CN108232023A - A kind of inverted structure light emitting diode with quantum dots and preparation method thereof - Google Patents
A kind of inverted structure light emitting diode with quantum dots and preparation method thereof Download PDFInfo
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Abstract
This application discloses a kind of inverted structure light emitting diode with quantum dots and preparation method thereof, including substrate, cathode, electron transfer layer, quantum dot light emitting layer, hole transmission layer and the anode stacked gradually, the electron transfer layer is metal-oxide film prepared by sol-gal process, and the upper surface of the electron transfer layer has interface-modifying layer.The QLED is inverted structure device, can be integrated with ripe n-channel a Si base TFT driving circuits, and by selecting transparent cathode or anode that can realize bottom emitting, top emitting, pushes up bottom emitting transparent devices.A kind of inverted structure light emitting diode with quantum dots described herein and preparation method thereof introduces electron transfer layer decorative layer, can effectively reduce the work function of cathode, and improve the pattern of electron transfer layer, reduces influence of the electron transfer layer to quantum dot light emitting layer.A kind of efficiency of inverted structure light emitting diode with quantum dots described herein is obviously improved, and efficiency leads and bounds ahead of other and is inverted quantum dot device.
Description
Technical field
The present invention relates to photoelectric device technical fields, and in particular to a kind of efficient two pole of inverted structure quantum dot light emitting
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
That grain size is less than or the semiconductor nanocrystal close to Exciton Bohr Radius, the scale of three of them dimension usually in 10nm hereinafter,
The movement of internal electrons and holes in all directions is restricted.Quantum dot applied to illumination field generally has
Nucleocapsid structure, surface is by ligand passive.Since electrons and holes are by quantum confinement, quantum dot has discrete level structure.This
The discrete level structure of kind causes quantum dot to have unique optical property.It is stimulated whenever by light or electricity, quantum dot will
Fluorescence is sent out, 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 out.The glow peak of quantum dot is narrow, luminescent color is with own dimensions are adjustable, luminous efficiency is high, very
It is suitable as the luminescent material of display device.OLED is compared, QLED has theoretical luminous efficiency higher, Color tunable, colour gamut more
Extensively, color saturation and vividness be more preferable, the more low advantage of energy consumption cost so that quanta point electroluminescent technology becomes the next generation
The advantageous candidate of novel display technology.
In recent years, the QLED progress that all acquirement can be very big on material and device architecture.Wherein, it is inverted in terms of device architecture
QLED devices because its with many significant advantages by extensive concern.Most prominent is exactly to be inverted device to have splendid duty ratio,
The aperture opening ratio of nearly 100 ﹪ can be achieved, so as to which pixel space is made full use of to design multitube driving circuit.Compared to LTPS techniques into
This height and can only small area applications the shortcomings that, being inverted device can integrate with ripe n-channel a-Si base TFT driving 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 electricity
Sub- transport layer shows very excellent performance to being inverted meaning of the QLED development with milestone, the QLED devices of preparation.But
It is the methods of preparation of these materials is generally required through magnetron sputtering, atomic layer deposition, not only takes and cost is very high.Cause
This, prepares electron-transport layer film with solwution methods such as sol-gel methods, is necessary so as to reduce QLED costs.But
Prepared by solwution method faces many technical barriers, such as how to eliminate or reduce in upper layer of material coating process to its subsurface material again
Influence it is most important to the performance of device.
On the other hand, the light extraction of QLED devices is confined, and the refractive index in device between layers mismatches, gold
Belong to the taking-up that electrode surface plasmon, base substrate loss etc. can all limit light, fundamentally limit its efficiency into one
Step development.Research shows that optimizing and improving to device using light control technique, interface optimization technique etc., device can be realized
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..
Chinese patent application No. is 200880007531.6 discloses a kind of inorganic light-emitting dress based on core shell quantum dots
It puts, including transparent substrates, first electrode, the second electrode opposite with first electrode, quantum dot polycrystalline luminescent layer.This shines
The device not electronics containing level-density parameter, hole transmission layer, not containing decorative layer and light extraction structures, device performance is poor, nothing
Method meets the needs of practical application.
