CN107293647A - A kind of light emitting diode with quantum dots and preparation method thereof - Google Patents
A kind of light emitting diode with quantum dots and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- 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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- H10K50/00—Organic light-emitting devices
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- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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Abstract
This application discloses a kind of light emitting diode with quantum dots and preparation method thereof, including substrate, negative electrode, electron transfer layer, quantum dot light emitting layer, hole transmission layer and the anode stacked gradually, it is characterised in that：The upper surface of described electron transfer layer is provided with the nano concavo-convex structure changed in gradient along outgoing light direction in paracycle or aperiodicity shape and refractive index.A kind of efficiency of inverted structure light emitting diode with quantum dots described herein is obviously improved, and its efficiency leads and bounds ahead of other and is inverted quantum dot device.
Description
Technical field
The present invention relates to photoelectric device technical field, and in particular to a kind of efficient pole of inverted structure quantum dot light emitting two
Pipe and preparation method thereof.
Background technology
Light emitting diode with quantum dots (QLED) is a kind of electroluminescent selfluminous element using quantum dot as luminescent layer.Quantum dot
It is that particle diameter is less than or close to the semiconductor nanocrystal of Exciton Bohr Radius, the yardstick of its three dimensions is usual in below 10nm,
The motion of internal electronics and hole in all directions is restricted.Quantum dot applied to illumination field typically has
Nucleocapsid structure, surface is by ligand passive.Because electronics and hole are by quantum confinement, quantum dot has discrete level structure.This
Planting discrete level structure causes quantum dot to have unique optical property.Stimulated whenever by light or electricity, quantum dot will
Fluorescence is sent, the wavelength of fluorescence determines that this characteristic enables quantum dot to change by the composition material and size shape of quantum dot
The light color that changing light is sent.The glow peak of quantum dot is narrow, glow color with own dimensions are adjustable, luminous efficiency is high, very
It is suitable as the luminescent material of display device.OLED is contrasted, QLED has higher theoretical luminous efficiency, Color tunable, colour gamut more
Extensively, color saturation and vividness more preferably, the more low advantage of energy consumption cost so that quanta point electroluminescent technology turns into the next generation
The favourable candidate of new Display Technique.
In recent years, all obtained on material and device architecture can very big progress by QLED.Wherein, it is inverted in terms of device architecture
QLED devices have many significant advantages by extensive concern because of it.Most prominent is exactly to be inverted device to have splendid dutycycle,
Nearly 100 ﹪ aperture opening ratio can be achieved, so as to make full use of pixel space to design many tube drive circuits.Compared to LTPS techniques into
This height and can only small area applications shortcoming, being inverted device can be integrated with ripe n-channel a-Si base TFT drive circuits, low
Cost prepares large-area displays panel.
In the continuous evolution process of technology, the materials such as ZnO nano particle, AZO are introduced as electron transfer layer to being inverted
Meaning of the QLED development with milestone, the QLED devices of preparation show very excellent performance.But, the system of these materials
It is standby to generally require, by methods such as magnetron sputtering, alds, not only to take and cost is very high.Therefore, with sol-gel process
Electric transmission layer film is prepared etc. solwution method, is necessary so as to reduce QLED costs.But prepared by solwution method faces again
How many technical barriers, for example, eliminate or reduce property of the influence in upper layer of material coating process to its subsurface material to device
Can be most important.
On the other hand, the light extraction of QLED devices is confined, and the refractive index in device between layers is mismatched, gold
Category electrode surface plasmon, base substrate loss etc. can all limit the taking-up of light, and fundamentally limit its efficiency enters one
Step development.Research shows, device is optimized and improved using light control technique, interface optimization technique etc., it is possible to achieve device
The significant increase of part performance.It can realize that light regulates and controls to a certain extent by introducing special optical texture in the devices, it is known that
Effective optical texture include microlens array, metal nanoparticle, aperiodic array, optical microcavity etc..
