CN105576144B - Light emitting diode and preparation method thereof - Google Patents
Light emitting diode and preparation method thereof Download PDFInfo
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- CN105576144B CN105576144B CN201610106447.6A CN201610106447A CN105576144B CN 105576144 B CN105576144 B CN 105576144B CN 201610106447 A CN201610106447 A CN 201610106447A CN 105576144 B CN105576144 B CN 105576144B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Abstract
Light emitting diode, including N-type layer, stress release layer, luminescent layer, P-type layer, it is characterised in that：The luminescent layer, which comprises at least one, has the nano-particle layer of quantum effect, and the material of the nano-particle layer is semiconductor, and after to N-type layer and P-type layer Injection Current, the nano-particle layer of the semi-conducting material outwards launches light.
Description
Technical field
The invention belongs to technical field of manufacturing semiconductors, more particularly to a kind of light emitting diode and preparation method thereof.
Background technology
Semiconductor light-emitting-diode has been manufactured since early stage the 1960s（LED）Device, and obtain
Widespread commercial use, its LED structure are to be based on such as metal organic chemical vapor deposition（MOCVD）The crystal of method growth is partly led
Body material layer forms.The LED has the advantages of long lifespan, low in energy consumption, but with the increasingly maturation of technology, LED's uses field
Also increasingly diversification, to LED brightness requirement also more and more higher, how to improve LED power is the difficulty run into LED development
One of topic.Some researchers are improved by adjusting luminous layer structure or P-type layer structure and both growth conditions in LED structure
Hole activation concentration, and then increase effective compound quantity subnumber in luminescent layer.But in order to avoid destroying quantum well layer structure so that
The growth temperature of P-type layer is unable to reach the scope for obtaining preferable crystal mass, and then can not obtain the more excellent P-type layer knot of quality
Structure, causes the electrical property of light-emitting diode can not meet application demand.Further, since the limitation of LED structure feature, can not
More colors output combination from same chip is realized, so as to fetter LED application.
The content of the invention
In view of the above-mentioned problems, the present invention proposes a kind of light emitting diode with nano particle, to improve luminous two
The luminous efficiency of pole pipe and the more colors output combination function for realizing same chip.
Technical solution of the present invention is：
Light emitting diode, including N-type layer, stress release layer, luminescent layer, P-type layer, wherein the luminescent layer comprises at least one
Nano-particle layer with quantum effect, the material of the nano-particle layer is semiconductor, electric when being injected to N-type layer and P-type layer
After stream, the nano-particle layer of the semi-conducting material outwards launches light.
Preferably, the luminescent layer includes a transition zone for improving the nano-particle layer luminous intensity, the transition zone
Material is AlxInyGaX（The ＜ y ＜ 1 of 0≤x ＜ 1,0）, the X is group Ⅴ element；The transition zone has lighting function.
Preferably, the luminescent layer also includes the InGaX/ being inserted between the stress release layer and the transition zone
GaX multi-quantum pit structures.
Preferably, the emission wavelength of the MQW, transition zone is consistent with the emission wavelength of nano-particle layer.
Preferably, the size range of the nano-particle layer is 10 ~ 100, and grain spacing is 0~500.
Preferably, the material of the nano-particle layer is any one or a few the combination in GaX, AlGaX, GaInX.
Preferably, the nano-particle layer is single layer structure.
Preferably, the X is the one of which of As, P or N element.
Preferably, the nano particle is spherical particle, cylindrical particle, spherical and column combination particle, irregular shape
One or more in grain.
Preferably, the P-type layer is made up of hole injection layer and hole transmission layer.
Preferably, the material of the hole injection layer is metal oxide.
Preferably, the material of the hole transmission layer is organic material.
The preparation method that the present invention proposes light emitting diode simultaneously, sequentially forms N-type layer, stress release layer, luminescent layer, P
Type layer, wherein, the luminescent layer formed includes the nano-particle layer with quantum effect, and the material of the nano-particle layer is half
Conductor；After to N-type layer and P-type layer Injection Current, the semiconductor nanoparticle layer outwards launches light.
Preferably, the size of particle in nano-particle layer is adjusted, controls the emission wavelength of light emitting diode.
Preferably, the spacing in nano-particle layer between nano particle is adjusted, realizes change of the nano particle to optical link,
Increase external quantum efficiency.
