency of LED.The advantage of this invention effect in nitride ultraviolet LED is comparatively remarkable, and in nitride deep ultraviolet LED, effect is particularly evident.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only 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., within all should being included in protection scope of the present invention.
Claims (15)
1. a nitride semiconductor LED epitaxial wafer, is characterized in that, comprising:
Substrate; And
Be deposited on successively template layer, N-shaped layer, quantum well active area, carrier barrier layer and the p-type layer of the nitride material on described substrate;
Wherein, in described p-type layer, doped chemical at least comprises Mg; Described carrier barrier layer is the nitride material that contains Al element, and the Mg element being infiltrated by p-type layer except the later stage, do not mix Mg element in depositing operation its early stage.
2. nitride semiconductor LED epitaxial wafer according to claim 1, is characterized in that, the energy gap of described carrier barrier layer is greater than the energy gap of described quantum well active area and described N-shaped layer.
3. nitride semiconductor LED epitaxial wafer according to claim 2, the material of described carrier barrier layer is Al
xin
yga
1-x-yn, wherein, 0<x<l, 0≤y≤0.2.
4. nitride semiconductor LED epitaxial wafer according to claim 1, is characterized in that, in the material of described carrier barrier layer, Al elemental constituent is greater than Al elemental constituent in the material of N-shaped layer and quantum well active area.
5. nitride semiconductor LED epitaxial wafer according to claim 4, described carrier barrier layer thickness is between between 2nm to 30nm.
6. nitride semiconductor LED epitaxial wafer according to claim 1, described quantum well active area is by one or more groups Al
ain
bga
1-a-bn/Al
cin
dga
1-c-dn structure composition, wherein, quantum well layer Al
ain
bga
1-a-bn energy gap E
gabe less than quantum barrier layer Al
cin
dga
1-c-dn energy gap E
gc, and 0≤a<1,0≤b≤0.2,0≤c<l, 0≤d≤0.2.
7. nitride semiconductor LED epitaxial wafer according to claim 6, the peak value of the main glow peak of the luminescent spectrum of described quantum well active area is in the scope of 210nm to 400nm.
8. nitride semiconductor LED epitaxial wafer according to claim 7, the peak value of the main glow peak of the luminescent spectrum of described quantum well active area is in the scope of 230nm to 300nm.
9. according to the nitride semiconductor LED epitaxial wafer described in any one in claim 1 to 8, the material of described substrate is sapphire, monocrystalline silicon, carborundum, zinc oxide, gallium nitride or aluminium nitride.
10. according to the nitride semiconductor LED epitaxial wafer described in any one in claim 1 to 8, described template layer comprises one or more layers nitride material, and every one deck at least contains the one in Al, Ga, In element set.
11. according to the nitride semiconductor LED epitaxial wafer described in any one in claim 1 to 8, and it is only transparent that the material of described template layer sends for the quantum well active area of described LED.
12. 1 kinds of nitride semiconductor LED devices, is characterized in that, comprising:
Substrate;
Be deposited on successively template layer, N-shaped layer, quantum well active area, carrier barrier layer, the p-type layer of the nitride material on described substrate;
Reflector and p-type electrode, be deposited on the top of described p-type layer; And
N-shaped electrode, is formed on a step, and this step is by p-type layer, carrier barrier layer and quantum well active area described in etching from bottom to top, and ends at N-shaped layer and form;
Wherein, in described p-type layer, doped chemical at least comprises Mg; Described carrier barrier layer is the nitride material that contains Al element, and except the Mg element being infiltrated by p-type layer, do not mix Mg element in depositing operation its early stage.
Described in 13. 1 kinds of claims 12, the preparation method of nitride semiconductor LED device, is characterized in that, comprising:
Step S202 deposits successively template layer, N-shaped layer, quantum well active area, carrier barrier layer, p-type layer on substrate, obtains iii-nitride light emitting devices epitaxial wafer, and it is carried out to annealing in process to activate the p-type dopant in p-type layer;
Step S204, the predeterminated position on described iii-nitride light emitting devices epitaxial wafer etches away p-type layer, carrier barrier layer and quantum well active area, exposes N-shaped layer, to form a step;
Step S206 prepares N-shaped electrode on the N-shaped layer of described step; And
Step S208 prepares reflector and p-type electrode, thereby forms described nitride semiconductor LED device on the p-type layer of etching not.
14. 1 kinds of nitride semiconductor LED devices, is characterized in that, comprising:
Conductive supporting substrate, its double p-type electrode that does;
Be positioned at successively the conductive reflective on conductive supporting substrate, and the p-type layer of nitride material, carrier barrier layer, quantum well active area, N-shaped layer; And
Be formed at the N-shaped electrode on described N-shaped layer;
Wherein, in described p-type layer, doped chemical at least comprises Mg; Described carrier barrier layer is the nitride material that contains Al element, and except the Mg element being infiltrated by p-type layer, do not mix Mg element in depositing operation its early stage.
Described in 15. 1 kinds of claims 14, the preparation method of nitride semiconductor LED device, is characterized in that, comprising:
Step S302 forms successively template layer, N-shaped layer, quantum well active area, carrier barrier layer, p-type layer on substrate, obtains nitride semiconductor LED epitaxial wafer, and it is carried out to annealing in process to activate the p-type dopant in p-type layer;
Step S304 in preparation reflector, described p-type layer surface, electroplates or bonding conductive supporting substrate on reflector; And
Step 306, removes substrate and template layer, exposes N-shaped layer, makes N-shaped electrode, forms described nitride semiconductor LED device.
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Application publication date: 20140521 |