The Chinese patent of Application No. 200880007531.6 discloses a kind of inorganic light-emitting dress based on core shell quantum dots
Put, including transparent substrates, first electrode, the second electrode relative with first electrode, quantum dot polycrystalline luminescent layer.This lights
The device not electronics containing level-density parameter, hole transmission layer, not containing decorative layer and light extraction structures, device performance is poor, nothing
The need for method meets practical application.
Application No. 201010171667.X, 201410146156.0 Chinese patent disclose a kind of quantum dot light emitting
Device, and electronics and hole transmission layer are introduced in the devices, but without decorative layer and light extraction structures, and not to being inverted
Prepared by structure devices and its solwution method proposes solution.
2014, Jin Jang etc. (ACS Appl.Mater.Interfaces 2014,6,2508-2515) published an article
Inverted structure QLED devices prepared by a kind of whole soln hair are disclosed, the AZO negative electrodes modified using Cs2CO3, device performance is obtained
Lifting.But due to light extraction efficiency is very low, device performance is poor, and the dopant containing alkali metal is unstable.
2016, Shuming Chen etc. (ACS Appl.Mater.Interfaces 2016,8,5493-5498) were delivered
Article discloses a kind of inversion QLED devices of utilization ZnO nano particle, because electron transfer layer is not modified, and light takes out limited
System, the device EQE of optimum performance is only 2.72%.
The content of the invention
In order to solve the above technical problems, the present inventor passes through long-term research and innovation, a kind of efficient be inverted is invented and has tied
Structure light emitting diode with quantum dots and preparation method thereof.
A kind of light emitting diode with quantum dots described herein, including stack gradually substrate, negative electrode, electron transfer layer,
Quantum dot light emitting layer, hole transmission layer and anode, it is characterised in that：It is in paracycle that the upper surface of described electron transfer layer, which is provided with,
Or the nano concavo-convex structure that aperiodicity shape and refractive index change in gradient along outgoing light direction.
Preferably, the electron transfer layer is metal-oxide film prepared by sol-gel process, described electric transmission
The upper surface of layer has interface-modifying layer.
Preferably, the substrate is glass or flexiplast, or glass or plastic base provided with TFT drive circuits.
Preferably, at least a kind of in the anode and negative electrode is transparent.
Preferably, the electrode that the negative electrode is made for indium tin oxide or aluminium zinc oxide or AgNW materials, or, it is described
Negative electrode is the electrode that Al or Ag or Mg or Ca or Ba materials are made.
Preferably, the anode is the electricity that indium tin oxide or fluorine tin-oxide or aluminium zinc oxide or AgNW materials are made
Pole, or, described anode are the electrode that Au or Pt or Pd materials are made.
Preferably, the electron transport layer materials are ZnO or TiOx, preparation method is sol-gel process.
Preferably, the hole transmission layer is Polyglycolic acid fibre-poly- (styrene sulfonate), poly- (9- vinyl clicks
Azoles), the one or more in poly- [double (4- phenyl) (2,4,6- trimethylphenyls) amine].
Preferably, the interface-modifying layer is polyethyleneimine, polyethoxy aziridine, 9,9- dioctyl fluorenes -9,9-
One or more in double (N, N- DimethylAminopropyl) fluorenes.
Preferably, the quantum dot in the quantum dot light emitting layer is the one or more in red, green, blue color quantum dot, amount
Son point is single or multiple lift containing that can form the part of stable coordination, described quantum dot light emitting layer with surface.
The application, which further relates to described preparation method, to be included：Cathode layer is set on substrate, in the substrate with cathode layer
Upper making electron transfer layer, coining nano concavo-convex structure, makes quantum dot successively on the electron transport layer on the electron transport layer
Luminescent layer, hole transmission layer and anode.