Preferably, N-type layer, stress release layer, transition zone are formed using chemical vapour deposition technique first, then using physics
Sedimentation forms semiconductor nanoparticle layer and P-type layer.
Preferably, deposited in the nano particle layer surface using physical deposition methods and noted by the hole of metal oxide materials
Enter the P-type layer of the hole transmission layer composition of layer and organic material.
The present invention at least has the advantages that：
1st, the present invention introduces the nano-particle layer of semi-conducting material in the luminescent layer of light emitting diode, by selecting nanometer
The size and material category of particle, adjust the emission wavelength of light emitting diode.
2nd, the transition zone of AlxInyGaX materials is inserted before nano-particle layer, nano-particle layer is reduced and is released with stress
The crystal lattice difference between layer is put, improves crystal mass；In contents in transition zone are adjusted simultaneously, adjust emission wavelength and nano particle
The emission wavelength of layer is consistent, increases the luminous intensity of light emitting diode.
3rd, P-type layer is formed using physical method compared to conventional LED structure, the present invention, its growth temperature is relatively low, avoids brokenly
Bad luminous layer structure, improve the light extraction efficiency of light emitting diode；Simultaneously relatively low growth temperature can reduce energy resource consumption, effectively
Reduce production cost.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and a part for constitution instruction, the reality with the present invention
Apply example to be used to explain the present invention together, be not construed as limiting the invention.In addition, accompanying drawing data be description summary, be not by
Ratio is drawn.
Fig. 1 is the light emitting diode construction schematic diagram of the embodiment of the present invention one.
Fig. 2 is the light emitting diode construction schematic diagram of the embodiment of the present invention two.
In figure：10. substrate；20. n type semiconductor layer；30. stress release layer；40. luminescent layer；41. transition zone；
42. nano-particle layer；43. multiple quantum well layer；50. P-type layer；51. hole injection layer；52. hole transmission layer.
Embodiment
The embodiment of the present invention is described in detail with reference to the accompanying drawings and examples.
Embodiment 1
Referring to accompanying drawing 1, light emitting diode construction includes substrate 10, and the substrate 10 is sapphire, carborundum, silicon, nitridation
The materials such as gallium；N type semiconductor layer 20 is placed in the upper surface of substrate 10, and the n type semiconductor layer 20 is single layer structure or doping concentration
Different sandwich constructions；Stress release layer 30 is placed in the upper surface of n type semiconductor layer 20, and the stress release layer 30 is InGaX/
GaX loop structures；The transition zone 41 that thickness is 10 ~ 100 grows in the upper surface of stress release layer 30, the material of transition zone 41
For AlxInyGaX, wherein 0≤x ＜ 1,0 ＜ y ＜ 1, the X are group Ⅴ element.Nano-particle layer 42 is placed in the upper table of transition zone 41
Face, luminescent layer 40 is formed with transition zone 41, the nano-particle layer 42 is spherical particle, cylindrical particle, spherical combined with column
One or more in particle, irregular shape particle, its material are one kind or several in GaX, AlGaX, GaInX semi-conducting material
The combination of kind；Wherein, the X is the one of which of As, P or N element.The size range of the nano-particle layer is 10 ~ 100
, the present embodiment preferably 20 ~ 50.The nano-particle layer is multilayer or single layer structure, and due to the layer and layer of sandwich construction
The transmittance process of electron hole between middle nano particle be present, and this transmittance process easily reduces electronics in nano-particle layer and answered with hole
Efficiency is closed, so as to cause luminosity and its uniformity to reduce, therefore prioritizing selection individual layer nano particle Rotating fields of the present invention, make
Its luminous efficiency and uniformity of luminance optimize.