Application No. is 201010171667.X, 201410146156.0 Chinese patents to disclose a kind of quantum dot light emitting
Device, and electrons and holes transport layer is 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, the AZO cathodes modified using Cs2CO3 are disclosed, device performance obtains
It is promoted.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 using ZnO nano particle, and since electron transfer layer is not modified, light takes out limited
System, the device EQE of optimum performance is only 2.72%.
Invention content
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.
This application involves a kind of inverted structure light emitting diode with quantum dots, substrate, cathode, electronics including stacking gradually pass
Defeated layer, quantum dot light emitting layer, hole transmission layer and anode, the metal oxidation that the electron transfer layer is prepared for sol-gel method
Object film, the upper surface of the electron transfer layer have interface-modifying layer.The QLED is inverted structure device, can be with maturation
N-channel a-Si base TFT driving circuits integrate, and by selecting transparent cathode or anode that can realize bottom emitting, top emitting, push up
Bottom emitting transparent devices.
Preferably, the upper surface of the electron transfer layer is additionally provided in paracycle or aperiodicity shape and refractive index edge
The nano concavo-convex structure that outgoing light direction changes in gradient.
Preferably, the substrate is glass or flexiplast or glass or plastic base equipped with TFT driving circuits.
Preferably, at least a kind of in the anode and cathode is transparent.
Preferably, cathode electrode or, described made of indium tin oxide or aluminium zinc oxide or AgNW materials
Cathode is electrode made of Al or Ag or Mg or Ca or Ba materials.
Preferably, the anode is electricity made of indium tin oxide or fluorine tin-oxide or aluminium zinc oxide or AgNW materials
Pole or, the anode are electrode made of Au or Pt or Pd materials.
Preferably, the electron transport layer materials are ZnO or TiOx, preparation method is sol-gel method.
Preferably, the hole transmission layer is Polyglycolic acid fibre-poly- (styrene sulfonate), poly- (9- vinyl clicks
Azoles), it is one or more in poly- [bis- (4- phenyl) (2,4,6- trimethylphenyls) amine].
Preferably, the interface-modifying layer is polyethyleneimine, polyethoxy aziridine, 9,9- dioctyl fluorenes -9,9-
It is one or more in bis- (N, N- DimethylAminopropyl) fluorenes.
Preferably, the quantum dot in the quantum dot light emitting layer is one or more in red, green, blue color quantum dot, amount
For son point containing the ligand that stable coordination can be formed with surface, the quantum dot light emitting layer is single-layer or multi-layer.
The application further relates to a kind of preparation method of inverted structure light emitting diode with quantum dots, the preparation method packet
It includes：Cathode layer is set on substrate, electron transfer layer is made on the substrate with cathode layer, in the electron transfer layer
Upper surface introduces interface-modifying layer, makes quantum dot light emitting layer, hole successively on the electron transfer layer with interface-modifying layer
Transport layer and anode.
Preferably, the 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, ethyl alcohol, deionized water and is cleaned by ultrasonic, dry after the completion of cleaning, then carry out
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, formed electron transfer layer, on the electron transport layer spin coating modification layer film, formed interface repair
Adorn layer；(4) by spin coating quantum dot solution on the decorative layer of step (3), quantum dot light emitting layer is formed；(5) in quantum dot light emitting layer
Upper spin coating hole transmission layer；(6) one layer of metal anode is plated on step (5) hole transmission layer.
Preferably, step (3) further includes, and coining goes out nano concavo-convex knot on the electron transfer layer with interface-modifying layer
Structure.
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
Impression block coining on the electron transfer layer with interface-modifying layer goes out a nanometer concaveconvex structure.The soft coining of 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, demoulding and etc..
Preferably, the 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 accounts between 20-30nm
Sky is than between 0.5-0.6.
Preferably, quantum dot light emitting layer thickness control is 30-100nm, thickness of hole transport layer 40-100nm, and anode is thick
Degree control is 100-200nm.