Preferably, described preparation method is specifically, (1) makes cathode layer on substrate, by the substrate with cathode layer
It is sequentially placed into detergent, deionized water, acetone, ethanol, deionized water and is cleaned by ultrasonic, dries, then carry out after the completion of cleaning
UV ozone processing；(2) preparing metal oxide precursor liquid solution；(3) on the substrate in step (1), in spin-coating step (2)
Metal oxide precursor solution, form electron transfer layer, on the electron transport layer coining nano concavo-convex structure；(4) will step
Suddenly spin coating quantum dot solution on the electron transfer layer of (3), forms quantum dot light emitting layer；(5) spin coating is empty on quantum dot light emitting layer
Cave transport layer；(6) layer of metal anode is plated on step (5) hole transmission layer.
Preferably, step (3) also includes, and interface-modifying layer is introduced in the upper surface of described electron transfer layer.
Preferably, by chemical etching, electron beam deposition, evaporation, sputtering, laser direct-writing, holography, self-assembling method
Any one technique prepares nano concavo-convex structure on template substrate, forms the impression block with nano concavo-convex structure, uses
Described impression block coining on the electron transfer layer with interface-modifying layer goes out a nanometer concaveconvex structure.The soft impressing of the nanometer
Technique includes impression block and electron transfer layer flat contact, application 3-10bar pressure, or heating ultraviolet to electron transfer layer are solid
Change, the step such as demoulding.
Preferably, described cathode thickness is controlled in 100-200nm；Electron transfer layer thickness control is 40-80nm；Interface
Decorative layer thickness control is 4-15nm；Between the preferred 200-600nm of nano concavo-convex structural cycle, groove depth is accounted between 20-30nm
Sky is than between 0.5-0.6.
Preferably, quantum dot light emitting layer thickness control is 30-100nm, and thickness of hole transport layer is 40-100nm, and anode is thick
Degree control is 100-200nm.
It is preferred that, the light emitting diode with quantum dots preparation method is solwution method, including rotary coating, slot coated, is scraped
One or more in painting, intaglio printing, silk-screen printing, inkjet printing, compatible volume to volume preparation technology.
It is preferred that, high temperature sintering need to be carried out to quanta point material in the light emitting diode with quantum dots solwution method manufacturing process
Processing, prevents the influence of upper strata solvent.Any one layer all needs selection specific solvent to reduce shadow of the coating process to lower film
Ring.
It is preferred that, the material of impression block is selected from quartz, silicon, nickel, carbon in described organic solar batteries preparation method
Plain steel, carborundum, Al-Doped ZnO, makrolon, polyvinyl chloride or polybutyl methacrylate, dimethione, polyphenyl
One kind in ethene, acrylic acid or PFPE.
By such scheme, the present invention at least has advantages below：
A kind of nano concavo-convex structure of light emitting diode with quantum dots described herein is for the regulatory mechanism of light：Hair
Nano concavo-convex structure on optical diode can then make it that the electric field line close to cathode side is more concentrated, and electric-field intensity is bigger, carries
The cut-in voltage of the injection reduction device of high electronics；The quasi- random structure that refractive index changes in gradient can reduce between layers
Refractive index it is unbalance, reduce light total reflection, in wide spectral range improve light extraction efficiency.A kind of be inverted described herein is tied
The efficiency of structure light emitting diode with quantum dots is obviously improved, and its efficiency leads and bounds ahead of other and is inverted quantum dot device.
Brief description of the drawings
Accompanying drawing 1 is the light emitting diode with quantum dots structural representation of the present invention；
Accompanying drawing 2 is light emitting diode with quantum dots of the present invention and the integrated structure active matrix driving of n-channel a-Si base TFT drive circuits
Array QLED (AMQLED) technical scheme schematic diagram；
Accompanying drawing 3 is the template schematic diagram that nanometer embossing of the present invention has nano concavo-convex structure；
Accompanying drawing 4 is the schematic shapes of nano concavo-convex structure under embodiment；
Accompanying drawing 5 is the SEM knot that the sol-gel process ZnO film of embodiment one is introduced after nano concavo-convex structure
Structure schematic diagram；
Accompanying drawing 6 is that the specific embodiment of the invention one, embodiment two and the contrast of comparative example current density voltage curve are shown
It is intended to；
Accompanying drawing 7 is that the specific embodiment of the invention one, embodiment two and comparative example brightness-voltage curve contrast signal
Figure；
Accompanying drawing 8 is that the specific embodiment of the invention one, embodiment two and comparative example power efficiency-voltage curve contrast are shown
It is intended to；
Accompanying drawing 9 is that the specific embodiment of the invention one, embodiment two and comparative example Current efficiency-voltage curve comparison show
It is intended to；
Accompanying drawing 10 is the specific embodiment of the invention one, embodiment two and comparative example EL spectrum contrast schematic diagrams.