When scantling has macro-size to be changed into nano-scale, the quasi-continuum of level near common metal fermi level
Can be changed into discrete energy level in nano particle, exist between each energy level can extreme difference, and when this energy level difference is more than heat energy, electric field energy
Or during magnetic field energy, the uncommon character different from macro object, i.e. quantum effect will be showed.Compared to current conventional use
Nano-metal particle or nanometer organic particle, the semi-conducting material particle of the present embodiment is because of narrow energy present in stock size
It is obvious to hinder the phenomenon to be broadened in nano-sized particles, causes the semiconductor nanoparticle that there is the characteristics of luminescence in itself, so as to
Avoid invalid luminescence phenomenon（Fever phenomenon）Generation, while reduce with the crystal lattice difference of transition zone 41, lift Light-Emitting Diode
Crystal mass.To save preparation technology and ensureing nano particle consistency of performance, the present embodiment uses the maturation of market sale
Semi-conducting material nano particle prepared by business method, and according to practical application request, select the size of nano particle.Due to not
With material and the nano particle of size, its energy gap differs greatly, and when electronics and hole-recombination, can launch different wave length
（That is different colours）Light, with the increase of nanometer diameter, energy gap diminishes, wavelength increase, when diameter of nano particles be 20 ~ 50
, when X is N element, the emission wavelength is 400 ~ 550nm, the light of predominantly bluish-green colour system.Using the nano-particle of different-diameter
The light of different wave length can be obtained, it can finally obtain the optical wavelength of practical application request after being mutually mixed, same so as to realize
The multi-colored light output combination function of chip.Meanwhile be improving luminous efficiency, spacing that can be between flexible modulation nano particle is
0 ~ 50, change of the nano particle to optical link is realized, increases external quantum efficiency.
P-type layer 50 most is set after luminescent layer surface, the P-type layer 50 includes the hole injection layer of metal oxide materials
51 and the hole transmission layer 52 of organic material.The hole injection layer material is tin indium oxide, and its thickness is 500 ~ 2000；Institute
State the material of hole transmission layer 52 and be selected from N, N '-bis-（3- aminomethyl phenyls）- N, N '-diphenyl -1,1 '-diphenyl -4, in 4 '-diamines
One kind, its thickness be 5 ~ 100.
The nano-particle layer of semi-conducting material is introduced in structure of the present invention, electron-hole is for compound hair at nano particle
Light, at the same before nano-particle layer 42 insert AlxInyGaX materials transition zone 41, although semiconductor of the present invention is received
Rice corpuscles both has lighting function in itself, but its effect also need to can just be better achieved by the transition zone of low-potential energy, therefore should
Transition zone 41 effectively provides low-potential energy interface and deposited for nano-particle, at the same avoid nano-particle layer and stress release layer it
Between generation because caused by crystal lattice difference is excessive the defects of, improve crystal mass；In contents in transition zone 41, regulation hair are adjusted simultaneously
Optical wavelength is consistent with the emission wavelength of nano-particle layer, increases the luminous intensity of light emitting diode.
To realize the structure of above-mentioned light emitting diode and its effect, the present invention proposes a kind of preparation method, and its step is main
Including：
Substrate 10 is provided；
Using chemical vapour deposition technique in the superficial growth N-type layer 20 of substrate 10 and stress release layer 30, the chemical gaseous phase
The preferred Metalorganic Chemical Vapor Deposition of sedimentation（Mocvd method）；
After continue deposit transition zone 41 in the surface of stress release layer 30；
Nano-particle layer 42 is deposited in the stress release layer surface using physical deposition methods, wherein the ＜ y ＜ of 0≤x ＜ 1,0
1, the physical deposition methods include sputtering method, vapour deposition method, spin-coating method, spraying process and infusion process, the preferred vapour deposition method of the present embodiment；Institute
State nano-particle layer 42 and the transition zone 41 composition luminescent layer 40；
Physical deposition methods are continued with 52 groups of the surface deposition of hole implanted layer 51 of nano-particle layer 42 and hole transmission layer
Into P-type layer 50, formed light emitting diode construction.In this method, the depositing temperature of the P-type layer is 200 ~ 400 DEG C, much low
The depositing temperature of P-type layer is formed in mocvd method（800~1000℃）, luminous layer structure is avoided damage to, improves light emitting diode
Light extraction efficiency；Simultaneously relatively low growth temperature can effectively reduce production cost.
Embodiment 2
The present embodiment and the difference of embodiment 1 are, in the present embodiment, after the growth of stress release layer 30 terminates, first with
Mocvd method deposition InGaX/GaX multiple quantum well layers 43, then at multiple quantum well layer 43 superficial growth, one layer of transition zone 41, the mistake
It is Al to cross the material of layer 41xInyGaX materials, wherein the ＜ y ＜ 1 of 0≤x ＜ 1,0, nano-particle layer is deposited followed by physical deposition methods
42；The multiple quantum well layer 43, transition zone 41 and nano-particle layer 42 collectively constitute luminescent layer 40；Last deposition of hole implanted layer
51 and hole transmission layer 52 form P-type layer 50 formed light emitting diode construction.