Preferably, the light emitting diode with quantum dots production method is solwution method, including rotary coating, slot coated, is scraped
It is one or more in painting, intaglio printing, silk-screen printing, inkjet printing, compatible roll-to-roll preparation process.
Preferably, 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
It rings.
Preferably, the material of impression block is selected from quartz, silicon, nickel, carbon in the organic solar batteries production method
Plain steel, silicon carbide, Al-Doped ZnO, makrolon, polyvinyl chloride or polybutyl methacrylate, dimethione, polyphenyl
One kind in ethylene, acrylic acid or perfluoropolyether.
According to the above aspect of the present invention, the present invention has at least the following advantages：
A kind of inverted structure light emitting diode with quantum dots described herein and preparation method thereof introduces electron transfer layer and repaiies
Layer is adornd, can effectively reduce the work function of cathode, and improve the pattern of electron transfer layer, electron transfer layer is reduced and quantum dot is sent out
The influence of photosphere.A kind of efficiency of inverted structure light emitting diode with quantum dots described herein is obviously improved, effect
Rate leads and bounds ahead of other and is inverted quantum dot device.
Description of the drawings
Attached drawing 1 is the light emitting diode with quantum dots structure diagram of the present invention；
Attached drawing 2 is that light emitting diode with quantum dots of the present invention integrates structure with n-channel a-Si base TFT driving circuits
The technical solution schematic diagram of active matrix driving array QLED (AMQLED)；
Attached drawing 3 is the template schematic diagram that nanometer embossing of the present invention has nano concavo-convex structure；
Attached drawing 4 is the schematic shapes of nano concavo-convex structure under specific embodiment；
Attached drawing 5 is that one sol-gel method ZnO film of embodiment introduces the scanning electron microscope knot after nano concavo-convex structure
Structure schematic diagram；
Attached drawing 6 is that the specific embodiment of the invention one, embodiment two and the comparison of comparative example current density voltage curve are shown
It is intended to；
Attached drawing 7 is that the specific embodiment of the invention one, embodiment two and the comparison of comparative example brightness-voltage curve are illustrated
Figure；
Attached drawing 8 is that the specific embodiment of the invention one, embodiment two and comparative example power efficiency-voltage curve comparison are shown
It is intended to；
Attached 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；
Attached drawing 10 is the specific embodiment of the invention one, embodiment two and comparative example EL spectrum contrast schematic diagrams.
Specific embodiment
In order to which those skilled in the art is made to more fully understand the technical solution in the present invention, below in conjunction with the accompanying drawings and implement
Example is described in further detail the specific embodiment of the present invention.Following embodiment is used to illustrate the present invention, but be not used to limit
The scope of the present invention processed.
The present 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, substrate 101, cathode 102, electronics including stacking gradually pass
Defeated layer 103, quantum dot light emitting layer 104, hole transmission layer 105 and anode 106.
The metal-oxide film that the electron transfer layer is prepared for sol-gel method, preferably ZnO film, upper surface
It is received with interface-modifying layer or equipped with what is changed in gradient in paracycle, aperiodicity shape and refractive index edge outgoing light direction
Rice concaveconvex structure 107 has both the two.
The inverted structure light emitting diode with quantum dots can be integrated with ripe n-channel a-Si base TFT driving circuits, and
By selecting transparent cathode or anode that can realize bottom emitting, top emitting, bottom emitting transparent devices are pushed up.
Fig. 2 gives a kind of utilization inversion light emitting diode with quantum dots and is integrated with n-channel a-Si base TFT driving circuits
Build the technical solution of active drive array QLED (AMQLED).Equipped with the base with n-channel a-Si base TFT driving circuits 202
On plate 201, preferably glass or transparent plastic substrate make the inverted structure QLED devices 100 and form rgb pixel array, as
Respectively the leads 203 such as independent cathode leg, scan line, data line are connected to driving circuit 207 to pixel array, then pass through winding displacement
205 are connected to sequential control circuit 208；The public anode 206 of pel array equally introduces timing control electricity by lead 204
Road forms active drive array QLED (QLED) display panel.QLED devices select transparent cathode or anode that can realize that bottom is sent out
It penetrates, top emitting, pushes up bottom emitting transparent devices.Wherein, top emitting QLED can realize the aperture opening ratio of nearly 100 ﹪, and pixel arrangement is closeer
Collection, display panel brightness higher.