Embodiment
In order that those skilled in the art more fully understand the technical scheme in the present invention, below in conjunction with the accompanying drawings and implement
Example, the embodiment to the present invention is described in further detail.Following examples are used to illustrate the present invention, but are not used to limit
The scope of the present invention processed.
The invention provides a kind of efficient inverted structure light emitting diode with quantum dots and preparation method thereof.As Fig. 1 is provided
The light emitting diode with quantum dots device architecture schematic diagram of the present invention, including the substrate 101, negative electrode 102, the electronics that stack gradually are passed
Defeated layer 103, quantum dot light emitting layer 104, hole transmission layer 105 and anode 106.
The electron transfer layer is metal-oxide film prepared by sol-gel process, preferably ZnO film, its upper surface
With interface-modifying layer, or provided with paracycle, aperiodicity shape and refractive index along receiving that outgoing light direction changes in gradient
Rice concaveconvex structure 107, or have both concurrently.
The inverted structure light emitting diode with quantum dots, can be integrated with ripe n-channel a-Si base TFT drive circuits, and
By selecting transparent negative electrode or anode to realize bottom emitting, top emitting, bottom emitting transparent devices are pushed up.
Fig. 2 gives a kind of integrated using the inversion light emitting diode with quantum dots and n-channel a-Si base TFT drive circuits
Build active matrix driving array QLED (AMQLED) technical scheme.Provided with the base with n-channel a-Si base TFT drive circuits 202
On plate 201, preferably glass or transparent plastic substrate make the formation of the inverted structure QLED devices 100 rgb pixel array, as
Each the lead 203 such as independent cathode leg, scan line, data wire is connected to drive circuit 207 to pixel array, then passes through winding displacement
205 are connected to sequential control circuit 208；The public anode 206 of pel array equally introduces SECO electricity by lead 204
Road, forms active matrix driving array QLED (QLED) display panel.The transparent negative electrode of QLED devices selection or anode can realize that bottom is sent out
Penetrate, top emitting, push up bottom emitting transparent devices.Wherein, top emitting QLED can realize nearly 100 ﹪ aperture opening ratio, and pixel arrangement is closeer
Collection, display panel brightness are higher.
Make in the integrated QLED device process, transparent indium tin oxide, aluminium zinc oxide may be selected in negative electrode 102
Or AgNW electrodes, or opaque Al, Ag, Mg, Ca, Ba low work function reflecting electrode, the preferred 100-200nm of thickness.Sun
Pole 106 may be selected transparent indium tin oxide, fluorine tin-oxide, aluminium zinc oxide or AgNW electrodes, or opaque Au,
The high work function reflecting electrode such as Pt and Pd, the preferred 100-200nm of thickness.But at least a kind of in anode and negative electrode is transparent.
Make in the integrated QLED device process, the material of electron transfer layer 103 is ZnO or TiOxSoft metal is aoxidized
Thing film, preparation method is sol-gel process, preferably ZnO film, the preferred 40-80nm of thickness.On soft electron transfer layer
Paracycle, aperiodicity shape and refractive index can be obtained along emergent light side by the nano impression of impression block 301 as shown in Figure 3
To the nano concavo-convex structure changed in gradient.