In the present embodiment, In components and nanometer in In components, transition zone 41 in regulation InGaX/GaX multiple quantum well layers 43
The particle diameter of granulosa 42, make the emission wavelength one of multiple quantum well layer 43, the emission wavelength of transition zone 41 and nano-particle layer 42
Cause, lift the brightness of light emitting diode, while adjust the spacing between nano particle, realize the change to light path line, increase hair
The light extraction efficiency of optical diode.
It should be appreciated that above-mentioned specific embodiment is the preferred embodiments of the present invention, the scope of the present invention is not limited to
The embodiment, all any changes done according to the present invention, all belongs within protection scope of the present invention.
Claims (15)
1. light emitting diode, including N-type layer, stress release layer, luminescent layer, P-type layer, it is characterised in that：The luminescent layer is by having
It is made up of the nano-particle layer of quantum effect and the transition zone of the raising nano-particle layer luminous intensity, or by with quantum
The nano-particle layer of effect and improve the transition zone of the nano-particle layer luminous intensity and positioned at the stress release layer and
InGaX/GaX multiple quantum well layers composition between the transition zone, the X is main group group Ⅴ element；The nano-particle layer
Material is semiconductor, and after to N-type layer and P-type layer Injection Current, the nano-particle layer of the semi-conducting material outwards launches light
Line；The buffer layer material is AlxInyGaN（0≤x≤1,0<y<1）, the transition zone has lighting function.
2. light emitting diode according to claim 1, it is characterised in that：The emission wavelength of the MQW, transition zone
It is consistent with the emission wavelength of nano-particle layer.
3. light emitting diode according to claim 1, it is characterised in that：The size range of the nano-particle layer be 10 ~
100, grain spacing is 0~50.
4. light emitting diode according to claim 1, it is characterised in that：The material of the nano-particle layer be GaX,
Any one or a few combination in AlGaX, GaInX.
5. light emitting diode according to claim 1, it is characterised in that：The nano-particle layer is single layer structure.
6. light emitting diode according to claim 1, it is characterised in that：The X is the one of which of As, P or N element.
7. light emitting diode according to claim 1, it is characterised in that：The nano particle is spherical particle, column
One or more in grain.
8. light emitting diode according to claim 1, it is characterised in that：The P-type layer is passed by hole injection layer and hole
Defeated layer composition.
9. light emitting diode according to claim 8, it is characterised in that：The material of the hole injection layer aoxidizes for metal
Thing.
10. light emitting diode according to claim 8, it is characterised in that：The material of the hole transmission layer is organic material
Material.
11. the preparation method of light emitting diode, sequentially form N-type layer, stress release layer, luminescent layer, P-type layer, it is characterised in that：
The luminescent layer formed is by the nano-particle layer with quantum effect and the transition zone of the raising nano-particle layer luminous intensity
Composition, or transition zone and position by the nano-particle layer with quantum effect and the raising nano-particle layer luminous intensity
InGaX/GaX multiple quantum well layers composition between the stress release layer and the transition zone, the X are the race of main group V member
Element；The material of the nano-particle layer is semiconductor；After to N-type layer and P-type layer Injection Current, the semiconductor nanoparticle
Layer outwards launches light；The buffer layer material is AlxInyGaN（0≤x≤1,0<y<1）, the transition zone is with luminous work(
Energy.
12. the preparation method of light emitting diode according to claim 11, it is characterised in that：Adjust nano-particle layer in
The size of grain, control the emission wavelength of light emitting diode.
13. the preparation method of light emitting diode according to claim 11, it is characterised in that：Received in regulation nano-particle layer
Spacing between rice grain, change of the nano particle to optical link is realized, increase external quantum efficiency.
14. the preparation method of light emitting diode according to claim 11, it is characterised in that：Chemical vapor deposition is used first
Area method forms N-type layer, stress release layer, transition zone, then forms semiconductor nanoparticle layer and p-type using physical deposition methods
Layer.
15. the preparation method of light emitting diode according to claim 14, it is characterised in that：Using physical deposition methods in institute
State the P that nano particle layer surface deposition is made up of the hole injection layer of metal oxide materials and the hole transmission layer of organic material
Type layer.
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