It makes in the integrated QLED device process, transparent indium tin oxide, aluminium zinc oxide may be selected in cathode 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 functions reflecting electrode such as Pt and Pd, the preferred 100-200nm of thickness.But at least a kind of in anode and cathode is transparent.
It makes in the integrated QLED device process, 103 material of electron transfer layer is ZnO or TiOxSoft metal aoxidizes
Object film, preparation method are sol-gel method, 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 301 nano impression of impression block 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, silicon carbide, Al-Doped ZnO, makrolon, polychlorostyrene second
One kind in alkene or polybutyl methacrylate, dimethione, polystyrene, acrylic acid or perfluoropolyether.In template
Pass through any one technique system in chemical etching, electron beam deposition, evaporation, sputtering, laser direct-writing, holography, self-assembling method
It is standby with the matched nano concavo-convex array of structures 302 of pixel size, and make alignment mark 303.
103 interface-modifying layer of electron transfer layer is polyethyleneimine (PEI), polyethoxy aziridine (PEIE), 9,9-
Any one or more in bis- (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
It is one or more in (9- vinyl carbazoles) (PVK), poly- [bis- (4- phenyl) (2,4,6- trimethylphenyl) amine] (PTAA), it is 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 the ligand that stable coordination can be formed with surface, which can be that individual layer be alternatively multilayer.
The advantageous effect further illustrated the present invention 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 period preferred 400nm, groove depth 50nm, duty ratio 0.6.
A kind of light emitting diode with quantum dots with nanometer light extraction structures, comprising on substrate transparent cathode,
ZnO electron transfer layers, CdSe/ZnS quaternary graded alloy quantum dot light emitting layer, PVK/PEDOT：PSS composite hole transporting layers and
The methods of Al metal anodes, the preferred solwution method spin coating of specific manufacture craft of each layer structure, vacuum thermal evaporation 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 cathode cleaning：After common float glass substrate base is cleaned with detergent, pattern is sputtered in one side
The ito thin film of change is as transparent cathode.By the substrate base with ITO be sequentially placed into detergent, deionized water, acetone, ethyl alcohol,
In deionized water, it is cleaned by ultrasonic 10min every time, cleaning is completed to be placed on 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 bis- water zinc acetate (Zn (CH of 110mg3COO)2·2H2O, 99.5%, Sigma-
Aldrich 1mL) is dissolved in 2-methyl cellosolve (CH3OCH2CH2OH, 99.8%, Sigma-Aldrich) in solution, then
Add in 30 μ L ethanol amines (NH2CH2CH2OH, Sigma-Aldrich) solution, stirs 12h at 50 DEG C, before obtaining ZnO sol-gels
Drive liquid solution.
(3) electron transfer layer makes and structure introduces：Spin coating one on the substrate base handled well in air in step (1)
Layer ZnO precursor solution.Control rotating speed is 4000rpm, time 60s, is subsequently placed in temperature control version and covers PDSM making ides
Plate, applies the pressure of 3bar, 150 DEG C of annealing 10min, obtains on the ZnO film and film that thickness is 40-60nm the period about
400nm, groove depth about 20nm, the random nano concavo-convex structure of standard that duty ratio is 0.6.Sol-gel method ZnO is given referring to Fig. 5
Film introduces the scanning electron microscope structural representation after structure.Particularly, the pressure of application need to accurately control to obtain low slot
Deep structure, reduces the influence to quantum dot light emitting layer pattern.