The material of impression block is selected from quartz, silicon, nickel, carbon steel, carborundum, Al-Doped ZnO, makrolon, polychlorostyrene second
One kind in alkene or polybutyl methacrylate, dimethione, polystyrene, acrylic acid or PFPE.In template
Pass through any one technique system in chemical etching, electron beam deposition, evaporation, sputtering, laser direct-writing, holography, self-assembling method
The standby nano concavo-convex array of structures 302 matched with pixel size, and make alignment mark 303.
The interface-modifying layer of electron transfer layer 103 is polyethyleneimine (PEI), polyethoxy aziridine (PEIE), 9,9-
Any one or more in double (N, the N- DimethylAminopropyl) fluorenes (PFN) of dioctyl fluorene -9,9-, the preferred 4-15nm of thickness.
Hole transmission layer 105 is organic material Polyglycolic acid fibre-poly- (styrene sulfonate) (PEDOT:PSS), gather
One or more in (9- vinyl carbazoles) (PVK), poly- [double (4- phenyl) (2,4,6- trimethylphenyl) amine] (PTAA) are thick
Spend preferred 40-100nm.
Quantum dot in quantum dot light emitting layer 104 is any one or more in red, green, blue color quantum dot, quantum dot
Containing that can form the part of stable coordination with surface, the quantum dot light emitting layer can be alternatively multilayer for individual layer.
Beneficial effects of the present invention are further illustrated below with reference to embodiment and comparative example.
Embodiment one
In one embodiment, impression block uses soft polydimethylsiloxane (PDMS), the shape of nano concavo-convex structure
Shape is as shown in figure 4, its cycle preferred 400nm, groove depth is 50nm, and dutycycle is 0.6.
A kind of light emitting diode with quantum dots with nanometer light extraction structures, transparent negative electrode on substrate,
ZnO electron transfer layers, CdSe/ZnS quaternary graded alloy quantum dot light emitting layer, PVK/PEDOT：PSS composite hole transporting layers and
Al metal anodes, the method such as the preferred solwution method spin coating of specific manufacture craft, the vacuum thermal evaporation of each Rotating fields, or other known sides
Method, it is preferable that in the present embodiment, the specific process of element manufacturing is as follows：
(1) substrate and negative electrode cleaning：After common float glass substrate base is cleaned with detergent, pattern is sputtered in one side
The ito thin film of change is used as transparent cathode.By the substrate base with ITO be sequentially placed into detergent, deionized water, acetone, ethanol,
In deionized water, it is cleaned by ultrasonic every time after the completion of 10min, cleaning and is placed in 110 DEG C of constant temperature dryings in baking oven, substrate base is put into
UV ozone processing 10min is carried out in UV ozone machine；
(2) ZnO precursor solution is prepared：By the water zinc acetate (Zn (CH of 110mg bis-3COO)2·2H2O, 99.5%, Sigma-
Aldrich 1mL) is dissolved in 2-methyl cellosolve (CH3OCH2CH2OH, 99.8%, Sigma-Aldrich) in solution, then
Add 30 μ L monoethanolamines (NH2CH2CH2OH, Sigma-Aldrich) solution, stirs 12h at 50 DEG C, obtains before ZnO sol-gels
Drive liquid solution.
(3) electron transfer layer is made and structure is introduced：The spin coating one on the substrate base that step (1) is handled well in air
Layer ZnO precursor solution.Control rotating speed be 4000rpm, time be 60s, be subsequently placed on temperature control plate and cover PDSM making ides
Plate, apply 3bar pressure, 150 DEG C annealing 10min, obtain thickness be 40-60nm ZnO film and film on the cycle about
400nm, groove depth about 20nm, the random nano concavo-convex structure of standard that dutycycle is 0.6.Sol-gel process ZnO is given referring to Fig. 5
The SEM structural representation that film is introduced after structure.Particularly, the pressure of application need to accurately control to obtain low groove
Deep structure, reduces the influence to quantum dot light emitting layer pattern.