(4) by step (3), treated that substrate is transferred to glove box, spin coating quantum dot solution.Quantum dot therein is
CdSe/ZnS nucleocapsids, and ternary alloy three-partalloy transition component is added in CdSe luminous nucleons and ZnS shells, realize the gradually mistake of lattice
It crosses, effectively reduces internal pressure caused by quantum dot lattice defect, so as to make quantum dot that there is higher luminous efficiency and steady
Qualitative, glow peak 529nm, half-peak breadth is about 24nm.Quantum dot is dispersed in normal octane, concentration about 10mg/ml, and spin coating turns
Speed is 1500rpm, time 60s.Then 150 DEG C of high annealing 10min, this process play 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 obtains the quantum dot that thickness is 40-60nm
Film.
(5) hole transmission layer makes：The o-dichlorobenzene solution (a concentration of 10mg/ml) of spin coating PVK, 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 are
2000rpm, spin-coating time 60s, then 90 DEG C of annealing 15min.Obtain the PVK/PEDOT of thickness about 80nm：The compound hole transports of PSS
Layer.
(6) metal anode makes：By above-mentioned steps (5) processing substrate be transferred to hot evaporation system, vacuum degree >=1 ×
10-4One layer of aluminium electrode is deposited under the conditions of Pa, thickness is sent out for 100-150nm to get to the quantum dot with nanometer light extraction structures
Optical diode.
Embodiment two
A kind of light emitting diode with quantum dots with electron transfer layer decorative layer, comprising on substrate transparent cathode,
ZnO electron transfer layers, PEI decorative layers, CdSe/ZnS quaternary graded alloy quantum dot light emitting layer, PVK/PEDOT：PSS compound airs
The methods of cave transport layer and Al metal anodes, the preferred solwution method spin coating of specific manufacture craft of each layer structure, vacuum thermal evaporation 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 cathode cleaning：With embodiment one.
(2) ZnO precursor solution is prepared：With embodiment one.
(3) electron transfer layer makes and modifies：One layer of spin coating on the substrate base handled well in air in step (1)
ZnO precursor solution.It is 4000rpm to control rotating speed, time 60s, 120 DEG C of annealing 10min obtain thickness as 40-60nm's
ZnO film；The 2-methyl cellosolve solution (a concentration of 0.4wt%) of spin coating PEI on ZnO film, control rotating speed are
5000rpm, time 60s, 100 DEG C of annealing 10min, obtain the modification layer film that thickness is 4-8nm.
(4) quantum dot light emitting layer makes：With embodiment one.
(5) hole transmission layer makes：With embodiment one.
(6) metal anode makes：As in the first embodiment, obtain two pole of quantum dot light emitting with electron transfer layer decorative layer
Pipe.
Comparative example
A kind of light emitting diode with quantum dots includes transparent cathode, 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 layer structure
The methods of 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 cathode cleaning：With embodiment one.
(2) ZnO precursor solution is prepared：With embodiment one.
(3) electron transfer layer makes：Spin coating layer of ZnO forerunner on the substrate base handled well in air in step (1)
Liquid solution.It is 4000rpm to control rotating speed, time 60s, 120 DEG C of annealing 10min obtain the ZnO film that thickness is 40-60nm.
(4) quantum dot light emitting layer makes：With embodiment one.
(5) hole transmission layer makes：With embodiment one.
(6) metal anode makes：As in the first embodiment, 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 are obviously improved.Light emitting diode with quantum dots is inverted using high-performance prepared by the present invention,
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 the electric field line close to cathode side can then be caused more to concentrate, electric field strength bigger improves electronics
Injection reduces the cut-in voltage of 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 cathode, and improve the pattern of sol-gel ZnO, reduce influences of the ZnO to quantum dot light emitting layer.
The above is only the preferred embodiment of the present invention, is not intended to restrict 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 several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (15)
1. a kind of inverted structure light emitting diode with quantum dots, including substrate, cathode, electron transfer layer, the quantum dot stacked gradually
Luminescent layer, hole transmission layer and anode, it is characterised in that：The metal oxidation that the electron transfer layer is prepared for sol-gel method
Object film, the upper surface of the electron transfer layer have interface-modifying layer.