(4) substrate after step (3) processing is transferred to glove box, spin coating quantum dot solution.Quantum dot therein is
CdSe/ZnS core shell structures, and ternary alloy three-partalloy transition component is added in CdSe luminous nucleons and ZnS shells, realize the progressively mistake of lattice
Cross, effectively reduce the internal pressure that quantum dot lattice defect is caused, so that quantum dot has higher luminous efficiency and steady
Qualitative, its glow peak is 529nm, and half-peak breadth is about 24nm.Quantum dot is dispersed in normal octane, concentration about 10mg/ml, and spin coating turns
Speed is 1500rpm, and the time is 60s.Then 150 DEG C of high annealing 10min, this process plays the work of high temperature sintering quantum dot layer
With influence of the solution spin coating to quantum dot light emitting layer after can greatly reducing finally gives the quantum dot that thickness is 40-60nm
Film.
(5) hole transmission layer makes：Spin coating PVK o-dichlorobenzene solution (concentration is 10mg/ml), spin coating in glove box
Rotating speed is 2500rpm, spin-coating time 60s, 150 DEG C of annealing 10min.Then spin coating PEDOT again：PSS solution, spin coating rotating speed is
2000rpm, spin-coating time 60s, then 90 DEG C of annealing 15min.Obtain thickness about 80nm PVK/PEDOT：PSS is combined hole transport
Layer.
(6) metal anode makes：By above-mentioned steps (5) processing substrate be transferred to hot evaporation system, vacuum >=1 ×
10-4One layer of aluminium electrode is deposited under the conditions of Pa, thickness is 100-150nm, that is, obtains the quantum dot hair with nanometer light extraction structures
Optical diode.
Embodiment two
A kind of light emitting diode with quantum dots with electron transfer layer decorative layer, transparent negative electrode on substrate,
ZnO electron transfer layers, PEI decorative layers, CdSe/ZnS quaternary graded alloy quantum dot light emitting layer, PVK/PEDOT：PSS compound airs
Cave transport layer and Al metal anodes, the method such as the preferred solwution method spin coating of specific manufacture craft, the vacuum thermal evaporation of each Rotating fields, or
Other known methods, it is preferable that in the present embodiment, it is as follows that light emitting diode with quantum dots makes specific process：
(1) substrate and negative electrode cleaning：Be the same as Example one.
(2) ZnO precursor solution is prepared：Be the same as Example one.
(3) electron transfer layer makes and modified：One layer of the spin coating on the substrate base that step (1) is handled well in air
ZnO precursor solution.Control rotating speed be 4000rpm, time be 60s, 120 DEG C of annealing 10min, it is 40-60nm's to obtain thickness
ZnO film；The spin coating PEI 2-methyl cellosolve solution (concentration is 0.4wt%) on ZnO film, controls the rotating speed to be
5000rpm, time are 60s, 100 DEG C of annealing 10min, obtain the modification layer film that thickness is 4-8nm.
(4) quantum dot light emitting layer makes：Be the same as Example one.
(5) hole transmission layer makes：Be the same as Example one.
(6) metal anode makes：Be the same as Example one, that is, obtain the pole of quantum dot light emitting two with electron transfer layer decorative layer
Pipe.
Comparative example
A kind of light emitting diode with quantum dots, transparent negative electrode, ZnO electron transfer layers, CdSe/ZnS on substrate
Quaternary graded alloy quantum dot light emitting layer, PVK/PEDOT：PSS composite hole transporting layers and Al metal anodes, the tool of each Rotating fields
The methods such as the preferred solwution method spin coating of body manufacture craft, vacuum thermal evaporation, or other known methods, it is preferable that in present embodiment
In, the specific process of element manufacturing is as follows：
(1) substrate and negative electrode cleaning：Be the same as Example one.
(2) ZnO precursor solution is prepared：Be the same as Example one.
(3) electron transfer layer makes：In air on the substrate base that step (1) is handled well spin coating layer of ZnO forerunner
Liquid solution.Control rotating speed be 4000rpm, time be 60s, 120 DEG C of annealing 10min, obtain the ZnO film that thickness is 40-60nm.
(4) quantum dot light emitting layer makes：Be the same as Example one.
(5) hole transmission layer makes：Be the same as Example one.
(6) metal anode makes：Be the same as Example one, that is, obtain light emitting diode with quantum dots.
Fig. 6-10 is the performance comparison schematic diagram of embodiment obtained device, is passed by introducing nanometer light extraction structures or electronics
Defeated layer decorative layer, device efficiency is obviously improved.The high-performance prepared using the present invention is inverted light emitting diode with quantum dots,
Its device efficiency leads and bounds ahead of other and is inverted quantum dot device.
The nano concavo-convex structure of light emitting diode with quantum dots of the present invention is for the regulatory mechanism of light：Light emitting diode
On nano concavo-convex structure can then cause the electric field line close to cathode side more to concentrate, electric-field intensity is bigger, improves electronics
The cut-in voltage of injection reduction device；The quasi- random structure that refractive index changes in gradient can reduce refractive index between layers
It is unbalance, light total reflection is reduced, light extraction efficiency is improved in wide spectral range.Introducing electron transfer layer decorative layer can effectively drop
The work function of low negative electrode, and improve sol-gel ZnO pattern, reduce influences of the ZnO to quantum dot light emitting layer.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is some improvement and
Modification, these improvement and modification also should be regarded as protection scope of the present invention.
Claims (16)
1. a kind of light emitting diode with quantum dots, including substrate, negative electrode, electron transfer layer, quantum dot light emitting layer, the sky stacked gradually
Cave transport layer and anode, it is characterised in that：The upper surface of described electron transfer layer is provided with refractive index along outgoing light direction in ladder
Spend the nano concavo-convex structure of change.
2. a kind of light emitting diode with quantum dots according to claim 1, it is characterised in that：Described nano concavo-convex structure
Between cycle 200-600nm, groove depth is between 20-30nm, between dutycycle 0.5-0.6.
3. a kind of light emitting diode with quantum dots according to claim 1, it is characterised in that the electron transfer layer is molten
Metal-oxide film prepared by glue-gel method, the upper surface of described electron transfer layer has interface-modifying layer.
4. a kind of light emitting diode with quantum dots according to claim 1, it is characterised in that the substrate is glass or flexibility
Plastics, or glass or plastic base provided with TFT drive circuits.
5. a kind of light emitting diode with quantum dots according to claim 1, it is characterised in that in the anode and negative electrode at least
It is transparent to have a kind of.
6. a kind of light emitting diode with quantum dots according to claim 4, it is characterised in that
The negative electrode is the electrode that indium tin oxide or aluminium zinc oxide or AgNW materials are made, or
Described negative electrode is the electrode that Al or Ag or Mg or Ca or Ba materials are made.
7. a kind of light emitting diode with quantum dots according to claim 4, it is characterised in that the anode is indium tin oxide
Or the electrode that fluorine tin-oxide or aluminium zinc oxide or AgNW materials are made, or, described anode is Au or Pt or Pd material systems
Into electrode.
8. a kind of light emitting diode with quantum dots according to claim 1, it is characterised in that the electron transport layer materials are
ZnO or TiOx。
9. a kind of light emitting diode with quantum dots according to claim 1, it is characterised in that the hole transmission layer is poly- second
Support dioxy thiophene-poly- (styrene sulfonate), poly- (9- vinyl carbazoles), poly- [double (4- phenyl) (2,4,6- trimethylphenyls)
Amine] in one or more.
10. a kind of light emitting diode with quantum dots according to claim 1, it is characterised in that the interface-modifying layer is poly-
One kind or many in double (N, the N- DimethylAminopropyl) fluorenes of aziridine, polyethoxy aziridine, 9,9- dioctyl fluorenes -9,9-
Kind.