2. a kind of inverted structure light emitting diode with quantum dots according to claim 1, which is characterized in that the electronics passes
The upper surface of defeated layer is additionally provided with the nanometer changed in gradient along outgoing light direction in paracycle or aperiodicity shape and refractive index
Concaveconvex structure.
3. a kind of inverted structure light emitting diode with quantum dots according to claim 1, which is characterized in that the substrate is glass
Glass or flexiplast or glass or plastic base equipped with TFT driving circuits.
4. a kind of inverted structure light emitting diode with quantum dots according to claim 1, which is characterized in that the anode and the moon
At least a kind of in extremely is transparent.
5. a kind of inverted structure light emitting diode with quantum dots according to claim 4, which is characterized in that
The cathode made of indium tin oxide or aluminium zinc oxide or AgNW materials electrode or
The cathode is electrode made of Al or Ag or Mg or Ca or Ba materials.
6. a kind of inverted structure light emitting diode with quantum dots according to claim 4, which is characterized in that the anode is indium
Electrode made of tin-oxide or fluorine tin-oxide or aluminium zinc oxide or AgNW materials or
The anode is electrode made of Au or Pt or Pd materials.
A kind of 7. inverted structure light emitting diode with quantum dots according to claim 1, which is characterized in that the electron-transport
Layer material is ZnO or TiOx。
A kind of 8. inverted structure light emitting diode with quantum dots according to claim 1, which is characterized in that the hole transport
Layer is Polyglycolic acid fibre-poly- (styrene sulfonate), poly- (9- vinyl carbazoles), poly- [bis- (4- phenyl) (2,4,6- front threes
Base phenyl) amine] in it is one or more.
A kind of 9. inverted structure light emitting diode with quantum dots according to claim 1, which is characterized in that the modifying interface
Layer is one in polyethyleneimine, polyethoxy aziridine, bis- (N, the N- DimethylAminopropyl) fluorenes of 9,9- dioctyl fluorenes -9,9-
Kind is a variety of.
A kind of 10. inverted structure light emitting diode with quantum dots according to claim 1, which is characterized in that the quantum dot
For quantum dot in luminescent layer to be one or more in red, green, blue color quantum dot, quantum dot contains can form stable match with surface
The ligand of position, the quantum dot light emitting layer are single-layer or multi-layer.
11. a kind of preparation method of inverted structure light emitting diode with quantum dots a kind of as described in any one of claim 1~10,
It is characterized in that, the preparation method includes：Cathode layer is set on substrate, electronics is made on the substrate with cathode layer and is passed
Defeated layer introduces interface-modifying layer, on the electron transfer layer with interface-modifying layer in the upper surface of the electron transfer layer
Quantum dot light emitting layer, hole transmission layer and anode are made successively.
12. a kind of preparation method of inverted structure light emitting diode with quantum dots according to claim 11, which is characterized in that
The preparation method specifically,
(1) cathode layer is made on substrate, and 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 electron-transport
Layer, spin coating modification layer film, forms interface-modifying layer on the electron transport layer；
(4) by spin coating quantum dot solution on the decorative 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) one layer of metal anode is plated on step (5) hole transmission layer.
13. a kind of preparation method of inverted structure light emitting diode with quantum dots according to claim 12, which is characterized in that
Step (3) further includes, the coining nano concavo-convex structure on the electron transfer layer with interface-modifying layer.
14. a kind of preparation method of inverted structure light emitting diode with quantum dots according to claim 13, which is characterized in that
The cathode thickness is controlled in 100-200nm；Electron transfer layer thickness control is 40-80nm；Interface-modifying layer thickness control
For 4-15nm；Between nano concavo-convex structural cycle 200-600nm, groove depth is between 20-30nm, between duty ratio 0.5-0.6.
15. a kind of preparation method of inverted structure light emitting diode with quantum dots according to claim 13, which is characterized in that
Quantum dot light emitting layer thickness control is 30-100nm, and thickness of hole transport layer 40-100nm, anode thickness control is 100-
200nm。
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