11. a kind of light emitting diode with quantum dots according to claim 1, it is characterised in that in the quantum dot light emitting layer
Quantum dot be one or more in red, green, blue color quantum dot, quantum dot contains can form matching somebody with somebody for stable coordination with surface
Body, described quantum dot light emitting layer is single or multiple lift.
12. a kind of preparation method of light emitting diode with quantum dots a kind of as described in any one of claim 1~10, its feature exists
In described preparation method includes：Cathode layer is set on substrate, electron transfer layer is made on the substrate with cathode layer,
Coining nano concavo-convex structure, makes quantum dot light emitting layer, hole transmission layer successively on the electron transport layer on the electron transport layer
And anode.
13. a kind of preparation method of light emitting diode with quantum dots according to claim 11, it is characterised in that described system
Preparation Method specifically,
(1) cathode layer is made on substrate, the substrate with cathode layer is sequentially placed into detergent, deionized water, acetone, second
It is cleaned by ultrasonic in alcohol, deionized water, is dried after the completion of cleaning, then carries out UV ozone processing；
(2) preparing metal oxide precursor liquid solution；
(3) on the substrate in step (1), the metal oxide precursor solution in spin-coating step (2) forms electric transmission
Layer, on the electron transport layer coining nano concavo-convex structure；
(4) by spin coating quantum dot solution on the electron transfer layer of step (3), quantum dot light emitting layer is formed；
(5) the spin coating hole transmission layer on quantum dot light emitting layer；
(6) layer of metal anode is plated on step (5) hole transmission layer.
14. a kind of preparation method of light emitting diode with quantum dots according to claim 12, it is characterised in that step (3)
Also include, interface-modifying layer is introduced in the upper surface of described electron transfer layer.
15. a kind of preparation method of light emitting diode with quantum dots according to claim 12, it is characterised in that described the moon
Pole thickness control is in 100-200nm；Electron transfer layer thickness control is 40-80nm；Interface-modifying layer thickness control is 4-15nm.
16. the preparation method of a kind of light emitting diode with quantum dots according to claim 13, it is characterised in that quantum dot is sent out
Photosphere thickness control is 30-100nm, and thickness of hole transport layer is 40-100nm, and anode thickness control is 100-200nm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683613A (en) * | 2012-05-02 | 2012-09-19 | 陕西科技大学 | Top emission organic electroluminescent display (OELD) and preparation method thereof |
| CN103078057A (en) * | 2013-01-29 | 2013-05-01 | 苏州大学 | Organic solar battery and manufacturing method thereof |
| CN103219476A (en) * | 2013-04-25 | 2013-07-24 | 苏州大学 | Organic electroluminescence light-emitting diode and manufacturing method thereof |
| CN103474586A (en) * | 2013-09-30 | 2013-12-25 | 苏州大学张家港工业技术研究院 | OLED device and manufacturing method thereof |
| CN105720206A (en) * | 2016-05-06 | 2016-06-29 | Tcl集团股份有限公司 | QLED device and preparation method thereof |
-
2017
- 2017-06-13 CN CN201710441615.1A patent/CN107293647A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683613A (en) * | 2012-05-02 | 2012-09-19 | 陕西科技大学 | Top emission organic electroluminescent display (OELD) and preparation method thereof |
| CN103078057A (en) * | 2013-01-29 | 2013-05-01 | 苏州大学 | Organic solar battery and manufacturing method thereof |
| CN103219476A (en) * | 2013-04-25 | 2013-07-24 | 苏州大学 | Organic electroluminescence light-emitting diode and manufacturing method thereof |
| CN103474586A (en) * | 2013-09-30 | 2013-12-25 | 苏州大学张家港工业技术研究院 | OLED device and manufacturing method thereof |
| CN105720206A (en) * | 2016-05-06 | 2016-06-29 | Tcl集团股份有限公司 | QLED device and preparation method thereof |
Cited By (32)
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|---|---|---|---|---|
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